JPH02191944A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve graininess and to attain high sensitivity by interposing green- and red-sensitive silver halide emulsion layers between a blue-sensitive silver halide emulsion layer positioned farthest from a support and a blue- sensitive silver halide emulsion layer having lower sensitivity than the farthest emulsion layer and specifying the diameter, thickness and area of silver halide particles in at least one of the silver halide emulsion layers. CONSTITUTION:At least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer are interposed between a blue-sensitive silver halide emulsion layer positioned farthest from a support and a blue-sensitive silver halide emulsion layer having lower sensitivity than the farthest emulsion layer and at least one silver halide emulsion layer consisting of three or more layers having the practically same sensitivity is formed. Flat platy silver halide particles having 0.1-30mum diameter and 1.1-100 ratio of diameter/thickness are used in at least one of the silver halide emulsion layers by >=50% of the total projection are of the silver halide particles in the layer.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material with high sensitivity and excellent image quality. The present invention relates to a silver halide color photographic material which can be obtained and also has excellent storage stability.

[Prior Art 1] In recent years, silver halide color photographic materials with high sensitivity and high image quality have been desired in this industry.

In other words, there are more opportunities to take photos under poor conditions with little light, such as indoors, or using telephoto lenses or zoom lenses where camera shake is likely to occur, and the small format of silver halide color photographic light-sensitive materials has increased. With this trend, there is a strong demand for the development of silver halide color photographic materials that are highly sensitive and have excellent image quality such as sharpness, graininess, and interimage effects.

However, it is difficult to achieve both higher sensitivity and improved image quality.

First, the following are known layer structures for achieving high sensitivity, etc. For example, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer sequentially coated on a support. In the jln layer structure of each light-sensitive silver halide emulsion layer of the layer and the blue-sensitive silver halide emulsion layer, for some or all of the light-sensitive silver halide emulsion layers, substantially the same color-sensitive layer, A high-sensitivity silver halide emulsion layer (hereinafter referred to as high-sensitivity emulsion layer) and a low-sensitivity silver halide emulsion layer (hereinafter referred to as
There is a layer structure (normal layer structure) in which the emulsion layer is separated into a low-speed emulsion layer and these layers are layered adjacently.

According to this normal layer structure, during exposure, the light-sensitive silver halide emulsion layer located closer to the support absorbs the amount of exposure light by another light-sensitive silver halide emulsion layer located farther away. However, there is a problem in that it takes time for the developer to diffuse during development.

That is, in such a normal layer structure, due to the loss of exposure H and the delay in development, it is difficult to increase the sensitivity of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer located in the lower layer (on the support side). cause a disadvantage.

On the other hand, a technique for changing the lamination order of each photosensitive silver halide emulsion layer (reverse W1 configuration) is known.

For example, U.S. Pat. No. 3,663,228 includes (a)
Coating each low-sensitivity emulsion layer (RGB low-sensitivity layer unit) of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer in order from the support side, (b) the RGB 1 m of each high-sensitivity emulsion of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are placed on the low-speed layer unit in order from the support side.
(RGB high-sensitivity layer unit) is adopted, and each laminate unit of the RGB high-sensitivity layer unit and RGB low-sensitivity layer unit is coated with an ND (neutral density) filter. The configurations separated by are described. Like this ND
As is clear from the fact that a filter is required, this technology has no problem with increasing sensitivity at all, and is insufficient to satisfy the performance of high image quality.

Next, in U.S. Pat. No. 3,658,536, the green-sensitive silver halide emulsion layer, which has a large effect on visibility, is positioned on the surface side farther from the support. Techniques have been disclosed that attempt to eliminate layer exposure loss. However, this layered layer configuration (
Inverted layer structure) alone is insufficient to improve graininess.

On the other hand, the following technology is known as an inverted layer structure that achieves high sensitivity.

[A] First, in Special Publication No. 55-34932, (a)
Each low-sensitivity emulsion layer (RG low-sensitivity layer unit) of a red-sensitive silver halide emulsion layer and a green-sensitivity silver halide emulsion layer is coated in order from the support side, and (b) on the RG low-sensitivity layer unit, a support is applied. Each high-sensitivity emulsion layer (RG high-sensitivity layer unit) of a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer is coated in order from the side of the body, and (C) a normal layer is applied on the RG high-sensitivity layer unit. As shown in the structure, high-speed and low-speed emulsions W (B
[B] Japanese Patent Publication No. Sho 61-22294 describes a red-sensitive silver halide emulsion of the RG low-speed layer unit in the silver halide color photographic light-sensitive material having the layer structure [A]. A configuration in which each of the green-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer is coated separately into medium-sensitivity and low-sensitivity layers;
A structure in which a low-sensitivity layer unit and an RGB high-sensitivity layer unit are sequentially coated on a support [D゛] Further, in JP-A-61-72235, in the layer structure of the above-mentioned [A], A configuration in which the maximum color density of the sensitive silver halide emulsion layer and/or the green-sensitive silver halide emulsion layer is 0.6 to 1.3 is described.

[Problems to be Solved by the Invention] These silver halide color photographic light-sensitive materials having layer configurations [A], [81, [C] and [D] all have a high-sensitivity green-sensitive silver halide emulsion layer and this layer. It is an effective means to achieve the objectives of high sensitivity and high image quality by having at least a red-sensitive silver halide emulsion layer of high sensitivity between a green-sensitive silver halide emulsion layer of lower sensitivity, but still. This was insufficient to satisfy the ultra-high image quality that is required these days.

Furthermore, while it is desired that these films have high sensitivity and high image quality, the films are also required to have good storage stability. In particular, in the recent development of high-sensitivity films, increased fog and deterioration of graininess due to exposure of the film to natural radiation during storage have become a problem, and countermeasures are desired.

An object of the present invention is to provide a silver halide color photographic material that maintains high sensitivity, has improved graininess, and has excellent storage stability.

[Means for Solving the Problems] The above object of the present invention is to provide at least one green-sensitive silver halide emulsion layer, at least one red-sensitive silver halide emulsion layer, and a plurality of layers having different photosensitivity on a support. In a silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, the plurality of blue-sensitive silver halide emulsion layers include:
One of the blue-sensitive silver halide emulsion layers is provided as a silver halide emulsion layer on the farthest side from the support, and one of the blue-sensitive silver halide emulsion layers provided on the far side has a higher photosensitivity. A low blue-sensitive silver halide emulsion layer is provided sandwiching at least one layer each of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer, and substantially consisting of three or more layers. There is at least one silver halide emulsion layer having the same color sensitivity, and at least one silver halide emulsion layer has a grain size of 0.1μ to 30μ and a grain size/grain thickness ratio of 1. .1 or more 100
The following tabular silver halide grains have a total projected area of 50
This was achieved by using a silver halide color photographic light-sensitive material characterized by containing % or more of silver halide.

The present invention will be explained in more detail below.

In the present invention, the high-sensitivity emulsion layer refers to a layer having the highest sensitivity among silver halide emulsion layers (hereinafter simply referred to as emulsion layer) having substantially the same color sensitivity.

Conversely, the low-speed emulsion layer refers to the layer with the lowest sensitivity.

A plurality of silver halide emulsion layers having substantially the same color sensitivity refers to a plurality of silver halide emulsion layers each having a maximum spectral sensitivity substantially in the blue light region, green light region, or red light W411. , the maximum spectral sensitivity wavelengths (λvaax) of the plurality of emulsion layers do not necessarily have to be exactly the same.

J3 in the silver halide color photographic light-sensitive material of the present invention,
The sensitivity difference between the high sensitivity emulsion layer and the low sensitivity emulsion layer is ffi
OgE (E: fJ light ff1) t,,T O,2~2
．． 0t' is preferable, more preferably 0.4~
It is 1.2. When separated into multiple layers with different sensitivities, the rA degree difference between the high-sensitivity emulsion layer and the next sensitive layer (referred to as a medium-sensitivity emulsion layer) is 0.2 to 1 as 1 oaE.
,0 is preferable.

The layer structure of the silver halide color photographic light-sensitive material of the present invention will be explained.

The above-mentioned three or more emulsion layers having substantially the same color sensitivity do not necessarily have to be located adjacent to each other, but
Preferably, the high-speed emulsion layer and the medium-speed emulsion layer are adjacent to each other.

In the silver halide color photographic light-sensitive material of the present invention, a non-light-sensitive intermediate layer may be provided between each light-sensitive emulsion layer, and especially when light-sensitive emulsion layers having different color sensitivities are adjacent to each other, a non-light-sensitive intermediate layer may be provided. Scavenger substances can also be included in such non-photosensitive interlayers, which are preferably provided.

In the silver halide color photographic material of the present invention, a yellow filter layer can also be provided. In that case,
It is preferable to provide it immediately below the blue-sensitive a-speed, medium-speed and/or low-speed emulsion layer.

The silver halide color photographic light-sensitive material of the present invention has at least one silver halide emulsion layer consisting of three or more emulsion layers having substantially the same color sensitivity, but the relationship between the emulsion layers of each sensitivity and the image quality may vary. It is preferable to have the configuration of point 3111.

Specific examples of preferred layer structures of the light-sensitive emulsion layer in the silver halide color photographic light-sensitive material of the present invention are listed below.
It is not limited to these.

Note that the side closest to the support is listed here first.

■ Each low-speed red-sensitive, green-sensitive and blue-sensitive emulsion layer, high-speed red-sensitive emulsion layer, medium-speed green-sensitive emulsion layer, and each high-speed green-sensitive and blue-sensitive emulsion layer.

■ Each low-speed red-sensitive, green-sensitive and 'R-sensitive emulsion layer,
Medium-speed red-sensitive emulsion layer, high-speed red-sensitive, green-sensitive and blue-sensitive emulsions WJ.

■ Each low-speed red-sensitive, green-sensitive and blue-sensitive emulsion layer, each high-speed red-sensitive and green-sensitive emulsion layer, and each medium-speed and high-speed blue-sensitive emulsion layer.

■ Each low-speed red-sensitive, green-sensitive and blue-sensitive emulsion layer, each medium-speed green-sensitive emulsion layer, and each high-speed green, red-sensitive and blue-sensitive emulsion layer.

■ Each low-speed red-sensitive, green-sensitive and blue-sensitive emulsion layer, high-speed green-sensitive emulsion layer, medium-speed red-sensitive emulsion layer, and each high-speed red-sensitive and blue-sensitive emulsion ff.

(2) A structure in which both the green-sensitive emulsion layer and the red-sensitive emulsion layer are 3ffl by combining the above (2) and (2).

Similarly, ■ and ■, ■ and ■, ■ and ■ and ■, and ■ and ■ and ■
A configuration that combines.

The tabular silver halide grains may be contained in any of the above emulsion layers, but they may be contained in the high-sensitivity emulsion layer of the emulsion layers having substantially the same color sensitivity and consisting of 3JI or more, or the next highest sensitivity. It is preferable to contain it in at least one of the layers.

In the present invention, the grain size of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain.

The thickness of a silver halide grain refers to the minimum distance between two parallel planes constituting a tabular silver halide grain.

The grain size range of the tabular silver halide grains mentioned above is 0.
．． 1μ- or more and 30μ or less, but 0.2μ- or more2
0μ11 or less is preferable, especially 0.3μm or more 10μs
The following are preferred. Further, the value of the ratio of particle size/particle thickness is 1.1 or more and 100 or less, preferably 1.2 or more and 50 or less, and particularly preferably 1.5 or more and 20 or less.

The effects of the present invention can be obtained when the projected area occupied by such tabular silver halide grains is 50% or more of the projected area of all grains in the silver halide emulsion layer containing the grains. The silver halide grains occupying the remaining projected area may be tabular grains whose grain size and grain size/grain thickness values are outside the range of the present invention, or may be grains of other shapes. .

The silver halide emulsion layer of the silver halide color photographic light-sensitive material of the present invention contains silver bromide, silver iodobromide, silver iodobromide,
Although any of the conventional silver halide emulsions such as silver iodochloride, silver chlorobromide, and silver chloride can be used, the preferred emulsion is silver iodobromide.

The silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

The silver halide bill may have any grain size distribution. In addition, emulsions with a wide particle size distribution (
A polydisperse emulsion (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow particle size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used, but a monodisperse emulsion is particularly preferred.

In the present invention, the silver halide emulsion may be a mixture of two or more types of silver halide emulsions formed separately.

Here, a monodisperse silver halide emulsion is defined as a silver halide emulsion containing silver halide ff within a grain size range of ±20% around an average grain size of 7.
1ffi is 60% or more of the total silver halide grains mm, preferably 70% or more, more preferably 80% or more.

Here, the average particle size γ is the frequency n1 of particles having particle size γi
The particle size γ when the product nixγi3 of and γi3 is maximum
Define as i.

(3 significant digits, minimum digits are rounded to 4 to 5 digits.) The grain size referred to here refers to the diameter of spherical silver halide grains, and the diameter of grains with shapes other than spherical, such as tabular. In case,
This is the diameter when the projected image is converted into a circular image with the same area.

The particle size can be obtained, for example, by magnifying the particles 10,000 to 50,000 times with an electron microscope, projecting the particles, and actually measuring the particle diameter or projected area on the print. (The number of grains to be measured shall be 1,000 or more for each type of grain.) Particularly preferred highly monodispersed emulsions are those with a distribution width defined by 20% or less,
More preferably, it is 15% or less.

Here, the average particle diameter and particle diameter standard deviation shall be determined from γi defined above.

Silver halide emulsions include emulsions consisting of silver halide grains with a constant silver iodide content (uniform composition emulsion), and silver halide grains consisting of two or more layers with different silver iodide contents. Any emulsion (core/shell type silver halide emulsion) can be used, but preferably a core/shell type silver halide emulsion is used.

The average silver iodide content in the silver halide grains used in the present invention is preferably 2 mol% or more and 20 mol% or less, more preferably 3 mol% or more and 15 mol% or less, and most preferably 4 mol% or more and 12 mol% or less. It is less than mol%.

The tabular silver halide grains used in the present invention can be produced by appropriately combining methods known to those skilled in the art. For example, in an atmosphere with a relatively high pAg value of p3r1.3 or less, Tabular silver halide grains are 40% in mm
It can be obtained by forming seed crystals existing as described above, and growing the seed crystals while simultaneously adding a silver salt solution and a halogen solution while keeping the pBr value at the same level. In this case, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei during the grain growth process.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, the type of solvent, the addition rate of the silver salt and halide used during grain growth, etc.

In the present invention, a known silver halide solvent such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

The above silver halide grains include a grain forming process and/or
Or during the growing process, cadmium salts, zinc salts, lead salts,
Metal ions are added using at least 1 F, i selected from thallium salts, iridium salts (including complex salts), Odium salts (including complex salts), and iron salts (including silver salts), and metal ions are added inside the particles and/or Alternatively, these metal elements can be contained on the particle surface, and reduction-sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

In the present invention, the silver halide emulsion may be one in which unnecessary soluble salts have been removed after the growth of silver halide grains has been completed, or may be one in which unnecessary soluble salts are still contained. Ojiv-(Res
(hereinafter abbreviated as RD)) This can be carried out based on the method described in Section 1 of No. 17643.

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

In the silver halide emulsion of the present invention, silver halide grains containing a desensitizer in at least a portion of the silver halide grains can be used.

In order to obtain a wide exposure radiation range, it is possible to mix and use silver halide grains with different average grain sizes, but silver halide grains containing a desensitizer can be used instead of low-sensitivity silver halide grains with small grain sizes. By using this method, it is possible to reduce the difference in average grain size without changing the sensitivity of the silver halide grains, and it is also possible to mix and use silver halide grains having the same average grain size and different sensitivities.

That is, by using silver halide grains containing a desensitizer, a wide exposure latitude can be obtained even if the coefficient of variation of the entire grain is made small.

Therefore, these silver halide grains having a small coefficient of variation that are exposed to the same environment are preferred because their photographic performance is stabilized against changes over time and fluctuations in development processing.

Furthermore, from the viewpoint of production technology, it becomes possible to chemically sensitize a mixed system of silver halide grains having different sensitivities in the same batch.

Various desensitizers can be used, such as metal ions, antifoggants, stabilizers, and desensitizing dyes. Among these, a metal ion doping method using metal ions is preferred.

Metal ions used in the doping method include Cu, Cd
, Zn, Pb, Fe, T1. Rh.

81, Ir, Au, Os, Pd, etc. f) fd & ion l
These metal ions can be used, for example, as halogen salts, and two or more types (can also be used for JF.Also, l)H of the AOX suspension system during doping is 5 or less. It is preferable that

In addition, the doping n of these metal ions varies depending on the type of metal ion, the particle size of the silver halide grain, the doping position of the metal ion, the desired sensitivity, etc., but AaX1
Preferably i Q-17 to 10-2 moles per mole,
Particularly preferred is iQ-16 to 10-' mol.

Also, if the metal ion is Rh ion, 1Q-14 to 10
-2 mol is preferred, particularly iQ-11 to 10-4 mol.

Furthermore, by selecting the type of metal ion, doping position and doping amount, various different sensitivity qualities can be imparted to the silver halide grains.

If the doping amount is less than 101 mol/Act can do.

It is also possible to chemically sensitize silver halide grains with different doping conditions, which have been prepared for practical use, by mixing them at a predetermined ω ratio and forming the same patch. Each silver halide grain receives a sensitizing effect based on its quality,
An emulsion with a wide latitude can be obtained depending on the sensitivity difference and mixture ratio.

The silver halide emulsion related to the present invention includes an antifoggant,
Stabilizers etc. can be added. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The present invention is preferably used for color photosensitive materials such as color negative films and color reversal films.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

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 developing agent, a silver halide solvent, a toning agent, a hardening agent, a fogging agent can be produced. Compounds that release photographically useful fragments can be used, such as antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, and the like.

These figures and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

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

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

In order to obtain a dye 'Fi image using the light-sensitive material of the present invention, light exposure and commonly known color photographic processing can be performed.

A non-diffusible compound (diffusible D[R compound) capable of reacting with the oxidized form of a developing agent to release a diffusive development-inhibiting compound may be added to the emulsion layer and/or the non-photosensitive emulsion layer related to the present invention. is preferred.

[Implementation P/4] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples.

In all of the following Examples, the amount added in the silver halide color photographic light-sensitive material is per 1f unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

Example 1 Multilayer color photographic materials samples I11 and 2 were prepared by sequentially forming layers having the compositions shown below on a triacetylcellulose film support from the support side. However, the emulsions added to each photosensitive emulsion layer (Em-1 to Em-
For 5), an emulsion prepared as shown in Table 1 was used.

1st layer; antihalation layer black colloidal silver silver coating fi 0.20 gelatin 1.7 g ultraviolet absorber (LJV-1) 0.3 (1 colored magenta coupler (CM-1) 0.2 g high boiling point solvent (0++- 1) 0.15a
High boiling point solvent (Oil-4) o, 15°? a? ji point solvent (Oil-3) 0.
2a 2nd M1: Intermediate layer gelatin 1.2g Third layer; First red-sensitive emulsion layer Silver iodobromide emulsion (EM-1) Silver coating amount 1.0g Silver iodobromide emulsion (EM-2) Silver coating fi O,51J gelatin 1.3g sensitizing dye (S
-2) 0.5 x 10-4 mol sensitizing dye (S-3) per 1 mol silver 2 x 10-4 mol sensitizing dye (S-1) 2 x 10-4 mol coupler (C) per 1 mol silver -2) 0.07g coupler (C-1) 0.30 coupler (C-3) 0.3° colored cyan coupler (CC-1) o, oZg DIR coupler (DI) 0.005
g high boiling point solvent (ot+-1) 0.2
a 4th Ji: Intermediate layer gelatin 0.8g 5th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (EM-1) Silver coating ff11. og silver iodobromide emulsion (EM-2) silver coated mo, s g gelatin 1.4g sensitizing dye (S-
7) 1.8x10-4 mol sensitizing dye (S-6) per 1 mol silver 1.3xlO-4 mol sensitizing dye JR (S-6) per 111 mol sensitizing dye (S-6)
-8) 9.2X10-5 moles per mole of silver Sensitizing dye (S-5) 6.8X 10 moles per mole of silver Sensitizing dye (S-4) 6.2X10-5 per mole of silver 4 mole coupler (M −1) 0.15(
1 Colored magenta coupler (CM-1) 0, ogg High boiling point solvent (Oil-2) 6th layer; Intermediate layer 0, 230 Gelatin 0.8g5c-
i 0.05g high boiling point solvent (Off -3) 0.05g 7th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion (EM-1) Kim cloth mO, 8g gelatin 0.6g sensitizing dye (
S-10) 3x10-1 mol per mol of silver Sensitizing dye (S-9) 1x10-4 mol per mol of silver Coupler (Y-1) 0.30 High boiling point solvent (Oil-3>0. 3a 8th layer; middle layer gelatin 0.8g5G-
10,050 High boiling point solvent (Oil-3) 0.05
゜9th Jfl; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (EM-1) Silver coating m 0.35a Silver iodobromide emulsion (EM-3) Silver wire cloth ff13.10 Fine grain Ag x Emulsion (average grain size 0.08μ.

AgI = 21 ol % (7) Silver iodobromide) Silver coating I!
i0.05゜Gelatin sensitizing dye (S-2) Sensitizing dye (S-3) per mole of silver Coupler (C-2> Coupler (C-1> Coupler (C-3)) c -i a1 boiling point solvent (Oil-1) 10th layer; Intermediate layer gelatin C-1 Colored magenta coupler g 0.2xlO-Dou mole 1.0X10' mole 0.2g o, osg O, 10Q o, osg 0.49 0.8 g 0.07Q (CM-1> High boiling point solvent (Oil-3> No. 11111; Second green-sensitive emulsion layer Silver iodobromide emulsion (EM-1) Limited coating m 0.04Q O, 251J Iodor Silveride emulsion (EM-3) tf! coating fi 2.0
0 gelatin t, sg sensitizing dye (S-7) 6.8 x l G-5 moles per mi mole Sensitizing dye (S-6) 6.7 x 10-5 moles per m mole sensitizing dye (S-8) 11 2 per mole. lX1G-6 molar coupler (M-1) 0.2° Colored magenta coupler (CM-1) 0, 02111 'Is boiling point RA medium (Oil-2) 0.
2゜1112: Medium layer fine grain AQX emulsion (average grain size 0.08μ).

AgI-2mol 1% silver iodobromide).

Silver coated ff1o, 3a Gelatin 0.8g5C-
1o, osg High boiling point solvent (Oil-3) 0.05
g No. 1311: No. 21! Sensitive emulsion layer Silver iodobromide emulsion (EM-1) tl [cloth fil 0.1
5゜Silver iodobromide emulsion (EM-4) Silver coating ff11.9
0 fine grain AoX emulsion (average grain size 0.08μ).

Ag l-2ao1% silver iodobromide) Silver coating ffi 0.050 Fine grain AOX emulsion (average grain size 0.3μ).

A (Jl-2101% silver iodobromide) II coating mff1 O,1.

Gelatin 2.10 sensitizing dye (S-9) 0.4x 10-1 mol sensitizing dye (S-9) per 1 mol silver
11) 1.2X1G-4 mole coupler (Y-1) 0.8Q high boiling point solvent (Oil-3) 0.49 No. 14 per mole of silver
Layer; 1st reference Gelatin 1.50 Ultraviolet absorber 1jV-1) 0.1 (J Ultraviolet absorber (LJV-2) 0.IQ Formalin scavenger (l(S-1)o, sg Formalin scavenger -(H8-2) 0.2g High boiling point solvent (Oil -1) 0.1
g High boiling point FFJ medium (Oil-4) 0.
1゜15th layer; 2nd retention layer Gelatin 0.69 Alkali-soluble matting agent (average particle size 2μy0, 1zg Polymethyl methacrylate (average particle size 3μ) 0,02σ Slip agent (WA X-1) o, o4
G? fFfflvIIlil agent (Su-1)
0.004g In addition to the above composition, each layer contains coating aid 3u-2, dispersion aid 5tl-2, 5tj-3, hardening agent H-1 and l-1-2, stabilizer 3tab-1. , antifoggants AF-1 and AF-2, and preservative DI-1 were added.

S-2 S -,9 G-1 CM-1 D-1 V-1 O-3 C-1 AX-1 0:1-1 0:1-2 C* H+ * (SV-2 S-1 S-2 (CHz=CH8OtCH*)*0 U-1 Na0sS-C-COOC)(t(CF*CF*)s8
C-C00CH*(CFICFs), He LI-2 Na0sS =, C-COOCmH+tCHa-COO
C-Hlt 0:1-3 0:1-4 F-1 F-2 In addition, each layer having the composition shown below is sequentially formed on the triacetyl cellulose film support from the support side to obtain multilayer color photographic exposure. Material sample-3°4 was prepared.

However, the emulsions added to each photosensitive emulsion layer (Elm-1 to
For El-5), an emulsion prepared as shown in Table 1 was used.

1st report; 2nd layer same as 1st F/IJ of samples-1 and 2; 3rd layer same as 2nd FJ of samples-1 and 2; 4th layer same as 3rd layer of samples-1 and 2; Sample The 5th layer is the same as the 4th layer of samples -1 and 2; The 6th layer is the same as the 5th layer of samples -1 and 2; The 7th layer is the same as the 6th layer of samples -1 and 2; The 7th layer is the same as the 6th layer of samples -1 and 2; 8th MI same as 7th skin: 9th report same as 8th layer of sample-1.2; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (EM-1) Troweling l O,3 (1 iodobromide emulsion) Silver emulsion (EM-5) 1.OQ gelatin 1.1g sensitizing dye (S-
2) 0.3 x 10-4 mol per mol of silver sensitizing dye (S-3) 1.6 x 10-4 mol per mol of silver Coupler (C-2) 0.12° coupler (C-1) o, o3g Coupler (C-3) 0.0608C-
10,03Q High boiling point solvent (Oif -1) 0.24
g 10th layer; 3rd red-sensitive emulsion layer Silver iodobromide emulsion (El-3) Trowel coating FF11.9 Fine grain AOX emulsion (average grain size 0.08μ).

AQI-2moZ% silver iodobromide) Trowel applied ff1o, 1° gelatin 1.4g sensitizing dye (S-2) Sensitizing dye (S-3) per mole of silver Coupler (C- 2) Coupler (C-1) 0.2X10'mol 1.0X10-4mol 0.080 0.02g Coupler (C-3) 0.04aS
C-10,02Q High boiling point solvent (Oil-1) 0.16
g 11th layer; same as the 10th layer of Sample-1 12th second green-sensitive emulsion layer Silver iodobromide emulsion (Em-1) Trowel coating m0.3 (1 Silver iodobromide emulsion (EIll-5) ) Silver coated fio, 8Q gelatin 1.1g sensitizing dye (
S-7) 1.0X1G-4 moles per mole of silver sensitizing dye (S-6) 1.0X10-4 moles per mole of silver sensitizing dye (S-8) 0.3X10 per mole of silver -S molar coupler (M-1”) 0.130
Colored magenta coupler (CM-1) high boiling point solvent (O
il-2) 13th layer; 3rd green-sensitive emulsion layer Silver iodobromide emulsion (Em-3) 0.011; 1 0.13Q Trowel applicationffl 1.39 Gelatin 1.7g Sensitizing dye (S-7) 0.7X 10-4 moles of sensitizing dye (S-6) per mole of silver 0.7X 10-4-E sensitizing dye (S-6) per mole of silver
S-8) 0.2X10-5 mole coupler (M-1) 0.07g per mole of silver
Colored magenta coupler (CM-1) o, oig High boiling point solvent (ON-2) o, o7g 14th layer; 15th layer same as 12th WJ of sample-1; 2nd ¥
! l Sensitive emulsion layer Silver iodobromide emulsion (EM-1> Trowel coating fi1.0tJ gelatin 0.64+1 sensitizing dye (S-9) 1.0 x 10-4 mol sensitizing dye (S-11) per 1 mol silver 3.0X 10→molar coupler (Y-1) 0.5g per mole of silver High boiling point solvent (Oil-3) O,:l a 16th layer; 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (El- 4) Silver coating ffi 1.15
9 Fine grain AgX emulsion (average particle size O, aSμ.

A (11-2 moJ!% silver iodobromide) II coating ffi O, 02 (+ Fine grain AQX emulsion (average grain size 0.3μ).

Silver coating fi 0.03+I+ Gelatin 1.1g Sensitizing dye (S-9) 0.4 x 10-4 mol per mol of silver Sensitizing dye (S-11) 111 1.2X10-4 mole coupler (Y-
1) 0.3° high boiling point Fag (O
il-3) 0.1 g 11th layer: Same as the 14th layer of Sample-1 18th film; Same as the 15th layer of Sample-1 Additionally, additives were added to each layer in the same manner as Sample-1.

When an emulsion containing tabular silver halide grains was used, the ratio of the projected area of the tabular silver halide grains to the total projected area of the silver halide grains in each layer of each sample was as follows.

Sample 2 m9HI (second red-sensitive emulsion layer) 85.3% No. 11 (second, second hll emulsion layer) 66.3% No. 13111 (second blue-sensitive emulsion layer) 55.2% Sample 4 No. 101i1 (second emulsion layer) 3 red-sensitive emulsion layer) 81.3
%131 (Third green-sensitive emulsion layer) 70.0%
16th layer (3rd TI-sensitive emulsion layer) 61.6% For the 8 samples F11 to 4 prepared above, the coated one [direct bond and the one stored at 55°C, 60% R, H, atmosphere for 3 days] Each bond was wedge-exposed using white light and subjected to the following development process.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds
Fixed in seconds 6 minutes 3
Wash with water for 0 seconds Stabilize for 3 minutes and 15 seconds Dry for 1 minute and 30 seconds
The composition of the processing liquid used in each drying process is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-(β-human oxyethyl) aniline sulfate 4.750 Anhydrous sodium sulfite 4.25 (1 hydroxylamine 1/211 acid salt 2 .0g Anhydrous potassium carbonate 37.50 Sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water
Let it be il. (1)H-10,1) [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 1G0. OQ ethylenediaminetetravinegar 12 ammonium salt 1o, og ammonium bromide 150.017 ice vinegar v
J10.0d Add water to make 1ffi, and use ammonia water to pH-
Adjust to 6.0.

[Fixer] Ammonium thiosulfate 175.0 (1
Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to 1
and adjust the pH to -13.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5ml
2 Konidax (manufactured by Konica > 7.5*R)
Add water to make 11.

Relative sensitivity (S) and RMS were measured for each sample after exposure and development. The results are shown in Table 2.

Note that the relative sensitivity (S) is the relative value of the reciprocal of the exposure amount that gives a fog depth of 10.1, and the sensitivity of sample N001 is 10.
It is shown as a value of 0.

RMSi[ is expressed as 1000 times the standard deviation of the variation in 1llf value that occurs when the minimum concentration + 1.0 concentration is scanned with a microdecimometer with an aperture scanning area of 250 μf.

As is clear from Table 2, Sample 4 of the present invention is Comparative Sample 1
, 2.3, 55%r(,H
It was found that even after storage for 3 days in an atmosphere, fog was low, sensitivity was high, and RMS granularity was small, indicating that these photographic performances were improved.

Moreover, these improvements were greater than expected from sample 2.3.

Example 2 The samples used in Example 1 were stored under the following four conditions and their photographic performance was evaluated.

Condition 1: Sample preparation is immediately processed.

Condition 2: Konica in Hino City, Tokyo ■ Processed after being left in the laboratory for one year.

Condition 3: Konica in Hino City, Tokyo Refrigerator in the research institute (5
Processed after storage for 1 year at ℃).

Condition 4: Konica in Hino City, Tokyo Refrigerator in the research institute (5
℃), further surrounded by 1.5 CI thick oxygen-free copper, and further surrounded by 10 cn+ thick lead block, and then stored for 1 year before processing.

Among them, Condition 2 is a case where the product was stored under very normal conditions.6 Condition 3 is a case where the product was stored under refrigeration to reduce the influence of changes in performance due to heat. Condition 4 is a condition that can almost eliminate the influence of the natural number rJ4 line. In addition, the natural radiation dose in the environment of conditions 2 and 3 is T L O (T I
+erio Lulnascanca-Detect
or ), it was about 52 mR/year.

The evaluation results of fog, relative g, and RMS granularity are shown in Table 3. The PF value method was the same as in Example-1.

The relative sensitivity is expressed as a value with the sensitivity of test n1 and condition 1 as 100.

As is clear from Table 3, the photographic performance in all cases of excellent preservation has deteriorated, with condition 2 showing the greatest deterioration, followed by condition 3.4. It was found that the influence of Nature/i51 DI II was large.

In addition, Sample 4 of the present invention shows less deterioration overall than Samples 1, 2, and 3, and especially the deterioration under Conditions 2 and 3 is surprisingly small, and can be said to have excellent storage stability. Furthermore, it was found that Sample 4 of the present invention is also effective for natural numbers 04m.

Example-3 Sample 5.6 with the same layer structure as Sample Fi1.2 of Example-1
With the same mIll configuration as samples 3 and 4, sample 7°8.9
．． 10 was created. However, the emulsions (E+++-1 to Egi-5) used in each photosensitive emulsion layer were prepared as shown in Table 4.

3 (continued) When an emulsion containing tabular silver halide grains is used, the ratio of the projected area of the tabular silver halide grains to the total projected area of the silver halide grains in each layer of each sample is as follows. Ta.

Sample 6 (comparison) 91iW (second red-sensitive emulsion layer) 64.4% 11th layer (second green-sensitive emulsion layer) 65.7% 1st
31 (m2111 emulsion ff) 55.2% Sample Q, 10 (both according to the invention) 10th layer (third red-sensitive emulsion layer) 60.1% 1st
3 layers (third green-sensitive emulsion layer) 70.0% 16th layer (third blue-sensitive emulsion layer) 6C3% sample 9.10 (
9th m (second red-sensitive emulsion layer) 66.8% 12th
Layer (second green-sensitive emulsion layer) 65.8% Each of Samples 5 to 10 prepared above was evaluated in the same manner as in Example-1. The results are shown in Table 5.

However, the relative sensitivity is expressed as a value based on sample No. 5, rA degree measured immediately after application as 100.

As is clear from Table 5, in contrast to comparative samples 5 and 6°7, samples 8,9 and 10 of the present invention had a coating of 6.
Even after storage at 55° C. and 60% R, H for 3 days in an atmosphere, fog, sensitivity, and RMS granularity were all excellent. In particular, the performance of sample 10 is i I! J! I have no choice but to do it.

Example-4 The same evaluation as in Example-2 was performed using Samples 5 to 10 prepared in Example-3. The fog, relative sensitivity, and RMS granularity of each sample obtained as a result are shown in Table 6.
Shown in 7.8.

However, regarding relative sensitivity, sample No. 015, condition table 6.
As is clear from 7.8, compared to comparative samples 5°6 and 7, samples 8 and 9.10 of the present invention had an unexpected increase in fog, a decrease in sensitivity, and a deterioration in graininess under conditions 2 and 3. (The effect of the present invention was clearly seen. Furthermore, a comparison between Conditions 3 and 4 shows that the sample of the present invention is also effective against natural radiation.

Example-5 Sample 11.1 with the same layer structure as Samples 1 and 2 of Example-1
2, and sample 13.14.1 with the same layer structure as samples 3 and 4.
5.1'6 was created. However, the emulsions used in each light-sensitive emulsion layer (Em-1 to E1m-5> are the emulsions prepared as shown in Table 9). When an emulsion containing tabular silver halide grains is used, The ratio of the projected area of tabular silver halide grains to the total projected area of silver halide grains in each layer of each sample was as follows.

Sample 1 (comparison) 9th layer (2nd red-sensitive emulsion layer) 66.4% 11th
11 (2nd green-sensitive emulsion layer) 65.9% 13th
111 (Second blue-sensitive emulsion layer) 59.2% sample 14.16 (both of the invention) 101II (Third red-sensitive? L agent 1 m) 66.
5% No. 1311 (Third green-sensitive emulsion layer) 68.
6% No. 1611 (3rd ti! Sensitive emulsion layer) 6
3.0% Sample Is, 16 (both according to the invention) 9th layer (second red-sensitive emulsion layer) 71.2% 12th
jil (second green-sensitive emulsion layer) 68.2% Each of Samples 11 to 16 prepared above was evaluated in the same manner as in Example-1. The results are shown in Table 10.

However, the relative sensitivity is expressed as a value based on sample No. 11 and the sensitivity measured immediately after coating as 100.

As can be seen from Table 10, comparative sample 11°12.1
In contrast to No. 3, Sample 14.15°16 of the present invention was excellent in all aspects of fog, sensitivity, and RMS granularity, both when directly coated and when stored for 3 days at 55° C. in a 60% R0H2 atmosphere. Among them, sample 16 showed particularly excellent performance.

[Effects of the Invention] According to the present invention, graininess is improved while maintaining sensitivity,
Furthermore, it was possible to provide a silver halide color photographic material with excellent storage stability.

Claims (1)

[Claims] A silver halide color photographic photosensitive material comprising, on a support, at least one green-sensitive silver halide emulsion layer, at least one red-sensitive silver halide emulsion layer, and a plurality of blue-sensitive silver halide emulsion layers having different sensitivities. In the material, one of the blue-sensitive silver halide emulsion layers is provided as a silver halide emulsion layer on the farthest side from the support, and the plurality of blue-sensitive silver halide emulsion layers is provided on the farthest side. At least one layer each of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is sandwiched between the green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer having lower photosensitivity. and there is at least one silver halide emulsion layer consisting of three or more layers having substantially the same color sensitivity, and at least one of the silver halide emulsion layers has a grain size of 0.1 μm or more. 30 μm or less, particle size/
A silver halide color photographic light-sensitive material characterized in that it contains tabular silver halide grains having a grain thickness ratio of 1.1 or more and 100 or less in an amount of 50% or more of the total projected area.