JPH03264955A - Silver halide color photographic sensitive material superior in hue reproducibility - Google Patents

Abstract

PURPOSE:To enable the hue of the bluish green of a subject to be reproduced especially in high fidelity by specifying the spectral sensitivity distributions of a blue-sensitive layer and a green-sensitive layer. CONSTITUTION:The spectral sensitivity distribution of the blue-sensitive silver halide emulsion layer gives its density DB as follows; DB=DBmin + 0.1, where DBmin is its minimum density, and gives the maximum sensitivity SBmax at the wavelength lambdaBmax, which is in the region as follows; 410nm <=lambdaBmax<=470nm, and the maximum sensitivity SBmax is as high as >=2 times SB480, where SB480 is the sensitivity at 480nm wavelength. The spectral sensitivity distribution of the green-sensitive layer giving its density DG1 as follows; DG1 = DGmin+0.1 gives the maximum sensitivity at the wavelength lambdaG1max as follows; 540nm <=lambdaG1max<=570nm, and that of the green-sensitivity layer giving its density DG2 as follows; DG2 =DGmin + 0.7 gives the maximum sensitivity at the wavelength lambdaG2max as follows; 520nm <=lambdaG2max<=550nm, and lambdaG1max - lambdaG2max = >= 15nm, thus permitting the hue of the bluish green subject to be especially reproduced in high fidelity.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color photographic material, and more specifically,
This invention relates to a color photographic material with excellent hue reproducibility.

[Background of the invention]

In recent years, the image quality of silver halide multilayer color photographic materials has significantly improved.

In other words, in recent color photographic materials, there are three types of image quality.
The three major factors of graininess, sharpness, and color reproducibility are all at very high levels. For example, when it comes to general color photographs, it is believed that there are usually no major complaints regarding the color prints and slide photographs that users receive.

However, among the three factors mentioned above, in terms of color reproducibility in particular, although color purity has improved, the situation has not changed much with respect to colors, which have traditionally been said to be difficult to reproduce in photographs. That is, there are still many imperfections in hue reproducibility. For example, 600n-
Violet colors such as violet and blue-violet that reflect longer wavelength light, or green colors such as blue-green and yellow-green, may be reproduced as completely different colors from the actual colors, which may disappoint users. .

The major factors related to color reproducibility include spectral sensitivity distribution and glabellar effect (interimage effect).

The following is known about the interimage effect. That is, in silver halide multilayer color photographic light-sensitive materials, it is known to add a compound that couples with the oxidized form of a color developing agent to form a development inhibitor or its precursor. It is known that by inhibiting the development of other color-forming layers using a development inhibitor, an interimage effect is produced and color reproducibility is improved.

Furthermore, in color negative films, it is possible to provide an effect similar to the interimage effect by using a colored coupler in an amount greater than the amount that offsets unnecessary absorption.

However, if you use a lot of colored couplers,
As the minimum density of the film increases, the colors and
Density correction becomes very difficult to judge and often results in poor color quality in the resulting print.

Incidentally, these techniques particularly contribute to improving color purity among color reproducibility. The so-called diffusive DIR, which has been frequently used recently and has a high mobility of inhibitor groups and their precursors, greatly contributes to the improvement of dark color purity. However, it is difficult to control the directionality of the interimage effect, and although it can achieve high color purity,
It also has the disadvantage of changing the hue (direction control of interimage effects is described in US Pat. No. 4,725,529, etc.).

On the other hand, regarding the spectral sensitivity distribution, U.S. Patent No. 3.672
, No. 898 discloses an appropriate spectral sensitivity distribution for reducing variations in color reproducibility due to differences in light sources during photographing.

However, this is not a means to improve the aforementioned poor color reproducibility.

In JP-A-61-34541, which also discloses a technology that combines spectral sensitivity distribution and interimage effect, an attempt was made to improve the colors that are difficult to reproduce with the aforementioned color film, and the attempt was made to some extent. It seems that you can get . Typical examples include not only the conventional interimage effect from the center wavelength of each of the blue, green, and red sensitive layers, but also the interimage effect from wavelengths other than the center of gravity of each color-sensitive layer. That is what it is.

This technology seems to be effective to some extent in improving the hue reproducibility of specific colors, but specifically, it is necessary to improve the hue reproducibility of specific colors. In addition, an interimage effect layer and a different type of photosensitive silver halide are required, which increases the amount of silver and the number of production steps, resulting in high production costs. However, the effect was not sufficient.

For the above reasons, conventional silver halide color photographic materials have been insufficient in terms of hue reproduction. In particular, it was difficult to faithfully reproduce the hue of blue-green, and the hue was sometimes far removed from the actual color.

The present inventors paid special attention to this blue-green hue reproducibility, and as a result of intensive studies, the density DB of the blue-sensitive silver halide emulsion layer
-The wavelength λB that gives the highest sensitivity of the spectral sensitivity distribution that gives the lowest concentration D B,... +0.1 saX is 410 to 47
0 nm and sensitivity SB at λB IIax,
, is designed to be more than twice the sensitivity of 5B4so at 480 nm, and furthermore, the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is shifted to the shorter wavelength side than before, and the wavelength λG + m that provides the highest sensitivity is ax is 530~560n1
11, and the sensitivity 5Gsao at 500nm is λGsm
It has been discovered that the above problem can be improved by designing one layer so that the sensitivity SC, . . . at x is 4 or more. However, on the other hand, it has been found that this technique significantly deteriorates the suitability for photographing under fluorescent lighting, particularly under three-wavelength fluorescent lighting.

[Purpose of the invention]

The present invention aims to provide an advantageous technique that overcomes the above-mentioned problems while taking advantage of the advantages of the above-mentioned techniques.A first object of the present invention is to improve the hue, especially blue, in color reproduction of an object. The second objective is to provide a color photographic material that can faithfully reproduce the hue of a green subject.The second objective is to achieve the above first objective and to provide a color photographic material that can be photographed under fluorescent lamps, particularly three-wavelength fluorescent lamps. An object of the present invention is to provide a color photographic material with improved suitability.

[Structure of the invention]

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

That is, on the support, at least one blue-sensitive silver halide emulsion layer (hereinafter also referred to as a "blue-sensitive layer" as appropriate) and a green-sensitive silver halide emulsion layer (hereinafter referred to as a "green-sensitive layer" as appropriate) are formed. In a color light-sensitive material having a red-sensitive silver halide emulsion layer (hereinafter sometimes referred to as a "red-sensitive layer"), the density DB of the blue-sensitive silver halide emulsion layer = minimum density D.
The wavelength λB□ giving the highest sensitivity of the spectral sensitivity distribution giving B,i, +0.1 is 410 nm≦λB +1lax≦470 nm,
And the sensitivity 5BoX at λB,...X is 480nm
A wavelength λG++* that is twice or more of the sensitivity 5B4110 of
ax is 540 nm≦λGIII≦570 nm,
Concentration DC of the green sensitive layer! =DC+ein +0.7 The wavelength λG that gives the highest sensitivity of the spectral sensitivity distribution The two-layer mx is 520 nm≦λGtmmx≦550 nm, and further λ
GIIIax-λG! The above object has been achieved by a silver halide color photographic material characterized by a wax of 15 nm or more.

The present invention will be explained in more detail below.

In the present invention, the spectral sensitivity distribution refers to the 40°
From n111 to 700n11, exposure is applied with spectral light at intervals of several nn+, and the exposure amount that provides a constant density at each wavelength is defined as the sensitivity at each wavelength, and the sensitivity is defined as a function of wavelength.

In the present invention, any suitable means can be used to set the spectral sensitivity distribution of the blue-sensitive layer and the green-sensitive layer to the structure of the present invention described above. For example, such a spectral sensitivity distribution can be obtained by using a spectral sensitizing dye.

Each color-sensitive layer will be described below.

In the present invention, the density DB of the blue-sensitive layer - the lowest density 10
The wavelength λB that gives the maximum sensitivity in the spectral sensitivity distribution that gives B, =, +0.1 is 410nm≦λ
It is necessary that B FIaX≦470 nm, and furthermore, the maximum sensitivity value SB of this blue-sensitive layer, X is the sensitivity of the blue-sensitive layer at λ = 480 nm, SB4. . It is necessary to have a configuration in which the number is twice or more.

Various means can be arbitrarily used to make the spectral sensitivity distribution of the blue-sensitive layer of the color photographic light-sensitive material of the present invention have the structure described above. A means for spectral sensitization with a sensitizing dye that has an absorption spectrum in the wavelength range, or a means for optimizing the halogen composition and distribution of silver halide without using a sensitizing dye to provide the desired spectral sensitivity, and furthermore, a light-sensitive material. There is a means for adjusting the desired spectral sensitivity distribution using an appropriate optical absorption side. Of course, these means may also be used in combination. The above also applies to adjustment of the spectral sensitivity distribution of other color-sensitive layers.

Examples of sensitizing dyes that can be used in the blue-sensitive silver halide emulsion layer in the photosensitive material of the invention to obtain the spectral sensitivity distribution of the invention are shown below. However, it is not limited to the examples below.

Note that the amount of the sensitizing dye added may be set to an optimum amount in order to obtain a desired spectral sensitivity distribution. Generally, the preferred total amount of enhancing dyes used in the pre-malignant emulsion layer is 5
X10-' mole or less.

S S-2 Below margin S-3 S-4 S S-5 S-S S-6 S O3H 03- 5υzHN(CJs)z S 12 5-13 Next, the color photographic window optical material of the present invention The wavelength λG111, which gives the highest sensitivity of the spectral sensitivity distribution giving the concentration DC,=minimum concentration DC,i, +0.1 of the green-sensitive layer, is 540 nm≦λG I@mx≦570 nm, and the concentration of the green-sensitive layer DGz = Dc, =.

The wavelength λG 2+@IIX giving the highest sensitivity of the spectral sensitivity distribution giving +0.7 is 520 nm≦λG 21118X≦550 nm,
Furthermore, λG llmllX−λG Zmax is 15 nm or more.

The spectral sensitivity distribution of the green-sensitive layer can be easily achieved by using the following exacerbating dyes alone or in combination in the green-sensitive layer.

Specific examples of sensitizing dyes that can be used in the green-sensitive layer are shown below.

However, it is not limited to these sensitizing dyes.

Note that the amount of the sensitizing dye added may be set to an optimum amount in order to obtain a desired spectral sensitivity distribution. Generally, the preferred total amount of sensitizing dyes used in the green-sensitive emulsion layer is l/mole of silver.
Xl0-' to 5X10-3 moles.

Below margins OD-1 0D-2 OD-5 OD-7 OD-8 OD OD-4 OD-5 OD-9 OD 0 OD-11 0D-12 0D 3 D-14 D 8 D-19 D-20 D- 15 D-16 D-17 OD -21 H3 The silver halide emulsion used in the color photographic light-sensitive material of the present invention can be chemically sensitized by a conventional method.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. As a binder for the emulsion, it is advantageous to use gelatin (however, it is not limited to this)
.

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 sparingly soluble synthetic polymer.

The present invention can be preferably applied to color negative films, color reversal films, and the like.

A color-forming coupler is generally used in the emulsion layer of the color photographic light-sensitive material of the present invention.

In addition, by coupling with a colored coupler having a correcting effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent can be obtained. , antifoggants, chemical aggravators,
Spectral sensitizers and chemicals that release photographically useful fragments, such as desensitizers, can optionally be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached or bleached from the light-sensitive material during the development process.

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color cast inhibitor, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Any material such as polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the color photosensitive material of the present invention,
After exposure, commonly known color photographic processing can be performed.

〔Example〕

Specific examples of the present invention will be described below, but the manner in which the present invention may be implemented is not limited thereto.

In all the examples below, the amount added in the silver halide photographic illumination material is expressed in grams per 1M unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

Example 1 A multilayer color photographic material sample 101 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side. In addition, Samples 102 to 105 were prepared as described below.

Sample 101 (comparison) 1st layer; antihalation layer (HC-1) black colloidal silver 0.20 UV absorber (UV-1)
0.20 high boiling point solvent (OiIl-1)
0.20 Gelatin 1.
5 2nd layer; Intermediate layer (IL-1) UV absorber (UV-1) 0.04 High boiling point solvent (Oif-1) 0.04 Gelatin 3rd layer; Low sensitivity red-sensitive emulsion layer (RL) Odor Silver iodobromide emulsion (Em-1) Silver iodobromide emulsion (Em-2) 0.2 sensitizing dye (
SD-1) 2.2X10-' (mol/silver 1 mol) Sensitizing dye (SI)-2) 2.2X10-' (mol/silver 1 mol) Sensitizing dye (SD-3) 0.44X10-' (mol/
1 mole of silver) Cyan coupler (C-1) 0.65 Colored cyan coupler (CC-1) 0,12 DIR compound (D-1) 0.004 DI
R compound (I)-2) 0.013 High boiling point solvent (Oif-1) 0.6 Gelatin
1.5 4th layer; high sensitivity red-sensitive emulsion layer (R
H) Silver iodobromide emulsion (Em-3) 0.8 sensitizing dye (
S D-1) 1.2X10-'0.6 1.2 (MoJshi/i 1 mol) Sensitizing dye (SD-2) 1.2xlO-' (mol/silver 1 mol) Sensitizing dye (SD -3) 0. lXl0-' (mol/silver 1 mol) Cyan coupler (C-2) 0.16 Cyan coupler (C-3) 0.02 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2) 0. 016 High boiling point solvent (Oif-1) 0.2 Gelatin
1.3 Fifth layer; Intermediate layer (IL-2) Gelatin 0.7 Sixth layer; Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.8 Sensitizing dye C
OD-1) 3.0X10-' (mol/1 mole of silver) Sensitizing dye (OD-2) 5.0X10-' (mol/1 mole of silver) 8th layer; Yellow filter layer (YC) Yellow colloidal silver 0 .1 color stain prevention agent (SC-1)
0.1 high boiling point solvent (Oif-3)
0.1 gelatin 0.8 9th layer; low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.35 Silver iodobromide emulsion (Em-2) 0.10 Sensitizing dye ( S
D-5) 0.6X10-3 (mol/silver 1 mol) Yellow coupler (Y-1) 0.6 yellow coupler (Y-2) 0.1 DIR compound (D
-2) 0.01 high boiling point solvent (Oiffi-
3) 0.3 gelatin
1.0 10th layer; High-sensitivity blue-irradiation emulsion layer (BH) Silver iodobromide emulsion (Em-3) 0.4 Silver iodobromide emulsion (E
m-1) 0.1 sensitizing dye (SD-4) IXI
O-' (mol/mol of silver) Magenta coupler (M-1) 0.2 Magenta coupler (M-2) 0.2 Colored magenta coupler (CM-1) 0.1 DIR compound (D-3) 0. 02DIR compound (D-4) 0.004 High boiling point solvent (
Oif-2) 0.4 gelatin
1.0 7th layer; High sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye C
0D-1) 1.5xlo-' (mol/silver 1 mol) Aggravating dye C0D-2) 2.5 Xl0-' (mol/i
11 mol) Magenta coupler (M-2) 0.09 Colored magenta coupler (CM-2) 0.04 DIR compound (D-3) 0.006 High boiling point solvent (Oiffi-2) 0.3 Gelatin
1.0 sensitizing dye (SD-5)
0.3X10-' (mol/mol of silver) Yellow coupler (Y-1) 0.20 Yellow coupler (Y-2) 0.03 High boiling point solvent (
Oiff-3) 0.07 gelatin
1.1 Eleventh layer; first protective layer (PRO-
1) Fine grain silver iodobromide emulsion (average grain size 0.08.cz mA g 12 mol%) o
, 2UV absorber (UV-1) 0.10LIV
Absorbent (UV-2) 0.05 High boiling point solvent (O
i 42-1 ) 0.1 high boiling point solvent (Oij
2-4) 0.1 formalin scavenger (
H3-1) 0.5 Formalin scavenger (H3-2) 0.2 Gelatin 1.0 12th layer; 2nd protective layer (PRO-2) Surfactant (S tJ-1) 0.005 Alkali-soluble Matting agent (average particle size 2 μm) 0.05 Polymethyl methacrylate (average particle size 3 μm) 0.05 Sliding agent (WAX-1) 0.04 Gelatin
0.5 In addition to the above composition, coating aid 5u-2, dispersion aid 5u-3 and 5u-4, hardener H-1, H-2, stabilizer 5T-1, antifoggant AF-
1, MW: 10.000 and 1 layer: 1.100.00
Two types of AF-2 were added.

The emulsion used in the above sample is as follows.

m-1 Average particle size 0.48 μm.

Average silver iodide content 6.0 mol%.

Monodisperse (width of distribution 18%) core/shell type silver iodobromide emulsion m-2 with a silver iodide content of 1 mol % in the outer edge phase, average grain size 0.25 μm.

Core/shell silver iodobromide emulsion m-3 with an average silver iodide content of 6.0 mol% and a monodisperse (width of distribution 18%) silver iodide content in the outer phase of 0.5 mol%. Average particle size 0.80 μm.

A core/shell type silver iodobromide emulsion with an average silver iodide content of 6.5 mol% and a monodisperse (distribution width of 16%) outer phase having a silver iodide content of 1.5%.Also, the above sample The compounds used are as follows.

Below is the margin Ni Riichi D ■ D zHs (CHHz) 4SO3θ D-3 m1 (LH3) 3503° -2 -3 M C M-1 H H -2 M-2 H Q 2 -3 S-1 u-1 u-3 CH CH S u u-4 CH JV-1 CH V-2 zHs CH.

CH3 CH3 CqH+q(t) Below margin sample 102 (comparison) Sample 102 was obtained by making the following changes to sample 101.

9. Change the aggravating dye 5D-5 in the 10th layer to 5S-5.

Sample 103 (comparison) Sample 103 was obtained by making the following changes to sample 101.

(1) The sensitizing dye in the sixth layer was changed as follows.

Sensitizing dye COD-1) 1. OXl0-' (mol/silver 1
Mol) Exacerbating dye COD-2) 5. OXl0-' (mol/silver 1
Mol) Sensitizing dye COD-20) 2. OXl0-' (mol/
(1 mole of silver) (2) Change the sensitizing dye in the 7th layer as follows.

Sensitizing dye COD = 1) 0.5 Xl0-' (mol/m1 mol) Sensitizing dye COD-2) 2.5 Xl0-' (mol/m1 mol)
1 mole of silver) Exacerbating dye (o D-20) 1. OxlO-' (mol/silver 1 mol) Sample 104 (present invention) The sensitizing dye in the seventh layer of sample 103 is changed as follows.

Sensitizing dye COD-1) 1. OxlO-' (mol/silver 1 mol) Exacerbating dye (OD-2) 3. OxlO-' (mol/silver 1
Mol) Sample 105 (Invention) Exacerbating dye 5S-5 in layers 9 and 10 of sample 104 is not used.

Using each sample No. 101 to 105 thus produced, a Macbeth color rendition chart and a blue-green cloth were photographed at the same time, and then the following development treatment was performed.

Processing process (38°C) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Used in each processing step The composition of the treatment solution was as follows.

Color developer> 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxyamine 1/2 sulfate 2.0g anhydrous Potassium carbonate 37.5 g Sodium bromide
1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water and II! , and so on. (pH=10.1) <Bleach solution> Ethylenediaminetetraacetic acid Iron (II [) Ammonium salt 100° Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10mf Add water and add I
The pH was adjusted to 6.0 using ammonium water.

Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water and mix 11
and adjust the pH to 6.0 using acetic acid.

Stabilizing liquid> Formalin (37% water solution) 1.5mf
Konidanx (manufactured by Konica Corporation) Add 1.5 ml of water to make 11.

The obtained film is printed on color paper (Konica Color PC Paper Type SR) so that the gray with an optical density of 0.7 has the same density to obtain a color image, and among the various color reproductions of the image, blue-green is Color analyzer (CM S-1200 manufactured by Murakami Color Co., Ltd.)
Figure 1 shows the results of color measurement using the L''a''b'' color system.

Further, after photographing the subject under a three-wavelength fluorescent lamp, the developing process was performed.

A print was made from the obtained film under the same exposure conditions as when making the print, and the hue of gray with an optical density of 0.7 was visually evaluated.

Table 1 summarizes the above results.

As shown in FIG. 1 and Table 1, it can be seen that the samples of the present invention have good color reproducibility and suitability for photographing under fluorescent lighting, and are superior to the comparative samples.

[Effects of the Invention] As mentioned above, the color photographic light-sensitive material of the present invention can faithfully reproduce the hue, especially the blue-green hue of the subject, in color reproduction of the subject, and can also be used under fluorescent lighting, especially three-wave fluorescent light. This has the effect of improving suitability for photographing under lights.

[Brief explanation of drawings]

FIG. 1 is a chromaticity diagram showing the hue reproducibility of each sample in one embodiment of the present invention. FIG. 3 is a diagram displaying color reproduction of a sample.

Claims (1)

[Scope of Claims] 1. A color light-sensitive material having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer each on a support, comprising: Density DB of blue-sensitive silver halide emulsion layer = minimum density DB
The wavelength λB_m_a_x giving the highest sensitivity of the spectral sensitivity distribution giving _m_i_n+0.1 is 410 nm≦λB_m_a_x≦470 nm, and the sensitivity SB_m_a_x at λB_m_a_x is,
The sensitivity at 480 nm is more than twice the sensitivity SB_4_8_0, and the concentration DG_1 of the green sensitive layer = lowest concentration DG
The wavelength λG_1_m_a_x giving the highest sensitivity of the spectral sensitivity distribution giving _m_i_n+0.1 is 540 nm≦λG_1_m_a_x≦570 nm, and the concentration of the green-sensitive layer DG_2=DG_m_i_n+0.
The wavelength λG that gives the highest sensitivity of the spectral sensitivity distribution that gives 7
A silver halide color photographic light-sensitive material, characterized in that 2_m_a_x is 520 nm≦λG_2_m_i_x≦550 nm, and further, λG_1_m_a_x−λG_2_m_a_x is 15 nm or more.