JPH0830873B2 - A silver halide color photographic light-sensitive material having excellent sharpness and graininess and good photographic performance. - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it is a halogenated compound which is excellent in graininess and sharpness and gives a color image having good photographic performance. The present invention relates to a silver color photographic light-sensitive material.

[Conventional technology]

It is demanded to improve the performance of silver halide color photographic light-sensitive materials in various respects. Especially, with the recent shift to small format of photographic light-sensitive materials, silver halide color photographic light-sensitive materials are also required to have graininess and sharpness. There is a demand for improvement to obtain high image quality.

Further, at present, a so-called negative / positive method in which color photographs are taken by using a color negative film, enlarged on color paper, and printed to obtain a color print is widely used. One of the reasons why the negative / positive method is popular is
The color negative film has a very large exposure range (latitude), and the probability of failure when shooting is very low,
It means that even general users without specialized knowledge can easily take color pictures. This is a major feature of the negative / positive system, unlike reversal films.
However, it is important for the color negative film to have a wide latitude in addition to the above-mentioned improvement in graininess and sharpness.

Conventionally, various proposals have been made in this kind of technical field with the intention of increasing the sensitivity or improving the graininess, but among them, there are those that try to improve the performance by improving the layer structure on the support. is there.

For example, instead of containing a red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer alone, each emulsion has a high sensitivity emulsion layer (faster emulsion layer).
r) and a slower emulsion layer (slower emulsion layer) are allowed to exist at the same time, and each color sensitivity is composed of a high-sensitivity layer and a low-sensitivity layer.

It is also known that a unit is composed of a plurality of layers, and each layer of the unit is sensitized to the same three sets of visible spectra, and is applied to a photographic element for color photography. British Patent No. 818687 discloses a relatively fast cyan-forming silver halide emulsion (sensitized for red light) coated, for example, on a relatively slow emulsion having otherwise similar characteristics. However, it is disclosed that the sensitivity (speed) can be increased thereby and the latitude can be improved. Applying the technique disclosed in this British patent to all three of the color composite units would have similar results. However, the sharpness and graininess are not a problem, and these points are not yet satisfactory.

Also, in U.S. Pat.No. 366228, for example, in FIG. 1C of the drawing, a layer having relatively high sensitivity and having undergone blue light sensitization, green light sensitization and red light sensitization has relatively low sensitivity. And coated above the sensitized emulsion layer corresponding to the above layers. This is intended to result in a photographic element having greater latitude than a conventional three layer color film element. However, in this U.S. patent, the units of the relatively high speed emulsion layer and the relatively low speed emulsion layer are separated by an ND (neutral density) filter. Therefore, as is apparent from the above, the improvement in speed and the increase in sensitivity are not the problems of the US patent, and the sharpness and graininess are not particularly problems. In this US patent, these sharpness and graininess are still considered to be insufficient.

Next, U.S. Pat. No. 3,658,536 discloses a green-sensitive emulsion layer, which has a great influence on the luminous efficiency, farther from a support, as shown in FIG. 5 of the drawings attached to the specification. Although a technique for eliminating the exposure amount loss of the layer by disposing the layer on the surface side is disclosed, this patent also fails to sufficiently improve the sharpness and graininess.

In addition to the above, the technique described in Japanese Patent Application Laid-Open No. 51-49027 is known as a technique relating to the change of layer structure. However, in all of these, the effect of improving the image quality such as the graininess of the emulsion layers having green and red sensitivities and especially the sharpness is insufficient.

Conventionally, in a color negative film for photographing, it is effective to reduce the average grain size of silver halide grains to be used in order to improve graininess, and in order to improve sharpness, the whole photographic composition is used. It is considered effective to reduce the thickness of the layer, and in fact, new products of each photographic material manufacturer in the past several years have been improved in graininess and sharpness by the above-mentioned means.

With color negative films for photography currently on the market,
In each case, a technique (multilayer constitution technique) in which each of the color-sensitive layers as described above is made plural and separated into a high-sensitivity emulsion layer and a low-sensitivity emulsion layer is adopted, but as a result of the research conducted by the present inventors, at least With a multi-layered structure like this for a conventional photosensitive material of ISO 100 level, even if the silver halide grains to be used are made smaller, it is difficult to see a significant improvement in graininess, and the sharpness is also improved in thinning. It has been found that it is very difficult to produce a remarkable color negative film having a dry film thickness of 15 μm or less without deteriorating various other photographic performances.

[Object of the Invention]

An object of the present invention is to solve the above-mentioned problems of the prior art,
It has excellent sharpness, excellent graininess, and does not damage the latitude.
Moreover, another object is to provide a silver halide color photographic light-sensitive material having sufficient other photographic performance (maximum density, etc.).

[Structure and Action of Invention]

The above-mentioned object is to provide a support and a silver halide color photographic light-sensitive material comprising a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer provided on the support, and the above blue-sensitive The color-sensitive emulsion layer is composed of at least two layers, and the layers farthest from the support among the blue-sensitive emulsion layers are arranged so that the maximum color density is maximized. This is achieved by a silver halide color photographic light-sensitive material characterized by containing a yellow coupler represented by the general formula [Y-I].

General formula [Y-I] However, in the above general formula [Y-I], R ₁ and R ₂ are respectively
Represents a hydrogen atom or a substituent.

The silver halide color photographic light-sensitive material of the present invention comprises a support and a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer provided on at least one surface of the support. If necessary, in addition to the above basic structure consisting of a support and a photosensitive layer, an underlayer, a backing layer, an intermediate layer,
A non-photosensitive layer such as a protective layer or an antihalation layer may be provided.

The above configuration is based on the results of earnest studies by the present inventors. That is, the inventors of the present invention went back to the basics of color photography and, in a simple layer structure (single layer structure) in which each color-sensitive layer consisted of only one layer, the latest silver halide grain technology of monodispersibility (Core / shell structure) When a silver halide grain and a specific yellow coupler with high color development but low molecular weight were applied, the single layer structure, which was surprisingly disadvantageous in the past, had both graininess and sharpness. I found out that there are cases where it will be advantageous.

Then, it was found that the improvement of the graininess and the sharpness in the above-mentioned single layer constitution is caused by reducing the film thickness of the layer on the color sensitive layer.

However, it has a problem that it is inferior to the conventional multi-layered light-sensitive material in which each color-sensitive layer has a multi-layered structure in that it has a wide latitude, which is a major feature of the color negative film.

Therefore, the present inventors have conducted intensive studies to overcome this problem and realize the surprising effect of improving the image quality of the above single-layer structure.

In the conventional color negative film, the layer farther from the support is the high-sensitivity layer, and the grain size of the silver halide grains as the photoconductor is large. To prevent deterioration of graininess, the high-sensitivity layer contains many silver halide grains. When present, the coupler was present in a small amount to keep the maximum color density low.

However, the main part of the exposure area used in normal photography is not such a highest sensitivity layer, but a low sensitivity layer closer to the support than that and a layer often used for image formation is
It is considered that the above-mentioned high-sensitivity layer was provided on the upper side, so that the graininess and sharpness were deteriorated.

The present inventors have energetically investigated the exposure area in which the actual negative film is used, and it is clear that among the latitudes of the wide color negative film, those actually used are concentrated in an extremely narrow area. I chose

In other words, the exposure area used for normal shooting (called the main exposure area) is quite narrow relative to the latitude of the negative film, so this area is the layer farthest from the support with less image deterioration in the same photosensitive layer. By arranging the same in the normal photographing range, an image quality equivalent to that of the above-mentioned single-layer photosensitive material can be obtained with a fairly high probability.

And by arranging a layer having a sensitivity deviating from the main exposure area in a layer near the support with a large deterioration in image quality, the image quality is inferior to that in the case of normal exposure even in the case of an exposure error that appears extremely rarely, The mistake is gone.

The layer farthest from the support of the present invention is not necessarily the low-sensitivity layer as shown in JP-A-62-63936. In short, it is a layer that has the sensitivity of the main exposure area with a high probability of being used,
It may contain a single silver halide emulsion or a mixture of a plurality of emulsions having different sensitivities.

According to the investigation by the present inventors, the main exposure area is 1.0 in the case of blue density (blue color sensitive layer) as the color density of the color negative.
Or more, preferably 1.5 or more, more preferably 1.9 or more, in the case of green density (green color sensitive layer) and red density (red color sensitive layer) 0.8 or more, preferably 1.0 or more, more preferably 1.2 or more. good. Also, each is designed to have a color density higher than the maximum color density of the same photosensitive layer depending on the support. Examples of typical layer structures are shown below, but the present invention is not limited to these structures.

Example of layer constitution (layer order is from the support side) (1) Support-red color non-main exposure area layer (hereinafter referred to as RS), red color main exposure area layer (hereinafter referred to as RM) -Green color main non-main exposure area layer (hereinafter referred to as GS) -Green color main exposure area (hereinafter referred to as GM) -Yellow filter layer (hereinafter referred to as YC)
-) Blue-sensitive non-primary exposure area layer (hereinafter referred to as BS)-
Blue color main exposure area layer (hereinafter referred to as BM) (2) Support-RS-GS-BS-RM-GM-YC-BM (3) Support-RM-GS-GM-YC-BS-BM (4) Support-RS-RM-GM-YC-BS-BM (however, the maximum color density is M> S) These silver halide color photographic light-sensitive materials are used between layers or between a layer and a support. , Any non-color sensitive layer (gelatin layer, dye-containing layer, protective layer) on the furthest layer from the support
Can have.

In the present invention, the dry film thickness of the entire photographic constituent layer is 20
The thickness is preferably not more than μm, but a dry film thickness of 10 to 15 μm is particularly preferable in order to greatly improve the graininess and sharpness.

When the dry film thickness is more than 20 μm, the improvement in graininess and sharpness, which is the object of the present invention, becomes small, and when the dry film thickness is 10 μm or less, it becomes difficult to obtain a sufficient maximum concentration.

In the present invention, monodisperse silver halide is preferably used. Here, the monodispersity means that the value obtained by dividing the standard deviation of the grain size distribution of silver halide grains by the average grain size is 0.20 or less. The grain size is the diameter when the spherical silver halide is converted into its diameter, and when the grain is not spherical, the projected image is converted into a circular image having the same area.

Core / shell type silver halide grains are particularly preferable. The core / shell type is a silver halide grain having different silver halide compositions between the inside and the surface area.

The grain size of the silver halide used in the present invention is not particularly limited, but the average grain size is preferably 0.6 μm or less from the viewpoint of graininess and sharpness, and particularly preferably the average grain size.
The use of silver halide grains of 0.2 μm to 0.5 μm.

When the average particle size is larger than 0.6 μm, the sharpness and graininess of the present invention are slightly improved, and the average particle size is 0.2 μm.
If it is less than m, it may be difficult to obtain sufficient sensitivity and maximum density.

The additives used in the present invention include sensitizing dyes, stabilizers,
Examples include hardeners and antifoggants. Any of these additives known in the art can be used.

The yellow coupler represented by formula [Y-I] will be described below.

General formula [Y-I] However, in the above general formula [Y-I], R ₁ and R ₂ are respectively
Representing a hydrogen atom or a substituent, preferred among the substituents are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, Carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryl There are oxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, and aryloxycarbonyl group. X represents a hydrogen atom, a halogen atom, a carboxyl group, or a group that couples with carbon at the coupling position via an oxygen atom, a nitrogen atom, or a sulfur atom to cause coupling off.

More preferably, R ₁ and R ₂ are halogen atoms (for example,
Chlorine atom, bromine atom, etc.), substituted or unsubstituted alkyl group (eg, methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, 3- (2,4-di-t)
-Amylphenoxy) propyl group, allyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-
Hexysulfonylethyl group, cyclopentyl group, benzyl group, etc., substituted or unsubstituted aryl group (eg phenyl group, 4-t-butylphenyl group, 2,4-di-t-)
Amylphenyl group, 4-tetradecamidophenyl group and the like), heterocyclic group (5-, 5-membered ring group including O, N, S, etc., such as 2-furyl group, 2-thienyl group, 2-pyrimidinyl group,
2-benzothiazolyl group, etc., cyano group, alkoxy group, (for example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group, (for example, phenoxy group). Group, 2-methylphenoxy group, 4-t-
Butylphenoxy group, etc.), heterocyclic oxy group (eg 2
-Benzimidazolyloxy group), acyloxy group (e.g. acetoxy group, hexadecanoyloxy group etc.), carbamoyloxy group, (e.g. N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group etc.), silyloxy group (e.g. Trimethylsilyloxy group etc.), sulfonyloxy group (eg dodecylsulfonyloxy group etc.), acylamino group (eg acetamide group, benzamide group, tetradecanamide group, etc.)
α- (2,4-di-t-amylphenoxy) butyramide group, γ- (3-t-butyl-4-hydroxyphenoxy) butyramide group, α- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide group Such),
Anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5 -{Α
-(3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino group etc.), ureido group (eg phenylureido group, methylureido group, N, N-dibutylureido group etc.), imide group (eg N-succinimide) Group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoylamino) phthalimido group, etc.), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino group, N-methyl-N-deoxy group). Cisulfamoylamino group, etc., alkylthio group (eg, methylthio group,
Octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-
(4-t-butylphenoxy) propylthio group etc.),
Arylthio group (eg, phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-
Tetradecanamidophenylthio group, etc.), heterocyclic thio group (eg 2-benzothiazolylthio group etc.), alkoxycarbonylamino group (eg methoxycarbonylamino group, tetradecyloxycarbonylamino group etc.), aryloxycarbonylamino group ( For example, phenoxycarbonylamino group, 2,4-di-t-butylphenoxycarbonylamino group, etc., sulfonamide group (eg, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecane) Sulfonamide group, 2
-Methyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-
Dodecyloxyethyl) carbamoyl group, N-methyl-
N-dodecylcarbamoyl group, N- {3- (2,4-di-
t-amylphenoxy) propyl} carbamoyl group, etc., acyl group (eg acetyl group, (2,4-di-t-
Amylphenoxy) acetyl group, benzoyl group, etc.),
Sulfamoyl group (for example, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N- (2-dodecyloxyethyl) sulfamoyl group, N-ethyl-
N-dodecylfamoyl group, N, N-diethylsulfamoyl group, etc., sulfonyl group (eg, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (eg, octansulfinyl group, dodecane) Sulfinyl group, benzenesulfinyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, 3-pentadecyloxycarbonyl group) Group, etc., and X is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.), a carboxy group, or a group linked by an oxygen atom (eg, acetoxy group, propanoyloxy group). Group, benzoyloxy group, 2,
4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyrvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidephenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group Group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-
Phenethyloxy group, 2-phenoxyethoxy group, 5-
Phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), groups linked by nitrogen atoms (for example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,4) , 5,6-Pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo- 3-oxazolidinyl group, 1-
Benzyl-5-ethoxy-3-hydantoinyl group, 2N-
1,1-dioxo-3 (2H) -oxo-1,2-benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 4-acetamido-1- Pyrazolyl group, 3,5-dimethylpyrazolyl group, 4- (3-hydroxypropyl) -1-pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl,
5- or 6-bromo-benzotriazol-1-yl group, 5-methyl-1,2,3-triazol-1-yl group,
Benzimidazolyl group, 3-benzyl-1-hydantoinyl group, 1-benzyl-5-hexadecyloxy-3-
Hydantoinyl group, 5-methyl-1-tetrazolyl group,
Arylazo group (for example, 4-methoxyphenylazo group,
4-pivaloylamino-3-hydroxyphenylazo group, β-naphthylazo group, 4-hydroxy-3-methylphenylazo group, 4-pivaloylaminophenylazo group, etc.), a group linked by a sulfur atom (for example, phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5
-T-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2- (2-hexanesulfonylethyl) -5-t-octylphenylthio group , Benzylthio group, 2-cyanoethylthio group, 1-
Ethoxycarbonyltridecylthio group, 5-phenyl-
2,3,4,5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group,
2-phenyl-3-dodecyl-1,2,4-triazolyl-
5-thio group). Further, X may form a dimer or higher multimer.

More specifically, the divalent group in which R ₁ , R ₂ or X is a divalent group to form a bis form is as follows. R ₁ or R ₂ is a substituted or unsubstituted alkylene group (eg methylene group, ethylene group, 1,10-decylene _{group, -CH 2 CH 2 -O-CH} 2 CH 2 - , etc.), a substituted or unsubstituted phenylene group (e.g., 1,4
Phenylene group, 1,3-phenylene group, -NHCO-R ₈ -CONH- group (R ₈ represents a substituted or unsubstituted alkyl group or a phenylene group, for example, -NHCOCH ₂ CH ₂ CONH-, -S-R ₉ -S group (R ₉ represents a substituted or unsubstituted alkylene group, _{e.g., -S-CH 2 CH 2 -S-} , Etc.) and X represents a divalent group at an appropriate place from the above monovalent group.

When the vinyl monomer contains one represented by the general formula [Y-I], the vinyl group may have a substituent other than the one represented by the general formula [Y-I], and a preferable substituent is hydrogen. Represents an atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group).

Monomers including those represented by the general formula [Y-I] may form a copolymer with a non-color forming ethylene-like monomer that does not couple with an oxidized product of a color developing agent.

As the non-color-forming, ethylene-like monomer that does not couple with the oxidized product of the color developing agent, acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid) and esters derived from these acrylic acids Or an amide (for example, acrylamide, butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, t-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, octyl Acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and β-hydroxymethacrylate), methylenedibisacrylamide, Nyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citracone Acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine, etc. There is. The non-color-forming ethylenically unsaturated monomers used here may be used in combination of two or more kinds. For example, butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the art of polymer color couplers, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomer couplers are the physical and / or chemical properties of the copolymer formed, For example, the solubility, compatibility with the binder of the photographic colloid composition, such as gelatin, its flexibility, thermal stability, etc., can be selected to be most suitable.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, and among them, the polymer coupler latex is particularly preferable.

More preferred as the yellow coupler according to the present invention represented by the general formula [Y-I] is the following general formula [Y-1]
and a compound represented by a].

General formula [Y-Ia] In the formula, R ₁ , R ₂ , m and n are the same as those in the general formula [I].
It is synonymous with R ₁ , R ₂ , m and n, respectively. Q represents a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom.

As the nitrogen-containing heterocyclic group represented by, among the groups specifically mentioned as the examples of X in the general formula [I], 1-piperidyl group and 5,5-dimethyl-2,4-dioxo-3 are included. -Oxazolidinyl group, 1-benzyl-5-ethoxy-3-hydantoinyl group, 2N-1,1-dioxo-3 (2H) -oxo-
1,2-benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, prazolyl group, 4-acetamido-1-pyrazolyl group, 3,5-dimethylpyrazolyl group, 4- (3-hydroxypropyl)-
1-pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-bromo-benztriazol-1-yl group, 5-methyl-1,2,3-triazole- 1-yl group, benzimidazolyl group, 3-benzyl-
Examples thereof include a 1-hydantoinyl group, a 1-benzyl-5-hexadecyloxy-3-hydantoinyl group and a 5-methyl-1-tetrazolyl group.

The coupler represented by the general formula [Y-I] may be used in combination with a yellow coupler other than the one represented by the general formula [Y-I], in which case 50 mol% of all the yellow couplers.
It is preferable that the above content is included, and more preferably 80%
It is better to contain more than mol. And the ratio is more preferable as the ratio of the coupler according to the present invention is higher.

In the present invention, the addition amount of the yellow coupler is usually preferably 1 × 10 ⁻³ to 1 mol, and more preferably 5.0 × 10 ^{−3 to} 8.0 × 10 ⁻¹ mol per mol of silver halide.

Typical examples of the yellow coupler represented by the general formula [Y-I] are shown below, but the yellow coupler used in the present invention is not limited thereto.

(Exemplified compound) In the present invention, there are no restrictions on materials other than the yellow coupler, but a cyan coupler represented by the following general formula [CI], a phenomenon inhibitor releasing coupler (DIR coupler), a colored coupler, a color developing agent. It is preferred to use an oxidant scavenger.

General formula [C-I] In the above general formula [CI], R ₁ is -CONR ₄ R ₅ , -NHCOR ₄ ,
-NHCOOR ₆ , -NHSO ₂ R ₆ , -NHCONR ₄ R ₅ or -NHSO ₂ NR ₄ R
₅ , R ₂ represents a monovalent group, R ₃ represents a substituent, and X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized product of an aromatic primary amine developer. 1 represents 0 or 1, and m represents 0 to 3. R ₄ and R ₅ represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group, R ₆ represents an aromatic group, an aliphatic group or a heterocyclic group, and when m is 2 or 3, each R is R. _{The 3's} may be the same or different and may be bonded to each other to form a ring, or R ₄ and R ₅ , R ₂ and R ₃ , and R ₂ and X may be bonded to form a ring. However, when ₁ is 0, m is 0 and R ₁ is -CONHR ₇ . R ₇ represents an aromatic group. The groups represented by R _{2 to} R ₇ include those having a substituent.

As R ₆ , an aliphatic group having 1 to 30 carbon atoms, 6 to 30 carbon atoms
An aromatic group, preferably a heterocyclic group having 1 to 30 carbon atoms,
R ₄ and R ₅ are preferably a hydrogen atom and those listed as preferred as R ₆ .

R ₂ is N, either directly or via NH, CO or SO _2.
Hydrogen atom bonded to H, aliphatic group having 1 to 30 carbon atoms, aromatic group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms, -OR
₈ , -COR ₈ , -PO (OR ₁₀ ) ₂ ), -CO ₂ R _10, -SO ₂ R ₁₀ or _{-SO 2 OR 10 (R 8,} R 9 and R ₁₀ are the same as defined in R _4, R ₅ and R ₆ of each of the, R ₈ And R ₉ may combine to form a heterocycle).

R ₇ is preferably an aromatic group having 6 to 30 carbon atoms, and R ₇
Representative examples of the substituent that can have are a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carboamide group, a sulfonamide group, a carbamoyl group, and a sulfamoyl group. Group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, Examples thereof include an imide group, an aliphatic group and an aliphatic oxycarbonyl group. When it is substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, and examples thereof include a dioxymethylene group.

Representative examples of R ₃ are halogen atom, hydroxy group, amino group, carboxyl group, sulfonic acid group, cyano group, aromatic group, heterocyclic group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group. ,
Acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group,
Examples thereof include a nitro group and an imide group, and the carbon number contained in R ₃ is preferably 0 to 30. circular when m = 2
Examples of R ₃ include a dioxymethylene group and the like.

When l is 1, R ₁ is particularly preferably —CONR ₄ R ₅ and m is 0.
And R ₂ is directly bonded to NH, —COR ₈ , —COOR ₁₀ ,
_{-SO 2 R 10, -CONR 8 R} 9, particularly preferably -SO ₂ NR ₈ R _9, more preferred, -COOR ₁₀ bond directly NH, -COR _8,
—SO ₂ R ₁₀ , with —COOR ₁₀ being most preferred.

The present invention also includes a polymer which forms a dimer or higher polymer through R _{1 to} R ₃ and X.

Specific examples of the coupler represented by the general formula [CI] are disclosed in JP-A-60-237448, 61-153640, 61-145557 and 62.
-85242, 48-15529, 50-117422, 52-18315
No. 52-90932, No. 53-52423, No. 54-48237, No. 54
-66129, 55-32071, 55-65957, 55-105226
No. 56-1938, No. 56-12643, No. 56-27147, No. 56
No. -126832, No. 58-95346, US Pat. No. 3,488,193, etc., and can be synthesized by the method described therein.

Depending on the physical properties (eg, solubility) of the coupler, an oil-in-water emulsion dispersion method using a water-insoluble high-boiling organic solvent, an alkali dispersion method of adding as an alkaline solution, and a latex dispersion may be used depending on the physical properties (eg, solubility) of the coupler. Various methods can be used, such as a solid dispersion method in which a solid is directly added as a fine solid.

 The amount of coupler added is usually 1. per mol of silver halide.
0x10^-1Mol ~ 1.0 mol, preferably 5.0 x 10^-3Mol ~ 8.0
× 10 _-1It is in the molar range.

Next, typical examples of the coupler represented by the general formula [C-I] are shown, but the invention is not limited thereto.

(Exemplified compound) In practicing the present invention, a developer releasing coupler (DI
R couplers) are preferably used. Examples of DIR couplers include U.S. Patents 3,227,554, 3,617,291, and
3,701,783, 3,790,384, 3,632,345, 3,93
3,500, 4,149,886, 3,958,993, 4,234,678
Issue, West German patent application (OLS) 2,414,006, 2,454,301
No. 2,454,329, British Patent 953,454, JP-A-52-696
No. 24, No. 49-122335, No. 61-189537, No. 51-13239,
Those described in No. 57-56837 and Japanese Patent Publication No. 51-16141 can be used.

Further, in the practice of the present invention, it is preferable to use a colored coupler. Examples of colored couplers include U.S. Patents 3,476,560, 2,521,908, and 3,034,89.
No. 2, Japanese Patent Publication No. 44-2016, No. 38-22335, No. 42-11304,
Those described in JP-A-44-32461, JP-A-51-26034, JP-A-52-42121, and West German Patent Application (OLS) 2,418,959 can be used.

Further, in the practice of the present invention, it is preferable to use a scavenger of an oxidized color developing agent. That is, the light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color developing agent oxidant scavenger, and specific examples thereof are U.S. Pat.
No., No. 2,336,327, No. 2,403,721, No. 2,418,613,
2,675,314, 2,701,197, 2,704,713, 2,7
28,659, 2,732,300, 2,735,765, JP-A-50-9
No. 2988, No. 50-92989, No. 50-93928, No. 50-110337
No. 52-146235, No. 62-49349, and Japanese Patent Publication No. 50-23813.

The support may be any one known in the art, but a triacetyl cellulose film, a polyethylene terephthalate film or the like is preferably used.

The development process is performed under normal conditions using a normal processing solution.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to examples. Of course, the invention is not limited to the examples.

Example-1 Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

In all the examples below, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Multilayer color photographic elements were prepared by sequentially forming on the triacetylcellulose film support each layer having the composition shown below from the support side.

Sample-1 (Comparison-1) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer: intermediate layer (IL-1) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RM) Monodisperse emulsion (Emulsion I) consisting of AgBrI with average particle size () 0.30 μm, AgI 6 mol% ... Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ^-5 mol per 1 mol of silver Sensitizing color II: 1.0 × 10 ^-5 mol per 1 mol of silver Cyan coupler (C-1): 1 mol of silver In contrast, 0.06 mol Colored cyan coupler (CC-1) ... 0.003 mol per mol of silver DIR compound (D-1) ... 0.0015 mol per mol of silver DIR compound (D-2) ... silver 1 0.002 mol per mol Fourth layer: high-sensitivity red-sensitive silver halide emulsion layer (RS) Monodisperse emulsion (Emulsion II) consisting of AgBrI containing 0.5 μm average grain size (), 7.0 mol% AgI ... Silver coating amount 1.3 g / m ² Sensitizing dye I …… 3 × 10 ^-5 mol for 1 mol of silver Sensitizing dye II …… 1.0 × 10 ^-5 mol for 1 mol of silver Cyan coupler (C-1 ) …… for 1 mole of silver Te 0.03 mol DIR compound (D-2) ...... Ag 0.001 mol per mol fifth layer; intermediate layer (IL-1) same as the second layer, the gelatin layer.

6th layer: low-sensitivity green-sensitive silver halide emulsion layer (GM) Emulsion-1 ... Coating amount of silver 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol increase per 1 mol of silver Sensitizing dye IV: 1.2 × 10 ^-5 moles per 1 mole of silver Magenta coupler (M-1): 0.045 moles per mole of silver Colored magenta coupler (CM-1): 1 mole of silver 0.009 mol DIR compound (D-1) ... 0.0010 mol per 1 mol of silver DIR compound (D-3) ... 0.0030 mol per 1 mol of silver 7th layer; high-sensitivity green color-sensitive silver halide emulsion Layer (GS) Emulsion-II: coating amount of silver 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 10 × 10 per mol of silver ^-5 mol Magenta coupler (M-1) ... 0.030 mol per 1 mol of silver DIR compound (D-3) ... 0.0010 mol per 1 mol of silver Eighth layer; Yellow filter layer (YC-1) Yellow Ko Gelatin layer containing emulsified dispersion of Id silver and 2,5-di -t- octylhydroquinone.

Ninth layer; low-sensitivity blue-sensitive silver halide emulsion layer (BM-1) Monodisperse emulsion (Emulsion III) consisting of AgBrI containing 0.48 μm average grain size and 6 mol% AgI. Silver coating amount 0.9 g / m ² sensitizing dye V: 1.3 × 10 ^-5 mol per 1 mol of silver Yellow coupler (YY-1): 0.29 mol per 1 mol of silver 10th layer: high-sensitivity blue-sensitive emulsion layer ( BS) Monodisperse emulsion consisting of AgBrI with an average grain size of 0.8 μm and AgI 6 mol% (Emulsion IV) …… Silver coating amount 0.5 g / m ² Sensitizing dye V …… 1.0 × 10 ⁻ per 1 mol of silver ⁵ mol Yellow coupler (YY-1) ... 0.08 mol per 1 mol of silver DIR compound (D-2) ... 0.0015 mol per 1 mol of silver 11th layer; 1st protective layer (Pro-1) iodine Silver bromide (AgI 1 mol% average particle size 0.07 μm) Silver coating amount
Gelatin layer containing 0.5g / m ² UV absorbers UV-1 and UV-2.

12th layer: 2nd protective layer (Pro-2) A gelatin layer containing polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1).

In addition to the above composition, each layer contains a gelatin hardening agent (H-
1) and a surfactant were added.

 The compounds contained in each layer are as follows.

Sensitizing dye 1; 5,5'-dichloro-9-ethyl-3,3'-di-
(3-Sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; 9-ethyl-3,3'-di- (3-sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; 5,5'-diphenyl-9-ethyl-3,3'-
Di- (3-sulfopropyl) oxacarboxyanine hydroxide Sensitizing dye IV; 9-ethyl-3,3'-di- (3-sulfopropyl) -5,6,5 ', 6'-dibenzoxalcarbo Cyanine hydroxide Sensitizing dye V; 3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxythiacyanine Each of the sample Nos. 1 to 6 thus prepared was subjected to wedge exposure using white light, and then subjected to the following development processing.

Treatment process (38 ℃) Color development phenomenon 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Used in each processing step The composition of the treatment liquid is as follows.

[Color developer] Add water to make 1.

[Bleaching solution]

Add water to make 1 and pH = 6.0 with ammonia water
Adjust to.

[Fixer]

Add water to make 1 and adjust to ph = 6.0 with acetic acid.

[Stabilizer]

Add water to make 1.

Measurement Method For each of the obtained samples, the latitude, the sharpness (MTF) and the RMS were measured using white light (W).

The latitude is the exposure amount (logarithmic value) that gives an optical density of (fog +0.1) on the characteristic curve and (maximum optical density −0.
The difference in the exposure dose (logarithmic value) that gives the optical density of 1) is shown. The larger the value, the wider the exposure area, which is preferable.

The effect of improving the sharpness is the MTF (Modulation Tran
sfer function) was calculated and shown as the MTF value (%) at 30 fibers / mm. The larger the value, the better.

The RMS value is the minimum density +1.2, and the circular scanning aperture is 25 μm.
The standard deviation of the variation of the concentration value caused by scanning with a microdensitometer of 1000 times was shown. The smaller the value, the better.

In addition, a single layer sample of each silver halide emulsion layer was similarly exposed, developed, and subjected to sensitometry to obtain the maximum color density of each layer.
Dmax was measured. In each color-sensitive layer, the ratio of the maximum color density Df of the layer farthest from the support and the maximum color density Dc of the layer closest to the support was determined.

Sample-2 (Comparison-2) First layer; Antihalation layer, same as (HC-1) Second layer; Intermediate layer, same as (IL-1) Third layer; High sensitivity blue color-sensitive silver halide Emulsion layer, same as (BS) Fourth layer; Intermediate layer, same as (IL-1) Fifth layer; High-sensitivity red-sensitive silver halide emulsion layer, Same as (RS) Sixth layer; Intermediate layer, Same as (IL-1) 7th layer; high-sensitivity green color-sensitive silver halide emulsion layer, same as (GS) 8th layer; intermediate layer, same as (IL-1) 9th layer; low-sensitivity red feeling Colored silver halide emulsion layer, same as (RM) 10th layer; Intermediate layer, same as (IL-1) 11th layer; Low sensitivity green color-sensitive silver halide emulsion layer, same as (GM) 12th Layer: Yellow filter layer, same as (YC-1) 13th layer: High sensitivity blue color sensitive silver halide emulsion layer, (BM-
2) Monodisperse emulsion consisting of AgBrI with an average grain size of 0.8 μm and AgI of 6 mol% (Emulsion IV): Silver coating amount 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ^-5 per mol of silver Yellow coupler (YY-1) ... 0.29 per mol of silver
Molar 14th layer; first protective layer, same as (Pro-1) 15th layer; second protective layer, same as (Pro-2) Sample-3 (Comparison-3) Each color-sensitive layer is one layer Sample consisting of: first layer; antihalation layer, same as (HC-1), second layer; intermediate layer, same as (IL-1), third layer; red-sensitive silver halide emulsion layer, (RM) Same 4th layer; intermediate layer, same as (IL-1) 5th layer; green color silver halide emulsion layer, same as (GM) 6th layer; yellow filter layer, same as (YC-1) 7 layers; blue color silver halide emulsion layer, same as (BM-3), yellow coupler in the same mole as (YY-1) (Y-31)
The same as (BM) except that it was changed to 8th layer; 1st protective layer, same as (Pro-1) 9th layer; 2nd protective layer, same as (Pro-2) Sample-4 (present invention) Sample -The 3rd layer and 13th layer of -2 were changed as follows.

Third layer: high-sensitivity blue-sensitive silver halide emulsion layer, (BS-
2) Same as (BS) except that the yellow coupler was replaced with (YY-1) and the same mole of (Y-31) 13th layer; high-sensitivity blue-sensitive silver halide emulsion phase (BM-4) yellow Same as (BM-2) except that the coupler was replaced with (Y-31) in the same mole as (YY-1) Sample-5 (invention) 1st layer; antihalation layer, same as (HC-1) Second layer: intermediate layer, same as (IL-1) Third layer: high-sensitivity blue color-sensitive silver halide emulsion layer, (BS-
2) 4th layer; intermediate layer, same as (IL-1) 5th layer; high-sensitivity red-sensitive silver halide emulsion layer, same as (RS) 6th layer; low-sensitivity red-sensitive silver halide Emulsion layer, same as (RM) 7th layer; Intermediate layer, same as (IL-1) 8th layer; High-sensitivity green color-sensitive silver halide emulsion layer, same as (GS) 9th layer; Low-sensitivity green Color-sensitive silver halide emulsion layer, same as (GM) 10th layer; yellow filter layer, same as (YC-1) 11th layer; high-sensitivity blue color-sensitive silver halide emulsion layer, (BM-
Same as 4) 12th layer; 1st protective layer, same as (Pro-1) 13th layer; 2nd protective layer, same as (Pro-2) Sample-6 (Comparison-4) 3rd layer (BS -2) is the same as Sample 5 except that (BS) is replaced with (BM-4) and (BM-2) of the 11th layer. Each silver halide emulsion layer constituting the sample is coated on a support to prepare a sample,
The maximum color density of each silver halide emulsion layer was determined.

The development processing of each sample was the same as that of sample-1, and the characteristics of each sample were measured in the same manner as sample-1.

 The measurement results of each sample are shown in Table-1.

From the results of Table-1, the samples 4 and 5 of the present invention have MTFs of 79 to 80,
Comparative samples 2 and 6 having RMS of 22, latitude of 3.1 to 3.2 and having the same layer structure as the samples 4 and 5 of the present invention are
MTF is 70 to 71, RMS is 28 to 29, latitude 3.1 to 3.2, the sample of the present invention is relatively excellent in granularity and sharpness compared to the sample (MTF value, judged from RMS value), It was found that an excellent image can be obtained without losing the latitude. Further, the comparative sample having a different layer structure from the sample of the present invention is inferior in granularity and sharpness to the sample of the present invention, and the comparative sample 3 in which each color-sensitive layer is a single layer has granularity and sharpness. It was found to be as good as the sample of the invention, but poor in latitude.

〔The invention's effect〕

As described above, according to the present invention, a silver halide color photographic light-sensitive material having excellent graininess, sharpness, latitude and other photographic performance (maximum density, etc.) can be obtained.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a support and a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer provided on the support, wherein the blue The blue-sensitive emulsion layer comprises at least two layers, and the blue-sensitive emulsion layer is arranged such that the layer farthest from the support has the maximum color density, and the blue-sensitive emulsion layer is A silver halide color photographic light-sensitive material containing a yellow coupler represented by the following general formula [Y-I]. General formula [Y-I] (However, in the general formula [Y-I], R ₁ and R ₂ are respectively
Represents a hydrogen atom or a substituent. )