JPH05210200A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the chromaticity and to decrease color turbidity and color contamination by incorporating a specified compd. into insensitive layer of a pohotosensitive material and incorporating at least one kind of specified compd. into the photosensitive material. CONSTITUTION:At least one kind of compd. selected from compds. expressed by formula I is incorporated into an insensitive layer of the photosensitive material. Also, a compd. selected from compds. expressed by formula II or the like is incorporated into the photosensitive material. In formula I, Q is ketomethylene residue, L1-L3 are methylene groups, R1-R5 are hydrogen atoms or substituents, R3 and R4, or R4 and R5 may be coupled to form a five-or six-member ring, and n is 0 or 1, however, Q has at least one carboxylic acid group, sulfone amide group or sulfocarbamoil group. In formula II, R<12>-R<15> are hydrogen atoms, alkyl groups or aryl groups, and Y is a halogen atom.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having improved color reproducibility.

[0002]

2. Description of the Related Art A method of forming a dye image in a silver halide color photographic material is usually a coupler which is contained in advance in the photographic material and an aromatic primary amine type color developing which is contained in a color developer. It is carried out by the coupling reaction of the oxidant of the main drug. In silver halide color photographic materials, three types of couplers forming yellow, magenta, and cyan dyes are used in order to reproduce a color by a subtractive method. These color-sensitive layers usually contain silver halide emulsions having blue, green, and red color sensitivities, respectively. In recent years, color photographic materials are required to have higher image quality. In particular, the importance of color reproducibility is increasing. Conventionally, spectral sensitizing dyes used in silver halide color photographic materials for imparting blue, green, and red color sensitivities have unnecessary spectral sensitivity in addition to the necessary wavelength range, and Color reproducibility was impaired due to the inherent sensitivity of the silver halide itself. In order to correct this, provision of a yellow filter layer, inclusion of a decolorizing dye of about 500 to 600 nm in the photosensitive material, and the like have been studied.

For example, a silver halide photographic light-sensitive material comprises a support and a hydrophilic colloid layer such as a light-sensitive silver halide emulsion layer formed on the support. Image-wise exposure is performed to record an image on the light-sensitivity. When this is done, it is necessary to control the spectral composition of light. Usually, a hydrophilic colloid layer which is located farther from the support than the light-sensitive silver halide emulsion layer contains a dye capable of absorbing light in a wavelength range unnecessary for the silver halide emulsion layer, and a filter layer. And a method of transmitting only light of a target wavelength is used. As the above-mentioned dye, in addition to water-soluble dyes and oil-soluble dyes, colored colloidal silver (yellow, magenta, black, etc.) is used. As a dye, it is desirable that the dye be colorless after development (completely washed out or decomposed into a colorless compound) and fixed in a specific layer in the light-sensitive material. Water-soluble dyes are easy to wash out and are preferable, but they are difficult to fix, and oil-soluble dyes are easy to fix, but they are easy to remain after the treatment. Therefore, the dye used for such a purpose has good absorption spectrum characteristics according to the purpose of use, and is substantially decolorized during the development process to cause residual color contamination by the dye after the development process. It is necessary to satisfy various conditions such as not being present, not being diffused from a colored layer to another layer, and being excellent in stability over time in a solution or a silver halide photographic light-sensitive material and not being deteriorated.

Many efforts have been made to search for dyes satisfying such conditions. For example, British Patent No. 506,38
5, pyrazolone oxonol dyes, US Pat. No. 3,247,127, barbituric acid oxonol dyes, US Pat. No. 2,390,707, azo dyes, US Pat. , 255,077, styryl dyes, British Patent No. 584,609.
Dyes described in U.S. Pat.
Examples thereof include merocyanine dyes described in 493,747, cyanine dyes described in U.S. Pat. No. 2,843,486, open chain methylene type benzylidene dyes described in U.S. Pat. No. 4,420,555, and the like.

Among them, the above-mentioned US Pat. No. 4,420,555
The dye-containing layer described in JP-A-61-2604630 fulfills a considerably good function as a filter layer. Further, US Pat. No. 2,548,564 discloses a method in which a hydrophilic polymer having an opposite charge to a dissociated anionic dye is allowed to coexist as a mordant to localize the dye in a specific layer by interacting with dye molecules. 4,124,386
No. 3,635,694 and the like. Further, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-56-12639 and JP-A-55-155350.
No. 58, No. 58-155351, No. 63-27838,
63-197943, European Patent No. 15,601,
274, 723, 276, 556, 299,
No. 435, International Patent No. 88/04798, etc.

[0006]

However, when the above method is used as a method for localizing a dye in a specific layer, it results from using a coating solution containing the dye or the polymer. There are side effects such as coating surface failure (for example, white spot-like failure) and the gradual diffusion and delocalization of the dye during storability of the light-sensitive material. It is desired to solve these problems. It was Therefore, a first object of the present invention is to provide a color photographic material having high color saturation, less color turbidity and color contamination, and excellent color reproducibility. A second object of the present invention is to provide a method for fixing a dye that does not cause a coating surface failure, and a third object is to provide a method for fixing a dye that does not impair the storability of a light-sensitive material. is there.

[0007]

The above objects of the present invention are as follows.
A silver halide photographic light-sensitive material having at least one blue color-sensitive layer, green color-sensitive layer and red color-sensitive layer and at least one non-light-sensitive layer on a support. The following general formula (F-1) is used for at least one of the layers.
Containing at least one compound selected from the compounds represented by the formulas (I) to (I
It was achieved by containing at least one compound selected from the compounds represented by X). General formula (F-1)

[0008]

[Chemical 11]

In the formula, Q represents a ketomethylene residue,
L ₁ , L ₂ and L ₃ represent a methylene group, and R ₁ , R ₂ and R
₃ , R ₄ , R ₅ each represent a hydrogen atom or a substituent, and R
₃ and R ₄ or R ₄ and R ₅ are connected to each other to form 5 or 6
A member ring may be formed. n represents 0 or 1. However,
Q has at least one carboxylic acid group, sulfonamide group or sulfocarbamoyl group. General formula (I)

[0010]

[Chemical 12]

General formula (II)

[0012]

[Chemical 13]

General formula (III)

[0014]

[Chemical 14]

General formula (IV)

[0016]

[Chemical 15]

General formula (V)

[0018]

[Chemical 16]

General formula (VI)

[0020]

[Chemical 17]

General formula (VII)

[0022]

[Chemical 18]

General formula (VIII)

[0024]

[Chemical 19]

General formula (IX)

[0026]

[Chemical 20]

The general formula (F-1) will be described in detail below. The ketomethylene residue represented by Q is not particularly limited, but is preferably phenyl cyanoacetate, cyanoacetic acid, alkyl cyanoacetate (as the alkyl group, preferably methyl, ethyl, butyl, propyl, etc.), benzoylacetonitrile, 2 -Pyrazolin-5-one, isoxazolone, pyrazolidinedione, indandione, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, 2,4-oxazolidinedione, more preferably 2-pyrazolin-5- On, isoxazolone,
Represents indandione, barbituric acid, benzoylacetonitrile.

The ketomethylene residue represented by Q is at least one carboxylic acid group, a sulfonamide group (eg, methanesulfonamide, ethanesulfonamide, benzenesulfonamide), or a sulfocarbamoyl group (eg, methanesulfonylcarbamoyl, It may have a substituent in addition to benzenesulfonylcarbamoyl). The kind of the substituent is not particularly limited as long as it does not dissolve the dye represented by formula (F-1) at the coating pH (for example, a sulfonic acid group). The substituent which the ketomethylene residue represented by Q may have is an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, hexyl, octyl), an alkoxy group having 1 to 8 carbon atoms. Groups (eg methoxy, ethoxy, butoxy,
Pentyloxy), halogen atoms (eg chlorine, bromine,
Fluorine), amino group (eg dimethylamino, diethylamino, dipropylamino), ester group (eg methoxycarbonyl, ethoxycarbonyl), cyano group, amide group (eg acetylamino, methanesulfonamide), carbamoyl group (eg methylcarbamoyl, Ethylcarbamoyl), sulfamoyl group (eg methylsulfamoyl), aryl group (eg phenyl, naphthyl), hydroxyl group, acyl group having 1 to 9 carbon atoms (eg acetyl, benzoyl, propanoyl), sulfonyl group (eg methanesulfonyl, benzene) Sulfonyl) and the like.

The methine group represented by L _1, L _{2 and} L ₃ may have a substituent (eg methyl, ethyl),
Substitution is preferred. The substituents represented by R _1, R _2, R _3, R _{4 and} R ₅ must be a group (for example, a sulfonic acid group) that can dissolve the dye of formula (F-1) at the coating pH. There is no particular limitation. Examples of the preferable group include the substituents that the ketomethylene group represented by Q may have. More preferably, R ₄ represents an amino group,
R _1, R _2, R _{3 and} R ₅ represent a hydrogen atom. R ₃ and R ₄ and /
Alternatively, examples of the ring formed by connecting R ₄ and R ₅ include a tetrahydroquinoline ring and a julolidine ring.

Specific examples of the dye represented by formula (F-1) are shown below, but the invention is not limited thereto.

[0031]

[Chemical 21]

[0032]

[Chemical formula 22]

[0033]

[Chemical formula 23]

[0034]

[Chemical formula 24]

[0035]

[Chemical 25]

[0036]

[Chemical formula 26]

[0037]

[Chemical 27]

[0038]

[Chemical 28]

The dye represented by the general formula (F-1) can be obtained by a method known to those skilled in the art, for example, in the presence of an acid or a base of a corresponding ketomethylene compound and a 3-formylmalin marine compound (in some cases, an acid is added). Condensation reaction (in the presence of a base), "The Cyanine Dyes and
Related Compounds ", F. Hame
r, Interscience Publisher
s, 1964 (The Cyanine Soybean and Related Compounds F. Harmer, Interscience Publishers 1964). The dye represented by formula (F-1) according to the present invention can be used in any of the non-photosensitive layers and may be used in a single layer or a plurality of layers. It is particularly preferably used for the non-photosensitive layer located on the support side of the green-sensitive layer.

The dye represented by formula (F-1) according to the present invention may be dissolved in an ordinary solvent and used, or may be used as a solid fine particle dispersion. Examples of the solvent for the dye represented by formula (F-1) according to the present invention include water, alcohols (methanol, ethanol, butanol, etc.),
Esters (acetic acid ethyl ester, acetic acid butyl ester, etc.) can be used. Furthermore, these two or more kinds can be mixed and used, or even a trace amount of alkali (sodium hydroxide, potassium hydroxide, sodium carbonate, aqueous ammonia, etc.) or acid (sulfuric acid, acetic acid, citric acid, etc.) can be used together. good.

As a method of using the dye represented by formula (F-1) according to the present invention as a solid fine particle dispersion, a known pulverization method in the presence of a dispersant (for example, ball mill, vibrating ball mill, planetary ball mill) It can be formed by a ball mill, a sand mill, a colloid mill, a jet mill, a roller mill), and in that case, a solvent (for example, water, alcohol) may coexist. Further, after dissolving the dye of the present invention in a suitable solvent, a poor solvent for the dye of the present invention may be added to precipitate a fine crystal powder, in which case a surfactant for dispersion is used. Good. Alternatively, it may be dissolved by controlling the pH, and then the pH may be changed to perform microcrystallization. The microcrystalline particles of the dye of the present invention in the dispersion have an average particle size of 10 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less,
In some cases, it is preferably 0.1 μm or less.

The amount of the dye represented by formula (F-1) according to the present invention is preferably 10 mg / m ^{2 to 4} g / m ² , and more preferably 100 mg / m ^{2 to 2} g / m ² .

Next, the compounds represented by formulas (I) to (IX) will be described. Among the compounds represented by the general formulas (I) to (IX), preferred ones are those represented by the general formulas (III), (VII),
(VIII) and (IX), more preferable are those represented by the general formulas (III), (VII) and (IX). Specific examples of the compounds represented by formulas (I) to (IX) used in the present invention are shown below, but the present invention is not limited thereto.

[0044]

[Chemical 29]

[0045]

[Chemical 30]

[0046]

[Chemical 31]

[0047]

[Chemical 32]

[0048]

[Chemical 33]

[0049]

[Chemical 34]

[0050]

[Chemical 35]

[0051]

[Chemical 36]

[0052]

[Chemical 37]

In the present invention, the compounds represented by formulas (I) to (IX) can be used in both the light-sensitive layer and the non-light-sensitive layer in the light-sensitive material. In particular, it is preferably used for the layer containing the compound represented by formula (F-1) in the light-sensitive material. The addition amount of the compounds represented by formulas (I) to (IX) is preferably 5 × 10 ⁻⁷ to 2 × 10 ⁻³ mol / m ² ,
Furthermore, it is 5 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / m ² . It is known that the compounds represented by the general formulas (I) to (IX) of the present invention act effectively against molds which appear in photographic images.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided 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 light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And 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, 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 such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as is usually used. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably use a two-layer constitution of 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. be able to. 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. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, 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 (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-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 62-63936
It is also possible to arrange the layers in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually 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 distant from the support in the same color-sensitive layer. The layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. In addition, they 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 layers or more, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat.
No. 663,271, No. 4,705,744, No. 4,707,436, and JP-A Nos. 62-160448 and 63-89850.
It is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material. The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains about 15 mol% or less of silver iodide, silver iodobromide, silver iodochloride, silver iodochlorobromide and bromide. It is silver, silver chlorobromide, or silver chloride. Particularly preferred is silver iodobromide or silver iodochlorobromide containing about 0 to about 8 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms 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 may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. Particularly, the low-sensitivity emulsion is preferably monodisperse. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (December 1978), 22-2.
Page 3, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid N.
o.307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Gl).
afkides, Chemie et Phisique Photographique, PaulMo
ntel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Ch
emistry (Focal Press, 1966)), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze).
likman et al., Making and Coating Photographic Emul
Sion, Focal Press, 1964) and the like. U.S. Pat.No. 3,574,628,
The monodisperse emulsions described in U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748 are also preferable.

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, PhotographicScience and Eng.
gineering), Vol. 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the method described in U.S. Pat. No. 4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure.
Further, silver halides having different compositions may be joined by epitaxial joining, and, for example, rhodan silver,
It may be bonded to a compound other than silver halide such as 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 in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image in both the surface and the inside. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542.
, JP-A-63-279242 or JP-A-1-282545. The shell thickness of this emulsion is preferably from 3 to 400 nm, particularly preferably from 5 to 200 nm. As the silver halide emulsion, those which have been physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the corresponding portions are summarized in the table below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, grain size distribution, 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. U.S. Pat.No. 4,082,553 described above, the surface of which is covered with silver halide grains, U.S. Pat.No. 4,626,498, and JP-A-59-214852. It can be preferably used for a photosensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain that 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 having a fogged grain inside or on its surface is described in U.S. Pat.
98, JP-A-59-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged 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 preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. 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 ± 40% of the average grain size). %) Is preferable. 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 developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine-grain silver halide has a silver bromide content of
It is 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Fine grain silver halide is
The average particle size (average value of the circle equivalent diameter of the projected area) is 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 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 nor spectral sensitization. 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 amount of silver coated on the light-sensitive material of the present invention is preferably 6.0 g / m ² or less in the case of a transmission type, and most preferably 4.5 g / m ² or less. 2 for reflective type.
It is preferably 0 g / m ² or less, more preferably 1.0 g / m ² or less.
The above-mentioned three Research Disclosures are described together with the light absorbers that can be used in combination with the known photographic additives that can be used in the present invention, and the relevant portions are shown in the following table.

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 Page 868 Supersensitizer to page 649 Right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention 24 to 25 page 649 Right column 868 to 870 Agent, stabilizer 6. Light absorber , Pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dyes, ultraviolet absorbers, stain 7. stain, page 25, right column, page 650, left column, page 872, inhibitor, right column 8. dye image, page 25, page 650, left Column Page 872 Stabilizer 9. Hardener 26 Page 651 Left column 874 to 875 10. Binder 26 Page 651 Left column 873 to 874 11. Plasticizer, Page 27 650 Right column 876 Lubricant 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surface active agent 13. Static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. .. In the light-sensitive material of the present invention, US Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fog agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof include Research Disclosure No. 17643, VII-C to G, and No. 307105, VII.
-C to G. Examples of yellow couplers include U.S. Pat.Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,752.
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, No. 1,476,760, and U.S. Patent No. 3,97.
Those described in 3,968, 4,314,023, 4,511,649, European Patent 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432, 3,725,067,
Research Disclosure No. 24220 (June 1984
Mon), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-71.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication No. 3,329,729, European Patent No. 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4,333,999, 4,775,616, 4,45
No. 1,559, No. 4,427,767, No. 4,690,889, No.
Those described in 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137, European Patent No. 341,188A and the like.
As couplers in which the colored dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent (Publication) 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No. 1
7643, VII-G, No. 307105, VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat.
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. In addition, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.
It is also preferable to use a coupler having a dye precursor group as a leaving group capable of reacting with a developing agent to form a dye as described in 4,777,120. Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are
RD17643, Item VII-F and No. 307105, VII-
Patents described in paragraph F, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, No. 63-37350
Nos. 4,248,962 and 4,782,012 are preferable. RD No. 11449, 24241, JP-A-61
-The bleaching accelerator releasing couplers described in 201247 etc. are effective in shortening the processing time having a bleaching ability,
In particular, the effect is great when it is added to the light-sensitive material using the above-mentioned tabular silver halide grains. As couplers that release a nucleating agent or a development accelerator imagewise during development, those described in British Patents 2,097,140 and 2,131,188 and JP-A-59-157638 and 59-170840 are preferable. Further, by a redox reaction with an oxidized product of a developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and 1-45687, a fogging agent and a development accelerator. ,
A compound that releases a silver halide solvent or the like is also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers releasing dyes that undergo color restoration after withdrawal described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bisyl phthalate). (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-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azetase Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents with temperatures above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Examples thereof include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and 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, further preferably 18 μm or less, particularly preferably 10 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is 25 ° C and 55% relative humidity (2 days)
The film swelling speed T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering by A. Green et al.
(Photogr.), 19 Certificates, No. 2, by using a 124 type described on pages to 129 Swellometer (swelling meter) can be measured, T _1/2 in color developer 30 The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when the film is treated at ℃ for 3 minutes and 15 seconds.
The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 1
50 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
A m hydrophilic colloid layer (referred to as a back layer) can be provided. In this back layer, 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, a surface active agent and the like. The swelling ratio of this back layer is
100 to 500% is preferable.

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 thereof include 3-methyl-4-amino-N, N diethylaniline and 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 sulfates, hydrochlorides or p-toluenesulfonates and the like. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose. The color developer should have a pH such as alkali metal carbonate, borate or phosphate.
It is common to include a development inhibitor such as a buffer, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic 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 Agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, 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, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and them Can be mentioned as a representative example.

The present invention can be used for all color light-sensitive materials such as a color negative film, a color paper, a color reversal film, a color reversal paper, a direct positive film and a direct positive paper. In particular, it is preferably used for a light-sensitive material for obtaining a positive image. For example, it is particularly preferable to use it for a color reversal film, a color reversal paper, a direct positive paper and the like.

The processing steps of the direct positive material of the present invention are as follows. 1) Color developing-washing-bleaching-fixing-washing 2) Color developing-washing-bleaching fixing-washing 3) Color developing-bleaching fixing-washing Particularly preferred is (3). As the direct positive material, the internal latent emulsion is used, and a nucleating agent and a nucleation accelerator are used. As the nucleating agent, those described in JP-A-63-106656 are preferable. As the nucleation accelerator, those described in JP-A-63-279242 are preferable.

Next, processing solutions and processing steps for the color reversal light-sensitive material of the present invention other than the color developing solution will be described. Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows. 1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all performed in US Pat.
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid. Next, the steps after color development will be described. 4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development-washing -Bleaching-washing-fixing-washing-stable 8) color development-bleaching-fixing-washing-stable 9) color development-bleaching-bleach-fixing-washing-stable 10) color development-bleaching-bleach-fixing-fixing-washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleaching fixing-washing-stable 13) Color developing-washing-bleaching fixing-washing-stable 14) Color development-bleaching fixing-washing- Stable 15) Color development-fixing-bleach-fixing-washing-stable 4) to 15), the washing step immediately before the stabilizing step may be omitted, or conversely the final stabilizing step is not performed. May be. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step. Especially 1)
And 4) or 2) and 13) are preferred.

Next, the processing liquid in the color reversal processing step of the present invention will be described. Known developing agents can be used in the black-and-white developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-).
3-pyrazolidone), aminophenols (eg N
-Methyl-p-aminophenol), 1-phenyl-3
-Pyrazolines, ascorbic acid and US Pat.
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 67,872 can be used alone or in combination. In the black and white developer used in the present invention, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents (eg, Hydroxides, carbonates), dissolution tablets (eg polyethylene glycols, esters thereof), pH adjusters (eg organic acids such as acetic acid),
Sensitizer (for example, quaternary ammonium salt), development accelerator,
A surfactant, a defoaming agent, a film hardening agent, a viscosity imparting agent, etc. can be contained. The black-and-white developing solution used in the present invention needs to contain a compound acting as a silver halide solvent, and a sulfite salt added as the above preservative usually serves its function. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN and NaSC.
N, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na _{2
S 2 O 5, K 2 S} 2 O 3, and the like Na ₂ S ₂ O _3. The pH of the developer adjusted in this way
The value is chosen to be sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5. In order to carry out the sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times the standard process. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be shortened.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed,
Generally, it is 3 liters or less per square meter of the light-sensitive material, preferably 500 ml or less, particularly preferably 200 ml or less. 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 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, and more preferably 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, 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 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The reversal bath used after black and white development may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, boron hydroxide compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
Instead of the reversal bath, a light reversal treatment by re-exposure may be performed, and the reversal step may be omitted by adding the fogging agent to the color developing solution. The silver halide color photographic light-sensitive material of the present invention is bleached or bleach-fixed in a color developer. These treatments may be carried out immediately after the color development reaction without passing through this treatment step.
In order to prevent unnecessary post-development, air fogging, and to reduce the amount of color developing solution brought into the desilvering process, and to the photosensitive material such as sensitizing dyes and dyes contained in the photographic light-sensitive material In order to wash out the impregnated color developing agent and render it harmless, it may be subjected to a bleaching treatment or a bleach-fixing treatment after a processing step such as stopping, adjusting and washing with water after the color developing treatment.

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. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment 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 a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing. The bleaching solution, bleach-fixing solution and their pre-bath are
A bleaching accelerator can be used if necessary. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A No. 53-32736, No. 53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
No. 17129 (July 1978), etc., a compound having a mercapto group or a disulfide group; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715,
Iodide salt described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; 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 having a large accelerating effect, and in particular, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 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. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like 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 EP 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. The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 1 to 3 minutes, more preferably 1 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 stirring using a rotating means of JP-A-62-183461 is used. Method of improving the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to make the emulsion surface turbulent to further improve the stirring effect, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective for 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 effect of the bleaching accelerator. Automatic developing machines used in the light-sensitive material of the present invention are disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have a photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably 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 the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive 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 other various conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Tele-vision Engineers Volume 64, P. 248-253 (1955)
May May 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 this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986) Sankyo Publishing, edited by Sanitary Technology, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used. PH of washing water in the processing of the light-sensitive material of the present invention
Is 4-9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is 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 stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is 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. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include 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 accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In processing using an automatic processor,
When each of the above treatment liquids 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 U.S. Pat.
42,597 Indoaniline compounds, 3,342,5
No. 99, Research Disclosure 14,850 and No. 1
Examples thereof include the Schiff base type compound described in 5,159, the aldol compound described in US Pat. No. 13,924, the metal salt complex described in US Pat. No. 3,719,492, and the urethane compound described in JP-A-53-135628. The silver halide color light-sensitive 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, JP-A-57-144547,
And No. 58-115438, etc. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

[0077]

EXAMPLES The present invention will now be specifically described by way of examples, which should not be construed as limiting the invention. (Example 1) Preparation of solid dispersion of dye 10 g of compound (I-4) was measured and a surfactant (Trit) was used.
on X-200), add 25 g of water and 200 ml of water, and add 2 mm.
The mixture was dispersed for 10 minutes by a ball mill using balls each having a diameter to obtain a solid dispersion having an average particle size of 0.5 micron. To this dispersion, 1000 g of 10% aqueous gelatin solution was added, and the solution was coated on a glass dry plate so that the amount of dye was 0.5 g / m ² . The absorption peak wavelength of the obtained glass dry plate was 545 nm, and the peak value was 1.62. Put this dry plate in pure water at 18 ℃.
When it was soaked for 0 minutes, dried and then measured again for absorption, the peak value was 1.65, which was slightly sharpened, but hardly changed.

Example 2 Preparation of Sample 101 A multilayer color light-sensitive material having the following compositions was formed on a 127 μm-thick cellulose triacetate film support which was undercoated to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic Solvent Oil-1 0.1 g Microcrystalline solid dispersion of Dye E-1 0.1 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling organic solvent Oil-3 0.1 g Dye D-4 0.4 mg

Third layer: intermediate layer Finely grained silver iodobromide emulsion (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) whose surface and inside are fogged Silver amount 0.05 g Gelatin 0.4 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-30 0.05 g Coupler C-9 0.05 g Compound Cpd-C 10 mg High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Fifth Layer: Medium Sensitivity Red Sensitive Emulsion Layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-30 .2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g

Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg UV absorber U-1 0.01 g UV absorber U-2 0.002 g UV absorber Agent U-5 0.01 g Dye D-1 0.02 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling organic solvent Oil-1 0.02 g

Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) silver amount 0.02 g gelatin 1 0.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-4 0.1 g Coupler C-7 0 .05 g Coupler C-8 0.20 g Compound Cpd-B 0.03 g Compound Cpd-C 10 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g High Boiling point organic solvent Oil-1 0.1 g High boiling point organic solvent Oil-2 0.1 g

10th layer: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-80 .1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g High boiling point organic solvent Oil-2 0.01 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0 0.08 g Compound Cpd-C 5 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling organic solvent Oil -1 0.02g High boiling point organic solvent Oil-2 0.02g

Twelfth layer: Intermediate layer Gelatin 0.6 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Dye E-2 microcrystalline solid dispersion Thing 0.05g

14th layer: Intermediate layer Gelatin 0.6 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-60 .1g Coupler C-10 0.4g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-100 .1 g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.3 g Coupler C-6 0.6 g Coupler C-10 0.1 g

Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1g Dye D-2 0.05g Dye D-3 0.1g

Layer 19: Second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g

20th layer: 3rd protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3]

[0103]

[Chemical 38]

[0104]

[Chemical Formula 39]

[0105]

[Chemical 40]

[0106]

[Chemical 41]

[0107]

[Chemical 42]

[0108]

[Chemical 43]

[0109]

[Chemical 44]

[0110]

[Chemical 45]

[0111]

[Chemical 46]

[0112]

[Chemical 47]

[0113]

[Chemical 48]

[0114]

[Chemical 49]

[0115]

[Chemical 50]

[0116]

[Chemical 51]

For sample No. 101, the compound represented by the general formula (F-1) dispersed in the eighth layer in the same manner as in Example 1 and the compounds represented by the general formulas (I) to (IX) Add the indicated compounds in methanol solution as shown in Table 4 to obtain a sample N
o.102 to 120 were produced.

[0118]

[Table 4]

When three kinds of compounds contained in the compounds (I) to (IX) are used in combination, they are added so that they are equimolar to each other. The comparative compounds used are shown below.

[0120]

[Chemical 52]

Sample Nos. 101 to 1 produced in this way
About 20, the following development process is performed by giving uniform exposure,
A uniform gray image with a density of 1.0 was obtained and the number of spot failures (diameter 20 microns or more) in 0.3 m ² was determined.
The sample was left in a completely dark place at 45 ° C and 80% RH for 3 days, and then a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.)
The sensitivity of the green-sensitive layer was decreased by measuring the optical density of the product that had been subjected to sensitometric gradation exposure and development processing.
E (G)) was calculated. Further, a Macbeth color checker (manufactured by Colmorgen [USA]) was photographed and processed in the same manner, and green and red patches were measured to obtain color saturation. The results are shown in Table 5.

Sample 101 was photographed normally and processed by the method described below using an automatic processor until the cumulative replenishment amount of the solution became three times its tank volume.
20 were processed. Treatment process time Temperature Tank capacity Replenishment amount 6 minutes 38 ℃ 12 liters 2200 ml / m ² First washing 45 seconds 38 ℃ 2 liters 2200 ml / m ² Reversing 45 seconds 38 ℃ 2 liters 1100 ml / m ² Color development Development 6 minutes 38 ° C 12 liters 2200 ml / m ² Bleach 2 minutes 38 ° C 4 liters 860 ml / m ² Bleach-fixing 4 minutes 38 ° C 8 liters 1100 ml / m ² Second water washing (1) 1 minute 38 ° C 2 liters -Second water washing (2) 1 minute 38 ° C 2 liters 1100 ml / m ² stability 1 minute 25 ° C 2 liters 1100 ml / m ² dry 1 minute 65 ° C --- A so-called countercurrent replenishment system was adopted in which the replenisher was introduced into the water washing (2) and the overflow liquid of the second water washing (2) was introduced into the second water washing (1).

The composition of each processing liquid was as follows. [First developer] [Tank liquid] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid / 5-sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Hydroquinone / potassium monosulfonate 20 g 20 g Potassium carbonate 33 g 33 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g 2.0 g potassium bromide 2.5 g 1.4 g potassium thiocyanate 1.2 g 1.2 g potassium iodide 2.0 mg-water added 1000 ml 1000 ml pH 9.60 9.60 The pH was adjusted with hydrochloric acid or potassium hydroxide.

[First Washing Liquid] [Tank Liquid] [Replenishing Liquid] Ethylenediaminetetramethylenephosphonic acid 2.0 g The same disodium phosphate 5.0 g was added to the tank liquid and 1000 ml pH 7.00 pH was hydrochloric acid or sodium hydroxide It was adjusted.

[Reversal solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Same as tank solution Stannous chloride dihydrate 1.0 g p- Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

[Color developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate 12 water Salt 36g 36g Potassium bromide 1.0g-Potassium iodide 90mg-Sodium hydroxide 3.0g 3.0g Citrazine acid 1.5g 1.5g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH was adjusted with hydrochloric acid or potassium hydroxide.

[Bleaching solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ dihydrate 10.0 g Same as tank solution Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 120 g Bromide potassium 100g Ammonium nitrate 10g bleach accelerator 0.005 mole _{(CH 3) 2 N-CH} 2 -CH 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl water to make 1000 ml pH 6.30 pH is hydrochloric acid or It was adjusted with aqueous ammonia.

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ dihydrate 5.0 g Same as tank solution Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonia ・ dihydrate 50 g Thio Ammonium sulfate 80 g Sodium sulfite 12.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia.

[Second Washing Solution] [Both Tank Solution and Replenisher] 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 anion exchange resin (Amberlite). IR-400) was passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg / liter sodium diisocyanurate dichloride and 1.5 g / liter sodium sulfate were added. Was added. The pH of this liquid is in the range of 6.5 to 7.5.

[Stabilizer] [Tank solution] [Replenisher] Formalin (37%) 0.5 ml Same as tank solution Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Triazole 1.7 g Piperazine-6 Hydrate 0.6g Add 1000ml water without adjusting pH

[0131]

[Table 5]

In Table 5, the value of color saturation (Croma) is obtained by modifying the photometric data of the color patch Munsell color system {JIS standard.
It is shown in the attached table of JIS Z 8721 (1971)}, and it can be said that the larger the value, the higher the saturation and the more preferable. The smaller the number of surface failures, the more desirable. The decrease in sensitivity under high humidity is a measure of the diffusion of the dye that occurs during storage, but the smaller the value, the better. As can be seen from the table, the sample using the dispersion of the dye of the present invention has a large effect of improving the color saturation. Further, the coating surface failure that occurs when a dye dispersion is used and the sensitivity decrease due to the diffusion of the dye are dramatically improved by using the dye dispersion of the present invention and the compound of the present invention in combination. I understand.

(Example 3) Sample No. 2 of color photographic light-sensitive material in which the following first to twelfth layers were multilayer-coated on a paper support having a thickness of 220 μm laminated on both sides with polyethylene
01 was created. 15 on the coated side of the first layer of polyethylene
It contains wt% of anatase titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye. The chromaticity of the surface of the support is (L ^* , a ^* , b ^* ) color system 89.0, −, respectively.
It was 0.18 and -0.73. (Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown.

First Layer (Gelatin Layer) Gelatin ... 0.30

Second Layer (Antihalation Layer) Black Colloidal Silver ・ ・ ・ 0.07 Gelatin ・ ・ ・ 0.50

Third Layer (Low Sensitivity Red Sensitive Layer) Silver chloroiodobromide (1 mol% silver chloride / 4 mol% silver iodide) spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) , Average grain size 0.3μ, grain size distribution 10%, cubic, core iodide type core-shell structure) 0.06 Spectral sensitized with red sensitizing dye (ExS-1, 2, 3) Silver bromide (4 mol% silver iodide, average grain size 0.5 μ, grain size distribution 15%, cubic) ・ ・ ・ 0.07 Gelatin ・ ・ ・ 1.00 Cyan coupler (ExC-1) ・ ・ ・ 0 .14 Cyan coupler (ExC-2) ... 0.07 Anti-fading agent (Cpd-2, 3, 4 equivalents) ... 0.12 Coupler dispersion medium (Cpd-6) ... 0.03 Coupler Solvent (Solv-1, 2, 3 equivalents) ... 0.06 Development accelerator (Cpd-13) ... 0.05

Fourth Layer (Highly Sensitive Red Sensitive Layer) Silver iodobromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (6 mol% silver iodide, average grain size 0.8 μm) , Particle size distribution 20%, flat plate (aspect ratio = 8, core iodine type) ... 0.15 gelatin ... 1.00 cyan coupler (ExC-1) ... 0.20 cyan coupler (ExC) -2) ... 0.10 Anti-fading agent (Cpd-2, 3, 4 equivalents) ... 0.15 Coupler dispersion medium (Cpd-6) ... 0.03 Coupler solvent (Solv-1, 2,3 equivalents) ... 0.10.

Fifth layer (intermediate layer) Magenta colloidal silver: 0.02 Gelatin: 1.00 Color mixing inhibitor (Cpd-7, 16): 0.08 Color mixing inhibitor solvent (Solv-4) 5) ... 0.16 polymer latex (Cpd-8) ... 0.10.

Sixth Layer (Low Sensitivity Green Sensitive Layer) Silver chloroiodobromide spectrally sensitized with a green sensitizing dye (ExS-4) (silver chloride 1 mol%, silver iodide 2.5 mol%, average grain size) 0.28μ, grain size distribution 8%, cubic, core iodide type core-shell structure) 0.04 Silver iodobromide spectrally sensitized with a green sensitizing dye (ExS-4) (silver iodide 2.5 mol% , Average particle size 0.48μ, particle size distribution 12%, cubic) ・ ・ ・ 0.06 gelatin ・ ・ ・ 0.80 magenta coupler (ExM-1, 2 equivalents) ・ ・ ・ 0.10 anti-fading agent (Cpd) -9) ... 0.10 Anti-staining agent (Cpd-10, 11 equivalents) ... 0.01 Anti-staining agent (Cpd-5) ... 0.001 Anti-staining agent (Cpd-12) ..0.01 coupler dispersion medium (Cpd-6) ... 0.05 coupler solvent (S lv-4,6) ··· 0.15

Seventh Layer (High-Sensitivity Green Sensitive Layer) Silver iodobromide spectrally sensitized with a green sensitizing dye (ExS-4) (3.5 mol% silver iodide, average grain size 1.0 μ, grain size distribution 21) %, Flat plate (aspect ratio = 9, uniform iodine type) ... 0.10 Gelatin ... 0.80 Magenta coupler (ExM-1, 2 equivalents) ... 0.10 Anti-fading agent ( Cpd-9) ... 0.10 Anti-staining agent (Cpd-10, 11 equivalents) ... 0.01 Anti-staining agent (Cpd-5) ... 0.001 Anti-staining agent (Cpd-12) ... 0.01 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4, 6) ... 0.15

Eighth Layer (Yellow Filter Layer) Yellow Colloidal Silver ... 0.14 Gelatin ... 1.00 Color Mixing Inhibitor (Cpd-7) ... 0.06 Color Mixing Inhibitor Solvent (Solv-4, 5) ... 0.15 Polymer latex (Cpd-8) ... 0.10.

Ninth Layer (Low Sensitivity Blue Sensitive Layer) Silver chloroiodobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (silver chloride 2 mol%, silver iodide 2.5 mol%, average) Grain size 0.38μ, grain size distribution 8%, cube, core iodide type core-shell structure ... 0.07 Silver iodobromide (iodine) spectrally sensitized with a blue sensitizing dye (ExS-5, 6) Silver halide 2.5 mol%, average particle size 0.55 μ, particle size distribution 11%, cubic) ・ ・ ・ 0.10 Gelatin ・ ・ ・ 0.50 Yellow coupler (ExY-1, 2 equivalents) ・ ・ ・ 0.20 Anti-staining agent (Cpd-5) ... 0.001 Anti-fading agent (Cpd-14) ... 0.10 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-2) ..0.05

Layer 10 (high-sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (2.5 mol% silver iodide, average grain size 1.4 μ, grain size) Distribution 21%, flat plate (aspect ratio = 14) ... 0.25 gelatin ... 1.00 Yellow coupler (ExY-1, 2 equivalents) ... 0.40 Anti-staining agent (Cpd-5) ... 0.002 Anti-fading agent (Cpd-14) ... 0.10 Coupler dispersion medium (Cpd-6) ... 0.15 Coupler solvent (Solv-2) ... 0.10

Eleventh Layer (UV Absorbing Layer) Gelatin ... 1.50 UV Absorber (Cpd-1, 2, 4, 15 Equivalent) ... 1.00 Color Mixing Inhibitor (Cpd-7, 16)・ ・ ・ 0.06 Dispersion medium (Cpd-6) UV absorber solvent (Solv-1, 2) ・ ・ ・ 0.15 Anti-irradiation dye (Cpd-17, 18) ・ ・ ・ 0.02 Anti-irradiation Dye (Cpd-19, 20) ... 0.02

Twelfth Layer (Protective Layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.2 μ) ・ ・ ・ 0.07 modified poval ・ ・ ・ 0.02 gelatin ・ ・ ・ 1.50 gelatin hardening Agent (H-1, 2 equivalents) ... 0.17

Further, in each layer, alkanol XC (Du Pont) as an emulsification / dispersion aid, and sodium alkylbenzenesulfonate were used, succinic acid ester as a coating aid and Magefac F-120 (manufactured by Dainippon Ink and Chemicals), For the layer containing silver halide or colloidal silver, as a stabilizer,
(Cpd-21, 22, 23) was used. The compounds used in the examples are shown below.

[0147]

[Chemical 53]

[0148]

[Chemical 54]

[0149]

[Chemical 55]

[0150]

[Chemical 56]

[0151]

[Chemical 57]

[0152]

[Chemical 58]

[0153]

[Chemical 59]

[0154]

[Chemical 60]

[0155]

[Chemical formula 61]

Solv-1 Di (2-ethylhexyl) phthalate Solv-2 Trinonyl Phosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Tricresyl Phosphate Solv-5 Dibutylphthalate Solv-6 Trioctyl Phosphate

H-1 1,2-bis (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na salt

For the sample No. 201, the compound represented by the general formula (F-1) dispersed in the fifth layer in the same manner as in Example 1 and the compounds represented by the general formulas (I) to (IX) Add the indicated compounds in a methanol solution as shown in Table 6 to obtain a sample N
o.202-214 were prepared.

[0159]

[Table 6]

When three kinds of the compounds contained in the compounds (I) to (IX) are used in combination, they are added so as to be equimolar to each other. The comparative compounds used are shown below.

[0161]

[Chemical formula 62]

Sample Nos. 201 and 2 prepared in this way
For No. 14, uniform exposure was performed and the following development processing was performed to obtain a uniform gray image having a density of 1.0, and the number of spot failures (diameter of 50 microns or more) in 0.1 m ² was determined. Also, after leaving the sample in a completely dark place of 45 ° C and 80% atmosphere for 3 days, it was subjected to gradation exposure for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film), and the optical density of the product was measured. Sensitivity of green layer decreases (Δlog E (G))
I asked. Further, a reversal film RDP (manufactured by Fuji Photo Film) obtained by taking a proper exposure with a Macbeth Color Checker (manufactured by Colmorgen [USA]) was printed on these samples, and color patches of a chart obtained by developing and processing were measured to measure the color saturation. I asked. The results are shown in Table 7.

Fuji Chrome Paper Type 34 (manufactured by Fuji Photo Film Co., Ltd.) was exposed to light normally and then processed by the following method using an automatic processor until the cumulative replenishment amount of the solution became 3 times the tank capacity. did. Then, the sample was developed. Treatment process time Temperature Tank capacity Replenishment amount First development 75 seconds 38 ° C 8 liters 330 ml / m ² First water washing (1) 45 seconds 33 ° C 5 liters-First water washing (2) 45 seconds 33 ° C 5 liters 5000 ml / m ² Reverse exposure 15 seconds 100 lux Color development 135 seconds 38 ° C 15 liters 330 ml / m ² Second washing 45 seconds 33 ° C 5 liters 1000 ml / m ² Bleach-fixing (1) 60 seconds 38 ° C 7 liters-bleach-fixing ( 2) 60 seconds 38 ℃ 7 liter 220 ml / m ² 3rd water wash (1) 45 seconds 33 ℃ 5 liters-third water wash (2) 45 seconds 33 ℃ 5 liters-third water wash (3) 45 seconds 33 ℃ 5 Liter 5000 ml / m ² dry 45 seconds 75 ° C. Here, the first and third water washes were countercurrent water washing methods. That is, flush water is made to flow into the first washing (2), the overflow is led to the first washing (1), and the third washing (3)
Rinse the rinsing water with water and wash the overflow with the third rinsing water (2)
And the overflow of the third water washing (2) was led to the third water washing (1).

The composition of each processing liquid was as follows. [First developer] [Tank liquid] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine 5 acetic acid / 5 sodium salt 3.0 g 3.0 g Potassium sulfite 30.0 g 30.0g Potassium thiocyanate 1.2g 1.2g Potassium carbonate 35.0g 35.0g Potassium hydroquinone monosulfonate 25.0g 25.0g 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0g 2.0g Potassium bromide 0.5g- Potassium iodide 5.0 mg-water was added to 1000 ml 1000 ml pH 9.60 9.70 The pH was adjusted with hydrochloric acid or potassium hydroxide.

[Color developer] [Tank solution] [Replenisher] Benzyl alcohol 15.0 ml 15.0 ml Diethylene glycol 12.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.20 g 0.25 g Nitrilo-N, N , N-trimethylenephosphonic acid-5 sodium salt 0.5g 0.5g diethylenetriamine pentaacetic acid / 5 sodium salt 2.0g 2.0g sodium sulfite 2.0g 2.5g hydroxylamine sulfate 3.0g 3.6g N-ethyl-N- (β- Methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 8.0 g Fluorescent brightener (diaminostilbene type) 1.0 g 1.2 g Potassium bromide 0.5 g-potassium iodide 1.0 mg-Add water 1000 ml 1000 ml pH 10.25 10.40 pH is hydrochloric acid or potassium hydroxide I adjusted it.

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid / sodium salt / dihydrate 5.0 g Same as mother liquor Ethylenediaminetetraacetic acid / Fe (III) / Ammonium / monohydrate 80.0 g Sulfurous acid Sodium 15.0 g Ammonium thiosulfate (700 g / l) 160 ml 2-Mercapto-1,3,4-triazole 0.5 g Water was added to 1000 ml pH 6.50 pH was adjusted with acetic acid or aqueous ammonia.

[0167]

[Table 7]

In the table, the values of color saturation (Croma), the number of surface defects, and the decrease in sensitivity under high humidity have the same meanings as in Example 2.
As can be seen from the table, the sample using the dispersion of the dye of the present invention has a large effect of improving the color saturation. Further, the coating surface failure that occurs when a dye dispersion is used and the sensitivity decrease due to the diffusion of the dye are dramatically improved by using the dye dispersion of the present invention and the compound of the present invention in combination. I understand. It is also understood that the dye dispersion of the present invention and the compound of the present invention have appropriate addition amounts.

Example 4 The following 1st to 14th layers were multilayer-coated on the front side of a paper support (thickness 100 microns) laminated on both sides with polyethylene, and 15th to 16th layers were multilayer-coated on the back side. A color photographic light-sensitive material was prepared. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine blue as a bluing dye (the surface chromaticity of the support is L ^* , A
88.0, -0.20, -0.7 in ^* and b ^* systems, respectively.
It was 5. ).

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, as the emulsion for the 14th layer, a Lippmann emulsion which was not surface-chemically sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver ・ ・ ・ 0.10 Color Mixing Inhibitor (Cpd-7) ・ ・ ・ 0.05 Gelatin ・ ・ ・ 0.70

Second layer (intermediate layer) gelatin: 0.70

Third Layer (Low Sensitivity Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.25 μ, grain size distribution [variation coefficient]) 8%, octahedron ・ ・ ・ 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (5 mol% silver chloride, average grain size 0.40μ, grain Size distribution 10%, octahedron) ・ ・ ・ 0.08 Gelatin ・ ・ ・ 1.00 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) ・ ・ ・ 0.30 Anti-fading agent ( Cpd-1, 2, 3, 4, 30 equivalents) 0.18 Anti-staining agent (Cpd-5) 0.003 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) ... 0.12

Fourth Layer (High-Sensitivity Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.60 μ, grain size distribution 15%, 8%). 0.14 Gelatin ... 1.00 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) ... 0.30 Anti-fading agent (Cpd-1, 2, 3, 4, 30 equivalents) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.12

Fifth layer (intermediate layer) Gelatin ... 1.00 Color mixing inhibitor (Cpd-7) ... 0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalents) ... 0.16 Polymer latex (Cpd-8) ... 0.10.

Sixth Layer (Low Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.25 μ, grain size distribution 8%, octahedron) ... 0.04 Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS-4) (silver chloride 5 mol%, average grain size 0.40 μ, grain size distribution 10%, octahedron) ... 06 Gelatin ・ ・ ・ 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) ・ ・ ・ 0.11 Anti-fading agent (Cpd-9, 26, 30 equivalents) ・ ・ ・ 0.15 Stain prevention Agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) ... 0.025 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4,6) Equivalent) 0.15

Seventh Layer (Highly Sensitive Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.65 μ, grain size distribution 16%, octahedron). 0.10 Gelatin: 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) 0.11 Anti-fading agent (Cpd-9, 26, 30 equivalents) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 at a ratio of 10: 7: 7: 1) ... 0.025 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4 , 6 equivalents) ... 0.15

Eighth layer (intermediate layer) Same as the fifth layer

Ninth layer (yellow filter layer) Yellow colloidal silver (particle size 100Å) ・ ・ ・ 0.12 Gelatin ・ ・ ・ 0.70 Color mixture inhibitor (Cpd-7) ・ ・ ・ 0.03 Solvent mixture solvent (Solv-4, 5 equivalents) ... 0.10 Polymer latex (Cpd-8) ... 0.07

10th layer (intermediate layer) Same as 5th layer

Eleventh Layer (Low Sensitivity Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.40 μ, grain size distribution 8%, octahedron). ... 0.07 Silver chlorobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (silver chloride 8 mol%, average grain size 0.60 µ, grain size distribution 11%, octahedron). ..0.14 gelatin ... 0.80 yellow coupler (ExY-1, 2, 3 equivalents) ... 0.35 anti-fading agent (Cpd-14) ... 0.10 anti-fading agent (Cpd) -30) ... 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) ... 0.007 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv- 2) ... 0.10

Twelfth Layer (High Sensitivity Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.85μ, grain size distribution 18%, octahedron).・ ・ ・ 0.15 Gelatin ・ ・ ・ 0.60 Yellow coupler (ExY-1, 2, 3 equivalents) ・ ・ ・ 0.30 Anti-fading agent (Cpd-14) ・ ・ ・ 0.10 Anti-fading agent ( Cpd-30) ... 0.05 Anti-staining agent (Cpd-5,15 in 1: 5 ratio) ... 0.007 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv -2) ... 0.10

Thirteenth Layer (UV Absorbing Layer) Gelatin ... 1.00 UV Absorber (Cpd-2, 4, 16 equivalents) ... 0.50 Color Mixing Inhibitor (Cpd-7, 17 equivalents) ... 0.03 Dispersion medium (Cpd-6) ... 0.02 UV absorber solvent (Solv-2, 7 equivalents) ... 0.08 Anti-irradiation dye (Cpd-18, 19, 20) , 21, 27 in the ratio 10: 10: 13: 15: 20) ... 0.05

Fourteenth Layer (Protective Layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1 μ) ... 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000) ... 01 Polymethylmethacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ) Equivalent ... 0.05 Gelatin ... 1.80 Gelatin hardening agent (H-1, H-2 equivalent) ) ... 0.18

Fifteenth layer (back layer) Gelatin ... 2.50 UV absorber (Cpd-2, 4, 16 equivalents) ... 0.50 Dye (Cpd-18, 19, 20, 21, 27) Equal amount) ... 0.06

Sixteenth Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent ... 0.05 Gelatin ... 2.00 Gelatin hardening Agent (H-1, H-2 equivalent) ... 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75 ° C. over 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.35μ were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.7 µ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ⁻³ for silver halide,
10 ^-2 % by weight, as a nucleation accelerator Cpd-22, 28,
29 were used at 10 ^-2 wt% each. Further, in each layer, alkanol XC (Du Pont) and sodium alkylbenzenesulfonate were used as emulsification / dispersion aids, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. (Cpd-23, 24, 25) was used as a stabilizer for the layer containing silver halide and colloidal silver.
This sample was designated as sample number 301. The compounds used in the examples are shown below.

[0189]

[Chemical 63]

[0190]

[Chemical 64]

[0191]

[Chemical 65]

[0192]

[Chemical 66]

[0193]

[Chemical 67]

[0194]

[Chemical 68]

[0195]

[Chemical 69]

[0196]

[Chemical 70]

[0197]

[Chemical 71]

[0198]

[Chemical 72]

[0199]

[Chemical formula 73]

Solv-1 di (2-ethylhexyl) sebacate Solv-2 trinonyl phosphate Solv-3 di (3-methylhexyl) phthalate Solv-4 tricresyl phosphate Solv-5 dibutyl phthalate Solv-6 trioctyl phosphate Solv- 7 Di (2-ethylhexyl) phthalate

H-1 1,2-bis (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na salt

ExZK-17- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2,3,3
4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5- {3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenyl) phenyl Carbamoyl] -4-hydroxy-1
-Naphthylthio} tetrazol-1-yl] phenyl}
Ureido] benzenesulfonamide} phenyl] -1-
Formyl hydrazine

For sample No. 301, a compound represented by the general formula (F-1) dispersed in the fifth layer in the same manner as in Example 1 and the compounds represented by the general formulas (I) to (IX) The indicated compounds were added in methanol solution as shown in Table 8 to give a sample N
o.302 to 304 were prepared.

[0204]

[Table 8]

When three kinds of the compounds contained in the compounds (I) to (IX) are used in combination, they are added so that they are equimolar to each other.

[0206] Sample Nos. 301 to 3 produced in this way
For 04, the same experiment as performed in Example 3 was performed. The results are shown in Table 9.

AP copy paper (manufactured by Fuji Photo Film Co., Ltd.) was imagewise exposed using the Fuji Color Copier AP5500 system, and then continuously processed until the cumulative replenishment amount of the solution became 3 times the tank capacity. Then, the sample was developed. Step Time Temperature Tank Capacity replenishment rate color developing 135 seconds 38 ° C. 11 liters 350 ml / m ² bleach-fixing 40 seconds 34 ° C. 3 liters 300 ml / m ² water washing (1) 40 sec 32 ° C. 3 liters - washing (2) 40 Second 32 ℃ 3 liter 350 ml / m ² dry 30 s 80 ℃ The replenishing method of washing water is to replenish the washing bath (2) and guide the overflow solution of the washing bath (2) to the washing bath (1). The countercurrent replenishment method was adopted. At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each processing liquid was as follows. [Color developer] [Tank solution] [Replenisher] D-sorbit 0.15g 0.20g Sodium naphthalenesulfonate / formalin condensate 0.15g 0.20g Nitrilotris (methylenephosphonic acid) penta sodium salt 1.8g 1.8g Diethylenetriamine penta Acetic acid 0.5 g 0.5 g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.15 g 0.15 g Diethylene glycol 12.0 ml 16.0 ml Benzyl alcohol 13.5 ml 18.0 ml Potassium bromide 0.70 g-benzotriazole 0.003 g 0.004 g Sodium sulfite 2.4 g 3.2 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.0 g 10.6 g Triethanolamine 6.0 g 8.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline.3 / 2 sulfuric acid monohydrate 6.0 g 8.0 g Potassium carbonate 30.0 g 25.0 g Optical brightener (diaminostilbene type) 1.3 g 1.7 g Water is added 1000 ml 1000 ml pH (25 ° C) (pH adjusted with KOH or sulfuric acid) 10.30 10.79

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ dihydrate 4.0 g Same as tank solution Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 55.0 g Ammonium thiosulfate (750 g / l) 168 ml Sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-Mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Water added 1000 ml pH (25 ° C) (ammonia (PH adjustment with water or acetic acid)

[Washing Water] [Both tank solution and replenisher] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

[0211]

[Table 9]

In the table, the values of color saturation (Croma), the number of surface defects, and the decrease in sensitivity under high humidity have the same meanings as in Example 2.
As can be seen from the table, the sample using the dispersion of the dye of the present invention has a large effect of improving the color saturation, the coating surface failure that occurs when the dispersion of the dye is used, and the sensitivity due to the diffusion of the dye. It can be seen that the reduction is improved.

Example 5 Sample 101 shown in Example 2
On the other hand, the compound represented by the general formula (F-1) was dissolved in a solvent having a ratio of water to methanol of 3: 1 and added to the eighth layer,
The compounds represented by the general formulas (I) to (IX) were added in a methanol solution as shown in Table 10 to prepare samples 502 to 502.

[0214]

[Table 10]

Sample Nos. 101 and 5 thus prepared
For Nos. 02 to 5, the same experiment as that performed in Example 2 was performed. The results are shown in Table 11.

[0216]

[Table 11]

As can be seen from Table 11, the sample using the dye of the present invention has a large effect of improving the color saturation.

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[Procedure amendment]

[Submission date] January 26, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0061

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[Correction content]

Incidentally, 6. Regarding the ultraviolet absorber contained in the item, in addition to the above-mentioned reference, for example, JP-A-46-3335.
"Triazine compounds" described in European Patent No. 520,938A or European Patent No. 521,823.
It is desirable to use the benzophenone compounds described in No. A. In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the light-sensitive material a compound capable of immobilizing by reacting with formaldehyde described in 4,435,503. In the light-sensitive material of the present invention, US Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fog agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof include Research Disclosure No. 17643, VII-C to G, and No. 307105, VII.
-C to G. Examples of yellow couplers include U.S. Pat.Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,752.
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, No. 1,476,760, and U.S. Patent No. 3,97.
Those described in 3,968, 4,314,023, 4,511,649, European Patent 249,473A and the like are preferable.

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First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g UV absorber U-6 0.1 g High boiling point organic solvent Oil-1 0.1 g Dye E-1 microcrystalline solid dispersion 0.1 g

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Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g UV absorber U-6 0. 1 g Formalin Scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g

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Eleventh Layer (UV Absorbing Layer) Gelatin ... 1.50 UV absorbent (Cpd-1, 2, 4, 15, 24, 25 equivalents) /1.00 Color mixing inhibitor (Cpd-7, 16) ・ ・ ・ 0.06 Dispersion medium (Cpd-6) UV absorber solvent (Solv-1, 2) ・ ・ ・ 0.15 Anti-irradiation dye (Cpd-17, 18) ・ ・ ・ 0.02 a Anti-radiation dye (Cpd-19, 20) ... 0.02

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[Chemical 59]

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Thirteenth layer (UV absorbing layer) Gelatin ... 1.00 UV absorbing agent (Cpd-2, 4, 16, 31 equivalents) ... 0.50 Color mixing inhibitor (Cpd-7, 17 etc.) Amount) ... 0.03 Dispersion medium (Cpd-6) ... 0.02 UV absorber solvent (Solv-2, 7 equivalents) ... 0.08 Anti-irradiation dye (Cpd-18, 19) , 20, 21, 27 in a 10: 10: 13: 15: 20 ratio) ... 0.05

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[Chemical 70]

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[Chemical 71]

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one blue-sensitive layer, green-sensitive layer and red-sensitive layer and at least one non-photosensitive layer on a support, said photosensitive material comprising: At least one compound represented by the following general formula (F-1) is contained in at least one of the non-photosensitive layers of the material, and the compound represented by the following general formulas (I) to (IX) is contained in the photosensitive material. A silver halide color photographic light-sensitive material containing at least one compound selected from the following. General formula (F-1): In the formula, Q represents a ketomethylene residue, and L ₁ , L ₂ , L ₃
Represents a methylene group, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a substituent, and R ₃ and R ₄ or R ₄ and R ₅ are linked to each other and have 5 or 6 members. You may form a ring. n represents 0 or 1. However, Q is at least 1
Having a carboxylic acid group, a sulfonamide group or a sulfocarbamoyl group. General formula (I) General formula (II): General formula (III): General formula (IV): General formula (V): General formula (VI) General formula (VII) General formula (VIII) General formula (IX) (In the formula, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ and R
¹⁹ represents a hydrogen atom, an alkyl group, or an aryl group, R ¹⁷ represents a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxy group, a sulfo group, a sulfamoyl group, a hydroxy group, a halogen atom, an alkoxy group, or Represents a thiazolyl group. R ²⁰ represents an alkylene group or an arylene group. R ²¹ , R ²² and R ²³ represent a halogen atom or an alkyl group, and R ²⁴ and R ²⁵ represent
It represents a hydrogen atom, an alkyl group, an aryl group, or a nitrogen-containing heterocyclic residue. R ²⁶ and R ²⁷ represent a hydrogen atom, an alkyl group or an aryl group, and R ²⁶ and R ²⁷ may combine with each other to form a benzene ring. R ²⁸ represents a hydrogen atom or an alkyl group. R ²⁹ and R ³⁰ represent an alkyl group or an aryl group. Y represents a halogen atom, Z
¹ represents a non-metal atom group necessary for forming a thiazolyl ring, and Z ² represents a non-metal atom group necessary for forming a 6-membered ring. n represents 0 or 1, and m represents 1 or 2. ) 2. A silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by formula (F-1) is contained as a solid fine particle dispersion.