JPH08211552A - Silver halide photographic sensitive material containing hexamethylenemerocyanine compound - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material superior in decolorability and dyed with a novel hexamethylenemerocyanine compound. CONSTITUTION: The photosensitive material has a hydrophilic colloidal layer containing the hexamethylenemerocyanine compound represented by the formula in which Z<1> is a metallic atomic group necessary to form a benzo- or naphtho- condensed ring; M is an H or metal atom or an atomic group forming a monovalent cation; (n) is 1, 2, or 3; each of R<1> -R<3> is, independently, an alkyl group; each of L<1> -L<6> is a methine group and each of adjacent substituents may combine with each other to form a ring; and Z<2> is an atomic group necessary to form a hetero ring selected from a pyrazolidindione, isooxazolone, pyrazolopyridone, barbituric acid, pyridone, and rhodanine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, and more specifically, a hexahalide which is photochemically inert and is easily decolorized during photographic processing. The present invention relates to a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a methine merocyanine compound.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material, a photographic emulsion layer or other hydrophilic layer is used for the purpose of controlling the spectral composition of incident light, light absorption filter, halation prevention, irradiation prevention, and sensitivity adjustment of a photosensitive emulsion layer. It is often the case that the functional colloid layer is colored with a dye. The dye used for these purposes needs to satisfy the following conditions. (1) It has a proper spectral absorption according to the purpose of use. (2) It has excellent stability over time in a solution and in a photographic material, and should not discolor or fade. (3) Photochemically inactive. That is, the performance of the silver halide photographic emulsion layer should not be adversely affected in a chemical sense, such as a decrease in sensitivity, regression of a latent image, or fog. Also, do not react with couplers or developing agents. (4) It should not be decolorized in the course of photographic processing or be eluted and removed in a processing solution or washing water to leave no harmful coloring on the photographic light-sensitive material after processing. Further, in a silver halide color photographic light-sensitive material, a cyan dye added to the photographic light-sensitive material for the purpose of improving the sharpness of the red-sensitive layer is required.

Those satisfying the above conditions are described, for example, in JP-A-63-34537, JP-A-63-34538, JP-A-63-34539, JP-A-1-13543, and US Pat. No. 4,102,688. Merocyanine dyes have been proposed. However, it has been difficult to find a good dye, especially a dye having high stability, which can be used in a light-sensitive material by satisfying all the above conditions. Further, as a method of including a merocyanine dye as a solid fine particle dispersion, JP-A-3-3206443 and JP-A-3-32080 are known.
45 and Japanese Patent Laid-Open No. 3-2008047 are proposed. However, in these methods, when the development processing is carried out by a rapid processing method, there are many residual colors, and it is difficult to find one that can be used.

[0004]

SUMMARY OF THE INVENTION The first object of the present invention is to:
Another object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer colored with a water-soluble dye having excellent absorption maximum as a cyan dye and excellent stability. The second object of the present invention is to provide a silver halide photographic light-sensitive material having a compound that rapidly decolorizes during development processing.

[0005]

As a result of intensive studies by the present inventors, the object of the present invention is to have a hydrophilic colloid layer containing at least one hexamethine merocyanine compound represented by the following general formula (1). Was achieved by a silver halide photographic light-sensitive material. General formula (1)

[0006]

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Z in the general formula (1)¹Is condensed to Ben
Non-metals required to form zo-fused or naphtho-fused rings
Represents a group of atoms. M is a hydrogen atom or a monovalent cation
Represents an atomic group or a metal atom, and n is an integer of 1 to 3.
Represent R¹, R², R³Are the same or different
Also, it represents a substituted or unsubstituted alkyl group.
L ¹, L², L³, L^Four, L^Five, L⁶Are each independent
Represents a substituted or unsubstituted methine group, or is adjacent to
Substituents may combine to form a 5- or 6-membered ring. Z
²Is pyrazolidinedione, isoxazolone, pyrazolo
Selected from pyridone, barbituric acid, pyridone, and rhodanine
Required to form a substituted or unsubstituted heterocycle
Represents a group of atoms.

The present invention will be described in detail below. First, the compound represented by formula (I) of the present invention will be described in detail. The alkyl group represented by R ¹ , R ² and R ³ preferably represents an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl, isopropyl, n-pentyl), and a substituent (Eg, sulfo, carboxyl, hydroxyl) may be included. More preferably, R ¹ is an alkyl group having a sulfonic acid group and having 1 to 5 carbon atoms (for example, 2-sulfoethyl, 3-sulfopropyl, 4
-Sulfobutyl). In the present invention, the sulfonic acid group means a sulfo group or a salt thereof, and the carboxylic acid group means a carboxyl group or a salt thereof. Examples of salts include alkali metal salts such as Na and K, ammonium salts,
Examples thereof include organic ammonium salts such as triethylamine, tributylamine and pyridine. The number of n is preferably 1 or 2.

The atomic group or metal atom to be a monovalent cation represented by M is preferably an alkali metal (eg, Li, Na, K) or ammonium or organic ammonium (eg, triethylammonium, tributylammonium, pyridinium). Represent. The heterocycle formed by Z ² is preferably a pyrazolidinedione, isoxazolone, pyrazolopyridone, barbituric acid, pyridone, or rhodanine having 1 to 4 acid substituents (for example, a sulfonic acid group or a carboxylic acid group). Of those heterocycles, those having 1 to 2 sulfonic acid groups or carboxylic acid groups are particularly preferred.

The substituent of the methine group represented by L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms (eg methyl, ethyl). ,
3-hydroxypropyl, benzyl, 2-sulfoethyl), a halogen atom (eg F, Cl, Br), a substituted or unsubstituted aryl group (eg phenyl, 4-chlorophenyl), a lower alkoxy group (eg methoxy, ethoxy), etc. preferable. Further, the substituent of the methine group includes a case where the substituents of the methine group are bonded to each other to form a ring, and for example, a 5-membered ring (for example, a cyclopentene ring) or a 6-membered ring containing three methine groups ( For example, a cyclohexene ring) may be formed.

Specific examples of the hexamethine merocyanine compound of the general formula (1) used in the present invention are shown below, but the present invention is not limited thereto.

[0012]

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[0013]

[Chemical 4]

[0014]

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[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

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The compound represented by the general formula (1) can be synthesized by referring to the method described in JP-A-50-145124, JP-B-59-28899, US Pat. I can.

Synthesis Example (Synthesis of Compound 1) To a mixed solution of 50 ml of acetic anhydride and 30 ml of acetic acid, 13.0 g of 5-anilino-N-phenyl-2,4-pentadienylideneiminium chloride and 20 ml of triethylamine were added. Dissolved. To this solution, 1,2-bis (4-sulfophenyl) -3,5- was added to a mixed solution of 30 ml of acetic anhydride, 1.2 ml of acetic acid and 2.8 ml of triethylamine.
A solution in which 4.12 g of pyrazolidinedione was dissolved was added dropwise with a syringe over 5 hours. 900 ml of ethyl acetate was added to the obtained red solution, and the precipitated crystals were collected by filtration and dried. The crystals were added and dissolved in a mixed solution of 40 ml of ethanol and 5.6 ml of triethylamine. To this solution, 3.64 g of 1- (4-sulfoethyl) -2,3,3-trimethyl-5-sulfoindolenin was added, and the mixture was stirred at room temperature for 3 hours.
Allowed to react for hours. The obtained blue solution was dust-filtered, and 5.0 g of potassium acetate dissolved in 50 ml of methanol was added to the filtrate.
Was added, and the deposited precipitate was filtered off. This precipitate was purified by a column (filler: Sephadex LH20) and then dried to obtain 1.47 g (15.1%) of Compound 1 powder. The structure was confirmed by NMR, mass spectrum and elemental analysis. λmax (water) 665 nm, melting point 300 ° C. or higher.

The compound represented by the general formula (1) of the present invention is preferably contained in the photosensitive layer or the non-photosensitive layer of the silver halide photographic light-sensitive material in a molecular dispersion state. Here, the molecular dispersion state is a state in which the compound is uniformly dispersed and dissolved in the emulsion layer and other hydrophilic colloid layers, and preferably observed by a transmission electron microscope (TEM) at a magnification of 100,000 times. It is a state in which no solid matter is detected.

The compound represented by the general formula (1) of the present invention can be molecularly dispersed in the photosensitive layer or the non-photosensitive layer of a silver halide photographic light-sensitive material by the following various methods. (1) A method of directly dispersing a compound in a photosensitive layer or a non-photosensitive layer. (2) The compound is a suitable solvent (for example, water, methanol, ethanol, propanol, halogenated alcohols described in JP-A-48-9715 or US Pat. No. 3,756,830, acetone, N, N, -dimethylformamide, Pyridine or the like, or a mixed solvent thereof, etc.) and added in the form of a solution. Of these, it is preferable to use water, methanol, or a water / methanol mixed solvent.

The compound represented by the general formula (1) of the present invention can be used in any effective amount, but is preferably used so that the optical density is in the range of 0.05 to 3.0. . The addition amount is 0.5 to 1000 mg / m ^2.
, More preferably from 1-500 mg / m ^2, more preferably from 5 to 200 mg / m ^2. The time of addition may be any step before coating.

Gelatin is a typical hydrophilic colloid, but any of those conventionally known to be usable for photography can be used.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH / GL
It can also be arranged in the order of / RL. In addition, JP-A-56-2573
8 and 62-63936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in case of 4 layers or more,
The arrangement may be changed as described above. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448, and 63-89850.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as RL, adjacent to or close to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 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 is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid 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, Paul M
ontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion C
hemistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze
likman, et al., Making and Coating Photographic Em
ulsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the method described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are RD No.17643 and RD No.187.
16 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat. No. 4,626,498, and JP-A-59-21.
4852, a silver halide grain in which the inside of the grain is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition.
As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
It is particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grains or polydisperse emulsions, but monodisperse grains (weight of silver halide grains or grain number of at least 95
% Having a particle size within ± 40% of the average particle size).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

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

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (bottom right of page 12), L-77 (bottom right of page 13); EP 456,257, A-4 -6
3 (134 pages), A-4 -73, -75 (139 pages); EP 486,965 M-4, -6
(Page 26), M-7 (page 27); M-45 of EP 571,959A (page 19);
5-204106 (M-1) (page 6); JP-A-4-362631, paragraph 0237, M-
twenty two. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: JP-A-2-44345, P-1, P-5 (page 11).

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. The coupler for correcting the unwanted absorption of the color forming dye is a yellow-colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
Page), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), US 4,837,136 (2) (column 8),
The colorless masking couplers represented by formula (A) in claim 1 of WO92 / 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP 37
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (particularly T-101 (page 30), T-104 (page 31), T-113 ( 36
Page), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 93
Compounds represented by formula (I) on page 7 of 8A2 (especially D-4
9 (page 51)), compounds represented by formula (1) of EP 568,037A (particularly (23) (page 11)), formulas (I), (II), and EP 440,195A2 on pages 5 to 6, Compounds represented by (III) (especially I- on page 29)
(1)); Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (particularly (60) and (6 on page 61)
1)) and a compound represented by the formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
Compounds represented by formulas (1), (2), and (3) in 4,656,123, column 3 (particularly (I-22) in column 25) and EP 450,637A2
ExZK-2, lines 75-36, page 75; Compounds that release dye groups only upon elimination: Formula (I) of claim 1 of US 4,857,447
Compounds represented by (especially Y-1 to Y-19 in columns 25 to 36)
.

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5 of JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140〜144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, column 2, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP 298321A, 4).
Formulas (I)-(III) on pages 30-33, especially I-47, 72, III-1, 27 (24
~ Page 48); Anti-fading agent: A-6,7,20,21,23,2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69〜118
Pp.), US 5,122,444, columns 25-38, II-1 to III-23, especially
III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Materials that reduce the use of color-enhancing agents or color-mixing inhibitors: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29, SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII), JP-A-2-
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizers, antifoggants: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
Compounds 1-22 represented by formula (I) of 8,622 (columns 3-1
0), a compound (1) represented by the formula (I) of US 4,923,788 ~
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
(Page 9), compounds (3) to (6 represented by formula (I) of EP 520938A.
6) (pages 10 to 44) and the compound HBT-1 represented by the formula (III).
~ 10 (page 14), compounds represented by formula (1) of EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention include
For example, the RD. No.17643, page 28, No.18716, 6
From page 47, 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, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds is the saturated film thickness. It is defined as The film thickness means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and T _1/2 is A Green (A.Gr
een) et al., Photographic Science and Engineering (Photogr.Sci.Eng.), 19 volumes, 2,124 ~
It can be measured by using a swellometer (swelling meter) of the type described on page 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness. The photographic material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

The light-sensitive material of the present invention has the RD. No.176
43, pp. 28-29, ibid. No. 18716, 651 left column-right column, and ibid.
Development can be carried out by a usual method described in No. 307105, pages 880 to 881. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples and preferred examples thereof are compounds described in EP 556700A, page 28, lines 43 to 52. Is mentioned. Two or more of these compounds can be used in combination depending on the purpose. The color developer is an alkali metal carbonate,
It contains a pH buffer such as borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. It is common. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. 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,
Add ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When reversal processing is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The processing effect of the contact between the photographic processing liquid and air in the processing tank is the aperture ratio (= [contact area between processing liquid and air c
m ² ] ÷ [volume of treatment liquid cm ³ ]). The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 and JP-A-63-216050 are disclosed. The slit development processing method described can be mentioned. The aperture ratio is preferably reduced not only in both the color development step and the black-and-white development step but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing, stabilizing and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The time of color development processing is usually set between 2 and 5 minutes, but by using a high temperature, high pH and using a color developing agent at a high concentration,
Further, the processing time can be shortened.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Of these, iron (III) aminopolycarboxylates such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts
Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US 3,893,858, DE 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-72623. ,
53-95630, 53-95631, 53-104232, 53-12442
4, Compounds 53-141623, 53-28426 and RD No. 17129 (July 1978), compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; , JP-A-52-20832, JP-A-53-32735,
Thiourea derivatives described in US 3,706,561; DE 1,127,715,
Iodide salts described in JP-A-58-16,235; DE 966,410,
2,748,430, polyoxyethylene compounds; JP-B-45-8836, polyamine compounds; and others, JP-A-49-4
0,943, 49-59,644, 53-94,927, 54-35,727,
55-26,506 and 58-163,940; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, US 3,893,858, DE 1,290,812, JP-A-53-95,63.
The compounds described in 0 are preferred. Further, the compounds described in US 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. Yes, especially ammonium thiosulfate can be used most widely. Also,
Thiosulfates and thiocyanates, thioether compounds,
A combined use of thiourea is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, addition of aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution is preferable for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole. It is preferable to add 0.1 to 10 mol per liter.

The total time of the desilvering process is preferably short as long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or a stirring effect by using a rotating means of JP-A-62-183461 is used. Method of raising, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, the circulation flow rate of the entire processing solution There is a method of increasing it. Such a stirring improving means is effective 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 consequently the desilvering rate. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material transporting means described in 60-191258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, has a high effect of preventing the performance deterioration of the treatment liquid, and It is particularly effective in shortening the processing time and reducing the replenishment amount of the processing liquid.

The light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and various other conditions Can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of t
he Society of MotionPicture and Television Enginee
It can be determined by the method described in rs Vol. 64, pp. 248-253 (May 1955). According to the multi-stage countercurrent method described in this document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced adheres to the photosensitive material. Problem arises. As a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 is extremely effective. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of antifungal agents"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used. The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8.
The washing water temperature and washing time can be set depending on the characteristics and use of the light-sensitive material, but in general, a range of 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C is selected. . Furthermore,
The light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-58-220345 can be applied. 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 used as a final bath of a color light-sensitive material for photographing. You can Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. For incorporation, it is preferable to use a precursor of a color developing agent. For example US 3,34
2,597 described indoaniline compound, 3,342,599,
Research Disclosure No.14,850 and No.15,
Schiff base type compounds described in US Pat. No. 159,159, aldol compounds described in US Pat. No. 3,719,492, metal salt complexes described in US Pat.
The urethane compounds described in 53-135628 can be mentioned. The photographic material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-64339,
57-144547 and 58-115438. The processing solution used for processing the light-sensitive material of the present invention is 10 ° C to 50 ° C.
Used in. Normally, a temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can.

[0041]

【Example】

Example 1 The stability of a dye in an aqueous solution was evaluated by the following method. Solvent: BR (Britton-Robinson) buffer (pH 6) Dye concentration: 1 x 10 ^-5 mol / liter Temperature: 25 ° C (using a constant temperature bath), shading Absorption maximum of absorption spectrum of solution immediately after preparation and after 24 hours Concentration (C) was measured and C (after 24 hours) / C
(Immediately after) was obtained and the residual ratio of the dye was calculated. The closer this value is to 1, the more stable the dye. The results obtained are shown in Table 1.

[0042]

[Table 1]

[0043]

[Chemical 9]

As is clear from Table 1, the compound represented by the general formula (1) of the present invention has high stability in an aqueous solution.

Example 2 (Preparation of photosensitive material 101) Various photographic constituent layers were coated on a reflective support to prepare a multilayer color photosensitive material, Sample 101, having the following layer structure. The coating liquid was prepared as in the following example.

Preparation of third layer coating solution Magenta coupler (ExM) 40.0 g, ultraviolet absorber (UV-2) 40.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-5) 25.0 g, color image stabilizer (Cpd-6) 2.5 g, color image stabilizer (Cpd-)
7) 20.0 g, color image stabilizer (Cpd-8) 2.5 g,
5.0 g of a color image stabilizer (Cpd-10) was added to a solvent (Sol
v-3) 32.5 g, solvent (Solv-4) 97.5
g, a solvent (Solv-6) 65.0 g, and ethyl acetate 110 cc, and this solution was emulsified and dispersed in 1500 g of 7% gelatin aqueous solution containing 10% sodium dodecylbenzenesulfonate 90 cc to prepare an emulsified dispersion A.
On the other hand, a silver chlorobromide emulsion B-1 (cubic, 1: 3 mixture of a large size emulsion having an average grain size of 0.55 μm and a small size emulsion having a grain size of 0.39 μm (silver molar ratio). The variation coefficient of the grain size distribution is 0.08 and 0.06, respectively, and 0.8 mol% of silver bromide was locally contained in a part of the surface of the grain based on silver chloride in each size emulsion. 0.1% potassium hexachloroiridium (IV)
1.0 mg together with potassium ferrocyanide
Included. ) Was prepared. In this emulsion, the green sensitizing dyes D, E and F shown below were added to large size emulsions in an amount of 3.0 × 10 ^-4 mol, 4.0 × 10 ^-5 mol and 2.0 × 10 mol per mol of silver. ^-4 mol was added, and for small-sized emulsions, 3.6 × 10 ^-4 mol and 7.0 × 10 mol per mol of silver, respectively.
^-5 mol and 2.8 × 10 ^-4 mol were added, and then a sulfur sensitizer and a gold sensitizer were added in the presence of a decomposed product of nucleic acid to perform optimum chemical sensitization. The above emulsified dispersion A and this silver chlorobromide emulsion B
-1 was mixed and dissolved, and a third layer coating solution was prepared so as to have the following composition.

Other coating solutions for the first to seventh layers were prepared in the same manner as the third layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-12 and C are added to each layer.
The total amount of pd-13 is 25.0 mg / m ² and 50.0, respectively.
It was added to be mg / m ² . The size of the silver chlorobromide emulsion in each light-sensitive emulsion layer was adjusted by the same preparation method as for the silver chlorobromide emulsion B-1, and the spectral sensitizing dyes shown below were used. Blue-sensitive emulsion layer

[0048]

[Chemical 10]

(1.4 × 10 ⁻⁴ mol was added to the large-sized emulsion and 1.7 × 10 ⁻⁴ mol was added to the small-sized emulsion per mol of silver halide.) Green Sensitive emulsion layer

[0050]

[Chemical 11]

(Sensitizing dye D was added in an amount of 3.0 × 10 ^-4 mol for a large-sized emulsion and 3.6 × 10 ^-4 mol for a small-sized emulsion, per mol of silver halide. .
Sensitizing dye E was added in an amount of 4.0 × 10 ^-5 mol for a large size emulsion and 7.0 × 10 ^-5 mol for a small size emulsion, per mol of silver halide. Sensitizing dye F is 2.0 mol per mol of silver halide for a large-sized emulsion.
× 10 ^-4 mol, or 2.8 × 1 for small emulsions
^0-4 mol was added. ) Red-sensitive emulsion layer

(Sensitizing dye S-1 per mol of silver halide is 4.0 × 10 ^-5 mol for large size emulsion and 5.0 × 10 ^-5 mol for small size emulsion) Sensitizing dye S-2 was added per mol of silver halide in an amount of 5.0 × 10 ^-5 mol for a large-sized emulsion and 6.0 × 10 ^-5 mol for a small-sized emulsion. did.)

[0053]

[Chemical 12]

Further, the following compounds were added to the red-sensitive silver halide emulsion in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0055]

[Chemical 13]

Blue-sensitive emulsion layer, green-sensitive emulsion layer, red-sensitive emulsion layer
1- (5-methylureidophenyl) -for the emulsion layer
5-Mercaptotetrazole to silver halide 1
8.5 x 10 per mole^-FourMole, 3.0 × 10^-3Mole,
2.5 x 10^-FourMole was added. The blue-sensitive emulsion layer and green
4-hydroxy-6-methyl-1,
Halogenated 3,3a, 7-tetrazaindene
1 x 10 per mole of silver ^-FourMole, 2 × 10^-FourMole added
Was.

(Layer Structure) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Reflective support (A polyethylene laminate layer containing 18% by weight of titanium dioxide surface-treated with aluminum oxide with respect to the resin was provided on a paper support, and a gelatin subbing was provided after corona discharge treatment.)

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A-1 0.27 (cubic, 5: 5 mixture of large size emulsion with average grain size 0.88 μm and small size emulsion with 0.70 μm) (Silver molar ratio) The coefficient of variation of the grain size distribution is 0.08 and 0.10, respectively. For each size emulsion, 0.3 mol% of silver bromide is localized on a part of the grain surface based on silver chloride. 0.1 mg of potassium hexachloroiridium (IV) in total and 1.0 mg of potassium ferrocyanide in total in the grain and in the silver bromide localized phase.) Gelatin 1.22 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) ) 0.01 Solvent (Solv-1) 0.13 Medium (Solv-5) 0.13

Second layer (color mixing prevention layer) Gelatin 0.90 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.25 solvent (Solv-8) 0.03

Third Layer (Green Sensitive Emulsion Layer) The Silver Chlorobromide Emulsion B-1 0.13 Gelatin 1.45 Magenta Coupler (ExM) 0.16 UV Absorber (UV-2) 0.16 Color Image Stability Agent (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.10 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.08 Color image stabilizer ( Cpd-8) 0.01 Color image stabilizer (Cpd-10) 0.02 Solvent (Solv-3) 0.13 Solvent (Solv-4) 0.39 Solvent (Solv-6) 0.26

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.68 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.18 Solvent (Solv-8) 0.02

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C-1 0.18 (cubic, 1: 4 mixture of large size emulsion with average grain size 0.50 μm and small size emulsion with 0.41 μm) (Silver molar ratio) The coefficient of variation of the grain size distribution is 0.09 and 0.11, respectively, and for each size emulsion 0.8 mol% of silver bromide is localized on a part of the grain surface based on silver chloride. 0.3 mg of potassium hexachloroiridium (IV) ate and 1.5 mg of potassium ferrocyanide were added to the inside of the grain and the localized phase of silver bromide.) Gelatin 0.80 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.0 Color Image Stabilizer (Cpd-9) 0.02 Color Image Stabilizer (Cpd-10) 0.01 solvent (Solv-1) 0.01 solvent (Solv-7) 0.22

Sixth Layer (UV Absorbing Layer) Gelatin 0.48 UV Absorber (UV-1) 0.38 Color Image Stabilizer (Cpd-5) 0.01 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-9) 0.05

Seventh Layer (Protective Layer) Gelatin 0.90 Acrylic Modified Copolymer of Polyvinyl Alcohol (Degree of Modification 17%) 0.05 Liquid Paraffin 0.02 Color Image Stabilizer (Cpd-11) 0.01

[0066]

Embedded image

[0067]

[Chemical 15]

[0068]

Embedded image

[0069]

[Chemical 17]

[0070]

Embedded image

[0071]

[Chemical 19]

[0072]

Embedded image

The following water-soluble dyes a and b were used as anti-irradiation dyes for blue and green light and added to the sixth layer. These water-soluble dyes are not only limited to the added layer, but also diffused almost uniformly in all layers during coating.

[0074]

[Chemical 21]

Samples 102 to 1 similar to sample 101 prepared as described above except that 50 mg / m ² of each water-soluble dye shown in Table 2 was added to the second layer and the fourth layer.
22 was created. (The dye added here is not only limited to the added layer, but also diffused almost uniformly in all layers during coating.)

[0076]

[Table 2]

For each of the prepared samples, the following evaluation was carried out after the completion of the dura mater reaction. a) Stability evaluation of dye in photosensitive material film Samples 102 to 121 were refrigerated and stored at 50 ° C. and 80% R.H.
After storing for 3 days under the above condition, the reflection spectrum of the light-sensitive material was measured, and the reflection density (R) at the absorption maximum of the dye was measured. R (50 ° C. 80%) / R (refrigerated) was calculated and the residual ratio of the dye was calculated. The closer this value is to 1, the more stable the dye.

B) Evaluation of Dye Residual Color First, for each of Samples 101 to 121, a sample 25 was applied by white exposure using different color developing solutions.
%, And the unexposed sample was 75%, and the continuous processing was performed with the following replenishment amounts.

Treatment process Temperature Time Replenishment amount ^* Tank capacity (liter) Color development 45 ° C. 30 seconds 35 ml 5 Bleach fixing 40 ° C. 15 seconds 38 ml 3 Rinse 35-40 ° C. 3 seconds −1 Rinse 35-40 ° C. 3 seconds − 1 Rinse 35-40 ° C 3 seconds -1 Rinse 35-40 ° C 3 seconds -1 Rinse 35-40 ° C 5 seconds 90ml 1 Dry 90 ° C 20 seconds * Replenishment amount per 1 m ² of photosensitive material (rinse is 5 tanks to → In the above treatment, the rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane was returned to the rinse for use. In order to shorten the crossover time between the rinses, a blade was installed between the tanks, and the photosensitive material was passed between them. As the small-sized developing machine used in this example, a developing machine having the same structure as that shown in FIGS. 1 and 2 on pages 45 to 46 of JP-A-5-66540 was used.

The composition of each processing liquid is as follows. Color developer Tank solution Replenisher Water 700 ml 700 ml Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6-disulfonate disodium salt Salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 15.8 g Potassium bromide 0.04 g Potassium carbonate 27.0 g 27.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonate ethyl) hydroxylamine 15.0 g 24.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 21.0 g Optical brightener ( SR-1) 5.0 g 6.0 g Water was added to 1000 ml 100 ml pH (25 ℃) 10.35 12.6

[0081]

[Chemical formula 22]

Bleach-fixing solution (a replenishing solution prepared by separating the components into two solutions was used.) [First Replenishing Solution] Water 150 ml Ethylenebisguanidine nitrate 30 g Ammonium sulfite / monohydrate 226 g Ethylenediaminetetraacetic acid 7.5 g Fluorescence enhancement Whitening agent (SR-1) 1.0 g Ammonium bromide 30 g Ammonium thiosulfate (700 g / liter) 340 ml Water was added to 1000 ml pH (25 ° C.) 5.82 [Second replenisher] Water 140 ml Ethylenediaminetetraacetic acid 11.0 g Ethylenediamine Iron (III) tetraacetate 384 g Acetic acid (50%) 230 ml Water added 1000 ml pH (25 ° C) 3.35 Bleach-fix solution tank solution 1st replenisher 260 ml 2nd replenisher 290 ml Water added 1000 ml pH ( 25 ° C) 5.0 Replenishing amount of bleach-fixing solution (below In total per 1 m ² 35 ml) first Replenisher 18ml second replenisher 20ml

Rinsing solution Ion-exchanged water (3 ppm each for calcium and magnesium)
Less than)

Photosensitizer (F, manufactured by Fuji Photo Film Co., Ltd.
After exposing each sample through a color separation filter and a gradation wedge using a WH type, a light source color temperature of 3200K),
The samples of the same number were developed with the processing solutions that were continuously processed.

The cyan density (Dc) of the unexposed area of the obtained sample was measured. The density difference from the cyan density (D ⁰ c) in Sample 101 is the residual color of the water-soluble dye used. The smaller the density difference, the smaller the residual color. The results obtained are also shown in Table 2.

As is clear from Table 2, the samples using the compound of the general formula (1) of the present invention showed a small decrease in concentration even when placed under the conditions of high temperature and high humidity, and after the treatment in the rapid treatment. It can be seen that the residual color of is also suppressed to a low level.

[0087]

The silver halide photographic light-sensitive material having a hydrophilic colloid layer colored with a water-soluble hexamethine merocyanine compound which does not adversely affect the photographic characteristics of the photographic emulsion and is easily decolorized by photographic processing and has excellent stability. Material can be provided.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 13, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

[0013]

[Chemical 4]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

[0016]

[Chemical 7]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

Synthesis Example (Synthesis of Compound 1) To a mixed solution of 50 ml of acetic anhydride and 30 ml of acetic acid, 13.0 g of 5-anilino-N-phenyl-2,4-pentadienylideneiminium chloride and 20 ml of triethylamine were added. Dissolved. To this solution, 1,2-bis (4-sulfophenyl) -3,5- was added to a mixed solution of 30 ml of acetic anhydride, 1.2 ml of acetic acid and 2.8 ml of triethylamine.
A solution in which 4.12 g of pyrazolidinedione was dissolved was added dropwise with a syringe over 5 hours. 900 ml of ethyl acetate was added to the obtained red solution, and the precipitated crystals were collected by filtration and dried. The crystals were added and dissolved in a mixed solution of 40 ml of ethanol and 5.6 ml of triethylamine. To this solution was added 1- (2-sulfoethyl) -2,3,3-trimethyl-5-sulfoindolenine (3.64 g), and the mixture was stirred at room temperature for 3 hours.
Allowed to react for hours. The obtained blue solution was dust-filtered, and 5.0 g of potassium acetate dissolved in 50 ml of methanol was added to the filtrate.
Was added, and the deposited precipitate was filtered off. This precipitate was purified by a column (filler: Sephadex LH20) and then dried to obtain 1.47 g (15.1%) of Compound 1 powder. The structure was confirmed by NMR, mass spectrum and elemental analysis. λmax (water) 665 nm, melting point 300 ° C. or higher.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

[0053]

[Chemical 12]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

[0067]

[Chemical 15]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

Samples 102 to 1 similar to sample 101 prepared as described above except that 50 mg / m ² of each water-soluble dye shown in Table 2 was added to the second layer and the fourth layer.
21 was created. (The dye added here is not only limited to the added layer, but also diffused almost uniformly in all layers during coating.)

Claims (1)

[Claims] 1. Hexamethy! Represented by the following general formula (1):
Hydrophilic containing at least one merocyanine compound
Silver halide photography characterized by having a colloid layer
Photosensitive material. General formula (1)Z in the general formula (1)¹Is condensed to a benzo-fused ring or
Represents the group of non-metal atoms required to form a naphtho-fused ring.
You. M is a hydrogen atom or an atomic group that becomes a monovalent cation.
Ru represents a metal atom, and n represents an integer of 1 to 3.
R¹, R², R³Can be the same or different from each other
Represents a substituted or unsubstituted alkyl group. L ¹, L
², L³, L^Four, L^Five, L⁶Are independently replaced.
Or an unsubstituted methine group, or an adjacent substituent is
They may combine to form a 5- or 6-membered ring. Z²Is a pill
Zolidinedione, isoxazolone, pyrazolopyride
, Barbituric acid, pyridone, rhodanin
Atoms required to form a substituted or unsubstituted heterocycle
Represents a group.