JP3018014B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly to a photographic material having improved image stability. More particularly, the present invention relates to a photographic light-sensitive material having improved photographic image mold resistance and color image fastness.

(Prior art) When a photographic image is stored under a high humidity condition, mold may be generated on the surface, and in some cases, the color developed by the acid secreted by the mold may be discolored or faded, thereby significantly deteriorating the image quality. There was a problem.

In order to solve this problem, several proposals have been made to apply a fungicide / antifungal agent to a silver halide photographic light-sensitive material. For example, JP-A-59-126533, JP-A-60-260952, and JP-A-58-10514 disclose a method of suppressing the occurrence of mold on an image by adding a fungicide / antifungal agent to a processing solution for a silver halide photographic light-sensitive material.
5, No. 61-39047, No. 61-75354, Japanese Patent Publication No. 62-62334, West German Patent No. 3438662A, and RD20526, etc. It is necessary to newly install a bath (antibacterial and antifungal bath, stabilizing bath), which requires remodeling of the equipment, and because the solubility of the antibacterial and antifungal agent in water is poor, it precipitates in the treatment bath. There is a problem that it adheres to the surface of the photosensitive material. Also, since a large amount of waste liquid is generated, there is a problem in environmental protection.

On the other hand, a method has been disclosed in which a fungicide / antifungal agent is added in advance to the silver halide photographic light-sensitive material itself to suppress the occurrence of mold on the image. Mold generation of unprocessed photographic light-sensitive materials can also be suppressed. This method is disclosed, for example, in Japanese Patent Application Laid-Open No. 60-26393.
8, 59-84237, 58-166343, and 60-114239.

However, since the amount of the antibacterial and fungicide which can be introduced into the photographic light-sensitive material is also limited by the above-mentioned method, mold must be used when the image surface is significantly stained with hand marks during storage, or when the storage conditions are poor. May occur. Therefore, in addition to taking measures to prevent the occurrence of mold, it is also necessary to take measures to prevent the occurrence of mold to some extent, that is, to prevent the color image from discoloring or fading even if mold occurs. Required.

Discoloration or fading of a color image due to the occurrence of mold is mainly caused by organic acids (acetic acid, citric acid, tartaric acid, gluconic acid, etc.) secreted by mold, and cyan and yellow dyes are bleached by these acids ( Acid fading).

For the yellow dye image, see JP-A-64-5048, 6
The use of cyclic ether compounds or epoxy group-containing compounds is disclosed in JP-A-4-50049, JP-A-61-4041, etc., although these compounds have some effect in improving acid fading, but It was not enough improvement. U.S. Pat. No. 3,265,506 discloses a yellow coupler having improved color image fastness, but has little effect on acid fading.

(Problems to be Solved by the Invention) An object of the present invention is to suppress the occurrence of mold on the image surface of a print obtained by processing a color photographic light-sensitive material, and to provide a silver halide photographic light-sensitive material having excellent color image preservability. Is to provide. More specifically, it is an object of the present invention to provide a reflective silver halide color photographic light-sensitive material in which the fading of a yellow dye image by an acid is improved.

(Means for Solving the Problems) As a result of earnest study, the present inventors have found that a combination of at least one of the yellow couplers represented by the following general formula (I) and at least one of the antibacterial and fungicide agents contains In addition, acid discoloration which occurs when mold is generated is suppressed, and the problem is solved.

(In the formula, R ₁ is an aryl group or a tertiary alkyl group, R ₂ is a fluorine atom, an alkyl group, an aryl group, an alkoxy group,
An aryloxy group, a dialkylamino group, an alkylthio group, or an arylthio group, R ₃ is a group capable of being substituted on a benzene ring, and X is a hydrogen atom or an oxidized aromatic primary amine-based developer. The groups capable of leaving by the reaction each represent an integer of 0 to 4. However the case of a plurality, the plurality of R ₃ may be the same or different. The compound [I] used in the present invention will be described in more detail.

In the general formula [I], R ₁ preferably has 6 carbon atoms.
To 24 aryl groups (e.g., phenyl, p-tolyl, o-
Tolyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-butoxyphenyl, 4-octyloxyphenyl, 4-hexadecyloxyphenyl, 1-naphthyl)
Or a tertiary alkyl group having 4 to 24 carbon atoms (for example, t-
Butyl, t-pentyl, t-hexyl, 1,1,3,3-tetramethylbutyl, 1-adamantyl, 1,1-dimethyl-
2-chloroethyl, 2-phenoxy-2-propyl, bicyclo [2,2,2] octan-1-yl).

In the general formula (I), R ₂ is preferably a fluorine atom,
An alkyl group having 1 to 24 carbon atoms (eg, methyl, ethyl, isopropyl, t-butyl, cyclopentyl, n-
Octyl, n-hexadecyl, benzyl), an aryl group having 6 to 24 carbon atoms (for example, phenyl, p-tolyl, o
-Tolyl, 4-methoxyphenyl), having 1 to 24 carbon atoms
(E.g., methoxy, ethoxy, butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy), having 6 to 24 carbon atoms
Aryloxy groups such as phenoxy, p-tolyloxy, o-tolyloxy, p-methoxyphenoxy, p
-Dimethylaminophenoxy, m-pentadecylphenoxy), a dialkylamino group having 2 to 24 carbon atoms (eg, dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino), an alkylthio group having 1 to 24 carbon atoms (eg, methylthio, butylthio) , N-octylthio, n-hexadecylthio) or an arylthio group having 6 to 24 carbon atoms (eg, phenylthio, 4-methoxyphenylthio, 4-t-butylphenylthio, 4-dodecylphenylthio).

In the general formula [I], R ₃ is preferably a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 24 carbon atoms (eg, methyl, t-butyl, n-dodecyl); An aryl group having 6 to 24 carbon atoms (eg, phenyl, p-tolyl, p-dodecyloxyphenyl), an alkoxy group having 1 to 24 carbon atoms (eg, methoxy, n-butoxy, n-octyloxy, n-tetradecyl) Oxy, benzyloxy, methoxyethoxy), an aryloxy group having 6 to 24 carbon atoms (eg, phenoxy, pt-butylphenoxy, 4-butoxyphenoxy), an alkoxycarbonyl group having 2 to 24 carbon atoms [eg, ethoxycarbonyl , Dodecyloxycarbonyl, 1- (dodecyloxycarbonyl) ethoxycarbonyl], an alkyl group having 7 to 24 carbon atoms A carbonyloxy group (for example, phenoxycarbonyl, 4-t-octylphenoxycarbonyl, 2,4-di-t-pentylphenoxycarbonyl), a carbonamide group having 1 to 24 carbon atoms [for example, acetamido, pivaloylamino, benzamide, -Ethylhexaneamide, tetradecaneamide, 1- (2,4-di-t-pentylphenoxy) butanamide, 3- (2,4-di-t-pentylphenoxy) butanamide, 3-dodecylsulfonyl-2-methylpropanamide A sulfonamide group having 1 to 24 carbon atoms (e.g., methanesulfonamide, p-toluenesulfonamide, hensadecanesulfonamide);
-24 carbamoyl groups (e.g., N-methylcarbamoyl, N-tetradecylcarbamoyl, N, N-dihexylcarbamoyl, N-octadecyl-N-methylcarbamoyl, N-phenylcarbamoyl);
(E.g., N-methylsulfamoyl, N-phenylsulfamoyl, N-acetylsulfamoyl, N-propanoylsulfamoyl, N-hexadecylsulfamoyl, N, N-dioctylsulfamoyl) ), An alkylsulfonyl group having 1 to 24 carbon atoms (eg, methylsulfonyl, benzylsulfonyl, hexadecylsulfonyl), an arylsulfonyl group having 26 to 24 carbon atoms (eg, phenylsulfonyl, p-tolylsulfonyl, p-dodecylsulfonyl, p-methoxysulfonyl), a ureido group having 1 to 24 carbon atoms (for example, 3-methylureido, 3-phenylureido, 3,3-dimethyluredo, 3-tetradecylureide), and a carbon number of 0 to 24
A sulfamoylamino group (e.g., N, N-dimethylsulfamoylamino), an alkoxycarbonylamino group having 2 to 24 carbon atoms (e.g., methoxycarbonylamino,
Isobutoxycarbonylamino, dodecyloxycarbonylamino), nitro group, heterocyclic group having 1 to 24 carbon atoms (for example, 4-pyridyl, 2-thienyl, phthalimide,
Octadecylsuccinimide), cyano group, acyl group having 1 to 24 carbon atoms (eg, acetyl, benzoyl, dodecanoyl), acyloxy group having 1 to 24 carbon atoms (eg, acetoxy, benzoyloxy, dodecanoyloxy), 1 carbon atom To 24 alkylsulfonyloxy groups (e.g., methylsulfonyloxy, heisadecylsulfonyloxy) or arylsulfonyloxy groups having 6 to 24 carbon atoms (e.g., p-toluenesulfonyloxy,
p-dodecylphenylsulfonyloxy).

In the general formula [I], is preferably an integer of 1 or 2.

In the general formula [I], X is preferably a group capable of leaving by a coupling reaction with an oxidized aromatic primary amine developing agent (referred to as a leaving group), and specifically, a halogen atom (fluorine, chlorine) , Bromine, iodine), having 1 to 24 carbon atoms
A heterocyclic group bonded to the coupling active site at the nitrogen atom of
Aryloxy group having 6 to 24 carbon atoms, 6 to carbon atoms
24 arylthio groups (e.g., phenylthio, pt-butylphenylthio, p-chlorophenylthio, p-carboxyphenylthio), acyloxy groups having 1 to 24 carbon atoms (e.g., acetoxy, benzoyloxy, dedocanoyloxy), An alkylsulfonyloxy group having 1 to 24 carbon atoms (eg, methylsulfonyloxy, butylsulfonyloxy, dodecylsulfonyloxy), an arylsulfonyloxy group having 6 to 24 carbon atoms (eg, benzenesulfonyloxy, p-chlorophenylsulfonyloxy) or A heterocyclic oxy group having 1 to 24 carbon atoms (for example, 3-pyridyloxy, 1-phenyl-1,2,3,4-tetrazol-5-yloxy), and more preferably a nitrogen atom at the coupling active position. A heterocyclic or aryloxy group to be bonded

When X represents a nitrogen ring group bonded to a coupling active site with a nitrogen atom, X is, in addition to the nitrogen atom, oxygen, sulfur,
Nitrogen, phosphorus, selenium and tellurium may be a 5- to 7-membered optionally substituted monocyclic or condensed heterocyclic ring which may contain a heteroatom selected from the group consisting of, for example,
Succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2 , 4-dione, thiazolidine-2,4-dione, imidazolidine-2-one, oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one,
Benzoxazolin-2-one, benzothiazoline-2
-One, 2-pyrrolin-5-one, 2-imidazoline-
5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6
-Pyridazone, 2-pyrazone and the like, and these heterocyclic groups may be substituted. Examples of the substituent include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group (eg, amino, N-methylamino, N, N-dimethylamino,
N, N-diethylamino, anilino, pyrrolidino, piperidino, morpholino) other, there is a substituent as examples of the R _3.

When X represents an aryloxy group, X is an aryloxy group having 6 to 24 carbon atoms, and when X is a heterocyclic group, it may be substituted with a group selected from the aforementioned substituent groups. . As a substituent, a carboxyl group, a sulfo group,
Preferred are a cyano group, a nitro group, an alkoxycarbonyl group, a halogen atom, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkyl group, an alkylsulfonyl group, an arylsulfonyl group and an acyl group.

Next, examples of the above-mentioned substituents R ₁ , R ₂ , R ₃ and X which are particularly preferably used in the present invention will be described.

In the general formula [I], R ₁ is particularly preferably a 2 or 4-alkoxyaryl group (eg, 4-methoxyphenyl, 4-butoxyphenyl, 2-methoxyphenyl)
Or a t-butyl group, with a t-butyl group being most preferred.

In the general formula (I), R ₂ is particularly preferably a methyl group, an ethyl group, an alkoxy group, an aryloxy group or a dialkylamino group, and most preferably a methyl group, an ethyl group, an alkoxy group, an aryloxy group or a dimethylamino group. preferable.

In the general formula [I], R ₃ is particularly preferably an alkoxy group, a carbonamido group or a sulfonamido group.

In the general formula [I], X is particularly preferably a heterocyclic group or an aryloxy group bonded to the coupling active site with a nitrogen atom.

When X represents the heterocyclic group, X is preferably represented by the following general formula [II].

In the general formula [II], Z is Represents Here, R ₄ , R ₅ , R ₈ and R ₉ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, or an alkoxycarbonyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₅ ,
R ₅ and R ₆ , R ₆ and R ₇ or R ₄ and R ₈ may combine with each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Particularly preferred among the heterocyclic groups represented by the general formula [II] are those wherein Z in the general formula [II] is Is a heterocyclic group.

The total number of carbon atoms of the heterocyclic group represented by the general formula [II] is 2 to 24, preferably 4 to 20, and more preferably 5 to 16. Examples of the heterocyclic group represented by the general formula (II) are a succinimide group, a maleimide group, a phthalimide group,
1-methylimidazolidin-2,4-dione-3-yl group, 1-benzylimidazolidin-2,4-dione-3-
Yl group, 5,5-dimethyloxazolidine-2,4-dione-
3-yl group, 5-methyl-5-propyloxazolidine-2,4-dione-3-yl group, 5,5-dimethylthiazolidine-2,4-dione-3-yl group, 5,5-dimethylimidazolidine -2,4-dione-3-yl group, 3-methylimidazolidintrion-1-yl group, 1,2,4-triazolidine-3,5-dione-4-yl group, 1-methyl-2-phenyl -1,2,4-triazolidine-3,5-dione-4-yl group, 1-benzyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4-yl group, 5-hexyl Oxy-1-methylimidazolidine-2,4-dione-3-yl group, 1-benzyl-5-ethoxyimidazolidin-2,4
-Dion-3-yl group and 1-benzyl-5-dodecyloxyimidazolidin-2,4-dione-3-yl group.

Among the above heterocyclic groups, an imidazolidine-2,4-dione-3-yl group (for example, 1-benzyl-imidazolidin-
2,4-dione-3-yl group) is the most preferred group.

When X represents an aryloxy group, a 4-carboxyphenyl group, a 4-methylsulfonylphenoxy group,
(4-benzyloxyphenylsulfonyl) phenoxy group, 4- (4-hydroxyphenylsulfonyl) phenoxy group, 2-chloro-4- (3-chloro-4-hydroxyphenylsulfonyl) phenoxy group, 4-methoxycarbonylphenoxy group, 2-chloro-4-methoxycarbonylphenoxy group, 2-acetamido-4-methoxycarbonylphenoxy group, 4-isopropoxycarbonylphenoxy group, 4-cyanophenoxy group, 2- [N-
(2-hydroxyethyl) carbamoyl] phenoxy group, 4-nitrophenoxy group, 2,5-dichlorophenoxy group, 2,3,5-trichlorophenoxy group, 4-methoxycarbonyl-2-methoxyphenoxy group, 4- (3 -Carboxypropanamide) phenoxy group is the most preferred example.

The coupler represented by the general formula [I] has a substituent R ₁ , X or May form a dimer or a multimer which bonds to each other via a divalent or divalent or higher valent group.
In this case, the number of carbon atoms may be out of the specified range for each substituent.

When the coupler represented by the general formula [I] forms a multimer, an addition polymer ethylenically unsaturated compound having a yellow dye-forming coupler residue (yellow color-forming monomer)
A homo- or copolymer is a typical example. In this case, the multimer contains repeating units of the general formula [III], and one or more types of the yellow coloring repeating units represented by the general formula [III] may be contained in the multimer. It may be a copolymer containing one or more color-forming ethylene-type monomers.

In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, A represents -CONH-, -COO-, or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene. A phenylene group or an aralkylene group, and L is -CONH-, -NHCONH-, -NHCOO
-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO
-, - CO -, - O -, - S -, - SO 2 -, - NHSO 2 - or represents a -SO ₂ NH-. a, b, and c represent 0 or 1. Q represents R ₁ , X or the compound of the formula (I) A yellow coupler residue from which a hydrogen atom has been further removed is shown.

As the polymer, a copolymer of a yellow-color-forming monomer represented by a coupler unit of the general formula [III] and a non-color-forming ethylene-like monomer described below is preferable.

Non-color-forming ethylenic monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid,
α-chloroacrylic acid, α-alkylacrylic acid (e.g., methacrylic acid) Amides or esters derived from these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide, t
-Butyl acrylamide, diacetone acrylamide,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile,
Aromatic vinyl compounds (such as styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid,
Examples include citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and -4-vinylpyridine.

In particular, acrylates, methacrylates, and maleates are preferred. The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

As is well known in the field of polymer couplers, the general formula (II)
The ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to (I) may be a copolymer having physical and / or chemical properties such as solubility, binding of the photographic colloid composition. An agent such as gelatin can be selected so that its compatibility, flexibility, thermal stability, and the like are favorably affected.

The yellow polymer coupler used in the present invention is prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl monomer to give a coupler unit represented by the above general formula [III] in an organic solvent, and preparing a latex in an aqueous gelatin solution. And may be made by emulsification and dispersion in the form of, or may be made directly by an emulsion polymerization method.

A method of emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in U.S. Pat.
No. 820, U.S. Pat.
The method described in 3,370,952 can be used.

Specific examples of yellow dye forming couplers R ₃ and X represented by formula (I) below, the present invention is not limited thereto.

 Specific examples of X are shown below.

Specific examples of R ³ are shown below.

Specific examples of the yellow dye-forming coupler represented by the general formula [I] are shown below.

The numbers in the () Table represents number assigned to the specific examples of the X and R _3, the numbers in [] represent the substitution positions on the anilide group.

The couplers of the present invention may be used alone or as a mixture of two to several types, or may be used as a mixture with known yellow dye-forming couplers.

The coupler of the present invention can be used in any layer of a light-sensitive material, but is preferably used in a light-sensitive silver halide emulsion layer or a layer adjacent thereto, and most preferably in a light-sensitive silver halide emulsion layer.

The coupler of the present invention can be synthesized by a conventionally known synthesis method.
There is a synthesis method described in 3047.

The amount of the coupler of the present invention used in the light-sensitive material is 1 × 10 ^-5 mol to 10 ^-2 mol, preferably 1 × 10 ^-4 mol per 1 m ^2.
Mol to 5 × 10 ^-3 mol, more preferably 2 × 10 ^-4 mol to 10 mol
^-3 mol.

As the antibacterial and fungicide used in the present invention, any generally known antibacterial and antifungal agents may be used.
Those described in "Sterilization, disinfection and fungicide technology of microorganisms" edited by the Society of Sanitary Engineers, "Encyclopedia of Fungus Control and Fungus" edited by the Japan Society of Fungicides and Fungi can be used.

Preferably, compounds represented by the following general formulas (FI) to (F-VIII) are used.

(Wherein, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ represent a hydrogen atom, an alkyl group, or an aryl group, and R ⁷ represents a hydrogen atom, an alkyl group, an aryl group , A nitro group, a carboxy group, a sulfo group, a sulfamoyl group, a hydroxy group, a halogen atom, an alkoxy group, or a thiazolyl group.R ¹⁰ represents an alkylene group or an arylene group.R ¹¹ , R ¹² , and R ¹³ , A halogen atom, or an alkyl group, and R ¹⁴ and R ¹⁵ represent a hydrogen atom, an alkyl group, an aryl group, or a nitrogen-containing heterocyclic residue.
R ¹⁶ and R ¹⁷ represent a hydrogen atom, an alkyl group, a halogen atom or an aryl group, and R ¹⁶ and R ¹⁷ may combine to form a benzene ring. R ¹⁸ represents a hydrogen atom or an alkyl group. R ¹⁹ represents an alkyl group or an aryl group.

Y represents a halogen atom; Z ¹ represents a group of non-metallic atoms necessary to form a thiazolyl ring; and Z ² represents a group of non-metallic atoms necessary to form a six-membered ring. n represents 0 or 1, and m represents 1 or 2. Specific examples of the compounds represented by formulas (FI) to (F-VIII) are shown below, but the present invention is not limited thereto.

In addition to the compounds represented by the general formulas (FI) to (F-VIII), methyl-1- (butylcarbamoyl) -2-benzimidazolecarbamate, methylbenzimidazolecarbamate, 2-pyridinethiol-1-oxide, 10, 10'-oxybisphenoxyarsine, N-dimethyl-N'-phenol-N '-(fluorodichloromethylthio) -sulfamide, benzyl bromoacetate 1-{(diiodomethyl) sulfonyl} -4-methylbenzene, 2,3,5 6,6-tetrachloro-4- (methylsulfonyl) pyridine, p-chlorophenyl-3-iodopropargylformal, o-phenylphenol, pentachlorophenol, 4-chloro-3,5-xylenol,
Phenol, thymol, phenoxyethanol, m-cresol, phenethyl alcohol, p-isopropylphenol, salicylic acid and the like may be used.

These antibacterial and antifungal agents may be used alone or in combination of two or more, and any layer may be added. That is,
It may be added to any one of the silver halide emulsion layer, the intermediate layer, the protective layer and the ultraviolet absorbing layer, or to a plurality of these layers. Amount will depend on the type of Antibacterial and Antifungal Agents, preferably 0.001~1.0g / m ^2, more preferably 0.05 to 0.5 g / m ²
It is.

The antibacterial and fungicidal agents used in the present invention are effective on almost all molds, including molds generated in silver halide photographic light-sensitive materials. Aspergil is an example of mold
lusniger, Pullularia pullulans, Chaefomium globosum,
Cladosporium resinae.Aspergillus flavus.Aspergillu
s oryzae.Penicillium citrinum, Penicillium luteum, T
richodermauiride uiride.Aspergillus restrclus, Aspe
rgillus glaucus, Chrysosporium, Aspergillus vesirolo
r, Eurotium rubrum, Eurotium tonophilum, Arthrium pes
talotia and Paecilomyces.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These light-sensitive emulsion layers include a silver halide emulsion layer having sensitivity in each wavelength region and a dye having a complementary color relationship with the light to be exposed-yellow for blue, magenta for green, and cyan for red. By including a so-called color coupler to be formed, color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [Layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle,
A structure in which different composition parts are joined on corners or surfaces)
And the like can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver halide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
95 mol% or more is more preferable.

Such high silver chloride emulsions preferably have a structure in which a silver bromide localized layer is formed in a layered or non-layered form as described above on the inside and / or on the surface of silver halide grains.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized layers can be on the inside of the grain, on the edge, corner, or plane of the grain surface. One preferred example is a layer grown epitaxially on the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in Chimi by P. Glafkides.
e et Phisique Photographique (published by Paul Montel, 196
7 years), Photographic Emulsion Chemistry by GFDuffin
(Focal Press, 1966) M by VLZelikman et al
aking and Coating Photographic Emuldion (Focal Pre
ss, published in 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-3 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. With respect to the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. Examples of spectral sensitizing dyes used at this time include, for example, Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. However, a surface latent image type emulsion is preferred. In the present invention, magenta couplers and cyan couplers which are coupled to an oxidized aromatic primary amine color developing agent and form magenta and cyan, respectively, are usually used in addition to the yellow coupler of the formula (I).

The cyan coupler and magenta coupler preferably used in the present invention are represented by the following general formulas (C-I) and (C
-II), (MI) and (M-II).

In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, they are aryl groups substituted by a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably phenyl group) of R ₇ and R ₉ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Desirable Y ₃ is of a type capable of releasing at any of a sulfur, oxygen or nitrogen atom, and particularly preferred is a type of releasing at a sulfur atom as described in, for example, US Pat. No. 4,351,897 and International Publication WO88 / 04795.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. When the Zb-Zc engagement is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazole described in U.S. Pat. No. 4,500,630 is advantageous in terms of low yellow side absorption and light fastness of a coloring dye. Are preferred, US Pat.
The pyrazolo [1,5-b] [1,2,4] triazole described in 4,540,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and pyrazoloazole couplers having an alkoxy group or aryloxy group at the 6-position as described in EP-A-226,849 and EP 294,785. The use of zorotriazole couplers is preferred.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the coupler represented by II) are listed below.

The couplers represented by the above general formulas (CI) to (M-II) are usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
It is contained in an amount of 1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the yellow coupler of the present invention or the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant of such coupler as dispersion medium (25 ° C)
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 (25 ° C.) and a water-insoluble polymer compound having a boiling point of 1.5 to 1.7.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

Wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and W ₄ represents W ₁ , OW ₁ or SW.
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. No. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of organic anti-fading agents are described in the following patent specifications.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP 52-152225, etc. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are disclosed in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.
No. 52-6623, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Pat.
No. 3,457,079, No. 4,332,886, JP-B-56-21144, etc., hindered amines are U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, JP-B-51-1420, JP-A-58
Nos. 1-114036, 59-53846 and 59-78344, metal complexes are disclosed in U.S. Pat.Nos. 4,050,938 and 4,241,155.
And British Patent No. 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a compound having a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with the second reaction rate constant with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ² is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic ammine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a hetero residue. n represents 1 or 0. A represents a group that forms a chemical bond by reacting with an aromatic ammine-based developer, and X represents a group that reacts with the aromatic amine-based developer to leave. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Where R ₁ and X, Y and R ₂
Alternatively, B and B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by the general formulas (FI) and (F II) include those described in JP-A-63-158545, JP-A-62-283338, EP-A-298321, and 277589. Those described are preferred.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development processing is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearso
n, et al., J. Am. Chem. Soc., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyani dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Weiss's The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As the support used in the present invention, a reflection type support generally used for a photographic light-sensitive material can be used.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. The metal may be aluminum, tin, silver, magnesium or an alloy thereof, and may be the surface of a metal plate, metal foil, or metal foil layer obtained by rolling, vapor deposition, plating, or the like on the surface.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 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 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 includes a pH buffer such as an alkali metal carbonate or phosphate, a development inhibitor such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or an antifoggant. It is common to include. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N
Hydrazines such as biscarboxymethylhydrazine, phenylsemicarbazides, various preservatives such as triethanolamine and catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines Accelerators, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity enhancers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids Various chelating agents represented by acids, for example, ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1 Diphosphonic acid, nitrilo -
N, N, N-trimethylenephosphonic acid, ethylenediamine-
N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal processing is performed, color development is usually performed after black-and-white development and reversal processing are performed. In this black and white developer,
Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. .

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenisher, 500 m
It can also be: When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact air between the photographic processing solution and the air in the processing tank can be represented by an aperture ratio defined below. That is, the aperture ratio = the contact area between the treatment liquid and the air (cm ² ) / the volume of the treatment liquid (cm ³ ). The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.

As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in Japanese Patent Application No. 62-241342, Examples of the method include a slit developing method described in JP-A-63-216050.

Reducing the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to all subsequent steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.

Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. 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-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III) is used. A typical bleach is iron (II
Organic complex salts of I), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycoletheraminetetraacetic acid, or citric acid and tartaric acid And complex salts such as malic acid. Of these, aminopolycarboxylate iron (III) complex salts such as ethylenediaminetetraacetate iron (III) complex salt are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually
4.0 to 8.0, but lower for faster processing
It can be treated at pH.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-812.
No. 95630, Research Disclosure No. 17,129 (July, 1978), etc .; compounds having a mercapto group or disulfide bond; thiazolidine derivatives described in JP-A-50-140129; US Pat. No. 3,706,561 Thiourea derivatives; iodide salts described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836; it can. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and particularly, U.S. Patent No. 3,893,858,
Compounds described in West German Patent No. 1,290,812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. Preservatives for the bleach-fix solution include sulfites and bisulfites, p
-Sulfinic acids such as toluenesulfinic acid or carbonyl bisulfite adducts are preferred.

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, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and t
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be significantly reduced, but bacteria increase due to an increase in the residence time of water in the tank, and the generated floating substances adhere to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Also, isothiazolone compounds, thiabendazoles, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A-57-8542, Hiroshi Horiguchi, "Bactericidal and antifungal chemistry," 1986
Year) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antimicrobial and Antifungal Society, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) A bactericide can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

In some cases, a stabilization treatment may be further 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, can be mentioned. 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-based compounds described in U.S. Pat. Complex, JP 5
Examples thereof include urethane compounds described in 3-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and JP-A-58-144547.
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive 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.

(Example) Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 A multilayer color photographic paper A having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-3) were added to 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7) and dissolved, and the resulting solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain ratio) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide
The following blue-sensitive sensitizing dyes are added to the large-sized emulsion in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver, and the small-sized emulsion is added to the small-sized emulsion. , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mole) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

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

Support Polyethylene laminated paper [Polyethylene on first layer side contains white pigment (Tio ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm and 0.39 μm) Ag molar ratio) The variation coefficient of the grain size distribution was 0.10 and 0.08, and each emulsion was AgBr
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv) −5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 μm average and 0.45 μm average grain size (Ag mole ratio), fluctuation in grain size distribution) Coefficients are 0.09 and 0.11, AgBr for each emulsion
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 1: 1 mixture with (molar ratio) 1: 1 mixture (molar ratio) 2: 4: 4 mixture by weight of each 2: 4: 4 mixture (weight ratio) 4: 2: 4 mixture (weight ratio) 2: 1 mixture (by volume) Preparation of color printing papers B to P Preparation of printing papers B to P in exactly the same manner as the printing paper A except that the yellow coupler of the color printing paper A was replaced with the exemplified compound and the exemplified compound of the antibacterial and fungicide was added. did. The amounts of the couplers in the photographic papers B to P were equimolar to each layer of the photographic paper A. Table 1 shows the compositions of the photographic papers BP.
It was shown to.

First, each sample was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

In addition, each sample was uniformly exposed to light through a transparent glass using the above-mentioned separate sensitometer. The exposure at this time was performed so that the exposure amount was 20,000 CMS with an exposure time of 2 seconds.

The sample subjected to the former three-color separation filter exposure and the latter sample exposed to the transparent glass were processed and then used in an acid fading test and a mold generation test, respectively.

The exposed sample was subjected to continuous processing (running test) using a paper processor until the replenishment was twice the tank capacity for color development in the next processing step. Processing process temperature Time replenisher ^* Tank capacity Color development 35 ° C 45 seconds 161m 17 Bleaching and fixing 30-35 ° C 45 seconds 215m 17 Rinse 30-35 ° C 20 seconds -10 rinse 30-35 ° C 20 seconds -10 rinse 30-35 ° C 20 seconds 350 meters 10 drying 70 to 80 ° C. 60 seconds * replenishment rate is composition (3 and a tank countercurrent system. to rinse →) each processing solution per photosensitive material 1 m ² is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400m Ammonium thiosulfate (70%) 100m Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Add water and 1000m pH ( 25 ° C) 6.0 Rinse solution (same for tank solution and replenisher) Deionized water (3ppm for calcium and magnesium respectively)
Acid fading test The treated acid fading test sample was immersed in a 1N citric acid solution for 1 minute, dried, and allowed to stand at 80 ° C 30% or 40 ° C 70% for 3 days. The drop was measured.

Mold development test Each sample for the mold development test that has been processed is cut into a size of 35 mm x 35 mm, and 1/10 dilution of M40Y medium (containing glucose, malt extract, yeast extract and BACT-Agar) in the center. Aspergillus.Penici generated on color photographic paper in liquid
llium or Paecilomyces sp.
It was dropped. Next, this was left under conditions of 20 ° C. and 100% relative humidity for 3 weeks, and the state of mold generation was observed. The results are shown in Table 1. The numerical values are the hypha and the diameter of the expanded area (m
m), which is represented in the range of 0 to 35. That is,
The smaller the numerical value is, the more excellent the antifungal effect is. The 0 indicates that no mold is generated, and the 35 indicates that the mold is generated on the entire surface of the sample. At the same time, the degree of fading of the portion where mold had occurred was observed. Table 1 shows the test results.

As is clear from the results shown in Table 1, the sample of the present invention is excellent in acid fading and has good antifungal property. Also, it can be seen that even when mold is generated, the fading of yellow is superior to that of the comparative example.

(Effects of the Present Invention) According to the present invention, a silver halide color photographic light-sensitive material can be obtained in which the occurrence of mold on the image surface is suppressed and the storage stability of the yellow dye image is excellent.

Claims (2)

(57) [Claims] 1. A reflective silver halide color photographic light-sensitive material comprising at least one yellow coupler represented by the following formula (I) and at least one antibacterial and fungicide. General formula (I) (In the formula, R ₁ is an aryl group or a tertiary alkyl group, R ₂ is a fluorine atom, an alkyl group, an aryl group, an alkoxy group,
An aryloxy group, a dialkylamino group, an alkylthio group, or an arylthio group, R ₃ represents a group capable of being substituted on a benzene ring, and X represents a hydrogen atom or an oxidized form of an aromatic primary amine-based developer. The groups capable of leaving by the reaction each represent an integer of 0 to 4. However the case of a plurality, the plurality of R ₂ may be the same or different. ] 2. The antibacterial and fungicidal agents are represented by the following general formulas (FI) to (F).
The reflective silver halide color photographic material according to claim 1, which is a compound represented by -VIII). (Wherein, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ represent a hydrogen atom, an alkyl group, or an aryl group, and R ⁷ represents a hydrogen atom, an alkyl group, an aryl group , A nitro group, a carboxy group, a sulfo group, a sulfamoyl group, a hydroxy group, a halogen atom, an alkoxy group, or a thiazolyl group.R ¹⁰ represents an alkylene group or an arylene group.R ¹¹ , R ¹² , and R ¹³ , A halogen atom, or an alkyl group, and R ¹⁴ and R ¹⁵ represent a hydrogen atom, an alkyl group, an aryl group, or a nitrogen-containing heterocyclic residue.
R ¹⁶ and R ¹⁷ represent a hydrogen atom, an alkyl group, a halogen atom or an aryl group, and R ¹⁶ and R ¹⁷ may combine to form a benzene ring. R ¹⁸ represents a hydrogen atom or an alkyl group. R ¹⁹ represents an alkyl group or an aryl group. Y represents a halogen atom; Z ₁ represents a group of non-metallic atoms necessary to form a thiazolyl ring; and Z ² represents a group of non-metallic atoms necessary to form a six-membered ring. n represents 0 or 1, and m represents 1 or 2. )