JPH02109039A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve stability of a photosensitive material during processing and its graininess by incorporating silver halide particles having a specified particle size and iodine content into a silver halide color photographic sensitive material. CONSTITUTION:In a photosensitive material constituted of plural silver halide emulsion layers, an average particle size of the whole silver halide particles is regulated to <=0.5mum, and an iodine content in the whole halogen compsn. is regulated to <=5mol.%. Further, silver halide particles constituted of >=2 phases having different AgI content, wherein an average AgI content is higher than the AgI content of particles in the peripheral phase, are contained in >=one emulsion layer. Monodispersive core/shell type silver iodobromide may be useable for a material for the particles, which may be chemically sensitized or sensitized with a sensitizing dye.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having excellent processing stability and graininess.

[Conventional technology]

In recent years, in the field of silver halide color photographic light-sensitive materials, there has been an increase in ultra-high sensitivities represented by ISO 1,600 to 3200, and small formats represented by disk films, and higher image quality is required. There is.

As one means of improving image quality, it has been proposed to reduce the size of silver halide grains. JP-A-62-262852 discloses a silver halide color photographic light-sensitive material with excellent sharpness of dye images by containing a semi-dispersed halide emulsion having an average grain volume of 0.06μ3 or less in the light-sensitive emulsion layer. It is disclosed that this can be obtained.

However, the Society of Motion Picture
and Television Engineers (5ociet)
y of Motion Picture and T
128th Technical Conference (1986, 10°24-29, New York)
As stated by Yura et al. (Print PIk112
8-76), when the grain size of silver halide grains is reduced, the problem of unexpected deviation from the nuclear diameter-sensitivity relationship, that is, desensitization, is encountered. For this reason, there is a serious problem in that not only is the graininess of the photosensitive material not improved, but the graininess is considerably deteriorated.

On the other hand, in recent years, short-time processing services for color printing have become popular, and there is a strong demand for processing stability in color development.

In JP-A-62-262852, the silver halide in the photosensitive silver halide emulsion layer has a silver iodide content of 5 mol% or more, and the processing stability in color development is satisfactory. It wasn't.

[Object 1A of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent processing stability and graininess. The goal is to achieve the following.

[Structure of the invention]

The above object of the present invention is to provide a silver halide color photographic light-sensitive material having a plurality of light-sensitive silver halide emulsion layers on a support. The average grain size of all silver halide grains is 0.5 μm or less, iodine in the average halogen composition is 5 mol % or less, and at least one of the silver halide emulsion layers has a silver iodide content of Silver halide grains composed of two or more different phases, containing silver halide grains with an average silver iodide content higher than the silver iodide content for the outer edge of the grain. This was achieved using a silver halide color photographic light-sensitive material characterized by the following characteristics:

The present invention will be specifically explained below.

The silver halide color photographic light-sensitive material of the present invention has a plurality of light-sensitive silver halide emulsion layers on a support. For example, there are multiple layers with different color sensitivities such as red sensitivity, green sensitivity, blue sensitivity, etc., and another example is a layer with high sensitivity. It refers to a plurality of layers, such as a high-speed layer, a medium-speed layer, and a different-speed layer, which have substantially the same color sensitivity but have a certain photographic sensitivity.

A particularly preferred layer structure in the present invention is a layer structure formed by coating a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer each having 1 to 3 layers with different sensitivities.
! It is suitable for color photographic materials.

In the silver halide color photographic material of the present invention,
The average grain size of all the silver halide grains in all the silver halide emulsion layers constituting the photosensitive H material is 0.5 μm or less. However, the average particle size of the photosensitive material as a whole should be 0.5 μm or less. Preferably, the average particle size is 0.1 to 0.5 μm,
Particularly preferred is 0.2 to 0.45 μm.

In a preferred embodiment of the present invention, the average grain size of each silver halide grain in all the silver halide emulsion layers constituting the light-sensitive material is 0.5 μm or less, and more preferably within the above-mentioned preferred grain size range. However, this is not limited to.

In the silver halide color photographic light-sensitive material of the present invention, the average halogen composition of all the silver halide grains in all the silver halide emulsion layers constituting the light-sensitive material is 5 mol % or less of iodine. Therefore, in this case as well, the iodine content of the entire light-sensitive material may be within this range, and some layers may be outside this range, but it is preferable that each of all the silver halide emulsion layers has this iodine content. . Preferably the iodine content is 0
．． 5 to 4.5 mol%, particularly preferably 1.0 to 3
．． It is 5 mol%. Silver halides other than iodine include:
Preferably, all bromine is, but not limited to,
For example, chlorine may be contained within a range that does not impair the effects of the present invention.

The average silver iodide content of silver halide can be determined by a fluorescent X-ray method.

In the present invention, the average grain size (ma) of the silver halide grains in the silver halide emulsion layer is the arithmetic mean molar ratio Σnixi/Σn
It can be determined by i. Gokoni ni is particle size xi
Represents the frequency of particles in μm.

In the case of spherical silver halide grains, the grain size referred to here means the diameter thereof, and in the case of grains having shapes other than spherical, the diameter when its projected image is converted into a circular image of 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 is assumed to be 1000 or more indiscriminately. ) Next, the photosensitive material of the present invention has at least one of the following:
The layer contains silver halide grains as described below.

That is, silver halide grains are composed of two or more phases having different silver iodide contents, and the average silver iodide content is higher than the silver iodide content for the outer edge of the grain. Contains silver particles.

Hereinafter, such silver halide grains are composed of two or more phases having different silver iodide contents, and the average silver iodide content is higher than the silver iodide content for the outer edge of the grain. High silver halide grains, and halides containing such grains! About emulsions (explain).

In the above halogenated root grains, the fact that the average silver iodide content of the grains is higher than the silver iodide content for the outer edge of the grains can be determined by the following method.

If the silver halide emulsion is a silver halide grain emulsion in which the average value of grain size/grain thickness is less than 5, the average silver iodide content (, Jl) determined by fluorescent X-ray analysis and When comparing the silver iodide content (J2) on the grain surface determined by line photoelectron spectroscopy, the following relationship is satisfied: Jl > J.

The particle size referred to here is the diameter of the circumscribed circle of the surface where the projected area of the particle is maximum.

XI photoelectron spectroscopy and its methods 111 will be explained.

Prior to measurement by X-ray photoelectron spectroscopy, the emulsion is pretreated as follows. First, a pronase solution is added to the emulsion and stirred at 40° C. for 1 hour to decompose gelatin. Next, the emulsion particles are sedimented by centrifugation, and after removing the supernatant, an aqueous pronase solution is added and gelatin decomposition is performed again under the above conditions.

The sample is centrifuged again, the supernatant liquid is removed, and then distilled water is added to redisperse the emulsion particles in the yarn reservoir water, centrifuged, and the supernatant liquid is removed. After repeating this water washing operation three times, the emulsion particles are redispersed in ethanol. This is applied thinly onto a mirror-polished silicon wafer to serve as a measurement sample.

For measurements using the XVA photoelectric photoelectron spectroscopy method, for example, an IEscA/SAM560 model manufactured by PH1 is used as the device, Mg Ka ray is used as the excitation X-ray, X-ray source voltage +5 KV, and X-ray source current 4 Q rn A s bath. This is carried out under the condition of an energy of 50 eV.

To determine the surface halogen composition, Ag3d.

Detect Br5d, 13d3/2 electrons. The composition ratio is calculated by the relative sensitivity coefficient method using the integrated intensity of each peak. By using 5.10.0, 81°4.592 as the Ag5d, Br5d, 13d3/2 relative sensitivity coefficients, respectively, the relative ratio is given in atomic percent as the iit position.

The silver halide emulsion has an average value of grain size/grain I'X of 5
It is preferred that the particle size distribution is monodisperse. A monodisperse silver halide emulsion means that silver halide type ■ contained within a grain size range of 20% centering on the average grain size d accounts for 60% of the total halide root grain weight.
% or more, preferably 70% or more, more preferably 80% or more.

Here, the average particle size d is the frequency n of particles having particle size d.
It is defined as the particle diameter d1 when the product nl x di3 of 1 and di3 is the maximum (3 significant figures, minimum digit is 4f and 5 people).

In the case of spherical silver halide grains, the grain size referred to here means the diameter thereof, and in the case of grains having shapes other than spherical, the diameter when its projected image is converted into a circular image of the same area.

The particle size can be determined, for example, by magnifying the particle 10,000 to 50,000 times with an electron microscope and projecting the image, and then measuring the area of the particle on the print (the number of particles measured). There are 1000 or more 1- indiscriminately).

Particularly preferred highly monodisperse emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less.

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

On the other hand, if the silver halide emulsion is an emulsion containing tabular silver halide with an average value of grain size/grain thickness of 5 or more, the average silver iodide content of the grains is the same as that of silver iodide for the outer edge of the grains. The content is higher than the average silver iodide content (J,) determined by the multi-layered fluorescent X-ray analysis method and the On the other hand, when comparing the average value (J3) of the silver iodide content measured at the northern limit of halogen crystals located more than 80% away from the center, J
, > j, by satisfying the relationship,
You can know.

The X-ray microanalysis method will be explained.

Silver halide particles were dispersed in an electron microscope observation grid equipped with an energy dispersive X-ray analyzer in an electron microscope, and the magnification was set so that one particle entered the Cfil T field of view with liquid nitrogen cooling. , gLa, and rLa ray intensities are integrated. Obtained 11. Based on the intensity ratio of a/A g L a, the silver iodide content can be calculated using a calibration curve prepared in advance.

In tabular silver halide emulsions in which the average value of grain size/grain thickness is 5 or more, the average value of grain size/grain thickness is 6.
It is more preferably 100 or more, and particularly preferably 7 or more and 50 or less.

The average silver iodide content in silver halide grains composed of two or more phases having different silver iodide contents is preferably 0.1 to 7.0 mol%, more preferably 0.5 to 5.
．． 0 mol%, particularly preferably 1.0 to 4.0 mol%.

In a silver halide emulsion having an average value of grain size/grain thickness of less than 5, the silver iodide content (J2) on the grain surface measured by X-ray photoelectron spectroscopy is preferably 6 to 0 mol%, and is particularly preferred. Preferably, it is 4 to 0.01 mol%.

80% from the center of silver halide grains in the grain diameter direction according to the
The average ill constant value (J3) of the silver iodide content measured on the halo:J genation-limited crystals separated by 〜0
It is mol%, particularly preferably 1.0 to 0.01 mol%. The average thickness of the tabular silver halide grains is preferably 0.5 to 0.01 .mu.m, particularly preferably 0.3 to 0.02 .mu.m. The average grain size of the silver halide grains contained in the tabular silver halide emulsion is 0.1 to 1.
0 μm is preferable, more preferably 0.2 to 0.6 μm
It is.

1v- of the aforementioned particle size/particles preferably used in the present invention
Silver halide emulsions having an average density of less than 5 are preferably monodisperse. Moreover, a core/shell type is preferable. The above-mentioned particle size preferably used in the present invention/
A tabular silver halide emulsion having an average grain thickness of 5 or more preferably has silver iodide localized in the center of the grain.

A core/shell type silver halide emulsion with an average value of grain size/grain thickness of less than 5 has a grain structure composed of two or more phases with different silver iodide contents. It consists of silver halide grains in which the phase containing the highest amount of N (referred to as the core) is other than the outermost surface N (referred to as the shell).

The inner phase (core) having the highest silver iodide content may preferably have a silver iodide content of 6 to 40 mol%, more preferably 8 to 30 mol%, particularly preferably 10 to 20 mol%.
It's mole%. The silver iodide content of the outermost layer is preferably less than 6 mol%, more preferably θ to 4.0 mol%.

The ratio of the shell portion of the core/shell type silver halide grains is preferably 10 to 80% by volume, more preferably 1
It is 5 to 70%, particularly preferably 20 to 60%.

In addition, the core portion accounts for 10 to 80% of the entire particle due to deposition.
%, more preferably 20 to 50%.

The content difference between the core portion with a high silver iodide content and the shell portion with a low silver iodide content of the silver halide grains may have a sharp boundary, or may have a continuous change in which the boundary is not necessarily clear. There may be. Further, those having an intermediate phase between the core and the shell having a silver iodide content between the core and the shell are also preferably used.

In the case of the core/shell type silver halide grains having the mesophase, the volume of the mesophase is preferably 5 to 60%, more preferably 20 to 55%, of the total grain. The difference in silver iodide content between the shell and the intermediate phase and between the intermediate phase and the core is preferably 3 mol% or more, and the difference in the silver iodide content between the shell and the core is preferably 6 mol% or more.

The core/shell type silver halide emulsion is preferably silver iodobromide, and its average silver iodide content is preferably 0.1 to 7.0 mol%, more preferably 0.5 to 5.0 mol%. %
The content is particularly preferably 1.0 to 4.0 mol%. Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

The core/shell type silver halide emulsion is disclosed in Japanese Patent Application Laid-Open No. 59-17
No. 7353, No. 60-138538, No. 59-522
No. 38, No. 60-1.13331, No. 60-3572
6 and Go-258536 and the like.

When a core/shell type silver halide emulsion is grown starting from seed grains as in the method described in the Examples of JP-A No. 60-138538, it is possible to have a halogen composition region different from the core in the center of the grain. It's possible.

In such cases, the halogen composition of the seed grains may be of any composition such as silver bromide, silver iodobromide, silver chloroiobromide, silver chlorobromide, silver chloride, etc., but if the silver iodide content is It is preferable that the amount of silver iodobromide or silver bromide is 10 mol % or less.

In addition, the proportion of seed grains in the total silver halide is 50% in the deposition.
% or less, particularly preferably 10% or less.

The distribution state of silver iodide in the L core/shell type silver halide grains can be detected by various physical measurement methods. It can be investigated by low-temperature luminescence measurements and X-ray analysis, such as those used in

The core/shell type silver halide grains may be normal crystals such as cubes, tetradecahedrons, and octahedrons, may be composed of twin crystals, or may be a mixture thereof, but they must be normal crystals. is preferred.

In tabular halide fN emulsions in which the average value of grain size/grain thickness is 5 or more and silver iodide is localized in the center of the grain, the high iodine content phase in the center is 80% of the total volume of
The following is preferable, and <60% to 10% is preferable. The silver iodide content in the center is preferably 5 to 40 mol%, particularly preferably 10 to 30 mol%. The low iodine content phase (periphery) surrounding the high iodine content phase in the center has a silver iodide content of 0 to 0.
Preferably it comprises 4.0 mole percent silver iodobromide, more preferably 0 to 0.3 mole percent.

A tabular silver halide emulsion in which silver iodide is localized at the center can be obtained by a known method as disclosed in JP-A-59-99433.

The silver halide emulsion used in the light-sensitive material of the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

In the present invention, at least a portion of the silver halide grains may contain a desensitizer.

In order to obtain a wide exposure latitude, 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.

These silver halide grains with 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, metal ion doping technology is preferred.

The metal ion used for doping is Cu.

Cd, Zn1Pb, Fe, TI, I? h, Ili, Ir
, Au, Os+Pd, etc., and these metal ions can be used, for example, as halogeno complex salts, etc., and can also be used in combination of two or more types.

Furthermore, the p I+ of the silver halide (silver halide) opaque system during doping is preferably 5 or less.

The doping amount of these metal ions varies depending on the type of metal ion, the particle size of the silver halide grains, the doping position of the metal ion, the desired sensitivity, etc. 10-17~io-”
Moles are preferred, particularly 10-IS to 10-4 moles.

When the metal ion is Rh ion, halogenated 1141
It is preferably used in an amount of 10-'' to 10-2 mol, particularly 10-1 to 10-4 mol.

Furthermore, by selecting the type of metal ion, the doping position, and the doping amount, various different sensitivity qualities can be imparted to the halogenated IN particles.

If the doping amount is less than 1O-2 mol/AgX mol, it will not have a large effect on grain growth, so even if the grain growth conditions are the same, and even if the grains are grown in the same batch, silver halide grains with a narrow grain size distribution can be prepared. can do.

It is also possible to prepare silver halide grains with different doping conditions so that they can be put to practical use, then mix them in a predetermined ratio to form the same batch and apply chemical sensitization. Each silver halide grain receives a sensitizing effect based on its qualities,
An emulsion with a wide latitude can be obtained depending on the sensitivity λ and the mixing ratio.

Furthermore, the silver halide emulsion used in the present invention may contain antifoggants, stabilizers and the like. Gelatin is advantageously used as the dye for the emulsion.

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

A coupler is used in the emulsion layer of a light-sensitive material for color photography. That is, when the present invention is applied to, for example, a full-color color photographic material, generally red-sensitive, green-sensitive, and blue-sensitive halogenated emulsion layers are provided, and each coupler is optionally used to develop a desired color. It can be configured as follows.

In addition, colored couplers that have a color correction effect, competitive couplers, and oxidized forms of developing agents can be combined to form development accelerators, developers, halogen silverable solvents, toning agents,
Compounds that release photographically useful fragments can be used, such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. It is in these layers and/or in the emulsion layer that it flows out of the light-sensitive material during the development process. Alternatively, bleaching dyes may be included.

A formalin scavenger, a fluorescent brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventer, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

The present invention is particularly useful for color negative films, color reversal films, and the like.

Supports include paper laminated with polyethylene, polyethylene terephthalate film, baryta paper,
Any material such as cellulose triacetate can be used.

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

[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 is expressed in grams per d unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

Example 1 On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic element sample-1.

Sample-1 (comparison) 1st layer: antihalation layer (HC-1) black colloidal silver 0.20 UV absorber (tJV-1
) 0.20 high boiling point solvent (OiI!-1)
0.20 gelatin 1
．． 5 Second layer; Intermediate layer (IL-1) UV absorber (UV-1) 0.01 High boiling point solvent (Oil-1) 0.01 Gelatin
l・5 3rd layer: Low sensitivity red sensitivity 7L
Agent layer (RL) Silver iodobromide emulsion (Em-1) 0.
6 silver iodobromide emulsion (Em-2) 0.2 sensitizing dye (SD-1) 2.2X104 (mol/1 mole) Sensitizing dye (SD-2>2.2xlO-' (mol/silver) 1 mol) Sensitizing dye (SD-3) 0.44 xlO-' (mol/S x 1 mol) Cyan coupler (C-1) 0.65 Colored cyan coupler (CC-1,) 0.06 1) IR Compound (D-1) 0.004 High boiling point solvent (Oll-1) 0.6 Gelatin
1.5 Fourth layer; High sensitivity red-sensitive emulsion layer (R1-1) Silver iodobromide emulsion (Em-3) 0.
8 Sensitizing dye (SD-1) 1.9xlO-' (mol/silver 1 mol) Sensitizing dye (SD-2) 1.9xlO-' (mol/silver 1 mol) Sensitizing dye (SD-3) O, lxl, O'□4 (mol/l
If! 1 mol) Cyan coupler (C-2> 0.16 Cyan coupler (C-3) 0.02 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2,) 0.007 High boiling point solvent (O41 -1) 0.2 gelatin
1.3 5th layer; middle layer (rL-2
) Gelatin 0.7 6th layer: Low-range green-sensitive emulsion rrIJ (GL) Silver iodobromide emulsion (Em-1
) 0.6 sensitizing dye (50-4)4. ,lXl
0-' (mol/silver 1 mol) Sensitizing dye (SD-5) 0.9XIO-' (mol/silver 1
mole) Magenta coupler (M-1) 0.1 Magenta coupler (M-2) 0.2 Colored magenta coupler (CM-1) 0゜1 DIR compound (Il-3) 0.02DIR
Compound (D-4> 0.00,1 High boiling point solvent (Oil-2) 0.3 Gelatin
1.0 7th J Tsuba; Highly sensitive green-sensitive emulsion layer (G
11) Silver iodobromide emulsion (Em-3) 0.7 sensitizing dye (SD-[3) 1.5X10-' (mol/i 1 mol) Sensitizing dye (SD-7) 2.5X10-' (mol/!艮1
mol) Sensitizing dye (SD-8) 0.55 xlO-' (mol/silver J mol) Magenta coupler (M-2) 0.09 Colored magenta coupler (CM-2) 0.04 D[R compound (D -3) 0.006 high boiling point solvent (Oi7!-2) 0.5 gelatin
1.0 8th layer; yellow filter layer (YC) yellow colloidal silver 0.1
Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Oil-3) 0.1 Gelatin
0.8 9th layer: low-speed blue-sensitive emulsion layer (BI-
) Silver iodobromide emulsion (FEm-1) 0.25 Silver iodobromide emulsion (Em-2) 0.10 Sensitizing dye (S
D-10) 0.6xiO-3 (mol/mol of silver) Yellow coupler (Y~1) 0.5 Yellow coupler (Y~2) 0. IDIR compound (D-2
) 0. Former high boiling point solvent Co11-3)
0.3 Gelatin 1.0 10th layer; Highly sensitive blue-sensitive emulsion layer (B11) Silver iodobromide emulsion (
Em-3) 0.3 silver iodobromide emulsion (Em-1>
0.1 Sensitizing dye (SD-9) IXIO-' (7 l/1 mol) Sensitizing dye (SD-10) 3XIO bow (mol/S 1 mol) Yellow coupler (Y'-1) 0 .30 yellow coupler (Y-2>0.05 high boiling point) medium (
Oi 1-3) 0.07 gelatin
1.1 First I layer; first protective layer (+) Ro
-1) Fine grain silver iodobromide emulsion (average grain size 0.08 pmAg 12 mol%) 0.2 UV
Absorbent (UV-1) 0.10 (J V absorber (UV-2) 0.05 High boiling point solvent (Oi
l-1) 0.1 high boiling point solvent (Oi n-4)
0.1 formalin scavenger (IIs-
1) 0.5 Formalin scavenger (Its-2>0.2 Gelatin 1.0 12th layer; 2nd protective layer (PRO-2) Surfactant (S[J-1,) 0.005 Alkali-soluble Matting agent (average particle size 2 μm) 0.05 Polymethyl methacrylate (average particle size 3 μm) 0.05 Slip agent (WAX-1) 0.04 Gelatin 0.5 In addition to the above composition, each layer contains a coating aid. 5u-2, min 1 & auxiliary 5u-3 and 5u-
4. Hardener H-1°H-2, Stabilizer 5T-1, Antifoggant ΔF-1, Aperture: 10. OOO and animals: 1,100
,000 of two types of A I"2 were added.

The emulsion used in the above sample is as follows.

Em-1 Average particle size 0.56 μm.

Average silver iodide content 7.0 mol%.

Monodisperse (width of distribution 18%) outer edge core/shell type silver iodobromide emulsion Em-2 with silver iodide content of 2 mol % Average grain size 0.30 μm.

5D-1 Average silver iodide content 2.0 mol%.

m dispersibility (Width of distribution 1 8%) Iodization for the outer edge of Core/shell silver iodobromide emulsion with a silver content of 0.5 mol% D m Average particle size 0.90 μm.

Average silver iodide content 7.0 mol%.

medium dispersity Width of distribution 1 6%) Iodization for the outer edge of Core/shell type silver iodobromide emulsion D with silver content of 1.0% Also, The compounds used in the above samples are: As below It is.

D D (CHI)3SO1e (Cllz) zsOJa D (Czlls) Jll's M CM ■] NO□ Shi4114 (L) C□tl 5 Su-1 C1]1 , (L) Next, in sample 1, each emulsion Samples 2 to 7 were prepared by changing the emulsions of the layers as shown in Table 1.

In Table-1, emulsions Cm-4 to [Em-17 are Table-2
This is shown below. Moreover, Ma is the average grain size of the emulsion used.

However, each emulsion Em-1 to En-17 was used after being optimally chemically sensitized with hypo, chloroauric acid, and ammonium thiocyanate.

In addition, in samples 3 to 7, sensitizing dye 5D in each emulsion layer
-1 to 5D-10 were all added in an amount of 55% of Sample-1.

After each sample No. 1 to 7 prepared in this manner was wedge exposed using white light, the following development treatment was performed.

Processing process (38℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes I 5 seconds Fixation
Washing with water for 6 minutes and 30 seconds Stabilization 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 4.25g 2.0g 37.58 Anhydrous sodium sulfite hydroxyamine 1 /2 sulfate anhydrous potassium carbonate sodium bromide 1. ．． 3g Nitrilotriacetic acid/3sodium J1 salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 11rz. (p IT = IO, 1) Bleach solution〉 Edge range °? Iron (Il+) ammonium mintetraacetate,
Salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid
Add 1.0 ml water to bring the volume to 11, and adjust to pl (~6.0) using ammonium water.

Fixer> Ammonium thiosulfate i75.0g Anhydrous sulfite 8.5g Sodium metasulfite 2.3g Add water and
and pl! using acetic acid! Adjust by Δ to =6.0.

<Stabilizing solution> Formalin (37% aqueous solution) 1,5-Konidasox (manufactured by Konica Corporation) 1.5Al water was added to make 11.

Graininess was evaluated by RMS value, and as a method of measuring RMS value, the part of 0.5 above the minimum density of green density was measured using Sakura Microdensitometer Model PDM-5 Type 8R (Konica Co., Ltd.). - 250 μm in diameter
The standard deviation of the density value fluctuation when measuring Sample 2 was determined and expressed as a relative value with the RMS graininess of each color-sensitive layer of Sample 1 as 100.

The results are shown in Table-3.

Table-;( Can be seen.

However, in the system of the present invention with an average particle size of 0.5 μm or less,
A remarkable effect of improving graininess was observed when the amount was less than mol %.

Example 2 The sample grades 1 to 7 used in Example 1 were evaluated in the same manner as in Example 1, but the p11 of the color developer was changed from IO1■ to ±O62, and the sensitometric curve was The gamma variation value was set at 4 (4), and processing stability was evaluated.

The results are shown in Table-4.

The result is gamma when p + ( is l013 and p 11
It is expressed as the ratio of gamma when is 9°9. The smaller this value is, the smaller the fluctuation is.

As can be seen from Table 3, when a core/shell emulsion is used and the average grain size exceeds 0.5 μm, the graininess deteriorates when the silver iodide content is less than 5 moles. A similar improvement effect was observed in the gamma variation.

〔Effect of the invention〕

As described above, according to the present invention, a silver halide color photographic light-sensitive material having excellent processing stability and graininess can be provided.

Claims (1)

[Scope of Claims] 1. In a silver halide color photographic light-sensitive material having a plurality of light-sensitive silver halide emulsion layers on a support, the light-sensitive silver halide emulsion layer constituting the silver halide color photographic light-sensitive material; The average grain size of all silver halide grains is 0
．． 5 μm or less, iodine in the average halogen composition is 5 mol % or less, and at least one layer of the silver halide emulsion layer is composed of two or more phases having different silver iodide contents. 1. A silver halide color photographic material comprising silver halide grains having an average silver iodide content higher than the silver iodide content of the outer edge phase of the grains.