JPS6267537A - Silver halide color photographic material - Google Patents

Abstract

PURPOSE:To obtain a photographic material having superior shading reproducibility in a high density region without deteriorating the color reproducibility in low and medium density regions by incorporating at least one kind of coupler having 0.7-0.01 relative coupling rate to the coupling rate of the main coupler in emulsion layers and developing a color different from a color developed by the main coupler by such an amount that the maximum density of the developed color is regulated to 0.03-0.40 in a photosensitive unit. CONSTITUTION:This silver halide color photographic material has a photosensitive unit on the support. The unit contains a coupler developing yellow, magenta or cyan color in two or more emulsion layers having the practically same color sensitivity and different photosensitivities. In the photosensitive unit, a photosensitive silver halide emulsion layer related to the color reproduction of the highest density part and/or a nonphotosensitive layer adjacent to the emulsion layer contains at least one kind of coupler having 0.7-0.01 relative coupling rate to the coupling rate of the main coupler in the two or more emulsion layers and developing a color different from the color developed by the main coupler by such an amount that the maximum density of the developed color is regulated to 0.03-0.40 in the photosensitive unit.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic material with improved image quality, and particularly to a silver halide color photographic material with improved tone reproduction and color reproducibility.

(Prior art) In recent years, color photographic materials are required to have increasingly higher image quality, and it is necessary to improve multifaceted and comprehensive photographic characteristics such as image structure such as sharpness and graininess, and color reproduction and tone reproduction. .

In terms of color reproducibility, it is desired not only to faithfully reproduce the hue of the subject, but also to reproduce the tone more vividly and more faithfully. To obtain more vivid color reproduction, so-called masking or interimage effects have been used, as disclosed in US Pat. No. 2,521,908.

Regarding the multilayer effect, for example, Hanson
n) et al., 'Journal of the Optical
Society of America (, Journalof
the 0ptical 5ociety of Am
Erica), Vol. 42, pp. 663-669, and A. Teils (8, Th1efs) Me - (2eitschrif
t f proud WissenschaftlicheP
photography, photophysique
e and Photochemie), Vol. 47, pp. 106-118 and pp. 246-255.

As a means for improving the interlayer effect, there is a method of using a so-called DIR coupler which reacts with an oxidized product of a developing agent to release a development inhibitor.

The DIR coupler has, in the coupling active position of the coupler,
It is a coupler in which a group having a development inhibiting effect or a precursor thereof is introduced separately from this, and specific examples thereof include U.S. Pat.
No. 3.615.506, No. 3.617.291
It is written in the number etc.

U.S. Pat. No. 3,536.486 also discloses that a diffusive 4-thiazoline-2-thione is introduced into an exposed color reversal photographic element in U.S. Pat. No. 3,536.
No. 487 describes a method for introducing diffusible 4-thiazoline-2-thione into an unexposed color reversal photographic element to obtain an interlayer effect.

Furthermore, in Japanese Patent Publication No. 48-34169, when developing a color photographic material to reduce silver halide to silver, N-substituted-
It is described that the presence of a 4-thiazoline-2-thione compound produces a significant multilayer effect.

A colloidal silver-containing layer may also be provided between the cyan and magenta layers of a color reversal photographic element to create a multilayer effect (see Research Disclosure).
Disclosure ), Nα13116 (19
(March 1975).

Furthermore, U.S. Pat. No. 4,082,553 discloses a color reversal photographic material having a layer arrangement that allows movement of iodide ions during development, in which one layer contains latent image-forming silver haloiodide grains. There is a method of obtaining a multilayer effect by containing latent image-forming silver halide grains and silver halide grains whose surfaces are fogged so that they can be developed independently of image exposure. Are listed.

By improving the multilayer effect in this way, it is possible to improve the color reproducibility, especially the saturation, of color photographic materials, but there is a drawback that delicate shading and shadows of primary colors cannot be reproduced satisfactorily. Such disappearance of gradation is considered to be due to the fact that, in an image area where the primary color of the object is reproduced, the gradation of the complementary color does not exist or becomes softer, which is a negative effect of the large multilayer effect.

For example, when photographing red, the gradation of cyan disappears or softens due to the large multilayer effect, producing a vivid red. However, in shadow areas, subtle shading cannot be reproduced, so-called red blindness. This results in the following result. Furthermore, when yellow is photographed, the density of cyan and magenta is low and the tone is soft, and although it is possible to reproduce vivid yellow, this results in so-called yellow blindness in which the tone of shadow areas cannot be reproduced.

As mentioned above, if the heavy effect is increased in order to improve the saturation, the tone reproduction of the shading and shading of the primary colors tends to deteriorate.In order to improve this, couplers with different color hues are Although there are some descriptions of mixing the primary colors, there is almost no tone reproduction in the shadow areas of the primary colors, and the disadvantages are that the color mixing is large for primary colors with high brightness, and the saturation and color reproducibility are extremely deteriorated, and the hue is shifted. There is.

(Objective of the Invention) The object of the present invention is to achieve high chroma and saturation in the low and medium density ranges without impairing color reproducibility, and to provide excellent reproduction of delicate shadows in the high density range. An object of the present invention is to provide a silver halide color photographic material.

(Structure of the Invention) The object of the present invention is to use a coupler (main coupler) in which two or more emulsion layers having substantially equal color sensitivities and different light sensitivities develop mainly yellow, magenta, or cyan. A silver halide color photographic material having on a support a light-sensitive unit containing a light-sensitive silver halide emulsion layer and/or a light-sensitive silver halide emulsion layer that is responsible for tone reproduction in the highest density area in the light-sensitive unit and/or adjacent to this emulsion layer. The non-photosensitive layer contains at least one coupler (auxiliary coupler) which has a relative coupling rate of 0.7 to 0.01 with respect to the main coupler contained in the emulsion layer and which develops a different hue. The maximum color density within this photosensitive unit is 0.
This was achieved by a silver halide color photographic material characterized by containing silver halide in an amount of 0.03 to 0.40.

The main coupler here means, for example, a yellow coupler in the case of a blue-sensitive silver halide emulsion layer, a magenta coupler in the case of a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, which are found in combination in commonly used color photographic materials. In the case of an emulsion layer, it refers to cyan coupler.

The photosensitive silver halide emulsion layer responsible for tone reproduction in the highest density area and/or the non-photosensitive layer adjacent to this emulsion layer contains a coupler (hereinafter referred to as auxiliary coupler) that develops a different hue from the main coupler. ) contains at least one kind, preferably two or more kinds, other than cyan, magenta, and yellow endogenous couplers.

The relative coupling speed of the auxiliary coupler to the main coupler is between 0.70 and 0.01, preferably 0.6
0 to 0.02, particularly preferably 0.50 to 0.05. If the coupling rate is less than 0.01, the effect of the present invention will not be achieved, and if the coupling rate is more than 0.70, color mixing will occur. Furthermore, when couplers of two or more hues are used as auxiliary couplers, it is preferable that the relative coupling speeds between the auxiliary couplers do not differ by more than 1:5.

In addition, the maximum color density of the auxiliary coupler is 0.03 to 0.4.
0, preferably 0.05 to 0.35, particularly preferably 0.10 to 0.30. The maximum color density is 0.
If it is smaller than 0.03, the effect of the present invention will not be exhibited;
If it is larger, color mixing will occur.

Further, when couplers of 1.2 or more hues are used as auxiliary couplers, it is preferable that the ratio of maximum color density between the auxiliary couplers does not deviate from more than 1:5.

The method for measuring relative coupling speed will be described below.

The relative coupling speed of the couplers is R M /
It is represented by RN, and in the case of a phenol coupler having a ureido group at the 2-position among yellow couplers and cyan couplers, it is represented by Re/Ro, which will be described later.

First, a method for measuring the RM/RN value will be described.

The coupling reactivity of the couplers is such that two types of couplers, M and N, give different dyes that can be clearly separated from each other.
It can be determined as a relative value by measuring the collapse of each pigment in a color image obtained by mixing and adding them to an emulsion and performing color development.

Maximum color density of coupler M (DM) max.

The color density at the intermediate stage is expressed as DM, and the coupler N
(DN)max respectively.

If expressed in DN, the ratio RM of the reaction activity of the two-force puller is
/RN is expressed by the following formula.

In other words, several DIVI and D
The coupling reaction activity ratio RM/RN is determined from the slope of the straight line obtained by plotting the value of N on two orthogonal axes.

By using a fixed coupler N and determining the value of RM/RN for various couplers as described above, the coupling reactivity, that is, the coupling rate can be relatively determined.

On the other hand, two of the yellow coupler and cyan coupler
Since the reactivity and hue of phenolic couplers that have a ureido group in the position vary depending on the seed neck and bond of the oil used, a comparison coupler (coupler N) is coexisting as described above to evaluate the reactivity. I don't like that. Therefore, among yellow couplers and cyan couplers, phenolic couplers having a ureido group at the 2-position are evaluated for reactivity as described below.

A sample prepared by adding the desired coupler alone to the emulsion is exposed and developed, and the maximum density of the developed color image is determined by (
Do) max. On the other hand, in the color developer, part 1
The maximum density of the developed color image when processed with a developer containing 1.5 g of citradinic acid per sample is defined as (Dc)max.

At this time, the coupling coloring property Rc /Ro of the coupler
is (Dc) max / (Do) max
can be evaluated relatively.

The photosensitive silver halide emulsion layer is responsible for reproducing the tone of the highest density area of the photosensitive unit, that is, reproducing subtle shadows, consisting of two or more silver halide emulsion layers that have substantially the same color sensitivity and different photosensitivity. In the case of color reversal film and color reversal paper, at least one photosensitive unit 7 of blue-sensitive, green-sensitive, red-sensitive or near-infrared sensitive photosensitive units;
} corresponds to the highest sensitivity layer. In addition, negative-acting color paper, color print film, color positive film,
In the case of color negative films, it corresponds to the lowest sensitivity layer of at least one photosensitive unit among blue-sensitive, green-sensitive, red-sensitive, or near-infrared sensitive photosensitive units.

When the present invention is applied to a color reversal film or a color reversal paper, it is preferable that the multilayer effect is large.

As a method for improving the multilayer effect, US Patent No. 3.
227, 554, 3, 701, 783
No. 3, 615, 506, 3. 617,
so-called DIR couplers that react with oxidation products of developing agents to release development inhibitors, as disclosed in US Pat. monothione, or N-B-converted-4 disclosed in Japanese Patent Publication No. 48-34169
- Method for containing thiazoline-2-thione compound, Research Disclosure +
Closure) No. 1 3 1 1 6( 1
A method of providing a colloidal silver-containing layer between a cyan layer and a magenta layer as disclosed in U.S. Pat. There is a method of containing silver halide grains whose surfaces are fogged so that they can be developed.

Furthermore, a core-shell type silver halide grain consisting of a silver halide inner core with a fogged surface and a silver halide outer shell covering the surface, as disclosed in JP-A No. 59-114852, is also used. The effect will improve.

Furthermore, the interlayer effect is also improved by a compound represented by the following general formula CI described in Japanese Patent Application No. 59-278856.

General formula [■] N-N? In the formula, R represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group, and Z represents a polar substituent. Y is R. (2) -S- or -N-, and R1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or aralkyl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that decomposes to produce a hydrogen atom. n represents 0 or 1.

The present invention applies to color films, regardless of negative type or reversal type.
Applicable to color paper, color print film, etc.

In particular, it is preferably applicable to color reversal film, color reversal paper, and color paper printed from color negative film with a large multilayer effect, color print film, and color body film.

In the case of color reversal films and color reversal papers, the photosensitive silver halide emulsion may be a so-called negative emulsion or an autopositive emulsion.

Next, the difference between the present invention and a known case where different types of couplers are used together in the same emulsion layer will be described.

Research disclosure? (Research D
Isclosure No. 18362 (July 1979), JP-A-53-133432 discloses that the reproducibility of gray to black colors can be improved by providing a light-sensitive silver halide emulsion layer containing a coupler that develops black color. Although disclosed, the present invention seeks to improve color reproduction without the use of black couplers.

Furthermore, Japanese Patent Publication No. 49-25901 discloses that in a color positive photographic material, a low-sensitivity emulsion layer contains a coupler that absorbs light in the vicinity of 500 nm and develops a red color, and a coupler that absorbs light in the vicinity of 600 nm and develops a blue color. It is disclosed that the visual density of a black image can be increased by filling the gap between the absorption of the three colors cyan, magenta, and yellow.

The present invention uses only three color pigments of cyan, magenta, and yellow to improve shadow reproduction in high density areas without impairing saturation and color reproduction in low density and medium density areas.
This invention is different from the above two inventions.

In addition, in the case of color papers and color positive photographic materials, if a blue coupler and a red coupler are included in the low-speed emulsion layer, the saturation in the low-density and medium-density regions will not be impaired, but color reversal film , for color reversal paper,
When a blue coupler and a red coupler are contained in a low-speed emulsion layer, unlike the case of color paper and color positive photographic materials, the saturation in the low and medium density regions is significantly deteriorated. Therefore, in the case of color reversal films and color reversal papers, it is not practical to include blue couplers and red couplers in low-speed emulsion layers.

U.S. Patent No. 2.592.511. The issue includes a blue-sensitive silver halide emulsion layer containing a cyan coupler and a magenta coupler in addition to a yellow coupler, an edge-sensitive silver halide emulsion layer containing a cyan coupler and a yellow coupler in addition to a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler and a yellow coupler in addition to a magenta coupler. It is described that the silver halide emulsion layer contains a yellow coupler and a magenta coupler in addition to the cyan coupler to correct the hue deviation of the color image of the main coupler. It is disclosed that by mixing a coloring agent of another color in addition to the original coloring agent, an intermediate gray image is added or added to the original color image to improve unnatural color appearance.

However, these inventions are similar to the present invention in that the coloring dye is composed of a cyan coupler, a magenta coupler, and a yellow coupler, but in these inventions, a coupler of another color is mixed in addition to the main coupler, and a main coupler is used. There is no mention or suggestion of the relative coupling speed with. Further, there is no suggestion whatsoever regarding the coloring density range and coloring density of a light-sensitive silver halide emulsion layer in which a coupler of another color is mixed into the main coupler.

As a result of extensive studies, the present inventors have discovered that the objects of the present invention can be achieved by adding a certain amount of a different color-forming coupler, that is, an auxiliary coupler, having a relative coupling rate within a certain range to a certain decoy. . If the coupling speed of a coupler of another color, that is, an auxiliary coupler, is relatively fast compared to the main coupler, the auxiliary coupler will develop the color preferentially, resulting in color mixing, which will affect the saturation and color reproduction. Sexuality becomes extremely worse. Furthermore, if the light-sensitive silver halide emulsion layer into which the auxiliary coupler is mixed is the emulsion layer that is responsible for tone reproduction in the low density range, it will cause color mixture in high brightness color images, resulting in poor saturation and color reproducibility. It gets extremely bad.

The dye-forming material (color coupler) used in the silver halide color photographic material of the present invention includes a) a coupler capable of forming a colored pigment by coupling with an oxidized product of an aromatic primary amine; ) There are dye-releasing compounds such as 3-pyrazolones that release dyes through a redox reaction with oxidized forms of black-and-white developers.

Typical examples of useful color couplers include naphyl or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or multi-ring ketomethylene compounds. These cyans that can be used in the present invention,
Specific examples of magenta and yellow couplers are available from Research.
Disclosure (RD) 17643 (1978
February)■-D section and 18717 (November 1979)
described in patents cited in May).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent coupler substituted with a coupling-off group is preferable to a two-equivalent coupler whose coupling active position is a hydrogen atom, since the amount of coated silver can be reduced.

Further, a coupler in which the coloring dye has appropriate diffusivity, a colorless coupler, a DIR coupler that releases a development inhibitor or a coupler that releases a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is a diffusion-resistant oil-soluble acylacetamide coupler. A specific example is U.S. Patent No. 2.407.
No. 210, No. 2.875.057 and No. 3
．． 265.506 etc. The use of two-equivalent yellow couplers is preferred for the present invention and is described in U.S. Pat.
．． Oxygen atom separation type yellow couplers described in Japanese Patent Publication No. 58-10739, U.S. Pat. No. 4.401.752, U.S. Pat.
RD18053 (April 1979), UK Patent No. 1
．． No. 425.020, West German Application No. 2.219.91
No. 7, No. 2.261.361, No. 2.329゜5
Typical examples include the nitrogen atom separation type yellow couplers described in No. 87 and No. 2.433.812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness.
On the other hand, α-peizoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include diffusion-resistant, oil-soluble indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. No. 2.343
．． No. 703, No. 2.600.788, No. 2.9
No. 08.573, No. 3.062.653, No. 3.
No. 152.896 and No. 3.936.015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the leaving group in U.S. Pat.
．． Particularly preferred are the arylthio groups described in No. 89'7. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3
．． Pyrazolobenzimidazoles as described in US Pat. No. 061.432, preferably pyrazolo[5,1-c][1,2,4]triazoles as described in U.S. Pat.
(June 1984) and JP-A No. 60-33552, and pyrazolopyrazoles described in Research Disclosure 24230 (June 1984) and JP-A No. 60-43659. .

The imidazo[
1,2-b]pyrazoles are preferred and are described in U.S. Patent No. 4.
Pyrazolo[1,5-b] described in No. 540.654
[1,2,4] Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include diffusion-resistant oil-soluble naphthol and phenolic couplers, such as those described in U.S. Pat. No. 2.474.293, preferably U.S. Pat. No. 4.052 .2
No. 12, No. 4.146.396, Ibid. 4, 228
．． Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 233 and No. 4.296.200. Specific examples of phenolic couplers include U.S. Patent Nos. 2.369.929 and 2.8.
No. 01.171, No. 2.772.162, No. 2.
895.826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3,772.
Phenolic cyan couplers having an alkyl group with a carbon number of 2 or more, such as an ethyl group, at the meta-position of the phenol nucleus described in No. ゜002, U.S. Pat. 4.126.39
No. 6, No. 4, 334.011, No. 4.327.
173, West German Patent Publication No. 3, 329.729 and European Patent No. 12L 365, etc.2,
5-Diacylamino substituted phenolic couplers and U.S. Pat. No. 3.446.622, U.S. Pat. No. 4.333.99
No. 9, No. 4.451.559 and No. 4, 42 of the same.
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 7.767. Patent application 1986-93605
, 59-264277 and 59-268135
A sulfonamide group at the 5-position of the naphthol described in
Cyan couplers substituted with amide groups or the like also have excellent fastness of colored images and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use a colored coupler in combination with a color negative sensitive material for photographing. U.S. Patent No. 4.163.670 and Japanese Patent Publication No. 5
7-39413, etc. or U.S. Pat. No. 4,004.929, U.S. Pat.
．． No. 138.258 and British Patent No. L i46.36
Typical examples include the magenta-colored cyan coupler described in No. 8.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4.366,237 and British Patent No. 2
．． Specific examples of magenta couplers are given in No. 125.570.
Also, European Patent No. 96.570 and West German Application No. 3
．． No. 234.533 describes specific examples of yellow, magenta and cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3.451.82.
No. 0 and No. 4.080.211. Specific examples of polymerized magenta couplers include British Patent No. 2.102.173 and U.S. Pat. No. 4,367,28.
No. 2, Patent Application No. 60-75041 and No. 60-113
596.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

The couplers used in the present invention can be introduced into the light-sensitive material by various known fractional methods. For example, typical examples include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions. Examples of high-boiling organic solvents are U.S. Pat.
322.027, etc. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, field filtration, etc. before use for application.

Dye-providing compounds that can be used in the present invention include those that form images of diffusible dyes or their precursors as a result of development; for example, dye developers and non-diffusible couplers that release diffusible dyes can also be used. However, dye-releasing redox compounds (well known as DRR compounds) are preferred. Particularly useful emitted dyes are cyan, magenta and yellow dyes.

When three or two of the cyan coupler, magenta coupler, and yellow coupler of the present invention are contained in a photosensitive emulsion layer or an adjacent non-photosensitive layer, the cyan coupler, magenta coupler, and yellow coupler are mixed. It can be contained as an emulsified dispersion that is emulsified and dispersed, or as an emulsified dispersion that is separately emulsified and dispersed.

The present invention is particularly effective when applied to color reversal and color print materials with high color separation. In order to improve color separation, it is effective to use image-forming dyes with low side absorption. Specifically, dyes that emit monoazo dyes with narrow absorption half-width and little unnecessary absorption are effective. Typical examples include color photographic materials containing a forming agent and color photographic materials containing a pyrazoloazole coupler with little unnecessary absorption.

The coupling speeds of the main couplers in silver halide emulsion layers composed of two or more layers of the same color sensitivity may be different.

Particularly in a color-sensitive layer in which an auxiliary coupler is added to the main coupler, the coupling rate of the main coupler in the emulsion layer to which the auxiliary coupler is added and the emulsion layer to which it is not added may be different.

When changing the coupling speed of the main coupler in emulsion layers composed of two or more layers with the same color sensitivity, the coupling speed of the main coupler in the layer to which the auxiliary coupler is added is different from that of the main coupler in the layer to which the auxiliary coupler is not added. It is preferable to make the coupling speed faster than the coupling speed of the coupler from the viewpoint of preventing color mixing.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the photographic material of the invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the photographic emulsion layer of the photographic material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

The preferred silver halide for color photographic materials is silver iodobromide or silver iodochlorobromide containing up to about 15 mole percent silver iodide. Particularly preferred is about 2 mol % to about 12 mol %.
Silver iodobromide containing up to mol% silver iodide. Silver bromide, silver chlorobromide and silver iodochlorobromide are preferred for color photographic materials for printing.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of about 10 microns, monodisperse emulsion with a narrow distribution, or polydisperse with a wide distribution. An emulsion may also be used.

As a monodisperse emulsion, silver halide grains having an average grain diameter of greater than about 0.1 micron, of which at least about 95
Emulsions in which the weight percent is within ±40% of the average grain diameter are typical. The present invention provides an emulsion having an average grain diameter of about 0.25 to 2 microns and having at least about 95% by weight or at least about 95% by number of silver halide grains within a range of ±20% of the average grain diameter. Can be used.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
nce ancl Bngineering
), Vol. 14, pp. 248-257 (19
1970); U.S. Patent No. 4.434.226, U.S. Patent No. 4.4
No. 14.310, No. 4.433.048, No. 4.43
9.520 and British Patent No. 2.112.157.

When tabular grains are used, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as disclosed in the above-cited U.S. Pat. No. 4.434.226.
It is described in detail in the issue.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1.027.1.
No. 46, U.S. Patent No. 3.505.068, U.S. Patent No. 4.44
4.877 and Japanese Patent Application No. 58-248469. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. These emulsion grains are described in US Pat. No. 4.094.684, US Pat. No. 4.142.900, US Pat.
No. 92, U.S. Patent No. 4.349.622, 4, 39
No. 5.478, No. 4.433.501, No. 4
．． No. 463.087, No. 3.656.962,
No. 3.852.067, JP-A-59-162540
Disclosed in the issue etc.

Also, mixtures of particles of various crystal forms may be used.

The emulsion of the present invention is usually used which has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No. 1
7643 and Nα18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

The spectral sensitizer and supersensitizer may be added at the time of silver halide grain formation, immediately after formation, immediately before chemical sensitization, during chemical sensitization, after chemical sensitization, or at the time of preparing the coating solution. .

1 Chemical sensitizer page 23 page 648 right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizers, pages 23-24 Page 648 right column - Super sensitizers
Page 649, right column 4 Brightener
Page 24 8 Dye image stabilizer Page 25 9 Hardener page 26 Page 651 left column 10
Binder page 26 Same as above 11
Plasticizers, lubricants Page 27 Page 650 Right column For photographic processing of layers consisting of photographic emulsions made using the present invention,
For example, Research Disclosure-176 No. 28~
Any of the known methods and known treatment liquids as described on page 30 can be applied. The treatment temperature is usually selected between 18°C and 50°C, but it may also be lower than 18°C or above 50°C.

When the silver halide color photographic material of the present invention is a negative-working color photographic material, ①) Color development, bleaching, and fixing steps are positive-working color photographic materials: 2) Black-and-white development, reversal, and color development. Development, bleaching, and fixing steps are performed respectively. Direct positive color photographic materials in which an internal latent image type silver halide emulsion is developed in the presence of a nucleating agent follow the process described in 1) above.

Black and white developer for color reversal photographic material used in the present invention (first
As the developer (developing solution), known developing agents can be used. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol),
1-phenyl-3-pyrazoline, ascorbic acid, and 1,2.
A heterocyclic compound in which a 3°4-tetrahydroquinoline ring and an intrene ring are condensed can be used alone or in combination.

In addition, the black and white developer used in the present invention may include preservatives (e.g., sulfites, bisulfites, etc.), buffers (e.g., carbonates, boric acid, borates, alkanolamines),
Alkaline agents (e.g. hydroxides, carbonates), solubilizing agents (
(e.g., polyethylene glycols, esters thereof), pH adjusters (e.g., organic acids such as acetic acid), sensitizers (e.g., quaternary ammonium salts), development accelerators, surfactants, toning agents, antifoaming agents. , a hardening agent, a viscosity imparting agent, etc. may be contained.

The first developer used in the present invention must contain a compound that acts as a silver halide solvent, and the above-mentioned sulfite added as a preservative usually plays this role. The sulfite and other usable silver halide solvents include, for example, KSCN, Na5CN, 2SO3, N
azS○3, ni, S, 05, Na2S2O5, K2
3203, Na2S2O3, etc.

In addition, a development accelerator is used to impart a development accelerating effect, and is particularly described in Japanese Patent Application Laid-Open No. 57-63580.
These compounds may be used alone or in combination of two or more, and the above-mentioned silver halide solvents may be used in combination.
' If the amount of these silver halide solvents used is too small, the progress of development will be slowed down, whereas if it is too large, fog will occur in the silver halide emulsion. Therefore, there is a preferable usage amount, which can be easily determined by those skilled in the art.

The p11 value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast;
Desirably, it ranges from about 8.5 to about 11.5.

To carry out sensitization using such a first developer, usually,
It is sufficient to extend the time up to about three times the standard processing time.

If the treatment temperature is raised at this time, the extension time for the sensitization treatment can be shortened.

The fogging bath used in the inversion step can contain a known fogging agent. That is, stannous ion-organophosphate complex salt (U.S. Pat. No. 3,617,282),
Stannous ion organic phosphonocarboxylic acid complex salt
B-32616), stannous ion complex salt borohydride compounds such as stannous ion-aminopolycarboxylic acid complex salts (UK Patent No. 1.209.050) (U.S. Pat. No. 2.9EI4.567) and boron compounds such as heterocyclic amine poran compounds (UK Patent No. 1.011.000).
The pu of the reversal bath has a wide range from the acidic side to the alkaline side, and has a pt of 12 to 12, preferably 2.5 to 12.
10, particularly preferably in the range of 3-9.

The color developer used in the color development treatment of the photographic material of the present invention has the composition of a general color developer containing an aromatic primary amine developing agent.

The color developer may also contain other known developer component compounds. For example, alkali agents, buffering agents, etc. include caustic soda, caustic potash, soda carbonate, potassium carbonate,
Tertiary sodium phosphate or potassium, potassium metaborate, borax, etc. are used alone or in combination.

Color developing solutions usually contain sulfites, which are used as preservatives.
For example, sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite) or hydroxylamine can be added.

If necessary, any development accelerator can be added to the color developing solution.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleaching agent, potassium ferricyanide,
Particularly useful are sodium iron(III) ethylenediaminetetraacetate, ammonium iron(I[I) ethylenediaminetetraacetate, and ammonium iron(III) diethylenetriaminepentaacetate.

Aminopolycarboxylic acid iron(III) complexes are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Bleach or bleach-fix solutions include U.S. Patent No. 3,042,520.
Specification of No. 3241966, Special Publication No. 1987-8
Various additives can also be added, including the bleach accelerators described in Japanese Patent Publication No. 506 and Japanese Patent Publication No. 45-8836.

The fixing bath of the present invention contains 30 g/1 ammonium salt, sodium salt, and potassium salt of thiosulfate as a fixing agent.
2~200g/j! In addition, stabilizers such as sulfites and isomeric bisulfites, hardening agents such as potassium alum, and PI buffers such as acetates, borates, phosphates, carbonates, etc. etc. can be included. fixer p)l
is 3-10, more preferably 5-9.

(Examples) Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example: On a subbed cellulose tertiary acid film support,
A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared and designated as sample 101.

1st layer: Antihalation layer Black colloidal silver 0.25g/m2 Ultraviolet absorber U-10,04g/m2 Ultraviolet absorber U-20,1g/m2 Ultraviolet absorber U-30,1g/m" High boiling point organic solvent 0-1 Gelatin layer containing 0.1 cc/m2 (dry film thickness 2μ) 2nd layer: Intermediate layer compound H-10,05 g/m2 Gelatin layer containing high boiling point organic solvent ○-20,05 cc 7 m” (dry Film thickness: 1 μ) Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 Silver amount: 0.5 g/m2 (Iodine content: 4 Mol%, average particle size 0.3 μ) Coupler C-10.2 g/m' Coupler C-10.05 g/m2 Gelatin layer containing 7 m2 of high boiling point organic solvent ○-20.12 cc (dry film thickness 1 μ) 4th Layer: Second red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-t and S-2 Silver amount: 0.8 g/m" (Iodine content: 2.5 mol%, average Particle size 0.55μ) Coupler C-10, 55g/m2 Coupler C-20゜14g/m2 Gelatin layer (dry film thickness 2.5μ) containing 0.33cc/m2 high-boiling organic solvent 5th Layer: Interlayer compound H-10, 1 g/m'' Gelatin layer containing high boiling point organic solvent 0-2 0.1 cc/m' (dry film thickness 1μ) 6th layer: 1st edge sensitizing emulsion layer sensitizing dye Weight of silver iodobromide emulsion spectrally sensitized with S-3 and S-4: 0.7 g/m' (Iodine content: 13 mol%, average grain size: 0.3 μ) Coupler C-30, 35 g/m' m2 Ceratin layer containing high boiling point organic solvent 0-2 0.26 cc/m' (dry film thickness 1 μ) 7th layer: 2nd edge-sensitive emulsion layer spectrally sensitized with sensitizing dyes S-3 and S-4 Silver iodobromide emulsion Silver amount: 0.7 g/m" (Iodine content @ 2.5 mol%, average grain size 0.8 μ) Coupler C-40, 25 g, 7 m" High boiling point organic solvent 0-2 Seratin layer containing 0.05cc/m2 (dry film thickness 2.5μ) 8th layer: Intermediate layer compound H-10.05g/m2 Gelatin layer containing high boiling point organic solvent ○-20.1g/m2 (dry film thickness 1μ) 9th layer: yellow filter single layer yellow colloidal silver 0.1 g/m” compound
H-10.02g/m" compound H-20.03g/m2 Gelatin layer containing high boiling point organic solvent 0.2 0.04cc/m" (dry 8 thickness 1μ) 10th layer: 1st blue-sensitive emulsion layer sensitization Silver iodobromide emulsion spectrally sensitized with dye S-5 Silver amount...0.6 g/m2 (Iodine content 2.5 mol%, average grain size 0.7μ) Coupler C-50,5 g/m2 Gelatin layer containing high boiling point organic solvent 0-2 0.1 cc/m2 (dry film thickness 1.5μ) 11th layer: second blue-sensitive emulsion layer Silver emulsion Silver amount: 1.1 g 7 m" (Iodine content 2.5 mol%, average grain size 1.2 μ) Coupler C-51.2 g/m" High boiling point organic solvent 0-2 0.23 cc/ Gelatin layer containing m" (dry film thickness 3μ) 12th layer: 1st protective layer UV absorber U-10,02g/m" UV absorber U-20,03g/m2 UV absorber U-30,03g/m2 m' Gelatin layer containing ultraviolet absorber U-40.29g/m2 high boiling point organic solvent 0-1 0.28cc/m2 (dry film thickness 2μ) 13th layer: fine particle odor covered with the surface of the second protective layer Silver emulsion Silver amount: 0.1 g/m2 (Iodine content: 1 mol%, average grain size: 0.06 μ) Gelatin layer containing polymethyl methacrylate particles (average grain: 1.5 μ) (dry film thickness: 0.8 μ) In addition to the above composition, gelatin hardener H-3 and a surfactant were added to each layer.

Preparation of sample 102 In addition to coupler C-4, coupler C was added to the seventh layer of sample 101.
-1 (relative coupling speed Rc with coupler C-4
+/RC4=0.8) when the maximum color density is 0.
Sample 102 was prepared in exactly the same manner as Sample 101 except that the content was increased to 30%.

Preparation of Sample 103 In addition to coupler C-3, coupler C-6 (relative coupling rate RC with coupler C-3) was added to the sixth layer of sample 101.
Sample 103 was prepared in exactly the same manner as Sample 101 except that s/Rc3=0.7) was contained so that the maximum color density was 0.30.

Samples 104 to 107 Coupler C-6 (relative coupling rate RC with coupler C-4) was added to coupler C-4 in the seventh layer of sample 101.
s/RC4=0.7) and the maximum color density is 0.
Samples 104-1 were prepared in exactly the same manner as sample 101 except that the content was adjusted to 50.0.20.0.30.0.10.
07 was produced.

Preparation of sample 108 In addition to coupler C-4, coupler = C-7 (relative coupling rate R with coupler C-4) was added to the seventh layer of sample 101.
C? Sample 108 was prepared in exactly the same manner as Sample 101, except that the sample 108 contained ./RC4=0.1) so that the maximum color density was 0.30.

Preparation of Sample 109 Sample 109 was prepared in exactly the same manner as Sample 101 except that the eighth layer of Sample 101 contained coupler C-6 so that the maximum color density was 0.30.

In addition to coupler C-4, coupler C-7 and coupler C-5 (relative coupling rate Rc5 /Rc, = 0.1 with coupler C-4) were added to the seventh layer of sample 101 prepared using sample +l'41100. Sample 1 except that it contained so that the maximum color density was 0.30.
Sample 110 was prepared in exactly the same manner as Sample 01.

Using these samples 101 to 110, a bright red subject with subtle shading was photographed, and the following development processing was performed.

Processing process Step Time Temperature First development 6 minutes 38℃ Water washing 2 minutes 7 times
Transfer 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Drifting
White 6 minutes 〃
Fixation 4 minutes 〃Water
Wash 4 minutes
Constant 1 minute Normal Wet/Dry The composition of the smoke treatment liquid used was as follows.

No. - developer water
700m, i! N, N,
N-) Limethylenephosphonic acid pentasodium salt 3g Sodium sulfite 20g Hydroquinone monosulfonate
30 g sodium carbonate (monohydrate)
30 g 1-phenyl 4-methyl 4-hydroxymethyl-3-pyrazolide 7 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) Add 2 ml water 1
0100O inverted liquid water
700mj! nitro ro ・N -N
-N-Trimethylenephosphonic acid, 5-sodium rum salt 3g Stannous chloride (dihydrate) Igp-aminophenol 0.1g Sodium hydroxide
8g glacial acetic acid 1
5mj! Add water to 1000ml color developer water
700 ml Nitrilo N-N-N-)
rimethylenephosphonic acid 5-sodium salt 3g Sodium sulfite 7g Sodium triphosphate (decahydrate) 36g Potassium bromide 1g Potassium iodide (0,
1% solution) 90ml sodium hydroxide
3g citradinic acid
Add 1.5g N.ethyl-N-(β-methanesulfonamidoethyl)-3.methyl-4-aminoaniline sulfate 11g ethylenediamine 3g water
1000mβ adjustment liquid water
700mj! Sodium sulfite 12
g Ethylenediamine sodium tetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid
Add 3mfl water
1000mA bleach solution water
8 0 0ml Sodium ethylenediaminetetraacetate (dihydrate) 2g Ethylenediaminetetraacetate iron ([II) ammonium (dihydrate) 120g Potassium bromide 100g Add water
10100O! fixer water
800mn Sodium thiosulfate 80.0
gSodium sulfite 5.0gSodium bisulfite 5.0gAdd water
1000ml stable liquid water
800rn 1 formalin (37% by weight)
5.0 g Fuji Drywell (surfactant manufactured by Fuji Film ■) Add 5.0 ml water to 1000 ml The results are shown in Table 1.

The compounds used to prepare the samples are as follows.

t C5flz ○H ○H C-4 Cβ I COOC, □ll. s -nt C4H9 J-3 -I H-2 CJsSO3-C3H6SO,)l C-7 H □ Example 2 The following first sample was placed on a support laminated on both sides with polyethylene.
Sample 201 was prepared by sequentially discarding the layers (bottom layer) to the ninth layer (top layer).

1st layer: 1st blue-sensitive emulsion layer Silver chlorobromide emulsion (silver bromide 80 mol% 0.5 μ) Silver 150 mg/m'
A IO-Ka15- 150 mg/m' (*6) Coupler solvent (*7) 75 mg/m' Gelatin 600 mg/m' 2nd layer: 2nd blue-sensitive emulsion layer Silver chlorobromide emulsion (80 moles of silver bromide) % 0, 7 μ) Silver 150mg/m' Yellow coupler 150mg/m' (*6) Coupler solvent (*7) 75mg/m' Gelatin 600mg/m' 3rd layer; Intermediate layer gelatin 1000mg/m' 4th layer Two-edge sensitive emulsion layer Silver chlorobromide emulsion (silver bromide 70 mol%) Silver 200 mg/m' Sensitized color* (*9) 0.5 mg/m' Magenta coupler 130 mg/m' (*4) Coupler solvent ( *5) 85mg/m' Gelatin 430mg/m' 5th layer: Intermediate layer UV absorber (*1) 600mg/m' UV absorber solvent 300mg/m' (*2) Gelatin: / 800mg/m' 6th layer Layer: Intermediate layer Ze597 500mg/m' Seventh layer: First red-sensitive emulsion layer Silver chlorobromide emulsion (silver bromide 50 mol% 0.3μ) Silver 150mg/m' Sensitizing dye (
*8) 0.02mg/m' cyan coupler 200 mg/rn' (*3) Coupler solvent (*2) 200mg/m'' gelatin 500mg/m' 8th layer: 2nd red-sensitive emulsion layer Silver chlorobromide emulsion (Silver bromide 50 mol% 0.5 μ) Silver 150 mg/m' Sensitizing dye (
*8) 0.02mg/m' cyan coupler
200mg/m'(*3) Coupler solvent Ok 2) 200mg/m'Gelatin 5QOmg/m'9th layer: UV absorbing layer UV absorber (*1) 600mg/m'UV absorber solvent 300mg/m'(* 2) Gelatin 800mg/m'10th layer:
Protective layer gelatin 1000mg/m' for each layer,
In addition to the above composition, gelatin hardener H-3 and a surfactant were added.

(*1) Ultraviolet absorber: 2-(2-hydroxy-3-s
ec-bunaru-5-tert-butylphinyl) benzotriazole (*2) solvent nidibutyl phthalate (*3) coupler: 2-[α-(2,4-di-tert-pentylphenoxy) butanamide]-4,6 -Dichloro-5-ethylphenol (*4) coupler: 1-(2,4,6-dolichlorophenyl)-'3-(2-chloro-5-tetradecanamide)anilino-4-(2-butoxy5 -tert-octylphenylthio)-2-pyrazolin-5-one (*5) Solvent Nitricresyl phosphate (*6)
Coupler: α-pivaloyl-α-(2゜4-dioxy-
5,5'-dimethyloxazolidin-3-yl)-2-chloro-5-[α-(2,4-di-tert-pentyloxy)butanamide]acetanilide (*7) Solvent Nidioctylbutylphosphate = = CQ = 11 (J-(J く=N〆Q=,,,(J Preparation of sample 202) In addition to yellow coupler (*6), cyan coupler (*3) (coupler (*6) ) to the relative coupling speed R to 3)/R(*6)=0.8)
Sample 202 was prepared in exactly the same manner as Sample 201 except that it contained so that the maximum color density was 0.30.

Preparation of sample 203 A sample was prepared in exactly the same manner as sample 201, except that the first layer of sample 201 contained cyan coupler (*3) in addition to yellow coupler (*6) so that the maximum color density was 0.30. 203 was produced.

Preparation of samples 204 to 207 In the second layer of sample 201, the relative coupling rate R(*10)/R( *6)=0
．． 7), the maximum color density is 0.50 and 0.02, respectively.
．． Samples 204 to 207 were prepared in exactly the same manner as sample 201 except that the content was 0.30.0 and 10.

Preparation of sample 208 In addition to yellow coupler (*6), cyan coupler (*10) and magenta coupler (*
11) (Relative coupling speed R with coupler (*6)
Sample 208 was prepared in exactly the same manner as Sample 201 except that (*11)/R(*6)=0.7) was contained so that the maximum color density was 0.30.

Cyan coupler (*10) Magenta coupler (*11) CA O (Cf12) 20 (CH2
) A bright red and yellow subject with subtle shading was photographed using a 20CH heavy color negative film with a large decay effect, printed using the above samples 201 to 208, and subjected to the following development processing.

The results are shown in Table 2.

Treatment process (33℃) The components of each treatment step are as follows.

Color developer benzyl alcohol 15mj! Diethylene glycol 5rr + A' Potassium carbonate 25g Sodium chloride
0.1 g sodium bromide
0.5 g anhydrous sodium sulfite
2g hydroxyamine sulfate 2
gN=Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate Add 4g water to 1
β and add NaOH to pH 10.

Bleach-fix ammonium thiosulfate 124.5 g Sodium metabisulfite 13.3 g Anhydrous sodium sulfite 2.7 g EDTA ferric ammonium salt 65 g Add water to adjust pH to 1β
Adjust to 6 or 8.

Example 3 Preparation of Sample 301 The third layer of Sample 101 was a silver halide emulsion (iodine content 1 mol %, average grain size 0.3) in which the grain surfaces were covered.
Sample 301 was prepared in exactly the same manner as Sample 101, except that µ, coated silver i: 0.05 g/m') was added.

Preparation of samples 302 and 303 1 Compound Δ and compound B were added to the third layer of the wipe 101, respectively.
Samples 302 and 303 were prepared in exactly the same manner as sample 301, except that 0.2 x 10-6 mol/m' of each sample was added.

Preparation of Samples 304-307 In addition to yellow coupler C-5, cyan coupler C-7 (relative coupling rate with coupler C-5 RC7/RC5=
Samples 304 to 307 were prepared in exactly the same manner as sample lots 301 to 303, except that 0.7) was contained so that the maximum color density was 0.3.

Preparation of Sample 308 In addition to yellow coupler C-5, cyan coupler C-7 and magenta coupler C-8 (
Relative coupling speed RCa/R of coupler C-8
Sample 308 was prepared in exactly the same manner as Sample 303 except that C4=:o,7) was added so that the maximum color density was 0.3.
was created.

Preparation of sample 309 In the seventh layer of sample 308, magenta coupler 0-4, cyan coupler C-7 (relative coupling speed with coupler C-4 RC7/RC4 = 0.1), and yellow coupler. Sample 309 was prepared in exactly the same manner as Sample 308 except that C-5 (relative coupling rate with coupler C-4 RC6/Rc==0.1) was added so that the maximum color density was 0.3. Created.

Magenta coupler C-8 Compound B These samples 301 to 310 were photographed in the same manner as in Example 1.
Development processing was performed.

The results are shown in Table 3.

〔Effect of the invention〕

The silver halide color photographic material of the present invention has excellent color reproducibility in the low density region and medium density region, high chroma and saturation, and excellent tone reproducibility of shadows in the high density region.

Procedural amendment 3, relationship with the person making the amendment Applicant name n (520) Fuji Photo Film Co., Ltd. 4
, Agent (1) Insert the following sentence after "The results are shown in Table 1" on page 50, line 10 of the specification.

``Also, similar results were obtained when washing with water after fixing was performed using the following washing liquid.

Washing liquid Add 0.4 g of ethylenediaminetetraacetic acid disodium salt and add 1000 ml of sodium hydroxide. 10 layers - 1 (3) "Add water to 1β and pH
Adjust to 6 or 8. Insert the following text after ``.

[Also, similar results were obtained when washing with water after bleach-fixing was performed using the following washing solution.

washing liquid Ethylenediaminetetraacetic acid

Claims (1)

[Claims] Two or more emulsion layers having substantially equal color sensitivities and different light sensitivities, each having on a support a photosensitive unit containing a coupler (main coupler) that develops a color primarily in yellow, magenta, or cyan. A silver halide color photographic material in which a light-sensitive silver halide emulsion layer and/or a non-light-sensitive layer adjacent to this emulsion layer is responsible for tone reproduction in the highest density area in this light-sensitive unit. Relative coupling rate to the main coupler contained is 0
．． 7 to 0.01 and at least one type of coupler (auxiliary coupler) that develops colors of different hues in an amount such that its maximum color density is 0.03 to 0.40 within this photosensitive unit. A silver halide color photographic material characterized by containing: