JP2772196B2 - Silver halide color photographic materials - 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 color photographic light-sensitive material having improved residual color and color image fastness during development.

[0002]

2. Description of the Related Art In recent years, silver halide color photographic materials have been increasingly required not only for high sensitivity and high image quality but also for image storability. Is the most important issue in the industry.

[0003] From this viewpoint, cyan couplers are disclosed in US Pat. No. 2,367,5, which has been conventionally used.
The 2-acylaminophenol cyan couplers described in JP-A Nos. 31 and 2,423,730 are generally inferior in light and heat fastness, and are disclosed in U.S. Pat. No. 3,772,002 and JP-A-61-3142. The 2-acylaminophenol cyan couplers described in JP-A No. 61-9653 are improved in color image fastness compared with the cyan couplers described above, but are still not sufficient, and have a color hue. Had a disadvantage in that side absorption on the short-wave side was large.

On the other hand, Japanese Patent Application Laid-Open Nos.
The 5-position-substituted naphthol cyan couplers and their polymer couplers described in 1-153640 and 61-145557 are excellent in light and heat fastness, but have the same color hue as the above-mentioned couplers. It has the disadvantage that side absorption on the short wavelength side is extremely large, and yellow stain is extremely generated upon light irradiation.

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
7,173, EP 0399183 A1, JP-A-63-75748, JP-A-63-89852 and JP-A-63-98661, and diacylamino-type cyan couplers described in U.S. Pat. No. 3,446,622. No. 3,996,253, No. 3,758,308,
No. 3,880,661 and JP-A-56-6513.
U.S. Pat. No. 4,430,423 and U.S. Pat.
A cyan coupler having a condensed ring structure described in -32261 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, a photographic light-sensitive material excellent in color image fastness can be surely obtained by using the above-mentioned cyan coupler. Although it was possible, it became clear that the sensitizing dye in the photographic light-sensitive material did not elute during the processing and remained colored, that is, the so-called residual color was greatly deteriorated.

In order to achieve both the residual color and the color image fastness,
The combination of a cyan coupler having high color image fastness and a sensitizing dye having an improved residual color can be easily analogized. For example, JP-A-1-147451, which has heretofore been known as a sensitizing dye having a small residual color, has been proposed. JP-A-61-294429
No., JP-B-45-32749, JP-A-61-7778.
In the case where a compound having a hydrophilic substituent such as a sulfamoyl group or a carbamoyl group disclosed in No. 3 is used, increasing the hydrophilicity of the sensitizing dye generally decreases the adsorptivity, so that the residual color is improved. However, desensitization due to desorption of the sensitizing dye was apt to occur, and sufficient performance could not be exhibited. The sensitizing dyes described in U.S. Pat. No. 3,282,933 also have an effect of improving the residual color, but have a low spectral sensitizing effect and have not been able to obtain a sufficient effect in terms of achieving both residual color and sensitivity. .

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

[0009]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a silver halide color photographic light-sensitive material having improved sensitivity to residual colors and color images at the time of development processing and good sensitivity.

[0010]

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

General formula (1)

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Embedded image 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
Represents 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 each represent a nonmetallic atom group necessary for forming a 5- or 6-membered heterocyclic ring, 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 a number necessary to adjust the intramolecular charge to zero.

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Embedded image 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,
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 to form 5 to 7
It may form a member ring. Z ³ represents a hydrogen atom or a group or atom capable of leaving by reaction with an oxidized form of the developing agent. X ₂ and X ₃ each represent a hydrogen atom or a halogen atom. n represents the integer of 0-18.

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, preferably has 4 or less carbon atoms, particularly preferably methyl, ethyl, hydroxyalkyl or amino. 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, 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 with each other, 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 are 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 is 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 non-metallic atomic groups represented by Z ¹ and Z ² includes a thiazole nucleus and a thiazole nucleus (eg, thiazole, 4-methylthiazole, 4-phenylthiazole, , 5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (for example, 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 (eg, oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (eg, benzoxazole) 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), naphthooxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2- d] oxazole, naphtho [2,
3-d] oxazole, 5-nitronaphtho [2,1-
d] oxazole)}, oxazoline nucleus (for example, 4,
4-dimethyloxazoline), selenazole nucleus selenazole nucleus (for example, 4-methyl selenazole, 4-nitro selenazole, 4-phenyl selenazole), benzo selenazole nucleus (for example, benzo selenazole, 5-chlorobenzo selenazole) , 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole,
5-chloro-6-nitrobenzoselenazole, 5,6-
Dimethyl benzo selenazole), naphtho selenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1, 2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-methyl selenazoline), tellurazole Nuclear ｛tellurazole nucleus (eg, tellurazole,
4-methyltellurazole, 4-phenyltellurazole), benzotellurazole nucleus (for example, benzotellurazole, 5-chlorobenzotellurazole, 5-methylbenzotellurazole, 5,6-dimethylbezotellurazole,
6-methoxybenzotellurazole), naphthotellurazole nucleus (eg, naphtho [2,1-d] tellurazole, naphtho [1,2-d] tellurazole)}, tellurazoline nucleus (eg, tellurazoline, 4-methyltellurazoline) ,
3,3-dialkylindolenine nucleus (for example, 3,3-
Dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,
3-dimethyl-6-nitroindolenin, 3,3-dimethyl-5-nitroindolenin, 3,3-dimethyl-5
-Methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus ｛imidazole nucleus (for example, 1-
Alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (for example, 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), a naphthoimidazole nucleus (for example, 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, and butyl, and a hydroxyalkyl group (for example, 2-
Hydroxyethyl, 3-hydroxypropyl) is preferred. Particularly preferred are methyl and ethyl. The aforementioned aryl groups represent phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl) substituted phenyl, alkoxy (eg, methoxy) substituted phenyl. ｝,
Pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5
-Methyl-2-pyridine, 3-methyl-4-pyridine), quinoline nucleus ｛quinoline nucleus (for example, 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 (for example, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b]. Quinoxalin nucleus (for example, 1,3-diethylimidazo [4,5-b] quinoxalin, 6-chloro-1,3-diallylimidazo [4,5
-B] quinoxalin), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.

Of these heterocyclic nuclei, preferred are a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a naphthimidazole nucleus and a 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 the substituent may be an optionally substituted alkyl group (eg, methyl, ethyl, 2-carboxyethyl), And an aryl group (eg, phenyl, o-carboxyphenyl), a halogen atom (eg, chlorine, bromine), an alkoxy group (eg, methoxy, ethoxy), an alkylthio group (eg, a methylthio group, an ethylthio group), and the like. And may form a ring with an auxochrome. Examples of the anion represented by X _1, the anion (e.g. chloride, bromide, iodide, p- toluenesulfonate, naphthalene sulfonate, methanesulfonate, methyl sulfate, ethyl sulfate, perchlorate, etc.) of an inorganic or organic acid No.

M is preferably 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 to these.

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[0029]

Embedded image 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" represents a linear, branched or cyclic aliphatic hydrocarbon group, such as an alkyl, alkenyl or alkynyl group. It is meant to include things. Representative examples include methyl, ethyl, butyl, dodecyl, octadecyl, eicosenyl, iso-propyl, tert.
-Butyl, tert-octyl, tert-dodecyl,
Cyclohexyl, cyclopentyl, allyl, vinyl, 2
-Hexadecenyl, propargyl and the like.

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 (for example, phenyl and naphthyl) and a heterocyclic group (for example, 3-pyridyl, 2-furyl) or an aromatic or heterocyclic amino group (eg, anilino, naphthylamino, 2-benzothiazolylamino, 2-pyridylamino), and these groups further include an alkyl group, Aryl group, heterocyclic group, alkoxy group (for example, methoxy,
2-methoxyethoxy), an aryloxy group (for example,
2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy), alkenyloxy group (eg, 2-propenyloxy), acyl group (eg, acetyl, benzoyl), ester group (eg,
Butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), amide group (eg, acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide, butylsulfamoyl), sulfamide group (eg, dipropyls) Rufamoylamino),
Imido groups (eg, succinimide, hydantoinyl), ureido groups (eg, phenylureido, dimethylureide), aliphatic or aromatic sulfonyl groups (eg, methanesulfonyl, phenylsulfonyl), aliphatic or aromatic thio groups (eg, ethylthio) , Phenylthio), hydroxyl, cyano, carboxy,
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)
⁷ may form a dimer or a multimer.

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

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

In the general formulas (2) and (3), R ⁹
Represents 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 (for example, methoxy and butoxy), and an aromatic oxy group (for example, phenoxy). Among these, a substitutable group has a substituent permitted by R ^7. It may be.

In the general formulas (2) and (3), Z ³
Represents a hydrogen atom or a coupling-off group, examples of which include a halogen atom (eg, fluorine, chlorine, bromine), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methyl) Sulfonylethoxy), aryloxy group (eg, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy group (eg, methanesulfonyl) Oxy, toluenesulfonyloxy), amide group (eg, dichloroacetylamino, heptafluorobutyrylamino, methanesulfonylamino, toluenesulfonylamino), alkoxycarbonyloxy group (eg, eth Cicarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy), aliphatic or aromatic thio groups (eg, ethylthio, phenylthio, tetrazolylthio), imide groups (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- or 6-membered ring is preferred, and a 5-membered ring is most preferred. When R ⁸ and R ⁹ form a ring, R ⁷ is preferably an optionally substituted phenyl group.

In the general formulas (2) and (3), Z ³ is preferably a hydrogen atom, a halogen atom, an alkyloxy group and 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 preferred.

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

Hereinafter, specific examples of the cyan coupler represented by the general formula (2) or (3) will be shown, but the present invention is not limited thereto.

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

Embedded image The amount of the cyan coupler represented by the general formula (2) or (3) used in the present invention to the light-sensitive material is as follows.
The amount is preferably from 1 × 10 ^-7 mol to 1 × 10 ^-1 mol, and particularly preferably from 1 × 10 ^-6 mol 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 the 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 or the like together with the compound represented by the general formula (1). 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, for example, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an 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, ie, 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, and a quinoline nucleus can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye includes, as nuclei having a ketomethylene structure, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidin-2,4-dione nucleus, and thiazolidine-2,4-nucleus.
A 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus and 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. Dye combinations are often used, especially for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,03,377 and 3,76
9,301, 3,814,609, 3,83
7,862 and 4,026,707, British Patent 1,
No. 344,281, No. 1,507,803, Shoko 4
3-49336, 53-12,375, JP-A-5
2-110,618 and 52-109,925.

In addition to the compound represented by the general formula (1), a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization is used as an emulsion. It may be included in it.

The compound represented by the above general formula (1) 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 completion of chemical sensitization but before coating, but US Pat. Nos. 3,628,969 and 4,
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-225-666. It can be carried out prior to chemical sensitization, or it can be added before completion of silver halide grain precipitation to start spectral sensitization. No. 4,225,66.
It is also possible to add these compounds separately as taught in No. 6, ie, to add some of these compounds prior to chemical sensitization and the rest after chemical sensitization. And at any time during the formation of silver halide grains, including the method taught in U.S. Pat. No. 4,183,756.

The addition amount is 4 × / mol of silver halide.
Although 10 ^-6 to 8 × 10 ^-3 mol can be used, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is more effective when the silver halide grain size is more preferably 0.2 to 1.2 μm. It is.

The silver halide emulsion used in the present invention may have any grain size distribution, but has a maximum grain size (average).
The weight of silver halide contained within a grain size range of ± 20% with respect to r is preferably 60% or more, more preferably 80% or more, 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 0.1%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing ３０30 mol% of 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 include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof.

The silver halide photographic emulsion usable in the present invention includes, for example, Research Disclosure (RD) N
o. 17643 (December 1978), 22-23,
"I. Emulsion preparat
ion and types) ”, No. 18716
(November 1979), p. 648, ibid. 307105
(November 1989), pages 863 to 865, "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P.G.
lafkides, Chemie et Physiq
ue Photographique, Paul Mo
ntel, 1967), by Duffin, "Photographic emulsion chemistry",
Published by Focal Press (GF Duffin, Pho
graphical Emulsion Chemis
try, Focal Press, 1966), and "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photog
raphic Emulsion, Focal Pre
ss, 1964).

US Pat. Nos. 3,574,628;
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred.

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

A silver halide emulsion composed of regular grains can be formed to a desired size by nucleation and grain growth while maintaining pAg at a constant level and a supersaturation level which does not cause renucleation by the double jet method. Particles can be obtained.

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 (P
photographic Science and E
6, 159-165 (1962); Journal of Photographic Science (Journal of Photogr).
aphic Science), Volume 12, 242-25
1 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

The crystal structure may be uniform, may be a material having a different halogen composition inside and outside, or may have a layered structure. These emulsion grains are described in GB 1,027,146 and GB 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 an epitaxial junction, or may be joined to a compound other than silver halide such as, for example, silver rhodanate or lead oxide.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in the grains. A typical example is JP-B-43-1316.
No. 2, JP-A-61-215540, JP-A-60-22
No. 2,845, 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 to the mere double structure,
It is possible to form a triple structure or a multilayer structure as disclosed in JP-A-222844, or to form a thin layer of silver halide having a different composition on the surface of a core-shell double structure grain.

In order to give a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure can be produced. These examples are disclosed in
9-133540, JP-A-58-108526, E
P199290A2, JP-B-58-24772, JP-A-59-16254 and the like. 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 bonded crystal can be formed even if the host crystal is uniform with respect to the halogen composition or the core crystal.
Even those having a shell type structure can be formed.

In the case of a joint 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 joint 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, Conversely, grains having a low silver iodide content in the core portion and a high shell portion may be used. 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.

The boundary portions having different halogen compositions of grains having these structures may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences. It may have a continuous 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 for use in the present invention is preferably a surface latent image type emulsion. However, 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. Also, a shallow internal latent image type emulsion covered with a thin shell described in JP-A-63-264740 is preferably used.

A silver halide solvent is useful for promoting ripening. For example, it is known to have excess halide ions present 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.

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

Chemical sensitization was carried out by James (TH Jam).
es), The Photographic Process, 4th
Edition, Macmillan, 1977, (TH James)
s, The Theory of the Photo
graphic Process, 4th ed, Ma
Cilllan, 1977) pp. 67-76, and can be performed using active gelatin, and Research Disclosure, Vol. 120, April 1974, 12008; Research Disclosure, 3
4, June 1975, 13452, U.S. Pat.
42,361, 3,297,446, 3,77
2,031, 3,857,711, 3,901,
Nos. 714, 4,266,018 and 3,90
4,415 and pAg 5-10, pH 5-8 and temperature 30-80 ° C as described in GB 1,315,755, sulfur, selenium, tellurium,
It can be performed using gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, and in U.S. Patent Nos. 3,857,711 and 4,26.
6,018 and 4,054,457, sulfur-containing compounds or hypo, thiourea compounds;
The reaction is performed 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, 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 improvers are described in U.S. Pat. Nos. 2,131,038 and 3,411,914.
No. 3,554,757, JP-A-58-12652.
No. 6 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, 138-
Page 143.

The photographic emulsion used in the present invention may 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, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (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) Many compounds known as antifoggants or stabilizers can be added, such as tetraazaindenes), pentaazaindenes. For example, those described in U.S. Pat. Nos. 3,954,474 and 3,982,947 and JP-B-52-28,660 can be used.

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

These additives are described in more detail in Research Disclosure Item 17643 (1978).
December 18) and Item 18716 (1979)
(November), and the relevant locations are summarized in the table below.

Additive type RD17643 RD18716 1 Chemical sensitizer page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24 page 648 page right column to page 649 right column Supersensitizer 4 Brightening Agent page 24 5 Antifoggant, page 24-25 page 649 right column and stabilizer 6 Light absorber, page 25-26 page 649 page right column to page 650 left column Filter dye, UV absorber 7 Stain inhibitor page 25 right Column 650 page left to right column 8 Dye image stabilizer page 25 9 Hardening agent page 26 651 page left column 10 Binder page 26 Same as above 11 Plasticizers and lubricants page 27 650 page right column 12 Coating aids, 26 to 27 Page Same as above Surfactant 13 Static inhibitor page 27 Same as above Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure (RD) No. 17643, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, Japanese Patent Publication No. 58-10739, British Patent No. 1,42
Nos. 5,020 and 1,476,760 are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630
And Nos. 4,540,654 are particularly preferable.

Examples of the cyan coupler used simultaneously with the cyan coupler other than the cyan coupler used in the present invention include phenol couplers and naphthol couplers. For example, US Pat. Nos. 4,052,212 and 4,146,396
No. 4,228,233 and 4,296,20
0, 2,369,929 and 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
No. 27,173, West German Patent Publication No. 3,329,729
Patent No. EP 121,365A, US Patent No. 3,4
No. 46,622, No. 4,333,999, No. 4,
Preferred are those described in 451,559, 4,427,767 and EP 161626A.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
No. 17643, section VII-G, U.S. Pat. No. 4,163,67
No. 0, JP-B-57-39413, U.S. Pat.
Nos. 4,929, 4,138,258 and British Patent 1,146,368 are preferred.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,084,820.
Nos. 0,211 and 4,367,282 and British Patent 2,102,137.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the same as described above for R
D17643, Patents described in Section VII-F,
Nos. 7-151944, 57-154234, 60
Preferred are those described in U.S. Pat. No. 4,248,962.

As a coupler which releases a nucleating agent or a development accelerator in an image-like manner at the time of development, UK Patent No. 2,099
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840.

Other couplers usable in the light-sensitive material of the present invention include those described in US Pat. No. 4,130,42.
No. 7,283, etc .; U.S. Pat.
No. 472, No. 4,338,393, No. 4,31
No. 0,618, etc.
No. 185950, JP-A-62-24252, etc., DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, and recovery after release described in EP 173,302A. Couplers that release coloring dyes, RD. 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 photographic material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling organic solvent having a boiling point 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, phosphoric acid or sulfone Acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-
2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoic acid esters (for example,
Ethylhexyl benzoate, dodecyl benzoate,
2-ethylhexyl-p-hydroxybenzoate),
Amides (for example, N, N-diethyldodecaneamide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (e.g., bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples include aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 16 ° C.
Organic solvents at 0 ° C. or lower can be used, and typical examples 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.
No. 63, West German Patent Application (OLS) No. 2,541,274
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.
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 used for a color photographing material, the present invention can be applied to a photosensitive material having various constitutions and a photosensitive material in which a layer constitution and a special color material are combined.

As a typical example, Japanese Patent Publication No. 47-490
No. 31, JP-B-49-3843, JP-B-50-212
No. 48, JP-A-59-58147, JP-A-59-60
No. 437, JP-A-60-227256, JP-A-61-267.
No. 4043, JP-A-61-43743 and JP-A-61-43743.
No. 42657, which combines the coupling speed and diffusivity of the color coupler with the layer composition.
No. 9-15495, U.S. Pat. No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, Japanese Patent Publication No. 53-37017, Japanese Patent Publication No. 53-37018, Japanese Patent Application Laid-Open No. -49027, JP-A-52-143016
JP-A-53-97424, JP-A-53-9783
No. 1, JP-A-62-200350, JP-A-59-17
No. 7,551, the arrangement of the high-sensitivity layer and the low-sensitivity layer and the arrangement of the layers having different color sensitivities are specified.

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

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. 17643, pp. 28-29, and N
o. Development processing can be carried out by a usual method described in the left column to the right column of page 1871 of page 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. 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-
N-ethyl-N-β-methoxyethylaniline and the sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a development inhibitor such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains an agent or an antifoggant. If necessary, such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane). Various preservatives, 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, fogging agents such as sodium boron hydride , An auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity-imparting agent, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, 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 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 in the black-and-white developer. Can be used alone or in combination.

The pH of these color developing solution and black-and-white developing solution
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 photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time of the color development processing is usually set to 2 to 5 minutes. However, the processing time can be further reduced by using a high temperature, a high pH and a high concentration of the color developing agent. it can.

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 compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitro compounds. Representative bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, Aminopolycarboxylic acids such as 3,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, and malic acid;
Persulfate; bromate; permanganate; nitrobenzenes can be used. Among these, iron (III) complex salts of aminopolycarboxylic acid, such as iron (III) complex salt of ethylenediaminetetraacetate, and persulfate are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further aminopolycarboxylate iron
(III) The complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. These aminopolycarboxylic acid iron (II
I) The pH of the bleaching solution or the bleach-fixing solution using a complex salt is usually 5.5 to 8, but the processing can be carried out at a lower pH in order 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.
Useful bleaching accelerators include US Pat. No. 3,893,8.
No. 58; West German Patent Nos. 1,290,812;
59,988, JP-A-53-32736 and JP-A-53-32736.
Nos. 57831, 53-37418, 53-726
No. 23, No. 53-95630, No. 53-95731
No. 53-104232, No. 53-124424
No., 53-141623, 53-28426,
Research Disclosure No. No. 17,129 (1
A compound having a mercapto group or a disulfide group described in, for example, July, 978); a thiazolidine derivative described in JP-A-50-140129; Japanese Patent Publication No. 45-8506;
Thiourea derivatives described in JP-A-52-20832 and JP-A-53-32735, U.S. Pat. No. 3,706,561; West German Patent 1,127,715, JP-A-58-1
Iodide salts described in No. 6235; West German Patent No. 966,41
Polyoxyethylene compounds described in JP-A Nos. 0 and 2,748,430; polyamine compounds described in JP-B No. 45-8836;
Nos. 9-59644, 53-94927, 54-3
Nos. 5727, 55-26506 and 58-1639
Compound No. 40; bromide ions. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, U.S. Pat.
No. 812 and compounds described in 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 thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodides, and thiosulfates are generally used. Ammonium thiosulfate can be used most widely. 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 depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions Can be set widely. Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal of the Soci
ety of Motion Pictureand
Television Engineers 64th
Vol. 248-253 (May, 1955).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, Japanese Patent Application Laid-Open No.
No. 8542, isothiazolone compounds and thiabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles. Sterilization of the
Sterilization and antifungal techniques ", and the germicides described in" Encyclopedia of Antifungal and Antifungal Agents "edited by the Japan Society of Antifungal and Fungicides.

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

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, a stabilization bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photography, may be mentioned. be able to. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

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. For example, indoaniline compounds described in US Pat. No. 3,342,597,
No. 3,342,599, Research Disclosure No. 14, 850 and the same. 15,159, Schiff base compounds, aldol compounds described in JP-A-13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane-based compounds described in JP-A-53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises:
If necessary, 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 in the present invention may be used at a temperature of 10 ° C. to 50 ° C.
Used at ° 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. Further, in order to save silver in the photosensitive material, a process 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;
-133449, 59-218443, 61-
It is also applicable to the photothermographic materials described in US Pat. No. 2,380,56 and EP 210,660 A2.

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

[0136]

【Example】

 Example 1 Preparation of Sample An undercoated 127 μm-thick cellulose triacetate filter was used.
Multi-layer color consisting of the following layers on a LUM support
A photosensitive material was prepared, and a sample was prepared. The number is m ^TwoPer hit
Indicates the amount added. The effects of the added compounds are described.
It is not limited to use. First layer: Antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g Ultraviolet absorber U-1 0.1 g Ultraviolet absorber U-3 0.04 g Ultraviolet 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 fogged on the surface and inside (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 Table 4 Coupler described 0.3 g Compound Cpd C 10 mg High-boiling organic solvent Oi1-2 0.1 g Additive P-1 0.1 g Fifth layer: Medium-sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler described in Table 4 0.5 g High boiling organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: Highly sensitive red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler described in Table 4 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 organic solvent Oil-1 0.02 g Eighth layer: Medium Layer Silver iodobromide emulsion fogged on the surface and inside (average particle 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 0.2 g Anti-color mixing agent Cpd-A 0.1 g Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E 0.1 g Emulsion F 0.2 g silver Emulsion G Silver 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 organic solvent Oil-1 0.1 g High-boiling organic solvent Oil-2 0.1 g Tenth layer: medium-sensitive green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver content 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 02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g High-boiling organic solvent Oil-2 0.01 g Eleventh layer: high-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C -4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.08 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 O 1-2 Layer 0.02 g Layer 12: Intermediate layer Gelatin 0.6 g Layer 13: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 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 content 0.1 g Emulsion M Silver content 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 No. 17 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: first 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 0.1 g 19th layer: 2nd 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 μ) 0.1 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size 1.5 μm) 0 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. Further, in each layer, in addition to the above composition,
Gelatin hardener H-1 and coating and emulsifying surfactant
W-3, W-4, W-5 and W-6 were added.

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

The structural formula of the compound used in Sample 101 is shown below.

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[Table 1] Emulsions E to N were subjected to spectral sensitization as shown in Tables 2 and 3 below.

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[Table 2]

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[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 thus-obtained sample was exposed to white light through a gray wedge at an exposure time of 1/100 second and an exposure amount of 20 CMS, and then subjected to sensitometry by the following processing steps.

The sample after the above treatment was placed in a dark place at 80.degree.
The sample was allowed to stand at 0% for 7 days or under a xenon lamp irradiation for 3 days, and the change in cyan density at that time was evaluated for dark fading and light fading.

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.

Processing time Time Temperature First development 6 minutes 38 ° C Washing water 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 Fixed 4 minutes 38 ° C Rinse 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 pentasodium salt 2.0 g Sodium sulfite 30 g Hydroquinone monomonosulfonate 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. The pH was adjusted with hydrochloric acid or potassium hydroxide. [Inversion liquid] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium 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 and 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide. [Color developing solution] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium 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 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 The pH was adjusted with hydrochloric acid or potassium hydroxide. [Adjustment liquid] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g sodium sulfite 12 g 1-thioglycerin 0.4 ml Water was added 1000 ml pH 6.20 pH was adjusted with hydrochloric acid or sodium hydroxide. . [Bleaching solution] 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 Add water to 1000 ml pH 5 .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. [Stabilizer] 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

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[Table 5] From the results in Table 5, it can be seen that, even when the dye of the present invention is used as in Samples 104 to 106, for example, the conventional cyan coupler has poor image storability. From Samples 107 to 130, even if the cyan coupler of the present invention was used, the image storability was improved, but if the dye of the present invention was not used, residual color and sensitivity would be problems, and the configuration of the present invention was used for the first time. Residual color,
It can be seen that a photographic material having excellent color image stability and good sensitivity can be obtained. Example 2 The sensitizing dye, cyan coupler and emulsion of the third to fourth layers of the color photographic material of the example of JP-A-1-158431 were used in Example 1.
In the same manner as in Example 1, it was clarified that the color image fastness, the residual color, and the sensitivity were both satisfied, as in Example 1.

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

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-47-3028 (JP, A) JP-A-52-16222 (JP, A) JP-A-47-12277 (JP, A) JP-A-62 32459 (JP, A) JP-A-59-166955 (JP, A) JP-A-2-281252 (JP, A) JP-B-48-21564 (JP, B1) (58) Fields investigated (Int. ⁶ , DB name) G03C 1/14 G03C 7/34

Claims (1)

(57) [Claims] 1. A silver halide color photographic material having at least one silver halide emulsion layer on a support, wherein at least one layer constituting the photographic material has a methine compound represented by the following general formula (1). Contains a silver halide photographic emulsion spectrally sensitized by 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
Represents 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 each represent a nonmetallic atom group necessary for forming a 5- or 6-membered heterocyclic ring, 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 a number necessary to adjust the intramolecular charge to zero. Embedded image Embedded image 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,
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 to form 5 to 7
It may form a member ring. Z ³ represents a hydrogen atom or a group or atom capable of leaving by reaction with an oxidized form of the developing agent. X ₂ and X ₃ each represent a hydrogen atom or a halogen atom. n represents the integer of 0-18.