JPH0876327A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a color negative photograph capable of obtaining a print high in image quality even in the case of a comparatively long time lapse from the manufacture of the photosensitive material to the development after exposure and even in the case of being photographed under high illumination, such as electronic flash. CONSTITUTION: The silver halide color photographic sensitive material has at least one of each of red-, green-, and blue-sensitive layers on a support, and it has a stability parameter (μ) of <=0.7 a linearity parameter (j) satisfying the condition: j=1.00±0.01 with respect to at least one curve.

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 light-sensitive material, and more particularly to a color negative light-sensitive photographic material for photography, which is excellent in stability over time and has good results against high illumination failure. It relates to a photosensitive material.

[0002]

2. Description of the Related Art In recent years, performance requirements for silver halide light-sensitive materials for photography have become more and more severe, and higher standard requirements have arisen for basic photographic characteristics such as sensitivity, fog and graininess. ing. Particularly in recent years, with the spread of compact zoom cameras and lens-equipped films generally called disposable cameras, high sensitivity has become an essential requirement for photographic light-sensitive materials. In addition, the higher functionality of the camera has made it easier for general users to make full use of various shooting techniques, and there is a strong demand for sensitivity and gradation reproducibility under all exposure conditions.

When the silver halide photographic light-sensitive material is exposed for a short time with a high illuminance and for a long time with a low illuminance, the obtained image density rarely becomes constant even if the exposure amount is the same. Such a change in sensitivity and gradation depending on exposure illuminance is called reciprocity law failure. With respect to the optimum exposure conditions, reciprocity failure when exposed to high illuminance is called high illumination failure, and reciprocity failure when exposed to low illumination is called low illumination failure.

In a photosensitive material having a large reciprocity law failure, the exposure time must be corrected according to the illuminance and the light source.
When the reciprocity law failure of each layer is different in the multilayer color light-sensitive material, color deviation appears in the image obtained by the exposure time. Especially in high illumination failure, for example, when shooting with a flash,
It is thought to occur frequently.

In order to improve such reciprocity law failure characteristics, various improvement techniques have been developed for silver halide photosensitive materials. As a conventional technique for improving the reciprocity law failure in a silver halide emulsion, a method of mainly doping a silver halide grain with a metal ion (mainly, Group 8 of the periodic table) is adopted. Regarding these technical contents, see Japanese Patent Laid-Open No. 2-
20852, 2-20853, 2-20854, 2-20855, and
It is disclosed in patents such as 3-118535 and 3-118536. Furthermore, as a configuration combining these technologies, Japanese Patent Laid-Open No.
There are disclosures in 21844, 2-156239, 2-234151, 2-20852, etc.

However, although these techniques are effective in improving illuminance failure, they have a problem that storage stability deteriorates.
There is a dilemma that if the doping amount of metal ions is reduced to such a range that the storage stability is not harmful, the original effect of improving illuminance failure is lost.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color negative photographic light-sensitive material having a high print yield at a developing station to provide end users with high quality color prints.

In particular, the print yield does not decrease even when the period from the end of the production of the light-sensitive material to the end of photography and development takes a relatively long time, or even when the photograph is taken under high illuminance. It is to provide a silver halide color negative photograph capable of obtaining a high-quality print.

[0009]

The objects of the present invention have been achieved by the following. That is, in a silver halide color photographic light-sensitive material having at least one red light-sensitive layer, green light-sensitive layer, and blue light-sensitive layer on a support, the stability parameter (μ) is 0.07 or less, A silver halide color photographic light-sensitive material having a linearity parameter (j) satisfying the following conditions.

J = 1.00 ± 0.01 Preferably, the silver halide color photographic light-sensitive material comprises a support having at least two red light-sensitive layers, a green light-sensitive layer and a blue light-sensitive layer. It is a silver color photographic light-sensitive material, and at least one emulsion layer which is not the highest light-sensitive layer of any color light-sensitive layer contains a silver halide emulsion having polyvalent metal ions inside the grains. A silver halide color photographic light-sensitive material characterized by:

The present invention will be described in detail below.

The stability parameter (μ) is determined by the following method.

That is, in a silver halide color photographic light-sensitive material having at least one red light-sensitive layer, green light-sensitive layer and blue light-sensitive layer on a support, the light-sensitive material is processed by the following treatment (1). It is defined by the following between a case (a) in which the development is performed after sequentially passing through (3) to a case (b) in which the development is performed through only the processing (4).

Treatment process (1) Pre-exposure storage 3 weeks at 45 ° C, 40% RH environment (2) Exposure I Shutter speed 10 ^-4 sec Light source with correlated color temperature 5500K, optical wedge (3) Storage after exposure 40 (4) Exposure II Shutter speed 1 / 200sec, Light source with correlated color temperature of 5500K, using optical wedges Magenta color density function curve D- (logE) obtained through the process of (b) above ) Is more than ΔlogE = 2.5 than the exposure dose logE0 that gives the minimum density Dmin [M] +0.15
In the range up to logE5, the density Dbi (i = 0,1,1) at the exposure dose point logEi (i = 0,1,2,3,4,5) taken every ΔlogE = 0.5 unit
2,3,4,5) and the density Dai (i = 0,1,2, i) of the D- (logE) curve obtained through the process of (a) at the same exposure dose point.
(3,4,5) difference for three colors (yellow, magenta, cyan), and a three-dimensional vector at the exposure amount point i that has these three components

[0015]

[Equation 1]

Assume that

At this time,

[0018]

[Equation 2]

The maximum value of the above μ0 to μ4 is defined as the value of the stability parameter μ of the silver halide color photographic light-sensitive material. In the present invention, the photosensitive material to be treated in both cases of the processing step (a) and the processing step (b) is obtained after the coating → drying → aging step is completed. However, when using a rapid-acting hardener as disclosed in, for example, Japanese Patent Laid-Open No. 5-292224, the unexposed room temperature and normal humidity conditions (after the application → drying step) The elapsed period is within 3 months.

Further, (a) and (b) undergo the same steps,
Also, the same period shall be used within the specified range for the elapsed time at room temperature and normal humidity.

Storage, exposure, development and density measurement in the present invention are carried out according to the following methods (partly JI).
According to SK7614-1981).

<1> Pre-exposure storage Stored at 45 ° C. and 40% RH for 3 weeks. However, the photosensitive material is previously cut into a size that allows exposure using an optical wedge.

<2> Exposure-1--The exposure test is carried out at a temperature of 20 ± 5 ° C. and a room temperature of 60 ± 10% RH, and the photosensitive material to be tested is left in this state for 1 hour or more before use.

(2) The relative spectral energy distribution of the reference light on the exposed surface is as shown below.

[0025]

[Table 1]

-3-Changes in illuminance on the exposed surface are performed using an optical wedge, and the optical wedge used has a spectral transmission density variation of 10% or less within 400 nm in a wavelength range of 360 to 700 nm, 400 nm in any portion. The above area should be within 5%.

<3> Storage after exposure Storage at 40 ° C. and 20% RH for 4 weeks.

<4> Development Processing During the process from (b) exposure to the development process, and (a) from the post-exposure storage to the development process. Temperature of the photosensitive material
Keep at ± 5 ° C and 60 ± 10% RH.

The development treatment is completed within 30 minutes to 6 hours after exposure when the processing step (b) is performed, and 30 minutes to 6 hours after the end of storage after exposure when the processing step (a) is performed. To complete.

Development Processing C-41 processing by Eastman Kodak Company is performed.

<5> Concentration measurement Concentration is expressed by log ₁₀ (Φ ₀ / Φ). Φ ₀ is an illumination light flux for density measurement, and Φ is a transmitted light flux of the measured portion. The geometric condition for density measurement is that the illumination light flux is a parallel light flux in the normal direction, and the standard is to use the total light flux that is transmitted as a transmitted light flux and diffused in a half space, and standard when other measurement methods are used. Correct with density strips. During the measurement, the emulsion film surface should be faced to the light receiving device side. Density is measured with blue, green, and red status M densities, and its spectral characteristics are as shown in Tables 2 and 3 as the overall characteristics of the light source, optical system, optical filter, and light receiving device used for the thermometer. To do.

[0032]

[Table 2]

[0033]

[Table 3]

The yellow, magenta and cyan densities obtained by storing, exposing and developing as described above and measuring the densities were plotted against the common logarithm (logE) of the exposure amount, and the density function curve D- (logE ) Is measured.

The present invention is characterized in that the stability parameter μ obtained by the following procedure is set, and the value of μ satisfies the following equation.

Μ ≦ 0.07 The effect of the present invention can be obtained by setting the value of the stability parameter μ thus obtained to 0.07 or less.
A more preferable range of stability parameter μ is 0.01 ≦ μ ≦ 0.
05.

The values of the stability parameter μ are (a) and (b)
The density function curve in the process of 1 has the same density for each of the three colors at the exposure amount points of i = 0 to 5, or 3 for each exposure amount point.
Although it is 0 when the colors change in the same way, it is technically extremely difficult to achieve a value of μ = 0, while if the value of μ is 0.05 or less, the color print The same level of results can be obtained regardless of the value of μ.

The linearity parameter j of the present invention will be described.

The density function curves D- (log of three colors of yellow, magenta, and cyan obtained through the process of (b) above.
In E), g (i) and h are calculated from the following formula, and this g
A ratio j (i) between (i) and h is obtained.

[0040]

(Equation 3)

A value farthest apart from 1 among the above j0 to j4 is defined as a linearity parameter j.

Further, the density function curve within the range defined by the following equation is preferably a magenta color density density function curve, and more preferably, each of the color density density function curves of magenta and cyan is satisfied. Most preferably, it is true for the color density function curves for all three colors of yellow, magenta, and cyan.

To prepare a light-sensitive material satisfying the above formula, for example, a plurality of emulsion layers are provided in a light-sensitive layer of the same color, or the grain size of silver halide grains to be used is appropriately selected. It can be obtained by adjusting the coating silver amount and the coupler addition amount in each of the plurality of emulsion layers in the same color light-sensitive layer or by incorporating a diffusible DIR compound in another light-sensitive layer.

The silver halide color photographic light-sensitive material of the present invention described in claim 1 can be achieved, for example, by the following technique. That is, a silver halide having at least one emulsion layer containing a reduction-sensitized emulsion inside the grain and at least one emulsion layer containing no reduction-sensitized emulsion inside the grain. It is a color photographic light-sensitive material. Here, the emulsion layer containing a reduction-sensitized emulsion may mean that the emulsion layer may contain an emulsion consisting of grains that are reduction-sensitized inside the grains and an emulsion that is not. It means that the coated silver amount of the former emulsion is 5% or more of the total coated silver amount of the emulsion layer.

When silver iodobromide grains are used as the silver halide emulsion, the difference in average iodide content between the red light sensitive emulsion layer, the green light sensitive emulsion layer and the blue light sensitive emulsion layer is 2 mol. % Is also effective in achieving the condition of claim 1.

The reduction sensitization is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth. Alternatively, a silver halide emulsion or a mixed solution for grain growth may be used under a low pAg of pAg 7 or less, or p
It is carried out by aging or grain growth under a high pH condition of H7 or higher. A method in which these methods are combined is a preferred embodiment in the present invention.

Preferred reducing agents used for reduction sensitization of the silver halide grains used in the present invention are thiourea dioxide, ascorbic acid and its derivatives, and stannous salt. Other suitable reducing agents include borane compounds, hydrazine derivatives, formamidinesulfinic acid,
Examples thereof include silane compounds, amines and polyamines, and sulfites. The addition amount is 10 per mol of silver halide.
^It is preferably ^-2 to 10 ^-8 mol.

A silver salt may be added for low pAg ripening, but a water-soluble silver salt is preferred, and silver nitrate is preferred as the water-soluble silver salt. The pAg during aging is suitably 7 or less, preferably 6 or less, more preferably 1 to 3
(Where pAg = −log [Ag ⁺ ]).

High pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As an alkaline compound,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia or the like can be used. In the method of adding ammoniacal silver nitrate for silver halide formation, an alkaline compound excluding ammonia is preferably used because the effect of ammonia decreases.

As a method for adding the silver salt or alkaline compound for reduction sensitization, rush addition may be performed, or addition may be performed over a certain period of time. In this case, the flow rate may be added at a constant flow rate, or the flow rate may be changed like a function. Also, the required amount may be added in several divided portions. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, they may be present in the reaction vessel, or they may be mixed in the soluble halide solution and added together with the halide. Furthermore, the addition may be performed separately from the soluble silver salt and the soluble halide.

In the production of the reduction-sensitized silver halide emulsion used in the present invention, when a form in which crystals are grown from seed grains is used, low pAg ripening is carried out after formation of the seed emulsion.
That is, it is preferable to add silver nitrate during the steps from immediately before desalting of the seed particles to after the desalting for ripening. In particular, it is preferable to add silver nitrate after the desalting of the seed particles for aging,
The aging temperature is 40 ° C or higher, preferably 50 ° C to 80 ° C. The aging time is preferably 30 minutes or more and 50 to 150 minutes.

In the form grown from seed particles, high p
When H aging is performed, the volume of the grains after growth is
It is necessary to grow the particles through the environment of pH 7 or more at least once before the portion corresponding to 70% grows, and the pH 7 is reached until the portion corresponding to 50% of the volume of the grown grains grows. It is more preferable to grow the particles through the above environment at least once, and the pH should be adjusted to 8% by the time the portion corresponding to 40% of the volume of the grown particles grows.
It is particularly preferable to grow the particles through the above environment at least once.

An oxidizing agent can be used in the reduction-sensitized silver halide emulsion used in the present invention. The following can be used as the oxidizing agent. For example, hydrogen peroxide (water) and an adduct _{thereof: H 2 O 2, NaBO 2} , H 2 O 2 -3H 2
O ₂ , Na ₄ P ₂ O ₇ −2H ₂ O ₂ , 2Na ₂ SO ₄ −H ₂ O ₂ −2H ₂ O, etc. Peroxy acid salt: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K ₄ P ₂ O ₃ , K ₂ [Ti (O ₂ ) C ₂ O ₄ ].
-3H ₂ O. Examples thereof include peracetic acid, ozone, iodine, bromine and thiosulfonic acid compounds.

The addition amount of the oxidizing agent used in the emulsion is influenced by the type of the reducing agent, the reduction sensitizing condition, the addition timing of the oxidizing agent, and the adding condition, but it is 10 ⁻ per mol of the reducing agent used. ^{2-10 -5} mol are preferred.

The oxidizing agent may be added at any time during the silver halide emulsion manufacturing process. It can also be added prior to the addition of the reducing agent.

The position where the silver halide grains according to the present invention are subjected to reduction sensitization may be inside the grains, and preferably, the substantial growth of silver halide is 50 in terms of silver halide amount.
%, Reduction sensitization is preferably carried out before the completion of the process, and the time point when substantial growth is started is more preferred.

Here, the inside of the particle means 50 from the outermost surface of the particle.
Refers to the part excluding Å.

In the present invention, the silver halide amount of 50% means a protective colloid in which the silver halide grains are grown during the period from the start to the end of the substantial growth of the silver halide grains in the present invention. It refers to 50% of the total amount of silver halide formed in the aqueous solution containing it.

In a more preferred embodiment of the silver halide color photographic light-sensitive material described in the present invention, at least one emulsion layer is used as a dispersion medium in the substantial growth process of silver halide grains. The gelatin contained contains silver halide grains having an adenine content of 0.2 ppm or less.

In the present invention, the method for measuring the amount of adenine per 1 g of gelatin is the photographic gelatin test method (photographic gelatin test method joint study council, 7th edition, items 19, 27 to 28).
The adenine content in gelatin can be quantified by using the method described in detail herein also for the gelatin according to the present invention.

Regarding the gelatin according to the present invention, the adenine content may be 0.2 ppm or less, preferably 0.1 ppm or less, more preferably 0.05 ppm or less.

The gelatin according to the present invention is used as a dispersion medium during the substantial grain growth described above in order to effectively bring out the effects of the present invention, and is also used during nucleation. May be.

It is generally known in the art that an aqueous gelatin solution is added to a desalted emulsion, and the mixture is stirred and dispersed at a certain temperature for several tens of minutes and then distilled water is added to once finish the emulsion. However, it is most preferable to use the gelatin according to the present invention as the gelatin in this gelatin aqueous solution and to use it as a dispersion medium during the above-described substantial growth.

The gelatin according to the present invention may be used alone or in combination of two or more. When combining two or more kinds of gelatin, the amount of adenine in gelatin does not refer to the amount of individual adenine to be combined, but refers to the content of adenine in the whole combined gelatin.

The silver halide color photographic light-sensitive material of the present invention preferably has a red-sensitive layer containing a cyan coupler, a green-sensitive layer containing a magenta coupler, and a blue-sensitive layer containing a yellow coupler. Further, each of these photosensitive layers is preferably two or more layers.

The silver halide color light-sensitive material preferably contains the above-mentioned metal compound inside the grains of at least one emulsion layer which is not the highest sensitivity layer among the color sensitivities.

The stacking order of the photosensitive layers is not particularly limited,
Various stacking orders can be taken according to the purpose. For example, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer can be laminated in this order from the support side, and conversely, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer can be laminated in that order from the support side. can do.

The photosensitive layers having different color sensitivities may be sandwiched between two photosensitive layers having the same color sensitivity. Further, for the purpose of improving color reproduction, in addition to the three layers of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer, a fourth or more photosensitive layer having a color sensitivity can be provided. Regarding the layer structure using a fourth or more color-sensitive photosensitive layer, JP-A Nos. 61-34541, 61-201245 and 61-198236,
No. 62-160448, which can be referred to.

In this case, the fourth or more color-sensitive photosensitive layers may be arranged at any laminating position. Further, the fourth or more color-sensitive photosensitive layer may be composed of a single layer or a plurality of layers.

Various non-photosensitive layers may be provided between the above-mentioned photosensitive layers and as the uppermost layer and the lowermost layer.

For these non-photosensitive layers, JP-A-61-43748 is used.
Issue 59-113438, Issue 59-113440, Issue 61-20037, Issue
Couplers such as those described in 61-20038, DI
The R compound and the like may be contained, and a color mixing inhibitor may be contained as is commonly used. Further, these non-photosensitive layers may be auxiliary layers such as a filter layer and an intermediate layer described in RD308119, page VII, item VII-K.

Examples of the layer structure which the light-sensitive material of the present invention can have include the normal layer, the reverse layer and the unit structure described in RD308119, page 1002, item VII-K.

When there are two photosensitive layers having the same color sensitivity, these photosensitive layers may be the same, and
High-sensitivity emulsion layer as described in West German Patent 923,045,
It may have a double-layer structure of a low-sensitivity emulsion layer. In this case, it is usually preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each emulsion layer. In addition, JP-A-57-112751 and 6
2-200350, 62-206541, 62-206543, etc. with a low-sensitivity emulsion layer on the side farther from the support and a high-sensitivity emulsion layer on the side closer to the support. Good.

As a specific example, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitive layer (GH) / low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or B
H / BL / GL / GH / RH / RL order or BH /
Installation in the order of BL / GH / GL / RL / RH can be mentioned.

As described in JP-B-55-34932, the blue-sensitive layer / GH / from the side farthest from the support.
It can also be arranged in the order of RH / GL / RL. Further, as described in JP-A-56-25738 and JP-A-62-63936, from the side farthest from the support, the blue-sensitive layer / GL / RL is used.
It can also be arranged in the order of / GH / RH.

Further, as described in JP-B-49-15495, three photosensitive layers having different sensitivities and having the same color sensitivity are provided.
Layers can be used. These three layers are arranged with a high-sensitivity silver halide emulsion layer as an upper layer, a middle-sensitivity silver halide emulsion layer as an intermediate layer, and a low-sensitivity silver halide emulsion layer as a lower layer.
Further, as described in JP-A-59-202464, a medium-sensitivity silver halide emulsion layer, a high-sensitivity silver halide emulsion layer, a low-sensitivity silver halide emulsion from the side remote from the support. You may arrange | position in order of a layer.

When three layers having different sensitivities are formed, the order of laminating these three layers is arbitrary. For example, the order of laminating is a high-sensitivity silver halide emulsion layer and a low-sensitivity silver halide. An emulsion layer and a medium-sensitivity silver halide emulsion layer are in this order, or a low-sensitivity silver halide emulsion layer, a medium-sensitivity silver halide emulsion layer, a high-sensitivity silver halide emulsion layer and the like. Further, the number of photosensitive layers having the same color sensitivity can be four or more. Also in this case, the arrangement is arbitrary as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each light-sensitive material.

The silver halide emulsion used in the present invention is, for example, Research Disclosure (RD) No. 17643, 22.
Pp. 23 (December 1978) "I. Emulsion prepara
tionand types) ”, and the same (RD) No.18716, 648
Page, Grafkid's "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkides, Chemic et Phishique Photogr)
aphique, Paul Motel, 1967), "Photoemulsion chemistry" by Duffin, published by Focal Press (GF Duffin, Phot)
ographic Emulsion Chemistry Focal Press 1966),
"Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (V, L. Zelikman et al, Making and Coa
ting Photographic Emulsion, FocalPress, 1964)
And the like.

Emulsions are US Pat. Nos. 3,574,628 and 3,665,394.
Monodisperse emulsions described in U.S. Pat.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may contain various photographic additives in the steps before and after physical ripening or chemical ripening.

Examples of the compound used in such a step include (RD) No. 17643, No. 18716, and No. 18716 described above.
Various compounds described in No. 308119 can be used. The types and locations of the compounds described in these three (RD) are listed below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, Item J 23-24 648-9 Supersensitizer 996 IV-AE, Item J 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Color turbidity inhibitor 1002 Item VII-I 25 650 Dye image stabilizer 1001 Item VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIIIC, XIII-C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matt agent 1007 XVI developer (included in photosensitive material) 1011 XXB The photosensitive material of the present invention is described in U.S. Pat. Nos. 4,411,987 and 4,435,503 in order to prevent deterioration of photographic performance due to formaldehyde gas. Reacts with the formaldehyde, it is preferable to add a compound capable of immobilizing the photosensitive material.

The chemical ripening of the emulsion according to the present invention can be carried out in the presence of adenine.

The silver halide emulsion according to the present invention preferably contains silver iodobromide having an average silver iodide content of 4 to 20 mol%, and the average silver iodide content of 5 to 15 mol%. It is particularly preferable to contain silver iodobromide. The silver halide emulsion according to the present invention may contain silver chloride within the range not impairing the object of the present invention.

In the present invention, when the other silver halide emulsion is used together with the silver halide emulsion containing the silver halide grains formed by deviating the development starting point to the specific portion on the surface of the silver halide grain and the vicinity thereof, Those silver halide emulsions include those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal forms such as spheres and plates, and crystals such as twin planes. It may have defects or a composite form thereof.

The grain size of silver halide grains other than those mentioned above is about 10 μm even if the grain size is about 0.2 μm or less.
It may be a large size grain up to the above, and may be a polydisperse emulsion or a monodisperse emulsion.

Various color couplers can be used in the silver halide color light-sensitive material of the present invention.

Examples of yellow couplers include US Pat. Nos. 3,933,051, 4,022,620, 4,326,024 and 4,4.
Those described in 01,752, 4,248,961, Japanese Patent Publication No. 58-10739, British Patents 1,425,020, 4,314,023, 4,511,649, European Patent 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat.
4,310,619, 4,351,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, (RD) 24220 (198
June 4), JP-A-60-33552, (RD) No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-35730.
No. 55-118034, No. 60-185951, U.S. Pat.
0, 4,540,654, 4,556,630, International Publication WO88 /
Those described in No. 04795 and the like are particularly preferred.

Examples of cyan couplers include known phenol-type and naphthol-type couplers in combination with the couplers of the present invention. Examples thereof include US Pat.
4,296,200, 2,369,929, 2,810,171, 2,77
2,162, 2,895,826, 3,772,002, 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication 3,32
9,729, European Patents 121,365A, 249,453A, US Patents 3,446,622, 4,333,999, 4,775,616, and
4,451,559, 4,427,767, 4,690,889, 4,25
Those described in 4,212, 4,296,199 and JP-A-61-242658 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are disclosed in US Pat. No. 4,163,670, Japanese Patent Publication No. 57-39.
Those described in 413, US Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368 are preferable. US patent
A coupler that corrects unnecessary absorption of a coloring dye by the fluorescent dye released at the time of coupling described in 4,744,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 which has a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,570.
Those described in Japanese Patent No. 3, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are US Pat. Nos. 3,451,820, 4,080,211 and 4,367,28.
No. 2, 4,409,320, 4,576,910, British patent 2,102,1
No. 73 etc.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention.

As a coupler which releases a nucleating agent or a development accelerator imagewise upon development, there are described in British Patent 2,097,140.
No. 2,131,188, JP-A-59-157638, and 59-170840.
Those described in No. 10 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427, US Pat. Nos. 4,283,472, and 4,338,393.
No. 4,310,618, multi-equivalent couplers, JP-A-60-
185950, DIR redox compound releasing couplers described in JP-A-62-24252, DIR coupler releasing couplers,
DIR coupler-releasing redox compound or DIR
Redox-releasing redox compounds, European patent 173,302A
, A coupler which releases a multicolored dye after separation,
(RD) Nos. 11449 and 24241, bleach accelerator releasing couplers described in JP-A-61-2201247, ligand releasing couplers described in U.S. Pat. No. 4,553,477, leuco disclosed in JP-A-63-75747. Examples thereof include couplers that release dyes.

Further, various couplers can be used in the present invention, and specific examples thereof are described in (RD) 17643 and (RD) 308119 below. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII C-G item Magenta coupler 1001 VII-D item VII C-G item Colored coupler 1002 VII-G item VII G item DIR Coupler 1001 VII-F VII F BAR coupler 1002 VII-F Other useful residues 1001 VII-F Release coupler Alkali-soluble coupler 1001 VII-E Additives used in the present invention are described in RD308119XIV. It can be added by a dispersion method.

Any support can be used as the support in the silver halide color light-sensitive material of the present invention. In the case of a transparent support, a dye is contained in this photographic support for the purpose of preventing a light piping phenomenon (edge fogging) that occurs when light enters the transparent support coated with a photographic emulsion layer from the edge. Preferably.

The thickness of the transparent support is not particularly limited, but is usually 120 μm or less, preferably 40 to 120 μm, more preferably 50 to 110 μm.

If necessary, a surface activation treatment such as corona discharge and / or a subbing layer may be applied to the surface of the transparent support on which the photographic constituent layer is formed, prior to the formation of the photographic constituent layer. it can.

When the silver halide color light-sensitive material of the present invention is used in the form of a roll, it is preferable that it is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, the cartridges proposed in the following patents can also be used.

No. 58-67329, JP-A-58-181035,
JP-A-58-182634, JP-A-58-195236, U.S. Pat.
1,479, Japanese Patent Application 63-57785, Japanese Patent Application 63-183344, Japanese Patent Application 63-325638, Japanese Patent Application 1-25362, Japanese Patent Application 1-21862,
Japanese Patent Application No. 1-30246, Japanese Patent Application No. 1-20222, Japanese Patent Application No. 1-21863
Japanese Patent Application No. 1-38171, Japanese Patent Application No. 1-33108, Japanese Patent Application No. 1-8519
No. 8, Japanese Patent Application No. 1-172595, Japanese Patent Application No. 1-172594, Japanese Patent Application No. 1-1
72593, U.S. Patent 4,846,418, U.S. Patent 4,848,693
U.S. Pat. No. 4,832,275.

In order to obtain a dye image using the silver halide color light-sensitive material of the present invention, a generally known color development process can be carried out after exposure. The silver halide color light-sensitive material of the present invention is described in (RD) 17643, pp. 28-29, (R
D) 18716, p. 647 and (RD) 308119 XIX.

The ISO sensitivity of the silver halide color photographic light-sensitive material of the present invention is preferably 100 or more.

The ISO sensitivity referred to here is determined by the following steps (1) to (2) from the curve obtained in the same manner as the concentration function curve D- (logE) described above.

The exposure amounts corresponding to 0.15 higher densities with respect to the minimum densities of blue, green, and red are expressed in lux · second and are respectively E _B , E _G , and E _R.

Among E _B , E _G , and E _R , the one with the largest value (the one with the lowest sensitivity) is designated as E _S.

The ISO sensitivity S is calculated according to the following formula.

[0111]

[Equation 4]

In the present invention, the above-mentioned Dmin [C]
Preferably has an optical density of 0.25 or less, and more preferably 0.20 or less.

Further, in the present invention, Dmin [M] -Dmin
The value of [C] is preferably 0.40 or less and more preferably 0.35 or less in terms of optical density difference.

Furthermore, in the present invention, Dmin [Y] -Dm
The value of in [M] is preferably in the range of −0.20 to 0.30, more preferably in the range of −0.10 to 0.20 in terms of optical density difference.

The light-sensitive material of the present invention contains cesium 137 (
¹³⁷ Cs) as the source of γ rays,
D after irradiating the wire with 2.5 mR / min intensity for 40 minutes
It is preferable that at least any one of min [Y], Dmin [M], and Dmin [C], particularly preferably all have a change width of 0.15 or less, more preferably 0.10 or less, further preferably 0.05 or less. .

[0116]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of gelatin A) Using hard bone of beef bone as a raw material,
It was treated with a slaked lime suspension for 60 days, extracted at 36 ° C., treated with an H type cation exchange resin, and then treated with an —OH type anion exchange resin. Adenine content is 0.02ppm /
g. This gelatin is designated as A.

(Preparation of gelatin B) Using beef bone as a raw material, treated with a slaked lime suspension for 60 days, extracted at 70 ° C., treated with an H type cation exchange resin, and then treated with an —OH type anion exchange resin. Processed. Adenine content is 0.25ppm / g
Is. This gelatin is designated as B.

The results of measuring the adenine content of the obtained gelatins A and B were 0.02 ppm / g for gelatin A and 0.2 for gelatin B.
It was 5 ppm / g.

(Seed emulsion T-, which was subjected to low pAg ripening after desalting.
Preparation of 1) A seed emulsion having two parallel twin planes was prepared by the following method.

(Solution A) Ocein gelatin 80.0 g Potassium bromide 47.0 g HO (CH ₂ CH ₂ O) m {CH (CH ₃ ) CH ₂ O} _19.8 (CH ₂ CH ₂ O) nH (m + n = 9.7) 10% by weight of methanol solution 0.48 ml Finish with distilled water to 8000.0 ml (B liquid) Silver nitrate 1200.0 g Finish with distilled water to 1600.0 ml Ocein gelatin 32.2 g (C liquid) Potassium bromide 790.0 g Potassium iodide 70.34 g Distilled water To 1600.0 ml (D) Ammonia water 470.0 ml Stir vigorously at 40 ° C (A), (B) and (C).
Was added for 7.7 minutes by the double jet method to generate nuclei. During this time, pBr was kept at 1.60.

Then, the temperature was lowered to 20 ° C. over 30 minutes. Furthermore, (D liquid) was added over 1 minute, followed by aging for 5 minutes. KBr concentration during aging is 0.03mol / l,
The ammonia concentration was 0.66 mol / l. After aging, p
H was adjusted to 6.0, and desalting was performed according to a conventional method.

To the emulsion after desalting, 1884 ml of a 10% by weight gelatin aqueous solution was added, and the mixture was stirred and dispersed at 60 ° C. for 15 minutes, and then 21.0.
Add 130 ml of an aqueous solution containing 1 g of silver nitrate to determine the pAg value of the emulsion.
It was adjusted to 1.9 for reduction sensitization, and subsequently aged with stirring at 60 ° C. for 80 minutes. Then, 193 ml of an aqueous solution containing 14.5 g of potassium bromide was added, the emulsion temperature was lowered to 40 ° C., and distilled water was added to complete an emulsion of 5360 g. When the seed emulsion grains were observed with an electron microscope, they were spherical grains having two twin planes parallel to each other.

The average grain size of this seed emulsion grain is 0.217 μm, 2
The number of grains having parallel twin planes was 75% (number ratio) of all grains.

(Seed emulsion T not subjected to low pAg ripening after desalting)
-2) Preparation until desalting is performed in the same manner as in the above seed emulsion T-1, and 10% by weight aqueous gelatin solution is added to the emulsion after desalting,
After stirring and dispersing at 60 ℃ for 30 minutes, add distilled water to obtain 5360g.
As an emulsion of.

(Preparation of Silver Halide Emulsion Em-1) The following eight kinds of solutions [(solution A) were added to the seed emulsion (T-
1) is included] to prepare a tabular monodisperse emulsion Em-1 having two parallel twin planes according to the present invention.

(Solution A) Gelatin A 67.0 g Distilled water 3176.0 ml HO (CH ₂ CH ₂ O) m {CH (CH ₃ ) CH ₂ O} _19.8 (CH ₂ CH ₂ O) nH (m + n = 9.77) 10 Weight% methanol solution 2.5 ml Seed emulsion (T-1) 98.51 g Finish with distilled water to 3500 ml (Solution B) 0.5N silver nitrate aqueous solution 948 ml (Solution C) Potassium bromide 52.88 g Gelatin A 35.55 g Finish with distilled water to 948 ml ( Solution D) 3.5N silver nitrate aqueous solution 4471 ml (Solution E) Potassium bromide 1862.2 g Ocein gelatin 200 g Finish to 4471 ml with distilled water (Solution F) From 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm) A method for preparing 2465.5 g (*) of the fine particle emulsion (*) is shown below.

To 5000 ml of a 6.0% by weight gelatin solution containing 0.06 mol of potassium iodide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was adjusted to 2.0 using nitric acid,
The temperature was controlled at 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. Finished weight is 1
It was 2.53 kg.

(Solution G) 1.75N potassium bromide aqueous solution Required amount (Solution H) 829 μg of K ₂ IrCl ₆ was added to 50 ml of 25 wt% sodium chloride aqueous solution, and the pH was adjusted to 1.0 or less with nitric acid. (Solution A) was added, and with vigorous stirring,
(Solution B) to (Solution F) were added according to the combination shown in Table 4 by the simultaneous mixing method to grow a seed crystal to prepare a core / shell type silver halide emulsion.

Here, (1) (solution B), (solution C) and (solution F) addition rate, (2) (solution D), (solution E) and (solution F) addition rate, (3) ) The addition rates of (Solution D) and (Solution E) are changed in a function-like manner with respect to the time corresponding to the critical growth rate of silver halide grains, and small grains other than the growing seed crystal are added. The addition rate was controlled so as not to cause polydispersion due to generation and Ostwald ripening.

The solution temperature in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. pA
If necessary to control g (Solution G)
Was added. Table 4 shows the grain size at that time and the silver iodide content of the silver halide phase forming the surface with respect to the addition time of the reaction solution.

After grain growth, desalting treatment was performed according to the method described in JP-A-5-72658, gelatin was then added and redispersed, and pH was adjusted to 5.80 and pAg to 8.06 at 40 ° C. From the electron micrograph of the obtained emulsion grains, the average grain size of 1.22μ
It was confirmed to be a tabular emulsion having m, an average aspect ratio of 1.9 and a grain size distribution of 13.7%.

[0133]

[Table 4]

(Preparation of Emulsion Em-2) Furthermore, Em-2
In the production method of, the seed emulsion in (Solution A) is
Emulsion Em-2 was prepared by the same production method as for Em-1, except that the step 2) was performed.

(Preparation of Emulsion Em-3) Further, in the method for producing Em-3, Em-1 was used except that gelatin was changed to B.
Emulsion Em-3 was prepared by the same manufacturing method as described above.

(Preparation of Emulsion Em-4) Also, in the method for producing Em-4, Em-2 was used except that gelatin was changed to B.
Emulsion Em-4 was prepared by the same production method as described above.

(Preparation of Emulsion Em-5) Emulsion Em-5 was prepared in the same manner as Em-1 except that Solution H was rushed at the solution addition time of 233.55 minutes shown in Table 4 in the method for producing Em-5. -5 was prepared.

(Preparation of Emulsion Em-6) Emulsion Em-6 was prepared by the same manufacturing method as Em-5 except that the seed emulsion in (Solution A) was changed to (T-2) in the manufacturing method of Em-6. Prepared.

(Preparation of Emulsion Em-7) Emulsion Em-7 was prepared by the same manufacturing method as Em-5 except that gelatin was changed to B in the manufacturing method of Em-7.

(Preparation of Emulsion Em-8) (Solution A) in which the seed emulsion was changed to (T-2) was added to a reaction vessel, and (Solution B) to (Solution D) were added to Table 5 while vigorously stirring. According to the combination shown in the above, addition was carried out by the simultaneous mixing method to grow a seed crystal to prepare a core / shell type silver halide emulsion.

Here, (1) (solution B), (solution C) and (solution D) addition rate, and (2) (solution B) and (solution C) addition rate, respectively, are the same as those of silver halide grains. It was changed like a function with respect to the time corresponding to the critical growth rate, and the addition rate was controlled appropriately so as not to cause polydispersion due to generation of small particles and Ostwald ripening other than the growing seed crystal.

The solution temperature in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. pA
If necessary to control g (solution E)
Was added. Table 5 shows the grain size and the silver iodide content of the silver halide phase forming the surface at that time with respect to the addition time of the reaction solution.

After grain growth, desalting treatment was performed according to the method described in JP-A-5-72658, gelatin was then added and redispersed, and pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C. From the electron micrograph of the obtained emulsion grains, an average grain size of 0.75μ
It was confirmed to be a tabular emulsion having m, an average aspect ratio of 2.0 and a grain size distribution of 18.0%.

[0144]

[Table 5]

(Preparation of Emulsion Em-9) Emulsion Em-9 was prepared in the same manner as Em-8 except that solution H was rushed at the solution addition time of 61.33 minutes shown in Table 5 in the method for preparing Em-9. 9 was prepared.

(Preparation of Emulsion Em-10) Emulsion Em-10 was prepared by the same manufacturing method as Em-9 except that gelatin was changed to B in the manufacturing method of Em-10.

Example 2 (Preparation of silver halide color photographic light-sensitive material sample) Em-
1 was subjected to gold / sulfur sensitization with an aqueous adenine solution added, and using these emulsions, each layer having the composition shown below was sequentially formed on the triacetyl cellulose film support from the support side to obtain a multilayer color film. Photosensitive material (Sample 10
1) was produced.

In all the following descriptions, the addition amount in the silver halide photographic light-sensitive material is 1 m ² unless otherwise specified.
The number of grams per unit is shown. Further, silver halide and colloidal silver are shown in terms of silver, and in the case of sensitizing dyes, they are shown as the number of moles per mol of silver halide in the same layer.

Further, all the silver iodobromide emulsions other than Em-1 used here were not subjected to reduction sensitization inside the grains, and the adenine content of 0.2 p
Gelatin below pm is not used.

First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point organic solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer High boiling point organic solvent (Oil-2) 0.17 Gelatin 1.27 Third layer; low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content) Ratio 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD -4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling solvent (Oil-1) 0.53 gelatin 1.30 fourth layer: middle sensitivity red-sensitive layer Em-8 0.62 sensitizing dye (SD─1) 2.3 × 10 ^-4 sensitizing dye (SD─2) 1.2 × 10 ^-4 sensitized color (SD─3) 1.6 × 10 ^-5 Sensitizing dye (SD─4) 1.2 × 10 ^-4 Cyan coupler (C─1) 0.15 Cyan Coupler (C─2) 0.18 Colored cyan coupler (CC─1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer; High-sensitivity red-sensitive layer Em-1 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) ) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 6th layer Intermediate layer High boiling organic solvent (Oil-2) 0.11 Gelatin 0.80 7th layer; Low sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.61 Silver iodobromide emulsion (average grain size 0.27 [mu] m, silver iodide content 2.0 mol%) 0.20 sensitizing dye (SD─4) 7.4 × 10 ^-5 sensitizing dye (SD─5) 6.6 × 10 ^-4 magenta coupler (M─ ) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.75 Gelatin 1.95 Eighth layer; Medium sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm) , Silver iodide content 8.0 mol%) 0.87 Sensitizing dye (SD-6) 2.4 × 10 ^-4 Sensitizing dye (SD-7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.058 Magenta coupler (M─ 2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.50 Gelatin 1.00 9th layer; high-sensitivity green-sensitive layer Iodour Silver halide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM-1) 0.012 High boiling point solvent (Oil) ─ 1) 0.27 High boiling point solvent (Oil ─ 2) 0.012 Gelatin 1.00 10th layer; Yellow fill -Layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 11th layer; Intermediate layer Formalin scavenger (HS-1) 0.20 Gelatin 0.60 12th layer; low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.073 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 3.0 0.16 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD-8) 2.2 × 10 ^-4 Sensitizing dye (SD-9) 2.7 × 10 ^-4 Yellow coupler (Y-1) 0.89 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 13th layer; high-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content of 10.0 mol%) 0.95 sensitizing dye (SD─8) 7.3 × 10 ^-5 sensitizing dye (SD─9) 2.8 × 10 ^-5 Ieroka High-boiling solvent (Oil-2) 0.093 Gelatin 0.80 14th layer; 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorption Agent (UV-1) 0.065 Ultraviolet absorber (UV-2) 0.10 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 15th layer; 2nd Protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid Agent Su-
2, viscosity modifier V-1, hardeners H-1, H-2, stabilizer ST-1, antifoggant AF-1, dye AI-1, AI
-2, weight average molecular weight: 10,000 and weight average molecular weight: 1,
100,000 of two AF-2 and preservative DI-1 were added. The amount of DI-1 added was 9.4 mg / m ² .

The structures of the compounds used in the above samples are shown below.

[0152]

Embedded image

[0153]

Embedded image

[0154]

[Chemical 3]

[0155]

[Chemical 4]

[0156]

[Chemical 5]

[0157]

[Chemical 6]

[0158]

[Chemical 7]

[0159]

Embedded image

[0160]

[Chemical 9]

Next, as shown in Table 6, a sample was prepared in exactly the same manner as sample 101 except that the emulsions used in the fourth and fifth layers and the coupler addition amounts in the third, seventh and twelfth layers were changed. 102 ~ 11
2 was produced.

[0162]

[Table 6]

The light-sensitive material sample thus obtained was
After completion of coating and drying, aging treatment was carried out at 40 ° C. and relative humidity of 60% for 5 days, and then the values of μ and j were calculated according to the above-mentioned method of determining the stability parameter μ and the linearity parameter j. The results are shown in Table 7.

Example 3 Samples 101 to 112 of Example 2 were loaded on a film with lens made by Konica "Kikikiri Konica Motto MiNi Flash".
100 outdoor scenes (scene 1) and 100 indoor scenes (scene 2) after fine morning
We shot 200 scenes in total. The photographed sample was subjected to the following development treatment within 12 hours after the photography to obtain a negative film after the exposure and development treatment.

Samples 101 to 112 were allowed to stand at 45 ° C. and 40% RH for 3 weeks, then loaded into a film with a Konica lens in the same manner as described above, and the outdoor scene (scene 1) after noon on a sunny day and Strobe usage scene (scene 2)
100 scenes each, 200 scenes in total, and then 40
After left for 3 weeks in an environment of 20 ° C. and 20% RH, the development processing shown below was performed.

(Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C 780cc Bleach 45 seconds 38 ± 2.0 ° C 150ml fixation 1 minute 30 seconds 38 ± 2.0 ° C 830ml stability 60 Second 38 ± 5.0 ℃ 830ml Drying 1 minute 55 ± 5.0 ℃ − * Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developing solution and color replenishing solution Developing solution Replenishing solution Water 800cc 800cc Potassium carbonate 30g 35g Sodium hydrogencarbonate 2.5g 3.0g Potassium sulfite 3.0g 5.0g Sodium bromide 1.3g 0.4g Potassium iodide 1.2mg-hydroxylamine sulfate Salt 2.5g 3.1g Sodium chloride 0.6g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g 6.3g Diethylenetriaminepentaacetic acid 3.0g 3.0g Potassium hydroxide 1.2g 2.0 g Add 1 liter of water and use potassium hydroxide or 20% sulfuric acid to adjust the color developer to pH 10.06 and the replenisher to pH 10.18.
Adjust to.

Bleaching solution and bleach replenishing solution Bleaching solution Replenishing solution Water 700cc 700cc 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125g 175g Ethylenediaminetetraacetic acid 2g 2g Sodium nitrate 40g 50g Ammonium bromide 150g 200g Glacial acetic acid 40g 56g Water Then, the bleaching solution is adjusted to pH 4.4 and the replenisher is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

Fixing Solution and Fixing Replenishing Solution Fixing Solution Replenishing Solution Water 800 cc 800 cc Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid was used as the fixer at pH 6.2, Adjust the replenisher to pH 6.5 and add water to make 1 liter.

Stabilizer and stable replenisher water 900 cc p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 0.1 g siloxane (UC-L-77 ) 0.1g Ammonia water 0.5cc Add water to make 1 liter, then use ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

Next, using this processed photosensitive material sample (negative film after exposure and development), NSP-15 manufactured by Konica Corporation
The color paper type QAA5 manufactured by Konica Corporation was printed and exposed using a 01QA printer, and an E size print was obtained by using a color paper processing process CPK-2 manufactured by Konica Corporation. Each of the obtained prints was subjected to a five-level absolute evaluation of 1 point (poor) to 5 points (best), with 6 employee families of Konica Corporation assuming general users as panelists.

The average score of each of Scene 1 and Scene 2 was calculated and shown in Table 7 for each sample.

The results are shown in Table 7.

[0175]

[Table 7]

As is clear from Table 7, in the samples of the present invention, there is almost no difference in print evaluation due to the environmental conditions from the end of production to the development, development and development, the period, and whether or not the flash photography is performed. It can be seen that there is no value and the value is high.

[0177]

EFFECTS OF THE INVENTION By setting the stability parameter and the linearity parameter within certain ranges, it is possible to obtain a stable printed image with no difference due to photographing conditions.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one red light-sensitive layer, green light-sensitive layer and blue light-sensitive layer on a support, each having a stability parameter (μ) of 0.07 or less. And a linearity parameter (j) satisfying the following conditions: a silver halide color photographic light-sensitive material. j = 1.00 ± 0.01 2. A silver halide color photographic light-sensitive material having at least two layers of a red light-sensitive layer, a green light-sensitive layer and a blue light-sensitive layer on a support. 2. A silver halide color photographic light-sensitive material according to claim 1, wherein at least one emulsion layer other than the highest light-sensitive layer contains a silver halide emulsion having polyvalent metal ions inside the grains.