JPH04274421A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material which faithfully reproduces the hues of a subject having purple and flesh color in color reproduction of the subject. CONSTITUTION:This silver halide color photographic sensitive material has respectively at least one layer of blue sensitive silver halide emulsion layers, green sensitive silver halide emulsion layers and red sensitive silver halide emulsion layers on a base. The max. sensitivity waelength lambdaRmax of the red sensitive silver halide emulsion layers, the sensitivity SRmax at this wavelength, the sensitivity SR610 at 610nm and the max. sensitivity wavelength lambdaG570 of the green sensitive silver halide emulsion layers, the sensitivity SGmax at this wavelength, the sensitivity SGmaz at 570nm of this silver halide coror photographic sensitive material satisfy the following conditions: 590nm<=lambdaRmax<=630nm, SR610>=0.8SRmax, 525nm<=lambdaGmax<=560nm. SG570 <=0.4SGmax.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic material, and more particularly to a silver halide color photographic material having excellent color reproducibility.

0002

BACKGROUND OF THE INVENTION In recent years, the image quality of silver halide multilayer color photographic materials has been significantly improved. In other words, the three major elements of image quality - graininess, sharpness, and color reproducibility - are all at fairly high levels, and users usually have major complaints about the prints and slides they receive in general color photography. It is thought that there is no such thing.

[0003] However, among the above three elements,
Regarding color reproducibility in particular, color purity has improved, but colors, which have traditionally been said to be difficult to reproduce in photographs, have not changed much.

That is, there are still many deficiencies in hue reproducibility. For example, violet, blue-violet, or greenish colors such as blue-green and yellow-green, which reflect light with wavelengths longer than 600 nm, may be reproduced as completely different colors from the actual colors, which may disappoint the user.

The major factors related to color reproducibility are spectral sensitivity distribution and interlayer effect (hereinafter referred to as IIE).
).

Regarding the interimage effect, the following is known. That is, it is known to add to a color photographic light-sensitive material a compound that couples with the oxidized form of a color developing agent to form a development inhibitor or its precursor, and the development inhibitor released from this so-called DIR compound. By suppressing the development of other color-forming layers, IIE occurs and the effect of improving color reproducibility is produced. Furthermore, in a color negative film, it is possible to provide the same effect as IIE by using a colored coupler in an amount greater than the amount that offsets unnecessary absorption.

However, when colored couplers are used extensively, the minimum density of the film increases, making it extremely difficult to judge color/density correction during printing, and as a result, the color quality of the resulting prints deteriorates. is often inferior.

By the way, these techniques contribute to improving color purity in particular in color reproducibility. Inhibitors that have recently been widely used and so-called diffusive DIR in which the mobility of their precursors is high are extremely effective in improving color purity. However, IIE has the drawback that it is difficult to control its directionality, and although it can achieve high color purity, it changes the hue. Directional control of IIE is described in US Pat. No. 4,725,529 and the like.

On the other hand, regarding the spectral sensitivity distribution, US Pat. No. 3,672,898 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.

Furthermore, as has long been known in the art, by shifting the spectral sensitivity distribution of the red-sensitive layer to the shorter wavelength side, the hue reproducibility of blue-violet and violet colors can be improved (Japanese Patent Laid-Open No. 53 -20926, No. 59-131937, etc.), but these had several drawbacks.

One of the problems is that the red sensitivity decreases. Although this defect can be improved by increasing the IIE between the red-sensitive layer and other layers, the original effect of improving blue-violet color reproduction is reduced.

[0012] In JP-A-61-34541, which also discloses a technique combining spectral sensitivity distribution and IIE, an attempt was made to improve the colors that are difficult to reproduce with the aforementioned color film, and some results were obtained. ing. A typical example is not only the conventional IIE from the center wavelength of each of the blue, green, and red sensitive layers, but also the IIE from a wavelength other than the center of gravity of each color-sensitive layer.

This technique seems to be effective to some extent in improving the hue reproducibility of specific colors, but specifically, in order to express IIE, in addition to the original blue-sensitive, green-sensitive and red-sensitive photosensitive layers, , an IIE expression layer and a different type of photosensitive silver halide are required, and the production cost is high due to an increase in the amount of silver and an increase in the number of production steps. The effect could not be said to be sufficient.

[0014] For the above reasons, conventional color photographic materials are insufficient in terms of hue reproduction, and it is particularly difficult to faithfully reproduce hues of purple, which may be reproduced in hues far away from the actual colors. There were many.

The present inventors focused on this purple hue and, as a result of intensive study, found that the maximum sensitivity wavelength λRmax of the red-sensitive emulsion layer
, its sensitivity SRmax, sensitivity SR610 at 610 nm
is 590nm≦λRmax≦630nm and SR61
It has been discovered that the above drawbacks can be improved by setting so that the relationship 0≧0.8SRmax is satisfied.

However, it has been found that this technique causes a new problem in that the hue of skin color shifts toward cyan, making it impossible to reproduce faithful hues.

[0017]

OBJECTS OF THE INVENTION The present invention aims to provide a useful technique for overcoming the above problems while taking advantage of the advantages of the above techniques.The first object of the present invention is to improve the hue and In particular, the object of the present invention is to provide a color photographic material that can faithfully reproduce the hue of a purple subject. A second object is to provide a color photographic material that achieves the first object and can faithfully reproduce the hue of a skin-colored subject.

[0018]

[Structure of the Invention] The above object of the present invention is to provide
In 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, the maximum sensitivity wavelength λRmax of the red-sensitive emulsion layer, its sensitivity SRmax,
Sensitivity SR610 at 610 nm, maximum sensitivity wavelength λGmax of the green-sensitive emulsion layer, sensitivity SGmax thereof, and sensitivity SG570 at 570 nm were achieved by a silver halide color photographic light-sensitive material satisfying the following conditions.

590nm≦λRmax≦630nm SR610≧
0.8SRmax525nm≦λGmax≦560nm
SG570≦0.4SGmax The present invention will be explained in more detail below.

In the present invention, the spectral sensitivity distribution refers to the reciprocal of the exposure amount that gives a density of minimum density + 0.70 at each wavelength when a light-sensitive material is exposed to a specified spectrum of light at intervals of several nm from 380 to 700 nm. The sensitivity at each wavelength is expressed as a function of wavelength.

The spectral sensitivity distribution of the red-sensitive layer in the present invention requires that λRmax be 590 nm≦λRmax≦630 nm, preferably 595 nm≦λR
max≦625 nm, more preferably 600 nm
≦λRmax≦620 nm.

[0022] The spectral sensitivity SR610 of the red-sensitive layer at 610 nm must be 80% or more of the spectral sensitivity SRmax of the red-sensitive layer at λRmax.
% or more is more preferable.

The spectral sensitivity distribution of the green-sensitive layer in the present invention requires that λGmax is 525 nm≦λGmax≦560 nm, but preferably 530 nm≦λGmax
x≦555nm, more preferably 535nm≦λGma
x≦550 nm. Further, the spectral sensitivity SG570 of the green-sensitive layer at 570 nm needs to be 40% or less of the spectral sensitivity SGmax of the green-sensitive layer at λGmax, preferably 20% or less, and more preferably 15% or less. .

In the present invention, the spectral sensitivity distribution of the green-sensitive layer is obtained as a function of the wavelength of the reciprocal of the exposure amount that gives the minimum density +0.70, as described above, but the minimum density +0.70 is obtained as a function of the wavelength. Not only 70 but also the lowest concentration +0.30
It is preferable that the spectral sensitivity distribution characteristics of the green-sensitive layer described above be provided even at the lowest density of +1.0.

Various methods can be used to form the spectral sensitivity distribution of the red-sensitive layer of the present invention, and for example, spectral sensitizing dyes can be used. For example, general formula [I]
, [II] and [III] may be used alone or in appropriate combinations.

In addition to the sensitizing dyes represented by the general formulas [I] to [III], supersensitizers can be used, such as benzothiazoles and the like described in Japanese Patent Publication No. 57-24533. Quinolones and quinoline derivatives described in Japanese Patent Publication No. 57-24899 can also be used depending on the purpose.

Next, general formulas [I], [II] and [II
The sensitizing dye represented by I] will be explained.

[0028]

[Chemical formula 1]

In the formula, R1 represents a hydrogen atom, an alkyl group or an aryl group, and R2, R3, R4 and R5 each represent an alkyl group or an aryl group.

Z1, Z2, Z3 and Z4 each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group,
It represents an amino group, 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. Z1 and Z2 and/or Z
3 and Z4 may be connected to each other to form a ring.

[0031] X1- represents an anion. n represents an integer of 1 or 2, but when the sensitizing dye forms an inner salt,
n represents 1.

[0032]

[Case 2]

In the formula, R6 represents a hydrogen atom, an alkyl group or an aryl group, and R7, R8, R9 and R10 each represent an alkyl group or an aryl group.

[0034] Y1 and Y2 each represent a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom, but when Y1 is a sulfur atom, an oxygen atom, or a selenium atom, it does not have the above R7. Further, Y1 and Y2 cannot be nitrogen atoms or sulfur atoms at the same time. Z5, Z6, Z7 and Z8 are each a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, amino group, acyl group, acylamino group, acyloxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyl Amino group, carbamoyl group, aryl group,
Represents an alkyl group, a cyano group, or a sulfonyl group. Z5 and Z6 and/or Z7 and Z8 may be connected to each other to form a ring. Moreover, X2- represents an anion. n represents an integer of 1 or 2; however, n represents 1 when the sensitizing dye forms an inner salt.

[0035]

[Chemical formula 3]

In the formula, R11 represents a hydrogen atom, an alkyl group or an aryl group, and R12 and R13 each represent an alkyl group or an aryl group. Moreover, Y3 and Y4 each represent a sulfur atom or a selenium atom.

Z9, Z10, Z11 and Z12 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,
Aryloxycarbonyl group, alkoxycarbonylamino group, sulfonyl group, carbamoyl group, aryl group,
Represents an alkyl group or a cyano group. Z9 and Z10 and/or Z11 and Z12 may be connected to each other to form a ring. X3- represents an anion. n represents an integer of 1 or 2; however, n represents 1 when the sensitizing dye forms an inner salt.

[0038] General formulas [I], [II], [III] are shown below.
] Typical specific examples of sensitizing dyes represented by:

[0039]

[C4]

[0040]

[C5]

[0041]

[C6]

[0042]

[C7]

[0043]

[Chemical formula 8]

[0044]

[Chemical formula 9]

[0045]

[Chemical formula 10]

[0046]

[Chemical formula 11]

[0047] In addition to the above representative examples, Japanese Patent Laid-Open No. 2-63
Among the compounds described on pages 13 to 42 of Specification No. 615, I-2, I-3, I-8 to 10, I-12 to 22,
I-24~26, I-29~31, I-33, I-34
, II-1 to 4, II-6, II-8 to 21, II-2
4-26, II-28, II-30, II-32-35
, II-38, II-39, III-2 to 4, III-
7-9, III-12-26, III-28-31, I
II-33~38, III-41~44, III-46
The following compounds can be mentioned. In the present invention, any appropriate means can be used to adjust the spectral sensitivity of 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.

Typical sensitizing dyes and supersensitizers that can be used in the green-sensitive layer of the present invention are shown below, but the invention is not limited thereto.

Further, the sensitizing dyes of the general formulas [I] and [II], which can be used to control the spectral sensitivity distribution of the red-sensitive layer described above, can also be preferably used.

[0050]

[Chemical formula 12]

[0051]

[Chemical formula 13]

[0052]

[Chemical formula 14]

Other specific examples of the above-mentioned representative examples include IV-1, IV-2, IV-4, IV-
5, IV-7, IV-8, IV-10 to 13, IV-1
6-21, IV-23-38, IV-40, IV-41
, IV-43 to IV-52.

Known photographic additives that can be used in the present invention are described in the Research Disclosure below.

[0055] The relevant descriptions are shown in the table below.

[Item] [RD3081
Page 19] [RD17643] [R
D18716] Color clouding prevention agent 1
002 Section VII-I
25 650 Dye image stabilizer
1001 Section VII-J
25 Brightener
998V
24 Ultraviolet absorber
1003 VIII-C, Section XIIIC
25-26 Light absorber
1003 VIII
25-26 Light scattering agent
1003 VIII Filter Dye
1003 VIII
25-26 Binder
1003 IX
26 651
Static inhibitor 1006 XIII
27
650 Hardener
1004 X
26 651 Plasticizer
1006 XII
27
650 Lubricant
1006 XII
27 650 Activator/coating aid 1005 XI
26-27 650
Matting agent 1007
VI Developer (contained in photosensitive material) 1011 XXB
A variety of couplers can be used in the present invention, specific examples of which are described in the Research Disclosure above.

[0057] The relevant descriptions are shown in the table below.

[Item] [RD3081
Page 19] [RD17643] Yellow coupler 1001 Section VII-D Section VIIC-G Magenta coupler
1001 VII-D Section VI
IC~G section cyan coupler 10
01 Section VII-D Section VIIC-G
Colored coupler 1002 VII-
Section G Section VIIG DIR coupler
1001 Section VII-F V
IIF section BAR coupler 100
2 Section VII-F Other useful residues
1001 Section VII-F Release Coupler Alkali Soluble Coupler 1001 VII-
Section E The additive used in the present invention is RD308119XI
It can be added by the dispersion method described in V.

In the present invention, the aforementioned RD17643
28 pages, RD18716647-8 and RD3081
The supports described in No. 19, XVII can be used.

The photosensitive material of the present invention includes the above-mentioned RD3081.
Auxiliary layers such as filter layers and intermediate layers as described in Section 19VII-K can be provided.

The photosensitive material of the present invention has the above-mentioned RD30811.
Various layer configurations such as forward layer, reverse layer, and unit configuration described in Section 9VII-K can be adopted.

The present invention can be applied to various color photosensitive materials such as color negative films for general use or movies, color reversal films for slides or television, color papers, color positive films, and color reversal papers. .

The photosensitive material of the present invention is the above-mentioned RD17643.
pages 28-29, RD18716 page 647 and RD30
By the usual method described in No. 8119 XVII,
It can be developed.

[0064]

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In the following examples, the amount added in the silver halide photographic light-sensitive material is expressed in grams per m 2 unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver. However, regarding the sensitizing dye, it is indicated by the number of moles per mole of silver halide in the same layer.

Multilayer color photographic material sample 101 was prepared by sequentially forming layers having the compositions shown below on a triacetylcellulose film support from the support side.

Sample-101 1st layer: antihalation layer black colloidal silver

0.18 UV absorber (UV-1)

0.23 High boiling point solvent (Oil-1)

0.20 Gelatin

1.46 Second layer: Intermediate layer gelatin

1.30 Third layer: low sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.30 μm, average silver iodide content 7 mol%) 0.80 Sensitizing dye (III-
9)
2.80×10-5
Sensitizing dye (III-3)
3.
57×10-4 Sensitizing dye (II-10)

3.15×10-4 Cyan coupler (C-1)
0.60 Colored cyan coupler (CC-1)
0.10 DIR compound (D-1)

0.05 DIR compound (D-3
)
0.005 High boiling point solvent (Oi
l-1)
0.50 Gelatin

0.90 4th layer: Intermediate layer gelatin

1.00 Fifth layer: Highly sensitive red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.42 μm, average silver iodide content 7 mol%) 1.00 Sensitizing dye (III-
9)
2.00×10-5
Sensitizing dye (III-3)
2.
55×10-4 Sensitizing dye (II-10)

2.25×10-4 Cyan coupler (C-1)
0.10 Colored cyan coupler (CC-1) 0.01
DIR compound (D-1)
0.0
3 DIR compound (D-3)
0.
003 High boiling point solvent (Oil-1)

0.15 gelatin

0.90 6th layer: Intermediate layer Color stain prevention agent (SC-1)
0.10
High boiling point solvent (Oil-2)
0.10
gelatin

1.00 7th layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.28 μm, average silver iodide content 7 mol%) 0.80 Sensitizing dye (IV-2
)
5.85×10-4
Sensitizing dye (IV-8)
3
．． 15×10-4 Magenta coupler (M-1)

0.53 Colored magenta coupler (CM-
2) 0.0
9 DIR compound (D-2)
0.
05 DIR compound (D-3)
0
．． 005 High boiling point solvent (Oil-2)

0.70 Gelatin

1.30 8th layer: Highly sensitive green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.39 μm, average silver iodide content 7 mol%) 0.90 Sensitizing dye (IV-2
)
3.64×10-4
Sensitizing dye (IV-8)
1.
96×10-4 Magenta coupler (M-1)

0.17 Colored magenta coupler (CM-1
) 0.0
6 DIR compound (D-2)
0.
04 DIR compound (D-3)
0
．． 004 High boiling point solvent (Oil-2)

0.40 Gelatin

0.80 9th layer: Yellow filter layer Yellow colloidal silver

0.10 Color stain prevention agent (SC-1)

0.10 High boiling point solvent (Oil-2)

0.10 Gelatin

1.00 10th layer: low-speed blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.30 μm, average silver iodide content 7 mol%) 0.50 Sensitizing dye (BD-
1)
6.0×10-4 Yellow coupler (Y-1)
0.40 Yellow coupler (Y-2)
0.30 DIR compound (D-1)
0.005 High boiling point solvent (Oil-2)
0.10 Gelatin

0.90 11th layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.40 μm, average silver iodide content 7 mol%) 0.65 Sensitizing dye (BD-1
)
5.0×10-4 Yellow coupler (Y-1)
0.20 High boiling point solvent (Oil-2)
0.08 gelatin
0.
55 12th layer: First protective layer Fine grain silver iodobromide emulsion (average grain size 0.08 μm)
0.40 Ultraviolet absorber (UV-1)
0.07 Ultraviolet absorber (UV-2)
0.10 High boiling point solvent (Oil-1)
0.07 High boiling point solvent (Oil-3)
0.07 Gelatin

0.60 13th layer: 2nd protective layer Alkaline soluble matting agent (average particle size 2 μm)
0.15 Polymethyl methacrylate (average particle size 3 μm)
0.04 Slip agent (WAX-1)

0.04 Gelatin

0.60

[0068]

[Chemical formula 15]

[0069]

[Chemical formula 16]

[0070]

[Chemical formula 17]

[0071]

[Chemical formula 18]

[0072]

[Chemical formula 19]

[0073] In addition to the above composition, a coating aid Su-1
, dispersion aid Su-2, viscosity modifier, hardener H-1, H-
2. Stabilizer ST-1, antifoggant AF-1, and two types of AF-2 having weight average molecular weights of 10,000 and 1,100,000 were added.

[0074]

[C20]

[0075]

[C21]

Next, Sample-101 was prepared in the same manner as Sample-101 except that the sensitizing dyes in the third, fifth, seventh, and eighth layers were changed as shown in Table-1. -10
2 to 105 were prepared. The total amount of sensitizing dyes shown in Table 1 is for sample 10 in each layer.
1 to 105 all have the same number of moles.

Therefore, the difference between samples is the combination of sensitizing dyes and their molar ratio.

Each of the emulsions contained in Samples 101 to 105 was optimally chemically sensitized using gold and sulfur sensitizers in a conventional manner.

Using these samples 101 to 105, a Macbeth color rendition chart and a person were photographed, and then the following color development process was performed.

Processing step (38°C) Color development 3 minutes 10 seconds Bleaching 6 minutes 3
Wash with water for 0 seconds 3
Fixed at minute 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) 4-amino-3-methyl-N-ethyl-N-(β-
Hydroxyethyl) Aniline Sulfate

4.75g anhydrous sodium sulfite
4.25g Hydroxylamine 1/2 sulfate
2.0g anhydrous potassium carbonate
37.5g Sodium Bromide
1.3
g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g potassium hydroxide
Add 1.0g water to make 1L. (pH=10.1) (Bleach solution) Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide

150.0g glacial acetic acid

10
．． Add 0 ml water to make 1 liter, and use ammonia water to make p
Adjust to H=6.0.

(Fixer) Ammonium thiosulfate
17
5.0g Anhydrous sodium sulfite

8.5g Sodium metasulfite

Add 2.3g of water to make 1l, and dilute with acetic acid.
Adjust to H=6.0.

(Stable liquid) Formalin (37% aqueous solution)
1.5
ml Konidax (manufactured by Konica Corporation)
Add 7.5 ml water to make 1 liter.

The optical density of each sample film obtained was 0.
．． Color paper (
Printed on Konica Color PC Paper Type SR),
Color reproducibility was visually evaluated.

[0085] Each of Samples-101 to 105 was exposed to a specified spectrum of light from 300 to 700 nm at intervals of 5 nm, and the color development process described above was performed to obtain a density of minimum density + 0.7 at each wavelength. Find the spectral sensitivity distribution given, and calculate each characteristic value (λRmax, SRmax, SR6
10, λGmax, SGmax, SG570). The results are shown in Table-1.

[0086]

[Table 1]

As is clear from Table 1, comparative sample-10
Samples 1 to 103 do not satisfy the color reproduction of both purple and skin tone, but samples 104 and 105 of the present invention are purple,
Faithfully reproduces both skin tones.

[0088]

[Effects of the Invention] According to the present invention, it was possible to provide a silver halide color photographic material which has excellent color reproducibility and faithfully reproduces purple and skin tones in particular.

Claims (1)

[Claims] 1. A silver halide color photographic 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 on a support, comprising: Maximum sensitivity wavelength λRmax of the sensitive emulsion layer, its sensitivity SRmax, sensitivity SR610 at 610 nm, maximum sensitivity wavelength λGmax of the green-sensitive emulsion layer,
A silver halide color photographic light-sensitive material characterized in that its sensitivity SGmax and sensitivity SG570 at 570 nm satisfy the following conditions. 590nm≦λRmax≦630nm SR610≧
0.8SRmax 525nm≦λGmax≦560
nm SG570≦0.4SGmax