JP2835631B2 - Silver halide color photographic materials with improved color reproduction - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material,
More specifically, the present invention relates to a silver halide color photographic material having improved color reproducibility.

(Prior art)

In recent years, the image quality of silver halide color photographic materials (hereinafter abbreviated as color photographic materials) has been remarkably improved, but the color reproducibility has not been sufficient yet. Factors that have a particularly large effect on color reproducibility include the spectral sensitivity distribution of color light-sensitive materials and the interimage effect (hereinafter abbreviated as IIE).

In Japanese Patent Publication No. 49-6207, the spectral sensitivity distributions of the blue photosensitive layer and the red photosensitive layer are both shifted toward the green photosensitive layer using a filter layer or the like, thereby preventing the deterioration of color reproducibility due to a change in the color temperature of the light source. However, such a change in the spectral sensitivity distribution causes a remarkable decrease in sensitivity, and a change in reproduced color due to a change in color temperature is reduced. As a result, there is a disadvantage that a color with high saturation is not reproduced and the color becomes dull.

Generally, in controlling the spectral sensitivity distribution, when aiming at faithful hue reproduction, shortening the red-sensitive phase is also important from the viewpoint of approaching human visibility. In particular, in the color reproduction of blue-violet flowers having so-called red non-reflection, it is essential to shorten the wavelength of the red-sensitive layer. However, as described above, shortening the wavelength of the red-sensitive layer caused a decrease in saturation, and in particular, caused a problem in skin color reproduction which is important in color reproduction of color photographs. That is, there is a drawback that the healthy red color peculiar to the skin color is lost, and the color reproduction becomes lifeless.

Japanese Patent Laid-Open No. 62-16044 discloses a technique that defines spectral sensitivity and IIE.
No. 9 is disclosed. This technique gives the direction of IIE to each color-sensitive layer.

Further, JP-A-62-160448 discloses that a cyan photosensitive layer is provided.
A technique intended for negative spectral sensitivity corresponding to the spectral sensitivity of the human eye by applying E to the red sensitive layer is disclosed,
In any case, the color reproducibility is not yet sufficient, and a photosensitive material having good color reproducibility has been desired.

[Object of the invention]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color light-sensitive material capable of faithfully reproducing hue, and in particular, to provide a color photographic light-sensitive material having improved purple hue reproduction and flesh color reproducibility.

[Configuration of the invention]

The present inventors have made intensive studies on the spectral sensitivity distribution of silver halide emulsion layers having different color sensitivities and the masking characteristics and color reproducibility of color-forming couplers, and as a result, have accomplished the present invention.

That is, at least one layer of a blue-sensitive silver halide emulsion layer containing a yellow-colored color coupler, at least one green-sensitive silver halide emulsion layer containing a magenta-colored color coupler, and a cyan-colored color coupler are formed on a support. Spectral sensitivity distribution S of the red-sensitive silver halide emulsion layer in a color light-sensitive material having a red-sensitive silver halide emulsion layer
_R (λ) is: (A) The wavelength λ _R ^{max at} which S _R (λ) is maximum is 595 nm ≦ λ _R ^max ≦ 635 nm (B) S _R (λ) is 50% of S _R (λ _R ^max ) Wavelength λ _R ⁵⁰
The wavelength on the long wave side is 630 nm ≦ λ _R ⁵⁰ ≦ 650 nm, and the masking characteristic of the green density obtained by red separation exposure is such that the green density is 0.04
A silver halide color photographic material characterized by having an overmask of not less than 0.15.

 Hereinafter, the present invention will be described specifically.

In the present invention, the wavelength λ _R ^{max at} which the spectral sensitivity distribution of the red-sensitive layer is the maximum is 595 nm ≦ λ _R ^max ≦ 635 nm. A light-sensitive material having a short-wave length exceeding the above range has a disadvantage that the chroma of reproduced colors is insufficient.

λ _R ^max is preferably in the range of 600 nm ≦ λ _R ^max ≦ 625 nm, more preferably 605 nm ≦ λ _R ^max ≦ 620 nm.

The wavelength of S _R (λ) is 50% of the ^{_{S R (λ R max) λ}} R
^It is essential that the wavelength on the long wave side of ⁵⁰ is 625 nm ≦ λ _R ⁵⁰ ≦ 650 nm. When the characteristic is extended beyond the above range and shows a long-wave characteristic, the reproduction of red is good, but the reproduction of purple is deteriorated, and it becomes undesirably reddish or the dependence on the photographing light source becomes large.

Preferably, 630 nm ≦ λ _R ⁵⁰ ≦ 645 nm, ^more preferably 630 nm ≦ λ _R ⁵⁰ ≦ 640 nm.

The wavelength of S _R (λ) is 50% of the ^{_{S R (λ R max) λ}} R
Wavelength of short side ⁵⁰ is preferably 575nm ≦ λ _R ⁵⁰ ≦ 600nm.

In the present invention, the spectral sensitivity distribution can be obtained by plotting the sensitivity giving a density of minimum density + 0.1 on the horizontal axis wavelength.

In the present invention, the spectral sensitivity distribution of the red-sensitive layer can be obtained, for example, by appropriately combining spectral sensitizing dyes having the structural formulas shown below.

The spectral sensitivity distribution of the present invention is obtained by combining at least one of the sensitizing dyes represented by the following general formula (I) with the general formula (II)
It can be constituted by combining with at least one of the sensitizing dyes represented by I), and more preferably at least one of each of the general formulas (I), (II) and (III) Good to combine.

In addition, supersensitizers other than the sensitizing dyes represented by the general formulas (I), (II) and (III) can be used. Examples of such sensitizers are described in JP-B-57-24533. Benzothiazoles and quinolones, and quinoline derivatives described in JP-B-57-24899 can be used according to the purpose.

The general formulas (I), (II) and (III) are described in detail below.

General formula (I) In the general formula (I), R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and R ² and R ³ each represent an alkyl group. Y ¹ and Y ² each represent a sulfur atom or a selenium atom.

 Then Z¹, Z^Two, Z^ThreeAnd Z^FourRepresents a hydrogen atom and a halogen, respectively.
Atom, hydroxyl group, alkoxy group, amino group, reed
Group, acylamino group, acyloxy group, aryloxy
Si group, alkoxycarbonyl group, aryloxycarbo
Nyl group, alkoxycarbonylamino group, sulfonyl
Group, carbamoyl group, aryl group, alkyl group or
Represents an ano group. Z¹And Z^TwoAnd / or Z^ThreeAnd Z^FourRespectively
They may be connected to each other to form a ring. Also X₁ Is ani
Indicates ON. m represents an integer of 1 or 2;
When the element forms an inner salt, m represents 1.

General formula (II) In the above formula (II), R ⁴ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent an alkyl group.

Y ^3, Y ⁴ represents a nitrogen atom, an oxygen atom, a sulfur atom or selenium atom, and when Y ³ is a sulfur atom, an oxygen atom or a selenium atom, and shall not have the above R ^5.

Also, Y ³ and Y ⁴ are not simultaneously nitrogen atoms.

 Then Z^Five, Z⁶, Z⁷And Z⁸Represents a hydrogen atom and a halogen, respectively.
Atom, hydroxyl group, alkoxy group, amino group, reed
Group, acylamino group, acyloxy group, aryloxy
Si group, alkoxycarbonyl group, aryloxycarbo
Nil group, alkoxycarbonylamino group, carbamoyl
Group, aryl group, alkyl group, cyano group or sulfoni
Represents a hydroxyl group. Z^FiveAnd Z⁶And / or Z⁷And Z⁸Are
They may be linked to form a ring. Also X_Two Is Anio
Represents n represents an integer of 1 or 2, but a sensitizing dye
When n forms an internal salt, n represents 1.

General formula (III) In the general formula (III), R ⁹ represents a hydrogen atom, an alkyl group or an aryl group, and R ¹⁰ , R ¹¹ , R ¹² and R
¹³ represents an alkyl group.

Next, Z ⁹ , Z ¹⁰ , Z ¹¹ and Z ¹² are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group,
Represents an acyl group, an acylamino group, an acyloxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonylamino group, a carbamoyl group, an aryl group, an alkyl group, a cyano group or a sulfonyl group.

Z ⁹ and Z ¹⁰ and / or Z ¹¹ and Z ¹² may be connected to each other to form a ring.

 Also X_Three Represents an anion. n is an integer of 1 or 2
When the sensitizing dye forms an inner salt, n is
Represents 1.

Next, the masking technique used in the present invention will be described. Generally, a masking technique such as a colored coupler or a fog mask is used in a color negative film to correct secondary absorption (illegal absorption) of a color coupler.
For example, a cyan color coupler has absorption not only in red density but also in the blue and green regions. A colored cyan coupler for correcting this secondary absorption is used in the red sensitive layer, and the green density is substantially the same as that of the cyan color coupler. The color reproducibility is improved by keeping it constant so as not to depend on the color density.

In the present invention, an overmask technique is required in which masking is performed to correct improper absorption of the green portion of the cyan coupler and green density is formed in a counter-image-like manner as the cyan image is formed. This technology is similar to the inter-image effect (IIE) from the red-sensitive layer to the green-sensitive layer, but has less processing variability than the method using DIR, and has one direction from the red-sensitive layer to the green-sensitive layer. The advantage is that you can control the IIE.

In the present invention, the green density masking characteristic obtained by red separation exposure is an overmask having a green density of 0.04 or more and 0.15 or less at an exposure amount that gives a minimum red density of +0.30. The above overmask characteristics are obtained by subjecting the photosensitive material to decomposing exposure using a red filter such as Eastman Kodak Co., Ltd.'s No. 29 red filter, and performing a development process described in Examples, and then using a status M filter. It is obtained by measuring. The degree of overmask is the green density of the unexposed area and the cyan color Dnirt 0.3 of red separation exposure
It can be determined from the difference in green density at an exposure that gives a red density of 0.

The above-mentioned overmask characteristics can be obtained by various methods. As a result, it is preferable to specifically use a colored coupler as long as overmask characteristics can be obtained.
The method of use may be appropriately controlled depending on the type of the colorless coupler or the colored coupler to obtain the overmask property, but the following method is effective.

A method in which a colored cyan coupler is used in a large amount relative to a colorless cyan coupler. In this case, when obtaining the overmask characteristic at the relatively leg of the characteristic curve as in the present invention,
It is effective and preferred that the ratio of the colored cyan coupler in the red-sensitive emulsion layer having the highest sensitivity be the highest in the red-sensitive emulsion layer.

A method in which a combination of a cyan coupler having a higher reactivity with an oxide of a developing agent than a colorless cyan coupler is selected and a colored cyan coupler is preferentially reacted to obtain an overmask. Also in this case, it is most effective when the above combination is realized in the highest sensitivity layer.
Specifically, a combination using a 4-equivalent cyan coupler with respect to a 2-equivalent colored cyan coupler is a preferable combination.

The cyan coupler effectively used in the present invention will be described below.

The colored cyan coupler preferably used in the present invention can be represented by the following general formula [1].

General formula [1] In the formula, COUP represents a cyan coupler residue, * represents a coupling site of the cyan coupler, J represents a divalent linking group, 1 represents 0 or 1, and R ₃ represents an aryl group.

The cyan coupler residue represented by COUP is a phenol type coupler residue or a naphthol type coupler residue, and particularly preferably a naphthol type coupler residue.

Preferred examples of the divalent linking group represented by J can be represented by the following general formula [2].

General formula [2] In the formula, R ₆ represents an alkylene group having 1 to 4 carbon atoms or an arylene group, R ₇ represents an alkylene group having 1 to 4 carbon atoms, and R ₈ and R ₇ are alkylene groups. It may be substituted by an alkyl group, a carboxy group, a hydroxy group, or a sulfo group.

Z is -O -, - S -, - SO -, - SO 2 -, - SO 2 NH -, - CONH
—, —COO—, —NHCO—, —NHSO ₂ —, —OCO—, and R ₉ and R ₁₀ represent an alkyl group or an aryl group.

R ₈ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a cyano group, a nitro group, a sulfonyl group, an alkoxy group, an aryloxy group, a carboxy group,
Represents a sulfo group, a halogen atom, a carbonamido group, a sulfonamido group, a carbamoyl group, an alkoxycarbonyl group or a sulfamoyl group.

P represents 0 or a positive integer, q represents 0 or 1, and γ represents an integer of 1 to 4. When P is 2 or more,
R ₆ and Z may be the same or different. When γ is 2 or more, R ₈ may be the same or different.

When 1 = 0, the aryl group represented by R ₃ is preferably a phenyl group or a naphthyl group. The phenyl group and the naphthyl group may have a substituent, and the substituent may be a halogen atom, an alkyl group, an alkoxy group,
Aryloxy group, hydroxy group, acyloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acylamino group, sulfonamide group,
Carbamoyl group, sulfamoyl group and the like.

When l = 1, the aryl group represented by R ₃ is preferably a naphthol group represented by the following general formula [3].

General formula [3] In the formula, R ₉ is a linear or branched alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, etc.) Wherein M is a photographically inert cation such as a hydrogen atom, a cation of an alkali metal such as a sodium atom or a potassium atom, ammonium, methyl ammonium, ethyl ammonium, diethyl ammonium,
Represents triethylammonium, ethanolammonium, diethanolammonium, pyridinium, piperidium, anilinium, toluidinium, P-nitroanilinium, anisidium and the like.

Next, specific examples of the representative colored coupler represented by the general formula [1] are shown, but the present invention is not limited thereto.

The above compounds are described in JP-A-50-123341 and JP-A-55-65957.
Nos. 56-94347, JP-B No. 42-11304, 44-32461
Nos. 48-17899, 53-34733, U.S. Pat.
No. 892, British Patent No. 1,084,480, and the like.

The cyan coupler used with the colored cyan coupler of the present invention is generally a colorless cyan coupler.

The colorless cyan coupler according to the present invention is a phenol type coupler or a naphthol type coupler, and preferably a coupler represented by the following general formula [4], [5] or [6].

General formula [4] General formula [5] General formula [6] In the above formula, A represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

R ¹ , R ² and R ³ are each a normal phenol or α-
Represents a group used in a naphthol coupler, specifically, R ¹ is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon residue, an N-arylureido group, an acylamino group, -OR ⁴ or -S
—R ⁴ (where R ⁴ is an aliphatic hydrocarbon residue), and when two or more R ₇ are present in the same molecule, two or more R ¹
May be different groups, and aliphatic hydrocarbon residues include those having a substituent.

When these substituents include an aryl group, the aryl group is an alkyl group, an alkenyl group, a cyclic alkyl group,
Aralkyl group, cyclic alkenyl group, halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, Diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group,
Arylthio, alkylthio, alkylamino,
It may have a dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, mercapto group and the like.

Examples of R ² and R ³ include a group selected from an aliphatic hydrocarbon residue, an aryl group and a heterocyclic residue, or one of these may be a hydrogen atom,
Further, those having a substituent in these groups are also included. Also
R ² and R ³ may together form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residue may be saturated or unsaturated, and may be linear, branched or cyclic. And preferably, an alkyl group (for example, each group of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and an alkenyl group (for example, each group of allyl, octenyl, etc.). .

Aryl groups include phenyl and naphthyl groups, and heterocyclic residues include pyridinyl, quinolyl,
Representative groups are thienyl, piperidyl, imidazolyl and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocyclic, alkoxy, Aryloxy, arylthio,
Examples include groups such as arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino.

The leaving group represented by A includes any group known as a leaving group of a 2-equivalent phenol cyan coupler and a 2-equivalent naphthol cyan coupler, and more preferably a halogen atom (for example, fluorine,
Chlorine or the like), a substituted or unsubstituted alkoxy group (for example, methoxy group, 2-methoxyethoxy group, 3-carboxypropoxy group, n-hexadecyloxy group), a substituted or unsubstituted aryloxy group (for example, phenoxy group) , 1-naphthoxy group, 4-methoxyphenoxy group, 4
-T-octylphenoxy group, 4-methanesulfonylphenoxy group, 3-pentadecylphenoxy group and the like, and substituted or unsubstituted heterocyclic oxy groups (for example, 2-pyridyloxy group, 4,6-dimethoxy-1,3 , 5-Triazine-
A substituted or unsubstituted alkylthio group (e.g., methylthio group, 2-methanesulfonylethylthio group, n-dodecylthio group, etc.), a substituted or unsubstituted arylthio group (e.g., phenylthio group, 4-n
-Dodecylphenylthio group, 2-methoxy-5-t-octylphenylthio group, etc.), substituted or unsubstituted alkylsulfonyl groups (eg, methylsulfonyl group, n-decylsulfonyl group, 4-hydroxybutylsulfonyl group, etc.), A substituted or unsubstituted heterocyclic group (for example, 3-
Nitropyrazolyl group, morpholino group, 1-benzyl-5
-Ethoxyhydantoin-3-yl group).

Of these, particularly preferred X includes a hydrogen atom, a chlorine atom, a fluorine atom, an aryloxy group, a heterocyclic oxy group, and an alkoxy group. Aryloxy groups are particularly preferred.

As the silver halide emulsion used in the light-sensitive material of the present invention, any of silver halide emulsions can be used, and the effect is particularly remarkable in the case of a silver iodobromide emulsion.

The emulsion can be chemically sensitized by a conventional method, and the emulsion used for the blue-sensitive layer and the green-sensitive layer is optically sensitized to a desired wavelength region using a publicly known sensitizing dye. it can.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer.

Known and publicly-known couplers can be used in each of the emulsion layers of the blue-sensitive layer and the green-sensitive layer.

Furthermore, a colored coupler having the effect of color correction,
Development accelerator, bleaching accelerator, developer, silver halide solvent, color tone, hardener, fogging agent, antifoggant, chemical sensitizer, spectral sensitizer by coupling with competing coupler and oxidized form of developing agent Compounds that release photographically useful fragments, such as sensitizers and desensitizers, can be used.

Photosensitive materials include filter layers, antihalation layers,
An auxiliary layer such as an irradiation prevention layer can be provided.

To the light-sensitive material, a formalin scavenger, a fluorescent brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder, a bleaching accelerator and the like can be added.

As the support, a polyethylene terephthalate film, a cellulose triacetate film, or the like can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, generally known color photographic processing can be performed after exposure.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

In all the following examples, the amount of the silver halide photographic light-sensitive material is particularly shows the number of grams per 1 m ² unless otherwise noted. Further, silver halide and colloidal silver are shown in terms of silver.

Example 1 A multilayer color photographic light-sensitive material sample No. 1 was prepared by sequentially forming each layer having the following composition on a triacetyl cellulose film support from the support side.

Sample-No. 1 (Comparative) First layer; Anti-halation layer (HC-1) Black colloidal silver 0.18 UV absorber (UV-1) 0.23 High boiling solvent (Oil-1) 0.18 Gelatin 1.4 Second layer; Intermediate layer (IL-1) Gelatin 1.0 Third layer; low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size: 0.4 μm) 1.0 Sensitizing dye (I-40) 1.8 × 10 ⁻⁵ (mol / Silver 1 mol) Sensitizing dye (I-6) 1.6 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.70 Colored cyan coupler (CC-1) 0.13 DIR compound (D-1) 0.04 DIR compound (D-3) 0.01 High boiling solvent (Oil-1) 0.64 Gelatin 1.2 Fourth layer; Medium-speed red-sensitive emulsion layer (RM) Silver iodobromide emulsion (average particle size 0.7 μm) 0.8 Sensitizing dye (I −40) 2.1 × 10 ⁻⁵ (mol / silver 1 mol) Sensitizing dye (I-6) 1.9 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-1) 0.28 Colored cyan coupler (CC -1) 0.027 DIR compound (D-1) 0.015 High boiling solvent (Oil-1) 0.26 Gelatin 0.62 Fifth layer; High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Average particle size 0.8 μm) 1.70 increase Sensitizing dye (I-40) 1.9 × 10 ^-5 (mol / silver 1 mol) Sensitizing dye (I-6) 1.7 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.05 Cikan coupler ( C-2) 0.10 Colored cyan coupler (CC-1) 0.025 DIR compound (D-1) 0.025 High boiling point solution (Oil-1) 0.17 Gelatin 1.2 6th layer; 2nd intermediate layer (IL-2) Gelatin 0.8 7th Layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average particle size 0.4 μm) 1.0 Sensitizing dye (SD-4) 6.8 × 10 ^-5 (mol / silver 1 mol) Sensitizing dye (SD- 5) 6.2 × 10 ^-4 (mol / mole of silver) magenta coupler (M-1) 0.54 magenta coupler (M-2) 0.19 colored magenta coupler (CM-1) 0.06 DIR compound (D-2) 0.017 DIR compound (D-3) 0.01 High boiling solvent (Oil-2) 0.81 Gelatin 1.8 Eighth layer; Medium-sensitive green-sensitive emulsion layer (GM) Silver iodobromide emulsion (average grain size 0.7 μm) 0.7 Sensitizing dye (SD-6) 1.9 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-7) 1.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-8) 1.5 × 10 ^-5 (mol / silver mol) Magenta coupler (M-1) 0.08 Magenta coupler (M-2) 0.03 Colored magenta coupler (CM-1) 0.04 DIR compound (D-2) 0.018 High boiling solvent (Oil- 2) 0.30 gelatin 0.8 ninth layer; high-sensitivity green-sensitive emulsion layer (GH) silver iodobromide emulsion (average particle size 1.0 μm) 1.7 sensitizing dye (SD-6) 1.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-7) 1.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-8) 3.4 × 10 ^-6 (mol / silver 1 mol) Magenta coupler (M-1) 0.09 Magenta coupler( -3) 0.04 Colored magenta coupler (CM-1) 0.10 High boiling solvent (Oil-2) 0.31 Gelatin 1.2 10th layer; Yellow filter layer (YC) Yellow colloidal silver 0.10 Color stain inhibitor (SC-1) 0.1 High boiling point Solvent (Oil-2) 0.13 Gelatin 0.7 Formalin scavenger (HS-1) 0.09 Formalin scavenger (HS-2) 0.07 12th layer; high-sensitivity blue-sensitive emulsion layer (BH) silver iodobromide emulsion (average particle size: 1.0 μm) 1.0 sensitizing dye (SD-9) 1.8 × 10 ^-4 (mol / silver 1 mol) SD-10) 7.9 × 10 ^-5 (mol / silver 1 mol) Yellow coupler (Y-1) 0.15 Yellow coupler (Y-2) 0.05 High boiling solvent (Oil-2) 0.074 Gelatin 1.30 Formalin scavenger (HS-1) 0.05 Formalin scavenger (HS-2) 0.12 13th layer; 1st protective layer (Pro-1) Fine grain silver iodobromide emulsion 0.4 (Average particle size 0.08 µm AgI 1 mol%) UV absorber (UV-1) 0.07 UV absorption (UV-2) 0.10 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.13 Formalin scavenger (HS-2) 0.37 Gelatin 1.3 14th layer; Second protection Layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethylmeth Acrylate (average particle size 3 [mu] m) 0.02 Slip agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, a coating aid Su-1 and a dispersion aid Su-
2, viscosity adjusting agent, hardener H-1, H-2, stabilizer ST-1,
Antifoggant AF-1, ▲ ▼: 10,000 and ▲ ▼: 1,
100,000 of the two AF-2s were added.

The average particle size was represented by a particle size converted into a cube. Each emulsion was optimally subjected to gold and sulfur sensitization.

Next, the sensitizing dyes used for the third, fourth, and fifth layers in Sample No. 1 were changed as shown in Table 1, and the amount of the color coupler contained in the fifth layer was changed as shown in Table 1. Change to the sample
Nos. 2 to 9 were produced.

In the third, fourth, and fifth layers of Samples No. 2 to No. 9, the total amount of the sensitizing dye was adjusted to be equimolar to that of Sample No. 1.
In Table 1, the molar ratio of the added amount of the sensitizing dye is shown in parentheses after the exemplified dye.

Each emulsion contained in Samples No. 1 to No. 9 was optimally subjected to chemical sensitization by a usual method using gold and sulfur sensitizers.

In addition, in order to determine the spectral sensitivity distribution, color development is performed by the following processing steps, spectral exposure is performed, and the density is 1.
At 0, each parameter for determining the spectral sensitivity distribution was measured. In addition, the density difference (ΔD) of the unexposed portion from the green density at the exposure amount where the reddish red density is given a minimum density of +0.3 by performing red sensitivity exposure using Eastman Kodak Wratten Filter No. 29 The results are shown in Table 1. Note that the higher the density value of ΔD is, the more overmasking is performed.

The processing was performed until a replenisher of three times the capacity of the stabilizing tank was charged.

(The replenishment amount is a value per 1 m ² of the photosensitive material.) However, the stabilization treatment was performed in a three-tank countercurrent, the replenishment was performed in the last tank of the stabilizing solution, and the overflow flowed into the preceding tank. .

Further, a part of the overflow (275 ml / m ² ) of the stabilization tank following the fixing tank was poured into the stabilization tank.

 The composition of the color developing solution used is as follows.

Potassium carbonate 30 g Sodium hydrogen carbonate 2.7 g Potassium sulfite 2.8 g Sodium bromide 1.3 g Hydroxylamine sulfate 3.2 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate Salt 4.6 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.3 g Add water to make 1 and adjust to pH 10.01 using potassium hydroxide or 20% sulfuric acid.

 The composition of the color developing solution replenisher used was as follows.

Potassium carbonate 40 g Sodium bicarbonate 3 g Potassium sulfite 7 g Sodium bromide 0.5 g Hydroxylamine sulfate 3.2 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 6.0 g Diethylenetriamine 3.0 g of pentaacetic acid 2 g of potassium hydroxide 2 g was added with water to adjust to 1 and adjusted to pH 10.12 with potassium hydroxide or 20% sulfuric acid.

 The composition of the bleaching solution used is as follows.

Ferric ammonium 1,3 diaminopropanetetraacetate 0.35 mol Disodium ethylenediamontetraacetate 2 g Ammonium bromide 150 g Glacial acetic acid 40 ml Ammonium nitrate 40 g Add water to 1 and adjust to pH 4.5 using aqueous ammonia or glacial acetic acid I do.

 The composition of the bleach replenisher used was as follows.

Ferric ammonium 1,3 diaminopropanetetraacetate 0.40 mol Disodium ethylenediamontetraacetate 2 g Ammonium bromide 170 g Ammonium nitrate 50 g Glacial acetic acid 61 ml Add water to 1 and adjust to pH 3.5 using aqueous ammonia or glacial acetic acid. Adjust appropriately so that the pH of the bleach tank solution can be maintained.

The compositions of the fixing solution and the fixing replenisher used are as follows.

Ammonium thiosulfate 100 g Ammonium thiocyanate 150 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Disodium ethylenediaminetetraacetate 1.0 g Add water to 700 ml, and adjust to pH 6.5 with glacial acetic acid and aqueous ammonia.

The compositions of the used stabilizing solution and stabilizing replenisher are as follows.

Water was added to adjust the pH to 1, and the pH was adjusted to 7.0 with potassium acetate and 50% sulfuric acid.

Treating agent sample in a thermo-hygrostat at a temperature of 65 ° C and a relative humidity of 60%
After storage for 14 days, optical densitometer (PDA-65) (Konica Corporation)
The maximum density and the blue density (transmission) of the unexposed part were measured as representative characteristics, and the difference of the blue density (transmission) from the sample not subjected to the treatment in the thermo-hygrostat was obtained.

 Table 1 shows the results.

In the table, EDTA · Fe means ferric ammonium ethylenediaminetetraacetate, NTA · Fe means ferric ammonium nitrilotriacetate, DTPA · Fe means ferric ammonium diethylenetriaminepentaacetate, (A-1) · Fe, (A-4) Fe or the like means a ferric ammonium salt such as (A-1) or (A-4).

In order to examine the color reproducibility of the obtained sample, a close-up of a person's face and a color chart including grey, red, flesh color, and purple and a purple cloth were photographed and subjected to the above-mentioned development processing. (Konica Color PC paper type
SR). The color reproducibility of the obtained color chart was measured by L ^* a using a colorimeter CMS-1200 manufactured by Murakami Color Research Laboratory.
^* B ^* Measure the chromaticity in the color system and determine the difference from the original a ^* b
^* Table 2 shows the distances on the plane. A smaller value indicates a more faithful reproduction. At this time, the color was adjusted so that the 18% gray reflector became gray.

As can be seen from Table 2, simply shortening the spectral sensitivity distribution does not have a significant effect on color reproduction, but as shown in Samples Nos. 4 to 8, the effect on color reproduction is improved when combined with an overmask. large. Sample No. 7, in which the ratio of the colored coupler was large in the red-sensitive layer and the reactivity ratio between the colored coupler and the colorless cyan coupler was increased, exhibited the most preferable color reproducibility.

Comparative Sample No. 9 had the disadvantage that the reproduction of red was deteriorated and the characteristic curve of the measured density of green light was hardened.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-160449 (JP, A) JP-A-62-160448 (JP, A) JP-A-62-170958 (JP, A) JP-A-59-160 131937 (JP, A) Journal of the Photographic Society of Japan, Vol. 52, No. 1, January 1989, p. 41-45 (58) Field surveyed (Int. Cl. ⁶ , DB name) G03C 7/00

Claims (1)

(57) [Claims] A blue-sensitive silver halide emulsion layer containing at least one yellow-color-forming color coupler, a green-sensitive silver halide emulsion layer containing a magenta-color-forming color coupler, and cyan color on a support. In a color light-sensitive material having a red-sensitive silver halide emulsion layer containing a color coupler, the spectral sensitivity distribution S _R (λ) of the red-sensitive silver halide emulsion layer is: (a) the wavelength at which S _R (λ) is the maximum. λ _R ^max is 595 nm ≦ λ _R
wavelength lambda _R ^{50 to max} ≦ 635 nm (b) S _{R (λ)} is 50% of the S _{R (λ R} ^max)
The wavelength on the long wave side is 630 nm ≦ λ _R ⁵⁰ ≦ 650 nm, and the masking characteristic of the green density obtained by red separation exposure gives the minimum red density + 0.30. A silver halide color photographic material characterized by being an overmask.