JP3189102B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In recent years, the quality of silver halide color photographic materials has been remarkably improved. That is, in recent silver halide color photographic materials, the three major factors of image quality, that is, graininess, sharpness, and color reproducibility, are all at a considerably high level. For example, "Konica Color Impreza"
The 50 ”has been well received in the market for its high image quality.
However, among the above three factors, the color reproducibility has been improved only in the color purity, but the hue reproducibility and the shading depiction are still insufficient. In particular, since red to magenta and purple are frequently photographed as main subjects, there is a great potential need for their hue reproducibility, color purity, and faithful reproduction of shading.

It is well known in the art that there are a correlation effect (inter-image effect) and a spectral sensitivity distribution as major factors relating to color reproducibility. However, conventional color photographic light-sensitive materials for photography mainly have a color purity. It has been designed and developed with priority on enhancement.

Therefore, in order to increase the inter-image effect, the same effect as the inter-image effect can be obtained by using a so-called DIR compound or using a colored coupler in a color negative film more than canceling unnecessary absorption. This has been used to improve color purity.

On the other hand, in order to reduce the overlap of the spectral sensitivity distributions of blue sensitivity, green sensitivity and red sensitivity, the spectral sensitivity distribution has been sharpened or moved away from each other to contribute to the color purity. However, in recent years, problems with the hue reproduction of intermediate colors and the faithful reproducibility of subtle shading and shading of primary colors have emerged as adverse effects of the above technology.

For the reproduction of intermediate color hues, especially for purple, it is effective to shorten the spectral sensitivity distribution of the red-sensitive layer as disclosed in JP-A-3-194546 and JP-A-3-94547.
Nos. 3-107139, 3-265845, 3-273239 and the like. The purpose of these techniques is to try to feel the spectral reflectance characteristic of purple at a wavelength close to the human eye.

[0007] However, if the spectral sensitivity distribution of red sensitivity is short-wavelength, the color purity of red color is remarkably deteriorated. Therefore, it is conceivable to shorten the spectral sensitivity distribution of red sensitivity and increase the inter-image effect, but it is still insufficient at present. In addition, it has become clear that the short-wavelength spectral sensitivity distribution of red sensitivity is insufficient for discriminating various purple colors.

On the other hand, regarding the faithful reproducibility of subtle shading and shading of primary colors, see, for example, JP-A-63-85545 and JP-A-4-2744.
No. 22 has a technical disclosure about red. These are the disadvantages of the inter-image effect that has been excessively increased. In the image area that reproduces the primary color of the subject, the solution of the problem that the gradation of the complementary color is lost or softened is solved by the spectral sensitivity. This is shown by optimally controlling the distribution and the inter-image effect. However, these disclosed techniques describe a difference in red lightness or a change in luminance, but do not provide a technical solution on a hue change of a subject having a different spectral reflectance and a discrimination property against the change in luminance.

That is, in order to sufficiently satisfy the purity of red and to improve the discriminability of red and violet having different spectral reflectances, a spectral sensitivity distribution which has been mainly performed in the past,
It turned out that it could not be solved only by easy combination such as inter-image effect.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which is red and satisfactorily satisfies its purity and which is excellent in discriminability between red and purple having different spectral reflectances. To provide.

[0011]

The above problems have been solved by the present invention described below. (1) On a support, at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler, and a cyan coupler are contained. In a silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer, the following red filters A and B
_A silver halide color photographic light-sensitive material, wherein γ _B / γ _A ≧ 1.05, where γ _A and γ _B represent the gradation of each cyan-colored image obtained by exposure with each other. Red filter A: Spectral transmittance is 2% or less in the range of 350 nm to 585 nm, and wavelength λ having a transmittance of 50% is 600 nm.
≦ λ ≦ 610 nm, and the transmittance at 630 nm to 800 nm is 8
Short wavelength absorption red filter having 0% or more Red filter B: Spectral transmittance in the range of 350 nm to 625 nm is 2% or less, and wavelength λ having a transmittance of 50% is 640 nm.
≦ λ ≦ 650 nm, and the transmittance at 670 nm to 800 nm is 8
(2) The wavelength λmax at which the maximum sensitivity of the spectral sensitivity distribution of the red-sensitive silver halide emulsion layer is 610 nm ≦ λmax ≦ 645 nm having a wavelength of 0% or more. The silver halide color photographic light-sensitive material described in the above.

(3) The following (1), wherein at least one of the compounds represented by the general formula [Q] is contained.
The silver halide color photographic light-sensitive material according to the item (2).

General formula [Q] Q (-TIME-) _n X [wherein Q represents an oxidation-reduction reaction in a developing process.
A redox residue releasing a moiety other than Q,
Represents a divalent group for adjusting the timing of releasing X. X
Represents a development inhibiting residue, and n represents 0 or 1.]
The present invention will be described in detail.

The red filter A used in the present invention has a spectral transmittance from 350 nm to 585 nm of 2% or less and 50%
Has a transmittance of 600 nm to 610 nm, and 63
This filter has a transmittance of 80% or more at 0 nm to 800 nm, and examples of commercially available filters include Wratten Gelatin Filter No. 26 manufactured by Eastman Kodak Company.

The red filter B is 350 nm to 620
A filter having a spectral transmittance of 2 nm or less, a wavelength having a transmittance of 50% from 635 nm to 645 nm, and a transmittance of 665 nm to 800 nm of 80% or more. Commercially available filters include: Eastman Kodak Co., Ltd. ratten gelatin filter No. 92 and the like. Γ _A and γ _B in the present invention are determined as follows.

First, the sample to be tested was subjected to ISO 5800 (1979)
The ISO sensitivity is obtained by the method defined by [E]. Next, the same exposure as when the ISO sensitivity was determined using a light source having the same relative spectral energy distribution as that used to determine the ISO sensitivity for a test sample of a silver halide color photographic light-sensitive material having an ISO sensitivity of S 1600 / S ・ lux ・ sec depending on time
The wedge exposure is given through the above-mentioned red filter A with the exposure amount of Similarly, the same light source as above for the test sample,
A wedge exposure is given through the above-mentioned red filter B at an exposure amount of 6400 / S · lux · sec in exposure time.

Until the two types of test samples exposed with the red filters A and B are developed, the temperature is 20 ± 5 ° C.
The relative humidity is maintained at 60 ± 10%, the development processing is completed within 30 minutes to 6 hours after exposure, and the processing method is the method recommended by the film manufacturer. The density measurement after the development processing is in accordance with the status M of ISO 5 / 3-1984 (E) in the case of a color negative photosensitive material for photographing test samples, and in accordance with the status A of ISO 5 / 3-1984 (E) in other cases. Do.

Based on the obtained density data, the logarithm of the exposure amount is plotted on the horizontal axis, and the minimum density of cyan density +0.4, +0.6, +0.8, +1.0 is plotted on the graph giving the density on the vertical axis. Are plotted, and these points are approximated by a straight line using the least squares method. The angle θ from the horizontal axis (where 0 ≦ θ <π / 2) is
Let nθ be γ. The gamma obtained from a test sample which is exposed in this case red filter A and gamma _A, the gamma obtained from the test sample is exposed similarly with red filter B and gamma _B.

The preferred range of γ _B / γ _A in the present invention is 1.1 ≦ γ _B / γ _A ≦ 1.8, more preferably 1.15 ≦ γ.
_B / γ _A ≦ 1.5. Making such γ _B / γ _A equal to or more than 1 seems to be similar to hardening the gradation of the complementary color for a red object at first glance, but the present inventor has proposed various red and purple colors. It has been found that by measuring the spectral reflectance of the subject, it is necessary to control the partial gradation in the exposure amount region having the above-mentioned density for the cyan gradation.

In the present invention, it is particularly preferable that the spectral sensitivity λmax of the red-sensitive silver halide emulsion layer be 610 nm to 645 nm in order to improve the discriminability of purple.

In the case of a color negative type photosensitive material, the wavelength λmax at which the maximum sensitivity of the spectral sensitivity distribution of the red-sensitive silver halide emulsion layer is measured by measuring the spectral sensitivity distribution at a density of cyan fog + 0.1. , The wavelength that gives the maximum sensitivity.

In the case of a color reversal photosensitive material, the spectral sensitivity distribution is measured at a density of -0.3 of the maximum density of cyan density, and the wavelength at which the maximum sensitivity is obtained. The preferable range of λmax obtained here is 610 nm ≦ λmax ≦ 640 nm.

In one preferred embodiment of γ _B / γ _A and λ max in the present invention, a silver halide emulsion is represented by the following general formulas [I], [II], [III] and [IV]. It can be achieved by using sensitizing dyes alone or in combination, but is not necessarily limited to only these spectral sensitizing dyes.

Short wavelength red-sensitive sensitizing dye

[0025]

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In the formula, R ₁ represents a hydrogen atom, and R ₂ , R ₃ ,
R ₄ and R ₅ each represent an alkyl group or an aryl group.

Z ₁ , Z ₂ , Z ₃ and Z ₄ are each a hydrogen atom,
Halogen atom, hydroxyl group, alkoxy group, amino group, acyl group, acylamino group, acyloxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, carbamoyl group, aryl group, alkyl group, cyano group Or a sulfonyl group.

Z ₁ and Z ₂ and / or Z ₃ and Z ₄ may be linked to each other to form a ring.

[0029] X ^- represents an anion. n represents an integer of 1 or 2, and when the sensitizing dye forms an internal salt, n
Represents 1.

Short wavelength red-sensitive sensitizing dye

[0031]

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In the formula, R ₆ represents a hydrogen atom, an alkyl group or an aryl group, and R ₇ , R ₈ , R ₉ and R ₁₀ each represent an alkyl group or an aryl group.

Y ₁ and Y ₂ each represent a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and when Y ₁ is a sulfur atom, an oxygen atom or a selenium atom, it does not have the above R _7. I do. Further, Y ₁ and Y ₂ are not simultaneously a nitrogen atom or a sulfur atom.

Z ₅ , Z ₆ , Z ₇ and Z ₈ are each a hydrogen atom,
Halogen atom, hydroxyl group, alkoxy group, amino group, acyl group, acylamino group, acyloxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, carbamoyl group, aryl group, alkyl group, cyano group Or a sulfonyl group. Z ₅ and Z ₆ and / or Z ₇ and Z ₈ may be linked to each other to form a ring. Also X
^- represents an anion. n represents an integer of 1 or 2, and when the sensitizing dye forms an internal salt, n represents 1.

Long wavelength red-sensitive sensitizing dye

[0036]

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In the formula, R ₁₁ represents a hydrogen atom, an alkyl group or an aryl group, and R ₁₂ and R ₁₃ each represent an alkyl group or an aryl group. Y ₃ and Y ₄ each represent a sulfur atom or a selenium atom.

Z ₉ , Z ₁₀ , Z ₁₁ and Z ₁₂ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an acyloxy group,
Aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group,
Represents a sulfonyl group, a carbamoyl group, an aryl group, an alkyl group or a cyano group. Z ₉ and Z ₁₀ and / or Z ₁₁ and Z
₁₂ may be connected to each other. The X ^-
Represents an anion. n represents an integer of 1 or 2,
When the sensitizing dye forms an inner salt, n represents 1.

Long wavelength red-sensitive sensitizing dye

[0040]

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In the formula, Z ₁ and Z ₂ each represent a nonmetallic atom group necessary for forming a 5-membered heterocyclic ring fused to a benzene ring or a naphthalene ring, and R ₁ and R ₂ each represent a group having 10 carbon atoms.
The following alkyl groups, pyridyl groups or carbamoyl groups, R ₄ and R ₅ each represent an alkyl group having 6 or less carbon atoms or a substituted alkyl group, and Y ₁ represents an oxygen atom or a sulfur atom.

The spectral sensitizing dyes represented by the above general formulas [I] to [IV] which can be used in the present invention are described in JP-A-3-239247 by the same applicant as the present invention. Spectral sensitizing dyes such as I-1 to I-34, II-1 to I
Examples thereof include I-40, III-1 to III-46 and Examples (2-1) to (2-16) described in Japanese Patent Application No. 63-29637.

Hereinafter, the above general formulas [I], [II], [II]
Examples of the spectral sensitizing dyes represented by [I] and [IV] are shown below, but the present invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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The spectral sensitizing dyes represented by the above general formulas may further be used as supersensitizers, for example, benzothiazoles, quinones and benzothiazoles described in JP-B-57-24533.
A quinoline derivative described in -24899 can be used according to the purpose. The above-mentioned sensitizing dyes used in the present invention each contain 1 mol per mol of silver halide.
× 10 ⁻⁶ mol to 5 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁵ mol
2.52.5 × 10 ^-3 mol, more preferably 4 × 10 ^-5 mol to 1 × 10 ^-3 mol, in the silver halide photographic emulsion.

As another preferred embodiment of γ _B / γ _A and λ max in the present invention, a specific hydrophilic colloid layer may be coated with a dye having a spectral density suitable for the purpose.

In the present invention, it is preferable to contain a compound represented by the general formula [Q] as a method for enhancing the interimage effect. By using these compounds, the color purity can be further improved.

Next, the development inhibitor releasing compound represented by the general formula [Q] will be described.

The redox residue represented by Q includes, for example, hydroquinone, catechol, p-aminophenol,
o-aminophenol, 1,2-naphthalene diol, 1,4-naphthalene diol, 1,6-naphthalene diol, 1,2-diaminonaphthol, 1,4-diaminonaphthol, 1,6-diaminonaphthol and the like. . At this time, the amino group is preferably substituted with a sulfonyl group having 1 to 20 carbon atoms or an acyl group having 1 to 20 carbon atoms. Examples of the sulfonyl group include an aliphatic sulfonyl group and an aromatic sulfonyl group which may be substituted. Examples of the acyl group include an aliphatic acyl group and an aromatic acyl group which may be substituted.

The hydroxyl group or amino group forming the redox residue of Q may be protected by a protecting group that can be removed during development. Examples of the protecting group include those having 1 to 20 carbon atoms, such as an acyl group, an alkoxycarbonyl group, a carbamoyl group, and the protecting groups described in JP-A-59-197037 and JP-A-59-201057. Can be Further, this protecting group may be bonded to a substituent of Q described below, if possible, to form a 5-, 6- or 7-membered ring.

The redox residue represented by Q may be substituted with a suitable substituent as long as the redox ability is not lost. Examples of these substituents are those having 25 or less carbon atoms, such as alkyl, aryl, alkylthio, arylthio, alkoxy, aryloxy, amino, amide, sulfonamide, alkoxycarbonylamino, ureido, carbamoyl, alkoxycarbonyl, sulfamoyl, Sulfonyl, cyano, halogen atom, acyl, carboxyl and the like.

In the general formula [Q], when the oxidation-reduction residue represented by Q undergoes a cross-oxidation reaction during development and becomes an oxidized form, it is a group which is released as (-TIME-) _n X for the first time.

TIME is a timing group linked to Q, preferably by a nitrogen atom or an oxygen atom, and releases X from (-TIME-) _n X released during development through one or more steps of reaction. Examples of the group include:

As TIME, for example, US Pat. No. 4,248,
No. 962, 4,409,323, British Patent 2,096,783, U.S. Pat. No. 4,146,396, JP-A-51-146828, and JP-A-57-56837. The TIME may be a combination of two or more selected from those described therein.

Examples of the development inhibitor residue represented by X include a compound having a mercapto group bonded to a heterocyclic ring or a heterocyclic compound capable of forming an imino group. Examples of the compound having a mercapto group bonded to the hetero ring include, for example, an optionally substituted mercaptoazole, an optionally substituted mercaptopyrimidine, and the like.

The heterocyclic compound capable of forming an imino group includes, for example, optionally substituted triazoles, optionally substituted indazoles, optionally substituted benzimidazoles and the like.

X is separated from the TIME of the general formula [Q] to once become a compound having a development inhibiting property, and further deactivates by causing a certain chemical reaction with a developer component. The compound may have substantially no development-suppressing properties or may be changed to a compound having a significantly reduced amount. Examples of the functional group that undergoes such a chemical reaction include an ester group, a carbonyl group, an imino group, an ammonium group, a Michael addition accepting group, and an imide group.

The compound represented by the general formula [Q] is described in detail in JP-A-62-103639.

Specific examples of the compound of the present invention represented by the general formula [Q] are shown below.

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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For the synthesis of the compound represented by the general formula [Q], the method described in JP-A-62-103637 can be referred to.

The compound represented by the above formula [Q] can be added to any hydrophilic colloid layer in a silver halide color photographic light-sensitive material. It is more preferable to include them in the sense of enhancing the interimage effect.

The layer containing the compound represented by the general formula [Q] may or may not contain a coupler which is a coloring dye, but is preferably a layer which does not substantially form a color image. Is preferably contained. Here, the layer which does not substantially form a color image means that the maximum density of the layer after the development processing is the transmission density in the transmission type photographic material and the reflection density in the reflection type photographic material, respectively, is 0.3 or less, preferably It is 0.2 or less, more preferably 0.1 or less.

As a method for adding the compound represented by the general formula [Q], a method of dissolving in a high-boiling organic solvent, dispersing it with high energy, and adding it as an oil-in-water dispersion, water-miscibility such as alcohol and acetone, etc. There are a method of dissolving in an organic solvent and adding, and a method of mechanically pulverizing and dispersing and adding, and any method may be used.

The amount added to the silver halide color photographic light-sensitive material is 1 × 10 ⁻⁷ mol / m ² to 1 × 10 ⁻³ mol / m ² , and 1 × 10 ⁻⁶ / m ^{2 to} 5 × 10 ⁻⁴ / m ² is preferred, and 3 ×
Most preferably, it is from 10 ⁻⁶ / m ² to 1 × 10 ⁻⁴ / m ² .

In the present invention, in addition to using the compound represented by the general formula [Q], a DIR compound can be used as a means for appropriately controlling the interimage effect. In the present invention, the DIR compound refers to a compound that releases a development inhibitor or a development inhibitor releasing precursor by reacting with an oxidized form of a color developing agent.

Specifically, US Pat. Nos. 4,234,678 and 3,22
7,554, 3,617,291, 3,958,993, 4,149,886
No. 3,933,500, 2,072,363, 2,070,266,
These are described in JP-A-57-56837 and JP-A-51-13239, Research Disclosure (RD) No. 21228 (December 1981), and the like. In the present invention, those having a diffusivity of 0.34 to 0.60 are preferably used as the diffusivity of the development inhibitor releasing from the DIR compound.

The diffusivity of the development inhibitor can be determined by the method described in JP-A-1-77056, pp. 36-42.

In the present invention, as another means for enhancing the interimage effect, for example, US Pat. No. 4,082,55
No. 3, 4,036,646, JP-A-59-135462, 59-137951
And the previously described fogged halide emulsions described in JP-A-59-214852 and the like can be used.

The total amount of silver coated on the light-sensitive material according to the present invention was 7.0 g.
/ M ² or less, preferably 6.5 g to 3.0 g / m ² , more preferably 6.1 g to 4.0 g / m ² .

The dry film thickness of the light-sensitive material according to the present invention is preferably 25 μm or less, more preferably from the lower end of the photosensitive emulsion layer closest to the support to the upper end of the photosensitive emulsion layer farthest from the support. The dry film thickness per layer of the green photosensitive layer, which is 18 μm or less, is preferably 0.5 to 4 μm.

Here, the dry film thickness means a film thickness measured at 23 ° C. and 55% humidity control. As for the thickness of each layer, a cross section of the dried sample is enlarged and photographed with a scanning electron microscope, and the thickness of each layer is measured.

At least one of the red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers of the present invention has at least one color-sensitive emulsion layer composed of two or more layers. It is preferable to adopt a configuration having a two-layer structure or three layers of high sensitivity, medium sensitivity, and low sensitivity.

The silver halide emulsion used in the light-sensitive material according to the present invention is preferably a monodisperse silver halide emulsion.
% Of silver halide contained within the grain size range of 70% or more of the total silver halide weight, preferably 80% by weight.
% Or more, more preferably 90% or more.

[0094] The average particle diameter dm herein, the product ni × di ³ of frequency ni and di ³ particles having a particle size di is defined as the particle size di of the time that maximizes (three significant figures, the least significant digit Is rounded off to the nearest 4).

The particle size mentioned here is a diameter when a projected image of the particle is converted into a circular image having the same area.

The particle size is determined by, for example, dispersing the particles on a flat sample table so that they do not overlap, taking an image at a magnification of 10,000 to 50,000 times with an electron microscope, and measuring the particle diameter on the print or the projection time. Can be obtained by actually measuring the area.
(The number of particles to be measured shall be 1000 or more indiscriminately.)

Particularly preferred monodisperse emulsions of the present invention are those having a distribution width of not more than 20% defined by (standard deviation of particle size / average particle size) × 100 = width of distribution (%),
It is more preferably at most 15%.

Here, the method of measuring the particle size is in accordance with the above-mentioned measuring method, and the average particle size is an arithmetic mean.

Average grain size = Σdini / Σn ₁ The average grain size of the silver halide emulsion according to the present invention is 0.1 to 10.
0 μm, more preferably 0.2 to 5.0 μm
m, particularly preferably 0.3 to 3.0 μm.

The silver halide emulsion according to the present invention is preferably made of silver iodobromide having an average silver iodide content of 0 to 20 mol%, particularly preferably 1 to 15 mol%.

The silver halide emulsion according to the present invention may contain silver chloride as long as the effects of the present invention are not impaired.

The silver halide emulsion according to the present invention has a high silver iodide content phase inside the grains.

The silver halide emulsion used in the present invention may be a normal crystal such as cubic, octahedral, tetradecahedral, or 24-hedral, or a twin crystal such as tabular. Further, a mixture thereof may be used.

In the case of tabular twins, it is preferable that the ratio between the diameter of a grain equivalent to the projected area of a grain and the grain thickness of 1 to 20 is at least 60% of the projected area, more preferably at least 1.2 and 8.0.
Is preferably less than 1.5, and particularly preferably 1.5 or more and less than 5.0.

Monodisperse normal crystal emulsions are described, for example, in
-177535, 60-138538, 59-52238, 60-14333
No. 1, No. 60-35726, No. 60-258536, and No. 61-14636.

Monodisperse twin emulsions are described, for example, in JP-A-61-1.
It can be obtained by referring to the method for growing a spherical seed emulsion disclosed in No. 4636.

For growth, it is preferable to add an aqueous silver nitrate solution and an aqueous halide solution by a double jet method. The iodine can also be supplied into the system as silver iodide. The addition rate is preferably such that no new nuclei are generated, and at such a rate that the size distribution does not spread due to Ostwald ripening, that is, 30 to 100% of the rate at which new nuclei are generated.

As another condition for enlarging particles, as can be seen from the 88th Annual Meeting of the Photographic Society of Japan 1983,
There is a method in which silver halide grains are added, dissolved and recrystallized to enlarge the grains.

The growth conditions of the silver halide emulsion include p
Ag 5-11, temperature 40-85 ° C, pH 1.5-12 are preferred.

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

In the present invention, as the silver halide emulsion, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used.

The following shows the places to be described.

[Items] [Page D308119] Iodine composition 993 IA Section Manufacturing method 993 IA and 994 E Crystal habit Normal crystal 993 IA twin crystal 993 IA Epitaxial 993 I- Item A Halogen composition Uniform 993 IB Item Not uniform 993 IB Item Halogen conversion 994 IC Halogen substitution 994 IC Metal-containing 994 ID Monodispersion 995 IF Solvent addition 995 Section IF Latent image formation position Surface 995 IG Inside 995 IG Section Applicable photosensitive material negative 995 IH Positive (including internal fog particles) 995 IH Section Emulsion is mixed and used 995 I- Section J Desalting 995 II-A In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. The additives used in such processes are Research Disclosure
No.17643, No.18716 and No.308119 (hereinafter referred to as RD17
643, RD18716 and RD308119).
The places to be described are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E-J 23 ~ 24 648 ~ 9 Supersensitizer 996 IV-AE, J section 23 ~ 24 648 ~ 9 Antifoggant 998 VI 24 ~ 25 649 Stabilizer 998 VI 24 ~ 25 649 Known photographs usable in the present invention Additives are also described in Research Disclosure, supra. The places to be described are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 998 V 24 UV absorber 1003 VIII- Item C, XIIIC 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Painter 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) 1011 XXB Section Various couplers can be used in the present invention. Specific examples are described in the above-mentioned Research Disclosure. The relevant sections are described below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G VIIG DIR coupler 1001 VII-F VIIF BAR coupler 1002 VII-F Other useful residues 1001 VII-F Emission coupler Alkali-soluble coupler 1001 VII-E Additive used in the present invention Can be added by a dispersion method described in RD308119XIV or the like.

In the present invention, the aforementioned RD17643, page 28, RD
The supports described in pages 18716 647-8 and RD308119 XIX can be used.

The light-sensitive material of the present invention is prepared by using the RD308119VII-
An auxiliary layer such as a filter layer or an intermediate layer described in the section K can be provided.

As a support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate film or the like can be used.

The present invention can be applied to various silver halide color photographic light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. However, it is preferably used for a silver halide color reversal photographic material for photography.

[0121]

Hereinafter, the present invention will be described with reference to examples.
Of course, the present invention is not limited to this.

Example 1 Each layer having the following composition was sequentially coated on a subbed cellulose triacetate film support from the support side to prepare a comparative sample 101 of a multilayer color photographic light-sensitive material.

The coating amount of each component is shown in g / m ² . However, with respect to silver halide, it is indicated by a coating amount converted to silver.

First layer (antihalation layer) Black colloidal silver 0.24 UV absorber U-1 0.14 UV absorber U-2 0.072 High boiling solvent O-1 0.31 High boiling solvent O-2 0.098 Poly-N-vinylpyrrolidone 0.15 Gelatin 2.02 Second layer (intermediate layer-1) Gelatin 0.50 Third layer (intermediate layer-2) Fine grain silver iodobromide emulsion with fogged surface (silver iodide 1.0 mol%, 0.06 μm) 0.05 Gelatin 0.50 Fourth layer (Low sensitivity red-sensitive silver halide emulsion layer) Em-1 0.6 coupler C-1 0.52 high boiling point solvent O-2 0.6 gelatin 1.3 spectrally sensitized by sensitizing dyes (III-2, IV-4) (High-sensitivity red-sensitive silver halide emulsion layer) Em-2 0.7 coupler C-1 0.78 high-boiling solvent O-2 1.2 gelatin 1.8 sixth layer spectrally sensitized by sensitizing dyes (III-2, IV-4) (Intermediate layer-3) 2,5-di-t-octylhydroquinone 0.1 high boiling Point solvent O-1 0.2 Gelatin 0.9 Seventh layer (intermediate layer-4) Fine grain silver iodobromide emulsion with fogged surface (silver iodide 1.0 mol%, 0.06 μm) 0.05 2,5-di-t-octylhydroquinone 0.1 High boiling point solvent O-3 0.25 Gelatin 0.9 Eighth layer (Low sensitivity green-sensitive silver halide emulsion layer) Em-3 0.55 Coupler M-1 spectrally sensitized by sensitizing dyes (S-1, S-2) 0.15 Coupler M-2 0.04 High boiling point solvent O-3 0.25 Gelatin 1.4 Ninth layer (High sensitivity green-sensitive silver halide emulsion layer) Em-2 spectrally sensitized by sensitizing dyes (S-1, S-2) 0.8 coupler M-1 0.56 coupler M-2 0.12 high boiling point solvent O-3 1.0 gelatin 1.5 10th layer (intermediate layer) Same as 6th layer 11th layer (yellow filter layer) yellow colloidal silver 0.15 gelatin 0.9 2,5- Di-t-octylhydroquinone 0.1 High boiling solvent O-1 0.2 Layer 12 (low sensitivity blue Silver halide emulsion layer) Em-4 0.6 coupler Y-1 1.4 high boiling point solvent O-3 0.6 gelatin spectrally sensitized by sensitizing dye (S-3) 1.3 Layer 13 (high-sensitivity blue-sensitive silver halide emulsion) Layer) Em-5 0.75 Coupler spectrally sensitized by sensitizing dye (S-3) Y-1 3.5 High boiling point solvent O-3 1.4 Gelatin 2.1 Layer 14: First protective layer Ultraviolet absorber U-1 0.3 Ultraviolet Absorbent U-2 0.4 2,5-di-t-octylhydroquinone 0.1 High boiling solvent O-3 0.6 Gelatin 1.2 Fifteenth layer: Second protective layer Average particle size 0.08 μm, iodine odor containing 1 mol% of silver iodide Non-photosensitive fine grain silver halide emulsion composed of silver halide 0.3 Polymethyl methacrylate grains (1.5 μm in diameter) 0.06 Surfactant SA-1 0.004 Gelatin 0.7 In addition to the above composition, each layer contains gelatin hardener H-1,
H-2, a surfactant, and a preservative DI-1 were added.

The silver halide emulsion used for each photosensitive layer was prepared by referring to the method of Example 1 in JP-A-59-178447. Each was a monodisperse emulsion having a distribution width of 20% or less.

Each of the emulsions was desalted and washed with water, and then subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to give a sensitizing dye, 4-hydroxy
-6-methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-
Mercaptotetrazole was added.

The total dry film thickness was 21 μm.

The structural formula of the composition used in the above sample is as follows.

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The following silver halide emulsions were used for each photosensitive layer.

Em-1 Silver iodobromide containing 4.0 mol% of silver iodide Average grain size of 0.30 μm Em-2 Silver iodobromide containing 2.5 mol% of silver iodide Average grain size of 0.60 μm Em-3 iodide Silver iodobromide containing 3.5 mol% silver, average grain size 0.25 μm Em-4 Silver iodobromide containing 2.5 mol% silver iodide, average grain size 0.35 μm Em-5 iodo containing 2.5 mol% silver iodide Silver bromide had an average particle size of 0.90 μm and was prepared by referring to the method of Example 1 in JP-A-57-178447. Each was a monodisperse emulsion having a distribution width of 20% or less.

Next, the silver halide emulsions in the fourth and fifth red-sensitive silver halide emulsion layers of Sample 101, their coating amounts, and the sensitizing dyes for sensitizing the silver halide emulsions are shown. 1
The sample was made from the sample 102 to the sample 112 by changing as shown in (1). However, the addition values of the sensitizing dyes described in Table 1 are described in terms of the addition molar ratio, and the total addition amount was adjusted to the addition amount used in Sample 101 as the total number of moles. Sample 1
Compound Q-14 was added to the fourth layer of Sample 05 and Sample 111, and Compound Q-25 and silver halide emulsion were added to the sixth layer of Sample 112 at the amounts shown in Table 1. At this time, compound Q-1
4. Q-25 used was emulsified with high boiling point solvent O-2.

[0136]

[Table 1]

The thus-prepared sample was measured for spectral sensitivity distribution by the above-described method to obtain λmax, and a ratten gelatin filter manufactured by Eastman Kodak Company was used.
The gamma _A from No.26, was obtained γ _B / γ _A search of gamma _B from the No.92.

Using each sample, a color rendition chart manufactured by Macbeth, a relatively dark red sweater, a purple kimono fabric, and reddish purple lavender petals were photographed and subjected to the following development processing. Later, visual evaluation was performed. Table 2 shows the results. Processing time Processing time Processing temperature First development 6 minutes 38 ° C Washing water 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C Adjustment 2 minutes 38 ° C Bleaching 6 minutes 38 ° C Fixed 4 minutes 38 ° C Water Washing 4 minutes 38 ° C Stable 1 minute Room temperature Drying The composition of the processing solution used in the above processing step is as follows.

First developer sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Thiocyan Potassium acid 1.2g Potassium iodide (0.1% solution) 2cc. Water was added to make up to 1000cc. (PH 9.60) Reversal solution Nitrilotrimethylene phosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 cc. Water was added to make up to 1000 cc. (PH 5.75) Color developing solution Sodium tetrapolyphosphate 3g Sodium sulfite 7g Sodium tertiary phosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90cc. Sodium hydroxide 3g Citrazinic acid 1.5g N-ethyl- N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Water was added to make up to 1000 cc. (PH 11.70) Conditioner Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 cc. Glacial acetic acid 3 cc. (PH 6.15) Bleaching solution Sodium ethylenediaminetetraacetate (dihydrate) 2 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120 g Ammonium bromide 100 g Water was added to make up to 1000 cc. (PH 5.56) Fixer ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Water was added to make up to 1000 cc. (PH 6.60) Stabilizing solution Formalin (37% by weight) 5 cc. KONIDAX (manufactured by Konica Corporation) 5 cc. (pH 7.00)

[0140]

[Table 2]

As is clear from Table 2, the composition of the present invention has a high red saturation and is excellent in discriminating red and purple. Sample 11 containing the compound represented by the general formula [Q]
1, Sample 112 has more red and green saturation,
This gives more favorable color reproduction. On the other hand, it can be seen that the comparative sample is inferior in red saturation or inferior in red or purple discrimination.

Example 2 Layers having the following compositions were sequentially formed on a triacetyl cellulose film support from the support side to prepare a comparative sample 201 of a multicolor photographic light-sensitive material.

Example 2 Layers having the following compositions were sequentially formed on a triacetylcellulose film support from the support side to prepare a comparative sample 201 of a multicolor photographic light-sensitive material.

In all of the following descriptions, the amount added in the silver halide photographic material is 1 m ² unless otherwise specified.
Indicates the number of grams per unit. Silver halide and colloidal silver were shown in terms of silver, and sensitizing dyes were shown in moles per mole of silver halide.

First layer: Antihalation layer Black colloidal silver 0.16 UV absorber (U-1) 0.30 Gelatin 1.70 Second layer: Intermediate layer (1L-1) Gelatin 0.80 Third layer: Low-sensitivity red-sensitive layer (R- L) Silver iodobromide emulsion Em-A 0.40 cyan coupler (C-2) 0.3 colored cyan coupler (S) spectrally sensitized by a red sensitizing dye (I-5, II-42, III-3, III-34) CC-1) 0.05 High boiling point solvent (O-1) 0.30 Gelatin 0.55 Fourth layer; Medium-sensitive red-sensitive layer (RM) Red sensitizing dye (I-5, II-12, III-3, III-16) ) Silver iodobromide emulsion Em-B 0.48 cyan coupler (C-2) 0.35 colored cyan coupler (CC-1) 0.05 high boiling solvent (O-1) 0.40 gelatin 0.60 5th layer; high sensitivity Red-sensitive layer (R-H) iodine spectrally sensitized by a red sensitizing dye (I-5, II-2, III-3, III-16) Silver halide emulsion Em-C 0.66 Cyan coupler (C-3) 0.13 Colored cyan coupler (CC-1) 0.01 DIR compound (D-1) 0.02 High boiling solvent (O-1) 0.15 Gelatin 0.53 6th layer; 1L-2) Gelatin 0.80 7th layer; low-sensitivity green-sensitive layer (GL) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (I-5, SI) Em-A 0.60 Em- B 0.40 Magenta coupler (M-1) 0.55 Colored magenta coupler (CM-1) 0.17 DIR compound (D-2) 0.03 High boiling solvent (O-2) 0.70 Gelatin 1.56 Eighth layer; Highly sensitive green-sensitive layer (G- H) Silver iodobromide emulsion spectrally sensitized with green sensitizing dyes (S-II, S-III, S-IV) Em-C 0.60 Magenta coupler (M-1) 0.06 Magenta coupler (M-3) 0.02 Colored magenta coupler (CM-2) 0.02 DIR compound (D-3) 0.002 High boiling solvent (O- 0.15 gelatin 0.45 ninth layer; yellow filter layer (YC) yellow colloidal silver 0.12 HS-1 0.20 HS-2 0.14 high boiling point solvent (O-3) 0.18 gelatin 0.80 10th layer; low-sensitivity blue-sensitive layer (BL) ) Silver iodobromide emulsion spectrally sensitized with red sensitizing bromine (SV, S-VI) Em-A 0.35 Em-B 0.18 Yellow coupler (Y-3) 0.58 Yellow coupler (Y-1) 0.30 High Boiling solvent (O-3) 0.15 Gelatin 1.20 11th layer; High-sensitivity blue-sensitive layer (BH) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dyes (SV, S-VI) Em- D 0.45 Yellow coupler (Y-3) 0.10 High boiling solvent (O-3) 0.04 Gelatin 0.50 12th layer; 1st protective layer (Pro-1) Silver iodobromide emulsion (average particle size 0.07 μm) 0.30 UV absorber (U-1) 0.07 UV absorber (U-2) 0.10 High boiling solvent (O-2) 0.07 High boiling solvent (O-3) 0.0 7 HS-1 0.25 Gelatin 0.80 13th layer; 2nd protective layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Gelatin 0.50 In addition, coating aid Su-1, dispersing aid Su-2, hardeners H-1, H-3, dyes AI-1, AI
-2 was added as appropriate.

The following silver halide emulsions were used for each photosensitive layer.

Em-A Silver iodobromide containing 2.5 mol% of silver iodide Average grain size of 0.30 μm Em-B Silver iodobromide containing 6.5 mol% of silver iodide Average grain size of 0.40 μm Em-C iodide Silver iodobromide containing 8.3 mol% silver, average grain size 0.55 μm Em-D Silver iodobromide containing 9.5 mol% silver iodide, average grain size 0.65 μm The structural formula of the compound used in the above sample is shown below. .

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Next, the silver halide emulsions in the red-sensitive silver halide emulsion layers of the third, fourth and fifth layers of the sample 201, their coating amounts and sensitization for color sensitizing the silver halide emulsions The dye was changed as shown in Table 3 to prepare Sample 209 from Sample 202. However, the addition values of the sensitizing dyes described in Table 3 are described in terms of the addition molar ratio, and the total addition amount was adjusted to the addition amount used in Sample 101 as the total number of moles. At this time, for the samples 203, 208 and 209, the colored cyan couplers (CC-
The amount of 1) was changed from the sample 201.

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[0156]

[Table 3]

Example 1 was obtained from the sample thus produced.
Similar to obtain .lambda.max, the γ _B / γ _A.

In the same manner, using each sample, a color rendition chart manufactured by Macbeth Co., Ltd., a relatively dark red sweater, purple kimono fabric, and reddish purple lavender petals were photographed. Optical density 0.
7 gray and color paper (Konica Color PC Paper Type S) so that this gray has the same density
R), and the visual evaluation was performed. Table 4 shows the obtained results. Samples 201 to 209 were subjected to the following development processing.

Processing Steps 1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ℃ 2. Bleaching 6 minutes 30 seconds 38.0 ± 3.0 ℃ 3. Rinse 3 minutes and 15 seconds 24 to 41 ° C 4. 6 minutes and 30 seconds 38.0 ± 3.0 ℃ 5. Rinse 3 minutes and 15 seconds 24 to 41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying 50 ° C or less The composition of the processing solution used in each processing step is as follows.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid / trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter, and adjust to pH = 10.1.

<Bleaching solution> Iron ammonium salt of ethylenediaminetetraacetic acid 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted using aqueous ammonia.
Adjust to 6.0.

<Fixing solution> Ammonium thiosulfate 175.0 g Sodium sulfite anhydrous 8.5 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and the pH was adjusted to 6.0 using acetic acid.

<Stabilizing Solution> Formalin (37% aqueous solution) 1.5 cc. KONIDAX (manufactured by Konica Corporation) 7.5 cc. Add water to make 1 liter.

[0164]

[Table 4]

As is clear from the table, similarly to Example 1, the sample according to the present invention is excellent in the discriminability of red and purple.

[0166]

According to the present invention, a silver halide color photographic light-sensitive material having improved color reproducibility can be obtained, and in particular, a silver halide color photographic light-sensitive material excellent in discriminability between red and purple can be obtained. Was.

Claims (3)

(57) [Claims] 1. A blue-sensitive silver halide emulsion layer containing at least one yellow coupler, a green-sensitive silver halide emulsion layer containing at least one magenta coupler, and at least one cyan layer on a support. In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer containing a coupler, the gradation of each cyan color image obtained by exposure with each of the red filters A and B shown below is γ _A , Γ _B , γ _B /
_A silver halide color photographic material, wherein γ _A ≧ 1.05. Red filter A: Spectral transmittance is 2% or less in the range of 350 nm to 585 nm, and wavelength λ having a transmittance of 50% is 600 nm.
≦ λ ≦ 610 nm, and the transmittance at 630 nm to 800 nm is 8
Short wavelength absorption red filter having 0% or more Red filter B: Spectral transmittance in the range of 350 nm to 625 nm is 2% or less, and wavelength λ having a transmittance of 50% is 640 nm.
≦ λ ≦ 650 nm, and the transmittance at 670 nm to 800 nm is 8
Long wavelength absorption red filter with 0% or more 2. The wavelength λmax giving the maximum sensitivity of the spectral sensitivity distribution of the red-sensitive silver halide emulsion layer is 610 nm ≦ λmax ≦ 645.
2. The silver halide color photographic light-sensitive material according to claim 1, wherein 3. A silver halide color photographic light-sensitive material according to claim 1, comprising at least one compound represented by the following general formula [Q]. General formula [Q] Q (-TIME-) _n X [wherein Q is an oxidation-reduction reaction in a developing process.
A redox residue releasing a moiety other than Q,
Represents a divalent group that adjusts the timing of releasing X.
X represents a development-inhibiting residue, and n represents 0 or 1.]