JPH07199407A - Silver halide color photographic material - Google Patents

Abstract

PURPOSE:To provide a photographic material having high sensitivity and being excellent in sharpness, preservability and dependency on processing by emulsifying and dispersing in a non-sensitive layer a specific yellow dye that is insoluble to water but soluble to organic solvents. CONSTITUTION:At least one kind of yellow dye represented by the formula that is insoluble to water but soluble to organic solvents is emulsified and dispersed in at least one non-sensitive layer, and at least one of photograph- forming layers, located farther away from a support than is either of green- sensitive layers, is dyed by at least one kind of magenta dye fixed, and/or at least one of photograph-forming layers located farther away from the support than is either of red-sensitive layers is dyed by at least one kind of cyan dye fixed. In the formula, X, Y each represent an electron withdrawing group or X and Y together represent an acid nucleus where they bond to each other, Ar represents a phenyl group or a heterocyclic group, L<1>-L<3> each represent a methine group, and (n) represents 0, 1 or 2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide light-sensitive material having a dyed layer, which contains a yellow dye which is photochemically inert and is easily decolorized and / or eluted by photographic processing. The present invention relates to a silver halide light-sensitive material having high sensitivity, improved sharpness, less processing dependency and excellent storage stability.

[0002]

2. Description of the Related Art In recent years, the technology of silver halide light-sensitive materials has advanced more and more, but the demands for sensitivity and image quality are incessant, and further progress is required. In particular, photographic light-sensitive materials are required to have high sensitivity and must be excellent in storability. For example, JP-A-5-232632 discloses a technique of using an organic yellow dye having sharper absorption in place of the yellow colloidal silver which has been conventionally used for the yellow filter layer for these purposes. By this technique, the broad absorption of yellow colloidal silver can be eliminated and the sensitivity of the lower layer can be improved, and the fog increase due to the use of yellow colloidal silver can be eliminated and the storage stability can be improved.

When we have been considering the introduction of these yellow dyes with the aim of improving the sensitivity, new problems have arisen. That is, when the light-sensitive material is designed using the yellow dye of the present invention, the sensitivity of the lower layer (mainly the green light-sensitive layer) can be improved, but in contrast, the sharpness of the lower layer decreases. occured.

For improving sharpness, a technique for preventing light scattering is known. For example, JP-A-5-188548 discloses a technique of fixing a magenta dye to a non-photosensitive layer adjacent to the side of the green-sensitive layer near the support. Although this method can minimize the reduction in sensitivity of green sensitivity, the effect of improving the sharpness, particularly the sharpness on the low frequency side (green and red photosensitive layers) was not sufficient.

Further, a technique for fixing a magenta and / or cyan dye on an upper layer of a green photosensitive layer and / or a red photosensitive layer is disclosed, for example, in JP-A-62-47640 and 62-62.
-166330 and the like. This method is notable for the demand for a photographic material having a higher sensitivity and a higher sharpness, although the sharpness-improving effect is remarkable, but the sensitivity is greatly lowered at the same time. Also EP0566415A
2, EP0566077A2 discloses a technique of using a fixedly dispersed yellow dye in a yellow filter layer. However, this solid-dispersed yellow dye has a problem that the photographic properties of the yellow dye when stored at high temperature and high humidity are largely deteriorated with time.

[0006]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a light-sensitive material having high sensitivity, excellent sharpness, storage stability and processing dependence.

[0007]

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

(1) A silver halide color having at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a non-photosensitive layer on a support. In a photographic light-sensitive material, at least one non-light-sensitive layer contains at least one water-insoluble, organic solvent-soluble yellow dye represented by the general formula (A) by emulsification and dispersion, and any green-sensitive layer At least one layer of the photographic constituent layers located farther from the support is dyed with at least one of the fixed magenta dyes, and / or on the side farther from the support than any red-sensitive layer. A silver halide color photographic light-sensitive material, characterized in that at least one of the photographic constituent layers located is dyed with at least one fixed cyan dye.

[0009]

[Chemical 3]

In the formula (A), X and Y each represent an electron-withdrawing group or an acidic nucleus bound by X and Y, Ar represents a phenyl group or a heterocyclic group, and L ¹ and L ² , L ³ each represent a methine group, and n represents 0, 1 or 2. (2) The silver halide color photographic light-sensitive material as described in the above item (1), wherein the water-insoluble, organic solvent-soluble yellow dye represented by the general formula (A) is the general formula (B).

[0011]

[Chemical 4]

In the formula (B), R ²¹ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a ureido group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkylthio group, an arylthio group, Oxycarbonyl group, acyl group, carbamoyl group,
It represents a cyano group, an alkoxy group, an aryloxy group, an amino group, or an amide group. Q is -O- or -NR ²² -
The stands, R ²² is a hydrogen atom, an alkyl group, an aryl group,
Or represents a heterocyclic group. R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms,
It represents an alkyl group or an aryl group, and R ²⁴ and R ²⁵ may form a 6-membered ring. R ²⁶ represents a hydrogen atom, an alkyl group, an aryl group or an amino group. L ¹ , L ² and L ³ represent a methine group, and k is 0 or 1.

(3) The silver halide color photographic light-sensitive material as described in the above item (1), wherein a magenta dye and / or a cyan dye is fixed by an emulsion dispersion method.

The present invention can solve the problems of the present invention by the above configuration. The yellow dye of the formula (A) of the present invention is emulsified and contained in the light-sensitive material, and it is possible to prevent the deterioration of the storage stability which occurs when the yellow dye is conventionally contained in the solid dispersion. Further, the yellow dye of the formula (A) of the present invention is preferably non-diffusible and contained in the yellow filter layer, so that the lower layer sensitivity can be improved. The magenta dye and the cyan dye of the present invention can improve the sharpness by being fixed to the photographic constituent layer at a specific position. Furthermore, the present invention synergistically includes a yellow dye of the formula (A) having a specific structure in a light-sensitive material and a specific magenta dye and a cyan dye in a layer at a specific position of the light-sensitive material. It is possible to improve the sensitivity, sharpness and storability of the lower layer, and it is also excellent in processing dependence.

The water-insoluble, organic solvent-soluble yellow dye represented by formula (A) used in the present invention will be described in detail. The electron-withdrawing groups represented by X and Y are cyano group, nitro group, alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, hydroxyethoxycarbonyl, t-amyloxycarbonyl), aryloxycarbonyl (eg, phenoxycarbonyl, 4
-Methoxycarbonyl), an acyl group (e.g. acetyl,
Pivaloyl, benzoyl, propionyl, 4-methanesulfonamidobenzoyl, 4-methoxy-3-methanesulfonamidobenzoyl, 1-methylcyclopropylcarbonyl), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dimethylcarbamoyl, piperidine-
1-ylcarbonyl, N- (3-methanesulfonamidophenyl) carbamoyl), a sulfonyl group (for example, benzenesulfonyl, p-toluenesulfonyl),
The acidic nucleus bound by X and Y is preferably a 5- or 6-membered ring, and examples of the 5-membered ring include 2-pyrazolin-5-one, 2-isoxazolin-5-one and pyrazolidine-
3,5-dione, 2,5-dihydrofuran-2-one,
Indan-1,3-dione is preferable, and as the 6-membered ring, for example, 1,2-dihydro-6-hydroxypyridin-2-one, barbituric acid and thiobarbituric acid are preferable.

The phenyl group represented by Ar is preferably a phenyl group substituted with an electron-donating group, and the electron-donating group is a dialkylamino group (eg, dimethylamino,
Di (ethoxycarbonylmethyl) amino, di (butoxycarbonylmethyl) amino, N-ethyl-N-ethoxycarbonylmethylamino, di (cyanoethyl) amino,
Preferred are piperidinyl, pyrrolidinyl, morpholino, N-ethyl-N-β-methanesulfonamidoethylamino, N-ethyl-N-β-hydroxyethyl), hydroxy group and alkoxy group (eg methoxy, ethoxy, ethoxycarbonylmethoxy).

As the heterocyclic group represented by Ar, a 5-membered heterocyclic ring is preferable, and for example, pyrrole, indole, furan and thiophene are particularly preferable. Coumarin is preferable as the 6-membered heterocycle.

The methine group represented by L ¹ , L ² and L ³ may have a substituent, but is preferably an unsubstituted methine group. The yellow dye represented by the general formula (A) of the present invention is preferably a compound represented by the general formula (B).

Next, the water-insoluble, organic solvent-soluble yellow dye represented by formula (B) used in the present invention will be described in detail. The alkyl group represented by R ²¹ may have a substituent, and is preferably an alkyl group having 1 to 8 carbon atoms,
For example, methyl, ethyl, propyl, tertiary butyl, normal butyl, 1-methylcyclopropyl, chloromethyl,
Trifluoromethyl, ethoxycarbonylmethyl and the like are preferable.

The aryl group represented by R ²¹ may have a substituent and is preferably an aryl group having 6 to 13 carbon atoms, for example, phenyl, 4-methoxyphenyl, 4-acetylaminophenyl, 4-methane. Sulfonamidophenyl, 4-benzenesulfonamidophenyl and 1-ethoxycarbonylpropanesulfonamide are preferred.

The alkyl group represented by R ²² may have a substituent and is preferably an alkyl group having 1 to 18 carbon atoms such as methyl, 2-cyanoethyl, 2-hydroxyethyl and 2-acetoxyethyl. preferable.

The phenyl group or substituted phenyl group represented by R ²² is preferably a phenyl group having 6 to 22 carbon atoms, for example, phenyl, 2-methoxy-5-ethoxycarbonylphenyl, 3,5-di (ethoxycarbonyl) phenyl,
4-di (ethoxycarbonylmethyl) aminocarbonylphenyl, 4-normaloctyloxycarbonylphenyl, 4-butanesulfonamidocarbonylphenyl,
4-methanesulfonamidocarbonylphenyl, 3-sulfamoylphenyl, 4-methanesulfonamidophenyl, 4-methanesulfonamidosulfonylphenyl,
4-Acetylsulfamoylphenyl, 4-propionylsulfamoylphenyl, 4-N-ethylcarbamoylsulfamoylphenyl and the like are preferable.

The heterocyclic group represented by R ²² is pyridyl, 4-hydroxy-6-methylpyrimidin-2-yl, 4-hydroxy-6-tert-butylpyrimidin-2-.
And sulfolan-3-yne.

The alkyl group represented by R ²³ , R ²⁴ and R ²⁵ is preferably an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl or propyl. A methyl group is particularly preferable.

The aryl group represented by R ²³ , R ²⁴ and R ²⁵ is preferably an aryl group having 6 to 13 carbon atoms, and particularly preferably a phenyl group. . The 6-membered ring formed by R ²⁴ and R ²⁵ may be saturated, unsaturated or a heterocyclic ring, but a benzene ring is particularly preferable.

The alkyl group represented by R ²⁶ may have a substituent, and is preferably an alkyl group having 1 to 18 carbon atoms,
For example, methyl, ethyl, ethoxycarbonylmethyl, tert-butoxycarbonylmethyl, ethoxycarbonylethyl, dimethylaminomethyl, 2-cyanoethyl, 3-acetamidopropyl, 3-propionylaminopropyl, 3-benzenesulfonamidopropyl, 3-propanesulfonamide. Propyl, tetrahydrofurfuryloxycarbonylethyl and the like are preferable.

The phenyl group or substituted phenyl group represented by R ²⁶ is preferably a phenyl group having 6 to 22 carbon atoms, for example, phenyl, 2-methoxy-5-ethoxycarbonylphenyl, 4-di (ethoxycarbonylmethyl) aminocarbonylphenyl. , 4-normaloctyloxycarbonylphenyl, 4-hydroxyethoxycarbonylphenyl, 4-propanesulfonamidophenyl, 4-butanesulfonamidocarbonylphenyl, 4-methanesulfonamidocarbonylphenyl, 4-acetylsulfamoylphenyl are preferred.

The amino group represented by R ²⁶ is preferably a dialkylamino group, for example, dimethylamino and diethylamino.

The compound represented by the general formula (B) must be sparingly soluble in water having a pH of 6 or less, and preferably does not contain a sulfo group, a salt of a sulfo group, a carboxy group or a salt of a carboxy group as a substituent. .

The compound represented by the general formula (B) preferably has a dissociative group other than the above. Preferred examples of dissociative group-substituted sulfonylamino group (e.g., _{CH 3 SO 2 NH-, C 6} H 5 SO 2 NH-), acyl sulfamoyl group, acylsulfamoyl group, a sulfonylcarbamoyl group, carbamoyl sulfamethoxazole There are moyl groups and phenolic hydroxyl groups.

The water-insoluble, organic solvent-soluble yellow dye represented by the general formula (A) or (B) is added to the non-photosensitive layer during the production of the color light-sensitive material and is substantially non-photosensitive without diffusing into other layers. The object of the present invention is achieved as long as it is present in the layer and has a spectral absorption maximum wavelength in the wavelength range of 400 to 500 nm in the non-photosensitive layer. The layer to which the yellow dye of the general formula (A) or (B) is added is not particularly limited, but it is preferably added to the yellow filter layer.

The method of using the dye for non-photosensitivity is as follows. The dye is dispersed in oil in water, that is, the boiling point at atmospheric pressure is 17
Using a high boiling organic solvent having a boiling point of 5 ° C. or higher, and if necessary, using an organic solvent having a boiling point of 50 ° C. or higher and 160 ° C. or lower, which is emulsified and dispersed in a gelatin aqueous solution containing a surfactant, is added. To use.

If necessary, a polymer dispersion medium may be used in place of the high boiling point organic solvent, or the high boiling point organic solvent and the polymer dispersion medium may be mixed and used.

The term "water-insoluble" as used herein means that a dye soluble in 100 cc of water at 40 ° C is 0.5 g or less, and the term "soluble in an organic solvent" means ethyl acetate 10 at 40 ° C.
It means that the dye soluble in 0 cc is 1.0 g or more.

The amount of the dye added is preferably 0.05 to 1.20 in the dry film of the non-photosensitive layer added, and the average optical density in the 400 nm to 500 nm region is preferably 0.05 to 1.20. It is more preferably 0.6. In the present invention, it suffices to add an amount capable of obtaining this average optical density and the dye dispersed by the above-mentioned dispersion method. As an actual measuring method, a sample obtained by applying a dye together with gelatin on a transparent support and drying the sample is measured for a density at 400 to 500 nm by a spectrophotometer, and an average optical density at 400 to 500 nm is obtained from an integrated value.

The dyes of the present invention may be used alone or in combination of several kinds. It is also preferable to use it in combination with yellow colloidal silver.

The dye-added layer of the present invention is a non-photosensitive layer located on the side opposite to the exposure side (support side) with respect to the blue-sensitive layer, and is localized in the layer to minimize deterioration of sensitivity of the blue-sensitive layer. You can keep it to the limit.

Specific examples of the compounds represented by the general formulas (A) and (B) of the present invention are shown below, but the present invention is not limited thereto.

[0039]

[Chemical 5]

[0040]

[Chemical 6]

[0041]

[Chemical 7]

[0042]

[Chemical 8]

[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

[0047]

[Chemical 13]

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17]

[0052]

[Chemical 18]

[0053]

[Chemical 19]

Next, the magenta dye and the cyan dye of the present invention will be described. The magenta dye in the present invention is substantially 50% in the dry film of the light-sensitive material to which the dye is added.
Any dye having a maximum spectral absorption wavelength in the range of 0 to 600 nm may be used, and the dye may be used alone or in combination of two or more.

The cyan dye in the present invention is substantially 600 to 700 n in the dry film of the light-sensitive material containing the dye.
Any dye having a maximum spectral absorption wavelength in m may be used, and the dye may be used alone or in combination of two or more.

In the present invention, the term "fixed dye" means that the dye added during the preparation of the intended layer during the production of the light-sensitive material diffuses to the layers other than the intended layer even after the production. None, it means that it exists substantially in the target layer. Any method may be used as the means for fixing the layer to the target layer, and for example, the following method is available.

The method of adding the dye to the target layer is to directly dye gelatin, or to disperse the dye in oil-in-water as described below, that is, to use a high-boiling organic solvent having a boiling point of 175 ° C. or higher at normal pressure. Boiling point of 50 ℃ or more and 160 ℃ if necessary
A method of dissolving using the following organic solvent and adding the emulsion-dispersed product in an aqueous gelatin solution containing a surfactant,
International Patent Publication WO88 / 4974, Japanese Patent Publication No. 1-502
No. 912 and European Patent Publication No. 456,148, there is a method of adding a so-called solid dispersion or a method of preventing diffusion of a dye through a polymer mordant. Representative polymer mordants include, for example, JP-A-5-1.
It is described in Chemical formula 9 of 88548. In the present invention, any of these methods can be used, but addition by the oil-in-water dispersion method is particularly preferable because it does not desensitize the emulsion layer. Therefore, the dye used in the present invention is preferably an oil-soluble dye.

In the present invention, the amount of the dye added is from 500 to 500 for the magenta dye in the dry film of the target layer.
For cyan dyes in the 600 nm range, 600-70
The average optical density in the 0 nm region is 0.005 to 0.50, preferably 0.02 to 0.30. This concentration is determined as follows. The actual measuring method is as follows: a dye is applied on a transparent support together with zeratan and dried, and a sample is dried with a spectrophotometer at 500 to 600 nm, or 600 to 70 nm.
The concentration of 0 nm is measured, and it is 500 to 600 from the integrated value.
nm or average optical density at 600-700 nm is determined.

The fixed magenta dye of the present invention needs to be contained farther from the support than the green photosensitive layer, but it is preferably added to the photosensitive emulsion layer, and the blue photosensitive emulsion layer is preferable. Is particularly preferably added to Conventionally, such a fixed magenta dye has been used in the non-light-sensitive emulsion layer as disclosed in JP-A-62-166330.
In particular, it is often added to the protective layer, and it has been considered preferable. However, as a result of various studies, the present inventors have found that addition to the photosensitive emulsion layer is particularly preferable for improving sharpness. Found out. Although the reason is not clear, it is presumed that the light scattering is suppressed by being in the same layer as the photosensitive silver halide emulsion layer which is the light scatterer.

The fixed cyan dye of the present invention is
It is necessary to add it to the photosensitive emulsion layer farther from the support than the red photosensitive layer, but it is preferable to add it to the photosensitive emulsion layer.
It is particularly preferable to add it to the blue or green photosensitive layer.

The most preferred embodiment of the present invention is to add a magenta dye to the blue photosensitive layer and a cyan dye to the blue and green photosensitive layers.

Specific examples of the magenta dye and cyan dye used in the present invention are shown below, but the present invention is not limited thereto.

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

The above exemplified compounds are disclosed in JP-A-61-488.
54, 61-7838, 60-243654.
No. 60-32851, No. 62-276539,
52-92716, International Patent WO88 / 04794.
No. 3, JP-A-3-7931, No. 4-45436, No. 5
No. 43809, or can be synthesized according to the method described.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are formed by sequentially exposing two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. Also, JP-A-57-112751, 62-200350, 62-206.
As described in 541, 62-206543, 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, the low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) /
High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL
It can be installed in the order of / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-63936
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 1. In addition, 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 silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even in the case of being composed of three layers having different sensitivities as described above, Japanese Patent Application Laid-Open No. 59-202464
In the same color-sensitive layer, the medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support. 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, in the case of four or more layers, the arrangement may be changed as described above. US 4,663,27 to improve color reproduction
1, same 4,705,744, same 4,707,436, JP-A-62-160448, same
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL or RL described in 63-89850, adjacent to or in proximity to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than about 30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less, and the projected area diameter is about 1
It may be large-sized grains up to 0 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid.
307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafki).
des, Chimie et Phisique Photographique, Paul Monte
l, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemi
stry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Zelikm).
an, et al., Making and Coating Photographic Emulsi
on, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the method described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined 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 emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-63
The core / shell internal latent image type emulsion described in JP-A-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell 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.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are RD No.17643 and RD No.187.
16 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with a silver halide grain, US Pat.
852, a silver halide grain in which the grain inside is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain 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. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition.
As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
It is particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grains or polydisperse emulsions, but monodisperse grains (weight of silver halide grains or grain number of at least 95
% Having a particle size within ± 40% of the average particle size).

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 fine grain of silver halide which 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 it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles equivalent to the projected area)
0.01 to 0.5 μm is preferable, and 0.02 to 0.2 μm is more preferable. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. 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 contained in the fine silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868 5. Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Right column 876-877 Inhibitors 10. Matting agents 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, but the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); Japanese Patent Application No. 4 -134523 a coupler of the general formula (I) of claim 1; US 5,066,576 column 1, lines 45-55, a coupler of the general formula (I);
A coupler represented by the general formula (I) of paragraph 0008 of JP-A-4-274425; a coupler described in claim 1 of EP 498, 38A1 on page 40 (particularly D-35 on page 18); EP 447, 969A1 of page 4 Couplers represented by formula (Y) (especially Y-1 (page 17), Y-54 (page 41)); US
Couplers represented by formulas (II) to (IV) on lines 36 to 58 of column 4, 476, 219 (particularly II-17, 19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (bottom right of page 11), L-6
8 (bottom right of page 12), L-77 (bottom right of page 13); EP 456,257 [A-4] -63
(P.134), [A-4] -73, -75 (p.139); M-4, -6 of EP 486,965 (26
Page), M-7 (page 27); M-45 of paragraph 0024 of Japanese Patent Application No. 4-234120; M-1 of paragraph 0036 of Japanese Patent Application No. 4-36917; paragraph 023 of Japanese Patent Application Laid-Open No. 4-362631.
7 M-22. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35), 34,35 of JP-A-4-43345.
(Page 37), (I-1), (I-17) (pages 42 to 43); The coupler represented by formula (Ia) or (Ib) of claim 1 of Japanese Patent Application No. 4-236333. Polymer coupler: P-1, P-5 of JP-A-2-44345 (page 11).

As couplers in which the color forming dye has an appropriate diffusibility, US 4,366,237, GB 2,125,570, EP 96,570, D
Those described in E 3,234,533 are preferable. The coupler for correcting the unwanted absorption of the coloring dye is a yellow color cyan dye coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
Page), EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 (column 8), CC described in US 4,833,069.
-13 (column 10), US 4,837,136 (2) (column 8), WO92 / 1
Colorless masking couplers of the formula (A) of claim 1 of 1575 (in particular the exemplified compounds on pages 36 to 45) are preferred.
Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP 378,236A1
Compounds represented by formulas (I), (II), (III), and (IV) described on page 11 of the (especially T-101 (page 30), T-104 (page 31), T-113 (page 36) ), T-13
1 (page 45), T-144 (page 51), T-158 (page 58)), a compound represented by the formula (I) described on page 7 of EP436, 938A2 (particularly D-49 (page 51)) ,
A compound represented by the formula (1) of Japanese Patent Application No. 4-134523 (particularly paragraph 0)
023 (23)), EP 440,195A2 formula (I), (I) described on page 5-6.
Compounds represented by I) and (III) (especially I- (1) on page 29); Bleach accelerator releasing compounds: Compounds represented by formulas (I) and (I ') on page 5 of EP 310,125A2 (especially (60, 61) on page 61 and Japanese Patent Application No. 4
-325564, a compound of formula (I) according to claim 1 (particularly (7) of paragraph 0022); a ligand-releasing compound: a compound of formula LIG-X according to claim 1 of US 4,555,478 (particularly column 21-21). ~ Line 41 compound); Leuco dye releasing compound: U
S 4,749,641 columns 3-8 compounds 1-6; fluorescent dye releasing compounds: compounds represented by COUP-DYE in claim 1 of US 4,774,181 (especially compounds 7-11 in columns 7-10); development accelerators or fogging agents Emitted compounds: Compounds represented by formulas (1), (2) and (3) in column 3, US Pat. No. 4,656,123 (particularly (I-22) in column 25) and EP 450,637 A2, page 75, lines 36 to 38, E
xZK-2; A compound that releases a dye group only after it leaves:
Compounds of formula (I) in claim 1 of US 4,857,447 (especially Y-1 to Y-19 in columns 25 to 36).

As the additives other than the coupler, the following are preferable. Dispersion medium for oil-soluble organic compound: JP-A-62-2
15272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,9
3 (pages 140-144); Latex for impregnation of oil-soluble organic compounds:
Latex as described in US 4,199,363; Oxidizer developer Scavenger: Formula of column 2, lines 54-62 of US 4,978,606.
Compounds represented by (I) (especially I-, (1), (2), (6), (12)
(Columns 4-5), US 4,923,787, column 2, lines 5-10 (particularly compound 1 (column 3); stain inhibitor: EP
298321A, page 4, lines 30-33, formulas (I)-(III), especially I-47,72, I
II-1,27 (pages 24-48); Anti-fading agents: EP 298321A, A-6,7,2
0,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164 (69
Pp. 118-), US 5,122,444 columns 25-38 II-1 to III-23,
In particular III-10, EP 471347A, pages 8-12, I-1 to III-4, especially I
I-2, US 5,139,931 columns 32-40 A-1 to 48, especially A-3
9,42; Materials that reduce the use of color-enhancing agents or color-mixing inhibitors: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-46;
Formalin Scavenger: EP 477932A SC on pages 24-29
V-1 to 28, especially SCV-8; Hardener: H on page 17 of JP-A 1-214845
-1,4,6,8,14, US 4,618,573 column 13-23 formula (VII) ~
The compound (H-1 to 54) represented by (XII), the compound (H-1 to 76) represented by the formula (6) at the lower right of page 8 of JP-A-2-214852, especially H-
14, Compound described in claim 1 of US 3,325,287; Development inhibitor precursor: P-24,37,39 (6 to JP-A-62-168139)
Page 7); compounds according to claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US 4,923,790 columns 3-15 I-1 to III-43, especially II-1. , 9,10,18, III-25;
Stabilizers, antifoggants: Columns 6 to 16 of US 4,923,793 I
-1 ~ (14), especially I-1,60, (2), (13), column 4, US 4,952,483
5 to 32 compounds 1 to 65, especially 36: chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324;
Dye: a-1 to b-20, particularly a- on pages 15 to 18 of JP-A-3-156450
1,12,18,27,35,36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, E
FI-1 to F-II-43, especially FI-11 and FI, on pages 33 to 55 of P 445627A
I-8, EP 457153A, pages 17-28, III-1 to 36, especially III-1,3,
Fine crystal dispersion of Dye-1 to 124 of 8 to 26 of WO 88/04794, E
P 319999A pages 6-11, compounds 1-22, especially compound 1, EP
Compounds D-1 to 87 represented by formulas (1) to (3) of 519306A
(Page 3-28), compound 1 represented by formula (I) of US 4,268,622.
22 (columns 3 to 10), compounds (1) to (31) (columns 2 to 9) represented by the formula (I) of US Pat. No. 4,923,788;
Compounds represented by formula (1) of 6-3335 (18b) ~ (18r), 101 ~
427 (pages 6-9), compounds of formula (I) of EP 520938A
(3) to (66) (pages 10 to 44) and compounds represented by formula (III)
HBT-1 to 10 (page 14), compounds (1) to (31) represented by formula (1) of EP 521823A (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Examined Fairness 2-32615, Actual Fairness 3
It is suitable for the film unit with a lens described in -39784. Suitable supports that can be used in the present invention are described, for example, in RD. No.17643, page 28, No.18716, 647
The right column of the page to the left column of the page 648 and the page 879 of the same No. 307105. 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, further preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. It is defined as
The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is A. Green et al.'S Photographic Science and Engineering. (Photogr. Sci. Eng.), Page 19, pages 2,124 to 129. It can be measured by using a swellometer (swelling meter) of the type. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or 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 conditions described above by the formula: (maximum swollen film thickness-
It can be calculated by (film thickness) / film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of μm to 20 μm. This back layer includes the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid,
It is preferable to include a surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

The light-sensitive material of the present invention has the above-mentioned RD. No.176
43, pages 28-29, ibid. No. 18716, 651 left column-right column, and ibid N
It can be developed by a usual method described on pages 880 to 881 of O.307105. 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. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples and preferred examples thereof are
The compounds described on page 28, lines 43-52 of EP 556700A are mentioned. Two or more of these compounds can be used in combination depending on the purpose. The color developer is a pH buffer such as alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound. It is common to include an inhibitor or an antifoggant. Also, 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, competitive couplers, 1-
Auxiliary developing agents such as 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, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, Add N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developer, 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. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenisher. 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 of the treatment tank with the air. The processing effect of the contact between the photographic processing liquid and air in the processing tank is the aperture ratio (= [contact area between processing liquid and air c
m ² ] ÷ [volume of treatment liquid cm ³ ]). The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, JP-A-63-216050 The slit development processing method described can be mentioned. The aperture ratio is preferably reduced not only in both the color development step and the black-and-white development step but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing, stabilizing 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 time of color development processing is usually set between 2 and 5 minutes, but by using a high temperature, high pH and using a color developing agent at a high concentration,
Further, the processing time can be shortened.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. 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. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Among them, ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III)
II) Complex salts and other aminopolycarboxylic acid iron (III) 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 for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US 3,893,858, DE 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-72623. ,
53-95630, 53-95631, 53-104232, 53-124424,
53-141623, 53-28426, RD No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832, and JP-A-53-32735;
Thiourea derivatives described in 3,706,561; DE 1,127,715, iodide salts described in JP-A-58-16235; DE 966,410, 2,74
Polyoxyethylene compounds described in 8,430; JP-B-45-
8836 Polyamine compounds; Others JP-A-49-40943,
Same 49-59644, same 53-94927, same 54-35727, same 55-26506, same
Compounds described in 58-163940; bromide ion can be used.
Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and particularly US 3,89
Compounds described in 3,858, DE 1,290,812 and JP-A-53-95630 are preferable. Further, the compounds described in US 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 photography. 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. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. 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, but thiosulfates are generally used. Yes, especially ammonium thiosulfate can be used most widely. Further, it is also preferable to use a combination of thiosulfate, thiocyanate, thioether compound and thiourea. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or
The sulfinic acid compounds described in EP 294769A are preferred. Further, addition of aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution is preferable for the purpose of stabilizing the solution. In the present invention, the fixer or the bleach-fixer has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole is used.
It is preferable to add 0.1 to 10 mol per liter.

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 treatment 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 process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460 or a stirring effect by using a rotating means of JP-A-62-183461 is used. Method of raising, 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, the circulation flow rate of the entire processing solution There is a method of increasing it. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. 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 and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and JP-A-6-191257.
It is preferable to have the photosensitive material conveying means described in 0-191258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. Shortening the processing time,
It is particularly effective in reducing the replenishment amount of the processing liquid.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and various other conditions Can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of t
he Society of MotionPicture and Television Enginee
It can be determined by the method described in rs Volume 64, P.248-253 (May 1955). According to the multi-stage countercurrent method described in this document, 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. Problem arises. As a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288838 is extremely effective. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used. The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8.
The washing water temperature and washing time can be set depending on the characteristics and use of the light-sensitive material, but in general, a range of 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C is selected. . Furthermore,
The light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. For such stabilization treatment, known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be applied. In addition, following the water washing treatment, there is a case where a further stabilization treatment is performed, and as an example,
A stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, can be mentioned. 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, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The photographic 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 a precursor of a color developing agent. For example US 3,34
2,597 described indoaniline compound, 3,342,599,
Research Disclosure No. 14850 and No. 15159
Schiff base type compounds described in US Pat. No. 3,719,492, and metal salt complexes described in US Pat. No. 3,719,492.
The urethane compound described in 35628 can be mentioned.
The photographic material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339 and JP-A-57-1.
44547 and 58-115438. The processing solution used for processing the light-sensitive material of the present invention is used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can.

[0089]

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,
A sample 101, which is a multi-layer color light-sensitive material composed of each layer having the composition shown below, was prepared. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, Ex
M: Magenta coupler, ExY: Yellow coupler, C
pd; additive

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

In addition to the above, the samples thus prepared include
1,2-Benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. In addition, each layer has appropriate storage properties, processability, pressure resistance, mildew / bacterial resistance,
In order to improve the antistatic property and coating property, W-1 to W-
6, B-1 to B-6, F-1 to F-16, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

[0107]

[Table 1]

In Table-A, (1) Emulsions A to N were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to N 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. It has been subjected. (3) For the preparation of tabular grains, low molecular weight gelatin is used 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. (5) Emulsions A to N are BH Carroll, Photographic Scien
Ce and Engineering, 24, 265 (1980) and the like contain iridium inside the particles.

[0109]

[Chemical 28]

[0110]

[Chemical 29]

[0111]

[Chemical 30]

[0112]

[Chemical 31]

[0113]

[Chemical 32]

[0114]

[Chemical 33]

[0115]

[Chemical 34]

[0116]

[Chemical 35]

[0117]

[Chemical 36]

[0118]

[Chemical 37]

[0119]

[Chemical 38]

[0120]

[Chemical Formula 39]

[0121]

[Chemical 40]

[0122]

[Chemical 41]

[0123]

[Chemical 42]

[0124]

[Chemical 43]

(Preparation of Samples 102 to 107) Sample 101
In the same manner as in Sample 101, D-27 and SEN-8 were added as shown in Table B.
5 was created. The method for adding the yellow dye D-27 is as follows. 32.0 g of D-17, 17.5 g of Cpd-1, 19 cc of high boiling organic solvent Solv-1,
4.9 g of W-3 and 100 cc of ethyl acetate were added and dissolved by heating. This ethyl acetate solution was mixed with 1100 g of a 10% gelatin aqueous solution, and emulsified and dispersed with a household mixer. The emulsified dispersion thus obtained was added to the desired layer.

The method for adding the magenta dye SEN-8 is as follows. 17.5 g of magenta dye (S
EN-8) and 15 cc of high boiling organic solvent (Solv
-1) and were added to 100 cc of ethyl acetate and heated to 40 ° C. to completely dissolve them. 40% of this ethyl acetate solution is a 13% aqueous gelatin solution containing 7.0 g of a surfactant (W-4).
It was mixed with 0 g and emulsified and dispersed by a homoblender. The emulsified dispersion thus obtained was added to the desired layer.

Sample 106 was similarly prepared by adding a 1% methanol solution of SEN-11 to the target layer. Sample 107 is EP0566415A2 p39
The yellow dye (EXSEN-1) described is EP056641.
5A2 was used by solid-dispersing it by the method described in 5A2, and the others were similarly prepared.

[0128]

[Chemical 44]

The sample thus prepared was subjected to wedge exposure with white light, and then development processing was carried out by the following processing steps to measure the density. Sensitivity is the minimum density of magenta +
The evaluation was made by the logarithm of the reciprocal of the exposure dose giving a density of 0.3.
The sharpness was determined as a relative value with respect to the sample 101 by exposing the MTF pattern and performing the same processing as above. The results obtained are summarized in Table B.

As for the evaluation of storability, the sample was stored for 3 days under the conditions of 50 ° C. and 80%, and then exposure and development were carried out in the same manner as described above to measure the yellow density to determine the sensitivity. The sensitivity was evaluated by the logarithm of the reciprocal of the exposure amount which gives the minimum density of yellow + 0.5. The difference between this value and the sensitivity when developed immediately after coating was determined and used as a representative value showing the storage stability. The more negative this value is, the greater the decrease in sensitivity during storage.

Processed as described below.

Next, the composition of the treatment liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water to 1.0 liter pH (adjust with potassium hydroxide and sulfuric acid) 10.05

(Bleach) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water ( 27%) 6.5 ml Water 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0

(Fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 295.0 ml Acetic acid (90%) 3.3 Add water to 1.0 liter pH (to ammonia water and acetic acid) 6.7)

(Stabilizer) (Unit: g) p-Nonylphenoxypolyglycidol (Glycidol average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole) -1-ylmethyl) piperazine 0.75 Hydroxyacetic acid 0.02 Hydroxyethylcellulose (Daicel Chemistry HEC SP-2000) 0.1 1,2-Benzisothiazolin-3-one 0.05 Water was added to 1.0 liter pH 8.5

The results are shown in Table-B. The results are summarized in Table B.

[0137]

[Table 2]

According to Table B, the light-sensitive material of the present invention in which the yellow dye of the present invention is emulsified and dispersed and the magenta dye is fixed above the green-sensitive layer has high sensitivity and high sharpness, and is excellent in storage stability. It is clearly superior. Further, it can be seen that the sample 105 in which the magenta dye is emulsified and dispersed is superior in sharpness to the sample 106 in which the magenta dye is added in the methanol solution and is particularly preferable.

Example 2 In Samples 104 and 105 of Example 1, the sixth, seventh, eighth,
The cyan dye SEN-13 was added to the 10, 11, 12, and 14 layers, and the same evaluation as in Example 1 was carried out.
The same effect as above was observed, and the sharpness of the red photosensitive layer could be improved.

Example 3 Samples 301 to 306, in which the yellow dye added to the 11th layer of the sample 105 described in Example 1 was replaced by equimolar amounts of the dye species as shown in Table 3, were the same as Sample 105. It was created by the method. These samples were tested for treatment dependence by the following method. In the treatment method described in Example 1,
A processing solution was prepared by reducing the amount of sodium sulfite contained in the color developing solution to 70%. Example 1 using this treatment liquid
After exposure and development in the same manner as described, the yellow image density of the unexposed area was measured. The increase in the yellow density of the unexposed area due to the reduction of the amount of sodium sulfite in the color developing solution to 70% was calculated, and this is shown in Table C as a representative value of processing dependence.

[0141]

[Table 3]

From Table C, all of Samples 301 to 306 are the light-sensitive materials of the present invention, but the light-sensitive materials 304 to 306 using the dyes included in the general formula (B) are excellent in processing dependence and are particularly preferable. I understand.

[0143]

The present invention has high sensitivity and excellent sharpness,
It is possible to obtain a light-sensitive material having excellent storage stability and processing dependence.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location G03C 7/20 (72) Inventor Keiji Mibayashi 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (72) Inventor Shigeru Ono 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (3)

[Claims] 1. A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and at least one layer each on a support.
In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer and a non-light-sensitive layer, at least 1
The non-photosensitive layer of the layer contains at least one water-insoluble, organic solvent-soluble yellow dye represented by the general formula (A) in an emulsified and dispersed state, and the side away from the support from any green-sensitive layer. At least one of the photographic constituent layers located on the side is dyed with at least one kind of fixed magenta dye, and / or at least one of the photographic constituent layers located on the side farther from the support than any red-sensitive layer. A silver halide color photographic light-sensitive material characterized in that one layer is dyed with at least one kind of fixed cyan dye. [Chemical 1] In formula (A), X and Y each represent an electron-withdrawing group, or
Represents an acidic nucleus bonded with Y, Ar represents a phenyl group or a heterocyclic group, L ¹ , L ² and L ³ each represent a methine group, and n represents 0, 1 or 2. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the water-insoluble, organic solvent-soluble yellow dye represented by formula (A) is represented by formula (B). [Chemical 2] In the formula (B), R ²¹ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a ureido group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkylthio group, an arylthio group, an oxycarbonyl group. Represents an acyl group, a carbamoyl group, a cyano group, an alkoxy group, an aryloxy group, an amino group, or an amide group. Q is -O- or -NR ²² - represents, R ²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ²³ , R ²⁴ , and R ²⁵ represent a hydrogen atom, an alkyl group, or an aryl group, and R ²⁴ and R ²⁵ may form a 6-membered ring. R ²⁶ represents a hydrogen atom, an alkyl group, an aryl group or an amino group. L ¹ , L ² and L ³ represent a methine group, and k is 0 or 1. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein a magenta dye and / or a cyan dye is fixed by an emulsion dispersion method.