JP2881330B2 - Color photographic light-sensitive material with excellent hue reproduction - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a color photographic light-sensitive material, and more particularly, to a color photographic light-sensitive material having high chroma, excellent hue reproducibility, and high sensitivity.

[Conventional technology]

In recent years, the image quality of silver halide multilayer color photographic light-sensitive materials has been remarkably improved.

That is, in recent color photographic light-sensitive materials, the three major factors of image quality, that is, graininess, sharpness, and color reproducibility, are all at a considerably high level. For example, with regard to general color photographs, it is generally thought that color prints and slide photographs obtained by a user do not have any major complaints. However, among the above three factors, the color purity has been improved, especially in color reproducibility, but the situation of colors which have been conventionally said to be difficult to reproduce in photographs has not changed much. That is, the hue reproducibility still has many insufficient points. For example, a greenish color such as violet or bluish violet, or a blue or yellow rim, which reflects light having a wavelength longer than 600 nm, is reproduced in a completely different color from the real thing, and may disappoint the user.

Major factors relating to color reproducibility include spectral sensitivity distribution and interlayer effect (inter-image effect).

The following is known about the interimage effect. That is, in a silver halide multilayer color photographic light-sensitive material, it is known to add a compound which forms a development inhibitor or a precursor thereof by coupling with an oxidized form of a color developing agent, and is released from this so-called DlR compound. It is known that by suppressing the development of other color-forming layers with a development inhibitor, an inter-image effect is produced and an effect of improving color reproducibility is produced.

In a color negative film, an effect similar to the inter-image effect can be obtained by using a colored coupler in an amount larger than an amount that cancels unnecessary absorption.

However, when the colored coupler is frequently used, the minimum density of the film increases, so that it is very difficult to determine the correction of the color and density at the time of printing, and as a result,
Often the resulting prints have poor color quality.

By the way, these techniques contribute to the improvement of color purity among color reproducibility. The so-called diffusive DIR, which has recently been frequently used as a suppressive group or has a large mobility of its precursor, greatly contributes to the improvement of the color purity. However, it is difficult to control the direction of the inter-image effect, and although the color purity can be increased, the inter-image effect has a disadvantage of changing the hue. The control of the direction of the inter-image effect is described in US Pat. No. 4,725,529 and the like.

On the other hand, regarding the spectral sensitivity distribution, U.S. Pat.
No. 8 discloses an appropriate spectral sensitivity distribution for reducing variation in color reproducibility due to a difference in light source at the time of shooting.

However, this is not a means for improving the aforementioned color having poor hue reproducibility.

Also, as previously known in the art, by shifting the spectral sensitivity distribution of the red-sensitive layer by a short wavelength, the reproduction of hues such as blue-violet and violet is improved. This is disclosed in
No. -20926 and JP-A-59-131937, the method described here has some drawbacks.

One is that the purity of red is reduced.
By increasing the inter-image effect between the red-sensitive layer and the other layers, this disadvantage is improved, but in this case, the original effect of improving blue-violet color reproduction is reduced.

Japanese Patent Application Laid-Open No. 61-34541 discloses a technique combining spectral sensitivity distribution and inter-image effect, and attempts have been made to improve the color in which hue reproduction is difficult with the aforementioned color film. Seems to be obtained.
As a typical example, not only the inter-image effect from the center-of-gravity wavelength of each of the conventional blue-sensitive layer, edge-sensitive layer, and red-sensitive layer, but also the inter-image effect from other than the center-of-gravity wavelength of each color-sensitive layer. That is.

Although this technique seems to be effective to some extent in improving the hue reproducibility of a specific color, specifically, it is necessary to improve the original blue-sensitive, green-sensitive, and red-sensitive photosensitive layers in order to develop the interimage effect. In addition, an inter-image effect-exhibiting layer and another type of photosensitive silver halide are required, resulting in a high production cost due to an increase in the amount of silver and an increase in the number of production steps. And the effect was not sufficient.

[Object of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material which faithfully achieves a blue-purple hue reproduction without lowering the purity of red, and furthermore has a sufficient yellow hue and green hue reproduction. It is in.

[Configuration of the invention]

As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved with the following configuration.

That is, at least one blue-sensitive silver halide emulsion layer (hereinafter, also referred to as “blue-sensitive layer”) and an edge-sensitive silver halide emulsion layer (hereinafter, referred to as “edge-sensitive layer” as appropriate) on a support. In some cases) and a red-sensitive silver halide emulsion layer (hereinafter sometimes referred to as “red-sensitive layer” as appropriate) in a silver halide color photographic light-sensitive material. The maximum sensitivity wavelength λ _R is 595 nm ≦ λ _R ≦ 625 nm, and the red-sensitive silver halide emulsion layer comprises at least one sensitizing dye represented by the following general formula (I) (described later) and the following general formula (III) (At least one of the sensitizing dyes described below)
Containing a combination of bracts, and maximum sensitivity S _R of red-sensitive silver halide emulsion layer in a wavelength range 480nm or 400nm are also 400nm or 480nm
The put in a wavelength band by a silver halide color photographic light-sensitive material, characterized in that at least 1.5% of the maximum sensitivity S _B of the blue-sensitive silver halide emulsion layer, was achieved the above objects.

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

In the present invention, the spectral sensitivity distribution refers to 400n
Exposure is performed with spectral light at intervals of several nm from m to 700 nm, the exposure amount that gives a constant density at each wavelength is the sensitivity at each wavelength, and the sensitivity is a function of wavelength.

Preferred embodiments of the light-sensitive material of the present invention are as follows.

That is, in one embodiment, the light-sensitive material of the present invention preferably has one or more blue-sensitive layers, an edge-sensitive layer, and a red-sensitive layer on a support in this order from the side close to the support. is there.

In the present invention, the wavelength λ having the maximum concentration of the red-sensitive layer
_R is 595 nm ≦ λ _R ≦ 625 nm, more preferably 595n
m ≦ λ _R ≦ 615 nm.

Further, the ratio of the maximum sensitivity of the red-sensitive layer in the wavelength region of 400 nm to 480 nm to the maximum sensitivity of the blue-sensitive layer in the same wavelength region is preferably 2.5% to 6%.

The present invention can be embodied in various photosensitive materials,
For example, the present invention can be preferably applied to a color negative photosensitive material, but is not particularly limited thereto, and a preferable hue reproduction can be similarly achieved by using another photosensitive material such as a color reversal photosensitive material.

In the present invention, an appropriate means can be arbitrarily used to make the spectral sensitivity distribution of the red-sensitive layer the configuration of the present invention described above. For example, means for sensitizing the spectrum of any silver halide with a sensitizing dye having an absorption spectrum in a target wavelength range, or optimizing the halogen composition of silver halide and the distribution thereof without using a sensitizing dye for the purpose. There is a means for giving a desired spectral sensitivity distribution, and a means for adjusting a target spectral sensitivity distribution by using an appropriate optical absorber in a light-sensitive material. Of course, these means may be used together. The above also applies to the adjustment of the spectral sensitivity distribution of other color-sensitive layers.

In order to make the spectral sensitivity distribution of the red-sensitive layer of the color photographic light-sensitive material of the present invention into the shape according to the present invention, at least one of the sensitizing dyes represented by the following general formula (I) and the general formula (III) In combination with at least one of the sensitizing dyes represented by More preferably, general formula (I),
It is preferable to combine at least one of each of (II) and (III). In addition, general formulas (I), (II),
It can be constituted by a combination of sensitizing dyes represented by (III) and (IV).

In addition, supersensitizers other than the sensitizing dyes represented by the general formulas (I) and (III) can be used, and examples thereof are described in JP-B-57-24533. Benzothiazoles and quinolones, and JP-B-57-24899
The quinoline derivative and the like described in the publication can be used according to the purpose.

The general formulas (I), (II), (III) and (IV) will be described in detail below.

General formula (I) In the above general formula (I), R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and R ² , R ³ , R ⁴ and R ⁵ each represent an alkyl group or an aryl group.

Z ¹ , Z ² , Z ³ and Z ⁴ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an acyloxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl Represents a group, an alkoxycarbonylamino group, a carbamoyl group, an aryl group, an alkyl group, a cyano group or a sulfonyl group.

Z ¹ and Z ² and / or Z ³ and Z ⁴ may be connected to each other to form a ring. (X ₁ ) _m represents a charge-balancing counter ion, and m represents a value required to neutralize a charge of 0 or more.

General formula (II) In the above general formula (II), R ⁶ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are
Each represents an alkyl group or an aryl group.

Y ¹ and Y ² are each nitrogen atom, an oxygen atom, a sulfur atom or selenium atom, and when Y ¹ is a sulfur atom, an oxygen atom or a selenium atom, and shall not have the above R ^7. Further, Y ¹ and Y ² are not simultaneously a nitrogen atom or a sulfur atom.

Z ⁵ , Z ⁶ , Z ⁷ and Z ⁸ are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an acyloxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl Represents a group, an alkoxycarbonylamino group, a carbamoyl group, an aryl group, an alkyl group, a cyano group or a sulfonyl group.

Z ⁵ and Z ^6, and / or Z ⁷ and Z ⁸ may each be connected to each other to form a ring. (X ₂ ) _n represents a charge balancing counter ion, and n represents a value necessary to neutralize 0 or more charges.

General formula (III) In the general formula (III), R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group, and R ¹² and R ¹³ each represent an alkyl group or an aryl group. Y ³ and Y ⁴ each represent a sulfur atom or a selenium atom.

Z ⁹ , Z ¹⁰ , Z ¹¹ and Z ¹² each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an acyloxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl Group, alkoxycarbonylamino group, sulfonyl group,
A carbamoyl group, an aryl group, an alkyl group or a cyano group; Z ⁹ and Z ¹⁰ and / or Z ¹¹ and Z ¹² may be connected to each other to form a ring. (X ₃ ) _p is
Represents a charge balancing counter ion, and p represents a value necessary to neutralize a charge of 0 or more.

General formula (IV) In the general formula (IV), R ¹⁴ represents an alkyl group, a phenyl group or an aralkyl group. R ¹⁵ and R ¹⁶ represent an alkyl group, an alkenyl group or an aralkyl group, and at least one of R ¹⁵ and R ¹⁶ has a sulfo group or a carboxyl group as a substituent.

Z ¹³ , Z ¹⁴ , Z ¹⁵ and Z ¹⁶ each represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group or an aryl group, provided that Z ¹³ and Z ¹⁴ and / or Z ¹⁵ and Z ¹⁶
Are linked to each other to form a fused benzene ring.
(X ₄ ) _q represents a charge-balancing counter ion, and q represents a value required to neutralize 0 or more charges.

The representative sensitizing dyes represented by formulas (I), (II), (III) and (IV) which can be used in the present invention are shown below. Is not limited to these. The following example (I
-1) to (I-34) are examples of sensitizing dyes represented by general formula (I), and (II-1) to (II-40) are sensitizing dyes represented by general formula (II) Examples of the dyes (III-1) to (III-47) are examples of the sensitizing dyes represented by the general formula (III), and (IV-1) to (IV)
-7) is an example of a sensitizing dye represented by the general formula (IV).

Next, in the photosensitive material of the present invention, 400nm or more 480nm
The maximum sensitivity S _R of the red-sensitive layer in the following wavelength range is 1.5% or more of the maximum sensitivity S _B of the blue-sensitive layer in the same wavelength range. Thus, means for relatively increasing the spectral sensitivity of the red-sensitive layer Also, any technique can be adopted. As one of the means for this purpose, for example, there is a method of reducing the amount of yellow colloidal silver which is usually used in a color photographic light-sensitive material to absorb irregular light in the inherent photosensitive wavelength range of silver halide, and various other methods. There is technology. Preferably, the blue-sensitive silver halide emulsion layer contains a coupler that develops cyan, so that this structure is adopted. Preferred cyan couplers which can be contained in the blue-sensitive layer when this means is employed are described below.

As the cyan coupler contained in the blue-sensitive layer, a 2-equivalent cyan coupler or a 4-equivalent cyan coupler can be used.

In general, the 2-equivalent cyan coupler that can be added to the blue-sensitive layer is preferably represented by the following general formula [CI].

General formula (CI) In the formula, Cp represents a coupler residue, * represents a coupling position of the coupler, and X represents a group which is released when a dye is formed by coupling with an oxidized form of an aromatic primary amine color developing agent. .

Representative cyan coupler residues Cp are U.S. Pat.Nos. 2,367,531, 2,423,730, and 2,474,293.
No. 2,772,162, No. 2,895,826, No. 3,002,83
No. 6, No. 3,034,892, No. 3,041,236 and the above Agf
a Mitteilung (BandII), pages 156 to 175 (1961). Of these, phenols and naphthols are preferred.

Examples of the leaving group represented by X include a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, (X ₁ represents a group of atoms necessary to form a 5- or 6-membered ring together with at least one atom selected from the group consisting of a nitrogen atom and a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom in the formula), an acylamino group, It is a monovalent group such as a sulfonamide group and a divalent group such as an alkylene group. In the case of a divalent group, X forms a dimer.

 The following is a specific example.

In the present invention, as the two-equivalent cyan coupler to be contained in the blue-sensitive layer, the following general formulas [CII], [CIII], [C
IV] are preferred.

In the formula, R ²¹ represents a hydrogen atom or a substituent, and R ²² and R ²³
Represents a substituent, m is 1-3, n is 1-2, p is 1-5
And when m, n, p is 2 or more, each R ²¹ may be the same or different. X has the same meaning as X in the general formula [CI].

Examples of the substituent represented by R ²¹ include groups such as a halogen atom, an alkyl, a cycloalkyl, an aryl, and a heterocycle directly or via a divalent atom or group.

Examples of the divalent atom or group include an oxygen atom, a nitrogen atom, a sulfur atom, carbonylamino, aminocarbonyl, sulfonylamino, aminosulfonyl, amino, carbonyl, carbonyloxy, oxycarbonyl, ureylene, thioureylene, thiocarbonylamino, Sulfonyl, sulfonyloxy and the like can be mentioned.

Also, the above alkyl, cycloalkyl, aryl,
Heterocycle includes those having a substituent. Examples of the substituent include a halogen atom, nitro, cyano, alkyl,
Alkenyl, cycloalkyl, aryl, alkoxy,
Aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxy, sulfo, sulfamoyl,
Examples include carbamoyl, acylamino, ureido, urethane, sulfonamide, heterocycle, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxy, imide, acyl and the like.

Examples of R ²² and R ²³ include alkyl, cycloalkyl, aryl, and heterocyclic groups.
These include those having a substituent.

In the 2-equivalent cyan couplers represented by the general formulas [CII] to [CIV], examples of X include the same as those exemplified in [CI], and include a halogen atom, an alkoxy group, and an aryloxy group. And sulfonamide groups are particularly preferred.

Further, the cyan couplers represented by the general formulas [CII] and [CIII] include those in which R ²¹ , R ²² or X forms a dimer or more multimer, and are represented by the general formula [CIV]. R ²¹ , R ²² , R ²³ or X
To form a dimer or more multimer.

In the present invention, specific examples of the 2-equivalent cyan coupler that can be used are shown below, but are not limited thereto.

2-equivalent cyan coupler Next, 4-equivalent couplers that can be used in the blue-sensitive layer in the present invention will be described.

The 4-equivalent coupler is a coupler having no substituent at the coupling position. As the cyan coupler, phenols and naphthols are preferable.

More preferred 4-equivalent couplers include those in which X at the coupling position in the above general formulas [CII] to [CIV] is a hydrogen atom. R ^{21 to} R in this case
Examples of ²³ include those exemplified in formulas (CII) to (CIV), and in each formula, R ²¹
But also the case where in to R ²³ to form a dimer or more multimer.

In the present invention, specific examples of the 4-equivalent coupler that can be used are shown below, but are not limited thereto.

4-equivalent cyan coupler Furthermore, the maximum sensitivity of the red-sensitive layer and the blue-sensitive layer in the 400nm or 480nm or less S _R, so that the present invention the relation S _B, it is possible to use the following so-called diffusible DIR couplers the blue-sensitive layer . The following diffusible DIR couplers are broadly included in the concept of the cyan coupler.

The diffusive DIR that can be used in the practice of the present invention is described below.
Examples of the compound of the coupler are shown below, but the present invention is not limited thereto, and the following are some examples.

As the cyan coupler to be added to the blue-sensitive layer, among the couplers described above, a diffusible DIR coupler is desirable.

The silver halide emulsion used in the color light-sensitive material of the present invention can be chemically sensitized by a conventional method.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous (but not limited to) 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.

The color photographic light-sensitive material of the present invention comprises, in its emulsion layer,
In general, a coupler for coloring is used, but a colored coupler having a further correcting effect, a competitor and a phenomenon accelerator by coupling with an oxidized form of a phenomenon active agent,
Photographically useful fragments such as bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral 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. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

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 phenomenon accelerator, a phenomenon retarder and a bleach accelerator can be added.

As the support, any material such as paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate and the like can be used.

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

〔Example〕

Hereinafter, examples of the present invention will be described. However, needless to say, the present invention is not limited only to the embodiments described below.

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-101 was prepared by sequentially forming layers having the following compositions on a triacetyl cellulose film support from the support side.

Sample-101 (Comparative) First layer; Anti-halation layer (HC-1) Black colloidal silver 0.20 UV absorber (UV-1) 0.20 High boiling solvent (Oil-1) 0.20 Gelatin 1.5 Second layer; Intermediate layer (IL -1) UV absorber (UV-1) 0.04 High boiling point solvent (Oil-1) 0.04 Gelatin 1.2 Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.6 Iodobromide Silver emulsion (Em-2) 0.2 Sensitizing dye (II-29) 2.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (III-6) 2.2 × 10 ^-4 (mol / silver 1 mol) dye (III-35) 0.44 × 10 -4 ( mol / mole of silver) cyan coupler (C ₄ -20) 0.65 colored cyan coupler (CC-1) 0.12 DIR coupler (C _D -9) 0.004 DIR coupler (C _D −11) 0.013 High boiling point solvent (Oil-1) 0.6 Gelatin 1.5 Fourth layer; High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 0.8 Sensitizing dye (II-29) 1.2 × 10 ⁴ (mol / mole of silver) Sensitive dye (III-6) 1.2 × 10 -4 ( mol / mole of silver) Sensitizing Dye (III-35) 0.1 × 10 -4 ( mol / mole of silver) Cyan Coupler (C ₂ -29) 0.16 Cyan coupler (C ₂ -8) 0.02 colored cyan coupler (CC-1) 0.03 DIR compound (C _D -11) 0.016 high boiling solvent (Oil-1) 0.2 gelatin 1.3 fifth layer: intermediate layer (IL-2) gelatin 0.7 the 6 layers; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.8 sensitizing dye (IV-1) 3.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-1) ) 5.0 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.2 Magenta coupler (M-2) 0.2 Colored magenta coupler (CM-1) 0.1 DIR compound (D-1) 0.02 DIR compound (D -2) 0.004 High boiling point solvent (Oil-2) 0.4 Gelatin 1.0 7th layer; High sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (IV-1) 1.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-1) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-2) 0.55 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-2) 0.09 Colored magenta coupler (CM-2) 0.04 DIR compound (D-1) 0.006 High boiling solvent (Oil-2) 0.3 Gelatin 1.0 Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Color stain inhibitor (SC-1) 0.1 High boiling solvent (Oil-3) 0.1 Gelatin 0.8 Ninth layer; Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.35 Silver iodobromide emulsion (Em-2)) 0.10 sensitizing dye (SD-4) O.6 × 10 -3 ( mole / mole of silver) yellow coupler (Y-1) 0.6 yellow coupler (Y-2) 0.1 DIR coupler (C _D −11) 0.01 High boiling point solvent (Oil-3) 0.3 Gelatin 1.0 10th layer; High sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-3) 0.4 Silver iodobromide emulsion (Em-1) 0.1 Sensitizing dye (SD-3) 1 × 10 -4 ( mol / mole of silver) Sensitizing dye (SD-4) 0.3 × 10 -3 ( mole / mole of silver) Yellow coupler (Y-1) 0.20 Yellow Coupler (Y-2) 0.03 High boiling point solvent (Oil-3) 0.07 Gelatin 1.1 11th layer; 1st protective layer (PRO-1) Fine grain silver iodobromide emulsion (average particle size 0.08μmAgI2mol%) 0.2 UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.05 High boiling solvent (Oil-1) 0.1 High boiling solvent (Oil-4) 0.1 Formalin scavenger (HS-1) 0.5 Formalin scavenger (HS-2) 0.2 Gelatin 1.0 12th layer; 2nd protective layer (PRO-2) Surfactant (SU-1) 0.005 Alkali-soluble matting agent (average particle size 2 μm) 0.05 Polymethyl methacrylate (average particle size 3 μm) 0.05 Slip agent (WAX-1) 0.04 gelatin 0.5 In addition to the above composition, coating aid Su-2 and dispersing aid Su-
Nos. 3 and Su-4, hardeners H-1, H-2, stabilizer ST-1, antifoggant AF-1, ▼: 10,000 and ▼: 1,10
0,000 two AF-2s were added.

The emulsions used in the above samples are as follows.

Em-1 core having an average grain size of 0.40 μm, an average silver iodide content of 7.2 mol%, a monodispersity (distribution width of 18%), and a relative standard deviation of 13% for silver iodide content of each grain. Shell-type silver iodobromide emulsion Em-2 Average grain size 0.27 µm, average silver iodide content 5.0 mol%, monodisperse (18% distribution area), relative standard of silver iodide content of individual grains Core / shell type silver iodobromide emulsion with a deviation of 12% Em-3 Average grain size of 0.86 μm, average silver iodide content of 7.5 mol%, monodispersity (width of distribution 16%) Core / shell type silver iodobromide emulsion having a relative standard deviation of silver halide content of 11% The compounds used in the above sample are as follows.

Next, the configuration of the sample was changed as shown in Table 1,
Samples -102 to 110 were prepared. That is, for the low-sensitivity red-sensitive layer (third layer) and the high-sensitivity red-sensitive layer (fourth layer) of Sample 101, the type and amount of the sensitizing dye were used, and for the yellow filter layer (eighth layer), Samples -102 to 110 were prepared by changing the amount of yellow colloidal silver and the type and amount of cyan coupler for the low-sensitivity blue-sensitive layer (ninth layer) as shown in Table 1, respectively. At this time, the coating amount of the low-sensitivity red-sensitive layer (third layer) and / or the low-sensitivity green-sensitive layer (sixth layer) is adjusted according to the type and amount of the cyan coupler contained in the low-sensitivity blue-sensitive layer. , As shown in Table 1,
Adjusted to 1 at any time.

The thus prepared samples 101 to 110 were wedge-exposed with white light and subjected to the following color development treatment. As a result, the same sensitometry was obtained.

Next, the samples -101 to 110 were subjected to spectral exposure using several types of interference filters effective in the visible region,
By performing the same development processing as described above, the sensitivity for giving a minimum density of +0.1 to the sample using each interference filter was determined, and a spectral sensitivity distribution over the entire visible region was obtained as a whole. From the obtained spectral sensitivity distribution, the wavelength λ _R at which the maximum sensitivity of the red-sensitive emulsion layer was obtained was determined and is shown in Table 2. Also, determine the percentage of maximum sensitivity S _B of the blue-sensitive emulsion layer of maximum sensitivity S _R of the red-sensitive emulsion layer in the wavelength range of 400 to 480 nm, a percentage, i.e., the value of (S _R / S _R) × 100 The results are shown in Table 2.

(Color development processing) Processing step (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixing 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry each The composition of the processing solution used in the processing step is as follows.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxyamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter. (PH = 10.1) <Bleaching solution> Ammonium ethylenediaminetetraacetate (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Add water to make 1 liter, and use ammonium water to make pH = 6.0.
Adjust to

<Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 liter, and adjust the pH to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1 liter.

Furthermore, after processing these samples so that they can be photographed using a camera, R (red), M (magenta), P (purple), BF (blue flowers), G
(Green), YG (yellowish green), and F (Green color). After the photographing, the above-described development processing was performed, and at the same time, the image was printed on a Konica Color PC paper type SR so that the gray standard reflection plate photographed was reproduced in gray.

Next, the above colors on the print were measured with a color analyzer (CMS-1200 manufactured by Murakami Color Co., Ltd.), and the chromaticity points (C light source) of each color were plotted on the a ^* and b ^* chromaticity diagrams. This result is shown in FIG.

In FIG. 1, what is on the straight line connecting the original of each color and the origin 0 shows the same hue as the original.

As shown in FIG. 1, the samples according to the present invention—105 to 108, 110
Means that purple (P),
The hues of blue flower (BF) and magenta (M) are reproduced with hues close to the original, and sufficiently good hue reproduction is achieved for samples 104 and 109 as well. On the other hand, comparative sample-10
1 to 103 have good red (R) saturation, but have inferior hues of reproduced colors of P and BF.

As described above, in the present invention, the hue reproduction of purple and blue-violet colors was able to be improved without lowering the chroma of red.

Further, in the present invention, as is apparent from the hue reproduction of the samples 104 to 110 according to the present invention, green (G), yellow-green (YG),
The hue reproduction of the brown color (F) was also improved. Particularly in Samples-109 and 110, the hues of YG and F are greatly improved. In particular, Sample-110 has a large chroma and can be sufficiently satisfied. This was a completely unexpected result for the present inventors.

Example 2 The samples 101 to 110 prepared in Example 1 were subjected to a development process under the following conditions, and the same evaluation was performed in the other manner as in Example 1. The same result was obtained. Obtained.

However, the treatment was performed until the replenisher of three times the capacity of the stabilization tank was filled. The stabilization treatment was performed in a three-tank countercurrent, and the replenisher was replenished to the last tank of the stabilizing liquid, and the overflow liquid flowed into the preceding tank.

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

<Composition of used color developing solution> Potassium carbonate 30 g Sodium bicarbonate 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 4.6 g diethylenetriaminepentaacetic acid 3.0 g potassium hydroxide 1.3 g Add water to make 1 l, and adjust to pH 10.01 using potassium hydroxide or 20% sulfuric acid.

<Composition of used color developing replenisher> 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 Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 2 g Add water to make 1 liter, and adjust to pH 10.12 using potassium hydroxide or 20% sulfuric acid.

<Composition of the used bleaching solution> Ammonium ferric 1,3-diaminopropanetetraacetate 0.35 mol Disodium ethylenediaminetetraacetate 2 g Ammonium bromide 150 g Glacial acetic acid 40 ml Ammonium nitrate 40 g Adjust to pH 4.5 using

<Composition of the used bleach replenisher> Ferric ammonium 1,3-diaminopropanetetraacetate 0.40 mol Disodium ethylenediaminetetraacetate 2 g Ammonium bromide 170 g Ammonium nitrate 50 g Glacial acetic acid 61 ml Add water to make 1 liter, then add ammonia water or ice The pH is adjusted to 3.5 using acetic acid, and the pH of the bleach tank solution is adjusted as appropriate.

<Composition of fixing solution and fixing replenisher used> Ammonium thiosulfate 100 g Ammonium thiocyanate 150 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Add water to 700 ml, add glacial acetic acid and ammonia water Adjust to pH 6.5 using

Water was added to make up to 1 l, and the pH was adjusted to 7.0 with potassium hydroxide and 50% sulfuric acid.

〔The invention's effect〕

As described above, the silver halide color photographic light-sensitive material of the present invention has a blue-purple hue without a decrease in red purity,
In addition, yellow and green hues can be faithfully reproduced.

[Brief description of the drawings]

FIG. 1 is a chromaticity diagram showing the hue reproducibility of each sample according to one embodiment of the present invention, in which (a ^* , a ^* , b ^* ) color systems (a ^* ,
b ^* ) It is the figure which displayed the color reproduction of each sample on the plane.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-89850 (JP, A) JP-A-64-19346 (JP, A) JP-A-62-160448 (JP, A) JP-A-62-160448 258453 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03C 7/20 G03C 1/18

Claims (1)

(57) [Claims] A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. The maximum sensitivity wavelength λ _R of the spectral sensitivity of the red-sensitive silver halide emulsion layer is 595 nm ≦ λ _R ≦ 625 nm, and the red-sensitive silver halide emulsion layer has at least one of the sensitizing dyes represented by the following general formula (I). And the following general formula (III)
In contains in combination at least one sensitizing dye represented, and blue-sensitive in the maximum sensitivity S _R is also 400nm or 480nm or less in the wavelength region of red-sensitive silver halide emulsion layer in the 480nm or less in a wavelength range above 400nm the silver halide color photographic light-sensitive material, characterized in that at least 1.5% of the maximum sensitivity S _B of the silver halide emulsion layer. General formula (I) In the general formula (I), R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and R ² , R ³ , R ⁴ and R ⁵ each represent an alkyl group or an aryl group. Z ¹ , Z ² , Z ³ and Z ⁴ are each a hydrogen atom, a halogen atom,
Hydroxyl group, alkoxy group, amino group, acyl group,
Acylamino group, acyloxy group, aryloxy group,
Alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, carbamoyl group,
Represents an aryl group, an alkyl group, a cyano group or a sulfonyl group. Z ¹ and Z ² and / or Z ³ and Z ⁴ may be connected to each other to form a ring. (X ₁ ) _m represents a charge-balancing counter ion, and m represents a value required to neutralize a charge of 0 or more. General formula (III) In the general formula (III), R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group, and R ¹² and R ¹³ each represent an alkyl group or an aryl group. Y ³ and Y ⁴ each represent a sulfur atom or a selenium atom. Z ⁹ , Z ¹⁰ , Z ¹¹ and Z ¹² each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an acyloxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl Group, alkoxycarbonylamino group, sulfonyl group,
Represents a carbamoyl group, an aryl group, an alkyl group or a cyano group. Z ⁹ and Z ¹⁰ and / or Z ¹¹ and Z ¹² may be connected to each other to form a ring. (X ₃ ) _p is
Represents a charge balancing counter ion, and p represents a value necessary to neutralize a charge of 0 or more.