JP2779722B2 - Silver halide photographic material - Google Patents

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 material having improved residual color and sensitivity during development processing.

[0002]

2. Description of the Related Art With the recent rapid development processing and the addition of a large amount of a sensitizing dye, the sensitizing dye contained in a silver halide photographic material does not elute during the processing, but the sensitizing dye is colored. The problem of leaving (so-called residual color) is increasing. Heretofore, sensitizing dyes having a small residual color have a hydrophilic substituent such as a sulfamoyl group or a carbamoyl group (for example, JP-A-1-147451, JP-A-61-294429, and JP-B-45-32749). And Japanese Patent Application Laid-Open No. Sho 61-77843) have been studied, but increasing the hydrophilicity of the sensitizing dye generally lowers the adsorptivity, and none of them has sufficient sensitivity. Also, the residual color is not at a sufficiently satisfactory level. The sensitizing dyes described in U.S. Pat. No. 3,282,933 also have an effect of improving the residual color, but similarly, no sufficient effect has been obtained in terms of achieving both the residual color and the sensitivity. In addition, many silver halide photographic materials contain various dyes for the purpose of adjusting spectral absorption or preventing irradiation or halation to enhance image sharpness. On the contrary, there are things that make the residual color worse, making it difficult to select.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material capable of achieving both the residual color and the sensitivity during the development processing.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to provide at least one methine compound represented by the following general formula (I).
This has been attained by a silver halide photographic material characterized by containing at least one of a seed and a water-soluble dye. General formula (I)

[0005]

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Wherein R ¹ is — (CH ₂ ) _r —CONHS
O ₂ —R ³ , — (CH ₂ ) _s —SO ₂ NHCO—R ⁴ ,
— (CH ₂ ) _t —CONHCO—R ⁵ , or — (CH
₂₎ represents a ^{_{u-SO 2 NHSO 2 -R 6}} . Here, R ³ , R ⁴ , R ⁵ , or R ⁶ represents an alkyl group, an alkoxy group, or an amino group, and r, s, t, or u
Represents an integer of 1 to 5. R ² is 2-sulfoethi
Group, 3-sulfopropyl group, 4-sulfobutyl group, or
Represents a 3-sulfobutyl group . Z ¹ and Z ² are each
Each represents a group of non-metallic atoms necessary to form a benzothiazole nucleus or a benzoselenazole nucleus , p and q
Represents 0 or 1. L ₁ , L ₂ , or L ₃ represents a methine group, and m represents 0, 1 or 2. X ₁ represents an anion, and k represents a number necessary to adjust the intramolecular charge to zero.

The methine compound of the general formula (I) and the water-soluble dye will be described in detail below. The alkyl group represented by R ³ , R ⁴ , R ⁵ , or R ⁶ may be substituted, and preferably has 4 or less carbon atoms, and particularly preferably has a methyl group, an ethyl group, a hydroxyalkyl group, or an aminoethyl group. Group. The alkoxy group may be substituted and preferably has 4 or less carbon atoms, and particularly preferably is a methoxy group, an ethoxy group, a methoxyethoxy group or a hydroxyethoxy group. The amino group may be substituted with an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, or the like, or may form a ring between the substituents, and preferably has 8 or less carbon atoms. Particularly preferred are a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a hydroxyethylamino group, a morpholino group, and a pyrrolidino group. Further, the hydrogen atom linked to the nitrogen atom adjacent to the carbonyl group or the sulfonyl group of R ¹ is dissociable, and therefore, R ¹ is-(CH ₂ ) _r -CON ^- SO _{2-due to} the presence of a base or the like.
R ³ , — (CH ₂ ) _s —SO ₂ N ^— CO—R ⁴ , — (C
^{_{H 2) t -CON - CO-}} R 5 or, - _{(CH 2) u}
It may take the form of _{^{SO 2 -R 6 - -SO 2 N}} . R ² is 2-
A sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, and a 3-sulfobutyl group. Preferred values of r, s, t, or u are 1, 2, and 3.

The 5- or 6-membered heterocyclic nucleus represented by Z ¹ and Z ² is a benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-chlorobenzothiazole, Nitrobenzothiazole, 4-methylbenzothiazole, 5-
Methyl benzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6
-Methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5
-Carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methyl Benzothiazole, tetrahydroxybenzothiazole, 4-phenylbenzothiazole) , benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxy benzoselenazole, 6-nitro benzoselenazole, 5-chloro-6-nitro benzoselenazole, with 5,6-dimethyl benzoselenazole)
is there.

[0009] L₁, L₂And L₃Methine represented by
The group may be substituted, and the substituent may be substituted.
Alkyl groups such as methyl, ethyl, 2-carbo
An xyl group), an optionally substituted aryl group (eg,
Phenyl group, o-carboxyphenyl group), halogen source
(For example, chlorine atom, bromine atom), alkoxy group (for example,
For example, methoxy group, ethoxy group), alkylthio group (for example,
Methylthio group, ethylthio group) and the like, and
It may form a ring with another methine group, or
Rings can also be formed. X₁And an anion represented by
And inorganic or organic acid anions (eg chloride,
Bromide, iodide, p-toluenesulfonate, naph
Talensulfonate, methanesulfonate, methyls
Rufate, ethyl sulfate, perchlorate
Etc.). m is preferably 0 or
It is one. A methine compound represented by the following general formula (I)
Specific examples of products are shown, but the scope of the present invention is not limited to these.
Not something.

[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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[0015]

[0016]

[0017]

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The methine compound represented by the general formula (I) can be synthesized according to the following method.

Synthesis Example 1 Synthesis of 5-chloro-3-methanesulfonylaminocarbonylmethyl-2-methylbenzothiazolium bromide N- (bromoacetyl) synthesized according to the method described in US Pat. No. 3,282,933. Methanesulfonamide 5
0 g, 5-chloro-2-methylbenzothiazole
6 g and 4 ml of methyl ethyl ketone in 10
Stir for 5 hours on a 5 ° C. oil bath. Acetone 20 in the reaction solution
After adding 0 ml and refluxing for 1 hour, the mixture is cooled with water.
After 1 hour, the crystals were collected by suction filtration, washed with 100 ml of acetone, and dried to give 59.6 g of the title compound (7
4.7%).

Synthesis of Exemplified Compound I-1 5-Chloro-3-methanesulfonylaminocarbonylmethyl-2-methylbenzothiazolium bromide
06g and 4- {5-chloro-2- (ethoxy-1-
477 ml of methanol was added to 40.46 g of (butenyl) -3-benzothiazolio-butanesulfonate, and the mixture was stirred.
One milliliter is added dropwise and stirred for one hour. 82 ml of acetic acid was added to the reaction solution, stirred for 20 minutes, and cooled with water.
After 1 hour, the crystals were filtered by suction, washed with 150 ml of methanol, and dried to obtain crude crystals of I-1.
7 g are obtained. The crude crystals are dissolved in methanol (600 ml) and triethylamine (30 ml), and the insoluble matter is removed by suction filtration. After washing with 300 ml of methanol, the filtrate is concentrated under normal pressure, and 400 ml is distilled off. 40 ml of acetic acid is added to the remaining solution at 55 ° C., and the mixture is stirred for 20 minutes and then cooled with water. After 1 hour, the crystals were filtered by suction, washed with 250 ml of methanol, and dried to obtain 36.2 g (56.1%) of I-1. λmax (MeOH) 554 nm (1.14 × 10 ⁵ ) Melting point> 300 ° C

Synthesis Example 2 Synthesis of 5-chloro-3-methanesulfonylaminocarbonylmethyl-2-methylbenzothiazolium bromide N- (β-bromo synthesized according to the method described in US Pat. No. 3,282,933. 46 g of propionyl) methanesulfonamide and 20 g of 5-chloro-2-methylbenzothiazole are stirred on a 115 ° C. oil bath for 60 hours. After 200 ml of ethyl acetate was poured into the reaction solution and stirred for 20 minutes, the crystals were filtered to obtain 40.8 g of the title compound.
(82%).

Synthesis of Exemplified Compound I-3 5-Chloro-3-
Methanesulfonylaminocarbonylmethyl-2-methylbenzothiazolium bromide (2.1 g) and 4- {5-chloro-2- (ethoxy-1-butenyl) -3-benzothiazolio} butanesulfonate (2.4 g) were added to benzyl alcohol 20. Then, 2 ml of triethylamine is added to this solution at room temperature, and the mixture is stirred for 1 hour. The insolubles were filtered off from the reaction solution, and ethyl acetate 10 was added to the filtrate.
Add 0 ml and 10 ml of glacial acetic acid and add 1
Stir for 0 minutes. The obtained crystals are dissolved in methanol-triethylamine, and the insolubles are filtered off. Then, 10 ml of glacial acetic acid is added to the filtrate, methanol is distilled off to one third at normal pressure, and the mixture is cooled with water. The obtained crystals were separated by filtration to obtain I-3.
Was obtained 0.6 g (17.4%). λmax (MeOH) 553 nm (ε 1.33 × 10 ⁵ ) Melting point> 300 ° C The physical properties of the methine compound of the present invention synthesized by the same method are shown below. Exemplified compound λmax (MeOH) Melting point I-2 550 (1.20 × 10 ⁵ )> 300 ° C. I-4 551 (1.21 × 10 ⁵ ) I-5 551 (1.13 × 10 ⁵ ) 〃I −6 551 (1.30 × 10 ⁵ ) 〃I-7 551 (1.19 × 10 ⁵ ) 〃I-8 560 (1.22 × 10 ⁵ ) 〃I-9 552 (1.30 × 10 ⁵ ) 〃

The water-soluble dye referred to in the present invention is 2
The dye is soluble in 0.5% or more of water at 5 ° C., preferably the dye is soluble in 1% or more. Such dyes include:
For example, British Patent Nos. 506,385 and 1,177,4
29, 1,311,884, 1,338,79
No. 9, No. 1, 385, 371, No. 1, 467, 214
No. 1,433,102, 1,553,516
No., JP-A-48-85,130 and JP-A-49-114,4.
No. 20, No. 52-117, No. 123, No. 52-9271
Nos. 6, 55-161, 233 and 59-111, 6
No. 40, JP-B-39-22,069 and 43-13
Nos. 168 and 62-273527, U.S. Pat.
47,127, 3,469,985, 4,07
Oxonol dyes having a pyrazolone nucleus or a barbituric acid nucleus described in U.S. Pat.
Other oxonol dyes described in U.S. Pat. Nos. 3,472, 3,379,533, and British Patent 1,278,621, and British Patents 575,691, 680,63.
Nos. 1, 599, 623, 786, 907 and 9
Azo dyes described in JP-A Nos. 07,125 and 1,045,609, U.S. Pat. No. 4,255,326, and JP-A-59-211,043;
No. 54-118,247, British Patent No. 2,01
Azomethine dyes described in US Pat. Nos. 4,598 and 750,031, anthraquinone dyes described in US Pat. No. 2,865,752, US Pat.
No. 9, No. 2,688,541, No. 2,538,008
No. 4,923,788 and British Patent No. 584,60.
Nos. 9 and 1,210,252, JP-A-50-40,6
No. 25, No. 51-3,623, No. 51-10,927
No. 54-118,247, JP-B-48-3,28
Nos. 6, 59-37, 303 and 63-197, 94
No. 3, etc., arylidene dyes, JP-B-28-
No. 3,082, No. 44-16, 594, No. 59-2
Styryl dyes described in U.S. Patent Nos. 8,898 and 8; UK Patent Nos. 446,583 and 1,335,422;
Triarylmethane dyes described in JP-A Nos. 9-228,250 and the like; British Patent Nos. 1,075,653 and 1,15;
No. 3,341, No. 1,284,730, No. 1,47
Merocyanine dyes described in US Pat. Nos. 2,843,486 and 5,228, 1,542,807;
And cyanine dyes described in JP-A Nos. 3,294,539 and 4,900,653.

Among these, the dyes which can be particularly preferably used in the present invention are represented by the following general formulas (II), (III) and (I)
Dyes represented by (V), (V), (VI) or (VII). General formula (II)

[0025]

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In the formula, Z ₃ and Z ₄ may be the same or different and each represents a group of non-metallic atoms necessary to form a heterocyclic ring; L ₄ , L ₅ , L ₆ , L ₇ L ₈ represents a methine group, n ₁ and n ₂ represent 0 or 1, and M ⁺ represents hydrogen or other monovalent cation. General formula (III)

[0027]

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In the general formula (III), X and Y may be the same or different and represent an electron-withdrawing group.
May be linked to form a ring. R ₄₁ and R ₄₂ may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, a substituted amino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or a sulfo group .
R _43, R ₄₄ may be the same or different, a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a sulfonyl group, are linked is R _43, R ₄₄ 5
A 6-membered ring may be formed. R ₄₁ and R ₄₃ , and R ₄₂ and R ₄₄ may be connected to each other to form a 5- to 6-membered ring. At least one of the above X, Y, R ₄₁ , R ₄₂ , R ₄₃ , and R ₄₄
One has a sulfo group or a carboxyl group as a substituent. L ₁₁ , L ₁₂ and L ₁₃ each represent a methine group. k ₁ represents 0 or 1. General formula (IV)

[0029]

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In the formula, Ar ₁ and Ar ₂ may be the same or different and represent an aryl group or a heterocyclic group. General formula (V)

[0031]

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In the formula, R ⁵¹ , R ⁵⁴ , R ⁵⁵ and R ⁵⁸ may be the same or different from each other and include a hydrogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a carbamoyl group, and an amino group (—NR ^′). R ″ R ^′ and R ″ may be the same or different and represent a hydrogen atom and an alkyl group or an aryl group having at least one sulfonic acid group or carboxyl group). R ⁵² , R ⁵³ , R ⁵⁶
And R ⁵⁷ may be the same or different and represent a hydrogen atom, a sulfonic acid group, a carboxyl group or an alkyl group or an aryl group having at least one sulfonic acid group or carboxyl group. General formula (VI)

[0033]

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In the formula, L and L 'represent a substituted or unsubstituted methine group or a nitrogen atom, and m represents 0, 1, 2 or 3. Z ₅ is a pyrazolone nucleus, hydroxypyridone nucleus, barbituric acid nucleus, thiobarbituric acid nucleus, dimedone nucleus, indan-1,3-dione nucleus, rhodanine nucleus, thiohydantoin nucleus, oxazolidine-4-one-2-thione nucleus A homophthalimide nucleus, a pyrimidine-2,4-dione nucleus,
Represents a group of nonmetallic atoms necessary for forming a 1,2,3,4-tetrahydroquinoline-2,4-dione nucleus. Z ₆
Are oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, pyridine nucleus,
Quinoline nucleus, benzimidazole nucleus, naphthoimidazole imidazole nucleus, imidazo quinoxaline nucleus, it represents an indolenine nucleus, isoxazole nucleus, benzisoxazole nucleus, naphthoxazole isoxazole nucleus, a non-metallic atomic group necessary for forming a acridine nucleus, Z ₅ And Z ₆ may further have a substituent. General formula (VII)

[0035]

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Or

[0037]

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In the formula, R and R 'may be the same or different and represent a substituted or unsubstituted alkyl group. L ₇₁ , L ₇₂ and L ₇₃ may be the same or different and represent a substituted or unsubstituted methine group, and m ₇ represents 0, 1, 2 or 3. Z and Z ′ may be the same or different from each other, and represent a group of nonmetallic atoms necessary for forming a substituted or unsubstituted 5- or 6-membered heterocyclic ring, and k ₇ and n ₇ are 0 or It is one. X ^- represents an anion. a represents 1 or 2, and a is 1 when the compound forms an internal salt. Hereinafter, each dye will be described in detail. In the general formula (II), Z ₃ , Z
_The heterocyclic ring formed by the non-metallic atomic group represented by ₄ is preferably a 5- or 6-membered ring, and may be a single ring or a condensed ring, such as 5-pyrazolone, 6-hydroxypyridone,
Pyrazolo [3,4-b] pyridine-3,6-dione, barbituric acid, pyrazolidinedione, thiobarbituric acid, rhodanin, imidazopyridine, pyrazolopyrimidine, pyrrolidone, pyrazoloimidazole and the like. The methine group represented by L ₄ , L ₅ , L ₆ , L ₇ , L ₈ has a substituent (eg, methyl, ethyl, phenyl, chlorine atom, sulfoethyl, carboxyethyl, dimethylamino, cyano). Alternatively, the substituents may be linked together to form a 5- or 6-membered ring (for example, cyclohexene, cyclopentene, 5,5-dimethylcyclohexene). Monovalent cations other than hydrogen represented by M ⁺ include, for example, Na ⁺ , K ⁺ , HN ⁺ (C ₂ H ₅ ) ₃ C ₆ H ₅ NH ⁺ , L
i ^{+ and the} like. Among the dyes represented by the general formula (II), particularly preferred dyes are those represented by the following general formula (II-
a), (II-b), (II-c), (II-d) or (II-
The dye represented by e). General formula (II-a)

[0039]

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In the formula, R ₇ and R ₉ represent an aliphatic group, an aromatic group or a heterocyclic group, and R ₈ and R ₁₀ represent an aliphatic group, an aromatic group, —OR ₁₁ , —COOR ₁₁ , and —NR. ₁₁ R ₁₂ , -CON
_{R 11 R 12, -NR 11 CONR} 11 R 12, -SO 2 R 13, -
COR ₁₃ , —NR ₁₂ COR ₁₃ , —NR ₁₂ SO ₂ R ₁₃ , a cyano group (here, R ₁₁ and R ₁₂ represent a hydrogen atom, an aliphatic group or an aromatic group, and R ₁₃ represents an aliphatic group or an aromatic group. R ₁₁ and R ₁₂ or R ₁₂ and R ₁₃ may be linked to form a 5- or 6-membered ring), and L ₄ , L ₅ ,
L ₆ , L ₇ , L ₈ and n ₁ , n ₂ , M ⁺ are represented by the general formula (I)
Is the same as the definition in General formula (II-b)

[0041]

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In the formula, R ₂₁ and R ₂₄ represent a hydrogen atom, an aliphatic group,
Aromatic group, heterocyclic group, -NR ₂₇ R ₂₈ , -NR ₂₇ CONR
₂₇ R ₂₈ , —NR ₂₈ COR ₂₉ , or —NR ₂₈ SO ₂ R ₂₉ , wherein R ₂₂ and R ₂₅ each represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a sulfonic acid group, -NR
₂₇ R ₂₈ , -NR ₂₈ COR ₂₉ , -NR ₂₈ SO ₂ R ₂₉ , -N
R ₂₇ CONR ₂₇ R ₂₈ , -COOR ₂₇ , -CONR
₂₇ R ₂₈ , -COR ₂₉ , -SO ₂ R ₂₉ or -SO ₂ NR ₂₇
R represents R ₂₈ , R ₂₃ and R ₂₆ each represent a hydrogen atom, an aliphatic group,
Aromatic group, heterocyclic group, -OR ₂₇ , -COOR ₂₇ , -CO
_{R 29, -CONR 27 R 28,} -NR 27 R 28, -NR 28 CO
R ₂₉ or _{-NR 28 SO 2 R 29, -NR} 27 CONR
_{27 R 28, -SO 2 R 29} , -SO 2 NR 27 R 28, -OR 27
Or a cyano group (wherein R ₂₇ and R ₂₈ each represent a hydrogen atom, an aliphatic group or an aromatic group, R ₂₉ represents an aliphatic group or an aromatic group, and R ₂₇ and R ₂₈ or R ₂₈ R ₂₉ may be linked to form a 5- or 6-membered ring.) L ₄ , L
₅ , L ₆ , L ₇ , L ₈ , n ₁ , n ₂ , and M ⁺ are represented by the general formula (I
It is the same as the definition in I). General formula (II-c)

[0043]

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In the formula, R ₃₁ and R ₃₄ each represent an aliphatic group, an aromatic group or a heterocyclic group; R ₃₂ and R ₃₅ each represent a hydrogen atom;
Aliphatic group, aromatic group, heterocyclic group, COR ₃₉ or SO ₂ R
_And R ₃₃ and R ₃₆ each represent a hydrogen atom, a cyano group, an alkyl group, an aryl group, -COOR ₃₇ , -OR ₃₇ , -N
_{R 37 R 38, -N (R} 38) COR 39, -N (R 38) SO 2
R ₃₉ , —CONR ₃₇ R ₃₈ , or —N (R ₃₇ ) CONR ₃₇
R ₃₈ (R ₃₉ represents an aliphatic group or an aromatic group, R _37, R
₃₈ represents a hydrogen atom, an aliphatic group or an aromatic group. )
Wherein Z ₃₁ is an oxygen atom or NR ₄₅ , Z ₃₂ is an oxygen atom or NR ₄₆ (R ₄₅ and R ₄₆ are each linked to R ₃₁ and R ₃₄ to form 5
Represents a group of non-metallic atoms necessary for forming a membered ring. ), L ₄ , L ₅ , L ₆ , L ₇ , L ₈ , n ₁ , n ₂ ,
M ⁺ has the same meaning as defined in formula (II). Where R
_{31, R 32, R 33,} R 34, R 35, R 36, L 4, L 5,
At least one of L ₆ , L ₇ or L ₈ represents a group having at least one carboxylic acid group or sulfonic acid group. General formula (II-d)

[0045]

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In the formula, R ₆₁ , R ₆₂ , R ₆₃ and R ₆₄ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group;
L ₄ , L ₅ , L ₆ , L ₇ , L ₈ , n ₁ , n ₂ and M ⁺ have the same meanings as defined in the general formula (II). General formula (II-e)

[0047]

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[0048] In the _{formula, R 65, R 66, R} 67, R 68 are each an aliphatic group, an aromatic group or a heterocyclic residue,, L _41,
L ₄₂ and L ₄₃ each represent a methine group. n ₄₁ represents 1, 2 or 3. However, any of R ₆₅ , R ₆₆ , R ₆₇ and R ₆₈ has a carboxyl group or a sulfo group, and the total is at least two or more. Next, the general formula (II-a) will be described in detail. R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R
_The aliphatic group represented by ₁₂ and R ₁₃ may be any of a linear, branched or cyclic alkyl group, an aralkyl group, and an alkenyl group, for example, methyl, for example, methyl, ethyl,
n-butyl, benzyl, 2-sulfoethyl, 4-sulfobutyl, 2-sulfobenzyl, 2-carboxyethyl,
Examples include groups such as carboxymethyl, trifluoromethyl, dimethylaminoethyl, and 2-hydroxyethyl.
Examples of the aromatic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ include phenyl, naphthyl, 4-
Examples include groups such as sulfophenyl, 3-sulfophenyl, 2,5-disulfophenyl, 4-carboxyphenyl, and 5,7-disulfo-3-naphthyl. The heterocyclic group represented by R ₇ or R ₉ represents a 5- or 6-membered nitrogen-containing heterocyclic group (including a condensed ring), for example, 5-sulfopyridin-2-yl, 5-sulfobenzothiazole-2-yl. And the like. Examples of the 5- or 6-membered ring formed by linking R ₁₁ and R ₁₂ and between R ₁₂ and R ₁₃ include a pyrrolidine ring, a piperidine ring, a pyrrolidone ring, and a morpholine ring. Examples of the dye represented by the general formula (II-a) are shown below,
The present invention is not limited to these.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

These dyes are described in GB 506,38.
No.5, No.1,177,429, No.1,338,79
No. 9, No. 1, 385, 371, No. 1, 467, 214
No. 1,433,102, 1,553,516
No., JP-A-48-85130, and JP-A-55-161233.
No. 52-20330, No. 59-11640,
It can be synthesized by the method described in JP-A-62-273527. Next, the dye represented by formula (II-b) will be described in detail. R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R
_The aliphatic group represented by ₂₆ , R ₂₇ , R ₂₈ or R ₂₉ is, for example, methyl, ethyl, isopropyl, 2-chloroethyl,
Trifluoromethyl, benzyl, 2-sulfobenzyl,
Examples include groups such as 4-sulfophenethyl, carboxymethyl, 2-carboxyethyl, 2-sulfoethyl, 2-hydroxyethyl, dimethylaminoethyl, and cyclopentyl. R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ ,
The aromatic group represented by R ₂₇ , R ₂₈ or R ₂₉ is, for example, phenyl, naphthyl, 3-sulfophenyl, 4-sulfophenyl, 2,5-disulfophenyl, 4- (3-sulfopropyloxy) phenyl, 3-carboxyphenyl,
And groups such as 2-carboxyphenyl. R ₂₁ , R
_22, the heterocyclic group represented by R _23, R _24, R ₂₅ or R _26, for example 2-pyridyl, morpholino, and a 5-sulfo-benzimidazol-2-yl and the like groups. Examples of the 5- or 6-membered ring formed by linking R ₂₇ and R ₂₈ or R ₂₈ and R ₂₉ include a piperidine ring, a pyrrolidine ring, a morpholine ring, and a pyrrolidone ring. Hereinafter, specific examples of the dye represented by Formula (II-b) are shown, but the present invention is not limited thereto.

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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The dyes represented by formula (II-b) are described in British Patents 1,278,621 and 1,512,863,
The compound can be synthesized by the method described in JP-A No. 1,579,899. Next, the general formula (II-c) will be described in detail.
The aliphatic group represented by R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ may be any of a linear, branched or cyclic alkyl group, an aralkyl group and an alkenyl group. Well, for example, methyl, ethyl, n-butyl, benzyl, 2
-Sulfoethyl, 4-sulfobutyl, 2-sulfobenzyl, 2,4-disulfobenzyl, 2-carboxyethyl, carboxymethyl, 2-hydroxyethyl, dimethylaminoethyl, trifluoromethyl and the like. R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈
And the aromatic group represented by R ₃₉ phenyl, naphthyl, 4-sulfophenyl, 2,5-sulfophenyl, 4-carboxyphenyl, 5,7-disulfo-3
Examples include groups such as naphthyl, 4-methoxyphenyl and p-tolyl. The heterocyclic group represented by R ₃₁ , R ₃₂ , R ₃₄ or R ₃₅ is a 5- or 6-membered nitrogen-containing heterocyclic group (including a condensed ring)
Represents, for example, 5-sulfopyridin-2-yl, 5-
And groups such as sulfobenzothiazol-2-yl. When Z ₃₁ represents NR ₄₅ and Z ₃₂ represents NR ₄₆ , R ₄₅
And a 5-membered ring formed by linking R ₃₁ and R ₄₆ and R ₃₄ include, for example, an imidazole ring, a benzimidazole ring, a triazole ring and the like, and a substituent [for example, a carboxylic acid group, a sulfonic acid group, a hydroxyl group, Halogen atom (for example, F, Cl,
Br, etc.), an alkyl group (eg, a methyl group, an ethyl group, etc.), an alkoxy group (eg, a methoxy group, a 4-sulfobutoxy group, etc.). Hereinafter, specific examples of the dye represented by formula (II-c) used in the invention are shown, but the invention is not limited thereto.

[0062]

[Table 6]

[0063]

[Table 7]

The dyes represented by the general formula (II-c) are described, for example, in JP-B-39-22069 and JP-B-43-3504.
No. 2-38056, No. 54-38129, No. 55-1
No. 0059, JP-A-49-99620 and JP-A-59-16.
No. 834 or U.S. Pat. No. 4,181,225. Next, the general formula (II-d) will be described in detail. R
_31, the aliphatic group represented by R _32, R _33, R ₃₄ represents _{R 1, R 2, R 3} , R 4 aliphatic group group having the same meaning as defined in the formula (II-a). The aromatic groups represented by R ₆₁ , R ₆₂ , R ₆₃ , and R ₆₄ are represented by R ₇ , R ₈ ,
And a group having the same meaning as the aromatic group defined for R ₉ and R ₁₀ . R
_61, the heterocyclic group represented by R _62, R _63, R ₆₄ represents _{R 7, R 8, R 9} , heterocyclic group as defined group as defined in R ₁₀ of formula (II-a). Specific examples of the dye represented by formula (II-d) are shown below, but the present invention is not limited thereto.

[0065]

[Table 8]

[0066]

[Table 9]

These dyes are described in US Pat. No. 3,247,
127, 3,469,985, 3,653,9
No. 05, 4,078,933 and the like. Next, the general formula (II-e) will be described in detail. The substituents R ₆₅ , R ₆₆ , R ₆₇ and R ₆₈ of the dye represented by the general formula (II-e) are an alkyl group (for example, methyl, ethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl, methoxyethyl) , 2-chloroethyl, benzyl, 2-sulfobenzyl, 4-sulfophenethyl), an aryl group (phenyl, 4-sulfophenyl, 3-sulfophenyl, 2-sulfophenyl, 4-
Represents carboxyphenyl, 3-carboxyphenyl, 4-hydroxyphenyl) or a heterocyclic residue (eg, 2-pyridyl, 2-imidazolyl). L ₄₁ , L ₄₂ , L
₄₃ represents a methine group, and these methine groups may be independently substituted by methyl, ethyl, phenyl, chlorine atom, sulfoethyl, carboxyethyl and the like. n ₄₁ is 1,
Represents 2, 3. However, any one of R ₆₅ , R ₆₆ , R ₆₇ and R ₆₈ has at least one carboxyl group or sulfo group, and the total is at least two or more. Further, these carboxyl groups and sulfo groups may form salts (for example, Na salts, K salts, ammonium salts) as well as free acids. Next, the dye represented by the general formula (II-
Although the specific example of e) is shown, the present invention is not limited to these.

[0068]

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[0069]

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[0070]

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[0071]

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The compound represented by the general formula (II-e) can be synthesized by various synthetic methods. For example, as shown in the following reaction formula, 1,2-disubstituted-3,5-pyrazolidinedione (A) and (B-1), (B-2), (B-
It can be synthesized by condensing the compound represented by 3), (B-4) or (B-5) in the presence of a base.

[0073]

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[0074]

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In the formula, R ₆₅ , R ₆₆ , R ₆₇ , R ₆₈ , L ₄₁ , L
₄₂ , L ₄₃ and n ₄₁ have the same meanings as above, and Z ₄₁ is a hydrogen atom, a nitro group, a halogen atom (eg, chloro, bromo)
Represents R ₆₉ represents a hydrogen atom, an alkyl group (eg, methyl, ethyl and the like), and a phenyl group. X ₄₁ represents an anion (for example, chloride, bromide, iodide, perchlorate, methyl sulfate, ethyl sulfate, p-toluene sulfonate, etc.). The compound represented by the general formula (A) can be easily synthesized by condensing a 1,2-disubstituted hydrazine with a malonic acid derivative as described in Chemical Abstracts, Vol. 50, 8743e (1956). Can be. Next, the dye represented by formula (III) will be described in detail. Examples of the electron-withdrawing group represented by X and Y include a cyano group, a carboxyl group, an alkylcarbonyl group [C 7
The following are preferred, for example, acetyl and propionyl, which may have a substituent (eg, a halogen atom such as chlorine)], an arylcarbonyl group [the aryl group is preferably a phenyl group or a naphthyl group, and has a substituent. It may be. As the substituent, a sulfo group, a carboxyl group,
Hydroxy group, halogen atom (for example, chlorine, bromine),
Cyano group, alkyl group (eg, methyl, ethyl), alkoxy group (eg, methoxy, ethoxy), carbamoyl group (eg, methylcarbamoyl), sulfamoyl group (eg, ethylsulfamoyl), nitro group, alkylsulfonyl group (eg, methane) Sulfonyl), an arylsulfonyl group (eg, benzenesulfonyl), an amino group (eg, dimethylamino), an acylamino group (eg, acetylamino, trichloroacetylamino), a sulfonamide group (eg, methanesulfonamide), and the like. A carbonyl group (optionally substituted alkoxycarbonyl group, preferably having 7 or less carbon atoms, for example, ethoxycarbonyl, methoxyethoxycarbonyl), an aryloxycarbonyl group (as an aryl group) , Phenyl group and a naphthyl group are preferred, which may have a substituent described in the aryl group), is also a carbamoyl group which is a carbamoyl group (substitution, preferably up to seven carbon atoms,
For example, methylcarbamoyl, phenylcarbamoyl,
3-sulfophenylcarbamoyl), alkylsulfonyl group (optionally substituted alkylsulfonyl group, for example, methanesulfonyl), arylsulfonyl group (optionally substituted arylsulfonyl group, for example, phenylsulfonyl, etc. ), A sulfamoyl group (optionally substituted sulfamoyl group,
For example, methylsulfamoyl, 4-chlorophenylsulfamoyl) can be mentioned. X and Y are linked to form a ring (eg, a pyrazolone ring, a pyrazolotriazole ring, an oxindole ring, an isoxazolone ring, a barbituric acid ring, a thiobarbituric acid ring, an indandione ring, a pyridone ring). May be. Preferred rings are pyrazolone rings. In the general formula (III), R ₄₁ and R ₄₂
Represents a hydrogen atom, a halogen atom (for example, chlorine or bromine),
An alkyl group (optionally substituted alkyl group having 5 or less carbon atoms, for example, methyl and ethyl) and an alkoxy group (optionally substituted alkoxy group having 5 or less carbon atoms, for example, methoxy, ethoxy, -Chloroethoxy), hydroxy group, carboxyl group, substituted amino group (for example, acetylamino, methylamino, diethylamino, methanesulfonylamino), carbamoyl group (optionally substituted carbamoyl group, for example, methylcarbamoyl), sulfamoyl group (Optionally substituted sulfamoyl group, for example, ethylsulfamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl), and a sulfo group. R ₄₃ and R ₄₄ are a hydrogen atom, an alkyl group (an alkyl group which may be substituted, and preferably has 8 or less carbon atoms, for example, methyl, ethyl, propyl, and butyl. As the substituent, a sulfo group, Carboxyl group, halogen atom, hydroxy group, cyano group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, acyloxy group, acylamino group, carbamoyl group, sulfamoyl group, alkylamino group,
Examples thereof include a dialkylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonylamino group, a ureido group, and an aryl group. ), An alkenyl group (optionally substituted alkenyl group, for example, 3-hexenyl), an aryl group (the aryl group is preferably a phenyl group, and has a substituent described in the section of the arylcarbonyl group for X and Y). ), An acyl group (acetyl, benzoyl), a sulfonyl group (eg, methanesulfonyl, phenylsulfonyl), and a 5- to 6-membered heterocyclic ring represented by R ₄₃ and R ₄₄ (eg, a piperidine ring, a morpholine ring, etc.) ) May be formed. R ₄₁ and R ₄₃ , and R ₄₂ and R ₄₄ may be respectively linked to form a 5- to 6-membered heterocycle. At least one of X, Y, R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ has a sulfo group or a carboxyl group. The sulfo group and the carboxyl group may form a free form or a salt form (for example, Na salt, K salt, (C ₂ H ₅ ) ₃ NH salt, pyridinium salt, ammonium salt). L ₁₁ , L
_The methine group represented by ₁₂ or L ₁₃ may have a substituent (eg, methyl, ethyl, cyano, phenyl, chlorine atom, sulfoethyl). k represents 0 or 1. Specific examples of the dye represented by formula (III) used in the present invention are shown below.

[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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The dye represented by formula (III) can be easily synthesized by the method described in JP-A-51-3623 and the like. Next, the dye represented by formula (IV) will be described in detail. The aryl group represented by Ar ₁ and Ar ₂ is preferably a phenyl group or a naphthyl group, and is preferably a substituent [for example, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, and a carbon atom having 1 carbon atom.
To 6 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl), C1-C6 alkoxy groups (e.g., methoxy, ethoxy, butoxy), carbamoyl group, sulfamoyl group, halogen atom (e.g.,
F, Cl, Br), a cyano group, a nitro group, etc.]. The heterocyclic group represented by Ar ₁ and Ar ₂ is 5
Or a 6-membered nitrogen-containing heterocyclic ring is preferable, for example, 1-
(4-sulfophenyl) -3-carboxy-5-hydroxy-4-pyrazolyl, 1- (4-sulfophenyl)-
3-methyl-5-hydroxy-4-pyrazolyl, 1-
(2,5-disulfophenyl) -3-carboxy-5-
Hydroxy-4-pyrazolyl, 1-carboxymethyl-
3-carbamoyl-1,2-dihydro-6-hydroxy-4-methyl-2-oxopyridine, 1- (2-sulfoethyl) -3-cyano-1,2-dihydro-6-hydroxy-4-methyl-2 -Oxopyridine and the like. Specific examples of the dye represented by the general formula (IV) are shown below.

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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The dyes represented by the general formula (IV) are described in British Patent Nos. 575,691, 907,125 and 1,35.
It can be synthesized by the method described in US Pat. Next, specific examples of the dye represented by the general formula (V) are shown.

[0093]

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[0094]

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[0095]

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The dye represented by formula (V) can be synthesized by the method described in US Pat. No. 2,865,752. Next, specific examples of the dye represented by the general formula (VI) are shown.

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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Next, specific examples of the dye represented by the general formula (VII) will be shown.

[0105]

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[0106]

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[0107]

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[0108]

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The photographic emulsion used in the present invention may be spectrally sensitized with other methine dyes and the like together with the methine compound of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes.
That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, an indolenine nucleus, a benzoindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may be substituted on carbon atoms. As a nucleus having a ketomethylene structure, pyrazoline-
5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus, etc.
Six-membered heterocyclic nuclei can be applied. The methine compound of the present invention may be used alone, or a combination thereof, and a combination of sensitizing dyes is often used particularly for supersensitization. A representative example is U.S. Pat.
8,545, 2,977,229, 3,39
7,060, 3,522,052, 3,52
No. 7,641, No. 3,617,293, No. 3,62
8,964, 3,666,480 and 3,67
2,898, 3,679,428 and 3,03
No. 7,377, No. 3,769,301, No. 3,81
4,609, 3,837,862, 4,02
No. 6,707, British Patent 1,344,281,
507, 803, JP-B-43-49336, 53
12, 375, and JP-A Nos. 52-110,618 and 52-109,925.

Along with the methine compound of the present invention, a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. The methine compound of the present invention may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, it is performed after the completion of chemical sensitization but before coating, but U.S. Pat. Nos. 3,628,969 and 4,225.
As described in JP-A-58-113,928, spectral sensitization may be carried out simultaneously with chemical sensitization by adding a chemical sensitizer at the same time as described in JP-A-666. The addition can be made prior to the completion of silver halide grain precipitation, and spectral sensitization can be started before addition. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder may be chemically sensitized. It is also possible to add the silver halide grains at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756.

The methine compound of the present invention can be used in an amount of from 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide, and more preferably from 0.2 to 10 mol of silver halide grains. Approximately 5 × 10 ^-5 to 2 × 10 for 1.2 μm
^-3 moles is more effective.

The dye used in the present invention can be dispersed in an emulsion layer or other hydrophilic colloid layers (intermediate layer, protective layer, antihalation layer, filter layer, etc.) by various known methods. A method in which the dye of the present invention is directly dissolved or dispersed in an emulsion layer or a hydrophilic colloid layer, or a method in which the dye is dissolved or dispersed in an aqueous solution or a solvent and then used in the emulsion layer or the hydrophilic colloid layer. Suitable solvents, for example, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, U.S. Pat.
No. 6,830, it can be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine or the like, or a mixed solvent thereof. A method in which a hydrophilic polymer having a charge opposite to that of a dye ion coexists in a layer as a mordant, and the dye is localized in a specific layer by the interaction with a dye molecule. The polymer mordant is a polymer containing a secondary and tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation group, and a polymer having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. . For example, vinylpyridine polymer and vinylpyridinium cationic polymer described in U.S. Pat. No. 2,548,564; vinylimidazolium cationic polymer disclosed in U.S. Pat. No. 4,124,386; U.S. Pat. No. 3,625,694, which discloses a polymer mordant capable of crosslinking with gelatin and the like disclosed in U.S. Pat.
Aqueous sol mordants disclosed in US Pat. No. 3,898,995 and JP-A-54-115228.
98,088; water-insoluble mordant disclosed in U.S. Pat. No. 4,168,976; reactive mordant capable of forming a covalent bond with the dye disclosed in U.S. Pat. No. 4,168,976; Polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described; products obtained by the reaction of a polyvinylalkyl ketone with aminoguanidine as described in GB 850,281; US Examples thereof include polymers derived from 2-methyl-1-vinylimidazole as described in Japanese Patent No. 3,445,231. A method in which a compound is dissolved using a surfactant. Useful surfactants may be oligomers or polymers.

For details of this polymer, see JP-A-60
No. 158439 (filed by Fuji Photo Film Co., Ltd. on Jan. 26, 1984), pages 19 to 27. In addition, for example, a hydrosol of a lipophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion obtained above.

A method for precipitating the compound of the present invention in the form of a solid fine particle dispersion, and / or a known pulverizing means in the presence of a dispersant, for example, ball milling (ball mill, vibrating ball mill, planetary ball mill, etc.), sand milling ,
It can be formed using a method of forming by colloid milling, jet milling, roller milling, or the like (in which case, a solvent (eg, water, alcohol, or the like) may coexist). Alternatively, after dissolving the compound of the present invention in a suitable solvent, a poor solvent for the compound of the present invention may be added to precipitate microcrystalline powder, in which case a surfactant for dispersion may be used. Good. Alternatively, the compound of the present invention may be first dissolved by controlling the pH, and then the pH may be changed to cause microcrystallization. The microcrystalline particles of the compound of the present invention in the dispersion are fine particles having an average particle diameter of 10 μm or less, more preferably 2 μm or less, particularly preferably 0.5 μm or less, and in some cases 0.1 μm or less. Is more preferred. The silver halide emulsion used in the present invention may have any grain size distribution, but the weight of silver halide contained in a grain size range of ± 20% around the maximum grain size (average) r is as follows. It is preferably at least 60%, more preferably at least 80% of the total silver halide grain weight.

The grain size of the silver halide may be fine grains of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm. The silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0.1 to 30 mol% of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide. Silver halide grains used in the present invention are cubic, octahedral, those having regular crystals such as tetradecahedron, spheres, those having irregular crystal forms such as plate-like, twin planes, etc. Or a composite form thereof. The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643.
(December 1978), pp. 22-23, "I. Emulsion preparation and types", No. 187
16 (November 997), p. 648, ibid., No. 30710
5 (November 1989), pp. 863-865, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P.Gl.
afkides.Chemie et Phisique Photographique, Paul Mo
ntel, 1967), Duffin, Photographic Emulsion Chemistry, Published by Focal Press (GF Duffin, Photographic Emulsion Ch.
emistry, Focal Press, 1966), and `` Manufacture and coating of photographic emulsions '' by Zerikman et al., Published by Focal Press (V.
L. Zelikman et al., Making and Coating Photographic
Emulsion, Focal Press, 1964).

US Pat. Nos. 3,574,628 and 3,574,628
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred. The aspect ratio (equivalent circle diameter of AgX particles / particle thickness) is about 3
Emulsions in which the above AgX grains are present in 50% or more (area) of all AgX grains in the emulsion can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, Photog).
raphicScience and Engineer
ing), Vol. 14, pp. 248-257 (1970);
U.S. Pat. Nos. 4,434,226 and 4,414,31
No. 0, 4,433,048, 4,439,520
And British Patent No. 2,112,157. A silver halide emulsion composed of regular grains is obtained by nucleation and grain growth while maintaining pAg constant and supersaturation by a double jet method so as not to cause renucleation, thereby obtaining grains of a desired size. be able to. Further, the method described in JP-A-54-48521 can be applied. In a preferred embodiment of the method, a potassium iodide-gelatin aqueous solution and an ammonium silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide grains while changing the addition rate as a function of time. At this time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of the addition rate, pH, pAg, temperature and the like. For details, see, for example, Photographic Science and Engineering (Photograph)
ic Science and Engineerine
g), Vol. 6, pp. 159-165 (1962); Journal of Photographic Science (Jou)
rnal of Photographic Scie
nce), 12, 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,4.
No. 13,748. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. These emulsion grains are disclosed in British Patent Nos. 1,027,146, 3,505,068, 4,444,877 and Japanese Patent Application No. 58-248649. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. The silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. A typical example is JP-B-43-13162.
JP-A-61-215540, JP-A-60-222
No. 845, JP-A-61-75337, etc. are core-shell type or double structure type particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions.
In addition, it is not a simple double structure.
Or a multilayer structure having three or more layers as disclosed in the above-mentioned publication, or a silver halide having a different composition can be thinly applied to the surface of a core-shell double-layer structure.

In order to provide a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonded structure can be produced. These examples are disclosed in
JP-133540, JP-A-58-108526, EP
199290A2, JP-B-58-24772, and JP-A-59-16254. The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure. In the case of a junction structure, a combination of silver halides is naturally possible, but a silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, can be combined with silver halide to form a junction structure. A non-silver salt compound such as PbO may be used as long as it can form a junction structure. In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, on the other hand, May have a low silver iodide content and a high shell portion. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. In addition, the boundary portion having a different halogen composition of the grains having these structures may be a clear boundary, or may be an unclear boundary formed by a mixed crystal due to a composition difference. It may have a structural change.

The silver halide emulsion used in the present invention is EP-
No. 0096727B1, EP-0064412B1, etc., to give roundness to particles, or DE-2306647C2, JP-A-60-2213.
The surface may be modified as disclosed in No. 20. The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but an internal latent image type emulsion may be used by selecting a developing solution or development conditions as disclosed in JP-A-59-133542. Can be. Also, JP-A-63
A shallow internal latent image type emulsion covered with a thin shell described in JP-A-264740 is also preferably used. Silver halide solvents are useful to promote ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. It is therefore clear that ripening can be promoted simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, these ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. And a peptizer may be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

As ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. Chemical sensitization is described in THJames, The Photographic Process, 4th Edition, Macmillan, 1977 (THJa
mes, (The Theory of the Photographic Process, 4 th
ed, Macmillan, 1977) using active gelatin as described on pages 67-76, and also by Research Disclosure, Volume 120, April 1974, 1
2008; Research Disclosure, 34 volumes, 1
June 975, 13452, U.S. Pat. No. 2,642,3
No. 61, 3,297,446, 3,772,03
No. 1, 3,857,711, 3,901,714
Nos. 4,266,018 and 3,904,4
No. 15 and pAg 5-10, pH 5-8 and temperature 3 as described in GB 1,315,755.
At 0 to 80 ° C, sulfur, selenium, tellurium, gold, platinum,
It can be carried out using palladium, iridium or a combination of these sensitizers. Chemical sensitization is optimally
In the presence of a gold compound and a thiocyanate compound, a sulfur-containing compound or a hypo- or thiourea-based compound described in U.S. Patent Nos. 3,857,711, 4,266,018 and 4,054,457. And in the presence of a sulfur-containing compound such as a rhodanine compound. Chemical sensitization can also be performed in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyrimidine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid improvers are described in US Pat.
No. 31,038, No. 3,411,914, No. 3,55
No. 4,757, JP-A-58-126526 and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazain Dens, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers, such as 3,3a, 7) tetraazaindenes, pentaazaindenes and the like can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,9
No. 47 and JP-B No. 52-28,660 can be used. The photosensitive material according to the present invention includes:
Although the various additives described above are used, various other additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978) and Item 18716 (November 1979).
), And the relevant locations are summarized in the table below. Type of additive RD17643 RD18716 1 Chemical sensitizer, right column, page 648 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, supersensitizer 23 to 24, right column on page 648 to right column, page 649 4 Brightener 24 Page 5 Antifoggant and safe Page 24 to 25 Page 649 Right column Specifier 6 Light absorber, filter dyeing 25 to 26 Page 649 Right column to 650 page Left column, UV absorber 7 Stain inhibitor 25 Page right Column 650 page left column to right column 8 Dye image stabilizer page 25 9 Hardener 26 page 651 left column 10 Binder 26 same as above 11 Plasticizers and lubricants page 27 650 right column 12 Coating aid, surface activity Page 26-27 page 650 right column 13 static inhibitor page 27 1 same as above

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG. . Examples of the yellow coupler include, for example, U.S. Patent Nos. 3,933,501 and 4,022,620.
No. 4,326,024, No. 4,401,752, Tokubo Sho 58-1
0739, UK Patent Nos. 1,425,020, 1,476,760
And the like are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and are described in US Pat. Nos. 4,310,619 and 4,351,897, and EP 73,739.
No. 636, U.S. Pat.Nos. 3,061,432 and 3,725,067
No., Research Disclosure No. 24220 (June 1984)
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Patent Nos. 4,500,630 and 4,540,654 are particularly preferable. . Cyan couplers include phenolic and naphthol couplers and are described in U.S. Pat.
No. 52,212, No. 4,146,396, No. 4,228,233, No.
No. 4,296,200, No. 2,369,929, No. 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication No. 3,329,729, European Patent No. 12
No. 1,365A, U.S. Pat.Nos. 3,446,622, 4,333,999
No. 4,451,559, No. 4,427,767, European Patent No. 1
Those described in 619, 626A are preferred. Colored couplers for correcting unnecessary absorption of color-forming dyes are described in Research Disclosure No. 17643, Sections VII-G, U.S. Pat.
Preferred are those described in 929, 4,138,258 and British Patent 1,146,368.

As couplers in which a coloring dye has an appropriate diffusivity, US Pat. No. 4,366,237 and British Patent No. 2,12
No. 5,570, European Patent No. 96,570, West German Patent (public) No.
Those described in 3,234,533 are preferred. Typical examples of polymerized dye-forming couplers are described in U.S. Pat.
No. 4,080,211; No. 4,367,282; UK Patent No.
No. 2,102,137. Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers releasing a development inhibitor are described in the aforementioned RD 17643, the patents described in Sections VII-F, JP-A-57-151944, JP-A-57-154234, and JP-A-60-18424.
No. 8, U.S. Pat. No. 4,248,962 is preferred. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and
Preferred are those described in 2,131,188, JP-A-59-157638 and JP-A-59-170840.

Other couplers usable in the light-sensitive material of the present invention include competing couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and
4,338,393, multi-equivalent couplers described in 4,310,618, etc., JP-A-60-185950, DIR redox compounds or DIR coupler releasing couplers or DIR coupler releasing couplers or redoxes described in JP-A-62-24252, etc., EP-A-173,302A, couplers which release dyes that recolor after release, R.I. D. No. 11449, 2424
1, bleach accelerator releasing couplers described in JP-A-61-201247 and the like, ligand releasing couplers described in U.S. Pat. No. 4,553,477 and the like.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1
-Diethylpropyl) phthalate, esters of phosphoric or phosphonic acids (e.g. triphenyl phosphate,
Tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate,
Tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoates (eg, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxy) Benzoates), amides (eg, N, N-diethyldodecamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amyl) Phenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, tri Chi Rushito rate), aniline derivatives (e.g. N, N-dibutyl-2-butoxy-5
tert-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene)
And the like. The auxiliary solvent has a boiling point of about 3
An organic solvent having a temperature of 0 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide. Can be The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) No. 2,541,2.
No. 74 and No. 2,541,230. The present invention can be applied to various photosensitive materials. Color negative film for general use or movie, color reversal film for slide or TV, color paper,
Typical examples include a color positive film and a color reversal paper. Preferred effects can be obtained even when used in black-and-white photographic materials, X-ray materials, and printing materials.

When the present invention is applied to a color photographic material, the present invention can be applied to photographic materials having various structures and photographic materials in which a layer structure and a special color material are combined. A representative example will be described. JP-B-47-49031, JP-B-49-3
No. 843, JP-B-50-21248, JP-A-59-58147, JP-A-59-60437, JP-A-60-227256, JP-A-61-4043
Nos. 4,087,086, 6,086,086, etc., which combine the coupling speed and diffusivity of the color coupler with the layer constitution. JP-B-49-15495, U.S. Pat. No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, JP-B-53-37017, JP-B-53-37018.
JP-A-51-49027, JP-A-52-143016, JP-A
53-97424, JP-A-53-97831, JP-A-62-200350
And Japanese Patent Application Laid-Open No. Sho 59-177551, in which the arrangement of a high-sensitivity layer and a low-sensitivity layer and the arrangement of layers having different color sensitivity are specified.

Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28, and No. 18716
It is described from page 647 right column to page 648 left column. The color photographic light-sensitive material according to the present invention is prepared by using the RD. No.17643
The development can be carried out by a usual method described on pages 28 to 29 and 651 left column to right column of No. 18716. 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 thereof include 3-methyl-4-amino-N, N-diethylaniline and Methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose. Color developing solutions include pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts,
It generally contains a development inhibitor or an antifoggant such as an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids,
Triethylenediamine (1,4-diazabicyclo [2,
Preservatives such as 2,2] octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competitive couplers , A fogging agent such as sodium boron hydride, an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, an aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid, and a phosphonocarboxylic acid. Various chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N,
N-trimethylene phosphonic acid, ethylenediamine-N,
N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples. 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, 2-pyrazolidones such as 1-phenyl-3-pyrazolidone and 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 values of these color developing solution and black and white developing solution
It is generally 9 to 12. The replenishment 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 light-sensitive material. 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. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for the color development processing is usually set to 2 to 5 minutes, but the processing time can be further shortened by using a high temperature and a high pH and using a high concentration of the color developing agent.

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. Examples of the bleaching agent include iron (III), cobalt
(III), compounds of polyvalent metals such as chromium (VI), copper (II),
Peracids, quinones, nitro compounds and the like are used. Typical bleaches include ferricyanide; dichromate; iron
(III) or an organic complex of cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Aminopolycarboxylic acids such as 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates;
Bromate; permanganate; nitrobenzenes and the like can be used. Of these, iron aminopolycarboxylates (I) such as iron (III) complex of ethylenediaminetetraacetate
II) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the iron (III) complex salt of aminopolycarboxylic acid 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 5.5 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 bleach accelerators are described in the following specification: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32,736, JP-A-53-57,8
No. 31, 53-37,418, 53-72,623, 53-95,630
Nos. 53-95,631, 53-104,232, 53-124,424
Compounds having a mercapto group or a disulfide group described in JP-A Nos. 53-141,623, 53-28,426, and Research Disclosure No. 17129 (July 1978);
Thiazolidine derivatives described in JP-A-50-140,129; JP-B-45-8,506; JP-A-52-20,832; JP-A-53-32,735;
Thiourea derivatives described in U.S. Pat. No. 3,706,561; iodide salts described in West German Patent No. 1,127,715, JP-A-58-16,235; polyoxyethylene compounds described in West German Patent Nos. 966,410 and 2,748,430; Polyamine compounds described in JP-B-45-8836;
No. 59,644, No. 53-94,927, No. 54-35,727, No. 55-2
Compounds described in 6,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,290,81
No. 2 and JP-A-53-95630 are preferred.
Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. 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. Examples of the fixing agent include thiosulfate, thiocyanate, thioether-based compounds, thioureas, and a large amount of iodide, but thiosulfate is generally used, and ammonium thiosulfate is most widely used. Can be used for As a preservative of the bleach-fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step can vary widely depending on the characteristics of the photosensitive material (for example, the material used such as a coupler), the application, the temperature of the rinsing water, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Can be set to
Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture an
d Television Engineers Vol. 64, pp. 248-253
(May, 1955). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. It is also possible to use bactericides described in "Sterilization, Sterilization and Antifungal Techniques of Microorganisms" edited by the Society of Sanitary Engineers, and "Encyclopedia of Antifungal and Antifungal Agents" edited by the Japan Society of Antifungals and Fungi. The pH of the washing water in the processing of the photosensitive material of the present invention is 4-9, preferably 5-8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the application, and the like.
Min, preferably in the range of 30-40 seconds at 25-40 ° C. Further, 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 stabilizing treatment, JP-A-57-8,543 and JP-A-58-8543 are used.
The known methods described in JP-A Nos. 14,834 and 60-220,345 can all be used. Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides may 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. The silver halide color 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 various precursors of a color developing agent. US Patent No.
Indoaniline compounds described in No. 3,342,597, No. 3,3
No. 42,599, Schiff base compounds described in Research Disclosure Nos. 14,850 and 15,159, and 13,9
Aldol compounds described in No. 24, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135,628 can be mentioned. The silver halide color 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,
Nos. 57-144,547 and 58-115,438. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to. Also, to save silver on photosensitive materials, West German Patent No. 2,226,7705 or U.S. Pat.
The treatment using cobalt intensification or hydrogen peroxide intensification described in 4,499 may be performed. A complementary silver halide light-sensitive material is disclosed in U.S. Pat.No. 4,500,626, and JP-A-60-1334.
No. 49, No. 59-218443, No. 61-238056, European Patent No. 21
It can be applied to the photothermographic materials described in Japanese Patent No. 0660A2. Examples of the present invention will be described below, but the present invention is not limited thereto.

[0134]

【Example】

Example 1 Preparation of Sample 101 A multilayer color photosensitive material comprising the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye A (see Table 13) 0.1 g

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

Third layer: Intermediate layer A fine-grain silver iodobromide emulsion whose surface and inside are fogged (average particle size 0.06 μm, variation coefficient 18%, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C -3 0.05 g Coupler C-9 0.05 g Compound Cpd-C 10 mg High boiling organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Fifth layer: middle-sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling organic solvent Oil-2 0.1 g Additive P-1 0.1 g

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

Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color-mixing inhibitor Cpd-I 2.6 mg Ultraviolet absorber U-1 0.01 g Ultraviolet absorber U-20. 002 g UV absorber U-5 0.01 g Dye B See Table 13 0.02 g Compound Cpd-C 5 mg Compound Cpd-J 5 g Compound Cpd-K 5 g High boiling organic solvent Oil-1 0.02 g

Eighth Layer: Intermediate Layer A silver iodobromide emulsion having a fogged surface and inside (average particle size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) Silver content 0.02 g Gelatin 1. 0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-4 0.1 g Coupler C-7 0.05g Coupler C-8 0.20g Compound Cpd-B 0.03g Compound Cpd-C 10mg Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd- G 0.02 g High-boiling organic solvent Oil-1 0.1 g High-boiling organic solvent Oil-2 0.1 g

Tenth layer: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g High boiling organic solvent Oil-2 0.01g

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

The twelfth layer: the intermediate layer gelatin 0.6 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Amount of silver 0.07 g Gelatin 1.1 g 0.01 g of color mixing inhibitor Cpd-A 0.01 g of high boiling organic solvent Oil-1 0.01 g Microcrystalline solid of dye E-2 Dispersion 0.05g

Fourteenth layer: Intermediate layer Gelatin 0.6 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g

Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.1 g Emulsion M silver amount 0.4 g gelatin 0.9 g coupler C-5 0.3 g coupler C-6 0.1 g Coupler C-10 0.1 g

17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.3 g Coupler C-6 0.6 g Coupler C-10 0.1 g

18th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g

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

20th layer: 3rd protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μm) 0.1 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size 1. 5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

Further, additives F-1 to F-8 were added to all emulsion layers in addition to the above composition. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol and phenethyl alcohol were added as preservatives and fungicides.

[0156]

[Table 10]

[0157]

[Table 11]

[0158]

[Table 12]

[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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Preparation of Samples 102 to 118 Samples 102 to 118 were prepared by replacing the sensitizing dyes and dyes A to C of Emulsions A to D used in Sample 101 as shown in Table 13. The sample thus obtained was white-exposed through a gray wedge at an exposure time of 1/100 second and an exposure amount of 20 CMS, and then processed by the following processing steps to perform sensitometry. Further, from the magenta density of the stain of the treated sample piece, 1
The residual color was evaluated by subtracting the magenta stain concentration of the 18 (dye blank) samples.

[0189]

[Table 13]

Processing Step Time Temperature First development 6 minutes 38 ° C. Rinse 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color development 6 minutes 38 ° C. Adjustment 2 minutes 38 ° C. Bleaching 6 minutes 38 ° C. Fixing 4 minutes 38 ° C Rinse for 4 minutes 38 ° C Stable 1 minute 25 ° C

The composition of each processing solution was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / monomonosulfonate 20 g Potassium carbonate 33 g 1-phenyl-4-methyl-4-hydroxy Methyl-3-pyrazodone 2.0 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Water was added to the mixture, and the mixture was adjusted to pH 1000 with hydrochloric acid or potassium hydroxide.

[Inversion liquid] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g Sodium hydroxide 8 g Ice Acetic acid 15 ml Water was added and 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or potassium hydroxide.

[Color developing solution] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate / 12 hydrate 36 g Potassium bromide 1.0 g Iodide Potassium 90 mg Sodium hydroxide 3.0 g Citrazinic acid 1.5 g N-ethyl- (β-methanesulfonamidoethyl) 3-methyl-4-aminoaniline sulfate 11 g 3,6-Dithiaoctane-1,8-diol 1.0 g Water was added and 1000 ml pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide.

[Adjustment Solution] Ethylenetriaminetetraacetic acid disodium salt dihydrate 8.0 g sodium sulfite 12 g 1-thioglycerin 0.4 ml Add water 1000 ml pH 6.20 Adjust pH with hydrochloric acid or sodium hydroxide did.

[Bleach] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium ammonium dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water is added to 1000 ml, pH 5 The .70 pH was adjusted with hydrochloric acid or sodium hydroxide.

[Fixing solution] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to the mixture, and the pH was adjusted to 1000 ml with hydrochloric acid or aqueous ammonia.

[Stabilizing Solution] Formalin (37%) 5.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.5 ml 1000 ml by adding water without pH adjustment Sensitometry in Table A below , And evaluation results of residual color. The RL relative sensitivity was compared based on the relative exposure from the minimum density to the density increased by 1.0.

[0198]

[Table 14]

As is evident from the results in Table A, the use of the methine compound and the water-soluble dye of the present invention makes it possible to obtain a light-sensitive material having less residual color and high sensitivity.

Example 2 Preparation of Sample 201 A color photographic light-sensitive material was prepared by coating the following first to twelfth layers on a paper support laminated on both sides with polyethylene. 15% by weight on the side coated with the first layer of polyethylene
Of anatase type titanium oxide as a white pigment and a trace amount of ultramarine blue as a bluish dye. (Photosensitive layer composition) The components and the coating amounts in g / m ² are shown below. For silver halide, the coating amount is shown in terms of silver. First layer (gelatin layer) Gelatin 1.30 Second layer (antihalation layer) Black colloidal silver 0.10 Gelatin 0.70 Third layer (low-sensitivity red-sensitive layer) Red increase Silver chloroiodobromide spectrally sensitized with dye D (silver chloride 1 mol%, silver iodide 4 mol%, average grain size 0.3 μ, grain size distribution 10%, cubic, core iodine type core shell) 0.06 Silver iodobromide spectrally sensitized with red sensitizing dye F (silver iodide 4 mol%, average grain size 0.5 μ, grain size distribution 15%, cubic) 0.10 Gelatin ... 1.00 Cyan coupler (ExC-1) 0.14 Cyan coupler (ExC-2) 0.07 Anti-fading agent (Cpd-2, 3, 4 equivalents) ... 0.12 Coupler dispersion medium (Cpd-6) ... 0.03 Coupler dissolution Medium (Solv-1, 2, 3 equivalents) 0.06 Development accelerator (Cpd-13) 0.05 Fourth layer (highly sensitive red-sensitive layer) Spectral sensitized with red sensitizing dye F Silver iodobromide felt (silver iodide 6 mol%, average grain size 0.8 μ, grain size distribution 20%, tabular (aspect ratio = 8, core iodine)) 0.15 gelatin 1.00 Cyan coupler (ExC-1) 0.20 Cyan coupler (ExC-2) 0.10 Anti-fading agent (Cpd-2, 3, 4 equivalents) 0.15 Coupler Dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.10

Fifth Layer (Intermediate Layer) Magenta Colloidal Silver 0.02 Gelatin 1.00 1.00 Color Mixing Inhibitor (Cpd-7, 16) 0.08 Color Mixing Inhibitor Solvent (Solv-4) 5) 0.16 polymer latex (Cpd-8) 0.10 6th layer (low-sensitivity green-sensitive layer) Salt spectrally sensitized with green sensitizing dye (ExS-3, 4) Silver iodobromide (1 mol% of silver chloride, 2.5 mol% of silver iodide, average grain size 0.28 μ, grain size distribution 8%, cubic, core iodine type core-shell) 0.04 Green sensitization Silver iodobromide (2.5 mol% silver iodide, average grain size 0.48 μm, grain size distribution 12%, cubic) spectrally sensitized with the dye (ExS-3, 4) 0.06 Gelatin 0.80 Magenta coupler (ExM-1, 2 equivalents) 0.10 Anti-fading agent (Cpd-9) 0.10 Stain inhibitor (Cpd-10, 11 equivalents) 0.01 Stain inhibitor (Cpd-5) 0.001 Stain inhibitor ( Cpd-12) 0.01 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6) 0.15 7th layer (highly sensitive green sensitive layer) Green Silver iodobromide (3.5 mol% silver iodide, average grain size 1.0 μm, grain size distribution 21%, tabular (aspect ratio = 9) spectrally sensitized with a sensitizing dye (ExS-3, 4) 0.10 Gelatin .... 0.80 Magenta coupler (ExM-1, 2 equivalents) ... 0.10 Anti-fading agent (Cpd-9) ... 10 Anti-stain agent (Cpd-10, 11, 22 equivalents) ... 0.01 Stain Inhibitor (Cpd-5) 0.001 Stain inhibitor (Cpd-12) 0.01 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6) 0.15 Eighth layer (yellow filter layer) Yellow colloidal silver 0.20 Gelatin 1.00 1.00 Color-mixing inhibitor (Cpd-7) 0.06 Color-mixing inhibitor solvent (Solv) -4, 5) 0.15 Polymer latex (Cpd-8) 0.10 Ninth layer (low-sensitivity blue-sensitive layer) Spectral sensitized by blue sensitizing dye (ExS-5, 6) Silver chloroiodobromide (2 mol% silver chloride / 2.5 mol% silver iodide, average grain size 0.38 μ, grain size distribution 8%, cubic, core iodine type core-shell) 0.07 Iodobromination spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (2.5 mol% silver iodide, average grain size 0.55 μ, grain size distribution 11%, cubic)… 0.10 Gelatin… 0.50 Yellow coupler (ExY-1, 2 equivalents) 0.20 Stain inhibitor (Cpd-5) 0.001 Anti-fading agent (Cpd-14) 0.10 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.05

Tenth Layer (High Sensitive Blue Sensitive Layer) Silver iodobromide (2.5 mol% silver iodide, average grain size: 1) spectrally sensitized with a blue sensitizing dye (ExS-5, 6). 4 μ, particle size distribution 21%, flat plate (aspect ratio = 14)) 0.25 gelatin 1.00 yellow coupler (ExY-1, 2 equivalents) 0.40 stain inhibitor ( Cpd-5) 0.002 Anti-fading agent (Cpd-14) 0.10 Coupler dispersion medium (Cpd-6) 0.15 Coupler solvent (Solv-2) 0. 10 Eleventh layer (ultraviolet absorbing layer) Gelatin 1.50 Ultraviolet absorbing agent (Cpd-1, 2, 4, 15 equivalents) 1.00 Color mixing inhibitor (Cpd-7, 16) ... ... 0.06 Dispersion medium (Cpd-6) Ultraviolet absorber solvent (Solv-1, 0.15 Anti-irradiation dyes A and B 0.02 Anti-irradiation dyes C and D 0.02 12th layer (protective layer) Fine grain silver chlorobromide (97 mol of silver chloride) %, Average size 0.2 μ) ...... 0.07 Modified poval ...... 0.02 Gelatin ...... 1.50 Gelatin hardener (H-1, 2 equivalents) ...... 0.17 Alkanol XC as emulsifying and dispersing aid
(Dupont) and sodium alkylbenzenesulfonate as succinic acid ester and Magefa
c F-120 (manufactured by Dainippon Ink) was used. In the layer containing silver halide or colloidal silver, (C
pd-21, 22, 23). The compounds used in the examples are shown below.

[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

[Table 15]

After exchanging the sensitizing dye F and the anti-irradiation dye of the sample 201 as shown in Table B and performing white wedge exposure, the following treatment was carried out and the same evaluation as in Example 1 was performed. As a result, it was found that the same effect as in Example 1 was obtained. <Processing step> First development (black and white development) 38 ° C 75 seconds water washing 38 ° C 90 seconds reversal exposure 100 lux or more 60 seconds or more color development 38 ° C 135 seconds water washing 38 ° C 45 seconds bleach-fixing 38 ° C 120 seconds water washing 38 ° C 135 seconds drying <Processing solution composition> (First developer) Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 0.6 g Diethylenetriaminepentaacetic acid pentasodium salt 4.0 g Potassium sulfite 30.0 g Thiocyan Potassium acid salt 1.2 g Potassium carbonate 35.0 g Hydroquinone monosulfonate / potassium salt 25.0 g Diethylene glycol 15.0 ml 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0 g Potassium bromide 0.5 g Iodine 5.0 mg of potassium iodide and 1 liter of water (pH 9.70) (color developer) Zyl alcohol 15.0 ml Diethylene glycol 12.0 ml 3,6-Dithia-1,8-octanediol 0.2 g Nitrilo-N, N, N-trimethylenephosphonic acid / pentasodium salt 0.5 g Diethylenetriaminepentaacetic acid / pentasodium salt 2.0 g sodium sulfite 2.0 g potassium carbonate 25.0 g hydroxylamine sulfate 3.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g odor Potassium iodide 0.5 g Potassium iodide 1.0 mg Add water to 1 liter (pH 10.40) (Bleach-fixing solution) 2-mercapto-1,3,4-triazole 1.0 g Ethylenediaminetetraacetic acid disodium diethanol Water salt 5.0 g ethylenediaminetetraacetic acid / Fe (III) / ammonium monohydrate 80.0 g sulfite Sodium 15.0g sodium thiosulfate (700 g / l solution) 160.0 mL glacial acetic acid 5.0ml Water to make 1 liter (pH 6.50)

Continuation of the front page (56) References JP-A-47-3028 (JP, A) JP-A-52-16222 (JP, A) JP-A-47-12277 (JP, A) JP-A-3-223745 (JP) JP-A-3-131846 (JP, A) JP-A-1-189649 (JP, A) JP-B-48-21564 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB G03C 1/14 G03C 1/83

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one methine compound represented by the following general formula (I) and at least one water-soluble dye. General formula (I) In the formula, R ¹ represents — (CH ₂ ) _r —CONHSO ₂ —R ³ ,
_{- (CH 2) s -SO 2} NHCO-R 4, - (CH 2)
_t ^{-CONHCO-R 5} or _{-CH 2)} u -SO 2,
NHSO represents a ₂ -R ^6. Where R ³ , R ⁴ , R ⁵ ,
Or, R ⁶ represents an alkyl group, an alkoxy group, or an amino group, and r, s, t, or u represents an integer of 1 to 5. R ² is a 2-sulfoethyl group, 3-sulfop
Ropyl group, 4-sulfobutyl group, or 3-sulfobutyl
Represents a group . Z ¹ and Z ² are each benzothiazole
Represents a group of nonmetallic atoms necessary for forming a nucleus or a benzoselenazole nucleus , and p and q represent 0 or 1. L ₁ , L ₂ , or L ₃ represents a methine group, and m represents 0, 1 or 2. X ₁ represents an anion;
Represents the number necessary to adjust the charge in the molecule to zero.