JPH10110108A - Diazaindanone compound and silver halide photosensitive material containing the same compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound being stable in a solution, hardly leaving farmful color by rapidly being decolored in developing treatment and useful as a dye for silver halide photosensitive materials excellent in stability. SOLUTION: This compound is represented by formula I [L<1> to L<3> are each (un)substituted methine; (m) is 0-2; M<1> is H or an atomic group which becomes a monovalent cation or a metal ion; R<1> to R<4> are each H or a substituent group, with the proviso that at least one of R<1> to R<4> is sulfo or a substituent group having sulfo and total of number of sulfo contained in R<1> to R<4> is 1-4], e.g. a compound of formula II. The compound is obtained by dissolving, e.g. 5- anilino-N-phehyl-2,4-pentadienylideneiminium chloride and 6-sulfo-imidazo[1,2- a]pyridine-2(3H)-one into a mixed solvent of dimethyl formamide with triethylamine and reacting both compounds under stirring for 2hr at room temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a diazaindanone oxonol compound represented by the general formula (I) useful as a dye or the like, and contains the compound represented by the general formula (I) in a molecular dispersed state. And a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material, a photographic emulsion layer or other hydrophilic material is used for the purpose of controlling the spectral composition of incident light, preventing light absorption, preventing halation, preventing irradiation, adjusting the sensitivity of the photosensitive emulsion layer, and the like. It is often practiced to color the aqueous colloid layer with a dye. Dyes used for these purposes must satisfy the following conditions. (1) To have appropriate spectral absorption according to the purpose of use. (2) It has excellent stability over time in a solution and in a photographic material, and does not discolor or fade. (3) Photochemically inert. 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) No harmful coloring is left on the processed photographic light-sensitive material by being decolorized in the course of photographic processing or being eluted and removed in a processing solution or washing water.

As a dye satisfying the above conditions, for example,
U.S. Pat.No. 2,274,782, JP-A-51-77,327, JP-A-3-28
Pyrazolone oxonol dyes described in JP-A-8-841, and JP-A-4-130,429 have been found. However, the stability in the solution and in the gelatin film cannot be said to be sufficiently high, and there are problems such as a decrease in color density during storage. Further, diazaindanone compounds described in, for example, JP-A-3-213847 and EP 0552646A have been reported as solid disperse dyes, but these have been a serious problem because of residual color contamination during processing. In particular, a photosensitive material having a photosensitive layer on a reflective support such as a color paper cannot be used because deterioration of the residual color tends to be conspicuous.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel oxonol compound which is stable in a solution and to provide a silver halide photographic material having excellent stability. A second object of the present invention is to provide a silver halide photographic material having a compound which is rapidly decolorized during development processing and has less residual color.

[0005]

The object of the first term has been achieved by the following (1) and (2). (1) A compound represented by the general formula (I). General formula (I)

[0006]

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(L ¹ , L ² and L ³ each represent a substituted or unsubstituted methine group, m represents 0, 1 or 2. M ¹ represents a hydrogen atom or an atomic group which becomes a monovalent cation or R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a substituent, and R ¹ , R ² , R
It is assumed that at least one of ³ and R ⁴ is a sulfo group or a substituent having a sulfo group, and the total number of sulfo groups contained in R ¹ to R ⁴ is ¹ to ⁴ . )

(2) A silver halide photographic material comprising a compound represented by the general formula (I) of (1) in a molecular dispersion.

More preferably, the general formula (I) of (1)
The object has been achieved by a silver halide photographic light-sensitive material containing a compound represented by the formula (I) and at least one compound represented by the following formula (II). General formula (II)

[0010]

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(R ⁵ represents a hydrogen atom or a substituent.
⁶ is the sum of the atomic weights of the atoms contained in R ⁵ and R ⁶ (R ⁵ +
R ⁶ ) represents a substituent having 16 to 160. n represents 0, 1 or 2. M ² represents a hydrogen atom or an alkali metal. )

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
First, the compound represented by formula (I) of the present invention will be described in detail. The methine group represented by L ¹ , L ² , or L ³ may have a substituent (eg, a methyl group, an ethyl group, a chlorine atom), and the substituents are linked to each other to form a 5- or 6-membered ring (eg, cyclopentene). A ring, a cyclohexene ring, or an isophorone ring), but is preferably unsubstituted.

The atomic group which can be a monovalent cation of M ¹ is preferably an ammonium salt, or an organic ammonium salt such as triethylamine, tributylamine or pyridine. Further, as the metal atom that can be M ¹ , an alkali metal such as sodium and potassium is preferable.

There are no particular restrictions on the substituents represented by R ¹ , R ² , R ³ , and R ⁴ , for example, an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, isopropyl, butyl, hexyl, octyl), A C1-8 alkoxyl group (e.g., methoxy, ethoxy, butoxy), a halogen atom (e.g., fluorine, chlorine, bromine), a C0-10 amino group (e.g., dimethylamino, diethylamino), a C2-10 carbon atom Ester groups (eg, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl), amide groups having 1 to 10 carbon atoms (eg, acetamido, benzamide), carbamoyl groups having 1 to 10 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl), 1 to 1 carbon atoms
10 sulfonamide groups (e.g., methanesulfonamide, benzenesulfonamide), C0-10 sulfamoyl groups (e.g., methylsulfamoyl, butylsulfamoyl), and C6-10 aryl groups (e.g., phenyl, naphthyl) , 4-methoxyphenyl, 3-methylphenyl), an acyl group having 2 to 10 carbon atoms (eg, acetyl, propanoyl, benzoyl), a sulfonyl group having 1 to 10 carbon atoms (eg, methanesulfonyl, benzenesulfonyl), 10 ureido groups (eg, ureido, methylureide), urethane groups having 2 to 10 carbon atoms (eg, methoxycarbonylamino, ethoxycarbonylamino), sulfonic acid ester groups (eg, methoxysulfonyl, phenoxysulfonyl), cyano group, nitro group, Hydroxyl group, Carboxyl group, sulfo group, and Hajime Tamaki (e.g., benzoxazole ring, pyridine ring, sulfolane ring, furan ring, pyrrole ring, thiophene ring), and the like. Further, a composite of two or more of these (for example, 2-hydroxyethyl, carboxyphenyl, butanesulfonamidophenyl) may be used.

Two adjacent substituents among R ¹ , R ² , R ³ and R ⁴ may be linked to each other to form a 5- or 6-membered ring. As the 5- or 6-membered ring formed by connecting two adjacent substituents among R ¹ , R ² , R ³ and R ^4, a benzene ring, a cyclohexene ring, a cyclopentene ring,
And a furan ring. The total number of sulfo groups contained in R ¹ to R ⁴ is preferably 1 to 2. Hereinafter, specific examples of the diazaindanone compound of the general formula (I) used in the present invention will be shown, but the present invention is not limited thereto.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

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Next, the compound represented by formula (II) will be described in detail. R of the dye represented by the general formula (II)
⁵ and R ⁶ are CONR ⁷ R ⁸ (R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group and may form a ring);
COOR ⁹ (R ⁹ represents an alkyl group), CN, a hydrogen atom, an alkyl group, OR ¹⁰ (R ¹⁰ represents a hydrogen atom or an alkyl group), NR ¹¹ R ¹² (R ¹¹ and R ¹² represent a hydrogen atom or an alkyl And may form a ring), NR ¹³
COR ¹⁴ (R ¹³ and R ¹⁴ represent a hydrogen atom or an alkyl group), NR ¹⁵ CONR ¹⁶ R ¹⁷ (R ¹⁵ , R ¹⁶ and R ¹⁷ represent a hydrogen atom or an alkyl group, and R ¹⁶ and R ¹⁷ represent a ring May be formed). Further R
It is preferred that ⁵ and R ⁶ have no dissociable group.
The dissociable group of these substituents is a dissociable group that is substantially dissociated in water at 25 ° C. and has a pKa of 12 or less and 1 or more. Specific examples of such a dissociable group include a sulfonic acid, a carboxyl group, and a phosphate group.

The alkyl group represented by R ⁵ is a methyl group,
An alkyl group having 3 or less carbon atoms such as an ethyl group and a propyl group is preferable, and may have a substituent. Examples of such a substituent include a hydroxyl group, an ether group, an ester group, a carbamoyl group, a sulfone group, a sulfamoyl group, and a cyano group. Among them, a hydroxyl group and an ether group are particularly preferable. R ⁵ is particularly preferably a methyl group.

The alkali metal represented by M ² is Li,
Na, K and Ca are preferred.

When the substituent represented by R ⁶ is CONR ⁷ R ⁸
In the case where R ⁷ and R ⁸ are each a hydrogen atom or an alkyl group, at least one of them is preferably an alkyl group. As the alkyl group, an alkyl group having 3 or less carbon atoms, such as a methyl group, an ethyl group, and a propyl group, is preferable, and these may have a substituent. As the substituent, a hydroxyl group and an ether group are particularly preferred. R ⁷ and R ⁸ may be linked to each other to form a ring. In this case, a morpholine ring is particularly preferred as the ring formed.

When the substituent represented by R ⁶ is represented by COOR ⁹ , the alkyl group of R ⁹ is preferably an alkyl group having 4 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group. Ethyl groups are particularly preferred. When the substituent represented by R ⁶ is hydrogen or an alkyl group, the alkyl group is preferably an alkyl group having 4 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and particularly preferably a methyl group or an ethyl group. . When the substituent represented by R ⁶ is represented by OR ¹⁰ or NR ¹¹ R ¹² , R ¹⁰ , R ¹¹ and R ¹² may be a hydrogen atom or an alkyl group. In the case of an alkyl group, an alkyl group having 3 or less carbon atoms, such as a methyl group, an ethyl group, and a propyl group, is particularly preferable.
Further, it may have a substituent. As the substituent, a hydroxyl group and an ether group are particularly preferred. R ¹¹ and R ¹² may be linked to form a ring.

R⁶Is a substituent represented by NR¹³COR¹⁴
When represented by R¹³And R¹⁴Is a hydrogen atom
It may be a kill group. Methyl group, ethyl group as alkyl group
Group, propyl group and the like are preferable, and a methyl group is particularly preferable.
No. Further, it may have a substituent. Water as a substituent
Acid groups and ether groups are preferred. R⁶A substituent represented by
Is NR^FifteenCONR¹⁶R¹⁷When represented by R^Fifteen,
R ¹⁶, R¹⁷May be a hydrogen atom or an alkyl group. Archi
The methyl group is preferably a methyl group, an ethyl group, a propyl group, or the like.
Particularly, a methyl group is particularly preferable. Also has a substituent
May be. As a substituent, a hydroxyl group or an ether group is preferred.
New R⁶Is R^FiveAnd R⁶Sum of atomic weights of atoms contained in
(R^Five+ R⁶) Is preferably from 16 to 160
And more preferably 18 or more and 140 or less.
Is also preferably 80 or more and 130 or less.

A preferred combination of substituents of the compound represented by formula (II) is that R ⁶ is CONR ⁷ R ⁸ wherein R ⁷ and R ⁸ are both a methyl group or are linked to each other to form a morpholine ring. And R ⁵ is a methyl group or an ethyl group, and the total atomic weight (R ⁵ + R ⁶ ) is 87 or more and 129 or less. Further preferred combinations are the case where R ⁶ forms a morpholine ring linked R ⁷ and R ⁸ are mutually the CONR ⁷ R ^8, and a case R ⁵ is a methyl group, sum atomic weight (R ⁵ + R ⁶⁾ is 115.

Specific examples of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto.

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

The dyes (I) and (II) of the present invention are preferably contained in a light-sensitive layer or a non-light-sensitive layer of a silver halide photographic light-sensitive material in a molecularly dispersed state. Here, the molecular dispersion state is a state in which the compound is uniformly dispersed and dissolved in the emulsion layer or other hydrophilic colloid layer, and is preferably observed by a transmission electron microscope (TEM) at a magnification of 100,000. Means that no solid is detected.

The compounds represented by the general formulas (I) and (II) of the present invention are molecularly dispersed in a photosensitive layer or a non-photosensitive layer of a silver halide photographic light-sensitive material by the following various methods. I can do it. (1) A method in which a compound is directly dispersed in a photosensitive layer or a non-photosensitive layer. (2) Using a compound such as water, methanol, ethanol, propanol, a halogenated alcohol described in JP-A-48-9715 or U.S. Pat. No. 3,756,830, acetone, N, N-dimethylformamide,
Pyridine, etc., or a mixed solvent thereof) and adding it in the form of a solution. Among them, it is preferable to use water, methanol, or a mixed solvent of water / methanol. When the compound of the present invention is added to either the photosensitive layer or the non-photosensitive layer, it diffuses almost uniformly throughout the light-sensitive material constituting layer upon application.

The compounds represented by formulas (I) and (II) of the present invention can be used in any effective amount, but are used so that the optical density is in the range of 0.05 to 3.0. Is preferred. 0.1-1000mg
/ M ² is preferable, more preferably 1 to 500 mg / m ² , and still more preferably 5 to 200 mg / m ² . The timing of addition may be any step before coating. Further, the dyes (I) and (II) of the present invention can be used in combination with a dye other than the present invention. When used in combination, it is preferable that the coating amount of the dye of the present invention is not less than the coating amount of the dye other than the present invention, and that the total coating amount is within the above-mentioned coating amount. As the hydrophilic colloid, gelatin is typical, but any other conventionally known colloids 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. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It 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 material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers of a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the degree is low. Also, JP-A-57-112751, 62-200350, 62-2
As described in JP-A Nos. 06541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed 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) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH. Also Tokunoaki
As described in JP-A-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the silver halide emulsion layer of lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a low silver halide emulsion layer is arranged and three layers of different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202464, the medium-sensitive emulsion layer / high The layers may be arranged in the order of a light-sensitive emulsion layer / a light-sensitive emulsion layer. In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers. US 4,663,271 to improve color reproduction
4,705,744; 4,707,436; JP-A-62-160448, 63-63
It is preferable to dispose a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the specification of 89850, adjacent to or close to the main photosensitive layer.

Preferred silver halides for use in the present invention are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent 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 include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.
The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 1
7643 (December 1978), pp. 22-23, "I. Emulsion Production (Emul
sion preparation and types) ”and No. 18716
(November 1979), p.648, No.307105 (November 1989), 863
865 pages, and Grafkid, "Physics and Chemistry of Photography",
Published by Paul Montell (P. Glafkides, Chemie et Phisiqu
e Photographique, Paul Montel, 1967), Duffin's "Emulsion Chemistry", Focal Press (GF Duffi
n, Photographic Emulsion Chemistry, Focal Press, 19
66), "Production and Coating of Photographic Emulsion" by Zelikman et al., Published by Focal Press (VL Zelikman, et al., Making a
nd Coating Photographic Emulsion, Focal Press, 196
It can be prepared using the method described in 4).

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

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in 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. U.S. Pat.No.4,082,553.
The silver halide grains covered with the grains according to 4852,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or to the substantially light-insensitive hydrophilic colloid layer. The term “silver halide particles having a fogged inside or surface” refers to silver halide grains which can be uniformly (non-imagewise) developed regardless of the unexposed portions and exposed portions of the photosensitive material. Its preparation is described in US Pat. No. 4,626,498, JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition.
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 average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
Particularly, the thickness is preferably 0.05 to 0.6 μm. The grains may be regular grains or polydispersed emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains).
% Having a particle diameter within ± 40% of the average particle diameter).

In the present invention, it is preferable to use 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 as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
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 grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. 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 which can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, page 23-24 page 648, right column 866-868 superstrong sensitizer ~ page 649, right column 4. Brightener 24 page 647, right column page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873 to 874 7. Plasticizers, page 27, page 650, right Column 876 Lubricant 8. Coating aid, pages 26 to 27 Page 650 Right column 875 to 876 Surfactant 9. Static 27 page 650 650 Right column 876 to 877 Inhibitor 10. Mast agent 878 to 879

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferred. Yellow couplers: couplers represented by formulas (I) and (II) in EP 502,424A; couplers represented by formulas (1) and (2) in EP 513,496A (especially Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by the general formula (I) in column 1, line 45 to 55 of US 5,066,576; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; Couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18); Couplers of the formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
4,476,219 couplers represented by formulas (II) to (IV) in columns 7 to 36 to 58 (particularly II-17, 19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); A-4 -6 of EP 456,257
3 (p. 134), A-4 -73, -75 (p. 139); M-4, -6 in EP 486,965
(Page 26), M-7 (page 27); EP-571,959A M-45 (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); JP-A-4-43345, C-7,10 (page 35), 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: P-1, P-5 (p. 11) of JP-A-2-44345.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers 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
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (page 51)), the compound of formula (1) of EP 568,037A (especially (23) (page 11)), and the compounds of formulas (I), (II), Compounds represented by (III) (especially I-
(1)); Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
A compound represented by LIG-X described in claim 1 of 4,555,478 (especially a compound on line 21 to 41 of column 12); a leuco dye-releasing compound: compound 1 of column 3 to 8 of US 4,749,641
~ 6; Fluorescent dye releasing compound: Claim 4, C of US 4,774,181
Compound represented by OUP-DYE (especially compounds 1 to 11 in columns 7 to 10); Development accelerator or fogging agent releasing compound: US
4,656,123, the compounds of formulas (1), (2) and (3) in column 3 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only when it is cleaved: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

The following additives are preferred as additives other than the coupler. Dispersion medium of oil-soluble organic compound: P-3,5, 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 according to No. 363; oxidized developing agent scavenger: a compound represented by the formula (I) in columns 2, 54 to 62 of US Pat. No. 4,978,606 (especially I-, (1), (2), (6), (12 ) (Column 4 ~
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); 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
P.), US 5,122,444, columns 25-38 II-1 to III-23, especially
III-10, EP 471347A I-1 to III-4 on pages 8 to 12, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; formalin scavenger: SCV-1 to 28 on pages 24 to 29 of EP 477932A, especially SCV-8; hardener: JP-A 1-214845
Formula of 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),
Compound represented by the formula (6) at the lower right of page 8 of 214852 (H-1 to 7
6), especially compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursor: P-2 of JP-A-62-168139
No. 4,37,39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7;
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
3 columns 6 to 16 I-1 to (14), especially I-1,60, (2), (13), U
Compounds 1-65 of columns 25-32 of S 4,952,483, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
Page a-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Page V-1 to 23, especially V-1, EP 445627A, page 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, 17 to 28 of EP 457153A
Pages III-1 to 36, especially III-1,3, WO 88/04794
Microcrystal dispersion of Dye-1 to 124, Compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular Compounds D-1 to 87 (3) of Compound 1, EP 519306A represented by formulas (1) to (3) ~ 28 pages), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (4) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color photographic 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, Tokuhei 2-32615, actual fairness
It is suitable for the film unit with lens described in 3-39784. Suitable supports that can be used in the present invention are
For example, the RD. Page 28 of No.17643, 6 of No.18716
No. 307105, page 879 from page 47 right column to page 648 left column. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less. Further, 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 required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swelled film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds. Is defined. The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is A.Gr.
een) et al., Photographic Science and Engineering (Photogr.Sci.Eng.), Vol. 19, 2,124-
It can be measured by using a serometer (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 by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention has the above-mentioned RD. No.176
No. 18716, No. 18716, left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used.Typical examples and preferred examples thereof are compounds described in EP 556700A, page 28, lines 43 to 52. Is mentioned. These compounds can be used in combination of two or more depending on the purpose. The color developing solution is an alkali metal carbonate,
PH buffers such as borates or phosphates, and development inhibitors or antifoggants such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. General. Also, as required, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphones Acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene- 1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts are added.

When the reversal process is performed, color development is usually performed after black and white development. 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 in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. 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 due to the contact between the photographic processing solution and the air in the processing tank is determined by the aperture ratio (= [the contact area between the processing solution and the air c
m ² ] ÷ [volume of treatment liquid cm ³ ]). This aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a shield 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. The described slit developing method can be mentioned. The aperture ratio is preferably reduced not only in both the color development and black-and-white development steps but also in the following various steps, for example, in all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for color development processing is usually set between 2 and 5 minutes, but by using high temperature, high pH, and using a high concentration of color developing agent,
Further, the processing time can be reduced.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, 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, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid Etc. can be used. Among these, iron (III) aminopolycarboxylates including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate complex
Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleaching accelerators are described in the following specification: US Pat. No. 3,893,858, DE 1,290,812, JP 2,059,988, JP-A-53-32736, JP-A 53-57831, JP-A 53-37418, JP-A 53-72623. ,
53-95630, 53-95631, 53-104232, 53-12442
4, compounds having a mercapto group or a disulfide group described in RD No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; , JP 52-20832, JP 53-32735,
Thiourea derivatives according to US 3,706,561; DE 1,127,715;
Iodide salts described in JP-A-58-16,235; DE 966,410;
Polyoxyethylene compounds described in 2,748,430; Polyamine compounds described in JP-B-45-8836;
0,943, 49-59,644, 53-94,927, 54-35,727,
Compounds described in JP-A-55-26,506 and JP-A-58-163,940; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and particularly, US 3,893,858, DE 1,290,812, and JP-A-53-95,63.
The compounds described in 0 are preferred. Further, compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids have an acid dissociation constant (p
Ka) is a compound having 2 to 5, specifically acetic acid, propionic acid, hydroxyacetic acid and the like. Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodides, and thiosulfates are generally used. Yes, especially ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, or thiourea. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in EP 294769A is preferable. Furthermore, aminopolycarboxylic acids or organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, a fixing solution or a bleach-fixing solution contains p for adjusting pH.
A compound having a Ka of 6.0 to 9.0, preferably imidazole,
Imidazoles such as 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole per liter
It is preferable to add 0.1 to 10 mol.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
As a specific method of strengthening the stirring, a method of impinging a jet of a processing solution on the emulsion surface of the photosensitive material described in JP-A-62-183460, or a stirring effect using the rotating means of JP-A-62-183461 can be used. A method of raising the stirring effect by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and making the emulsion surface turbulent. There is a method of increasing. 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 increases the desilvering speed. 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 developing machine 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 conveying 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 processing solution from the pre-bath to the post-bath, and have a high effect of preventing the performance of the processing solution from deteriorating. This is particularly effective in reducing the processing time and the replenishing amount of the processing solution.

The photographic material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the intended use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of t
he Society of MotionPicture and Television Enginee
rs, Vol. 64, pages 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 bacteria increase due to the increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to this, a method of reducing calcium ions and magnesium ions described in JP-A-62-288,838 is extremely effective. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, other benzotriazoles, Hiroshi Horiguchi, "Bactericidal and antifungal chemistry"
(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 the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8.
The washing temperature and washing time can also be set according to the characteristics and application of the photosensitive material, but in general, the range is 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C. . Furthermore,
The light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization treatment, known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be applied. Further, after the water washing treatment, a stabilization treatment may be further performed, and examples thereof include a stabilizing bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photography. Can be. Examples of the dye stabilizer 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 and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is 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. In order to incorporate the color developing agent, it is preferable to use a precursor of a color developing agent. For example, US 3,34
Indaniline compounds described in 2,597, 3,342,599,
Research Disclosure No.14,850 and No.15,
159, an aldol compound described in 13,924, a metal salt complex described in US 3,719,492,
53-135628. The light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339,
57-144547 and 58-115438. The processing solution used for processing the photosensitive material of the present invention is 10 ° C to 50 ° C.
Used in Usually, a temperature of 33 ° C to 38 ° C is standard, but higher temperatures can accelerate the processing and shorten the processing time, and lower temperatures can improve the image quality and improve the stability of the processing solution. it can.

[0054]

【Example】

Example 1 (Synthesis of Compound A-1) 0.71 g of 5-anilino-N-phenyl-2,4-pentadienylideneiminium chloride and 6-sulfo-imidazo [1,2-a] pyridine-2 ( 3H) -one (1.22 g) in dimethylformamide (5 ml) and triethylamine (2.44)
The mixture was dissolved in ml of the mixed solvent and stirred at room temperature for 2 hours. After dust filtration, a solution of 0.98 g of potassium acetate dissolved in 10 ml of methanol was added, and the precipitated crystals were filtered. The resulting blue crystals were dissolved in water (30 ml), and methanol (50 ml) was added dropwise.
g was obtained (33% yield). The structure was confirmed by mass spectrum and 1H NMR spectrum. λmax (water) = 705 nm, melting point: 300 ° C or higher.

Example 2 (Synthesis of Compound A-4) 1.42 g of 5-anilino-N-phenyl-2,4-pentadienylideneiminium chloride and 6,8-disulfo-imidazo [1,2-a 2.94 g of pyridine-2 (3H) -one
To 10 ml of dimethylformamide and 3.5 ml of triethylamine
And the mixture was stirred at room temperature for 2 hours. After dust filtration, a solution of 2.94 g of potassium acetate dissolved in 20 ml of methanol was added, and the precipitated crystals were filtered. The resulting blue crystals were dissolved in 40 ml of water, 100 ml of methanol was added dropwise, and the precipitated crystals were filtered to give 0.84 of compound A-4.
g was obtained (yield 21%). The structure was confirmed by mass spectrum and 1H NMR spectrum. λmax (water) = 731 nm, melting point: 300 ° C or higher.

Example 3 The stability of the dye in an aqueous solution was evaluated by the following method. Solvent: BR (Briton-Robinson) buffer (pH 6) Dye concentration: 1 × 10 ⁻⁵ mol / l Temperature: 25 ° C. (using a thermostat), light-shielded Absorption maximum of solution absorption spectrum immediately after preparation and after 24 hours (C) was measured at 24 hours, and C (after 24 hours) / C
The value of (immediately after) was determined, and the residual ratio of the dye was calculated. The closer this value is to 1, the more stable the dye. Table 7 shows the obtained results.

[0057]

[Table 7]

[0058]

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As is clear from Table 7, the compound represented by the general formula (I) of the present invention has high stability even in an aqueous solution.

Example 4 (Preparation of Photosensitive Material 101) Various photographic constituent layers were coated on a reflective support to prepare a multilayer color photographic material, Sample 101 having the following layer constitution. The coating solution was prepared as in the following example.

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

The other coating solutions for the first to seventh layers were prepared in the same manner as for the third layer coating solution. 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener for each layer. Cpd-12 and C
pd-13 was 25.0 mg / m ² and 50.0 mg respectively.
mg / m ² . The size of the silver chlorobromide emulsion in each photosensitive emulsion layer was adjusted by the same preparation method as that of the silver chlorobromide emulsion B-1, and the following spectral sensitizing dyes were used. Blue-sensitive emulsion layer

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(Per mol of silver halide, 1.4 × 10 ^-4 mol was added to a large-size emulsion and 1.7 × 10 ^-4 mol was added to a small-size emulsion, respectively.) Sensitive emulsion layer

[0065]

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(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 per mol of silver halide and 7.0 × 10 ⁻⁵ mol per mol of silver halide per mol of silver halide. Sensitizing dye F was used in an amount of 2.0 per mol of silver halide for a large-sized emulsion.
× 10 ^-4 mol, and 2.8 × 1 for small size emulsions
^0-4 moles were added. ) Red-sensitive emulsion layer

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

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

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Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer
1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 per mole^-FourMol, 3.0 × 10^-3Mole,
2.5 × 10^-FourMole was added. Blue sensitive emulsion layer and green
4-hydroxy-6-methyl-1,
Halogenate 3,3a, 7-tetrazaindene
1 × 10 per mole of silver ^-FourMole, 2 × 10^-FourMole added
Was.

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

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

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A-1 0.27 (cubic, 5: 5 mixture of large-sized emulsion having an average grain size of 0.88 μm and small-sized emulsion having an average grain size of 0.70 μm) (Silver mole ratio) The variation coefficients of the grain size distribution were 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was localized on a part of the grain surface using silver chloride as a base in each size emulsion. 0.12 mg of potassium hexachloroiridate (IV) and 1.0 mg of potassium ferrocyanide were added to the inside of the grains and the localized phase of silver bromide.) 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 mixture preventing layer) Gelatin 0.90 Color mixture 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) Silver chlorobromide emulsion B-1 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 Ultraviolet 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 mixture prevention layer) Gelatin 0.68 Color mixture prevention agent (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 having an average grain size of 0.50 μm and small-size emulsion of 0.41 μm) (Silver mole ratio) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was localized on a part of the grain surface using silver chloride as a base. 0.3 mg of potassium hexachloroiridate (IV) in total and 1.5 mg of potassium ferrocyanide in total in the inside of the grains and the localized phase of silver bromide.) Gelatin 0.80 Cyan coupler (ExC) 0.33 UV 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 (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (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

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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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 diffuse not only in the additive layer but also in all the layers at the time of coating.

[0089]

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Samples 102 to 1 were prepared in the same manner as described above except that 50 mg / m ^{2 of} a water-soluble dye as shown in Table 8 was added to the second layer and the fourth layer to the sample 101 prepared as described above.
09 was created. (The dye added here also diffuses almost uniformly in all the layers at the time of coating, not only in the added layer.)

[0091]

[Table 8]

The following evaluation was performed on each of the prepared samples after the hardening reaction was completed. a) Evaluation of stability of dye in light-sensitive material film Samples 102 to 109 were refrigerated, and 50 ° C. and 80% R.C.
The reflection spectra of the light-sensitive material and those stored for 3 days under the conditions of H. were measured, and the reflection density (R) at the absorption maximum of the dye was measured. R (50 ° C 80%) / R
(Refrigerated) and the residual ratio of the dye was calculated. The closer this value is to 1, the more stable the dye.

B) Evaluation of residual color of dye First, for each of Samples 101 to 109, a covering sample 25 was formed by white exposure using a separate color developing solution.
% And an unexposed sample at a rate of 75%, and the following replenishing amounts were used for continuous processing.

Processing Step Temperature Time Replenishment amount * Tank capacity (liter) Color development 45 ° C. 30 seconds 35 ml 5 Bleaching and 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 90 ml 1 drying 90 ° C. 20 seconds * replenishment rate is 5 tank countercurrent to per photosensitive material 1 m ² (rinse → 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 the blades. As the compact developing machine used in this embodiment, a developing machine having the same configuration 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 solution 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 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 (sulfonatoethyl) hydroxylamine 15.0 g 24.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 21.0 g Fluorescent brightener (SR-1) 5.0 g 6.0 g Water was added to 1000 ml 1 000 ml pH (25 ° C) 10.35 12.6

[0096]

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Bleach-fixing solution (a replenisher in which the components were separated into two solutions was used) [First replenisher] Water 150 ml Ethylene bisguanidine nitrate 30 g Ammonium sulfite / monohydrate 226 g Ethylenediaminetetraacetic acid 7.5 g Increase in fluorescence Whitening agent (SR-1) 1.0 g Ammonium bromide 30 g Ammonium thiosulfate (700 g / liter) 340 ml Water is added to 1000 ml pH (25 ° C.) 5.82

[Second replenisher] water 140 ml ethylenediaminetetraacetic acid 11.0 g iron (III) ammonium ethylenediaminetetraacetate 384 g acetic acid (50%) 230 ml water was added, and 1000 ml pH (25 ° C.) 3.35

Tank solution of bleach-fix solution First replenisher 260 ml Second replenisher 290 ml Water is added to 1000 ml pH (25 ° C.) 5.0 Replenishment amount of bleach-fix solution (total amount of 35 ml per m ^{2 in the following} amount) Replenisher 18ml Second replenisher 20ml

Rinse solution Deionized water (Calcium and magnesium each 3 ppm
Less than)

Sensitometer (Fuji Photo Film Co., Ltd., F
After exposing each sample through a color separation filter and a gradation wedge using a WH type light source with a color temperature of 3200K),
Samples of the same number were each developed with a processing solution that was continuously processed. The cyan density (D
c) was measured. Cyan density (D0
The density difference from c) is the residual color of the water-soluble dye used. The smaller the density difference, the smaller the residual color. The results obtained are shown in Table 8 at the same time. As is clear from Table 8, the sample using the compound of the general formula (I) of the present invention
Even when placed in high-temperature, high-humidity conditions, the concentration decreases little,
Moreover, it can be seen that the residual color after the processing in the rapid processing is also suppressed to a low level.

[0102]

According to the present invention, a silver halide photographic material having a hydrophilic colloid layer colored with a water-soluble diazaindanone compound which is easily decolored by photographic processing and has excellent stability can be provided.

Claims (2)

[Claims] 1. A compound represented by the general formula (I). General formula (I) In the general formula (I), L ¹ , L ² and L ³ each represent a substituted or unsubstituted methine group, and m represents 0, 1 or 2. M ¹ represents a hydrogen atom, an atomic group that becomes a monovalent cation, or a metal ion. R ¹ , R ² , R ³ , R ⁴
Represents a hydrogen atom or a substituent, and R ¹ , R ² ,
At least one of R ³ and R ⁴ is a sulfo group or a substituent having a sulfo group, and the total number of sulfo groups included in R ¹ to R ⁴ is ¹ to ⁴ . 2. A silver halide photographic material comprising a compound represented by the formula (I) according to claim 1 in a molecular dispersion.