JPH07117729B2 - Color photographic light-sensitive material - Google Patents

Description

The present invention relates to a color photographic light-sensitive material having high sensitivity and excellent color reproducibility.

[Conventional technology]

The spectral sensitivity distribution of the blue, green, and red sensitive silver halide emulsion layers is within a certain range for the purpose of faithful color reproducibility and for providing a photographic light-sensitive material in which the color reproducibility does not change significantly under photographing with various light sources. A method limited to US Pat. No. 3,672,898 is disclosed in US Pat. According to this patented invention, the spectral sensitivity distribution of the red-sensitive layer is shortened in order to faithfully reproduce the color of an object having purple or near-infrared reflection, which has been difficult to faithfully reproduce. It is effective to bring it closer to the spectral sensitivity distribution of the eye.

[Problems to be solved by the invention]

As a result of examining the above means, the present inventor has found that the fidelity of color reproduction is increased, but the color saturation is slightly decreased.

In order to compensate for this decrease in color saturation, a method is known in which a diffusible DIR compound disclosed in JP-A-59-131937 is used in combination. With this method, it is possible to reduce the saturation of highly pure colors such as red. However, the recovery effect was small and insufficient.

Further, an attempt to combine a strengthening of masking by a colored coupler and a layering effect by the above-mentioned diffusible DIR compound to increase color saturation has been disclosed in JP-A-61-43743 and JP-A-62-1.
60448 and Japanese Patent Laid-Open No. 62-160449, there is a serious drawback that the sensitivity of the red-sensitive layer, particularly the sensitivity of the red-sensitive layer on the short wavelength side, is remarkably lowered when masking enhancement by a magenta colored coupler is performed. Was.

An object of the present invention is to provide a silver halide color photographic light-sensitive material that faithfully reproduces spectral colors, has high saturation, and does not cause deterioration in sensitivity.

[Means for solving problems]

The above object of the present invention is to provide at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least two red-sensitive silver halide emulsion layers having different sensitivities on a support. In the color photographic light-sensitive material, the red-sensitive silver halide emulsion layer contains a magenta colored cyan coupler represented by the following general formula (I), and the centroid sensitivity of the spectral sensitivity distribution of the entire red-sensitive silver halide emulsion layer is In any two emulsion layers of the red-sensitive silver halide emulsion layer having a wavelength (λ _R ) in the range of 600 nm to 630 nm, the magenta colored cyan coupler to the cyan coupler in the slower layer. The ratio of
Achieved by a silver halide color light-sensitive material characterized by higher than that of the more sensitive layer.

It

General formula (I) In the formula, R ₁ represents an aromatic group or a heterocyclic group, R ₂ represents a group capable of substituting for a naphthol ring, A-B-N = N-D represents a coupling-off group, and A represents color development. Represents a divalent group in which the bond between the carbon atom at the coupling active position of this coupler and A is cleaved by the reaction between the oxidized form of the main drug and the coupler of the general formula (I), and B is a divalent group. Represents an aromatic group or a heterocyclic group, D represents an aromatic group or a heterocyclic group, and n represents an integer of 0 to 4.

The centroid sensitivity wavelength _R here is given by the following equation.

S _R (λ) is an equienergy spectral sensitivity distribution curve of the red sensitive layer.

The present invention will be described in detail below.

In order to faithfully reproduce the colors from yellow to red and the colors with colors reflected in purple and near infrared, for example, the spectral sensitivity of the red sensitive layer as shown by the solid line in A of FIG. 1 is set. Consider the case. This spectral sensitivity distribution is remarkably shortened as the spectral sensitivity of the red-sensitive layer of many conventional color photographic light-sensitive materials, and the centroid sensitivity wavelength is within the range of the present invention. It is a matter of course that such a shortening of the wavelength causes a significant decrease in saturation because the overlap with the spectral sensitivity distribution of the green-sensitive layer becomes large.

In order to make up for this decrease in saturation, a method has been considered in which the multi-layer effect is made more effective. A method using a DIR compound and a method using masking are known as methods for exerting the multilayer effect. Of these, it was revealed that the method using the DIR compound does not contribute to the recovery of the saturation of highly pure colors such as pure red.

On the other hand, when the method by masking, that is, the method of increasing the amount of magenta colored coupler in the red-sensitive layer to strengthen the masking, as shown in the change from the solid line to the broken line in FIG.
In particular, it has been found that not only the sensitivity on the short wavelength side is lowered and the sensitivity of the red-sensitive layer is lowered, but also the color reproduction is shifted in an unfavorable direction. The present inventors have found that this is because the long wavelength side of the absorption spectrum of the magenta colored coupler is on the short wavelength side of the spectral sensitivity distribution of the red-sensitive layer, as shown in FIG.

Therefore, as a result of earnest studies, the present inventor has found that any two emulsion layers in the red-sensitive layer containing a plurality of magenta colored cyan couplers represented by the general formula (I) having different sensitivities have lower sensitivity. Higher ratios of magenta colored cyan couplers to total cyan couplers in a layer than in the more sensitive layers have succeeded in minimizing sensitivity loss and color reproduction distortion.

At least one of the groups represented by A, B and D in the general formula (I) has a sulfo group, a carboxyl group, an alkali metal salt or an ammonium salt thereof as a substituent,
It has an alkylamine salt and a pyridinium salt. By having such a water-soluble group, the coupling-off group represented by ABN = ND is released from the coupler residue and then flows out into the developing solution.

The aromatic group represented by R ₁ has 6 carbon atoms.
Up to 30 substituted or unsubstituted aromatic groups. Examples of the heterocyclic group include a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms in the heterocyclic residue, and the heteroatom in the heterocyclic ring is N, O, S, Se, etc., preferably Is an unsaturated heterocycle containing nitrogen.

R ₂ represents a group capable of substituting on a naphthol ring (including atoms, the same applies hereinafter), and representative examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, and a heterocyclic group. , Carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, azyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic Examples thereof include a group sulfonyl group, a sulfamoylamino group, a nitro group and an imide group, and the number of carbon atoms contained in R ₂ is 0 to 30. When there are _two R ₂ , examples of cyclic R ₂ include a dioxymethylene group and the like. Here, the aliphatic group is an aliphatic hydrocarbon group including an alkyl, alkenyl and alkynyl group, and may have a usual substituent.

The magenta colored cyan coupler represented by the formula (I) is preferably a magenta colored cyan coupler represented by the general formula (II).

General formula (II) In the formula, R ₂ , A, B and n have the same meanings as in formula (I), and R ₃ and
At least one of R ₇ is -R ₃₁ , -OR ₃₁ , -SR ₃₁ , -NHSO ₂ R ₃₁ , (Wherein R ₃₁ represents a linear or branched alkyl group having 3 to 24 carbon atoms), R ₄ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom or an alkyl group or alkoxy group having 1 to 3 carbon atoms. Represent. R ₈ represents an alkyl group having 1 to 3 carbon atoms. M
Represents a hydrogen atom or 1 / m of an m-valent cation.

Here, n = 0 is preferable, and specific examples of the magenta colored cyan coupler represented by the general formula (II) are shown below.

In the present invention, magenta colored cyan couplers other than the magenta cyan coupler represented by the general formula (I) can be used, and those magenta colored cyan couplers represented by the following general formula (III) are preferable.

General formula (III) In the formula, R ₅ represents an aliphatic group or a polycyclic group, R ₆ represents a group capable of substituting for a naphthol ring, and n represents an integer of 0 to 4. A-B-N = N-D represents a coupling-off group and is the same as that shown in formula (I).

Next, specific examples of the magenta colored cyan coupler represented by the general formula (III) are shown below.

The magenta colored cyan coupler represented by the general formula (III) is disclosed in, for example, U.S. Pat. Nos. 4,004,929 and 4,1.
38,258 and British Patent 1,146,368.

In addition to the above couplers, it is included in the general formula (I).

Magenta color cyan dye couplers such as the above can also be used. The magenta colored cyan coupler is used together with the cyan coupler in the red-sensitive emulsion layer in order to correct the unnecessary absorption of the coloring dye, but by using the magenta colored coupler in a special manner as in the present invention, the sensitivity is not lowered as described above. It is possible to obtain a color photographic light-sensitive material which faithfully reproduces spectral colors and has high saturation.

When the red-sensitive silver halide emulsion layer has a two-layer structure, the ratio of magenta colored cyan couplers to all cyan couplers in the high-sensitivity layer is preferably in the range of 0 mol% to 20 mol%, and that in the low-sensitivity layer is 5 mol%. Mol% ~ 40
It is preferably in the range of mol%. In the case of a three-layer structure, the ratio of magenta colored cyan couplers to all cyan couplers in the highest sensitivity layer is 0 to 20 mol%.
It is preferable that it is in the range of 0, and it is 0 in the medium sensitivity layer.
Mol% to 30 mol% in the low sensitivity layer is 10 mol% to 50 mol%
It is preferably in the range of mol%. The mole fraction of the magenta colored cyan coupler of the present invention with respect to the total amount of the cyan coupler in the all red-sensitive emulsion layer is preferably in the range of 1-20%.

The magenta colored cyan coupler of the present invention can be incorporated in the non-photosensitive layer adjacent to the red-sensitive emulsion layer. In particular, by including the magenta colored cyan coupler of the present invention in the non-light-sensitive layer on the support side of the red-sensitive emulsion layer, it is possible to improve the distortion of the masking size from the low exposure region to the high exposure region. Is a very useful tool.

The coupling speed of the magenta colored cyan coupler is preferably substantially higher than that of the main cyan coupler, and more preferably 1.5 times or more.

The coupling speed can be measured by the method described in US Pat. No. 4,567,135.

When the centroid sensitivity wavelength of the spectral sensitivity distribution is 630 nm or more, as described above, it is clear that reproduction of a color having a reflection spectrum in violet or near infrared is remarkably broken, but the centroid sensitivity wavelength of 600 nm or less As described below, it became clear that even in such cases, there are significant adverse effects.

It has been a very difficult technique since the saturation of red and green is remarkably reduced when the wavelength of the red-sensitive layer is shortened. In recent years, attempts have been made to shorten the wavelength of the red-sensitive layer by devising the method of applying the multilayer effect and the size thereof as disclosed in, for example, JP-A-59-131937 and JP-A-62-160448. However, the present inventor carried out using these methods, without impairing the color saturation by these known methods, the range where the wavelength can be shortened is 600 nm at the limit, and below that range from green to red. It became clear that the degree of remarkably decreased and the reproducibility of the spectrum light deteriorated.

In the present invention, the all-cyan coupler is meant to include all couplers that form a cyan dye, and includes not only 4 equivalent cyan couplers but also 2 equivalent couplers having a usual leaving group, DIR couplers, colored cyan couplers and the like. .

The arrangement of the red-sensitive emulsion layer of the present invention is preferably on the side closer to the support, that is, on the side farther from the incident light side, as the emulsion layer has lower sensitivity.

One of the features of the present invention is that the center-of-gravity sensitivity wavelength ( _R ) is in the range of 600 nm to 630 nm, but it is preferably in the range of 600 nm to 726 nm in order to further improve the fidelity of color reproduction. Most preferably, it is in the range of 600 nm to 620 nm.

The sensitivity difference of the red-sensitive silver halide emulsion layer of the present invention is 0.1 to 1.0, preferably 0.2 to 0.6, in units of log (exposure amount).
Even when a plurality of layers having different sensitivities are provided in the blue-sensitive emulsion layer and the green-sensitive emulsion layer, it is preferable to set the difference in sensitivity between adjacent emulsion layers within the above range.

When a plurality of layers having different sensitivities are provided in the blue-sensitive and green-sensitive emulsion layers of the present invention and in the plurality of red-sensitive emulsion layers, each emulsion layer has substantially the same spectral sensitivity, but the maximum sensitivity wavelength and sensitivity distribution Do not have to be exactly the same.

The present invention comprises a support, a red-sensitive emulsion layer, a green-sensitive emulsion layer,
It is preferable to provide a blue-sensitive emulsion layer. However, it is not limited to this arrangement.

The object of the present invention relates to a red-sensitive layer, but also in a green-sensitive emulsion layer, a similar coupler structure, that is, all magenta couplers of yellow-colored couplers in any two layers of a plurality of differently sensitive green-sensitive emulsion layers. It is also possible to further combine a configuration in which the low-sensitivity layer has a higher ratio in the middle, and it is preferable to use this configuration in combination because higher sensitivity can be realized.

Any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing from about 2 mol% to about 25 mol% silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having an irregular crystal shape such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.1 micron or less or large size grains having a projected area diameter of up to about 10 microns, and it may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. Good.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure (RD), No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation". and types) ”and the same,
No. 18716 (November, 1979), p.648 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Monten (P.Glafkides, Chim.
ie et Physique Photographique Paul Montel, 1967),
Duffin, "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chimistry (Foca
Press, 1966), “Manufacturing and coating of photographic emulsions” by Zelikmann et al., “VL Zelikman et al, Mak” published by Focal Press.
ing and Coating Photographic Emulsion, 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 a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the above-mentioned regular grains can be obtained by controlling pAg and pH during grain formation. For more information, see, for example, Photographic Science and Engineering.
eering) Vol. 6, pp. 159-165 (1962); Journal of Photo Science (Journal of Photo)
graphic Science, 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

The monodisperse emulsion is a silver halide grain having an average grain diameter of about 0.1 micron or more, of which at least about 95
Emulsions are typically such that the weight percentage is within ± 40% of the average grain diameter. An average particle diameter of about 0.25 to 2 microns, at least about 95% by weight or at least about 95% in quantity
An emulsion in which the above silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention. Methods for making such emulsions are described in U.S. Pat. Nos. 3,574,628, 3,655,394 and British Patent 1,413,748. Also, JP-A-48-8600, 51-39027, 51-83097, 53-13
7133, 54-48521, 54-99419, 58-37635,
Monodisperse emulsions such as those described in JP-A-58-49938 can also be preferably used in the present invention.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gadov, Photographic Science and Engineering (Gutoff, Photographic Science and Engineering)
Volume 14, Pages 248-257 (1970); U.S. Pat. No. 4,434,226
No. 4,414,310, No. 4,433,048, No. 4,439,520, and British Patent No. 2,112,157, and the like. When tabular grains are used,
The advantages of the sensitizing dye such as improvement of color sensitization efficiency, improvement of graininess and increase of latent image are described in detail in US Pat. No. 4,434,226 cited above.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146,
U.S. Pat.Nos. 3,505,068, 4,444,877 and Japanese Patent Application No. 58
-248469 etc. are disclosed. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Patent Nos. 4,094,684, 4,142,900 and
4,459,353, British Patent 2,038,792, U.S. Patent 4,34
9,622, 4,395,478, 4,433,501, 4,463,087
No. 3,656,962, No. 3,852,067, JP-A-59-162540
No., etc.

Also, a mixture of particles having various crystal forms may be used.

The emulsion of the present invention is usually used after physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the locations described in the table below are shown.

As the yellow filter used in the color photographic light-sensitive material of the present invention, colloidal silver which is usually used can be used. Also, a yellow colored magenta coupler and / or a yellow diffusion-resistant organic dye can be used in place of the colloidal silver particles.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. As the dye-forming coupler, a coupler that gives the three primary colors of the decolorizing method (that is, yellow, magenta, and cyan) by color development is important, and is a diffusion-resistant coupler.
Specific examples of 4-equivalent or 2-equivalent couplers are the above-mentioned RD17643, V
In addition to the couplers described in the patents described in II-C and D, the following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
No. 7,210, No. 2,875,057 and No. 3,265,506. The use of 2 equivalent yellow couplers is preferred in the present invention and is described in US Pat. Nos. 3,408,194 and 3,4.
No. 47,928, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-58-10739, U.S. Pat.Nos. 4,401,752 and 4,3.
26,024, RD18053 (April 1979), British Patent No. 1,425,0
No. 20, West German Application Publication No. 2,219,917, No. 2,261,361,
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A-2,329,587 and JP-A-2,433,812. [alpha] -Piparoylacetonialide couplers are excellent in the fastness of color forming dyes, particularly light fastness, while [alpha] -benzoylacetanilide couplers provide high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat.
1,082, 2,343,703, 2,600,788, 2,9
No. 08,573, No. 3,062,653, No. 3,152,896 and No. 3,936,015. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,
Nitrogen atom leaving groups described in 619 or U.S. Pat.
The arylthio groups described in 51,897 are particularly preferred.
Further, it has a ballast group described in European Patent No. 73,636. 5
-Pyrazolone couplers provide high color density. As the pyrazoloazole coupler, U.S. Pat.
432 pyrazolobenzimidazoles, preferably pyrazolo [5,1−, described in U.S. Pat.No. 3,725,067
C] [1,2,4] triazoles, Research Disclosure 24220 (June 1984) and pyrazolotetrazoles and Research Disclosure 24230 (June 1984) described in JP-A-60-33552 and Kaisho 60-43
The pyrazolopyrazoles described in No. 659 can be mentioned. The imidazo [1,2-b] pyrazoles described in U.S. Pat.No. 4,500,630 are preferred in view of the small yellow sub-absorption of the color forming dye and light fastness, and the pyrazolo [1,5 in U.S. Pat. -B] [1,2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and the naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4 , 1
Representative examples thereof include oxygen atom elimination type two-equivalent naphthol couplers described in JP-A-46,396, JP-A-4,228,233 and JP-A-4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,171.
No. 2,772,162, No. 2,895,826 and the like. Couplers capable of forming a cyan dye that is fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include an alkyl group having an ethyl group or higher at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Phenolic cyan coupler having a group, U.S. Pat.No. 2,772,
No. 162, No. 3,758,308, No. 4,126,396, No. 4,33
4,011, 4,327,173, West German Patent Publication 3,329,729
2,5-diacylamino-substituted phenol-based couplers described in U.S. Pat.
Nos. 446,622, 4,333,999, 4,451,559, and 4,427,767, and the like, include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position. A sulfonamide group at the 5-position of the naphthol described in EP 161,626A,
Cyan couplers substituted with a carbonamide group, a carbamate group and the like are also excellent in fastness of a color image and can be preferably used in the present invention.

Among the above cyan couplers, the cyan couplers particularly preferably used in the present invention are represented by the following general formulas (IV) (V) (VI)
It is shown by.

General formula (IV) General formula (V) General formula (VI) In the formula, R ₉ represents an aromatic group or a heterocyclic group, R ₁₀ represents a group capable of substituting for a naphthol ring, R ₁₁ represents an aliphatic group,
Represents a heterocyclic group or an aromatic group, R ₁₂ represents an aromatic group, R ₁₃ represents an aromatic group or a heterocyclic group, R ₁₄ represents an aliphatic group, and n represents an integer of 0 to 4. , M represents an integer of 0 to 3, Y represents a hydrogen atom or a coupling-off group, and X represents —O—, —S— or R ₁₅ Represents However, R ₁₅ represents a hydrogen atom or an organic substituent, and when n and m are plural, R ₁₀ may be the same or different and may be bonded to each other to form a ring. In the general formula (VI), R ₁₀ and X or Y
And may combine with each other to form a ring. Further, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , X or Y may form a dimer or higher multimer.

Incidentally, specific examples of these compounds are described in detail in JP-A-61-273543.

In the present invention, as described above, the magenta colored cyan coupler is used in combination with the red-sensitive emulsion layer, but the colored coupler may be used in other emulsion layers in order to correct unnecessary absorption of the color forming dye. . US Patent No.
Yellow colored magenta couplers described in JP-B No. 4,163,670 and JP-B No. 57-39413 can be used in the green-sensitive emulsion layer. Other colored couplers are RD
17643, Sections VII-G.

Further, as a coupler for masking for correcting unnecessary absorption of a color forming dye, a group described in U.S. Pat.Nos. 4,555,477 and 4,555,478, which can be colored by coordinating with a metal as a leaving group, is used. Compounds having can also be used.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
Specific examples of magenta couplers are described in U.S. Pat. No. 4,366,237 and British Patent 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Patent Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the above-mentioned RD17643, VII to F are useful.

A preferred combination with the present invention is JP-A-57-151.
Developer inactivation type represented by 944; U.S. Pat. No. 4,248,962
And the timing type represented by JP-A-57-154234; the reaction type represented by JP-A-59-39653, and particularly preferable are JP-A-57-151944 and JP-A-58-217932. ,
Developer deactivating DIR couplers described in Japanese Patent Application Nos. 59-75474, 59-82214 and 59-90438, and Japanese Patent Application No. 59-75
It is a reactive DIR coupler described in 39653 and the like.

In the light-sensitive material of the present invention, a coupler capable of releasing a nucleating agent or a development accelerator or a precursor thereof imagewise during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. A coupler which releases a nucleating agent having an adsorbing action on silver halide is particularly preferable, and specific examples thereof are described in JP-A-59-157638 and JP-A-59-170840.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same, No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.
Development can be carried out by a usual method described in pages 28 to 29 of 643 and page 651, left column to right column of No. 18716.

The color photographic light-sensitive material of the present invention is usually subjected to washing treatment or stabilizing treatment after development, bleach-fixing or fixing treatment.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. A typical example of the stabilizing treatment is a multistage countercurrent stabilizing treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting the membrane pH (eg pH 3 to 8) Representative examples include monocarboxylic acid, dicarboxylic acid, polycarboxylic acid and the like) and formalin. In addition, water softener (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole), if necessary. , Halogenated phenols), surfactants, fluorescent brighteners, hardeners and the like, 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 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. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-.
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and sulfates thereof,
Hydrochloride or p-toluene sulfonic acid salt etc. are mentioned. Two or more of these compounds can be used in combination depending on the purpose.

The color developer includes a pH buffer such as an alkali metal carbonate, phonate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives such as, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. Agent, 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, Representative examples are N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developing solution, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the evaporation of liquid and air oxidation by reducing the contact area of the treatment tank with air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set to 4 to 5 minutes, but the processing time can be further shortened by using a high temperature, high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopropanecarboxylic acid, glycol ether diamine tetraacetic acid, or other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc .; persulfates; bromates; permanganates; nitrobenzenes, etc. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
No. 53 / 32,736, 53-57,831, 53-37,418
No. 53, No. 53-72,623, No. 53-95,630, No. 53-95,631,
53-10,4232, 53-124,424, 53-141,623,
53-28,426, Research Disclosure No.17,129
Compounds having a mercapto group or a disulfide group described in JP-A No. 1978, July 1978; thiazolidine derivatives described in JP-A Nos. 50-140,129; JP-B-45-8,506 and JP-A-52-2.
0,832, 53-32,735, thiourea derivatives described in US Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-5
Iodide salts described in 8-16,235; West German Patent No. 966,410,
Polyoxyethylene compounds described in No. 2,748,430;
Polyamine compounds described in JP-B-45-8836; Other JP-A-49-42,434, 49-59,644, 53-94,927, 54-
Compounds described in Nos. 35,727 and 55-26,506 and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in U.S. Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95,630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is the most widely used. Can be used for As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward current, and various other conditions. Can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is
l of the Society of Motion Picture and Television
It can be determined by the method described in Engineers Vol. 64, P. 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In processing the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated isocyanuric sodium oxide, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Technology" edited by The Society of Sanitary Engineers, "Encyclopedia of Antibacterial and Antifungal Agents", edited by the Society for Antibacterial and Antifungal Society of Japan.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range is 20 seconds to 10 minutes at 15-45 ° C, and preferably 30 seconds to 5 minutes at 25-40 ° C. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No.
All known methods described in Nos. -8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color photographic 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. For example, U.S. Pat.No. 3,342,597
No. 3,342,599, indoaniline compounds described in No.
Research Disclosure No. 14,850 and Schiff base type compounds described in No. 15,159, and Andole compounds described in No. 13,924, metal salt complexes described in U.S. Patent No. 3,719,492,
The urethane compounds described in JP-A-53-135,628 can be mentioned.

The silver halide color photographic light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of promoting color development. Typical compounds are JP-A-56-64,339, JP-A-57-14,4547, and JP-A-58-64,339.
115,438, etc.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative filters for general use or movies, color reversal filters for slides or televisions, and color reversal papers for direct photography. The present invention can also be applied to a black-and-white light-sensitive material using a three-color coupler mixture described in Research Disclosure 17123 (July 1978).

The present invention also relates to U.S. Pat.No. 4,500,626, JP-A-60-1334.
It can also be applied to the heat-developable or high-temperature developable light-sensitive materials described in JP-A-49-49, JP-A-59-218443 and Japanese Patent Application No. 60-79709.

Next, the present invention will be described in more detail with reference to examples.

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by. The chemical structure formulas in the form of salt conform to the notation of chemical abstract.

1st layer (antihalation layer) Black colloidal silver …… 0.15 Gelatin …… 2.9 UV-1 (UV absorber) …… 0.03 UV-2 (UV absorber) …… 0.06 UV-3 (UV absorber) …… 0.07 Solv-2 (solvent) ...... 0.08 ExF-1 (cyan dye) ...... 0.01 ExF-2 (cyan dye) ...... 0.01 2nd layer (low-sensitivity red emulsion layer) AgI 4 mol% Uniform sphere equivalent diameter 0.4 Number of fluctuations in equivalent diameter of μ spheres 37%, plate-like particles Diameter / thickness ratio 3.0 Coating silver amount …… 0.4 Gelatin …… 0.8 ExS-1 (sensitizing dye) …… 2.3 × 10 ^-4 ExS-2 (sensitizing dye ) …… 1.4 × 10 ^-4 ExS-5 (sensitizing dye) …… 2.3 × 10 ^-4 ExS-7 (sensitizing dye) …… 8.0 × 10 ^-6 ExC-1 (cyan coupler) …… 0.17 ExC- 2 (cyan coupler) ...... 0.03 ExC-3 (magenta colored cyan coupler) (III-
3) …… 0.045 3rd layer (medium-speed red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core / shell ratio 2: 1, internal high AgI sphere equivalent diameter 0.65μ, variation coefficient of sphere equivalent diameter 25% , Plate-like grains, diameter / thickness ratio 2.0) Coating amount of silver …… 0.65 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter of 0.
4μ, coefficient of variation of equivalent spherical diameter 37%, plate-shaped particles, diameter / thickness ratio 3.0) Silver coating amount …… 0.1 Gelatin …… 1.0 ExS-1 (sensitizing dye) …… 2 × 10 ^-4 ExS-2 ( Sensitizing dye …… 1.2 × 10 ^-4 ExS-5 (sensitizing dye) …… 2 × 10 ^-4 ExS-7 (sensitizing dye) …… 7 × 10 ^-6 ExC-1 (magenta coupler) …… 0.31 ExC-2 (cyan coupler) …… 0.01 ExC-3 (magenta color cyan coupler) (III-
3) ...... 0.09 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with core-shell ratio 2: 1, equivalent sphere diameter 0.7μ, variation coefficient of equivalent sphere diameter) 25%, tabular grains, diameter / thickness ratio 2.5) Coating silver amount …… 0.9 Gelatin …… 0.8 ExS-1 (sensitizing dye) …… 1.6 × 10 ^-4 ExS-2 (sensitizing dye) …… 1.0 × 10 ^-4 ExS-5 (sensitizing dye) …… 1.6 × 10 ^-4 ExS-7 (sensitizing dye) …… 6 × 10 ^-6 ExC-1 (cyan coupler) …… 0.07 ExC-4 (cyan coupler) ...... 0.05 ExC-3 (magenta color cyan dye coupler) (III-
3) …… 0.05 Solv-1 (solvent) …… 0.07 Solv-2 (solvent) …… 0.20 Cpd-7 (antifoggant) …… 4.6 × 10 ^-4 Fifth layer (intermediate layer) Gelatin …… 0.6 UV -4 (UV absorber) ...... 0.03 UV-5 (UV absorber) ...... 0.04 Cpd-1 (color mixing inhibitor) ...... 0.1 Polyethyl acrylate latex ...... 0.08 Solv-1 (solvent) ...... 0.05 6th Layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion AgI 4 mol% uniform type. Equivalent sphere diameter 0.4μ, Equivalent sphere diameter 0.7μ, coefficient of variation of sphere equivalent diameter 37%, Plate-shaped particles, Diameter / thickness ratio 2.0 Coating amount of silver …… 0.18 Gelatin …… 0.4 ExS-3 (sensitizing dye) …… 2 × 10 ^-4 ExS-4 (sensitizing dye) …… 7 × 10 ^-4 ExS-5 (sensitizing dye) …… 1 × 10 ^-4 ExM-5 (magenta coupler) …… 0.11 ExM-7 (yellow) Colored magenta coupler) …… 0.0
3 ExY-8 (DIR coupler) …… 0.01 Solv-1 (solvent) …… 0.09 Solv-4 (solvent) …… 0.01 7th layer (medium sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%) , Surface height AgI type with 1: 1 core-shell ratio, sphere-equivalent type, sphere-equivalent diameter 0.5μ, coefficient of variation of sphere-equivalent diameter 20%, plate-shaped particles, diameter / thickness ratio 4.0) Silver coating amount 0.27 Gelatin ...... 0.6 ExS-3 (sensitizing dye) …… 2 × 10 ^-4 ExS-4 (sensitizing dye) …… 7 × 10 ^-4 ExS-5 (sensitizing dye) …… 1 × 10 ^-4 ExM-5 ( Magenta coupler) …… 0.17 ExM-7 (Yellow colored magenta coupler) …… 0.0
4 ExY-8 (DIR coupler) …… 0.02 Solv-1 (solvent) …… 0.14 Solv-4 (solvent) …… 0.02 Eighth layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 8.7 mol%) , Silver content ratio 3: 4: 2 multilayer structure particles, AgI content from the inside 24 mol, 0 mol%, 3 mol%, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 25%, plate-like particles, diameter / Thickness ratio 1.6) Silver coating …… 0.7 Gelatin …… 0.8 ExS-4 (sensitizing dye) …… 5.2 × 10 ^-4 ExS-5 (sensitizing dye) …… 1 × 10 ^-4 ExS-8 (sensitizing dye) Sensitizing dye) ... 0.3 x 10 ^-4 ExM-5 (magenta coupler) ... 0.1 ExM-6 (yellow colored magenta coupler) ... 0.0
3 ExY-8 (DIR coupler) …… 0.02 ExC-1 (cyan coupler) …… 0.02 ExC-4 (cyan coupler) …… 0.01 Solv-1 (solvent) …… 0.25 Solv-2 (solvent) …… 0.06 Solv -4 (solvent) ...... 0.01 Cpd-7 (antifoggant) ...... 1 × 10 ^-4 9th layer (intermediate layer) gelatin ...... 0.6 Cpd-1 (color mixing inhibitor) ...... 0.04 Polyethyl acrylate latex ... … 0.12 Solv-1 (solvent) …… 0.02 10th layer (donor layer of multi-layer effect for red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1, internal high AgI type, equivalent spherical diameter) 0.7μ, coefficient of variation of equivalent spherical diameter 25%, plate-like grain, diameter / thickness ratio 2.0) Coating amount of silver …… 0.68 Silver iodobromide emulsion (AgI 4 mol%, variation coefficient of equivalent spherical equivalent diameter 37%, Plate-shaped particles, diameter / thickness ratio 3.0) Silver coating amount …… 0.19 Gelatin …… 1.0 ExS-3 (sensitizing dye) …… 6 × 10 ^-4 ExM-10 (DIR coupler …… 0.19 Solv-1 (Solvent) ...... 0.20 Layer 11 (Yellow filter layer) Yellow colloidal silver ...... 0.06 Gelatin ...... 0.8 Cpd-2 (Yellow dye) …… 0.13 Solv-1 …… 0.13 Cpd-1 (Color mixture inhibitor) ) ...... 0.07 Cpd-6 (antifoggant) ...... 0.002 H-1 (hardener) ...... 0.13 12th layer (low sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI) Type, sphere equivalent diameter
0.7μ, coefficient of variation of equivalent sphere diameter 15%, tabular grains, diameter / thickness ratio 7.0) Coating silver amount ... 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 3.
0μ, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter / thickness ratio 7.0) Coating silver amount …… 0.15 Gelatin …… 1.8 ExS-6 (sensitizing dye) …… 9 × 10 ^-4 ExC-1 ( Cyan coupler) ... 0.06 ExC-4 (cyan coupler) ... 0.03 ExY-1 (DIR coupler) ... 0.14 ExY-11 (yellow coupler) ... 0.89 Solv-1 (solvent) ... 0.42 Gelatin ... 0.7 ExY -12 (DIR coupler) ...... 0.20 Solv-1 (solvent) ...... 0.34 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion layer (AgI 10 mol%, internal high AgI type, equivalent spherical diameter 1.0) μ, coefficient of variation of spherical equivalent diameter 25%, multiple twin plate particles, diameter / thickness ratio 2.0) Coating amount of silver …… 0.5 Gelatin …… 0.5 ExS-6 (sensitizing dye) …… 1 × 10 ^-4 ExY -9 (DIR coupler) …… 0.01 ExY-11 (yellow coupler) …… 0.20 ExC-1 (cyan coupler) …… 0.02 Solv-1 (solvent) …… 0.10 15th layer (1st protective layer) Fine particle odor Silver emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter 0.07μ) Coating silver amount …… 0.12 Gelatin …… 0.9 UV-4 (UV absorber) …… 0.11 UV-5 (UV absorber) …… 0.16 Solv-5 (solvent) ...... 0.02 H-1 (hardener) ...... 0.13 Cpd-5 (scavenger) ...... 0.10 Polyethyl acrylate latex ...... 0.09 16th layer (2nd protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, sphere equivalent diameter 0.07μ) Coating silver amount …… 0.36 Gelatin …… 0.55 Polymethyl acrylate particle diameter 1.5μ …… 0.2 H-1 (hardener) …… 0.17 Each layer In addition to the above components, the emulsion stabilizer Cpd-3 (0.0
7 g / m ² ) Surfactant Cpd-4 (0.03 g / m ² ) was added as a coating aid.

Preparation of Comparative Sample 102 Comparative Sample 101 was prepared in the same manner as Comparative Sample 101 except that the sensitizing dyes of the second, third and fourth layers of Comparative Sample 101 were changed as follows.

Second layer ExS-1 …… 1.2 × 10 ^-4 ExS-2 …… 3.5 × 10 ^-4 ExS-7 …… 1.2 × 10 ^-4 Third layer ExS-1 …… 1.0 × 10 ^-4 ExS-2… … 3.0 × 10 ^-4 ExS-7 …… 1.0 × 10 ^-4 4th layer ExS-1 …… 0.7 × 10 ^-4 ExS-2 …… 2.4 × 10 ^-4 ExS-7 …… 0.6 × 10 ^-4 Comparison Preparation of Sample 103 Sample 103 was the same as Comparative Sample 102 except that ExC-3 of the second layer was 0.12, ExS-3 of the third layer was 0.05, and ExC-3 of the fourth layer was removed in Comparative Sample 102. Was produced.

Preparation of Comparative Sample 104 ExC-3 of the second layer, the third layer, and the fourth layer in Comparative Sample 101
A sample 104 was prepared in the same manner as the comparative sample 101, except that was changed to the exemplified compound (4) in the text in an equimolar amount.

Preparation of Comparative Sample 105 ExC-3 of the second layer, the third layer, and the fourth layer in Comparative Sample 103
Sample 105 was prepared in the same manner as Comparative Sample 103, except that was changed to Exemplified Compound (4) in the text in an equimolar amount.

Preparation of Comparative Sample 106 A sample similar to Comparative Sample 101 except that ExC-3 of the second layer was 0.12, ExC-3 of the third layer was 0.05, and ExC-3 of the fourth layer was removed in Comparative Sample 101. 106 was produced.

Preparation of Inventive Sample 107 Sample 107 was prepared in the same manner as Comparative Sample 106 except that ExC-3 of the second layer and the third layer of Inventive Sample 106 was changed to Exemplified Compound (4) in the text in an equimolar amount. .

Preparation of Inventive Sample 108 Sample 108 was prepared in the same manner as Comparative Sample 106 except that ExC-3 of the second layer and the third layer of Inventive Sample 106 was changed to Exemplified Compound (1) (equimolar) in the text. did.

Preparation of Comparative Sample 109 Same as Sample 106 except that the magenta colored cyan coupler ExC-3 of the second and third layers of the invention sample 106 was changed to the magenta colored cyan coupler ExC-13 (III-1) shown below. Sample 109 was prepared.

Preparation of Inventive Sample 110 In Inventive Sample 107, the compound (4) in the second layer was 0.05, the compound (4) in the third layer was 0.13, and the compound (4) was in the fourth layer.
Sample 110 was prepared in the same manner as sample 107 except that 0.01 was added.

A sensitometric measurement was carried out after a tungsten light source was used for this photographic element, the color temperature was adjusted to 4800 ° K with a filter, exposure was carried out with a wedge, and development processing was carried out at 38 ° C according to the following processing steps.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each process is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1.0l pH10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water 1.0l pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water is added 1.0l pH6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g Water was added to 1.0 l The sensitivity of the red-sensitive layer was determined from the results of this sensitometry and shown in Table-1 (Sample 101). Is expressed as a relative value when 100 is set).

Further, using these samples, Munsell color charts of red and magenta purple were selected and photographed, and printed on a color paper (Fuji Color Paper AGL) so that the gray of an optical density of 0.7 taken at the same time had the same density. First, this result of visually evaluating color fidelity and saturation is also shown in Table 1. Of these, sample 6 and sample 107 have value 6,
The point of chroma 8 was plotted with the L ^* a ^* b ^* surface dye, and the results are shown in FIG.

That is, FIG. 3 is a diagram showing the fidelity of color reproduction,
The original Munsell color chart is marked with a circle, the reproduction result with sample 107 is ○, and the reproduction result with sample 102 is a ^* , b
^{* Indicated on the} coordinate axes. The farther from the origin, the more vivid it is, and when the angles connecting the origin and the result are equal, the hues are equal.

From these results, it can be seen that Samples 107, 106, and 110 are color reproducible, especially that they are faithful to purple, have high saturation of red, and have high sensitivity of the red-sensitive layer.

In Samples 106 to 109, the ratio of magenta colored cyan coupler to cyan coupler in the lower sensitivity layer of the three-layer red-sensitive emulsion layer was higher than that in the higher sensitivity layer [second layer (low sensitivity layer)> third layer]. (Middle and high sensitivity layer)> Fourth layer (high sensitivity layer)], Sample 110 is the case of the second layer> the fourth layer and the third layer> the fourth layer, and any two emulsion layers referred to in the present invention. The higher ratio of magenta colored cyan couplers to cyan couplers in the slower layers than in the more sensitive layers means that when the red sensitive emulsion layer is composed of three or more layers, for example, Sample 110 It means that the above-mentioned ratio relation should be present between any two constituent layers as seen in FIG.

[Advantages of the Invention] As described above, according to the present invention, a color photographic light-sensitive material having excellent color reproducibility, high red saturation and high sensitivity can be obtained.

[Brief description of drawings]

FIG. 1 shows the spectral sensitivity distribution of the red-sensitive layer of a silver halide color photographic light-sensitive material. The solid line is an example of the preferred spectral sensitivity and the dashed line shows the spectral sensitivity affected by the magenta colored cyan coupler. FIG. 2 shows the spectral absorption spectrum of a typical magenta colored cyan coupler. FIG. 3 is a diagram showing the fidelity of color reproduction.

Claims (1)

[Claims] 1. A support having at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least two red-sensitive silver halide emulsion layers having different sensitivities. In the color photographic light-sensitive material, the red-sensitive silver halide emulsion layer contains a magenta colored cyan coupler represented by the following general formula (I), and the centroid sensitivity wavelength of the spectral sensitivity distribution of the entire red-sensitive silver halide emulsion layer is (Λ _R ) is in the range of 600 nm to 630 nm, and in any two emulsion layers of the red-sensitive silver halide emulsion layer, the magenta colored cyan coupler to the cyan coupler in the slower layer is used. A silver halide color light-sensitive material characterized in that the ratio is higher than that of the more sensitive layer. General formula (I) In the formula, R ₁ represents an aromatic group or a heterocyclic group, R ₂ represents a group capable of substituting for a naphthol ring, A-B-N = N-D represents a coupling-off group, and A represents color development. Represents a divalent group in which the bond between the carbon atom at the coupling active position of this coupler and A is cleaved by the reaction between the oxidized form of the main drug and the coupler of the general formula (I), and B is a divalent group. Represents an aromatic group or a heterocyclic group, D represents an aromatic group or a heterocyclic group, and n represents an integer of 0 to 4.