JPH05249598A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce residual dye stains, to improve color image fastness, and to enhance sensitivity by incorporating a silver halide photographic emulsion sensitized with a specified compound and a specified cyan dye-forming coupler in a layer constituting the silver halide color photographic sensitive material. CONSTITUTION:One layer constituting the photosensitive material contains the silver halide photographic emulsion spectrally sensitized with a methine compound of formula I and the cyan dye-forming coupler represented by formula II or III. In formulae I-III, each of R<1> and R<2> is -(CH2)r-CONHSO2-R<3> or the like; R<3> is alkyl or the like; (r) is an integer of 1-5; each of Z<1> and Z<2> is a nonmetallic atomic group; each of (p) and (q) is 0 or 1; each of L1-L3 is methine; m is 0, 1, or 2; X1 is an anion; (k) is a number for balancing electric charge in the molecule; each of R<7> and R<8> is an aliphatic group; R<9> is H, halogen, or the like; and each of Z<3> and X2 and X3 is H or a group releasable by reaction or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material which has improved residual color upon development and color image fastness.

[0002]

2. Description of the Related Art In recent years, silver halide color photographic light-sensitive materials are required not only to have high sensitivity and high image quality, but also to have image storability. Has become the most important issue in the industry.

From this point of view, the cyan coupler conventionally used in US Pat. No. 2,367,5 has been used.
The 2-acylaminophenol cyan couplers described in Nos. 31 and 2,423,730 are generally inferior in light and heat fastness, and are also disclosed in U.S. Pat. No. 3,772,002 and JP-A-61-3142. Although the 2-acylaminophenol cyan couplers described in JP-A No. 61-9653 are improved in color image fastness than the above-mentioned cyan couplers, they cannot be said to be sufficient, and the coloring hues are high. Had a drawback that the side absorption on the short wave side was large.

On the other hand, JP-A-60-37448 and JP-A-6-37448.
The 5-position-substituted naphthol cyan couplers and polymer couplers thereof described in JP-A No. 1-153640 and JP-A No. 61-145557 have excellent light and heat fastness, but like the above-mentioned couplers, have a coloring hue. It has the drawbacks that the secondary absorption on the short-wave side is extremely large and that the generation of yellow stain during light irradiation is extremely large.

As a cyan coupler having improved color image fastness and color hue, for example, US Pat.
No. 286, No. 4,333, 999, No. 4,32
No. 7,173, European Patent No. 0399183A1, JP-A Nos. 63-75748, 63-89852 and 63-98661, and diacylamino cyan couplers described in U.S. Pat. No. 3,446,622. No. 3, No. 3,996,253, No. 3,758,308,
No. 3,880,661 and JP-A-56-6513.
No. 4, a cyan coupler having a ureido connection, and US Pat. No. 4,430,423 and JP-A-64
A cyan coupler having a condensed ring structure described in JP-A-326261 is known.

As a result of investigations by the present inventors for the purpose of obtaining a photographic light-sensitive material having high color image fastness, it is possible to obtain a photographic light-sensitive material excellent in color image fastness by using the cyan coupler. Although it was possible, it became clear that the sensitizing dye in the photographic light-sensitive material did not elute during processing and remained colored, that is, the so-called residual color was significantly deteriorated.

In order to achieve both residual color and color image fastness,
The combination of a cyan coupler having a high color image fastness and a sensitizing dye having an improved residual color can be easily analogized. For example, JP-A-1-147451 known as a sensitizing dye having a small residual color has been known so far. JP-A-61-294429
No. 4, Japanese Patent Publication No. 32749/1985, Japanese Patent Laid-Open No. 61-7784.
When the one having a hydrophilic substituent such as a sulfamoyl group or a carbamoyl group disclosed in No. 3 is used, if the hydrophilicity of the sensitizing dye is increased, the adsorptivity is generally lowered, so that the residual color is improved. However, desensitization due to desorption of the sensitizing dye was likely to occur, and sufficient performance could not be exhibited. Further, the sensitizing dyes described in U.S. Pat. No. 3,282,933 also have the effect of improving residual color, but the spectral sensitizing effect is low, and sufficient effects cannot be obtained in terms of achieving both residual color and sensitivity. ..

As described above, a photographic light-sensitive material satisfying all of color image fastness, residual color, and sensitivity cannot be obtained by simply combining the conventional techniques, and the technique has been eagerly awaited.

[0009]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide color photographic light-sensitive material having improved sensitivity in residual color and color image fastness during development processing.

[0010]

The above object of the present invention is, in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one layer constituting the light-sensitive material is A cyan dye containing a silver halide photographic emulsion spectrally sensitized with at least one methine compound represented by the general formula (1) and having at least one layer represented by the following general formula (2) or (3). It has been made clear that this is achieved by a silver halide color photographic light-sensitive material characterized by containing at least one forming coupler.

General formula (1)

[0012]

[Chemical 4] In the formula, R ¹ is — (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
Representing a 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 has the same meaning as R ¹ or represents an alkyl group.
Z ¹ and Z ² represent a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle, and p and q represent 0 or 1. L ₁ , L ₂ and L ₃ represent a methine group, and m represents 0, 1 or 2. X ₁ represents an anion, and k represents the number necessary for adjusting the charge in the molecule to zero.

[0013]

[Chemical 5]

[0014]

[Chemical 6] In the formula, R ⁷ represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R ⁸ represents an aliphatic group,
It represents an aromatic group or a heterocyclic group, and R ⁹ represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, an acylamino group or an aliphatic oxy group. R ⁸ and R ⁹ are bonded to each other and are 5 to 7
A member ring may be formed. Z ³ represents a hydrogen atom or a group or atom capable of splitting off upon reaction with an oxidized product of a developing agent. X ₂ and X ₃ each represent a hydrogen atom or a halogen atom.

The methine compound of the general formula (1) 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 methyl, ethyl, hydroxyalkyl or amino. It is ethyl. R ³ ,
The alkoxy group represented by R ⁴ , R ⁵ or R ⁶ may be substituted, preferably has 4 or less carbon atoms, and particularly preferably methoxy, ethoxy, methoxyethoxy,
Or hydroxyethoxy. R ³ , R ⁴ , R ⁵ ,
Alternatively, the amino group represented by R ⁶ may be substituted with an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or the like. These substituents may form a ring among the substituents, and preferably have 8 or less carbon atoms. R ³ ,
Particularly preferred as the amino group represented by R ⁴ , R ⁵ or R ⁶ is methylamino, dimethylamino, ethylamino, diethylamino, hydroxyethylamino, morpholino or pyrrolidino. The alkyl group represented by R ² may be substituted, preferably has 5 or less carbon atoms, and particularly preferably 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, or 3-sulfobutyl. r, s, t, and u are preferably 1,
2 or 3.

The 5- or 6-membered heterocyclic nucleus formed by the group of non-metal atoms represented by Z ¹ and Z ² is a thiazole nucleus {thiazole nucleus (eg thiazole, 4-methylthiazole, 4-phenylthiazole, 4 , 5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6
-Chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenyl Benzothiazole, 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-methylbenzothiazole, tetrahydroxybenzothiazole, 4-phenylbenzo Thiazole),
Naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,
2-d] thiazole, 7-ethoxynaphtho [2,1-
d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole)}, a thiazoline nucleus (for example, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), Oxazole nucleus {Oxazole nucleus (for example, oxazole, 4-methyloxazole, 4-nitroxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (for example, benzo Oxazole, 5
-Chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5 -Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6
-Hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2- d] oxazole, naphtho [2,
3-d] oxazole, 5-nitronaphtho [2,1-
d] oxazole)}, an oxazoline nucleus (for example, 4,
4-dimethyloxazoline), selenazole nucleus (selenazole nucleus (eg, 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus (eg, benzoselenazole, 5-chlorobenzoselenazole) , 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole,
5-chloro-6-nitrobenzoselenazole, 5,6-
Dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-methylselenazoline), tellurazole Nuclei {terrazole nuclei (eg, tellurazole,
4-methylterrazole, 4-phenylterrazole), a benzoterrazole nucleus (for example, benzoterrazole, 5-chlorobenzoterrazole, 5-methylbenzoterrazole, 5,6-dimethylbezoterrazole,
6-methoxybenzoterrazole), naphthoterrazole nucleus (for example, naphtho [2,1-d] telrazole, naphtho [1,2-d] telrazole)}, tellurazoline nucleus (for example, tellrazoline, 4-methylterrazoline) ,
3,3-dialkylindolenine nuclei (eg 3,3-
Dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,
3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5-nitroindolenine, 3,3-dimethyl-5
-Methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus {imidazole nucleus (eg 1-
Alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nuclei (eg 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1
-Alkyl-5,6-dichlorobenzimidazole, 1
-Alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5
-Trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-
Alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-
5-chlorobenzimidazole, 1-aryl-5,6
-Dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthoimidazole nucleus (e.g. alkylnaphtho [1,2-d] imidazole, 1-
Arylnaphtho [1,2-d] imidazole). The above-mentioned alkyl group has 1 to 8 carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl or a hydroxyalkyl group (for example, 2-alkyl group).
Hydroxyethyl, 3-hydroxypropyl) are preferred. Particularly preferred are methyl and ethyl. The aforementioned aryl group represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. },
Pyridine nuclei (eg 2-pyridine, 4-pyridine, 5
-Methyl-2-pyridine, 3-methyl-4-pyridine), quinoline nucleus {quinoline nucleus (eg, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-) Quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-
2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4
-Quinoline, 6-nitro-4-quinoline, 8-chloro-
4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-
Methyl-4-quinoline, 6-methoxy-4-quinoline,
6-chloro-4-quinoline), isoquinoline nucleus (eg, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] Quinoxaline nuclei (eg 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5]
-B] quinoxaline), an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus.

Among these heterocyclic nuclei, preferred are thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, quinoline nucleus, Most preferably, it is a benzothiazole nucleus, a benzoselenazole nucleus, or a quinoline nucleus.

The methine group represented by L ₁ , L ₂ and L ₃ may be substituted, and as the substituent, an optionally substituted alkyl group (eg, methyl, ethyl, 2-carboxyethyl) or substituted. Optionally aryl group (eg phenyl, o-carboxyphenyl), halogen atom (eg chlorine, bromine), alkoxy group (eg methoxy, ethoxy), alkylthio group (eg methylthio group, ethylthio group) and the like, and others It may form a ring with the methine group, or may form a ring with the auxochrome. The anion represented by X ₁ is an anion of an inorganic acid or an organic acid (for example, chloride, bromide, iodide, p-toluenesulfonate, naphthalenedisulfonate, methanesulfonate, methylsulfate, ethylsulfate, perchlorate, etc.). Can be mentioned.

It is preferable that m is 0 or 1.

Specific examples of the methine compound represented by the general formula (1) are shown below, but the scope of the present invention is not limited thereto.

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical formula 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14] Next, the coupler represented by formula (2) or (3) will be described in detail below.

In the general formulas (2) and (3), the term "aliphatic group" means a linear, branched or cyclic aliphatic hydrocarbon group, which may be a saturated or unsaturated alkyl, alkenyl or alkynyl group. It is meant to include things. Typical examples are methyl, ethyl, butyl, dodecyl, octadecyl, eicosenyl, iso-propyl, tert.
-Butyl, tert-octyl, tert-dodecyl,
Cyclohexyl, cyclopentyl, allyl, vinyl, 2
-Hexadecenyl, propargyl, etc.

R ^{7 in the} general formula (2) is preferably an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms (eg phenyl, naphthyl), a heterocyclic group (eg, 3-pyridyl, 2-furyl) or an aromatic or heterocyclic amino group (for example, anilino, naphthylamino, 2-benzothiazolylamino, 2-pyridylamino), and these groups further include an alkyl group, Aryl group, heterocyclic group, alkoxy group (eg, methoxy,
2-methoxyethoxy), an aryloxy group (for example,
2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy), alkenyloxy group (for example, 2-propenyloxy), acyl group (for example, acetyl, benzoyl), ester group (for example,
Butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), amide group (eg acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide, butylsulfamoyl), sulfamide group (eg dipropyls) Rufamoylamino),
Imido group (eg, succinimide, hydantoinyl), ureido group (eg, phenylureido, dimethylureido), aliphatic or aromatic sulfonyl group (eg, methanesulfonyl, phenylsulfonyl), aliphatic or aromatic thio group (eg, ethylthio) , Phenylthio), hydroxyl group, cyano group, carboxy group,
It may be substituted with a group selected from a nitro group, a sulfo group, a halogen atom and the like.

The coupler represented by the general formula (2) has R
⁷ may form a dimer or multimer.

In the general formula (2), preferred R ⁷ is a halogen-substituted alkyl group, an aromatic group which may be substituted,
And a substituted aromatic amino group.

In the general formulas (2) and (3), R ⁸
Is preferably an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms, or a heterocyclic group, and these are R
^It may have a substituent allowed in ⁷ .

In the general formulas (2) and (3), R ⁹
Is a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine), an aliphatic group, an aromatic group, an acylamino group (eg,
Acetylamino, benzoylamino), an aliphatic oxy group (eg, methoxy, butoxy), an aromatic oxy group (eg, phenoxy), of which the substitutable group has a substituent acceptable for R ^7. You may have.

In the general formulas (2) and (3), Z ³
Represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (eg, fluorine, chlorine, bromine), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypurpyroxy, methyl). Sulfonylethoxy), an aryloxy group (for example, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), an acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), a sulfonyloxy group (for example, methanesulfonyl) Oxy, toluenesulfonyloxy), amide group (eg, dichloroacetylamino, heptafluorobutyrylamino, methanesulfonylamino, toluenesulfonylamino), alkoxycarbonyloxy group (eg, ethone) Sicarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy), aliphatic or aromatic thio group (eg, ethylthio, phenylthio, tetrazolylthio), imide group (eg, succinimide, hydantoinyl), There are aromatic azo groups (eg, phenylazo). These leaving groups may include photographically useful groups.

In the general formulas (2) and (3), R ⁸
And R ⁹ may form a ring, in which case a 5-membered ring and a 6-membered ring are preferable, and a 5-membered ring is most preferable. When R ⁸ and R ⁹ form a ring, R ⁷ is preferably an optionally substituted phenyl group.

In formulas (2) and (3), Z ³ is preferably a hydrogen atom, a halogen atom, an alkyloxy group or an aryloxy group.

In the general formula (3), X ² and X ³ represent a hydrogen atom or a halogen atom, and a fluorine atom is particularly preferable.

N represents an integer of 0 to 18, preferably 0 to 6, and most preferably 2 to 6.

Specific examples of the cyan coupler represented by the general formula (2) or (3) are shown below, but the invention is not limited thereto.

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

[0051]

[Chemical formula 24]

[0052]

[Chemical 25]

[0053]

[Chemical formula 26]

[0054]

[Chemical 27]

[0055]

[Chemical 28]

[0056]

[Chemical 29]

[0057]

[Chemical 30]

[0058]

[Chemical 31]

[0059]

[Chemical 32]

[0060]

[Chemical 33]

[0061]

[Chemical 34]

[0062]

[Chemical 35]

[0063]

[Chemical 36]

[0064]

[Chemical 37]

[0065]

[Chemical 38]

[0066]

[Chemical Formula 39]

[0067]

[Chemical 40] The addition amount of the cyan coupler represented by the general formula (2) or (3) used in the present invention to the light-sensitive material is 1
It is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mol, and particularly preferably 1 × 10 ⁻⁶ to 5 × 10 ⁻² mol per m ² . The cyan coupler represented by formula (2) or (3) used in the present invention can be added to all layers of the light-sensitive material, but is preferably added to the light-sensitive emulsion layer. Particularly, it is more preferable to add it to the red-sensitive emulsion layer.

The photographic emulsion used in the present invention may be spectrally sensitized with other methine dyes and the like together with the compound represented by the general formula (1). The 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 normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
A tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzoindolenine nucleus, an indole nucleus, Benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5-6 membered heterocyclic nucleus, such as a dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, can be applied.

The compound represented by the general formula (1) may be used alone, or a combination of the compound represented by the general formula (1) and another sensitizer may be used. Combinations of dyes are often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,03,377, 3,76
9,301, 3,814,609, 3,83
7,862, 4,026,707, British Patent 1,
No. 344, 281, No. 1,507, 803, Japanese Patent Publication No. 4
3-49336, 53-12,375, JP-A-5
2-110,618 and 52-109,925.

In addition to the compound represented by the above general formula (1), a dye that does not have a spectral sensitizing action by itself or a substance that does not substantially absorb visible light and that exhibits supersensitization is emulsion. May be included in.

The compound represented by the general formula (1) may be added to the emulsion at any stage during the preparation of the emulsion which has been known to be useful so far. Most commonly, it is done after the completion of chemical sensitization and before coating, but U.S. Pat. Nos. 3,628,969, and 4,
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-58-113,928. It can be carried out prior to chemical sensitization, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, US Pat. No. 4,225,66
It is also possible to add these said compounds separately as taught in No. 6, ie to add some of these compounds prior to chemical sensitization and the rest after chemical sensitization. At any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756.

The addition amount is 4 × per mol of silver halide.
Although 10 ⁻⁶ to 8 × 10 ⁻³ mol can be used, in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is.

The silver halide emulsion used in the present invention may have any grain size distribution, but the maximum grain size (average)
The weight of silver halide contained within a grain size range of ± 20% centered on r is preferably 60% or more, and more preferably 80% or more of the total weight of silver halide grains.

The grain size of the silver halide may be fine grains of 0.1 micron or less, or large grains having a projected area diameter of up to 10 microns.

The silver halide used in the present invention is 0.1
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing ˜30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

The silver halide grains used in the present invention have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ", ibid. No. 18716.
(November 1979), p.648, ibid. 307105
(November 1989), pp. 863-865, "The Physics and Chemistry of Photography" by Grafkeide, published by Paul Montell (PG).
rafkides, Chemie et Phisiq
ue Photographique, Paul Mo
Ntel, 1967), "Photoemulsion Chemistry" by Duffin,
Published by Focal Press, Inc. (GF Duffin, Pho
tographic Emulsion Chemis
try, Focal Press, 1966), and Zelikmann et al., "Production and Coating of Photographic Emulsions", published by Focal Press, Inc. (VL Zelikman et al.,).
Making and Coating Photog
radical Emulsion, Focal Pre
ss, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent No. 1,413,748.
The monodisperse emulsions described in JP-A No. 1994-1999 are also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photographi
c Science and Engineererin
g), Vol. 14, pp. 248-257 (1970), U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, and the like.

A silver halide emulsion composed of regular grains can be formed into a desired size by nucleation and grain growth while maintaining a pAg constant and a supersaturation degree that does not cause re-nucleation by the double jet method. Particles can be obtained.

Further, the method described in JP-A-54-48521 can be applied. In the method, a preferred embodiment is a method in which a potassium iodide-gelatin aqueous solution and an ammonium-based 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 addition rate, pH, pAg, temperature and the like. For details, see, for example, Photographic Science and Engineering (P
photographic Science and E
Volume, 159-165 (1962); Journal of Photographic Science (Journal of Photogr.
apic Science), 12 volumes, 242-25
1 (1964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146 and British Patent No. 3,505,068.
No. 4,444,877 and JP-A-60-143.
No. 331 and the like. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in its grains. The typical one is Japanese Patent Publication No. 43-1316.
2, JP-A-61-215540, and JP-A-60-22.
No. 2845, JP-A No. 61-75337 and the like are core-shell type or double type type grains having a halogen composition in which the inside and the surface layer of the grains are different.

Further, it is not a simple double structure, but is disclosed in JP-A-60-
It is possible to form a triple structure as disclosed in No. 222844 or to form a multilayer structure of more than that, or to thin the silver halide having a different composition on the surface of the grain of the core-shell double structure.

In order to give a structure to the inside of the particle, not only the wrapping structure as described above, but also a particle having a so-called bond structure can be prepared. Examples of these are JP-A-5
9-133540, JP-A-58-108526, E
P199290A2, JP-B-58-24772, and JP-A-59-16254. The crystal to be bonded can be generated by bonding to the edge, corner, or surface of the host crystal with a composition different from that of the host crystal. Such a bonded crystal has a uniform core composition even if the host crystal has a uniform halogen composition.
It can be formed even if it has a shell type structure.

In the case of a junction structure, it is naturally possible to combine silver halides with each other, but a silver salt compound having a non-rock salt structure such as silver rhodan or silver carbonate may be combined with silver halide to form a junction structure. In addition, a non-silver salt compound such as PbO may be used as long as a junction structure is possible.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core portion has a high silver iodide content and the shell portion has a low silver iodide content, Conversely, grains having a low silver iodide content in the core portion and a high shell portion may be used. Similarly, with regard to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and the silver iodide content in the junction crystal being relatively low, or vice versa.

The boundary portion having different halogen compositions of the grains having these structures may be a clear boundary or an unclear boundary by forming a mixed crystal due to a difference in composition. It may be one with continuous structural changes.

The silver halide emulsion used in the present invention is EP-
Treatment for rounding particles as disclosed in 0096727B1, EP-0064412B1, etc., or DE-2306447C2, JP-A-60-2213.
Surface modification as disclosed in No. 20 may be performed.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but as disclosed in JP-A-59-133542, an internal latent image type emulsion can be prepared by selecting a developing solution or developing conditions. Can also be used. Further, a shallow internal latent image type emulsion covered with a thin shell described in JP-A-63-264740 is also preferably used.

Silver halide solvents are useful in promoting ripening. For example, it is known to have an excess of halogen ions present in the reactor to accelerate aging. Therefore, it is clear that mere introduction of a halide salt solution into the reactor can accelerate aging. Other ripening agents can be used, and the total amount of these ripening agents can be added to the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. It is also possible to add a halide salt, a silver salt or a deflocculant, and to introduce them into the reactor. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As the 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.

In the present invention, it is extremely important to carry out chemical sensitization represented by sulfur sensitization and gold sensitization. The photographic properties of particles doped with 1 × 10 ⁻⁴ mol / mol Ag or more of polyvalent metal ions have no characteristic in the unripened state, and a remarkable effect is exhibited when chemically sensitized. The location of chemical sensitization varies depending on the composition, structure and shape of the emulsion grains and the intended use of the emulsion. There is a case where a chemical sensitized nucleus is embedded inside the grain, a case where it is embedded at a shallow position from the grain surface, or a chemical sensitized nucleus is formed on the surface. The effect of the present invention is effective in any case, but it is particularly preferable to form a chemically sensitized nucleus near the surface.
That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

Chemical sensitization is carried out by James (TH Jam
es), The Photographic Process, 4th
Edition, published by MacMillan, 1977, (TH Jame
s, The Theory of the Photo
graphic Process, 4th ed, Ma
cmillan, 1977) 67-76, and may be carried out using active gelatin, and Research Disclosure, 120, April 1974, 12008; Research Disclosure, 3;
Volume 4, June 1975, 13452, U.S. Pat. No. 2,6
42,361, 3,297,446, 3,77
No. 2,031, No. 3,857,711, No. 3,901,
714, ibid. 4,266,018, and ibid. 3,90
4,415, and pAg 5-10, pH 5-8 and temperature 30-80 ° C as described in British Patent 1,315,755, sulfur, selenium, tellurium,
It can be carried out using gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. Chemical sensitization is optimally carried out in the presence of gold compounds and thiocyanate compounds and also in US Pat. Nos. 3,857,711 and 4,26.
Sulfur-containing compounds or hypo, thiourea compounds described in 6,018 and 4,054,457;
It is carried out in the presence of a sulfur-containing compound such as a rhodanine compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyridine, and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,411,914.
No. 3,554,757, JP-A-58-12652.
No. 6 and Duffin, "Photoemulsion Chemistry", 138-
Pp. 143.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. .. That is, azoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes), pentaazaindenes and many other compounds known as antifoggants or stabilizers can be added. For example, those described in U.S. Pat. Nos. 3,954,474, 3,982,947 and JP-B-52-28,660 can be used.

The above-mentioned various additives are used in the light-sensitive material of the present invention, but various additives other than the above can be used according to the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (1978).
December) and Item 18716 (1979)
(November, 2013), and the relevant parts are summarized in the table below.

Additive type RD17643 RD18716 1 Chemical sensitizer 648 page right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23 to 24 648 page right column to page 649 right column Supersensitizer 4 Whitening Agent page 24 5 Antifoggant, pages 24 to 25 649 Right column and stabilizer 6 Light absorber, pages 25 to 26 649 Page right column to page 650 Left column Filter dye, UV absorber 7 Stain inhibitor page 25 Right Column 650 Page left-right column 8 Dye image stabilizer page 25 9 Hardener 26 page 651 Page left column 10 Binder page 26 Same as above 11 Plasticizer, lubricant 27 page 650 Page right column 12 Coating aid, 26-27 Page Same as above Surface active agent 13 Antistatic agent page 27 Same as above Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure (RD) No. 17643, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, Japanese Patent Publication No. 58-10739, British Patent No. 1,42
Those described in No. 5,020 and No. 1,476,760 are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
1,432, 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630.
Nos. 4,540,654 and the like are particularly preferable.

Examples of cyan couplers that can be used at the same time as the cyan couplers used in the present invention include phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, 4,296,20
No. 0, No. 2,369,929, No. 2,801,1
No. 71, No. 2,772, 162, No. 2,895.
No. 826, No. 3,772,002, No. 3,75
No. 8,308, No. 4,334,011, No. 4,3
27,173, West German Patent Publication No. 3,329,729
No., EP 121,365A, US Pat.
No. 46,622, No. 4,333, 999, No. 4,
Those described in No. 451,559, No. 4,427,767, and European Patent No. 161,626A are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
17643, Section VII-G, U.S. Pat. No. 4,163,67
No. 0, Japanese Patent Publication No. 57-39413, US Pat.
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable.

Examples of couplers in which the color forming dye has a suitable diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, and British Patent No. 2,102,137.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler releasing a development inhibitor is the above-mentioned R
Patents described in D17643, VII-F, JP-A-5
7-151944, 57-154234, 60
Those described in US Pat. No. 4,184,248 and US Pat. No. 4,248,962 are preferable.

As couplers which imagewise release a nucleating agent or a development accelerator during development, British Patent No. 2,093
7,140, 2,131,188, JP-A-59.
Those described in Nos. 157638 and 59-170840 are preferable.

Other couplers which can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
Competitive couplers described in US Pat.
No. 472, No. 4,338,393, No. 4,31
Multiequivalent couplers described in JP-A No. 0,618, JP-A-60-
No. 185950, JP-A No. 62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173,302A. Couplers that release colored dyes, RD. No. 11449 and 2424
1, bleaching accelerator releasing couplers described in JP-A-61-2201247, ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

The coupler used in the present invention can be introduced into the 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 US Pat. No. 2,322,027.

Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalates (eg, 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, phosphoric acid or sulfone Esters of acids (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-
2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-
Ethylhexyl benzoate, dodecyl benzoate,
2-ethylhexyl-p-hydroxybenzoate),
Amides (for example, N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples thereof include aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). Further, the auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Even when it is used as a black-and-white photographic light-sensitive material, an X-ray light-sensitive material, and a printing light-sensitive material, preferable effects are obtained.

When the present invention is applied to a color photographic material, it can be applied to a light-sensitive material in which various kinds of light-sensitive materials and layer structures are combined with a special color material.

As a typical example thereof, Japanese Patent Publication No. 47-490.
No. 31, Japanese Patent Publication No. 49-3843, Japanese Patent Publication No. 50-212
48, JP-A-59-58147, JP-A-59-60
No. 437, JP-A-60-227256, JP-A-61-1.
4043, JP-A 61-43743, JP-A 61-
No. 42657, which is a combination of the coupling speed and diffusivity of a color coupler and the layer constitution, Japanese Patent Publication No.
9-15495 and U.S. Pat. No. 3,843,469, the same color-sensitive layer is divided into two or more layers, JP-B-53-37017, JP-B-53-37018 and JP-A-51. -49027, JP-A-52-143016.
JP-A-53-97424, JP-A-53-9783
1, JP-A-62-200350, and JP-A-59-17.
No. 7551, which defines the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers having different color sensitivities.

Suitable supports that can be used in the present invention are, for example, those described in RD. No. 17643, page 28, and ibid.
o. 18716, page 647, right column to page 648, left column.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, and ibid.
o. Development can be carried out by a usual method described in the left column to the right column of page 651 of 18716.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Mention may be made of N-ethyl-N-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Two or more of these compounds may be used in combination depending on the purpose.

The color developing solution contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include agents or antifoggants. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) s can be used. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. Various chelating agents represented by auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, Ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -
N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid,
Ethylenediamine-di (o-hydroxyphenylacetic acid)
And their salts can be mentioned as typical examples.

When the reversing process is carried out, black and white development is usually carried out and then color development is carried out. This black-and-white developing solution contains 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. Can be used alone or in combination.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing amount of the developing solution depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by setting the temperature and the pH to high and using the color developing agent at a high concentration. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be optionally carried out. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitro compounds are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1 , Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid or complex salts of citric acid, tartaric acid, malic acid;
Persulfates; bromates; permanganates; nitrobenzenes can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and persulfates are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further aminopolycarboxylic acid iron
The (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. These aminopolycarboxylic acid iron (II
The pH of the bleaching solution or bleach-fixing solution using the complex salt I) is usually 5.5 to 8, but it is possible to process at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Useful bleaching accelerators include US Pat. No. 3,893,8
58, West German Patents 1,290,812 and 2,0
59,988, JP-A-53-32736, JP-A-53-
No. 57831, No. 53-37418, No. 53-726.
No. 23, No. 53-95630, No. 53-95631.
No. 53-104232, No. 53-124424
No. 53-141623, No. 53-28426,
Research Disclosure No. No. 17,129 (1
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; JP-B No. 45-8506;
Thiourea derivatives described in JP-A-52-20832, JP-A-53-32735 and US Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-58-1.
6235, iodide salt; West German Patent No. 966,41
Nos. 0 and 2,748,430; polyoxyethylene compounds described in JP-B-45-8836; and others, JP-A-49-42434 and JP-A-49-42434.
9-59644, 53-94927, 54-3
5727, 55-26506, 58-1639.
And the bromide ion. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,893,858 and West German Patent 1,290,
Compounds described in JP-A No. 812 and JP-A-53-95630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, and the use of thiosulfates is common, and particularly Ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and various other conditions. Can be set in a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Soci.
tty of Motion Picture
64 Television Engineers
Vol. 248 to 253 (May 1955 issue).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of rinsing water can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and the produced suspended matter adhering to the photosensitive material. 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 ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
No. 8542, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents," Sanitary Technology Society, "Microorganisms" Sterilization of
The bactericides described in "Sterilization and Antifungal Technology" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc.
A range of 30 seconds to 5 minutes at 25 to 40 ° C. is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

In addition, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the washing with water and / or the replenishment of the stabilizing solution can be reused in other steps such as the 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 accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597,
No. 3,342,599, Research Disclosure No. 14,850 and the same No. Schiff base type compounds described in JP-A Nos. 15,159,159, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described, for example, in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed. .

The silver halide light-sensitive material of the present invention comprises
For example, U.S. Pat. No. 4,500,626, JP-A-60
-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in No. 238056 and European Patent 210,660A2.

Examples of the present invention will be shown below, but the invention is not limited thereto.

[0136]

【Example】

 Example 1 Preparation of Samples Cellulose triacetate powder having a thickness of 127 μm and provided with an undercoat.
Multi-layer color consisting of layers of the following composition on a lum support
A photosensitive material was prepared and a sample was prepared. Number is m ²Hit
Indicates the amount added. The effects of the added compounds are described
Not limited to use. First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic Solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Fine grain silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, coefficient of variation 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 Table 4 Described coupler 0.3 g compound Cpd C 10 mg High-boiling point organic solvent Oi1-2 0.1 g Additive P-1 0.1 g Fifth layer: medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler shown in Table 0.5 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler shown in Table 1.0 g Additive P-1 0.1 g Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg UV absorber U-1 0.01 g UV absorber U-2 0.002 g UV absorber U-5 0.01 g Dye D-1 0.02 g Compound Cpd-C 5 mg Compound Cpd-J 5 g Compound Cpd-K 5 g High boiling point organic solvent Oil-1 0.02 g Eighth layer: Medium Layer Silver iodobromide emulsion fogged on the surface and inside (average grain size 0.06 μm, coefficient of variation 16%, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 1.0 g Additive P-10 .2 g Anti-color mixing agent Cpd-A 0.1 g Ninth layer: low-sensitivity green sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0. 5 g coupler C-4 0.1 g coupler C-7 0.05 g coupler C-8 0.20 g compound Cpd-B 0.03 g compound Cpd-C 10 mg compound Cpd-D 0.02 g compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g High-boiling point organic solvent Oil-1 0.1 g High-boiling point organic solvent Oil-2 0.1 g Tenth layer: medium-speed green sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0. 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 point organic solvent Oil-2 0.01 g 11th 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 0.02g Compound Cpd-G 0.02g Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling point organic solvent Oil-1 0.02 g High boiling point organic solvent O l-2 0.02 g 12th layer: intermediate layer gelatin 0.6 g 13th layer: yellow filter layer yellow colloidal silver silver amount 0.07 g gelatin 1.1 g color mixture inhibitor Cpd-A 0.01 g high boiling organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 14th layer: Intermediate layer Gelatin 0.6 g 15th 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 16th 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 Ultraviolet absorber U-10. 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-30 .1 g 19th layer: second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate and acrylic acid 4: 6 copolymer (average particle size 1.5 μm) 0 .1 g Silicone oil 0.03 g Other additives of the active agent W-1 3.0 mg Surfactant W-2 0.03 g In addition, the composition in all of the emulsion layers F-
1-F-8 were added. In addition to the above composition for each layer
Gelatin hardener H-1 and coating and emulsifying surfactant
W-3, W-4, W-5 and W-6 were added.

Further, as antiseptic and antifungal agents, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol were added.

The structural formulas of the compounds used in Sample 101 are shown below.

[0139]

[Chemical 41]

[0140]

[Chemical 42]

[0141]

[Chemical 43]

[0142]

[Chemical 44]

[0143]

[Chemical 45]

[0144]

[Chemical 46]

[0145]

[Chemical 47]

[0146]

[Chemical 48]

[0147]

[Chemical 49]

[0148]

[Chemical 50]

[0149]

[Chemical 51]

[0150]

[Chemical 52]

[0151]

[Chemical 53]

[0152]

[Chemical 54]

[0153]

[Chemical 55]

[0154]

[Table 1] Emulsions E to N were spectrally sensitized as shown in Tables 2 and 3 below.

[0155]

[Table 2]

[0156]

[Table 3] Further, at the time of sample preparation, samples 102 to 130 were prepared using the couplers of the fourth to sixth layers and the compounds shown in Table 4 below as sensitizing dyes of emulsions A to D.

[0157]

[Table 4] The sample piece thus obtained was white-exposed through a gray wedge with an exposure time of 1/100 second and an exposure amount of 20 CMS, and then sensitometry was performed by the processing steps shown below.

Further, the sample after the above treatment was placed in a dark place at 80 ° C. for 7 hours.
It was left at 0% for 7 days or left under xenon lamp irradiation for 3 days, and the dark fading and photofading were evaluated based on the change in cyan density at that time.

Further, the magenta stain of the dye blank sample was subtracted from the magenta density of the stain after the treatment, and the residual color was evaluated. The results are shown in Table 5 below.

Treatment process time Temperature First development 6 minutes 38 ° C Water washing 2 minutes 38 ° C Reversal 2 minutes 38 ° C Color development 6 minutes 38 ° C Adjustment 2 minutes 38 ° Bleach 6 minutes 38 ° C 4 minutes 38 ° C Washing with water 4 minutes 38 ° C Stability 1 minute 25 ° C The composition of each treatment solution was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 33 g 1-Phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone 2.0 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Water was added to 1000 ml pH 9.60 pH was adjusted 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 Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide. [Color developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate dodecahydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazine 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 1000 ml pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide. [Adjusting liquid] Ethylenediaminetetraacetic acid / disodium salt / dihydrate 8.0 g Sodium sulfite 12 g 1-thioglycerin 0.4 ml Water was added to 1000 ml pH 6.20 pH was adjusted with hydrochloric acid or sodium hydroxide. . [Bleach] Ethylenediaminetetraacetic acid / disodium salt / dihydrate 2.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium / dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water 1000 ml pH 5 The .70 pH was adjusted with hydrochloric acid or sodium hydroxide. [Fixer] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia. [Stabilizer] Formalin (37%) 5.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5 ml Water added 1000 ml Without pH adjustment

[0161]

[Table 5] From the results in Table 5, it can be seen that the conventional cyan couplers are inferior in image storability even when the dyes of the present invention are used as in Samples 104 to 106. Further, from Samples 107 to 130, although the image storability is improved even when the cyan coupler of the present invention is used, the residual color and sensitivity become problems if the dye of the present invention is not used. Residual color,
It can be seen that a photographic light-sensitive material having excellent color image stability and high sensitivity can be obtained. Example 2 The sensitizing dyes, cyan couplers and emulsions of the third to fourth layers of the color light-sensitive material of Example 1 of JP-A-1-158431 were used.
As a result of a replacement experiment similar to the above, it was revealed that the color image fastness, residual color, and sensitivity were compatible for the first time with the configuration of the present invention, as in Example 1.

[0162]

As described above, the silver halide color photographic light-sensitive material according to the present invention is excellent in residual color upon development processing and color image fastness, and also has good sensitivity.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, and at least one layer constituting the light-sensitive material has a methine compound represented by the following general formula (1). Containing a silver halide photographic emulsion spectrally sensitized with at least one of
A silver halide color photographic light-sensitive material characterized in that at least one layer constituting the light-sensitive material contains at least one cyan dye forming coupler represented by the following general formula (2) or (3). General formula (1) In the formula, R ¹ is — (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
Representing a 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 has the same meaning as R ¹ or represents an alkyl group.
Z ¹ and Z ² represent a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle, and p and q represent 0 or 1. L ₁ , L ₂ and L ₃ represent a methine group, and m represents 0, 1 or 2. X ₁ represents an anion, and k represents the number necessary for adjusting the charge in the molecule to zero. [Chemical 2] [Chemical 3] In the formula, R ⁷ represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R ⁸ represents an aliphatic group,
It represents an aromatic group or a heterocyclic group, and R ⁹ represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, an acylamino group or an aliphatic oxy group. R ⁸ and R ⁹ are bonded to each other and are 5 to 7
A member ring may be formed. Z ³ represents a hydrogen atom or a group or atom capable of splitting off upon reaction with an oxidized product of a developing agent. X ₂ and X ₃ each represent a hydrogen atom or a halogen atom.