JPH03264954A - 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=DMmin+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 gives its density DG; DG=DGmin+0.7, and gives the maximum sensitivity SGmax at the wavelength lambdaGmax; 530nm <=lambdaGmax<=560nm, and a ratio of sensitivity at 500 nm SG500 to SGmax is >=1/4, and the spectral sensitivity distributions can be obtained by using, for example, a spectral sensitiz ing dyestuff, 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 a fairly high level. 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. In other words, there are still many imperfections in hue reproducibility.For example, 600 nm
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, in which the mobility of inhibitor groups and their precursors, which have been frequently used recently, is high, greatly contributes to the improvement of 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 interimage effect from the conventional wavelengths of the center of gravity of each of the blue-sensitive layer, green-sensitive layer, and red-sensitive layer, but also the interimage effect from wavelengths other than the center of gravity of each color-sensitive layer. It means making them work.

This technology seems to be effective to some extent in improving the hue reproducibility of specific colors, but specifically, in order to express the interimage effect, it is necessary to improve the original blue sensitivity, green sensitivity, and red color sensitivity. In addition to the optical layer, an interimage effect layer and another type of photosensitive silver halide are required, which increases the amount of silver and the number of production steps, resulting in high production costs. It had some drawbacks and was not very effective.

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.

On the other hand, further improvement in color purity is also desired. In particular, it is desired to improve the color purity of yellow-green and green objects.

[Purpose of the invention]

The present invention aims to solve such conventional problems, and the first object of the present invention is to provide a color photographic material that can faithfully reproduce the hue of an object, especially the blue-green hue of an object. The second object is to provide a color photographic material that has improved color purity in color reproduction of objects, particularly yellow-green and green objects.

[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 mKK giving the highest sensitivity of the spectral sensitivity distribution giving B,i, +0.1 is 410 nm≦λB +mmx≦470 nn+,
and the sensitivity SB at λB +*ax is 480
Sensitivity 5B4s in nm. is more than twice as large as
Density DG of the green sensitive layer=minimum density DC;

The wavelength λG III a X giving the highest sensitivity of the spectral sensitivity distribution giving +0.7 is 530 nm≦λG a 1111≦560 nm
and sensitivity SGS at 500 nm. . is λG wax
The above object has been achieved by a silver halide color photographic material characterized by a sensitivity SGmax of 4 or more for one layer.

The present invention will be explained in more detail below.

In the present invention, the spectral sensitivity distribution refers to the spectral sensitivity distribution of 400
Exposure is applied with spectral light from nII to 700 nll at intervals of several rtm, 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.

In the present invention, the density DB of the blue-sensitive layer=minimum density 10 D
The wavelength λB that gives the maximum sensitivity in the spectral sensitivity distribution that gives B, , , +0.1 +max is 410nm≦λB
□8≦470. ．． It is necessary that
The maximum sensitivity value SB,X of this blue-sensitive layer is λ of the blue-sensitive layer.
= sensitivity 5Bns at 480nm. 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 of spectral sensitization with an enhancing dye having an absorption spectrum in the wavelength range, or a means of optimizing the halogen composition and distribution of silver halide without using an enhancing dye to provide the desired spectral sensitivity, and furthermore, There is a means of adjusting the desired spectral sensitivity distribution using a suitable optical absorber. 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 light-sensitive 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 addition of sensitizing dyes used in the blue-sensitive emulsion layer is 5 (13HN (L2t
1%] 3 5 υ 3 ) υ 3 Na Margin below 5S-12 0D D-2 Next, the color photographic material of the present invention has a spectral sensitivity distribution giving the density DG of the green-sensitive layer = minimum density DG, □, +0.7 The wavelength λCJ s m x that gives the highest sensitivity is SO, -5OdlN (CzHs).

530nm≦λG, 11x≦560nm, and sensitivity SG at 500ns. . is λG□. The sensitivity is 1/4 or more of the sensitivity SGmax.

The spectral sensitivity distribution of the green-sensitive layer can be easily achieved by using the following sensitizing 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 aggravating pigments.

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 1 per mole of silver.
×10″S to 5×10−” moles.

D-3 D-4 Margin below.

D-5 (Llt,)35υ:INa D 6 D-7 D-8 D-12 D 3 D-14 D D-10 D-11 D-15 D 6 D-17 OD~18 OD -21 Js C,H.

□ (CHI) 3503e D-19 □ H3 D-20 Below Margin In the color photographic light-sensitive material of the present invention, a yellow filter can be used to achieve a preferable spectral sensitivity of the green-sensitive layer. As the yellow filter, commonly used colloidal silver particles can be used. Moreover, a yellow colored magenta coupler or a yellow diffusion-resistant organic dye can be used instead of colloidal silver particles.

The yellow-colored magenta coupler that can be used can be arbitrarily selected from known ones and is not particularly limited, but the following can be mentioned as preferred examples.

F F-3 As a method for introducing the above-mentioned yellow colored magenta coupler into a yellow filter, generally known methods for introducing a coupler into a silver halide emulsion layer, such as the method described in U.S. Pat. No. 2,322,027, etc. can be used. Also, Japanese Patent Publication No. 5139853, Japanese Patent Publication No. 51
The dispersion method using a polymer described in Japanese Patent No. 59943 may also be used.

The yellow diffusion-resistant organic dye that can be used can be arbitrarily selected from known ones and is not particularly limited, but the following can be mentioned as preferred examples.

F F-4 F Below margin F F N F 1 F F-12 F-10 A known method can be used to introduce the above-mentioned diffusion-resistant organic dye into the yellow filter. For example, when the organic dye used is oil-soluble, it can be introduced into a hydrophilic colloid as an aqueous solution or alkaline water-soluble in the same manner as the yellow-colored magenta coupler described above, or when the organic dye is water-soluble. I can do it.

In order to achieve a preferable spectral sensitivity of the green-sensitive layer in the present invention, the amounts of colloidal silver particles, yellow color-magenta coupler and organic dye added can be appropriately and optimally adjusted.

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 also contain a dispersion (latex) of a desensitizing agent and a water-insoluble or sparingly soluble synthetic polymer.

The present invention can be preferably applied to color negative films, color rehearsal 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 sensitizers,
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 anti-irradiation 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, a fluorescent whitening agent, a matting agent, an image stabilizer, a surfactant, a color cast preventive agent, a development accelerator, a development retardant, and a bleaching 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 embodiments of the present invention will be described below, but it is important to understand how the present invention can be carried out. I4-sama is not limited to these.

In all the examples below, the amount added in the silver halide photographic material is expressed in grams per vinyl 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 (I (C-1) black colloidal silver 0.20 UV absorber (UV-
1) 0.20 high boiling point solvent (Oiffi-1
) 0.20 gelatin
1.5 Second layer; Intermediate layer (IL-1) Uv@collector (UV-1) 0.04 High boiling point solvent (Oi 1-1 ) 0.04 Gelatin
1.2 Third layer; low sensitivity red angry emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.6 Silver iodobromide emulsion (Em-2) 0.2 Sensitizing dye (SD-1 )
1.9X10-' (mol/l! 1 mol) Sensitizing dye (SD-2) 1.0X10-' (mol/l!1 mol)
Silver 1 mol) Sensitizing dye (SD-3) 1.9X10-' (mol/
1 mole of silver) Cyan coupler (C-1) 0.65 Colored cyan coupler (CC-1) 0.12 DIR Compound (D-1) 0.004 DIR
Compound (D-2) 0.013 High boiling point solvent (Oiffi-1) 0.6 Gelatin
1.5 4th layer; high-frequency red-sensitive emulsion layer (
RH) Silver iodobromide emulsion (Em~3) 0.8 sensitizing dye (SD-1) 1.0X10-' magenta coupler (
M-1) 0.2 magenta coupler (M-2)
0.2 Colored Magenta Coupler (CM-1) 0
．． 1 DIR compound (D-3) 0.02 DIR compound (D-4) 0.004 High boiling point solvent (O
ff-2) 0.4 gelatin
1.O 7th layer; High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 0.9 sensitizing dye (
○D-1) l, 5X10-' (mol/1 mole of silver) Sensitizing dye C0D-2) 2.5X10-' (mol/1 mole of silver) Magenta coupler (M-2) 0.09 colored magenta coupler ( CM-2) 0.04 DIR compound (D-3> 0.006 High boiling point solvent (Oil2-2) 0.3 Gelatin
1.0 (mol/1 mole of silver) Sensitizing dye (SD-2) 0.5X10-' (mol/1 mole of silver) Sensitizing dye (SD-3) 1.0X10-' (mol/1 mole of silver) Cyan coupler (C-2) 0.16 Cyan coupler (C-3) 0.02 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2) Q, OL6 high boiling point solvent (Oiffi-1) 0 .2 Gelatin
1.3 5th layer; intermediate layer (IL-
2) Gelatin 0.7 6th layer; low-anger green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.8 sensitizing dye C
OD -1) 3.0X10-' (mol/!I11 mole) Exacerbating dye COD~2) 5.0X10-' (mol/1 mole of silver) 8th layer: Yellow filter layer (YC) Yellow colloid!
0.1 Color contamination prevention side (SC-1)
0.1 high boiling point solvent (O4i!, -3)
0.1 gelatin 0.8 9th
Layer: Low-range blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.35 Silver iodobromide emulsion (Em-2) 0.10 Sensitizing dye (SD-
5) 0.6X10-3 (mol/mol of silver) Yellow coupler (Y-1) 0.6 yellow coupler (Y-2) 0.1 DIR compound (D-2
), 0.01 high boiling point solvent (Oil-3)
0.3 gelatin 1.0
10th layer: High-speed blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (
Em-3) 0.4 silver iodobromide emulsion (Em-1)
0.1 Sensitizing dye (SD-4) I Xl0-' (mol/silver 1
mol) Sensitizing dye (SD-5) Yellow coupler (Y Yellow coupler (Y) High boiling point solvent (Oi It Gelatin 11th layer; 1st protective layer (PRO-1) Fine grain silver iodobromide emulsion (average grain size 0. 08μmAg UV absorber (UV-1) UV absorber (UV-2) High boiling point solvent (Oiffi-1) High boiling point solvent (Ol(1-4) Formalin scavenger - 0,3X10-" (mol/silver 1 mol) ) 1) 0.20 2) 0.03 3) 0.07 1.1 12 mol%) 0.2 0.10 0.05 0.1 0.1 (H3-1) 0.5 Formalin scavenger (MS -2) 0.2 Gelatin 1.0 12th layer; 2nd protective layer (PRO-2) Surfactant (SU-1) 0.005 Alkali-soluble mantle 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 5u-2, dispersion aid 5u-3 and 5u-4, dura side H-1, H2, stabilizer 5T-1, antifoggant AF
-1, Mw: 10,000 and Mw: 1.
100,000 of two types of AF2 were added.

The emulsion used in the above sample is as follows.

m-1 Average grain size 0.48 μm Average silver iodide content 6.0 mol% Core/shell type iodine with a monodisperse (width of distribution 18%) silver iodide content in the outer phase of 1 mol% Silver bromide emulsion m-2 Average grain size 0.27 μm.

Average silver iodide content 6.0 mol%.

Monodisperse (width of distribution 18%) core/shell type silver iodobromide emulsion m-3 with a silver iodide content of 0.5 mol % in the outer edge phase, average grain size 0.78 μm.

Core/shell type silver iodobromide emulsion D with average silver iodide content of 7.0 mol% and monodisperse (width of distribution 16%) outer phase having a silver iodide content of 1.0%. The compounds used in the above sample are as follows.

Margin below D 4 4119 l C ■ M-1 ll M-2 D V-1 V-2 M M M Js M -3 M S S -1 -2 M-1 M-2 Nap: +S CHCOOCHz (CFzCFz) J
NaO, 5 C) ICOOCsH+? CFIzCOOCHz(CFzCFz)JCHzCOO
CaH M-3 M 3tl? 130 no υffNa CH3CH3CL 11 CH25iOust 0h-3+ CFlzCHs
CH* C) + 3 M w = 3,000 Sample 102 (comparison) Sample 10 is a sample with the following changes made to sample 101.
It was set as 2.

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

Sample 103 (comparison) Sample 10 is a sample with the following changes made to sample 101.
It was set as 3.

(1) The aggravating dye in the 6th layer is changed as follows.

Exacerbating pigment (OD-1) 1. OXl0-'(mol/f
f11 mol) Sensitizing dye COD-2) 5. OxlO-' (mol/silver 1 mol) Sensitizing dye (OD -20) 2. OxlO-' (mol/
1 mole of silver) (2) Change the aggravating dye in the 7th layer as follows.

Exacerbating dye COD-1) 0.5 Xl0-' (mol/
Silver 1 mol) Sensitizing dye (OD -2) 2.5 Xl0-' (mol/
Silver 1 mol) Sensitizing dye C0D-20) 1.0 Xl0-' (mol/
1 mole of silver) Sample 104 (invention) Sample 10 is a sample obtained by making the following changes to sample 103.
It was set as 4.

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

Sample 105 (present invention) Sample 105 was obtained by making the following changes to sample 103.

9. Sensitizing dye 5S-5 in the 10th layer is not used.

Using each of the samples Nα101 to Nα105 thus produced, a color rendition chart manufactured by Macbeth and a cloth having blue-green color were simultaneously photographed, and then the following development treatment was performed.

Processing steps (38℃) 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 liquid is as follows.

Color developer> 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
1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water and 1! shall be. (pH=10.1) Bleaching solution> Ethylenediaminetetraacetic acid iron(II) Ammonium salt 100g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10ml water and 1
1 and adjust the pH to 6.0 using ammonium water.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to make the solution 11, and the pH was adjusted to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5nf!
Konidax (manufactured by Konica Corporation) 7.5mj2
Add water and 1! shall be.

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 Using a color analyzer (CMS1200 manufactured by Murakami Color Co., Ltd.), measure the color of the fabric (BC), the green (G) of Maches color chart, and the yellow-green (YG) of Macbeth, and calculate this as L*a″b″
Figure 1 shows the color system, and Table 1 summarizes the results. As shown in FIG. 1 and Table 1, it can be seen that the samples according to the present invention have improved hue reproducibility of blue-green and green, improved color purity of yellow, and excellent color reproducibility.

Margins below [Effects of the Invention] As described above, the color photographic material of the present invention can faithfully reproduce the hue, especially the blue-green hue of the subject, in reproducing the color of the subject. In particular, it has the effect of improving the color purity of yellow-green and green objects.

[Brief explanation of drawings]

FIG. 1 is a chromaticity diagram showing the hue reproducibility of each sample in an example of the present invention, and shows the (Lm, a*b”) color system (
Fig. 4 is a diagram showing the color reproduction of each sample on a plane (a'', b'').

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 of the green sensitive layer = minimum concentration DG_m
The wavelength λG_m_a_x giving the highest sensitivity of the spectral sensitivity distribution giving _i_n+0.7 is 530 nm≦λG_m_a_x≦560 nm, and the sensitivity SG_5_0_0 at 500 nm is λG_m
A silver halide color photographic material characterized by having a sensitivity at _a_x of 1/4 or more of SG_m_a_x.