JPH0664312B2 - Silver halide photographic light-sensitive material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a halogenated photographic light-sensitive material, and in particular, a halogenated compound containing an isoxazolone compound to prevent fog during storage over time. The present invention relates to a silver photographic light-sensitive material.

(Prior Art) A photosensitive silver halide photographic light-sensitive material tends to generate fog by generating nuclei that induce development even if it is not exposed to light.
In particular, the occurrence of fog during storage with time often causes a decrease in sensitivity or deterioration of gradation.

Many compounds have been proposed in the past for the purpose of improving such a phenomenon, for example, 4-hydroxy-6-methyl-
Heterocyclic compounds having a mercapto group such as 1,3,3a, 7-tetraazaindene or 1-phenyl-5-mercaptotetrazole are widely known.

(Problems to be Solved by the Invention) However, these compounds do not always sufficiently suppress fog during storage of a light-sensitive material, and when used in a large amount in anticipation of an effect, sensitivity is lowered and gradation is softened. Will result in coming.

Further, when a large amount of this type of stabilizer is used, the spectral sensitivity is reduced due to the desorption of the sensitizing dye, and further, as a result of diffusion into the adjacent photosensitive layer, a fatal defect such as an undesirable change is caused. May suffer.

Thus, there has been a strong demand for the development of an antifoggant that does not adversely affect other photographic performances and can withstand the long-term storage of silver halide photographic light-sensitive materials.

(Objects of the Invention) The present invention has been achieved in view of the above-mentioned circumstances, and the first object thereof is during storage of a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material) with time. It is an object of the present invention to provide a light-sensitive material containing an antifoggant or stabilizer capable of maintaining stable photographic characteristics.

A second object of the present invention is to provide an antifoggant capable of obtaining a fog-inhibiting property with less desensitization even when used in a large amount in a light-sensitive material, and not hindering spectral depletion and having no diffusion transfer to an adjacent layer. It is to provide a light-sensitive material containing the same.

(Means for Solving the Problems) The above-mentioned object is achieved by a light-sensitive material containing at least one compound represented by the following general formula [I] or [II].

General formula [I] General formula (II) In the formula, R ₁ is a hydrogen atom, a cyano group, a carboxy group, a sulfo group, a mercapto group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group or an aralkyl group (which may be substituted). Optionally an alkyl group or an aralkyl group, for example, methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group, aminomethyl group, phenethyl group, acetylaminomethyl group, ethyl group , 2- (4-dodecanoylaminophenyl) ethyl group, carboxyethyl group, allyl group, 3,3,3-trichloropropyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group Group, sec-butyl group, t-butyl group, n-pentyl group, sec-pentyl group, t-pentyl group Cyclopentyl group, n-hexyl group, sec-hexyl group, t-hexyl group, cyclohexyl group, n-octyl group, sec-octyl group, t-octyl group, n-decyl group, n-undecyl group, n-dodecyl group , N-tetradecyl group, n-pentadecyl group, n
-Hexadecyl group, sec-hexadecyl group, t-hexadecyl group, n-octadecyl group, t-octadecyl group, etc., alkenyl group (which may be substituted, for example, vinyl group, 2-chlorovinyl group, 1 -Methyl vinyl group, 2-cyanovinyl group, cyclohexene-
1-yl group, etc.) alkynyl group (optionally substituted alkynyl group. For example, ethynyl group, 1-propynyl group,
2-ethoxycarbonylethyl group, etc., aryl group (optionally substituted aryl group. For example, phenyl group,
Naphthyl group, 3-hydroxyphenyl group, 3-chlorophenyl group, 4-acetylaminophenyl group, 4-hexadecanesulfonylaminophenyl group, 2-methanesulfonyl-4-nitrophenyl group, 3-nitrophenyl group,
4-methoxyphenyl group, 5-acetylaminophenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, 4-tetradecyloxyphenyl group, etc., heterocyclic group (substituted) A heterocyclic group which may be, for example,
1-imidazolyl group, 2-furyl group, 2-pyridyl group,
5-nitro-2-pyridyl group, 3-pyridyl group, 3,5
-Dicyano-2-pyridyl group, 5-tetrazolyl group, 5
-Phenyl-1-tetrazolyl group, 2-benzthiazolyl group, 2-benzimidazolyl group, 2-benzoxazolyl group, 2-oxazolin-2-yl group, morpholino group, etc.), alkoxy group (may be substituted) An alkoxy group, for example, a methoxy group, an ethoxy group, an n-propyloxy group, an iso-propyloxy group, a cyclohexylmethoxy group, an aryloxy group or a heteroaryloxy group (an optionally substituted aryloxy group or heteroaryl) An oxy group, for example, a phenoxy group,
Naphthyloxy group, 4-acetylaminophenoxy group,
Pyrimidin-2-yloxy group, 2-pyridyloxy group, etc., Alkylthio group (Alkylthio group which may be substituted. For example, methylthio group, ethylthio group, n-
Butylthio group, n-octylthio group, t-octylthio group, n-dodecylthio group, n-hexadecylthio group, ethoxycarbonylmethylthio group, benzylthio group, 2-
Hydroxyethylthio group, etc.) arylthio group, heteroarylthio group (arylthio group which may be substituted,
Heteroarylthio group. For example, a phenylthio group, 4-
Chlorophenylthio group, 2-n-butoxy-5-t-octylphenylthio group, 4-nitrophenylthio group, 2
-Nitrophenylthio group, 4-acetylaminophenylthio group, 1-phenyl-5-tetrazolylthio group, 5-
Methanesulfonylbenzothiazol-2-ylthio group,
Etc.), carbamoyl group (optionally substituted carbamoyl group. For example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2-methoxyethyl) carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group, di-n- Octylcarbamoyl group, 3-dodecyloxypropylcarbamoyl group, hexadecylcarbamoyl group, 3- (2,4-di-t-pentylphenoxy) propylcarbamoyl group, 3-octanesulfonylaminophenylcarbamoyl group, di-n
-Octadecylcarbamoyl group, etc.), and particularly preferably a hydrogen atom, an alkyl group, an aralkyl group or an aryl group.

R ₂ is a hydrogen atom, a cyano group, a carboxy group, an alkyl group or an aralkyl group (an optionally substituted alkyl group or aralkyl group. For example, a methyl group, a trifluoromethyl group, a benzyl group, a chloromethyl group, a dimethylaminomethyl group. , Ethoxycarbonylmethyl group, aminomethyl group, acetylaminomethyl group, ethyl group, 2- (4-dodecanoylaminophenyl) ethyl group, carboxyethyl group, allyl group, 3,3,3-trichloropropyl group,
n-propyl group, iso-propyl group, n-butyl group,
iso-butyl group, sec-butyl group, t-butyl group,
n-pentyl group, sec-pentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, sec-hexyl group, t-hexyl group, cyclohexyl group, n-octyl group, sec-octyl group, t-octyl group , N-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, sec-hexadecyl group, t-hexadecyl group, n
-Octadecyl group, t-octadecyl group, etc.), alkenyl group (alkenyl group which may be substituted. For example, vinyl group, 2-chlorovinyl group, 1-methylvinyl group, 2
-Cyanovinyl group, cyclohexen-1-yl group, etc.) Alkynyl group (optionally substituted alkynyl group. For example, ethynyl group, 1-propynyl group, 2-ethoxycarbobonylethynyl group, etc.), aryl group (substituted) Optionally an aryl group, for example, a phenyl group, a naphthyl group,
3-hydroxyphenyl group, 3-chlorophenyl group, 4
-Acetylaminophenyl group, 4-hexadecanesulfonylaminophenyl group, 2-methanesulfonyl-4-nitrophenyl group, 3-nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonyl group Phenyl group, 2,4-dimethylphenyl group, 4-tetradecyloxyphenyl group, etc., heterocyclic group (heterocyclic group which may be substituted. For example, 1-imidazolyl group, 2-furyl group, 2-pyridyl group, 5-nitro-2-pyridyl group, 3-pyridyl group, 3,5-dicyano-2-pyridyl group, 5-tetrazolyl group, 5-phenyl-1-tetrazolyl group, 2-benzthiazolyl group, 2 −
Benzimidazolyl group, 2-benzoxazolyl group, 2
-Oxazolin-2-yl group, morpholino group, etc.),
Amino group (Amino group which may be substituted. For example, amino group, methylamino group, dimethylamino group, ethylamino group, ethyl-3-carboxypropylamino group, ethyl-2-sulfoethylamino group, phenylamino group, methyl Phenylamino group, methyloctylamino group, methylhexadecylamino group, etc.), alkoxy group (alkoxy group which may be substituted. For example, methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, A cyclohexylmethoxy group, etc.), an aryloxy group or a heteroaryloxy group (an optionally substituted aryloxy group or heteroaryloxy group. For example, a phenoxy group, a naphthyloxy group, a 4-acetylaminophenoxy group, a pyrimidine- group. 2-yloxy group, 2
-Pyridyloxy group, etc.), alkylthio group (optionally substituted alkylthio group, for example, methylthio group, ethylthio group, n-butylthio group, n-octylthio group,
t-octylthio group, n-dodecylthio group, n-hexadecylthio group, ethoxycarbonylmethylthio group, benzylthio group, 2-hydroxyethylthio group, etc., arylthio group or heteroarylthio group (optionally substituted arylthio group or hetero) An arylthio group, for example, a phenylthio group, a 4-chlorophenylthio group, 2
-N-butoxy-5-t-octylphenylthio group, 4
-Nitrophenylthio group, 2-nitrophenylthio group,
4-acetylaminophenylthio group, 1-phenyl-5
-Tetrazolylthio group, 5-methanesulfonylbenzothiazol-2-ylthio group, etc., carbamoyl group (carbamoyl group which may be substituted, for example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2-methoxyethyl) ) Carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group, di-n-octylcarbamoyl group, 3-dodecyloxypropylcarbamoyl group, hexadecylcarbamoyl group, 3- (2,4-di-t-pentylphenoxy) propyl Carbamoyl group, 3-octanesulfonylaminophenylcarbamoyl group, di-n-octadecylcarbamoyl group, etc., sulfamoyl group (sulfamoyl group which may be substituted, for example, methylsulfamoyl group, dimethylsulfamoyl group). Group, diethylsulfamoyl group, bis- (2-methoxyethyl) sulfamoyl group, di-n-butylsulfamoyl group, methyl-n-octylsulfamoyl group, n-hexadecylmethylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N-phenyl-N-methylsulfamoyl group,
4-decyloxyphenylsulfamoyl group, methyloctadecylsulfamoyl group, etc., acylamino group (acylamino group which may be substituted. For example, acetylamino group, 2-carboxybenzoylamino group, 3-nitrobenzoylamino group Group, 3-diethylaminopropanoylamino group, acryloylamino group, etc., sulfonylamino group (optionally substituted sulfonylamino group).
For example, methanesulfonylamino group, benzenesulfonylamino group, 2-methoxy-5-n-methylbenzenesulfonylamino group, 2-chloro-5-dodecanoylaminobenzenesulfonylamino group, etc., alkoxycarbonylamino group (substituted) Optionally an alkoxycarbonylamino group, for example, a methoxycarbonylamino group,
Ethoxycarbonylamino group, 2-methoxyethoxycarbonylamino group, iso-butoxycarbonylamino group, benzyloxycarbonylamino group, t-butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc.), aryloxycarbonylamino group ( An optionally substituted aryloxycarbonylamino group, for example, a phenoxycarbonylamino group, 2,4-
A dimethylphenoxycarbonylamino group, a 4-nitrophenoxycarbonylamino group, a 4-t-butoxyphenoxycarbonylamino group, and the like, an aminocarbonylamino group (an optionally substituted aminocarbonylamino group).
For example, methylaminocarbonylamino group, morpholinocarbonylamino group, diethylaminocarbonylamino group, N-ethyl-N-phenylaminocarbonylamino group, 4-cyanophenylaminocarbonylamino group, 4
-Methanesulfonylphenylaminocarbonylamino group, etc.), aminosulfonylamino group (optionally substituted aminosulfonylamino group, for example, diethylaminosulfonylamino group, di-n-butylaminosulfonylamino group, phenylaminosulfonylamino group) Group, etc.), and particularly preferably a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an acylamino group,
Alternatively, it is a sulfonylamino group.

R ₁ and R ₂ may combine with each other to form a saturated or unsaturated ring.

The compounds of the general formulas [I] and [II] have the following relationship and are usually mixed, so that they may be used as they are.

Next, specific examples of the compound used in the present invention will be listed.
The scope of the present invention is not limited to these specific examples.

The compound of the present invention can be easily synthesized with reference to the methods described in the following documents and patents.

Sankyo Institute Annual Report, Vol. 22, 215 (1970), Japanese Examined Patent Publication No. 52-9675, Bulletin de la societe chimique
de France) page 1978, JP-A-57-206668
No. 57-206667, Tetrahetron
dron), 20: 2835, (1964), JP-A-5
No. 8-194867, No. 57-70878, Japanese Patent Publication No. 4
9-48953, JP-A-59-190977, and Journal of Organism Chemistry (Journal o.
f Organic Chemistry), 48, 4307 (1983)
), Chemical and Pharmaceutical Bulletin, 1
Volume 4, 277, Heterocycles, Volume 12, Issue 10, 12
97 pages, Canadian Journal of Chemistry, 62, 194.
Page 0, JP-A-59-501907 Next, a specific method for synthesizing a compound will be described in order to specifically explain the content of the present invention.

Example-1 Synthesis of 5-t-butyl-3-hydroxyisoxazole (Compound Example 4) 583.7 g of hydroxylamine hydrochloride was dissolved in 2 liters of a 4N sodium hydroxide aqueous solution, and 2 liters of ethanol were added thereto under ice cooling. The pH of the solution was adjusted to 10.0 by adding a 4N sodium hydroxide-ethanol (1: 1) mixed solution. Pivaloyl acetic acid ethyl ester 13 was added to this solution.
80 g of a 4N sodium hydroxide aqueous solution-ethanol (1: 1) mixed solution was used to adjust the pH of the reaction solution to 10.0 ± 0.
2. The temperature was adjusted to 0-5 ° C and added dropwise.

After the completion of dropping, the mixture was stirred at room temperature for 2 hours, poured into 6 kg of concentrated hydrochloric acid water at 0 ° C and left for 12 hours. The precipitated crystals were collected, washed thoroughly with water and dried.

Yield 770 g, yield 68.2%, melting point 99-101 ° C. Example-2 Synthesis of 5-phenyl-3-hydroxyisoxazole (Compound Example 11) Chemical and Pharmaceutical Bulletin Vol. 14, No. 11, pp. 1277-1286. Synthesized by the method.

Melting point 150-151 ° C Example-3 Synthesis of 5-undecyl-3-hydroxyisoxazole (Compound Example 25) Synthesis was carried out according to the method of Example-1.

Yield 59.2%, melting point 55-56 ° C Example-4 Synthesis of 5-methyl-3-hydroxyisoxazole (Compound Example 28) It was synthesized by the method described in JP-A-59-501907.

Melting point 85-86 ° C Example-5 Synthesis of 5- (4-methoxyphenyl) -3-hydroxyisoxazole (Compound Example 31) Synthesis was carried out according to the method of Example-2.

Melting point 191-193 ° C. (decomposition) The compound of the present invention can be used in a layer containing or not containing silver halide, but it is used in a ratio of 10 ^-6 to 1 mol per mol of silver halide. Is preferable, and it is particularly preferable to use it in a ratio of 10 ⁻⁵ mol to 10 ⁻¹ mol.

The silver halide emulsion of the light-sensitive material used in the present invention may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride. For example, in the case of performing rapid processing or low replenishment processing of color paper or the like, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and the silver chloride content is 80 to 100. The case of mol% is particularly preferable. When high sensitivity is required and fog during production, storage and / or processing is required to be particularly low, a silver chlorobromide emulsion containing 50 mol% or more of silver bromide or an odor is used. A grain emulsion (which may contain 3 mol% or less of silver iodide) is preferable, and 70 mol% or more is more preferable. For the color light-sensitive material for photography, silver iodobromide,
Silver chloroiodobromide is preferred, where the silver iodide content is 3-15.
% Is preferred.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multilayer structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention is represented by the grain diameter (in the case of spherical grains or grains close to spheres) and the ridge length in the case of cubic grains, which is the average based on the projected area. Is expressed in terms of yen) is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm.
That is all. The grain size distribution may be narrow or broad, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is 20.
It is preferred to use a so-called monodisperse silver halide emulsion in the present invention within the range of 15%, particularly preferably 15%. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). It is preferable that those having a variation rate) be mixed in the same layer or multilayer-coated in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, an octahedron, a rhombic dodecahedron, and a tetradecahedron, or may have a coexisting form thereof. It may have an irregular crystal form such as a spherical shape, or may have a composite form of these crystal forms. Tabular grains may also be used, in particular the length /
An emulsion in which tabular grains having a thickness ratio value of 5 to 8 or 8 or more account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is Research Disclosure, Volume 170, No. 1764.
It can be prepared using the method described in Section 3 (I, II, III) (December 1978).

The emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure Volume 176, No. 17643 (December 1978) and Volume 187, No. 18716 (November 1978).
The relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

Examples of the photographic light-sensitive material used include various color and black-and-white light-sensitive materials.

For example, a color negative film for photography (general use, movie etc.), a color reversal film (for slide, movie etc. and sometimes not containing a coupler), color photographic paper, color positive film (movie etc.), Color reversal photographic paper, photothermographic material (see US Pat.
00,626, JP-A-60-133449, 59.
No. 218443, JP-A-61-238056), a color light-sensitive material using a silver dye bleaching method, a photographic light-sensitive material for plate making (lith film, scanner film, etc.),
X-ray photographic light-sensitive material (direct / indirect medical use, industrial use, etc.),
Examples thereof include black-and-white negative film for photographing, black-and-white photographic paper, micro light-sensitive material (for COM, micro film, etc.), color diffusion transfer light-sensitive material (DTR), silver salt diffusion transfer light-sensitive material and print-out light-sensitive material.

When applied to color light-sensitive materials, various couplers can be used.

Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers which can be used in the present invention are Research Disclosure (RD) No. 17643.
(December 1978) Item VII-D and ibid. No. 18717.
(November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The coating amount of silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted with a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use couplers in which the color forming dye has a suitable diffusivity, uncolored couplers or DIR couplers which release a development inhibitor upon coupling reaction or couplers which release a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is US Pat. No. 2,40.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620, etc., or an oxygen atom-releasing type yellow coupler or Japanese Patent Publication No. 55-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, Research Disclosure No. 18053 (1979). April, 2004), British Patent No. 1,425,020, West German Patent Application Publication Nos. 2,219,917, and 2,261,361.
No. 2,329,587 and 2,433.
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A No. 812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye and especially the light fastness, while the α-benzoyl acetanilide type coupler can obtain a high color density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat. No. 2,311,082. Same number 2,
343, 703, 2,600,788, 2,908,573, 3,062,635, 3,152,896 and 3,936,015.
No. etc. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,619
Nitrogen atom leaving group described in U.S. Pat.
The arylthio groups described in 51,897 are preferred. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole coupler, US Pat.
369,879 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure. No. 24220
(June 1984) and pyrazolotetrazoles and Research Disclosure No. 24230 (1).
Pyrazolopyrazoles described in Jun. 984). The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable from the viewpoint of low yellow sub-absorption of the color forming dye and light fastness, and European Patent No. 1
Pyrazolo [1,5-b] [1, described in 19,860.
2,4] triazole is particularly preferred.

Cyan couplers usable in the present invention include oil-protection type naphthol type and phenol type couplers, and the naphthol type couplers described in US Pat. No. 2,474,293, preferably US Pat. No. 4,05.
No. 2,212, No. 4,146,396, No. 4,2
Representative examples thereof include nitrogen atom desorption type two-equivalent naphthol couplers described in JP-A Nos. 28,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Pat. No. 2,369,929 and No. 2,369,929.
801,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, of which typical examples are US Pat.
No. 72,002, a phenolic cyan coupler having an ethyl group or higher alkyl group at the meta-position of the phenol nucleus, U.S. Pat. Nos. 2,772,162 and 3,3.
758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication No. 3,329,729 and JP-A-59-.
2,5-diacylamino-substituted phenol-based couplers described in 166956 and the like and US Pat. No. 3,44.
No. 6,622, No. 4,333,999, No. 4,4
51,559 and 4,427,767, etc., and has a phenylureido group at the 2-position and 5-
Examples thereof include a phenol type coupler having an acylamino group at the position, and a 5-amido-1-naphthol type coupler described in JP-A No. 61-179438.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are exemplified by magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570, and also in European Patent No. 96,570 and West German Application No. No. 234,533, specific examples of yellow, magenta or cyan couplers are described.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
0 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,
282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and two or more layers in which the same compound is different. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,02.
No. 7, etc. Further, steps of latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. No. etc.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0.003 for the magenta coupler. In the cyan coupler, it is 0.002 to 0.3 mol.

The photographic light-sensitive material used in the present invention is applied to a rigid support such as a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or glass. For details of the support and the coating method, see Research Dice Closure, Volume 176, No. 17643X.
Page V (P.27) Section XVII (P.28) (1978 12
Monthly issue).

In the present invention, a reflective support is preferably used.

The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

There is no particular limitation on the developing method of the silver halide photographic light-sensitive material. For example, Research Disclosure, No. 1
Any of known methods and known processing solutions such as those described in Vol. 76, pp. 28-30 can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose.
Treatment temperature is usually selected between 18 ° C and 50 ° C, but 1
The temperature may be lower than 8 ° C or higher than 50 ° C.

Conventional methods can be applied to form a dye image. For example, the negative-positive method (for example, “Journal of the Society of
Motion Picture and Teleuision Engineers ”, 61st
Vol. (1953), pp. 667-701); developed with a developer containing a black-and-white developing agent to produce a negative silver image, then at least one uniform exposure or other suitable fog treatment. And a color reversal method for obtaining a dye positive image by subsequent color development; a silver dye bleaching method in which a photographic emulsion layer containing the dye is exposed and then developed to form a silver image, and the silver image is bleached using the bleaching catalyst as a bleach catalyst. Are used.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methanesulfoamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

LFA Mason Photographic Processing Chemist
ry (Focal Press, 1966), pages 226-229,
US Patents 2,193,015 and 2,592,364
Nos. 4,483,849, and JP-A-48-64933 may be used.

Color developers also include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides,
A development inhibitor such as iodide and an organic antifoggant or an antifoggant can be contained. If necessary, a water softener, a preservative such as hydroxylamine,
Organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid chelating agents, antioxidants It may also contain agents.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used.

For example, ferricyanide, dichromate, iron (II
I) or an organic complex salt of cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid. Complex salts; persulfates, permanganates, nitrosphenols, etc. can be used. Of these, potassium ferrocyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron (III)
The complex salts are useful in either a stand-alone bleaching solution or a one-bath bleach-fixing solution.

As the fixer, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after desilvering such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the rinsing water, the number of rinsing tanks (the number of tiers), the replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Among these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is as follows: Journal of the Society of Motion Picture and Television Engineers (Journal o
f the Society of Motion Picture and Television Eng
ineers) 64, 248-253 (May 1955). Usually, the number of stages in the multi-stage countercurrent system is preferably 2-6, particularly 2-4
Is preferred.

The developing solution used for black-and-white photographic processing may contain a known developing agent. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-
Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p)
-Aminophenol) and the like can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, etc.,
Further, if necessary, a solubilizing agent, a color tone agent, a development accelerator, a surfactant, a defoaming agent, a hard water hardening agent, a film hardening agent, a viscosity imparting agent and the like may be contained.

A so-called "lith type" development process can be applied to the photographic emulsion of the present invention. What is "lith type" development processing? For the photographic reproduction of line images or the photographic reproduction of halftone images with halftone images, dihydroxybenzenes are usually used as the developing agent, and the development process is performed under a low sulfite ion concentration. Is a contagious development process (details are described in Mason's "Photographic Processing Chemistry" (1966), pages 163-165).

(Example) Hereinafter, the present invention will be described in more detail with reference to Examples.

Example-1 A silver iodobromide emulsion (average silver halide grain size 0.8 µm) containing 6 mol% of silver iodide was chemically ripened to the maximum sensitivity by a gold and sulfur sensitization method to obtain a high sensitivity iodobromide. A silver emulsion was obtained.

Then, the emulsion was divided into equal parts and the compound of the present invention and the comparative compound were added as shown in Table 1 below to prepare 1-oxy-
An appropriate amount of 3,5-dichloro-s-triazine sodium salt and saponin as a coating aid were added. These emulsions were dried on a polyester support which had been subbed to give a dry film thickness of 5 μm.
Was applied and dried to obtain Samples 1 to 11.

One set of the obtained samples was placed in a refrigerator set at 5 ° C, and the other two sets were placed under high temperature and low humidity and high temperature and high humidity, respectively (Table 1).
After leaving it to stand for 7 days, the three sets were exposed through an optical wedge by a usual method, developed with Kodak D-76 developer at 20 ° C for 7 days, fixed, washed with water and dried by a usual method. After that, the photographic properties (sensitivity and fog) were measured, and the results shown in Table 1 were obtained.

The sensitivities in the tables are expressed as relative sensitivities, using the logarithm of the exposure amount required to obtain an optical density of fog value + 0.2, with the comparative sample being 100, and the fog values are values obtained by subtracting the base density. .

As is clear from Table 1, the compound according to the present invention suppresses the generation of fog and has a smaller decrease in sensitivity than the comparative compound even when the compound is left under severe storage conditions.

Example-2 On a paper support laminated on both sides with polyethylene, a multi-layer color photographic paper having the layer constitution shown in Table 2 was prepared.

The coating liquid was prepared as follows.

Preparation of coating liquid for the first layer To 19.1 g of the yellow coupler (a) and 4.4 g of the color image stabilizer (b), 27.2 m of ethyl acetate and 7.9 m of the solvent (c) were added and dissolved, and this solution was diluted with 10% dodecyl. 10% including 8m sodium benzenesulfonate
It was emulsified and dispersed in a gelatin aqueous solution of 185 m. On the other hand, the following blue-sensitive sensitizing dye was added to a silver chlorobromide emulsion (containing 1 mol% of silver bromide and 70 g / kg of Ag) at 5.0 × per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 10 ^-4 mol. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted so that the composition shown in Table 2 was obtained to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue-sensitive emulsion layer (5.0 × 10 ⁻⁴ mol added per mol of silver halide) Green sensitive emulsion layer (Adding 4.0 × 10 ⁻⁴ mol per mol of silver halide) (7.0 × 10 ⁻⁴ mol added per mol of silver halide) Red-sensitive emulsion layer (1.0 × 10 ⁻⁴ mol added per mol of silver halide) For the red-sensitive emulsion layer, the following compounds were added to silver halide 1
2.6 × 10 ⁻³ mol was added per mol.

The following dyes were used as the anti-irradiation dye in each emulsion layer.

Green sensitive emulsion layer Red-sensitive emulsion layer Structural formulas of compounds such as couplers used in this example are as follows.

(a) Yellow coupler (b) Color image stabilizer (c) solvent (d) Color mixing inhibitor (e) Magenta coupler (f) Color image stabilizer (g) a solvent _{(C 8 H 17) 3 -P} = O and 2: 1 mixture (weight ratio) (h) UV absorber 1: 5: 3 mixture (molar ratio) of (i) Color mixing inhibitor (j) Solvent (iso C ₉ H ₁₉ O ₃ P = O (k) Cyan coupler 1: 1 mixture (molar ratio) (l) Color image stabilizer 1: 3: 3 mixture (molar ratio) (m) solvent After adding a sensitizing dye to each of the third and fifth layers, which are the silver halide emulsion layers, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene is 150 × 10 ⁻⁴ mol per mol of silver halide and 1-phenyl-5-mercaptotetrazole is 1.5 per mol of silver halide. Stabilized by the addition of × 10 ^-4 mol.

Before adding the yellow coupler (a) to the first layer (blue-sensitive layer), the comparative compound and the compound of the present invention were added as shown in Table 2 below, and then adjusted and coated.

The obtained multilayer color light-sensitive material was subjected to a high temperature and high humidity treatment for a storability test in the same manner as in Example 1, and then subjected to ordinary wedge exposure, and then subjected to the following color treatment. Treatment process Temperature Time Color development 35 ° C 45 seconds Bleach fixing 35 ° C 45 seconds Rinse 1 35 ° C 20 seconds Rinse 2 35 ° C 20 seconds Rinse 3 35 ° C 20 seconds Dry 80 ° C 60 seconds Rinse from rinse 3 Rinsing 1 was carried out by flushing with water in 3 tanks. The treatment liquids used are as follows.

Color developer Hydroxylamine 0.04 mol Benzyl alcohol 15m Diethylene glycol 10m Sodium sulfite 0.2g Potassium carbonate 30g EDTA.2Na 1g Sodium chloride 1.5g 4-Amino-3-methyl-N-ethyl-N- [β- (methane sulfonamido) ethyl] - p-phenylenediamine sulfate 5.0g bleach (4,4'-diamino stilbene) was added to 3.0g water 1000 m pH 10.05 bleach-fixing solution EDTAFe (III) NH ₄ · 2H ₂ O 60 g EDTA · 2Na · 2H ₂ O 4 g Ammonium thiosulfate (70%) 120 m Sodium sulfite 16 g Glacial acetic acid 7 g Water was added to 1000 m pH 5.5 Rinse solution Formalin (37%) 0.1 m 1-Hydroxyethylidene-1 , 1-diphosphonic acid (60 %) 1.6 m bismuth chloride 0.35g ammonia water (26%) 2.5 m nitrilotriacetic acid _{· 3Na 1.0g EDTA · 4H 2 O} 0.5g of sodium sulfite 1.0 g 5-chloro-2-methyl-4- Isothiazolin-3-one 50 mg Water was added 1000 m Table 3 shows the results of the storage test on the blue-sensitive layer. The results also show that the compound according to the present invention showed no deterioration in photographic characteristics due to aging. It can be seen that the antifoggant effect with less sensitivity is exhibited.

(Effects of the Invention) As is apparent from the above examples, according to the present invention, a silver halide photographic light-sensitive material can be obtained which does not cause fog or decrease in sensitivity even under severe storage conditions. ,
A preferable photosensitive material can be provided.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing a compound represented by the following general formula [I] or [II]. General formula [I] General formula (II) In the formula, R ₁ is a hydrogen atom, a cyano group, a carboxy group, a sulfo group, a mercapto group, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group,
Represents a heterocyclic group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, a carbamoyl group, and R ₂ represents a hydrogen atom, a cyano group, a carboxy group, an alkyl group, an aralkyl group, an alkenyl group. Group, alkynyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group,
Heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, carbamoyl group, sulfamoyl group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, aminocarbonylamino group, aminosulfonylamino group Represent. R ₁ and R ₂ may combine with each other to form a saturated or unsaturated ring.