JPH0616161B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic which gives a color photographic image with good color reproducibility and image quality. It relates to a photosensitive material.

(Prior Art) In order to form a color photographic image, a photographic coupler of three colors of yellow, magenta and cyan is contained in a photosensitive layer, and after exposure, it is processed with a color developing solution containing a color developing agent. In this process, the oxidation product of the aromatic primary amine gives a coloring dye by the coupling reaction with the coupler, and the coupling speed at this time is as high as possible, so that a high coloring density is given within a limited developing time. Those having good color development are preferable. Further, the color-forming dyes are all vivid cyan, magenta and yellow dyes with little sub-absorption and are required to give color photographic images with good color reproducibility.

Further, in order to obtain a high-quality image, it is extremely important that the density of the highlight portion of the image is low, in addition to the color forming dye having the above-described excellent hue, and the high density due to the presence of slight fog It is well known that an increase in the density of the light portion deteriorates the image quality. The increase in the density of the highlight portion due to the fog has a great adverse effect on the reflective type light-sensitive material which is affected by the multiple reflection, even if the amount is extremely small.

In order to meet the above-mentioned requirements for color photographic light-sensitive materials, the role of couplers as color image forming agents is great,
Conventionally, many improvements have been made by changing the coupler structure. Conventionally, a 5-pyrazolone derivative has been mainly used as a magenta coupler which is particularly important from the viewpoint of visibility, but the color image formed from this is not required not only in the desired green light region but also in the blue light region and the red light region. It has absorption and cannot be said to have sufficient performance. Further, the 5-pyrazolone derivative was easily decomposed under light irradiation or under high humidity and turned into yellow, which was not satisfactory in terms of image storability.

On the other hand, a color image obtained from a pyrazoloazole-based magenta coupler (for example, a magenta coupler represented by the general formula (I) described below) has less unnecessary absorption in the blue light region and the red light region and is advantageous not only in color reproduction. It is also an excellent coupler with little yellowing even when stored under high humidity with light irradiation.

(Problems to be solved by the invention) However, conventionally, when a pyrazoloazole-based magenta coupler is used to design a light-sensitive material in combination with a blue-sensitive silver halide emulsion layer containing a yellow coupler, a blue containing a yellow coupler is used. There is a drawback that the degree of fog in the sensitive silver halide emulsion layer is increased, and this improvement has been desired.

In particular, a color sensitizer having a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a pyrazoloazole-based magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler on a support. In the material, the layers are arranged in the order of blue-sensitive emulsion, green-sensitive emulsion and red-sensitive emulsion from the side closer to the support, or in the order of blue-sensitive emulsion, red-sensitive emulsion and green-sensitive emulsion. , And when this photosensitive material is exposed from the side opposite to the support side,
It was found that the degree of fog in the blue-sensitive silver halide emulsion layer containing the yellow coupler was large, and this improvement was necessary. In this case, the following points can be considered as the cause of the increased fog in the blue-sensitive layer. That is, when the above-mentioned layer arrangement is adopted and the blue-sensitive emulsion layer is exposed through the green-sensitive emulsion layer and the red-sensitive emulsion layer, the blue sensitivity of the blue-sensitive emulsion is the blue sensitivity and the red-sensitive emulsion layer of the green-sensitive emulsion layer. It is necessary to set the sensitivity higher than the blue sensitivity of. Because if this condition is not satisfied, the color sensitivity of the silver halide grain is that the spectral sensitivity sensitizing dye is added to the silver halide emulsion having an intrinsic sensitivity in the blue region to give the green sensitivity and the red sensitivity. This is because magenta and cyan are remarkably mixed in the portion that should originally develop yellow. When the green-sensitive emulsion layer and the red-sensitive emulsion layer are exposed through the blue-sensitive emulsion layer, a yellow filter layer for cutting blue light may be provided between the blue-sensitive emulsion layer and other emulsion layers to achieve the above color mixture. However, the yellow filter layer is not effective in the layer arrangement described above.

In order to design the blue sensitivity of the blue-sensitive emulsion layer higher than the blue sensitivity of the green-sensitive emulsion layer and the blue sensitivity of the red-sensitive emulsion layer, generally, the average grain size of silver halide grains in the blue-sensitive emulsion layer is The average grain size of the silver halide grains in the sensitive emulsion layer or the red sensitive emulsion layer (the average grain size based on the projected area with the grain diameter as the grain size for spherical or near-sphere grains and the ridge length as for cubic grains). Greater than is required. Therefore, a blue-sensitive emulsion layer in which the average grain size of silver halide grains is relatively large is under a condition in which fog is more easily generated than other emulsion layers, and particularly in a color light-sensitive material in which a pyrazoloazole-based magenta coupler is combined. In the case of the blue photosensitive layer, it is considered that fogging is likely to occur under the above conditions. Therefore, a first object of the present invention is to provide a color photographic light-sensitive material which forms a magenta image having a good light absorption property and is excellent in color reproducibility. A second object of the present invention is to provide a color photographic light-sensitive material having an excellent white background in which the density of the highlight portion of the image is low, and particularly, the minimum density of yellow is low. A third object is to provide a color light-sensitive material that provides stable performance with a small amount of change in response to various changes in developing conditions.

(Means for Solving Problems) The present inventors have overcome the above problems of a silver halide color photographic light-sensitive material having a layer arrangement as described above and using a pyrazoloazole-based magenta coupler. Therefore, as a result of intensive studies, (1) the average grain size of each silver halide grain in the blue-sensitive emulsion layer containing a yellow coupler and the green-sensitive emulsion layer containing a magenta coupler was controlled to a predetermined ratio, and (2 ) In a blue-sensitive silver halide emulsion layer, or
(3) The green-sensitive silver halide emulsion, wherein a silver halide fine grain emulsion is contained in a non-photosensitive layer (intermediate layer) existing between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer. By using a pyrazoloazole-based coupler as a magenta coupler in the layer, it was found that emulsion fog in the blue-sensitive silver halide emulsion layer can be suppressed and the above objects can be achieved all at once, and the present invention was completed based on this finding. Came to do.

That is, the present invention provides a silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer containing a yellow coupler between a green-sensitive silver halide emulsion layer containing a magenta coupler and a support. The silver halide emulsion layer contains a pyrazoloazole-based magenta coupler represented by the following general formula (I), and (b) the average grain size of silver halide grains excluding the following silver halide fine grains in the blue-sensitive emulsion layer is The average grain size of silver halide grains in the green-sensitive emulsion layer is 1.2 times or more, and (c) in the blue-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer and the green-sensitive layer. A silver halide color photographic material characterized by containing a silver halide fine grain emulsion in at least one of the non-photosensitive layers interposed between the silver halide emulsion layer and the non-photosensitive layer. It is intended to provide the material.

General formula [I] (In the formula, Za and Zb are Or = N-, R ₁ and R ₂ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. When Za = Zb is a carbon-carbon double bond, it may be part of an aromatic ring, and further R ₁ ,
R ₂ or X may form a dimer or higher multimer. Provided that at least one of R ₁ or R ₂ represents a group bonded to the pyrazoloazole nucleus through a secondary or tertiary carbon, yet R ₁ or R ₂ is at least one -NHSO 2 _- containing substituent . ) In the magenta coupler represented by the above general formula [I] used in the present invention, Za is preferably And when Zb is ═N—, R ₂ is a group other than a substituted or unsubstituted aralkyl group.

Hereinafter, the present invention will be described in more detail.

In the compound represented by the general formula (I), a multimer is 1
It means one having two or more groups represented by the general formula (I) in the molecule, and a bis form and a polymer coupler are also included in this. Here, the polymer coupler has the general formula (I)
A homopolymer consisting only of a monomer having a moiety represented by (preferably a vinyl group-containing monomer, hereinafter referred to as a vinyl monomer) may be used, or a non-coupling agent that does not couple with an oxidized aromatic primary amine developing agent. A copolymer may be prepared with a color-forming ethylene-like monomer.

Among the pyrazoloazole-based magenta couplers represented by the general formula (I), preferred are the following general formula (II),
It is represented by (III), (IV), (V), and (VI).

Among the couplers represented by the general formulas (II) to (VI), preferred are the general formulas (II), (IV) and (V) for the purpose of the present invention, and more preferred are the general formula (V). It is represented.

In the general formulas (II) to (VI), R ¹¹ , R ¹² and R ¹³
May be the same or different from each other, and each is a hydrogen atom, 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, a carbamoyloxy group, a 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, aryloxycarbonylamino group,
Represents a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxy group or an oxygen atom, a nitrogen atom or a sulfur atom. A group which is coupled to the carbon at the coupling position via the coupling-off group. R ¹¹ , R ¹² , R ¹³ or X may be a divalent group to form a bis form.

Further, it may be in the form of a polymer coupler in which the coupler residue represented by the general formulas (II) to (VI) is present in the main chain or side chain of the polymer, and particularly derived from a vinyl monomer having a moiety represented by the general formula. Polymers are preferred in which R ¹¹ , R ¹² , R ¹³ or X represents a vinyl group or a linking group.

More specifically, R ¹¹ , R ¹² and R ¹³ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.),
Alkyl group (for example, methyl group, propyl group, isoprovir group, t-butyl group, trifluoromethyl group, tridecyl group, 2- [α- {3- (2-octyloxy-5-
tert-octylbenzenesulfonamide) phenoxy} tetradecanamide] ethyl group, 3- (2,4-di-t-amylphenoxy) propyl group, allyl group, 2-
Dodecyloxyethyl group, 1- (2-octyloxy-
5-tert-octylbenzenesulfonamide) -2
-Propyl group, 1-ethyl-1- {4- (2-butoxy-5-tert-octylbenzenesulfonamide) phenyl} methyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl Group, etc.), aryl group (eg, phenyl group, 4-t
-Butylphenyl group, 2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), hethene ring group (for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group) Group, etc.), cyano group,
Alkoxy group (eg, methoxy group, ethoxy group, 2-
Methoxyethoxy group, 2-dodecyloxyethoxy group,
2-methanesulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group, 2-methylphenoxy group,
4-t-butylphenoxy group etc.), heterocyclic oxy group (eg 2-benzimidazolyloxy group etc.), acyloxy group (eg acetoxy group, hexadecanoyloxy group etc.), carbamoyloxy group (eg N- Phenylcarbamoyloxy group, N-ethylcarbamoyloxy group etc.), silyloxy group (eg trimethylsilyloxy group etc.), sulfonyloxy group (eg dodecylsulfonyloxy group etc.), acylamino group (eg acetamide group, benzamide group, tetradecane) Amide group, α- (2,4-di-t-amylphenoxy) butylamide group, γ- (3-t-butyl-4-hydroxyphenoxy) butylamide group, α- {4- (4-hydroxyphenylsulfonyl) phenoxy group } Decanamide group, etc., anilino group (eg, , Phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecaneamido anilino group, 2-chloro-5-dodecyloxycarbonylphenyl anilino group, N- acetyl anilino 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 (for example, N-succinimide group, 3-benzylhydantoinyl group, 4-
(2-ethylhexanoylamino) phthalimide group etc.), sulfamoylamino group (eg N, N-dipropylsulfamoylamino group, N-methyl-decylsulfamoylamino 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 (for example, 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), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group) , 2,4-di-t
ert-butylphenoxycarbonylano group, etc.), sulfonamide group (eg, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5) -T-butylbenzenesulfonamide group, etc.), carbamoyl group (eg,
N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-
{3- (2,4-di-tert-amylphenoxy) propyl} carbamoyl group, etc.), acyl group (eg, acetyl group, (2,4-di-tert-amylphenoxy))
Acetyl group, benzoyl group, etc.), sulfamoyl group (eg, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N- (2-dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecyl group. Sulfamoyl group, N, N-diethylsulfamoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (eg, octansulfinyl group, Dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (for example,
Methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.),
Represents an aryloxycarbonyl group (eg, phenyloxycarbonyl group, 3-pentadecyloxy-carbonyl group, etc.), X represents a hydrogen atom, a halogen atom (eg,
Chlorine atom, bromine atom, iodine atom, etc.), carboxy group,
Or a group linked by an oxygen atom (for example, an acetoxy group,
Propanoyloxy group, benzoyloxy group, 2,4-
Dichlorobenzoyloxy group, ethoxooxaloyloxy group, pyrvinyloxy group, cinnamoyloxy group,
Phenoxy group, 4-cyanophenoxyl group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy Group, benzyloxy group, 2-
Phenethyloxy group, 2-phenoxyethoxy group, 5-
Phenyltetrazolyloxy group, 2-benzothiazolyloxo group, etc.), groups linked by nitrogen atoms (for example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, peptafluorobutanamide 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-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, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-bromo-benzotriazol-1-yl, 5 -Methyl-1,2,3,4
-Triazol-1-yl group, benzimidazolyl group,
3-benzyl-1-hydantoinyl group, 1-benzyl-
5-hexadecyloxy-3-hydantoinyl group, 5-
Methyl-1-tetrazolyl group etc.), arylazo group (for example, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-naphthylazo group, 3-methyl-4-hydroxyphenylazo group etc.), sulfur Groups linked by atoms (for example, phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-
Octanesulfonamide phenylthio group, 2-butoxyphenylthio group, 2- (2-hexanesulfonylethyl) -5-tert-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-triazole-
5-thio group).

In the coupler represented by formula (II), R ¹² and R ¹³ may combine to form a 5- to 7-membered ring.

When R ¹¹ , R ¹² , R ¹³ or X is a divalent group to form a bis form, preferably R ¹¹ , R ¹² and R ¹³ are substituted or unsubstituted alkylene groups (eg methylene group, ethylene group, 1,10-decylene _group, -CH ₂ CH ₂ -O-C
H ₂ CH ₂ — and the like), a substituted or unsubstituted phenylene group (eg, 1,4-phenylene group, 1,3-phenylene group, Etc.), a —NHCO—R ¹⁴ —CONH— group (R ¹⁴ represents a substituted or unsubstituted alkylene group or phenylene group, for example, —NHCOCH ₂ CH ₂ CONH—, Etc.), a —S—R ¹⁴ —S— group (R ¹⁴ represents a substituted or unsubstituted alkylene group, for example, —S—CH ₂ CH ₂ —S, Etc., and X represents a divalent group at an appropriate place from the above monovalent group.

Formulas (II), (III), (IV), (V), and (V
When what is represented by I) is contained in a vinyl monomer, the linking group represented by R ¹¹ , R ¹² , R ¹³ or X is an alkylene group (a substituted or unsubstituted alkylene group, for example, a methylene group). , ethylene group, 1,10-decylene _group, -CH 2 _CH 2 OC
H ₂ CH ₂ —, etc., phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group, 1,
3-phenylene group, Etc.), —NHCO—, CONH—, —O—, —OCO— and aralkylene groups (eg, Etc.) and groups that are established by combining those selected from the above.

The following are preferred linking groups.

_{-NHCO -, - CH 2 CH 2} -, -CH ₂ CH ₂ NHCO-, _{-CONH-CH 2 CH 2 NHCO-,} -CH 2 CH 2 O-CH 2 CH 2 -NHCO-, The vinyl group has the general formulas (II), (III), (IV),
Substituents other than those represented by (V) and (VI) may be used, and preferred substituents are hydrogen atom, chlorine atom or lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group). Represent.

Formulas (II), (III), (IV), (V), and (V
Monomers including those represented by I) may form copolymers with non-color forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers.

Acrylic acid, α is used as the non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent.
-Chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid, etc.) and esters or amides derived from these acrylic acids (for example, acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-
Hydroxymethacrylate), methylenedibisacrylamide, vinyl 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, citraconic acid, crotonic acid,
There are vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can be used together.
For example, n-butyl acrylate and methyl acrylate,
Examples are styrene and methacrylic acid, methacrylic acid and acrylamide, and methyl acrylate and diacetone acrylamide.

As is well known in the art of polymer color couplers, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers are the physical and / or chemical properties of the copolymers formed such as Solubility, compatibility with photographic colloid composition binders such as gelatin, its flexibility,
It can be chosen such that the thermal stability etc. is positively affected.

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.

Specific examples of the pyrazoloazole-based magenta couplers represented by the general formula (I) used in the present invention and the synthesis method are described in Japanese Patent Application Nos. 58-23434 and 58-151354.
58-45512, 59-27745, 58-1
42801 and U.S. Pat. No. 3,061,432.

Specific examples of typical magenta couplers and vinyl monomers thereof according to the present invention are shown below, but the present invention is not limited thereto.

Of the following exemplified compounds, compounds 1 to 27, 34 and 35 (the compounds represented by the general formulas (II), (IV) and (V)) are preferable as the magenta coupler of the present invention, and 28
The compounds (about 33) (the compounds of the general formulas (III) and (VI)) are shown for reference.

(Exemplified compounds) 1. 2. 3. 4. 5. 6. 7. 8. 9. Ten. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. twenty one. twenty two. twenty three. twenty four. twenty five. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. In the present invention, the silver halide fine grain emulsion added to the blue-sensitive silver halide emulsion layer or the non-photosensitive layer preferably has an average grain size of 0.01 to 0.20 μm, and the smaller the grain size, the more preferable. Any of silver chloride, silver chlorobromide and silver bromide can be used as the emulsion, but an emulsion containing 50 mol% or more of silver bromide is preferable. As the fine grain emulsion, both light-sensitive and light-insensitive are used, but low-sensitivity silver halide grains which are not substantially developed are more advantageous for the purpose of the present invention. Addition amount 0.005~0.1g / m ² is suitably 0.01 to 0.05 g / m ² is preferred as the silver.

Incidentally, such low-sensitivity silver halide grains are prepared in the same manner as in the case of preparing an ordinary non-photosensitive silver halide emulsion. In this case, the surface of the silver halide grain may not be chemically sensitized, and may not be spectrally sensitized.

Such a silver halide fine grain emulsion is added to a blue light-sensitive emulsion layer containing a yellow coupler, or is added between a blue-sensitive emulsion layer containing a yellow coupler and a green-sensitive emulsion layer containing a magenta coupler of the general formula (I). Is added to the non-photosensitive layer present in. It may be added to two or more layers at the same time.

It is preferable that a known stabilizer such as a triazole-based compound, an azaindene-based compound, a benzothiazolium-based compound, or a mercapto compound is added to such a silver halide fine grain emulsion prior to adding it to a coating solution. .

The average grain size of the silver halide grains in the blue-sensitive emulsion layer used in the present invention, excluding the above-mentioned silver halide grains, is 1.2 times or more the average grain size of the green-sensitive emulsion layer, preferably 1.3. It is 5 times to 5 times. It is particularly preferably 1.5 times to 2 times. If the average grain size is less than 1.2 times, the portion of the image to be colored in yellow causes a remarkable color mixing with magenta, and if it exceeds 5 times and is too large, it is between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. However, an unnecessarily large sensitivity difference may occur, and the sensitivity balance of each layer may become inappropriate.

The silver halide grains of the blue-sensitive emulsion layer used in the present invention other than the above-mentioned silver halide grains are described in detail below. Particularly preferably, the silver chlorobromide emulsion is 2 mol%.
It contains the following iodine ions and 70 mol% or more of bromine ions, and the particle size is the diameter when the particles are spherical, and the spherical equivalent diameter determined by the projected area method when the particles are not spherical, Average 0.4-1.
5μ, especially 0.6 to 1.0μ.

The silver halide that can be used in the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer of the present invention contains no silver iodide, or even if it contains 3 mol% or less of silver (iodo) bromide or (iodo) odor. It is silver oxide. The silver halide grains that can be used in the present invention may have different phases in the inside and the surface layer, and may have a junction structure or a multiphase structure, or the entire grain except the surface layer may have a uniform phase. Moreover, they may be mixed. For example, it may be a grain having a silver chlorobromide-rich nucleus having a different phase or a single or plural layers in the grain.
Further, it may be a grain having a nucleus rich in silver chloride from the average halogen composition or a single or multiple layers in the grain. The average grain size of silver halide grains that can be used in the red-sensitive layer and the green-sensitive layer is preferably 2 μ or less and 0.1 μ or more,
Particularly preferred is 1 μ or less and 0.15 or more. So-called monodisperse silver halide emulsions are preferably used in the present invention. The degree of monodispersion is a variation rate (a value obtained by dividing the standard deviation of the grain size distribution curve of silver halide by the average grain size), and is 0.
It is preferably 15 or less, more preferably 0.10 or less. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in an emulsion layer having substantially the same color sensitivity are mixed in the same layer or different layers. Can be applied in multiple layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The shape of the silver halide grains used in the present invention is preferably a crystal having a regular crystal such as a cube, an octahedron, a dodecahedron and a tetradecahedron, but an irregular shape such as a sphere. It may have an (irregular) crystal form, or may have a composite form of these crystal forms. Further, tabular grains may be used, and an emulsion in which an average grain having a length / thickness ratio value of 5 or more, particularly 8 or more occupies 50% or more of the total projected area of the grain may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is described in "Chemie et Physique Photographique" by P. Glafkides.
(Published by Paul Montel, 1967), GF Duffin, "Photographic Emulsion Chemistry" (F
Ocal Press, 1966), VL Zelikman etaal, "Making and Coating Photog"
raphic Emulsion) (published by Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and almost uniform grains can be obtained.

Next, the additives used in producing the silver halide emulsion according to the present invention will be described.

When forming silver halide grains according to the present invention, as a silver halide solvent for controlling grain growth, for example, ammonia, rhodancali, rhodammone, thioether compound (for example, US Pat. No. 3,271,157).
No. 3,574,628, No. 3,704,13
0, 4,297,439, 4,276,3
74) and thione compounds (for example, JP-A-53-14).
No. 4319, No. 53-82408, No. 55-7773.
No. 7, etc.), amine compounds (for example, JP-A-54-100).
No. 717) and the like can be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, thallium salt, iridium salt or chain salt thereof, rhodium salt or complex salt thereof, iron salt or iron complex salt and the like may coexist.

The photographic emulsion according to the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salt, nitroindazole salt, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazole , Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; Thioketo compounds, for example, oxazoline thiones; azaindenes, for example, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); Sulfonic acids; benzenesulfinic acid; many compounds known as antifoggants or stabilizers, such as can be added.

The coupler of the present invention represented by the general formula (I) contains 1 × 10 ⁻³ mol to 1 mol per mol of silver halide present in the same layer.
It is added to the emulsion layer in a molar ratio of preferably 5 × 10 ^{-2 to} 5 × 10 ^-1 mol. It is also possible to add two or more couplers of the present invention to the same emulsion layer.

Typical examples of cyan couplers and yellow couplers used in the present invention include naphthol- or phenol-based compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan and yellow couplers that can be used in the present invention are described in Research Disclosure (RD) 17643 (December 1978) Section VII-D and the patent cited in 18717 (November 1979). Has been done.

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. A two-equivalent color coupler in which a coupling active position is substituted with a leaving group can reduce the amount of coated silver rather than a four-equivalent color coupler having a hydrogen atom. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is US Pat. No. 2,40.
No. 7,210, No. 22,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom elimination type yellow couplers described in Nos. 2,261,361 and 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Cyan couplers that can be used in the present invention include oil-protect type naphthol-type and phenol-type couplers. The naphthol-type couplers described in US Pat. No. 2,474,293, preferably US Pat.
No. 2,212, No. 4,146,396, No. 4,2
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in Nos. 28,233 and 4,296,200. Specific examples of the phenol-based coupler are described in US Pat. Nos. 2,369,929 and 2
No. 2,801,171, No. 2,772,162, No. 2,895,826. Moisture and temperature resistant cyan couplers are preferably used in the present invention, and typical examples thereof include US Pat.
No. 2,772,162, US Pat. No. 3,758,308, and US Pat. No. 3,758,308, each of which has an alkyl group having an ethyl group or more at the meta-position of the phenol nucleus described in US Pat. No. 2,772,162. , 126, 396,
No. 4,334,011, No. 24,327,173
2, West German Patent Publication No. 23,329,729 and Japanese Patent Application No. 58-42671, and 2,5-diacylamino-substituted phenol couplers and US Pat. Nos. 3,446,622 and 4,4. 333,999, 4,451,559 and 4,427,766.
And the like, which have a phenylureido group at the 2-position and an acylamino group at the 5-position.

The various couplers used in the present invention may be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound may be used in two or more different layers. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, and examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex fractionation method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water fractionation method, after dissolving in either a single solution of a high boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point or a mixed solution of both, water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are US Pat. No. 2,32
2, 027 and the like.

The standard amount of color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0. 002 to 0.3 mol.

The silver halide emulsion used in the present invention usually comprises a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halogen salt (for example, potassium bromide, sodium chloride, potassium iodide alone or a mixture thereof) gelatin solution. It is manufactured by mixing in the presence of an aqueous polymer solution.

The silver halide emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation.

Known silver halide solvents (e.g., ammonia, Rhodan potassium or U.S. Pat. No. 3,271,157;
No. 1-12360, JP-A No. 53-82408, JP-A No. 53-144319, JP-A No. 54-100717 or JP-A No. 54-155828. It can be used in aging and chemical aging. In order to remove the soluble silver salt from the emulsion after physical ripening, a Nudel water washing, a flocculation sedimentation method, an ultrafiltration method or the like is used.

The photographic emulsion used in the present invention can be spectrally sensitized with methine dyes and the like, if necessary.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance.

The light-sensitive material produced by using the present invention, as a color antifoggant or color mixing inhibitor, is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention.

In the light-sensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). But it's okay.

In the light-sensitive material of the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, developers or their precursors,
A development accelerator or its precursor, a lubricant, a mordant, a matting agent, an antistatic agent, a plasticizer, or other various additives useful for a photographic light-sensitive material may be added. Typical examples of these additives are Research Disclosure 1764
3 (December 1978) and the same) 18716 (197)
(November 9).

The invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film, paper or cloth usually used for a photographic light-sensitive material or a rigid support such as glass, pottery or metal. To be done.

The support used in the present invention is preferably a baryter paper or a polyethylene-supported paper support containing a white pigment (for example, titanium oxide) in polyethylene.

The present invention can be applied to various light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention also relates to Research Disclosure 17123 (July 1978).
It is also applicable to a black and white light-sensitive material using a mixture of three-color couplers described in (Mon.).

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, a p-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N, N.
-Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl- 4-amino-N-
Examples thereof include ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates.

Color developers include pH buffers such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds or antifoggants. Etc. are generally included.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds. Typical bleaching agents are ferricyanides; dichromates; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2.
-Aminopolycarboxylic acids such as propanol tetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates; manganates; nitrosophenol and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in an independent bleaching solution as well as in a ... bath bleach-fixing solution.

If necessary, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution.

After the bleach-fixing process or the fixing process, a washing process is usually performed. Various known compounds may be added to the washing process for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae and mold, magnesium salts and aluminum. A hardening agent typified by a salt, or a surfactant for preventing drying load and unevenness can be added if necessary. Alternatively, L. E. West "Water Quality Criteria", "Science and Engineering of Photography" (Photo.Sci.Eng.), Volume 6, 344-3
You may add the compound as described in page 59 (1965) etc. It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. Furthermore, instead of the water washing step, JP-A-57 / 57
You may implement the multistage countercurrent stabilization treatment process as described in -8543. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, etc.) for adjusting the membrane pH (eg pH 3-8).
Typical examples include metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. You can In addition, water softener (inorganic phosphoric acid,
Aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzoisothiazolinone, irithiazolone, 4-thiazoline benzimidazole, halogenated phenol, etc.), surfactant, fluorescent brightening Various additives such as agents and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

The silver halide light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.

The silver halide light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.

Typical compounds thereof are JP-A-56-64339,
57-144547, 57-2111147, 58-50532, 58-50536, 58-.
No. 50533, No. 58-50534, No. 58-505.
35 and 58-115438.

The various processing solutions used in the present invention are used at 10 ° C to 50 ° C, but it is preferable to develop at a temperature of 33 ° C to 38 ° C. In addition, West German Patent No. 2, for saving silver in the light-sensitive material
226,770 or US Pat. No. 23,674,49
Treatment using cobalt intensification or hydrogen peroxide intensification described in No. 9 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

(Effect of the Invention) Since the silver halide color photographic light-sensitive material of the present invention forms a magenta image having a good light absorption property, a color photographic image having excellent color reproducibility is formed. Further, the silver halide color photographic light-sensitive material of the present invention can suppress the formation of fog in the red-sensitive silver halide emulsion layer, which has been a problem when using a pyrazoloazole-based magenta coupler. Therefore, an excellent color photographic image having a low density in the highlight portion of the image, in particular, a minimum yellow minimum density is provided on a white background. Further, the silver halide color photographic light-sensitive material of the present invention has an excellent effect of exhibiting stable photographic performance against various changes in developing conditions.

In the present invention, the mechanism by which the emulsion fog of the blue-sensitive silver halide emulsion layer containing the yellow coupler is suppressed has not been sufficiently clarified. However, at least in part, the magenta coupler of the present invention causes fog due to interaction between the magenta coupler of the present invention and the silver halide in the blue-sensitive silver halide emulsion layer containing the yellow coupler during development, resulting in fog. It is considered that this fog is suppressed by the silver halide emulsion.

Emulsion fog in the blue-sensitive emulsion layer containing such a yellow coupler is likely to occur especially in a developing solution having a high pH, a low KBr amount, or a high sodium sulfite amount. By adding the fine grain emulsion of the present invention, the emulsion fog can be remarkably improved, and a light-sensitive material can be obtained in which fog does not easily occur even when the composition of the developer is changed.

(Examples) The present invention is described below with reference to examples, but the present invention is not limited to these.

Example 1 A multi-layer color photographic paper having the layer constitution shown in (Table 1) was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution: 10 g of ethyl coupler and 3.1 m of solvent (c) were added to 10 g of yellow coupler (a) and 2.3 g of color image stabilizer (b) and dissolved, and this solution was dissolved in 1% dodecylbenzenesulfonic acid. 10 including 10m sodium
% Gelatin aqueous solution 90 m was emulsified and dispersed. On the other hand, the following blue-sensitive dyes were added to a silver chlorobromide emulsion (containing 80 mol% of silver bromide and 70 g / kg of Ag) per mol of silver chlorobromide.
95 g of a blue-sensitive emulsion was prepared by adding 25 × 10 ⁻⁴ mol. The emulsified dispersion and emulsion were mixed and dissolved, and the concentration was adjusted with gelatin so that the composition shown in Table 1 was obtained to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1-oxy- as a gelatin hardening agent for each layer
3,5-dichloro-s-driadine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue sensitive emulsion layer; Green-sensitive emulsion layer; Red-sensitive emulsion layer; The following dyes were used as the anti-irradiation dye in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; (h) UV absorber 1: 5: 3 mixture (molar ratio) of (i) Color mixing inhibitor (j) solvent Structural formulas of compounds such as couplers used in this example are as follows.

(a) Yellow coupler (b) Color image stabilizer (c) solvent (d) (e) Magenta coupler (Exemplified compound 10) (f) Color image stabilizer (g) solvent 2: 1 mixture (weight ratio) (k) Cyan coupler 1: 1 mixture of (l) color image stabilizer 1: 3: 3 mixture (m) solvent A large amount of silver halide color photographic light-sensitive material can be prepared by simultaneously coating the coating solutions of the first to seventh layers after adjusting the balance of surface tension and viscosity.

This photosensitive material was used as Sample 101.

Then, as shown in Table 2, Sample 102 was prepared in the same manner except that a silver halide fine grain emulsion or an antifoggant was added.
~ 107 were created. These samples were subjected to gradation exposure for sensitometry with a stretcher (Fuji Color Head 609 manufactured by Fuji Photo Film Co., Ltd.) and then developed by the following processing steps. The developing solution in this case is (a).

Processing step Temperature Time Color development 33 ° C. 3 minutes 30 seconds or 7 minutes Bleach fixing 33 ° C. 1 minute 30 seconds Water wash 25-35 ° C. Dry 80 ° C. 3 minutes Color developer composition Nitrilotriacetic acid / 3Na 2.0 g Benzyl alcohol 15 m Diethylene glycol 10 m Sulfite Sodium 2.0 g Potassium bromide 0.5 g Hydroxylamine sulfate 3.0 g 4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -p = phenylenediamine sulfate 5. 0g Sodium carbonate (monohydrate) sound 30g Add water 1000 (pH 10.1) Bleach-fix solution composition Ammonium thiosulfate (70%) 150m Sodium sulfite 15g (EDTA) Iron ammonium 55g (EDTA) ・ Disodium 4g Add water 1000m (pH 6.9) Further developer Exactly the same developer except for changing the content of the liquid pH below component (b) prepared against a), the same experiment was conducted by changing the developing solution (A).

The reflection density of blue light of the sample thus obtained was measured and the results shown in Table 3 were obtained.

As can be seen from Table 3, a color-mixing inhibitor layer (second layer) existing between the green-sensitive emulsion layer containing magenta coupler (third layer) and the blue-sensitive emulsion layer containing yellow coupler (second layer).
The fog density can be reduced by incorporating a silver halide fine grain emulsion into the (layer). This decrease in fog density is caused by 7 minutes of color development corresponding to the time when the developer (a) is pressed, and 3 minutes 30 seconds and 7 minutes of color development in the developer (b) where the blue-sensitive emulsion layer is easily fogged. In case of.

Further, sample Nos. 106 and 107 shown for comparison
Further, when the antifoggant (A) or the antifoggant (B) is used, it is found that the sensitivity is lowered at the addition amount necessary for reducing the fog, as compared with the present invention. From this, it is confirmed that the use of the fine grain emulsion of the present invention is extremely effective in reducing the fog of the red-sensitive emulsion.

Further, as an experiment showing the relationship between the silver halide grain size of the blue-sensitive layer and the silver halide grain size of the green-sensitive layer in the present invention, the silver halide emulsion of the blue-sensitive layer of sample No. 101 (Cl content 20 mol%, Particle size 0.76μ)
Silver halide emulsions with different grain sizes (Cl content of 20
Mol%, particle size 0.50μ)
A light-sensitive material sample No. 108, which is the same as No. 101, was prepared.
The grain size of the silver halide emulsion in the green-sensitive layer was 0.
It is 50μ. This sample was exposed in the same manner as above, and color development was performed for 3 minutes and 30 seconds and 7 minutes with the developer (a) or (b), respectively. A mixed color state was recognized. As a result, the grain size of the silver halide emulsion in the blue photosensitive layer becomes smaller, and when the sensitivity level is relatively close to the sensitivity level of the silver halide emulsion in the green photosensitive layer, the magenta color should appear where yellow should be developed. You can see that the colors are mixed.

Example 2 As in Example 1, the magenta coupler of the third layer in Sample 101 was replaced by the magenta coupler structural formula (1),
Changed to (7), (11) and (15), and further containing 0.03 g / m ^{2 of} silver halide fine grain emulsion (silver bromide, grain size 0.1 μ) in the first blue-sensitive emulsion layer. Samples 109 to 112 similar to the sample 101 except that the above were prepared.

Exposure, treatment and measurement were carried out for Example 1 and its application, and the fog density for blue light was measured to obtain the results shown in Table 4. The sensitivity and the maximum color density were hardly affected by the addition of the fine grain emulsion. From Table 4, it can be seen that the addition of the fine grain emulsion of the present invention to the blue-sensitive layer reduces the fog in this emulsion layer.

Example 3 Corresponding Samples 201 to 207 were prepared in exactly the same manner as Samples 101 to 107 in Example 1 except that the magenta coupler in the third layer was changed to the exemplified compound (23). The samples 201 to 207 were exposed, processed and measured in the same manner as in Example 1. The results are shown in Table 5.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer containing a yellow coupler between a green-sensitive silver halide emulsion layer containing a magenta coupler and a support. The silver halide emulsion layer contains a pyrazoloazole-based magenta coupler represented by the following general formula (II), (IV) or (V), and (b) halogen except for the following silver halide fine particles in the blue-sensitive emulsion layer. The average grain size of the silver halide grains is 1.2 times or more the average grain size of the silver halide grains in the green-sensitive emulsion layer, and (c) the blue-sensitive silver halide emulsion layer and the blue-sensitive emulsion. A silver halide fine grain emulsion characterized by containing a silver halide fine grain emulsion in at least one of the non-photosensitive layers interposed between the silver halide emulsion layer and the green-sensitive silver halide emulsion layer. Photographic material. General formula (II) General formula (IV) General formula (V) (In the formula, R ¹¹ , R ¹² and R ¹³ may be the same or different from each other and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic group. Oxy group, 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, Represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxy group. Or a group which is bonded to carbon at the coupling position via an oxygen atom, a nitrogen atom or a sulfur atom and can be released by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. ¹¹ , R
¹² , R ¹³ or X may be a divalent group to form a bis form, or R ¹¹ , R ¹² , R ¹³ or X may be a vinyl group or a linking group to form a polymer coupler. However, R ^11, at least one of R ¹² or R ¹³ represents a group bonded to the pyrazoloazole nucleus through a secondary or tertiary carbon, yet R ^11, R ¹² or R ¹³ at least one -NHSO Including a ₂ -substituent. )