JPH05165148A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve graininess, sharpness, and desilverability and to enhance storage stability of the photosensitive material. CONSTITUTION:The photosensitive material comprises red-sensitive, green- sensitive, and blue-sensitive silver halide emulsion layers each containing a cyan coupler, a magenta coupler, and a yellow coupler, respectively, on a support, and a nonphotosensitive layer in contact with the green-sensitive layer on the side near to the support. The size distribution of silver halide grains in at least one silver halide emulsion layer is in a state of monodispersion, and the nonphotosensitive layer contains the dye having the spectral absorption maximum in the wavelength region of 500-600nm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material which is excellent in image quality such as graininess, sharpness and desilvering property and has improved storability over time.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material), particularly a light-sensitive material for photographing, is a light-sensitive material having the same photosensitivity.
Needless to say, it is desired to have excellent image quality such as sharpness, graininess, and desilvering property, and to have stable performance in which the photographic property does not change due to storage time until the photosensitive material is developed.

One of the means for improving the image quality, especially the sharpness is to prevent light scattering.

In this technique, for example, by coating an antihalation layer, light transmitted through the silver halide emulsion layer becomes reflected light on the support surface, and the silver halide emulsion layer is exposed again to form an image. A method for preventing blurring is disclosed in, for example, JP-A Nos. 52-92716 and 55-120030.
Nos. 55-120660 and 56-12639.

As another irradiation prevention method, as described in US Pat. No. 3,409,433, scattered light resulting from silver halide crystals in a photosensitive emulsion layer is added to the emulsion layer. However, the use of the dye in a photosensitive material for photographing which requires high sensitivity is naturally limited.

Further, another non-photosensitive layer (intermediate layer)
As a method of dyeing, for example, JP-A-61-2926
No. 36, No. 61-295550, No. 62-10650.
No. 62-103641 and No. 62-103641. In both cases, the non-photosensitive layer on the exposure light source side is dyed with a photosensitive silver halide emulsion layer whose sharpness is desired to be improved. The method of the invention is quite different. Further, in the method described in JP-A-62-166330, the positional relationship in the layer constitution between the photosensitive silver halide emulsion layer whose sharpness is desired to be improved and the non-photosensitive layer to be dyed is particularly specified. However, it is described that it is preferable to dye the non-photosensitive layer on the exposure light source side of the photosensitive silver halide emulsion layer, which is basically different from the present invention.

On the other hand, JP-A-1-105947 and 1-
No. 222257 has a non-photosensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer close to the support, and the non-photosensitive layer has a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm in the film. A light-sensitive material containing a non-diffusible dye contained therein and a development inhibitor-releasing compound in at least one of the silver halide light-sensitive layers is disclosed.

However, the development inhibitor releasing compounds described therein are not sufficient in sharpness, and further improvement is desired.

Further, the graininess is not satisfactory either, and it has been desired to improve the graininess in order to improve the image quality, and the desilvering property associated with the graininess improvement is improved to further improve the image quality. It is also desired that the photographic properties of the photographic material vary greatly during storage over time, which is also a problem and must be improved.

[0010]

Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in image quality such as graininess, sharpness and desilvering property. The second object is to provide a silver halosaponide color photographic light-sensitive material in which fluctuations in photographic properties of the light-sensitive material due to aging are reduced.

[0011]

The above-mentioned object can be achieved by the silver halide color photographic light-sensitive material described below.

The silver halide color photographic light-sensitive material of the present invention contains at least one cyan coupler on the support.
A red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler, and a green-sensitive silver halide emulsion layer. In a silver halide color photographic light-sensitive material having a non-light-sensitive layer adjacent to the side closer to the support, the size distribution of silver halide grains in at least one silver halide emulsion layer is monodisperse, and , A wavelength range of 500 to 60 in the gelatin film on the non-photosensitive layer
It is characterized by containing a dye having a spectral absorption maximum wavelength at 0 nm.

Further, the silver halide color photographic light-sensitive material of the present invention comprises at least one red-sensitive silver halide emulsion layer containing a cyan coupler and at least one green-sensitive halogen containing magenta coupler on a support. Halogenated having a silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, and having a non-photosensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer close to the support. In a silver color photographic light-sensitive material, at least one layer constituting the silver halide color photographic light-sensitive material contains a compound represented by the following general formula (B), and the non-light-sensitive layer has a wavelength in a gelatin film. It is characterized in that it contains a dye having a spectral absorption maximum wavelength in the range of 500 to 600 nm.

In the general formula (B) A- (L ₁ ) _p -Z, A represents a group which cleaves (L ₁ ) _p -Z by reacting with the oxidant of the phenomenon main agent, and L ₁ represents A. Z after the bond is cleaved
Represents a group that cleaves, p represents 0 or 1, and Z represents a bleaching accelerator.

Further, the silver halide color photographic light-sensitive material of the present invention contains a cyan coupler represented by the general formula (C) represented by the following "Chemical Formula 2" in at least one of the silver halide emulsion layers. preferable.

General formula (C)

[0017]

[Chemical 2] In the formula, R ₂₁ is —CONR ₂₄ R ₂₅ , —SO ₂ NR ₂₄ R ₂₅ ,
-NHCOR ₂₄ , -NHCOOR ₂₆ , -NHSO
₂ R ₂₆ , -NHCONR ₂₄ R ₂₅ or -NHSO ₂ NR
₂₄ R ₂₅ and R ₂₂ are groups capable of substituting on a naphthalene ring, and k is 0
R ₂₃ represents a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However, R ₂₄ and R ₂₅ may be the same or different and each represents a hydrogen atom, an alkyl, aryl or heterocyclic group, and R ₂₆ represents an alkyl, aryl or heterocyclic group. When k is plural, R _{22 s} may be the same or different and may combine with each other to form a ring. R ₂₂ and R ₂₃ or R ₂₃ and X ₂₁ may combine with each other to form a ring.

First, a green-sensitive silver halide emulsion layer in the present invention has a non-photosensitive layer adjacent to the side closer to the support, and the non-photosensitive layer has a wavelength range of 500 to 600 nm in the film.
The dye having the maximum wavelength of spectral absorption will be described below.

In the dye used in the present invention, the dye added to the non-photosensitive layer at the time of producing a color light-sensitive material is substantially present in the non-photosensitive layer without diffusing into other layers, and the dye is 500 to 600.
The object of the present invention can be achieved as long as it has a spectral absorption maximum wavelength in nm.

As for the method of using the dye in the non-photosensitive layer, a method of directly dyeing gelatin, an oil-in-water dispersion method of the dye as described below, that is, an organic solvent having a boiling point of 175 ° C. or less at normal pressure is required Depending on the above, a method of dissolving using an organic solvent having a boiling point of 50 ° C. or more and 160 ° C. or less and adding the emulsion-dispersed product in an aqueous gelatin solution containing a surfactant, International Publication WO 88/4974 , Tokuyouhei 1-5029
No. 12 and European Patent Publication 456,148, a method of adding a so-called solid dispersion, or a method of preventing diffusion of a dye through a representative polymer mordant 1 to 4 shown in the following "Chemical Formula 3". However, any of these methods can be used in the present invention.

[0021]

[Chemical 3] The light-absorbing property of the dye used in the present invention may be such that it has a spectral absorption maximum wavelength substantially in the range of 500 to 600 nm in the dry film of the non-photosensitive layer to which the dye is added. May be used together.

The amount of the dye added is such that the average optical density in the dry film of the added non-photosensitive layer is 500 to 600 nm.
It is 1 to 0.50, and preferably 0.03 to 0.30. In the present invention, a dye dispersed by the above-mentioned dispersion method in an amount capable of obtaining this average optical density may be added. The actual measuring method is to measure the density of 500 to 600 nm with a spectrophotometer on a sample obtained by coating a dye with gelatin on a transparent support and drying, and determine the average optical density at 500 to 600 nm from the integrated value.

The dye-containing layer of the present invention is a non-photosensitive layer adjacent to the green-sensitive emulsion layer on the non-exposure side (support side), and is localized in this layer to minimize the sensitivity reduction of the green-sensitive layer. The sharpness can be remarkably improved by the antihalation effect while keeping the limit.

In the layer-structured light-sensitive material in which at least one of the red-sensitive emulsion layers is on the support side of the dye-insensitive layer according to the present invention, the dye-insensitive layer causes the red-sensitive emulsion layer to be on the short wavelength side. By lowering the sensitivity in the (green range), changes in hue due to the amount of exposure light are reduced, and more faithful color reproduction is possible.

The dyes listed below are known as dyes which satisfy these conditions when used in the present invention. For example, British Patent Nos. 506,385, 1,177,429, 1,
311,884, 1,338,799, 1,3
85,371, 1,467,214, 1,43
3,102, 1,553,516, JP-A-48-
85, 130, 49-114, 420, 52-
119, 123, 55-161, 233, 59.
-111,640, 61-7,838, Japanese Patent Publication Sho 3
9-22, 069, 43-13, 168, 41
-18,459, U.S. Pat. No. 3,247,127,
Oxonol dyes having a pyrazolone nucleus and a barbituric acid nucleus described in U.S. Pat. Nos. 3,469,985 and 4,078,933, U.S. Pat. Nos. 2,533,472 and 3,379,533, British Patent No. 1,278,621
No. 1,538,943 and other oxonol dyes described therein, British Patent Nos. 575,691 and 68.
0,631, 599,623, 786,907
No. 907,125, No. 1,045,609, U.S. Pat. No. 4,255,326, JP-A-59-211,
No. 043, No. 60-170, 845 and the like, azo dyes described in JP-A Nos. 50-100, 116 and 54-11.
No. 8,247, No. 60-32, 851, No. 60-18
6,567, British Patents 2,014,598 and 7
50,031 and the like, azomethine dyes, US Pat. No. 2,865,752, anthraquinone dyes, US Pat. Nos. 2,538,009, and 2,682.
No. 8,541, No. 2,538,008, British Patent No. 5
84,609, 1,210,252, JP-A-50
-40,625, 51-3,623, 51-1
No. 0,927, No. 54-118,247, Japanese Patent Publication No. 48
No. 3,286, No. 59-37, 303 and the like, arylidene dyes, Japanese Patent Publication Nos. 28-3,082 and 4;
4-16,594, 59-28,898 and the like, styryl dyes, British Patents 446,583, 1,335,422 and JP-A-59-228,250. Triarylmethane dyes, British Patent Nos. 1,075,653, 1,153,341, 1,284,730, 1,475,228, 1,542,807, etc. Described merocyanine dyes, US Pat. Nos. 2,843,486, 3,294,294
Examples include cyanine dyes described in No. 539 and the like.

Next, as a more preferable specific example of the dye, D-
1 to D-44, but not limited to these, and any dyes are included in the scope of the present invention as long as they are used in accordance with the above-mentioned gist.

Further, these dyes can be easily synthesized by the method described in the above-mentioned patent specifications or a method similar thereto.

[0028]

[Chemical 4]

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12]

[0037]

[Chemical 13]

[0038]

[Chemical 14]

[0039]

[Chemical 15]

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18] Next, the monodisperse emulsion used in the present invention will be described.

In the present invention, the monodisperse emulsion refers to an emulsion having a variation coefficient of grain size distribution of 20% or less, but in the present invention, an emulsion having a variation coefficient of less than 15% is particularly preferable. A more preferable range of this coefficient of variation is 12% or less.

The coefficient of variation can be determined by a known method disclosed in JP-A-59-48754.

Various methods are known as a method for producing a monodisperse emulsion which can be used in the present invention, and representative examples thereof are shown below by the patent numbers.

Japanese Patent Publications Nos. 52-153482 and 55-4
2739, U.S. Pat. Nos. 4,431,729, 4,
259,438, British Patent No. 1,535,016,
U.S. Pat. Nos. 4,259,438 and 4,431,7
29, JP-A-51-39027 and 51-8801.
No. 7, No. 54-158220, No. 55-36829.
No. 58, No. 58-196541, No. 54-48521,
54-99419, 56-78831, 57.
-178235, 58-49938, 58-3
7653, 58-106532, 58-149.
No. 037.

The method described in JP-A-55-142329 can be preferably used.

That is, by using a silver halide seed crystal emulsion having an arbitrary grain size distribution, the addition rate of silver ions and halogen ions during the crystal growth period is set to 3 of the crystal critical growth rate.
When added so that the crystal growth rate is 0 to 100%,
A monodisperse silver halide emulsion can be obtained.

The monodisperse silver halide grain of the present invention may have a regular crystal form such as a cube or an octagon, or may have an irregular crystal form such as a sphere or a plate. It may have a crystal defect such as a twin plane or a composite form of these crystal forms. It may consist of a mixture of particles of various crystal forms.

It is particularly preferable to use the monodisperse hexagonal tabular grains described in JP-A-63-11928.

The silver halide of the monodisperse emulsion used in the present invention is silver bromide or silver iodobromide, silver iodochloride or silver chlorobromide containing about 30 mol% or less of silver iodide.
Particularly preferred is silver iodobromide or silver iodochlorobromide containing about 2 to 25 mol% silver iodide.

More preferably, it is a silver iodobromide containing about 2 to 10 mol% of silver iodide for color negative photographic materials and about 1 to 5 mol% of silver iodide for color reversal photographic materials.

The monodisperse silver halide grains usable in the present invention may have a uniform halogen distribution or two or more phases having different halogen compositions.

For example, grains having a higher silver iodide content in the surface layer than the internal phase, such as grains disclosed in JP-A-62-19843, or grains inside the grains disclosed in JP-A-60-143331. Particles having a high iodine phase are also preferred.

The monodisperse silver halide grains which can be used in the present invention may be ordinary surface latent image type silver halide grains or internal latent image type silver halide grains which mainly form a latent image inside. It may be. Further, monodisperse particles having an improved pressure characteristic having a ratio of surface sensitivity to internal sensitivity of 0.5 to 2 can be preferably used.

The chemical sensitization of the monodisperse emulsion which can be used in the present invention is described by TH James, The Theory of Photographic Process, 4th Edition, published by Macmillan Co., 1977, ( TH James, T
he Theory of the Photograph
hic Process, 4th ed, Macmil
Lan, 1977) 67-76 and using active gelatin, and Research Disclosure, Vol. 120, April 1974, 1
2008; Research Disclosure, Vol. 34, 1
June 975, 13452, U.S. Pat. No. 2,642,3
No. 61, No. 3,297,446, No. 3,772,03
No. 1, 3,857,711, 3,901,714
No. 4,266,018, and 3,904,4.
15 and pAg 5-10, pH 5-8 and temperature 30-as described in British Patent 1,315,755.
It can be carried out at 80 ° C. using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. Chemical sensitization is optimally carried out in the presence of gold and thiocyanate compounds, and sulfur-containing compounds as described in US Pat. Nos. 3,857,711, 4,266,018 and 4,054,457. It is performed in the presence of a compound or a sulfur-containing compound such as hypo, a thiourea compound, and a rhodanine compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are described in US Pat.
1,038, 3,411,914, 3,55
No. 4,757, JP-A No. 58-126526 and the above-mentioned Daffin's "Photographic Emulsion Chemistry", pages 138-143. In addition to, or as an alternative to chemical sensitization, US Pat. Nos. 3,891,446 and 3,984,24
It can be reduction sensitized with, for example, hydrogen as described in US Pat. No. 2,518,698.
No. 2,743,182 and No. 2,743,18
No. 3, using reducing agents such as stannous chloride, thiourea dioxide, polyamines, or low pAg.
Reduction sensitization can be achieved by (eg less than 5) and / or high pH (eg greater than 8) treatment. U.S. Pat. Nos. 3,917,485 and 3,966,47.
The chemical sensitization method described in No. 6 can also improve the color sensitization.

Further, JP-A-61-3134 and 61-3
A sensitizing method can also be applied by using an oxidizing agent described in No. 136.

These monodisperse emulsions are used in layers other than the highest sensitivity emulsion in the same light-sensitive emulsion layer, and one or more kinds are contained in the same layer, but it is preferable to use a mixture of two or three kinds. A mixture of four or more types is preferable.

In the present invention, the size distribution of at least one silver halide grain is monodisperse, and the non-light-sensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer closer to the support is a gelatin film in the gelatin film. Image quality such as sharpness and graininess can be improved by using a dye having a maximum spectral absorption wavelength in the wavelength range of 500 to 600 nm.

The light-sensitive material of the present invention may be provided with at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one color-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Material, the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, couplers such as those described in the specification, DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is commonly used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

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

The silver halide emulsions other than the present invention will be described below.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. About 2 mol% is particularly preferred.
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 μm or less or large size grains having a projected area diameter of up to about 10 μm, but as described above, it is a monodisperse emulsion rather than a polydisperse emulsion. Is preferred.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. 187
16 (November 1979), p. 648, ibid. 3071
05 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by P. Glafkides, Chemie et Ph.
isique Photographie, Pau
L Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press, Inc. (G.F. Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), Vol. 14, 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image on both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, ibid. 18716 and ibid.
No. 307105, and the relevant parts are summarized in Table 1 below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553, and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide emulsion inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± 40% of the average grain size). It is preferable that the particles have a particle size of

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide grain that is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that the fog is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains.

The silver coating amount of the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Next, the compound represented by formula (B) will be described in more detail.

In the general formula (B), A represents a coupler residue.

For example, a yellow coupler residue (for example, an open chain ketomethylene type), a magenta coupler residue (5-pyrazolone type, a pyrazoloimidazole type, a pyrazolotriazole type, etc.), a cyan coupler residue (phenol type, a naphthol type, etc.), And uncolored coupler residues (indanone type, acetophenone type, etc.). Also, US Pat. Nos. 4,315,070 and 4,183,752
No. 3,961,959 or 4,171,22
It may be a heterocyclic type coupler residue described in No. 3.

A preferred example of A is the following general formula (Cp-
1), (Cp-2), (Cp-3), (Cp-4),
(Cp-5), (Cp-6), (Cp-7), (Cp-
8), a coupler residue represented by (Cp-9) or (Cp-10). These couplers are preferred because of their high coupling speed.

[0091]

[Chemical 19]

[0092]

[Chemical 20]

[0093]

[Chemical 21]

[0094]

[Chemical formula 22]

[0095]

[Chemical formula 23]

[0096]

[Chemical formula 24]

[0097]

[Chemical 25]

[0098]

[Chemical formula 26]

[0099]

[Chemical 27]

[0100]

[Chemical 28] The free bond derived from the coupling position in the above formula represents the bonding position of the coupling leaving group.

In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ and R
_{When 55} , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ or R ₆₃ contains a diffusion resistant group, it has a total number of carbon atoms of 8 to 40, preferably 10 to 30. Otherwise, the total number of carbon atoms is preferably 15 or less. In the case of a bis type, telomer type or polymer type coupler, one of the above substituents represents a divalent group,
Connect repeating units. In this case, the range of carbon number may be out of regulation.

R _{51 to} R ₆₃ , b, d and e will be described in detail below. In the following, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group or an aromatic group. Represents a group or heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . b represents 0 or 1. R ₅₂ and R ₅₃ have the same meanings as R ₄₂ . R ₅₄ is a group R ₄₁ CON same meaning as R ₄₁
(R ₄₃ ) -group, (R ₄₁ ) (R ₄₃ ) N-group, R ₄₁ SO ₂ N
(R ₄₃ ) -group, R ₄₁ S-group, R ₄₃ O-group, (R ₄₅ ) (R
₄₃₎ NCON (R ₄₄₎ represents a group or a N C-group. R
₅₅ represents a group having the same meaning as R ₄₁ . R ₅₆ and R ₅₇ are each a group having the same meaning as R ₄₃ , R ₄₁ S-group, R ₄₃ O-group, R ₄₁
It represents a CON (R ₄₃ )-group or an R ₄₁ SO ₂ N (R ₄₃ )-group. R ₅₈ represents a group having the same meaning as R ₄₁ . And R ₅₉ groups of the same meaning as _{R 41, R 41 CON (R} 43) - group, R ₄₁ O
CON (R ₄₃ ) -group, R ₄₁ SO ₂ N (R ₄₃ ) -group, (R
_{43) (R 44) NCON (} R 45) - group, R ₄₁ O-group, R ₄₁
It represents an S-group, a halogen atom, or a (R ₄₁ ) (R ₄₃ ) N-group. d represents 0 to 3. When d is plural, plural R _59's represent the same substituent or different substituents.
Further, each R ₅₉ may be a divalent group and connected to each other to form a cyclic structure. Examples of divalent groups for forming a cyclic structure are

[0104]

[Chemical 29] Or

[0105]

[Chemical 30] Is a typical example. Where f is 0 to 4
And g is an integer from 0 to 2, respectively. R ₆₀ has the same meaning as R ₄₁ . R ₆₁ represents a group having the same meaning as R _41, R ₆₂ represents a group having the same meaning as R _41, R ₄₁ OCONH- group,
R ₄₁ SO ₂ NH group, (R ₄₃ ) (R ₄₄ ) NCON (R ₄₅ ).
- _{group, (R 43) (R 44} ) NSO 2 N (R 45) group, R ₄₃ O
-Group, R ₄₁ S-group, halogen atom or (R ₄₁ )
(R ₄₃ ) represents an N-group. R ₆₃ is a group having the same meaning as R ₄₁ ,
(R ₄₃ ) (R ₄₄ ) NCON (R ₄₅ ) — group, (R ₄₃ ) (R
₄₄₎ NCO-- _{group, R 41 SO 2 N (R} 44) - group, (R ₄₃₎
(R ₄₄₎ NSO ₂ - group, R ₄₁ SO ₂ - group, R ₄₃ OCO-
Represents a group, R ₄₃ O—SO ₂ — group, halogen atom, nitro group, cyano group or R ₄₃ CO— group. e represents an integer of 0 to 4. When a plurality of R ₆₂ or R ₆₃ are present, they represent the same or different.

In the above, the aliphatic group has 1 to 3 carbon atoms.
2, preferably 1 to 22 saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group. Typical examples are methyl, ethyl, propyl, isopropyl, allyl, butyl, (t)
-Butyl, (i) -butyl, (t) -amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl,
Examples include 1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

The aromatic group is a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted naphthyl group.

The heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, and is selected from a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, and is preferably a substituted or unsubstituted 3- to 8-membered ring. It is a heterocyclic group. Typical examples of the heterocyclic group are 2-pyridyl, 2-thienyl, 2-furyl, 1,3,4-thiadiazol-2-yl, 2,4.
-Dioxo-1,3-imidazolidin-5-yl, 1,
2,4-triazol-2-yl or 1-pyrazolyl may be mentioned.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents are:
Halogen atom, R ₄₇ O- group, R ₄₆ S- group, R ₄₇ CON
(R ₄₈₎ - _{group, (R 47) (R 48} ) NCO- group, R ₄₆ OC
ON (R ₄₇ )-group, R ₄₆ SO ₂ N (R ₄₇ )-group,
(R ₄₇ ) (R ₄₈ ) NSO ₂ — group, R ₄₆ SO ₂ — group, R ₄₇
OCO- _{group, (R 47) (R 48} ) NCON (R 49) - group,
A group having the same meaning as R ₄₆ , a group represented by the following “Chemical Formula 31”

[0110]

[Chemical 31] R ₄₆ COO − group, R ₄₇ OSO ₂ — group, cyano group or nitro group can be mentioned. Here, R ₄₆ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₄₇ , R _48, and R ₄₉ each represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. The meaning of the aliphatic group, aromatic group or heterocyclic group has the same meaning as defined above.

Next, preferred ranges of R _{51 to} R ₆₃ , d and e will be described.

R ₅₁ is preferably an aliphatic group or an aromatic group.

R ₅₂ , R ₅₃ and R ₅₅ are preferably aromatic groups.

R ₅₄ is an R ₄₁ CONH-group, or (R ₄₁ ).
The (R ₄₃ ) N-group is preferred. R ₅₆ and R 57 are preferably aliphatic groups, aromatic groups, R ₄₁ O— groups or R ₄₁ S— groups. R ₅₈ is preferably an aliphatic group or an aromatic group. In the general formula (Cp-6), R ₅₉ is a chlorine atom, an aliphatic group or R
_{The 41} CONH- group is preferred. d is preferably 1 or 2. R ₆₀ is preferably an aromatic group. In formula (Cp-7), R ₅₉ is preferably R ₄₁ CONH-group. General formula (C
In p-7), d is preferably 1. R ₆₁ is preferably an aliphatic group or an aromatic group. In general formula (Cp-8), e is preferably 0 or 1. R ₆₂ is R ₄₁ OCON
H-group, R ₄₁ CONH-group or R ₄₁ SO ₂ NH-group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. In the general formula (Cp-9), R ₆₃ is R ₄₁ C.
ONH-group, R ₄₁ SO ₂ NH, (R ₄₁ ) (R ₄₃ ) NSO
₂ -group, R ₄₁ SO ₂ -group, (R ₄₁ ) (R ₄₃ ) NCO-
Groups, nitro groups or cyano groups are preferred.

In the general formula (Cp-10), R ₆₃ is (R
₄₃ ) ₂ NCO- group, R ₄₃ OCO- group or R ₄₃ CO- group is preferred.

Next, typical examples of R _{51 to} R ₆₃ will be described.

Examples of R ₅₁ include (t) -butyl and 4-
Methoxyphenyl, phenyl, 3- {2 (2,4-di-
t-amylphenoxy) butanamido} phenyl, or methyl. Examples of R ₅₂ and R ₅₃ include phenyl, 2-chloro-5-ethoxy, 2-chloro-
5-dodecyloxycarbonylphenyl, 2-chloro-
5-hexadecylsulfonamidophenyl, 2-chloro-5-tetradecanoamidophenyl, 2-chloro-5-
{4- (2,4-di-t-amylphenoxy) butanamide} phenyl, 2-chloro-5- {2- (2,4-di-t-amylphenoxy) butanamide} phenyl, 2
-Methoxyphenyl, 2-methoxy-5-tetradecyloxycarbonylphenyl, 2-chloro-5- (1-ethoxycarbonylethoxycarbonyl) phenyl, 2-
Pyridyl, 2-chloro-5-octyloxycarbonylphenyl, 2,4-dichlorophenyl, 2-chloro-5
Examples include-(1-dodecyloxycarbonylethoxycarbonyl) phenyl, 2-chlorophenyl or 2-ethoxyphenyl.

R ₅₄ is, for example, butanoylamino,
2-chloro-3-propanoylaminoanilino, 3-
{2- (2,4-di-t-amylphenoxy) butanamide} benzamide, 3- {4- (2,4-di-t-amylphenoxy) butanamide} benzamide, 2-chloro-5-tetradecanamide aniline, 5- (2,4
-Di-t-amylphenoxyacetamido) benzamide, 2-chloro-5-dodecenylsuccinimide anilino, 2-chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) tetradecanamide} anilino ,
2,2-dimethylpropanamide, 2- (3-pentadecylphenoxy) butanamide, pyrrolidino or N,
N-dibutylamino is mentioned. Examples of R ₅₅ include 2,4,6-trichlorophenyl, 2-chlorophenyl group, 2,5-dichlorophenyl, 2,3-dichlorophenyl, 2,6-dichloro-4-methoxyphenyl and 4
-{2- (2,4-di-t-amylphenoxy) butanamide} phenyl or 2,6-dichloro-4-methanesulfonylphenyl is a preferred example. Examples of R ₅₆ include methyl, ethyl, isopropyl, methoxy, ethoxy, methylthio, ethylthio, 3-phenylureido, or 3- (2,4-di-t-amylphenoxy).
Examples include propyl. As R ₅₇ , for example, 3- (2,
4-di-t-amylphenoxy) propyl, 3- [4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] tetradecanamide} phenyl] propyl,
Methoxy, methylthio, ethylthio, methyl, 1-methyl-2- (2-octyloxy-5- [2-octyloxy-5- (1,1,3,3-tetramethylbutyl) phenylsulfonamide] phenylsulfonamide ] Ethyl, 3- {4- (4-dodecyloxyphenylsulfonamido) phenyl} propyl, 1,1-dimethyl-2-
(2-octyloxy-5- (1,1,3,3-tetramethylbutyl) phenylsulfonamido] ethyl, or dodecylthio may be mentioned. Examples of R ₅₈ are 2-
Chlorophenyl, pentafluorophenyl, heptafluoropropyl, 1- (2,4-di-t-amylphenoxy) propyl, 3- (2,4-di-t-amylphenoxy) propyl, 2,4-di-t- Amylmethyl or furyl may be mentioned.

R ₅₉ is, for example, chloro atom, methyl,
Ethyl, propyl, butyl, isopropyl, 2- (2,
4-di-t-amylphenoxy) butanamide, 2-
(2,4-di-t-amylphenoxy) hexanamide, 2- (2,4-di-t-octylphenoxy) octanamide, 2- (2-chlorophenoxy) tetradecanamide, 2- {4- (4 -Hydroxyphenylsulfonyl) phenoxy} tetradecanamide, or 2-
Examples include {2- (2,4-di-t-amylphenoxyacetamide) phenoxy} butanamide. Examples of R ₆₀ include 4-cyanophenyl, 2-cyanophenyl,
4-Butylsulfonylphenyl, 4-propylsulfonylphenyl, 4-chloro-3-cyanophenyl, 4-ethoxycarbonylphenyl, or 3,4-dichlorophenyl are mentioned. R ₆₁ is, for example, propyl,
2-methoxyphenyl, dodecyl, hexadecyl, cyclohexyl, 3- (2,4-di-t-amylphenoxy) propyl, 4- (2,4-di-t-amylphenoxy) butyl, 3-dodecyloxypropyl, t -Butyl, 2-methoxy-5-dodecyloxycarbonylphenyl, or 1-naphthyl. Examples of R ₆₂ include isobutyloxycarbonylamino, ethoxycarbonylamino group, phenylsulfonylamino, methanesulfonamide, benzamide, trifluoroacetamide, 3-phenylureido, butoxycarbonylamino, or acetamide. As R ₆₃ ,
For example, 2,4-di-t-amylphenoxyacetamide, 2- (2,4-di-t-amylphenoxy) butanamide, hexadecylsulfonamide, N-methyl-N
-Octadecylsulfamoyl, N, N-dioctylsulfamoyl, 4-t-octylbenzoyl, dodecyloxycarbonyl, chloro atom, nitro, cyano, N-
{4- (2,4-di-t-amylphenoxy) butyl}
Carbamoyl, N-3- (2,4-di-t-amylphenoxy) propylsulfamoyl, methanesulfonyl or hexadecylsulfonyl are mentioned.

In the general formula (B), L ₁ is preferably the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
No. 249148 and No. 60-249149, which are groups represented by the following general formula. Here, the * mark represents the position of bonding with A, L ₁ or L _{2 of the} compound represented by the general formula (I), and the ** mark represents L ₁ , L ₂ or PU.
It represents the position where G is bonded. Formula (T-1) * - ( W-C (R 11) (R 12)) t - ** In formula, W is an oxygen atom, a sulfur atom or -N (R ₁₃₎ -
Represents a group, R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2. When t is 2, the two _{-W-C (R 11) (} R 12) -
Represents the same or different. R ₁₁ and R
_{When 12} represents a substituent and typical examples of R ₁₃ are R ₁₅ group, R ₁₅ CO— group, R ₁₅ SO ₂ — group, (R ₁₅ ) (R _15
16) NCO-- group or _{(R 15) (R 16)} NSO 2 - group. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₁₆ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is linked to form a cyclic structure is also included. Specific examples of the group represented by formula (T-1) include the following groups.

[0121]

[Chemical 32] (2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,292 can be mentioned. It can be represented by the following general formula. General formula (T-2) * -Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, Nu Link is a group capable of being more nucleophilically attacked and cleaving the bond with the ** mark, and Link represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by formula (T-2) are as follows.

[0122]

[Chemical 33] (3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, US Pat. No. 4,409,323,
U.S. Pat. No. 4,421,845, JP-A-57-188035.
No. 58-98728, 58-209736,
No. 58-209737, No. 58-209738, etc., and is represented by the following general formula (T-3). General formula (T-3)

[0124]

[Chemical 34] In the formula, *, **, W, R ₁₁ , R ₁₂ and t are (T-
It has the same meaning as described in 1). However, R
₁₁ and R ₁₂ may be combined to form a benzene ring or a heterocyclic ring. Further, R ₁₁ or R ₁₂ and W may combine with each other to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y represent 0 or 1. When Z ₁ is a carbon atom, x is 1, and when Z ₁ is a nitrogen atom, x is 0.
Is. The relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Further, t represents 1 or 2, and when t is 2, 2
Horn

[0125]

[Chemical 35] May be the same or different.

Specific examples of (T-3) will be given below.

[0127]

[Chemical 36]

[0128]

[Chemical 37] (4) Group Utilizing Cleavage Reaction by Hydrolysis of Ester For example, the following groups are the linking groups described in West German Laid-Open Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1). General formula (T-4) General formula (T-5) -O-CO-**-S-CS-** (5) Group utilizing cleavage reaction of imino ketal For example, in U.S. Pat. No. 4,546,073. It is a connecting group described and is a group represented by the following general formula. General formula (T-6)

[0129]

[Chemical 38] In the formula, * mark, ** mark and W have the same meanings as described in formula (T-1), and R ₁₄ has the same meaning as R ₁₃ . Specific examples of the group represented by formula (T-6) include the following groups.

[0130]

[Chemical Formula 39] L ₁ is preferably one represented by (T-1) to (T-5), particularly preferably (T-1) and (T-4).
Is.

P is preferably 0 or 1.

The group represented by Z in the general formula (B) is specifically a known bleaching accelerator residue. For example, U.S. Pat. No. 3,893,858, British Patent No. 11
No. 38842, various mercapto compounds as described in JP-A-53-141623, compounds having a disulfide bond as described in JP-A-53-95630, and JP-B-53-9854. Thiazolidine derivatives as described in JP-A-53 / 1988
Isothiourea derivatives as described in JP-A-94927, JP-B-45-8506 and JP-B-49-2
A thiourea derivative as described in 6586,
Thioamide compounds as described in JP-A-49-42349, dithiocarbamate salts as described in JP-A-55-26506, US Pat.
And arylene diamine compounds as described in the specification of 5-52834. These compounds preferably bond with A- (L ₁ ) _p- in the general formula (B) at a substitutable heteroatom contained in the molecule.

The group represented by Z is preferably a group represented by the following general formula (I), (II) or (III). General formula (I)

[0134]

[Chemical 40] General formula (II)

[0135]

[Chemical 41] General formula (III)

[0136]

[Chemical 42] In the formula, * indicates the position at which A- (L ₁ ) _p − is bonded,
R ₃₁ represents a divalent aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5, R ₃₂ represents a group having the same meaning as R ₃₁ , a divalent aromatic group having 6 to 10 carbon atoms, or 3 to 8 members. Membered ring, preferably 5
A 6-membered or 6-membered divalent heterocyclic group, X ₁ is-
O -, - S-, COO-, SO 2 -, - N (R 33) -,
_{-N (R 33) -CO -,} - N (R 33) -SO 2 -, - S
-CO-, -CO-, -N ( _R33 ) COO-, -N = C
(R ₃₃ )-, -N (R ₃₃ ) CO-N (R ₃₄ )-, or -N (R ₃₃ ) SO ₂ N (R ₃₄ )-, wherein X ₂ is an fragrance having 6 to 10 carbon atoms. Represents a group group, and X ₃ is a 3 to 8 member having at least one carbon atom bonded to S in the ring.
A heterocyclic group having a member ring, preferably a 5- or 6-membered ring, wherein Y ₁ is a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, a phosphonic acid group or a salt thereof, an amino group (having 1 carbon atom). may be substituted with to 4 aliphatic group), - NHSO ₂ -R ₃₅ or -SO ₂ NH
Represents an —R ₃₅ group (a salt means a sodium salt, a potassium salt, an ammonium salt or the like), Y ₂ represents a group having the same meaning as described for Y ₁ or a hydrogen atom, and r represents 0 or 1, 1 represents an integer of 0 to 4, j represents an integer of 1 to 4, and k represents an integer of 0 to 4. However, j Y ₁ is R ₃₁ −
_{{(X 1) r -R 32} } i and _{X 2 - {(X 1)} r -R
₃₂ } _i at substitutable positions, k Y ₁ are bonded at substitutable positions at X ₃ -{(X ₁ ) _r −R ₃₂ } _i , and when k and j are plural, each k is k. And j Y ₁ represent the same or different, and when i is plural, i (X ₁ ) _r —R ₃₂ represents the same or different. Here, R ₃₃ , R ₃₄ and R ₃₅ each represent a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. When R ₃₁ to R ₃₅ represent an aliphatic group, they are linear or cyclic, linear or branched, saturated or unsaturated,
It may be substituted or unsubstituted. Although it is preferably unsubstituted, examples of the substituent include a halogen atom, an alkoxy group (eg, methoxy, ethoxy), an alkylthio group (eg, methylthio, ethylthio) and the like.

The aromatic group represented by X ₂ and the aromatic group when R ₃₂ represents an aromatic group may have a substituent. For example, those enumerated as the aliphatic group substituents may be mentioned.

The heterocyclic group represented by X ₃ and the heterocyclic group when R ₂ represents a heterocyclic group are a saturated or unsaturated, substituted or unsubstituted heterocyclic group having an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom. It is a cyclic group. Examples thereof include a pyridine ring, an imidazole ring, a piperidine ring, an oxirane ring, a sulfolane ring, an imidazolidine ring, a thiazepine ring and a pyrazole ring. Examples of the substituent include those enumerated above as the aliphatic group substituents.

Specific examples of the group represented by the general formula (VI) include the followings.

[0140]

[Chemical 43]

[0141]

[Chemical 44] Specific examples of the group represented by the general formula (VII) include the following.

[0142]

[Chemical 45] Specific examples of the group represented by the general formula (VIII) include the following.

[0143]

[Chemical 46]

[0144]

[Chemical 47] Next, specific examples of the bleaching accelerator-releasing compound preferably used in the present invention will be given, but the present invention is not limited thereto.

[0145]

[Chemical 48]

[0146]

[Chemical 49]

[0147]

[Chemical 50]

[0148]

[Chemical 51]

[0149]

[Chemical 52]

[0150]

[Chemical 53]

[0151]

[Chemical 54]

[0152]

[Chemical 55]

[0153]

[Chemical 56]

[0154]

[Chemical 57]

[0155]

[Chemical 58] Others, Research Disclosure Item No.
No. 24241, No. 11449 and JP-A No. 61-2012.
47, Japanese Patent Application Nos. 61-252847 and 61-2.
The compounds described in 688770 and 61-268871 are also used in the same manner.

Also. The bleach accelerator releasing compound used in the present invention can be easily synthesized based on the description in the above patent specification.

The compound of the general formula (B) can be added to all layers of the light-sensitive material, but it is preferable to add it to the light-sensitive emulsion layer, and further it is effective to add it to more light-sensitive emulsion layers. Is remarkable.

[0158] Formula addition amount structures by different but preferably 1 mol per mol of silver 1 × 10 ^-5 existing in the same layer or an adjacent layer of a compound of the compound of (B), particularly preferably 1 × 10 ^{- 4} to 0.5 mol.

The compound of the general formula (B) can be added to the light-sensitive material in the same manner as in the ordinary couplers described later.

The compound of formula (B) improves the color reproducibility and improves the image quality due to the improved desilvering property. In the gelatin film of the present invention, a dye having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm is used in the non-photosensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer close to the support, and the general formula ( The effect of improving the desilvering property is increased by using the compound represented by B). Due to this effect, the processing time of the desilvering step in the color development processing can be shortened. Further, it shows another effect that the storage stability of the light-sensitive material is improved.

Next, the cyan coupler represented by the general formula (C) will be described.

In the general formula (C), R ₂₁ is —CONR ₂₄
R ₂₅ , -SO ₂ NR ₂₄ R ₂₅ , -NHCOR ₂₄ , -NHC
OOR _26, -NHSO ₂ R _26, a -NHCONR ₂₄ R ₂₅ or -NHSO ₂ NR ₂₄ R _25, the R ₂₂ is a group substitutable on a naphthalene ring, k represents an integer of 0 to 3, R ₂₃ is a substituted group X ₂₁ represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However, R ₂₄ and R ₂₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₂₆ represents an alkyl group, an aryl group or a heterocyclic group. When k is plural, R _{22 s} may be the same or different and may combine with each other to form a ring. Also R
₂₂ and R ₂₃ or R ₂₃ and X ₂₁ may combine with each other to form a ring.

The coupler represented by the general formula (C) is a dimer or higher polymer (higher compound) which is bonded to each other via a divalent or divalent group in R ₂₁ , R ₂₂ , R ₂₃ or X ₂₁ . (Including a polymer in which a coupler is bonded to the molecular main chain).

In the present invention, the alkyl group may be linear, branched or cyclic, and may have a substituent (eg, halogen atom, aryl, heterocycle, alkoxy, aryl) even if it contains an unsaturated bond. Oxy, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, acylaoxy, acyl).

Even if the aryl group is a condensed ring (for example, a naphthyl group), a substituent (for example, an alkyl group other than the above-mentioned alkyl group, cyano, carbonamide, sulfonamide, carbamoyl, sulfamoyl, ureido,
Alkoxycarbonylamino).

The heterocyclic group is O, N, S, P, Se,
3 to 8 containing at least one heteroatom of Te in the ring
Membered monocyclic or condensed ring heterocyclic group, which may have a substituent (for example, a substituent of the above aryl group, hydroxyl, carboxyl, nitro, amino, aryloxycarbonyl).

R ₂₁ is preferably a carbamoyl group having 1 to 30 total carbon atoms (hereinafter referred to as C number) (for example, Nn-butylcarbamoyl, Nn-hexadecylcarbamoyl, N- [3- (2,4) -Di-t-pentylphenoxy) propyl] carbamoyl, N- (3-n-dodecyloxypropyl) carbamoyl, N- (3-n-dodecyloxy-2-methylpropyl) carbamoyl, N-
[3- (4-t-octylphenoxy) propyl] carbamoyl) or a sulfamoyl group having a C number of 0 to 30 (for example, N- (3-n-dodecyloxypropyl) sulfamoyl, N- [4- (2,4-di) -T-pentylphenoxy) butyl] sulfamoyl), particularly preferably a carbamoyl group.

K is preferably 0 or 1, particularly preferably 0. R ₂₂ is preferably a halogen atom (F, C
l, Br, I, and so on. ), Cyano group, C number of 1 to 12
Is an alkyl group, an alkoxy group, a carbonamido group or a sulfonamide group.

R ₂₃ is preferably --COR ₂₇ , --SO ₂ R
_{28, -CO 2 R 28, -PO} (OR 28) 2 , or, -PO
(R ₂₈ ) ₂ where R ₇ is R ₂₄ and R ₂₈ is R
₂₆ have the same meaning. R ₂₃ is particularly preferably C
-COR ₂₇ (e.g. acetyl, trifluoroacetyl, pivaloyl, benzoyl) of the number 1 to 30, C number 1 to 30
-SO ₂ R ₂₈ , (for example, methylsulfonyl, n-butylsulfonyl, p-tolylsulfonyl) or a C number of 2 to
30 —CO ₂ R ₂₈ (eg methoxycarbonyl, isobutoxycarbonyl, 2-ethylhexyloxycarbonyl), with —CO ₂ R ₂₈ being more preferred.

X ₂₁ is preferably a hydrogen atom, a halogen atom, an alkoxy group having a C number of 1 to 30 (eg 2-hydroxyethoxy, 2- (carboxymethylthio) ethoxy,
3-carboxyethoxy, 2-methoxyethoxy), C
An aryloxy group having a number of 6 to 30, (for example, 4-methoxyphenoxy, 4- (3-carboxypropanamide) phenoxy), an alkylthio group having a C number of 2 to 30 (for example, carboxymethylthio, 2-carboxyethylthio, 2-
Hydroxyethylthio, 2,3-dihydroxypropylthio) or an arylthio group having a C number of 6 to 30 (for example, 4
-T-butylphenylthio, 4- (3-carboxypropanamide) phenylthio), and particularly preferably hydrogen atom, chlorine atom, alkoxy group or alkylthio group.

Specific examples C-1 to C-16 of the cyan coupler represented by formula (C) are shown below.

[0172]

[Chemical 59]

[0173]

[Chemical 60]

[0174]

[Chemical formula 61]

[0175]

[Chemical formula 62] Specific examples of cyan couplers represented by the general formula (C) other than the above and / or methods for synthesizing these compounds are described in, for example, US Pat. No. 4,690,889 and JP-A-60-2374.
No. 48, No. 61-153640, No. 61-14555.
No. 7, 63-208042 and West German Patent No. 3,82.
No. 3,049A.

The total amount of addition of the cyan coupler represented by the general formula (C) is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol%, further preferably 90 mol% or more of the total cyan couplers. Is.

The cyan coupler represented by the general formula (C) is preferably used in combination of two or more kinds. When the same color-sensitive layer is divided into two or more layers having different sensitivities, the highest sensitivity layer has two It is preferable to use an equivalent cyan coupler and a 4 equivalent cyan coupler in the lowest sensitivity layer. It is preferable to use either or both of the same color-sensitive layers other than those.

For the cyan coupler represented by the general formula (C), as described in JP-A-62-269958, it is preferable to use a small amount of a high-boiling point organic solvent for dispersion in sharpness and an image after processing. It is more preferable for improving the storability.

The cyan coupler represented by formula (C) has a wavelength range of 500 to 6 in the gelatin film in the non-photosensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer near the support.
Contains a dye having a spectral absorption maximum wavelength at 00 nm, and the size distribution of silver halide grains is monodisperse,
Alternatively, by using the compound represented by the general formula (B) in a light-sensitive material system, it improves image quality such as graininess, sharpness and desilvering property and improves storage stability of the light-sensitive material.

Photographic additives that can be used in the light-sensitive material of the present invention will be described below.

The photographic additives that can be used in the light-sensitive material of the present invention are described in the above-mentioned three Research Disclosures, and the relevant portions are shown in the following table.

Table Types of additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 866 page 2 Sensitivity enhancer 648 page right column 3 Spectral sensitizer, page 23-24 page 648 right column ~ 866-868 Page Supersensitizer 649 page right column 4 whitening agent page 24 647 page right column 868 page 5 antifoggant, page 24-25 page 649 right column 868-870 page stabilizer 6 light absorber, 25-26 Page 649 page right column to page 873 filter dye, page 650 left column UV absorber 7 stain inhibitor page 25 right column page 650 left column to page 872 right column 8 dye image stabilizer page 25 650 page left column 872 page 9 hard Film 26 pages 651 left column 874 to 875 pages 10 Binder page 26 651 pages left column 873 to 874 pages 11 plasticizers and lubricants page 27 650 pages right column 876 pages 12 coating aids, 26 to 27 pages 650 right pages Column 875 to 876 Surface active agent 13 Static 27 page 650 page Right column 876 to 877 Anti-blocking agent 14 Matting agent 878 to 879 Also prevent deterioration of photographic performance due to formaldehyde gas. Therefore, the U.S. reacts with by formaldehyde described in Japanese Patent 4,411,987 No. and the 4,435,503, it is preferable to add a compound capable of immobilizing the photosensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be prepared by the method described in JP-A-1-1060.
It is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, as described in No. 52, regardless of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention has the international publication WO 88.
No. 04794, and dyes or EP317,308A dispersed by the method described in JP-A-1-502912.
No. 4,420,555, Japanese Patent Laid-Open No. 1-25
It is preferable to incorporate the dye described in No. 9358.

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG, and N
o. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds are preferable, for example, US Pat. Nos. 4,310,619 and 4,351,8.
97, European Patent 73,636, US Patent 3,0.
61,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A Nos. 60-43659, 61-72238, and 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630, and International Publication WO 88/04795 are particularly preferable.

Examples of cyan couplers include the following phenol-type and naphthol-type couplers, in addition to the couplers represented by the general formula (C) of the present invention, for example, US Pat. Nos. 4,052,212 and 4th. , 146, 39
No. 6, No. 4,228, 233, No. 4,296, 2
No. 00, No. 2,369,929, No. 2,801,
No. 171, No. 2,772, 162, No. 2,89
No. 5,826, No. 3,772,002, No. 3,7
No. 58,308, No. 4,334,011, No. 4,
327,173, West German Patent Publication No. 3,329,729
No., European Patent Nos. 121,365A and 249,45
3A, US Pat. Nos. 3,446,622 and 4,3.
No. 33,999, No. 4,775,616, No. 4,
451,559, 4,427,767, 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658. Are preferred. Furthermore, JP-A-64-553
No. 64, No. 554, No. 64-555, No. 64-5
The pyrazoloazole-based couplers described in No. 56 and the imidazole-based couplers described in US Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers include, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282 and 4,409. No. 320, No. 4,576,910,
British Patent No. 2,102,137, European Patent 341,
188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include, for example, US Pat. No. 4,366,237, British Patent 2,125,570, and European Patent 96,57.
Those described in No. 0 and West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in, for example, Research Disclosure No. 17643, Item VII-G, ibid. Of 307105
Section VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
No. 6,368, European Patent No. 423727, Japanese Patent Laid-Open Nos. 1-319744, 3-177836, and 3-1.
Those described in No. 77837 are preferable. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, section VII-F and ibid. 307105, VII-
Patents described in paragraph F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

In addition to the compound of the general formula (B) of the present invention, R.I. D. No. 11449, 24241, JP-A-61-1.
The bleaching accelerator releasing coupler described in 2012247 is effective in shortening the time of a processing step having a bleaching ability, and particularly when added to a light-sensitive material using the tabular silver halide grains described above, The effect is great.

Examples of the coupler which releases a nucleating agent or a development accelerator imagewise during development include those described in British Patent No. 2,
097,140, 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferable. Also, JP-A-60-107029
No. 60-252340, JP-A-1-44940.
No. 1-45687, by a redox reaction with an oxidized product of a developing agent, for example, a fogging agent, a development accelerator,
Compounds that release silver halide solvents are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers described in U.S. Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60-185950 and JP-A-64-2425 other than the present invention
No. 2 DIR redox compound releasing coupler, D
IR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, European Patent Nos. 173,302A and 313,3
No. 08A, a coupler which releases a dye that recolors after separation, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, a coupler which releases a leuco dye described in JP-A-63-75747, U.S. Pat. No. 4,774,4
Examples thereof include couplers releasing a fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl).
Phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate) , Tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc., benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-
p-hydroxybenzoate, etc., amides (N, N
-Diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl))
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C. or higher, preferably 5
An organic solvent having a temperature of 0 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-1257.
272248 and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents of 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Color negative film for general use or movies,
It is a color reversal film for slides or televisions.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid. 18
716, page 647, right column to page 648, left column, and the same No.
307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een, et al., Photographic Science and Engineering (Photogr. Sci. E)
ng. ), Vol. 19, No. 2, pp. 124-129, the measurement can be carried out by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer includes, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener,
It is preferable to contain a binder, a plasticizer, a lubricant, a coating aid, and a surface active agent. The swelling ratio of this back layer is 1
50 to 500% is preferable.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid. 18
716, 651 left column to right column, and the same No. 307105
It can be developed by a usual method described on pages 880-881.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Among these, especially 3-methyl-
4-Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developing solution contains, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developing solution, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Or in combination. The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = (contact area between treatment liquid and air (cm ² )) / (volume of treatment liquid (cm ³ )) The above aperture ratio is preferably 0.1 or less, more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of a color developing agent. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. Can be used. Of these, aminodicarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are included.
II) Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths.
Specific examples of useful bleaching accelerators are described in the following specifications: for example US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-28426, Research Disclosure No. 17129 (July 1978), a compound having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-208.
32, No. 53-32735, U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,7.
Polyoxyethylene compounds described in No. 48,430;
Polyamine compounds described in JP-B-45-8836; Others, JP-A-49-40943, JP-A-49-59644,
53-94927, 54-57727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,893,85
No. 8, West German Patent No. 1,290,812, JP-A-53-
The compounds described in No. 95,630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is 2 to 5, specifically, for example, acetic acid,
Propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, for example, a combination of thiosulfate, thiocyanate, thioether compound and thiourea is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment.
Preferably imidazole, 1-methylimidazole, 1
It is preferable to add 0.1 to 10 mol / liter of imidazoles such as -ethylimidazole and 2-methylimidazole.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to improve the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect or eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is, for example, disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the material used, such as a coupler), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, etc. It can be set in a wide range depending on the conditions. Of these, the relationship between the number of washing tanks and the water amount in the multi-stage countercurrent system is described in the Journal of the Soc.
yety of Motion Picture an
d Tele-vision Engineers Vol. 64, P.D. 248 to 253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention,
As a solution to such a problem, Japanese Patent Application Laid-Open No. 62-288,
The method of reducing calcium ion and magnesium ion described in No. 838 can be used very effectively. Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as sodium chlorinated isocyanurate described in JP-A-57-8542, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986
Sankyo Publishing, Sanitary Technology Society, "Sterilization, Sterilization, and Antifungal Technology of Microorganisms" (1982), Industrial Technology Association, Japan Society for Antibacterial and Antifungal, Encyclopedia of Antibacterial and Antifungal Agents (1986) A bactericide can also be used.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58
All known methods described in Nos. 14834 and 60-220345 can be used.

Further, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizer containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Research Disclosure
No. 14,850 and the same No. Schiff base type compounds described in JP-A Nos. 15,159,159, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are, for example, JP-A Nos. 56-64339 and 57-57.
-144547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide light-sensitive material of the present invention is described in, for example, US Pat. No. 4,500,626 and JP-A-60-1.
No. 33449, No. 59-218443, No. 61-23.
It can also be applied to the photothermographic materials described in No. 8056 and European Patent 210.660A2.

[0229]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The materials used for each layer are classified as follows: ExC: Cyan coupler HBS: High boiling point organic solvent ExM: Magenta coupler ExO: Color mixture inhibitor ExY: Yellow coupler W: Surfactant ExS: Sensitizing dye H: Gelatin hardening agent ExU: Ultraviolet absorber B: Polymer S: Formalin scavenger or antifoggant F: Additive (stabilizer, antifoggant, etc.) The number corresponding to each component is g / m ² unit The coating amount represented by is shown, and for silver halide, the coating amount in terms of silver is shown. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. However, the organic solid disperse dye represents the addition amount of the dispersion prepared by the following dispersion method. Preparation of Dispersion A of Organic Solid Disperse Dye ExF-1 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of 5% aqueous solution of sodium P-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of 5% aqueous solution of P-octylphenoxy polyoxyethylene ether (polymerization degree 10) and 0.5 g were put in a 700 ml pot mill. , Dye ExF
-1 5.0g and zirconium oxide beads (diameter 1mm)
500 ml was added and the contents were dispersed for 2 hours. A BO type vibration ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the content was taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion A of a dye. Preparation of Dispersion B of Organic Solid Disperse Dye ExF-2 below was replaced with ExF-1 of Dispersion A above. The following was prepared in the same manner as Dispersion A. (Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.090 Dispersion A of organic solid disperse dye 10.0 Dispersion B of organic solid disperse dye 5.0 Gelatin 1.4 Second layer (intermediate) Layer) 2,5-di-t-pentadecylhydroquinone 0.18 ExM-1 0.070 ExC-1 0.020 ExS-1 0.0020 ExU-1 0.060 ExU-2 0.080 ExU-30 .10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.0 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.30 Emulsion B Silver 0.30 ExS-3 1.8 × 10 ^{− 4} ExS-4 2.2 × 10 ⁻⁵ ExS-5 3.0 × 10 ⁻⁴ ExC-2 0.020 ExC-3 0.135 ExC-4 0.136 ExC-5 0.020 ExM-3 0. 020 ExU-10. 70 ExU-2 0.050 ExU-3 0.070 HBS-1 0.050 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D silver 1.60 ExS-3 1.0 × 10 ^-4 ExS-4 1.4x10 ^-5 ExS-5 2.0x10 ^-4 ExC-1 0.010 ExC-2 0.010 ExC-3 0.040 ExC-4 0.040 ExC-6 0.067 Gelatin 0.70 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion G Silver 1.2 ExS-3 1.2 × 10 ⁻⁴ ExS-4 1.7 × 10 ⁻⁵ ExS-5 2.2 × 10 ^{− 4} ExC-1 0.050 ExC-2 0.015 ExC-3 0.016 ExC-4 0.016 ExC-7 0.20 ExC-8 0.020 ExU-1 0.070 ExU-2 0.050 ExU -3 0.070 HBS-1 0.20 HBS-2 0.08 Gelatin 1.6 Sixth layer (intermediate layer) ExO-1 0.040 ExM-4 0.050 HBS-1 0.020 Gelatin 0.80 Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion A Silver 0 .18 Emulsion B Silver 0.18 Emulsion C Silver 0.12 ExS-2 6.0 × 10 ^-5 ExS-6 3.6 × 10 ^-5 ExS-7 1.2 × 10 ^-4 ExS-8 4.6 × 10 ^-4 ExM-1 0.021 ExM-3 0.030 ExM-5 0.018 ExM-6 0.0050 ExM-7 0.08 ExM-10 0.04 HBS-1 0.08 HBS-30 .008 gelatin 0.63 eighth layer (intermediate layer) ExM-4 0.018 ExC-8 0.040 HBS-1 0.16 HBS-3 0.0080 gelatin 0.50 ninth layer (high-sensitivity green-sensitive emulsion) Layer) Emulsion E Silver 1.32 ExS-2 0. ^{5 × 10 -5 ExS-6 3.85} × 10 -5 ExS-7 8.8 × 10 -4 ExS-8 3.3 × 10 -4 ExM-3 0.025 ExM-8 0.03 ExM-9 0.50 ExY-1 0.020 HBS-1 0.20 HBS-2 0.08 gelatin 1.5 10th layer (intermediate layer) ExO-1 0.040 HBS-1 0.020 gelatin 0.80 11th Layer (donor layer having a multi-layer effect on the red-sensitive layer) Emulsion J Silver 1.2 Emulsion K Silver 2.0 ExS-2 4.0 × 10 ⁻⁴ ExC-2 0.10 ExM-2 0.10 HBS-10 .10 HBS-2 0.10 Gelatin 0.80 12th layer (yellow filter layer) Yellow colloidal silver Silver 0.050 Dispersion B of organic solid disperse dye 15.0 ExO-1 0.080 HBS-1 0.030 Gelatin 0.95 13th layer (Low sensitivity Degree blue-sensitive emulsion layer) Emulsion A Silver 0.080 Emulsion B Silver 0.070 Emulsion F Silver 0.070 ExS-9 3.5 × 10 ⁻⁴ ExC-3 0.033 ExY-2 0.72 ExY-30 .020 HBS-1 0.30 gelatin 1.1 14th layer (medium speed blue emulsion layer) emulsion G silver 0.45 ExS-9 2.1 × 10 ⁻⁴ ExY-2 0.15 ExC-2 0. HBS-1 0.060 Gelatin 0.78 Fifteenth layer (high sensitivity blue sensitive emulsion layer) Emulsion H Silver 0.77 ExS-9 2.2 × 10 ⁻⁴ ExY-1 0.010 ExY-2 0.60 ExY-3 0.010 HBS-1 0.10 Gelatin 0.69 16th layer (protective layer) Emulsion I Silver 0.20 ExU-4 0.11 ExU-5 0.17 HBS-1 0.050 Organic solid dispersion Dye dispersion A 0.50 Organic solid disperse dye Dispersion B 0.50 W-1 0.020 H-1 0.40 B-1 (diameter about 1.5 μm) 0.10 B-2 (diameter about 1.5 μm) 0.10 B-3 0. 020 S-1 1.20 Gelatin 1.8 In addition to the above, 1,2-benzisothiazolin-3-one (average of 2 for gelatin was added to the sample thus prepared).
00 ppm), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm). Furthermore W
-2 to W-4, B-4 to B-6, F-1 to F-17, iron salts, lead salts, gold salts, platinum salts, iridium salts and rhodium salts are contained.

[0230]

[Table 1] In Table 1, (1) Emulsions A to K were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to K were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. . (3) Low molecular weight gelatin is used for the preparation of tabular grains to be described later according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

Specific examples of materials used for the photosensitive layer are shown below.

[0232]

[Chemical 63]

[0233]

[Chemical 64]

[0234]

[Chemical 65]

[0235]

[Chemical 66]

[0236]

[Chemical 67]

[0237]

[Chemical 68]

[0238]

[Chemical 69]

[0239]

[Chemical 70]

[0240]

[Chemical 71]

[0241]

[Chemical 72]

[0242]

[Chemical formula 73]

[0243]

[Chemical 74]

[0244]

[Chemical 75]

[0245]

[Chemical 76]

[0246]

[Chemical 77]

[0247]

[Chemical 78] Then, in the same manner as in Sample 101, the dye D-14 was added to the sixth and eighth layers of the non-photosensitive layer adjacent to the side of the green-sensitive emulsion layer near the support, in the same manner as in Sample 101. A sample 102 was prepared.

Sample 103 is a cyan coupler, ExC-3, used in the third to fifth red-sensitive emulsion layers of Sample 101.
ExC-4 and ExC-6 are represented by the general formula (C) of the present invention.
Sample 101 by replacing the coupler represented by
It was made in the same manner as.

Sample 104 As shown in Table 2, the average AgI content (%) of silver halide emulsions A to K in Sample 101,
The average particle size, diameter / thickness ratio, silver amount ratio, etc. are adjusted so as to be the same as those shown in Table 1, and the coefficient of variation related to the particle size is shown in Table 2 in which the size distribution of the present invention is monodisperse. A sample was prepared by substituting the same amount of silver halide emulsion. In preparing the silver halide emulsion, the sensitivities were adjusted so as to be consistent.

Samples 105 to 111 were prepared by using the same silver halide emulsion as in Sample 104, except that the dye and cyan coupler were changed as shown in Tables 5 and 6.

In Samples 112 to 116, the silver halide emulsion was changed to a tabular grain silver halide emulsion shown in Tables 3 and 4, the silver coating amount was also changed, and the dyes and cyan couplers shown in Table 6 were used. A sample was prepared by using. Dye D-1
4, D-32 was prepared as an aqueous solution, and D-34 was prepared by adding a dispersion according to the method for preparing the dispersion A of the organic solid disperse dye.

[0252]

[Table 2]

[0253]

[Table 3]

[0254]

[Table 4]

[0255]

[Table 5]

[0256]

[Table 6] These produced samples 101 to 105 were evaluated for the various characteristics described below.

(1) White light (color temperature of light source: 4800 ° K)
Then, a wedge exposure for sensitometry is applied, the color development processing shown below is performed, and the R and G densities of the processed samples are measured, and from the characteristic curve, the sensitivity (S) of the minimum density +0.2 is obtained. The logarithm of the reciprocal of the exposure dose that gives the density is obtained, and the difference (Δ
S _R , ΔS _G ) was calculated.

(2) Two sets of each sample were prepared, one set was stored under the conditions of 50 ° C. and 80% RH for 3 days, and the other set was stored in a refrigerator at 5 ° C. After the completion, the two sets of samples were exposed to white light and simultaneously subjected to the color development process shown below, and the sensitivity was obtained in the same manner as in (1). ΔH _R , ΔH _G ) was obtained. The closer the value is to zero, the better the aging stability of the light-sensitive material.

(3) As one of the evaluations of the image quality, each sample is exposed to white light through an MTF pattern, and the following development processing is performed, and then the MTF value (40 cycles / mm) of a magenta color image is measured to obtain a sharp image. The degree was compared.

(4) As the second image quality evaluation, each sample was subjected to imagewise exposure using an interference filter having a wavelength of 550 nm (half-value width of 5 nm), the following development processing was performed, and then the R concentration of the processed sample, The G density was measured, and the ratio of the R density at the point of the same exposure amount to the G density obtained by subtracting the minimum density at the point of the exposure amount giving G density 2.0 was obtained, and this density ratio was used as a scale of color reproducibility. Compared. The smaller the value of the obtained density ratio, the smaller the mixing of unnecessary red component into the green color, which is preferable for color reproduction.

(5) As another image quality evaluation, with respect to the sample which was subjected to the following development processing by subjecting it to wedge exposure of white light, a minimum density of +0.5 was obtained with an aperture having a diameter of 48 μm.
The RMS value at the concentration of was measured. The measured value of magenta density is shown as a representative, and the smaller the value, the better the graininess.

The color development processing used for the above performance evaluation is shown below.

The processing was carried out by using an automatic developing machine FP-560B manufactured by Fuji Photo Film Co., Ltd., and processing a sample which was separately imagewise exposed until the replenishing amount of the color developing solution became three times the tank volume. I went from

The processing steps and processing liquid compositions are shown below.

(Processing process) Process processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 10 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixed 50 seconds 38.0 ° C 420 ml 5 liters Water wash 30 seconds 38.0 ° C 980 ml 3.5 liters Stability (1) 20 seconds 38.0 ° C −3 liters Stability (2) 20 seconds 38.0 ° C 560 mls 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 1 m ² of light-sensitive material The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided at the top of the bleaching tank of the automatic developing machine and at the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the light-sensitive material. 65
Milliliters, 50 milliliters, 50 milliliters,
It was 50 milliliters. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1 3.3 3.3-Diphosphonic acid Sodium sulfite 3.9 5.1 Carbonic acid Potassium 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-4.5 6.0 N- (β-hydroxyethyl) amino] aniline sulphate Add water 1.0 liter 1.0 liter pH 10.05 10.15 (bleaching solution) Tank solution (g) Replenisher solution (g) 1,3- Diaminopropane tetraacetic acid 130 195 Ferric ammonium monohydrate Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 Torr 1.0 l pH [prepared in aqueous ammonia] 4.4 4.4 (bleach-fixing tank solution) the bleaching tank solution and the mixed solution of 15 pairs 85 below the fixing tank solution (volume ratio).

(PH 7.0) (Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution 280 840 (700 g / liter) Milliliter milliliter Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water was added. 1.0 liter 1.0 liter pH [prepared with ammonia water and acetic acid] 7.4 7.45 (wash water) Tap water is used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas).
And an OH-type strongly basic anion exchange resin (Amberlite IRA-400) were passed through the column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by isocyanuric dichloride. Sodium acid 20 mg / liter and sodium sulfate 150 mg / liter were added. The pH of this solution was in the range of 6.5 to 7.5. (Stabilizing liquid) Common to tank liquid and replenishing liquid (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) Disodium salt of ethylenediaminetetraacetic acid 0. 05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 The results are summarized in Table 7.

[0268]

[Table 7] From the results shown in Table 7, the green-sensitive silver halide emulsion has a non-photosensitive layer adjacent to the side closer to the support, and the non-photosensitive layer has a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm in the gelatin film. Samples 105 to 110 and 113 to 116 which contain the dye having the formula (1) and which satisfy the constitution of the present invention using the emulsion in which the grain size distribution of the silver halide emulsion is monodisperse are samples which are outside the constitution of the present invention. 101-104, 111, 11
It is clear that the sharpness, color reproducibility and graininess are improved without lowering the sensitivity in photographic properties as compared with 2, and the sample is excellent in stability over time.

Further, in the sample satisfying the constitution of the present invention, the tabular grains are superior in the above-mentioned various performances even if the silver halide emulsions are the same monodisperse grains.
It can be seen from the comparison between 6, 108 and 110 and the samples 113 to 115.

Further, also in the sample satisfying the constitution of the present invention, when the main cyan coupler used in the red-sensitive emulsion layer is the coupler represented by the above general formula (C) of the present invention, the sensitivity of photographic property and the preservation of the sample with time are higher. It can also be seen that it is advantageous in the properties, sharpness, and graininess.

The non-photosensitive dyes of the present invention, even if they are the same dye, should be used non-photosensitively adjacent to the side of the green-sensitive silver halide emulsion layer closer to the support. It is clear from the comparison of the sample 105 and the sample 111 that there is an effect to achieve the above. Example 2 According to the sample prepared in Example 1, as shown in Tables 8 and 9, a sample was prepared by adding the dye, the compound represented by the general formula (B) and the like described in the present invention, and the coating amount. 201-2
13 was produced.

Dyes D-15, D-17, D-32
Is added as an aqueous solution, and D-34 and D-36 are used in Example 1.
A dispersion was prepared according to the method for preparing Dispersion A of the organic solid disperse dye, and used.

The samples 201 to 213 thus produced were subjected to the color development processing described below, and the same photographic sensitivity, temporal stability of the photosensitive material, sharpness, graininess and color reproducibility as in Example 1 were obtained. An evaluation was carried out.

Furthermore, in addition to these performance evaluations, solid color exposure of white light (1.0 Lux · sec) was applied to perform the following color development processing, and then the amount of silver remaining in the processed sample was determined by the fluorescent X It was quantified by the line analysis method.

The results are summarized in Table 10.

[0276]

[Table 8]

[0277]

[Table 9]

[0278]

[Table 10] The processing method and the composition of the processing solution for the color development processing are shown below. For the color development processing, an image was separately exposed by an automatic developing machine until the cumulative replenishment amount of the developing solution was replenished by 3 times the tank volume. Was treated, and then a sample for performance evaluation was treated. (Processing method) Process processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ℃ 22 ml 10 liters Bleaching 1 minute 40 seconds 38 ℃ 25 ml 20 liters Water washing 30 seconds 24 ℃ 1200 ml 10 liters Fixed 3 Minutes 00 seconds 38 ℃ 25ml 20liters Water wash (1) 30 seconds 24 ℃ (2) to (1) 10 liters Countercurrent piping method Water wash (2) 30 seconds 24 ℃ 1200ml 10liters Stability 30 seconds 38 ° C 25 ml 10 liter Dry 4 min 20 sec 55 ° C Replenishment amount per 35 mm width 1 m length The composition of the treatment liquid is described below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1 3.0 3.2-Diphosphonic acid Sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydro 4.5 6. 2 Xylethylamino] -2-methylaniline sulfate Add water 1.0 liter 1.0 liter pH 10.05 10.15 (bleaching solution) Tank solution (g) Replenisher solution (g) Ethylenediaminetetraacetic acid second Iron 100.0 120.0 Sodium trihydrate Ethylenediaminetetraacetic acid 10.0 11.0 Disodium salt 3-Mercapto-1,2,4-triazole 0.08 0.09 Odor Ammonium 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 4.0 ml Milliliter Add water 1.0 liter 1.0 liter pH 6.0 5.7 (fixing solution ) Tank liquid (g) Replenishing liquid (g) Ethylenediaminetetraacetic acid 0.5 0.7 Disodium salt Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution 290.0 320.0 (700 g / liter) Milliliter Water was added. 1.0 liter 1.0 liter pH 6.7 7.0 (stabilizing liquid) common tank liquid / replenishing liquid (g) sodium p-toluenesulfinate 0.03 polyoxyethylene-p-monononyl 0.2 phenyl ether (Average degree of polymerization 10) Disodium salt of ethylenediaminetetraacetic acid 0.05 1, , 4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 From the results of Table 10, from the results of the present invention, A magenta dye having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm in a gelatin film is used as a non-photosensitive layer adjacent to a side of a green-sensitive silver halide emulsion layer satisfying the constitution in a silver halide emulsion layer. Samples 204, 206 to 213 in which the size distribution of the silver halide grains in the above are monodisperse or contain the compound represented by the general formula (B) are Comparative Samples 2 which are not included in the present invention.
It is apparent that when compared with Nos. 01 to 203 and 205, the temporal stability of the sample is improved without deteriorating the sensitivity of photographic properties and the image quality of sharpness, graininess, and color reproducibility is excellent.

In addition, it is clear that even in desilvering, the amount of residual silver is small and excellent performance is exhibited. Regarding the residual silver amount, it is known that when the residual silver amount is 30 mg / m ² or more, color reproducibility is impaired in a color photographic material. In this respect, it can be seen that the sample satisfying the constitutional requirements of the present invention further improves color reproducibility and improves image quality.

It is well known that the compound represented by the general formula (B) of the present invention improves desilvering property, but in the constitution of the present invention, not only desilvering property but also stability over time, It is clear that the sharpness and graininess are also improved.

Further, the present invention comprising the above-mentioned magenta dye and an emulsion in which the grain size distribution of silver halide is monodisperse and the present invention comprising the use of the magenta dye and the compound represented by the general formula (B). It can be seen from the comparison between Samples 204 and 207 and Comparative Samples 201 to 203 that both the constitution can improve the image quality and stabilize the storability of the light-sensitive material, which are the problems to be solved by the present invention.

Further, in the use of the magenta dye having the constitution of the present invention and the compound represented by the general formula (B), it is preferable to use the coupler represented by the general formula (C) as the cyan coupler in order to achieve the above object. Sample 2 is preferred
It can be seen from the comparison between 04 and sample 206, and sample 208 and sample 209.

Also in the constitution of the magenta dye and the compound represented by the general formula (B), it is more preferable that the grain size distribution of silver halide is monodisperse, and that tabular grains are more preferable. The samples 204, 208,
This can be seen from the intercomparison of 210 and the intercomparison of samples 206, 209 and 211. Example 3 Iodine content used in the seventh layer and the first green-sensitive emulsion layer of Sample 101 used in Example 1 described in JP-A-2-854, 1 mol%, average grain size 0.2 μ, Sample 301 was prepared in exactly the same manner except that the emulsion having a variation coefficient of 14% was changed to a variation coefficient of 16%.

Next, Sample 302 is the third, fourth, fifth and seventh layers of the silver halide emulsion used for Sample 301.
The coefficient of variation of the emulsions of the 8th layer, 8th layer and 9th layer is 14,
12, 12, 14, 12, and 12% were prepared and used without changing the iodine content, the average particle size, and the sensitivity, and further used as an intermediate layer of the sixth layer of the present invention. Magenta dye, D-14, coating amount is 0.005
A sample was prepared by adding an aqueous solution to g / m ² .
At this time, λmax in the gelatin film of dye D-14 is 565n.
m and the optical density was 0.07.

Subsequently, D-14 was changed to D-32, the coating amount was changed to 0.020 g / m ² , and Sample 303 was prepared.
The λmax in the gelatin film was 525/570 nm, and the optical density was 0.06. Sample 304 is a dye D-3
4, the coating amount was 0.018 g / m ² , and a sample was prepared. λmax was 545 nm and its optical density was 0.06.

The samples 301 to 304 thus prepared were subjected to the color development processing step and processing solution composition described in Example 1 of JP-A-3-854, and the same performance evaluation as in Example 1 was carried out. ..

The results obtained are similar to those of Example 1 in that the sharpness, graininess and color reproducibility are excellent and the storability of the sample is excellent without changing the sensitivity of photographic properties. ,
Comparative sample of sample 301 and sample 30 satisfying the constitution of the present invention
It could be clearly confirmed by comparison with 2 to 304.

[0288]

EFFECT OF THE INVENTION In the non-photosensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer near the support, a wavelength range of 50 in the gelatin film is provided.
It contains a magenta dye having an absorption maximum wavelength in the range of 0 to 600 nm, and the size distribution of silver halide grains in the silver halide emulsion layer is monodisperse, or it contains the magenta dye and has the general formula (B The light-sensitive material containing the compound represented by) gives a color image excellent in sharpness, graininess, color reproducibility and desilvering property without changing the photographic property, and is also excellent in stability over time of the light-sensitive material. ..

Therefore, it is possible to provide a color photographic light-sensitive material excellent in storability and image quality.

[Procedure amendment]

[Submission date] March 11, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

[0014] Formula (B) _{A- (L 1)} in p -Z formula, A represents a group which cleaves reacts with the current image oxidized to _{(L 1) p -Z, L} 1 is and A After the bond of Z is cleaved
Represents a group that cleaves, p represents 0 or 1, and Z represents a bleaching accelerator.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

[0038]

[Chemical 14]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0088

[Correction method] Change

[Correction content]

In the general formula (B), A is a coupler residue
Alternatively, it represents a redox group .

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

[Correction content]

Examples of the coupler residue represented by A include a yellow coupler residue (for example, an open-chain ketomethylene type), a magenta coupler residue (5-pyrazolone type, a pyrazoloimidazole type, a pyrazolotriazole type, etc.),
Cyan coupler residue (phenol type, such as naphthol type), you and a colorless compound forming coupler residue (indanone type, acetophenone type, etc.) and the like. Further, it may be a heterocyclic coupler residue described in U.S. Pat. Nos. 4,315,070, 4,183,752, 3,961,959 or 4,171,223. .. A is
When expressing a redox group, the redox group is the oxidation of the developing agent.
Groups that can be cross-oxidized by the body, such as hydro
Quinones, catechols, pyrogallols, 1,4-na
Phtohydroquinones, 1,2-naphthohydroquinone
, Sulfonamide phenols, hydrazides or
Examples include sulfonamide naphthols. These groups
Specifically, for example, JP-A-61-230135 and JP-A-6-230135.
No. 2-251746, No. 61-278852, US special
Xu 3,364,022, 3,379,529,
No. 3,639,417, No. 4,684,604,
Or J. Org. Chem. , 29, 588 (196
4).

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0139

[Correction method] Change

[Correction content]

Specific examples of the group represented by formula ( I ) include the followings.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0141

[Correction method] Change

[Correction content]

[0141]

[Chemical 44] Specific examples of the group represented by formula ( II ) include the followings.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0142

[Correction method] Change

[Correction content]

[0142]

[Chemical 45] Specific examples of the group represented by the general formula ( III ) include the followings.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0153

[Correction method] Change

[Correction content]

[0153]

[Chemical 56]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0176

[Correction method] Change

[Correction content]

The total amount of addition of the cyan coupler represented by the general formula (C) is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol%, further preferably 90 mol% or more of the total cyan couplers. Is. This and
The total amount of cyan cyan coupler added is 1 mol of silver halide.
The range is 1 × 10 ^{−3 to} 2 mol per unit . Preferably 1
It is in the range of × 10 ⁻² to 1 mol, and more preferably 2
In the range of × ¹⁰ -2 ~5 × ^{10 -1} mol.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0256

[Correction method] Change

[Correction content]

[0256]

[Table 6] These produced samples 101 to 116 were evaluated for the various characteristics shown below.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0276

[Correction method] Change

[Correction content]

[0276]

[Table 8]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 7/34 7/388

Claims (3)

[Claims] 1. A support having a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler. The size of silver halide grains in at least one silver halide emulsion layer in a silver halide color photographic light-sensitive material having a non-light-sensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer close to the support. A silver halide color photographic light-sensitive material having a monodispersed distribution and containing a dye having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm in a gelatin film in the non-photosensitive layer. 2. A support having a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler. A silver halide color photographic light-sensitive material having a non-photosensitive layer adjacent to the side of the green-sensitive silver halide emulsion layer close to the support, the non-photosensitive layer having a spectral absorption in a wavelength range of 500 to 600 nm in a gelatin film. A silver halide color photographic light-sensitive material comprising a dye having a maximum wavelength and a compound represented by the following general formula (B). General formula (B) A- (L ₁ ) _p -Z In the formula, A represents a group which cleaves (L ₁ ) _p -Z by reacting with an oxidant of the phenomenon-promoting agent, and L ₁ cleaves the bond with A. After doing Z
Represents a group that cleaves, p represents 0 or 1, and Z represents a bleaching accelerator. 3. The silver coupler according to claim 1, wherein at least one of the silver halide emulsion layers contains a cyan coupler represented by the following general formula (C) and represented by the general formula (C). Silver halide color photographic light-sensitive material. General formula (C) In the formula, R ₂₁ is —CONR ₂₄ R ₂₅ , —SO ₂ NR ₂₄ R ₂₅ ,
-NHCOR ₂₄ , -NHCOOR ₂₆ , -NHSO
₂ R ₂₆ , -NHCONR ₂₄ R ₂₅ or -NHSO ₂ NR
₂₄ R ₂₅ and R ₂₂ are groups capable of substituting on a naphthalene ring, and k is 0
R ₂₃ represents a substituent, X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However, R ₂₄ and R
₂₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₂₆ is an alkyl group,
Represents an aryl group or a heterocyclic group. R when k is multiple
₂₂ may be the same or different and may be bonded to each other to form a ring. R ₂₂ and R ₂₃ or R ₂₃ and X ₂₁ may combine with each other to form a ring.