JPH04358148A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material having a high sensitivity and excellent color reproducibility. CONSTITUTION:This silver halide color photographic sensitive material consists has red photosensitive layers, green photosensitive layers and blue photosensitive layers. The respective photosensitive layers consist of 2 layers varying in sensitivity. The max.-sensitivity green photosensitive layers and max.-sensitivity red photosensitive layers among these layers come into contact with each other via nonphotosensitive intermediate layers and at least one layer of the low- sensitivity green photosensitive layers are provided in the position nearer the base than the max.-sensitivity red photosensitive layers. The dry thickness of the photograph constituting layers upper than the max.-sensitivity red photosensitive layers of such photosensitive material is <=9mum and the total sum of the coated amt. of the silver halide incorporated into the emulsion layers of the photosensitive material is <=8.0g/m<2> in terms of metal silver. Colored couplers are not incorporated into the max.-sensitivity red photosensitive layers.

Description

[Detailed description of the invention]

0001

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

0002

Background of the Invention Generally, silver halide color photographic light-sensitive materials (hereinafter sometimes simply referred to as light-sensitive materials) include a red-sensitive silver halide emulsion layer containing a cyan color-forming coupler and a green light-sensitive silver halide emulsion layer containing a magenta color-forming coupler on a support. It has a light-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer containing a yellow color-forming coupler, and is also composed of an antihalation layer, an intermediate layer, a filter layer, a protective layer, etc. as necessary.

In silver halide color photographic materials, high sensitivity and high quality images have always been desired, and many efforts have been made to achieve this goal. Especially in terms of sensitivity, ultra-high sensitivity photosensitive materials such as ISO-1600 and ISO-3200 have been developed in recent years.

[0004] As one method for increasing sensitivity, it is known to variously change the position of each of the photosensitive layers described above.
No. 09041, Japanese Unexamined Patent Publication No. 51-49027, and US Pat. No. 3,658,536.

However, although these conventional techniques improve sensitivity, they are not satisfactory in terms of image quality, particularly color reproducibility. Regarding the improvement of color reproducibility, the use of diffusive DIR has shown remarkable effects in recent years, and it has become a technology that can fully meet the needs of users, but the sensitivity decreases so much that it is not easy to achieve both improved color reproducibility and higher sensitivity. This was the current situation, and a new technology was desired.

[0006]

OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and excellent color reproducibility.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a result of extensive studies, the inventors of the present invention have found that the above object can be achieved by the following method, and have completed the present invention. That is, (1) a support has a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, each of which is composed of two or more layers with different sensitivities, of which the green-sensitive layer has the highest sensitivity; silver halide, which has at least one low-sensitivity green-sensitive layer in a position closer to the support than the highest-sensitivity red-sensitive layer, in which the red-sensitive layer and the highest-sensitivity red-sensitive layer are in contact with each other via a non-photosensitive intermediate layer; In a color photographic light-sensitive material, the dry film thickness of the photographic constituent layer coated above the highest sensitivity red light-sensitive layer is 9 μm or less, and the coating amount of silver halide contained in the emulsion layer of the photographic light-sensitive material. and (2) the highest sensitivity red photosensitive layer substantially contains a colored coupler. This is achieved by the silver halide color photographic light-sensitive material described in item (1) above, which is characterized in that it does not contain any of the following.

The present invention will be explained in detail below. In the present invention, the highest sensitivity green photosensitive layer and the highest sensitivity red photosensitive layer are in contact with each other via a non-photosensitive intermediate layer. Here, the non-photosensitive intermediate layer prevents color clouding between the two layers due to the oxidized developing agent during development, but it is preferable to further add a known color clouding preventive agent as required.

In the present invention, the dry film thickness (hereinafter referred to as DT) of the photographic constituent layer coated above the highest sensitivity red light-sensitive layer is 9 μm or less, preferably 8.5 μm or less. The photographic constituent layer referred to herein refers to a green photosensitive layer, a blue photosensitive layer, an intermediate layer, a filter layer, a protective layer, etc. provided as necessary. The total thickness of the photosensitive layer, intermediate layer, filter layer, etc. excluding the support in the photosensitive material of the present invention is preferably 25 μm or less, particularly 20 to 16 μm.
is preferred.

[0010] In the present invention, the dry film thickness is determined at a temperature of 23°C,
The film thickness is measured under 55% humidity control, and can be measured by enlarging the cross section of a dry sample with a scanning electron microscope. Using this measurement method, the film thickness of each constituent layer in a multilayer structure can be measured individually. can be asked for.

Next, a preferred layer structure in the present invention is shown below.

(Note) Pro; protective layer IL; intermediate layer YC; yellow filter layer BH; high-sensitivity blue-sensitive layer BM; medium-sensitivity blue-sensitive layer BL; low-sensitivity blue-sensitive layer GH; high-sensitivity green-sensitivity layer Layer GM; Medium-sensitivity green-sensitive layer GL; Low-sensitivity green-sensitive layer RH; High-sensitivity red-sensitive layer RM; Medium-sensitivity red-sensitive layer RL; Low-sensitivity red-sensitive layer In the photosensitive material in the present invention, The total amount of silver halide contained in the silver halide emulsion is 8.0 g/m2
The following range is preferably 4.5 to 7.5 g/m2, more preferably 5.0 to 7.0 g/m2.

The amount of silver halide emulsion can be determined by a fluorescent X-ray method, and the amount of silver halide is expressed in terms of silver. In the present invention, the highest speed red-sensitive layer is preferably substantially free of colored couplers. In the present invention, the number of red photosensitive layers is 2 or more.
It is preferable that the layer is composed of layers, and when the high-sensitivity red photosensitive layer and the medium-sensitivity red photosensitive layer are adjacent to each other,
Preferably, the two layers do not contain colored couplers. The colored cyan coupler referred to in the present invention is described in Research Disclosure (RD-308119, page 1002, V.
Refers to the items listed in Section IIG). The present invention is an IS
When applied to a photosensitive material having an O sensitivity of 320 or more, the effect is large and preferred.

Next, the silver halide emulsion forming the color-sensitive layer will be explained.

It is preferable to use a monodisperse silver halide emulsion in the silver halide color photographic light-sensitive material of the present invention. Monodisperse silver halide emulsion refers to one in which the weight of silver halide contained within a grain size range of ±20% around the average grain size d is 70% or more of the total weight of silver halide, and is preferably It is 80% or more, more preferably 90% or more.

Here, the average particle diameter d is defined as the particle diameter di when the product ni×di3 of the frequency ni of particles having the particle diameter di and di3 is maximum. (3 significant figures,
(The smallest digit number is rounded to the nearest 4.) The particle diameter here is the diameter when the projected image of the particle is converted into a circular image with the same area. The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print. (The number of particles to be measured shall be at least 1000 indiscriminately.)
.

A particularly preferred highly monodisperse emulsion of the present invention has a distribution width defined by grain size standard deviation/average grain size x 100 = distribution width (%) of 20% or less,
More preferably, it is 15% or less.

[0018] The particle size measurement method here follows the measurement method described above, and the average particle size is the arithmetic mean.

Σdini/Σni The silver halide emulsion according to the present invention has an average silver iodide content of 4
It preferably consists of ~20 mol% silver iodobromide;
Particularly preferred is 5 to 15 mol%.

The silver halide emulsion of the present invention may contain silver chloride to the extent that the effects of the present invention are not impaired.

The silver halide emulsion of the present invention has a high silver iodide content phase inside the grains. The silver iodide content of the high silver iodide content phase is preferably 15 to 45 mol%, more preferably 20 to 42 mol%, particularly preferably 25 to 45 mol%.
It is 40 mol%.

The silver halide grains of the present invention having a high silver iodide content phase inside the grains have a high silver iodide content phase with a low silver iodide content phase having a lower silver iodide content. It is coated.

The average silver iodide content of the silver iodide content phase lower than the high silver iodide content phase forming the outermost phase is preferably 6 mol% or less, particularly preferably 0 to 4 mol%. be. In addition, there is a silver iodide-containing phase between the outermost phase and the high silver iodide content phase (
(intermediate phase) may also be present. The silver iodide content of the intermediate phase is 1
0 to 22 mol% is preferable, particularly preferably 12 to 20 mol%
It is mole%.

The difference in silver iodide content between the outermost phase and the intermediate phase, and between the intermediate phase and the inner high silver iodide content phase is preferably 6 mol % or more, particularly preferably 10 mol % or more, respectively. There is a difference of more than mol%.

In the above embodiment, further silver halide is present in the center of the internal high silver iodide content phase, between the internal high silver iodide content phase and the intermediate phase, and between the intermediate phase and the outermost phase. Phases may be present.

[0026] The volume of the outermost phase is preferably 4 to 70 mol%, more preferably 10 to 50 mol% of the entire particle. The volume of the high silver iodide content phase is preferably 10 to 80% of the total grain, more preferably 20 to 50%, and more preferably 20 to 45%. The volume of the intermediate phase is preferably 5 to 60%, more preferably 20 to 55%, of the entire particle.

[0027] These phases may be a single phase with a uniform composition, a phase group consisting of multiple phases with a uniform composition and whose composition changes in a stepwise manner, or any phase in any phase. It may be a continuous phase in which the composition changes continuously, or it may be a combination of these.

In another embodiment of the silver halide emulsion of the present invention, the silver iodide localized within the grains does not form a substantially uniform phase, but the silver iodide content varies from the grain center to the outer part. An example of this is a mode in which the value changes continuously in the opposite direction. In this case, it is preferable that the silver iodide content decreases monotonically from the point where the silver iodide content within the grain is maximum toward the outer side of the grain. The silver iodide content at the maximum point is preferably 15 to 45 mol%, more preferably 25 to 40 mol%. Further, the silver iodide content of the grain surface phase is preferably 6 mol% or less, particularly preferably 0 to 4 mol% silver iodobromide.

The silver halide emulsion of the present invention has cubic, 1
It may be a normal crystal such as a tetrahedron or an octahedron, or a twin crystal such as a tabular crystal. Alternatively, a mixture of these may be used. In the case of tabular twin crystals, it is preferable that the ratio of the projected area equivalent circular diameter of the grain to the grain thickness is 60% or more of the projected area, more preferably 1.2 or more, 8.0. Less than 1.5 is preferable, especially 1.5 or more and 5.0
Less than is preferred.

[0030] Monodisperse normal crystal emulsions are disclosed in, for example, JP-A-5
No. 9-177535, No. 60-138538, No. 5
No. 9-52238, No. 60-143331, No. 6
No. 0-35726, No. 60-258536 and No. 61
It can be produced by referring to the method disclosed in JP-A-14636 and the like.

[0031] Monodisperse twin emulsions are disclosed in, for example, JP-A-61
It can be obtained by referring to the method for growing a spherical seed emulsion disclosed in Japanese Patent No. 14636. During growth, it is preferable to add a silver nitrate aqueous solution and a halide aqueous solution by a double jet method. Moreover, iodine can also be supplied into the system in the form of silver iodide. The addition rate is preferably such that new nuclei are not generated and the size distribution does not widen due to Ostwald ripening, that is, 30 to 100% of the rate at which new nuclei are generated.

As another condition for enlarging the grains, there is a method of enlarging the grains by adding, dissolving and recrystallizing fine silver halide grains, as shown on page 88 of the Proceedings of the Annual Conference of the Photographic Society of Japan in 1988.

The growth conditions for the silver halide emulsion include p
Ag5-11, temperature 40-85℃, pH 1.5-12
is preferred.

In the present invention, the silver halide emulsion used is one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No. 17643, No. 18716 and no. 308119 (hereinafter referred to as RD17643)
, RD18716 and RD308119).

[0035] The table below shows the description.

[Item] [Page of RD308119]
[RD17643]
[RD18716] Chemical sensitizer 99
6 Section III-A
23 648 Spectral sensitizer 996 IV-A-A, B, C, D
, E-J sections 23-24 648-9
Supersensitizer 996 IV-A-
E, J terms 23-24 6
48-9 Antifoggant 998 VI
2
4-25 649 Stabilizer
998 VI Known photographic additives that can be used in the present invention are also described in Research Disclosure, supra.

[0037] The relevant descriptions are shown in the table below.

[Item] [RD3081
Page 19] [RD17643] [
RD18716] Color clouding prevention agent
1002 Section VII-I
25 650 Dye image stabilizer 1001 Item VII-J
25 Brightener
998V
24 Ultraviolet absorber 1003 VIII-C, XI
Section IIC 25-26 Light absorber
1003 VIII
25-26 Light scattering agent
1003 VIII
filter dye
1003 VIII
25-26 Binder
1003 IX
26 65
1 Static inhibitor 1006 XII
I 27
650 Hardener
1004 X
26 651 Plasticizer 1006 XI
I 27
650 Lubricant
1006 XII
27 650
Activator/coating aid 1005 XI
26-27
650 Matting agent
1007 XVI
Developer (contained in sensitive material) 1011 Item XXB Various couplers can be used in the present invention, and specific examples thereof are described in the above-mentioned Research Disclosure.

[0039] The relevant descriptions are shown in the table below.

[Item] [RD30
Page 8119] [RD17
643] Yellow coupler 1001
Section VII-D VIIC
~G section magenta coupler 1001
Section VII-D VIIC~
G term cyan coupler 1001
Section VII-D VIIC~
Section G Colored coupler 1002
Section VII-G Section VIIG
DIR coupler 1001 VI
IF term VIIF term B
AR coupler 1002 VII-
Section F Other useful residues
Release coupler 1001
Section VII-F Alkali-soluble coupler 1001
Section VII-E
In addition, the coupler used in the present invention is that the red photosensitive layer contains a cyan coupler, and the cyan coupler is as follows:
Naphthol couplers and phenolic couplers can be preferably used.

The green photosensitive layer contains a magenta coupler, and as the magenta coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, and open-chain acylacetonitrile couplers are preferably used. Can be done.

The blue-sensitive layer contains a yellow coupler, and as the yellow coupler, for example, acylacetanilide couplers can be preferably used, and among these, benzoylacetanilide and pivaloylacetanilide compounds are preferred.

Furthermore, the development of highly color-forming couplers makes it possible to further promote the thinning of the photosensitive layer. Examples of the highly color-forming couplers include the polymer couplers described in JP-A-59-36249; Examples include a pyrazolotriazole type magenta coupler and a benzoyl type yellow coupler described in 1988-88394. Therefore, it is preferable to use a highly color-forming coupler as a means of thinning the film.

Furthermore, in the present invention, at least one of the photosensitive silver halide emulsion layers described above contains a diffusible DIR compound. In order to improve the image quality of each photosensitive layer, it is preferable that all of the above emulsion layers contain a diffusive DIR compound, for example, as disclosed in JP-A-62-14895.
Preferred diffusivity D for No. 0 and JP-A No. 62-54255
IR compounds and methods of their addition are described.

The photosensitive material of the present invention can be found on pages 28-29 of RD17643, pages 647 of RD18716, and RD30.
8119, XVII.

[0046]

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

In all the examples below, the amount added in the silver halide photographic light-sensitive material was 1 m2 unless otherwise specified.
Shows the number of grams per serving. Furthermore, silver halide and colloidal silver are shown in terms of silver. Furthermore, the sensitizing dye is mol/silver 1
Expressed in moles.

Example 1 Multilayer color photographic material samples 101 and 102 were prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-101 1st layer; antihalation layer (HC-1) black colloidal silver 0.2
UV absorber (UV-1) 0
．． 23 High boiling point solvent (Oil-1)
0.18 gelatin
1.4 Second layer; Intermediate layer (IL
─1) Gelatin
1.3 Third layer; low-sensitivity red-sensitive emulsion layer (RL
) Silver iodobromide emulsion (average grain size 0.4 μm) 1.0
Sensitizing dye (SD-1) 1.
8×10-5 sensitizing dye (SD-2)
2.8×10-4 sensitizing dye (SD-3)
3.0×10-4 cyan coupler (C-1) 0.70 colored cyan coupler (CC-1) 0.066DIR
Compound (D-1) 0.
03DIR compound (D-3)
0.01 high boiling point solvent (Oil-1)
0.64 gelatin
1.2 Fourth layer; Medium red-sensitive emulsion layer (RM) Silver iodobromide emulsion (average grain size 0.7 μm) 0.8
Sensitizing dye (SD-1) 2.
1x10-5 sensitizing dye (SD-2)
1.9×10-4 sensitizing dye (SD-3)
1.9×10-4 cyan coupler (C-1) 0.28 colored cyan coupler (CC-1) 0.027DIR
Compound (D-1) 0.
01 High boiling point solvent (Oil-1)
0.26 gelatin
0.6 5th layer; High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.8 μm) 1.7
0 Sensitizing dye (SD-1) 1
．． 9×10-5 sensitizing dye (SD-2)
1.7×10-4 sensitizing dye (SD-3)
1.7×10-4 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (Oil-1) 0
．． 17 gelatin
1.2 6th layer; Intermediate layer (IL-2) Gelatin
0.8 7th layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) 1.1 Sensitizing dye (SD-4) 6.8×
10-5 sensitizing dye (SD-5)
6.2×10-4 magenta coupler (M-1)
0.54 magenta coupler (M-2)
0.19 colored magenta coupler (CM-1) 0.06DIR compound (D-2
) 0.017DIR compound
(D-3) 0.01 High boiling point solvent (Oil-2) 0.81 Gelatin
1.8 8th layer; Medium-sensitivity green-sensitive emulsion layer (GM) Silver iodobromide emulsion (average grain size 0.7 μm) 0.7 Sensitizing dye (SD-6) 1.9×
10-4 sensitizing dye (SD-7)
1.2×10-4 sensitizing dye (SD-8)
1.5×10-5 magenta coupler (M─
1) 0.07 magenta coupler (
M-2) 0.03 colored magenta coupler (CM-1) 0.04 DIR compound
(D-2) 0.018 High boiling point solvent (Oil-2) 0.30 Gelatin
0.8 9th layer; High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 1.0 μm) 1.7 Sensitizing dye (SD-6) 1.2×1
0-4 sensitizing dye (SD-7)
1.0x10-4 sensitizing dye (SD-8)
3.4×10-6 magenta coupler (M-1
) 0.09 magenta coupler (M
-3) 0.04 colored magenta coupler (CM-1) 0.04 high boiling point solvent
(Oil-2) 0.31 gelatin
1.
2 10th layer; yellow filter layer (YC) yellow colloidal silver 0.05
Color stain prevention agent (SC-1) 0.1
High boiling point solvent (Oil-2) 0.
13 gelatin
0.7 formalin scavenger (HS-
1) 0.09 formalin scavenger (HS-2)
0.07 11th layer; low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.4 μm) 0.5 Silver iodobromide emulsion (average grain size 0.7 μm) 0.5 Sensitization Pigment (
SD-9) 5.2×10-
4 sensitizing dye (SD-10)
1.9×10-5 yellow coupler (Y-1)...
0.65 yellow coupler (Y-2)
0.24DIR compound (D-1)
0.03 High boiling point solvent (Oi
l-2) 0.18 gelatin
1.3 Formalin scavenger (HS-1) 0.08 12th layer; High sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 1.0 μm) 1.0 Sensitizing dye (SD-9 )
1.8×10-4 sensitizing dye (
SD-10) 7.9×10
-5 yellow coupler (Y-1)...0.
15 Yellow coupler (Y-2) 0.
05 High boiling point solvent (Oil-2)
0.074 gelatin
1.3 Formalin Scavenger (HS-1) 0.05 Formalin Scavenger (H
S-2) 0.12 In addition to the above composition, coating aid S
Appropriate amounts of u-1, dispersion aid Su-2, stabilizer ST-1, and antifoggant AF-1 were added. (It is added to sample 102 in the same way.) The average grain size of the emulsion used in the above sample is expressed as a grain size converted to a cube. Furthermore, each emulsion was optimally subjected to gold/sulfur sensitization.

Sample-102 1st layer; antihalation layer black colloidal silver
0.18
gelatin
1.57
UV absorber (UV-1)
0.17 High boiling point solvent (Oil-1)
0.14 2nd layer; 1st intermediate layer gelatin
1.
00 Third layer; First red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.38 μm)
0.76 Silver iodobromide emulsion (average grain size 0.85 μm)
0.34 Gelatin

1.49 Sensitizing dye (SD-3)
3.14×
10-4 Sensitizing dye (SD-2)
2.93×10-4
Sensitizing dye (SD-1)
1.88×10-5
Coupler (C-2)
0.96 Colored coupler (CC-1)
0.066 DIR compound (D-3)
0
．． 03 High boiling point solvent (Oil-1)
0.52 4th layer;
2nd middle layer gelatin
0.7
5 Fifth layer; first green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.85 μm)
1.25 Gelatin
0.80 Sensitizing dye (SD-4)
2.43×10-5 Sensitizing dye (SD
-5)
3.82×10-6 sensitizing dye (SD-6)
1.4
5×10-4 sensitizing dye (SD-7)
1.21×10
-4 Coupler (M-3)
0.33
Colored coupler (CM-2)
0.07 DIR compound (
D-2)
0.01 High boiling point solvent (Oil-4)
0.3
7 6th layer; 3rd intermediate layer gelatin
0.5
5 SC-2
0.
032 High boiling point solvent (Oil-2)
0.037 7th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.2 μm)
2.3 Gelatin

1.49 Sensitizing dye (
SD-1)
1.25×10-5 sensitizing dye (SD-2
) 1
．． 2×10-4 sensitizing dye (SD-3)
1.2×10
-4 Coupler (C-2)
0.37
Colored coupler (CC-1)
0.024 DIR compound (D-3)
0.008 SC-2

0.027 High boiling point solvent (Oil
-1)
0.43 8th layer; 4th intermediate layer gelatin
0.0
75 SC-2
0
．． 088 High boiling point solvent

0.13 9th layer; 2nd green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.3 μm)
2.0 Gelatin

0.80 Sensitizing dye (
SD-4)
1.61×10-5 sensitizing dye (SD-5
) 2
．． 53×10-6 sensitizing dye (SD-6)
9.62×
10-5 Sensitizing dye (SD-7)
8.00×10-5
Coupler (M-3)
0.11
Colored coupler (CM-2)
0.03 DIR compound (D-
2)
0.003 High boiling point solvent (Oil-4)
0.43
10th layer; yellow filter layer yellow colloidal silver
0.04
SC-2
0.044
gelatin
0.
75 High boiling point solvent (Oil-2)
0.05 11th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.4 μm)
0.24 Silver iodobromide emulsion (average grain size 0.85 μm)
0.96 gelatin

3.1 Sensitizing dye (SD-9)
2.17×1
0-4 Sensitizing dye (SD-10)
1.12×10-5
Coupler (C-1)
1.30 D.I.
R compound (D-3)
0.03 High boiling point solvent (Oi
l-2)
0.53 12th layer; 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.4 μm)
1.9 Gelatin

1.82 Sensitizing dye (
SD-9)
1.44×10-4 sensitizing dye (SD-1
0) 5.
65×10-5 coupler (Y-1)
0
．． 78 High boiling point solvent (Oil-2)
0.31 13th layer; 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm AgI
1 mol%) 0.10 gelatin

1.52 UV absorber (UV-1)

0.006 UV absorber (UV-2)
0.090
High boiling point solvent (Oil-1)
0.0065 High boiling point solvent (Oil-3)
0.0065 14th layer; 2nd protective layer gelatin
0.5
5 Alkali-soluble matting agent
0.13 Polymethyl methacrylate (average particle size 3 μm)
0.02 Slip agent (WAX-1)
0.04

[0051]

[Chemical formula 1]

[0052]

[Case 2]

[0053]

[Chemical formula 3]

[0054]

[C4]

[0055]

[C5]

[0056]

[C6]

[0057]

[C7]

[0058]

[Chemical formula 8]

[0059]

[Chemical formula 9]

Furthermore, in Sample 102, the thickness of the photographic constituent layers above the highest sensitivity red-sensitive layer was reduced by equal parts of the amount of gelatin applied in each layer, so that the total amount of silver halide converted to metallic silver was divided equally. Sample No. 103-110 were created.

[0061]

[Table 1]

Each sample No. prepared in this manner. 10
Samples Nos. 1 to 110 were exposed to wedge light using white light, and a color chart was photographed for another set, and then the following development process was performed. Processing process Processing process Processing time Processing temperature Replenishment amount *Color development 3 minutes 15 seconds 38± 0.3℃ 78
0ml bleach 45 seconds 38± 2
．． 0℃ 150ml fixation 1 minute 30 seconds
38±2.0℃ 830ml stable
60 seconds 38±5.0℃ 830ml
Drying 1 minute 55±5.0℃
-*The amount of replenishment is the value per 1 m2 of photosensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and their replenisher were used.

Color developer water

800ml potassium carbonate

30g sodium bicarbonate
2.5g potassium sulfite

3.0g sodium bromide
1.3g potassium iodide
1.2m
g Hydroxylamine sulfate
2.5g
sodium chloride
0.
6g 4-amino-3-methyl-N-ethyl-N-aniline sulfate (β-hydroxylethyl)

4.5g diethylenetriaminepentaacetic acid
3.0
g potassium hydroxide

Add 1.2 g water to make 1 liter, and adjust the pH to 10.06 using potassium hydroxide or 20% sulfuric acid.

Color developer replenisher water

800ml potassium carbonate

35g sodium bicarbonate
3g potassium sulfite

5g sodium bromide
0.4g Hydroxylamine sulfate
3.1g 4-amino-
Methyl-N-ethyl-N-aniline sulfate (β
-hydroxylethyl)
6.3g potassium hydroxide
2g diethylenetriaminepentaacetic acid
3.0g Add water to 1l
and pH 10. using potassium hydroxide or 20%.
Adjust to 18.

Bleach solution water

700ml 1,3 Diaminopropane Tetraacetate Iron (III) Ammonium 125
g ethylenediaminetetraacetic acid
2g
sodium nitrate
4
0g ammonium bromide

150g glacial acetic acid

Add 40 g water to make 1 liter, and adjust the pH to 4.4 using aqueous ammonia or glacial acetic acid. bleach replenisher water

700ml 1,3 Diaminopropane Tetraacetate Iron (III) Ammonium 175
g ethylenediaminetetraacetic acid
2g
sodium nitrate
5
0g ammonium bromide

200g glacial acetic acid

56g Adjust the pH to 4.4 using aqueous ammonia or glacial acetic acid, then add water to make 1 liter.

Fixer water

800ml ammonium thiocyanate

120g ammonium thiosulfate

150g sodium sulfite

15g ethylenediaminetetraacetic acid

After adjusting the pH to 6.2 using 2 g ammonia water or glacial acetic acid, add water to make 1 liter.

Fixer replenisher water

800ml ammonium thiocyanate

150g ammonium thiosulfate

180g sodium sulfite

20g ethylenediaminetetraacetic acid

Adjust the pH to 6.5 using 2 g ammonia water or glacial acetic acid, then add water to make 1 liter.

Stabilizing liquid and stable replenishing liquid Water

900ml P-octylphenyl-polyethylene oxide ether (ethylene oxide 10
molar addition)
2.0g dimethylolurea

0.5g hexamethylenetetramine

0.2g 1,2-benzisothiazoline-
3-on
0.1g siloxane (UCC L-77)
0
．． 1g ammonia water

After adding 0.5 ml of water to make 1 liter, the pH is adjusted to 8.5 using aqueous ammonia or 50% sulfuric acid.

After the above treatment, the relative sensitivity to red light was measured for each sample obtained. However, the relative sensitivity is expressed as a relative value with the sensitivity of sample 102 as 100.

[0071] Color reproducibility was also evaluated by printing the negative of the color chart onto color photographic paper so that the gray was of the same density, and then performing the development process for color photographic paper and then measuring the density. .

The measurement results at this time are shown in Table 2 below.

[0073]

[Table 2]

As is clear from Table 2, when the film thickness (DT) of the photographic constituent layer above the high-sensitivity red-sensitive layer was 9 μm or less, an increase in sensitivity was observed in all cases compared to the comparison.
Furthermore, the samples of the present invention prepared with a total amount of silver halide of 8.0 g/m2 or less have high sensitivity and improved red and green color reproducibility. Furthermore, it can be seen that even when the colored coupler in the seventh layer is removed as in Sample 110, improved color reproducibility and higher sensitivity are similarly obtained.

[0075]

According to the present invention, a silver halide color photographic material having high sensitivity and excellent color reproducibility could be obtained.

Claims (2)

[Claims] Claim 1: A support having a red photosensitive layer, a green photosensitive layer, and a blue photosensitive layer, each of which has two different sensitivities.
The layer is composed of two or more layers, of which the highest sensitivity green light-sensitive layer and the highest sensitivity red light sensitive layer are in contact with each other via a non-photosensitive intermediate layer, and the layer is located closer to the support than the highest sensitivity red light sensitive layer. In a silver halide color photographic light-sensitive material having at least one low-sensitivity green light-sensitive layer, the dry film thickness of the photographic constituent layer coated above the highest sensitivity red light-sensitive layer is 9 μm or less, and A silver halide color photographic material, characterized in that the total amount of silver halide coated in an emulsion layer of the material is 8.0 g/m2 or less in terms of metallic silver. 2. The silver halide color photographic material according to claim 1, wherein the highest sensitivity red photosensitive layer does not substantially contain a colored coupler.