JPH0581024B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photosensitive material containing a phenolic cyan image-forming coupler. More specifically, the present invention relates to a method for preventing staining after developing a photosensitive material containing a cyan image-forming coupler (hereinafter referred to as cyan coupler). (Prior art) After exposing a silver halide photographic material to light,
By color development processing, the aromatic primary amine developing agent oxidized by silver halide reacts with the color-forming coupler to form a color image. Typical cyan image-forming couplers include phenolic couplers and naphthol couplers.
No. 3772002, No. 2772162, No. 3758308, No. 3772002, No. 2772162, No. 3758308, No.
No. 4126396, No. 4334011, No. 4327173, No.
No. 3446622, No. 4333999, No. 4451559, etc.
4427767, etc., and naphthol type couplers are described in U.S. Patent No. 2474293, U.S. Patent No. 4052212,
It is described in No. 4146396, No. 4228233, No. 4296200, etc. (Problems to be Solved by the Invention) However, the color images obtained in this way may produce stains (increased density in unexposed areas) after processing, and this drawback has not been significantly improved. Although there were some, it was not enough. Stain in unexposed areas of a silver halide color photographic material is undesirable because it not only determines the quality of white areas in the image but also worsens color staining of the color image and impairs visual sharpness. Particularly in the case of reflective materials (for example, color paper), the reflection density of the stain is theoretically emphasized several times as much as the transmission density, and even a weak stain impairs image quality, so this is a very important factor. The occurrence of stains in silver halide color photographic materials is roughly classified into four types depending on the cause. 1
One of these is caused by heat and humidity after the unprocessed photosensitive material is manufactured and before it is processed.The other is caused by development fog of silver halide.The third is that caused by the development process of color couplers. Color contamination caused by the liquid (e.g. air fog), or developing agent remaining in the emulsion film is oxidized by the subsequent bleaching bath or oxygen in the air, reacts with the coupler, and becomes a dye (e.g. (Bleach stain) and four other causes include changes in the sensitive material over time due to light and moist heat after development processing. The stain resulting from the development treatment of the phenolic cyan coupler according to the present invention means stains 3 and 4 described above. Therefore, it is an object of the present invention to provide a color photographic material that is less likely to stain after color development as described above. An example of using 3-pyrazolidone derivatives to prevent staining is known from JP-A-57-211147.
This 3-pyrazolidone compound has a substituent on the 2-position nitrogen atom, and is completely different from the present invention. By the way, patents are known that use 3-pyrazolidone derivatives, particularly their precursors, in silver halide photographic materials. For example, 2-(substituted methyl)-2-pyrazolidone is known from US Pat. No. 3,241,967, but this is completely different from the present invention and does not have the effects of the present invention. 3 in JP-A-57-40245 and JP-A-59-104641.
- Precursor compounds in which the 3-enol of pyrazolidone is protected with an acyl ester or a carbonate ester are known. However, the purpose of adding these compounds to silver halide photographic materials is to provide good photographic sensitivity, maximum density, and desired sensitometric properties, and the content described in JP-A-57-40245 is adapted to black and white photographic materials. On the other hand, the content described in JP-A-59-104641 achieves high sensitivity without increasing fog density, and although it may be applied to color photographic materials, it is not the objective of the present invention. They are different. (Means for Solving the Problems) As a result of various studies to achieve the above object of the present invention, at least one cyan image forming coupler represented by the following general formula () and the following general formula () are combined. It has been found that the objects of the present invention can be effectively achieved by a silver halide color photographic light-sensitive material containing an emulsified dispersion obtained by dissolving or impregnating at least one of the compounds shown above in lipophilic fine particles. General formula ()

[Formula] In the formula, R ₁ is a substituted or unsubstituted aliphatic group,
aromatic group, heterocyclic group, aromatic amino group, or
represents a heterocyclic amino group, R ₂ represents a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 or more carbon atoms, or an acylamino group, and X represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group; group, aromatic group or acylamino group,
Z represents a hydrogen atom or a group capable of leaving during oxidative coupling with a developing agent. Here R ₂ and X
may be linked to each other to form a 5- to 7-membered ring (excluding a benzene ring), or R ₁ , R ₂ ,
One group among X and Z may form a dimer or more multimeric coupler. General formula []

[Formula] In the formula, A represents a substituted or unsubstituted alkyl group, aryl group, acyl group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, or amino group,
R ₂₁ and R ₂₂ each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group, R ₂₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group, and R ₂₄ represents a substituted or unsubstituted alkyl group. It represents an aryl group, and P represents an oxygen atom or a sulfur atom. The compound of general formula () can be synthesized by the method described in JP-A-57-40245 and JP-A-59-104641, or a method analogous thereto. The phenolic cyan coupler in the general formula () will be explained. R ₁ is preferably an aliphatic group having 1 to 36 carbon atoms,
Preferably, aromatic groups having 6 to 36 carbon atoms (e.g., phenyl group, naphthyl group, etc.), heterocyclic groups (e.g.,
3-pyridyl group, 2-furyl group, etc.), or
represents an aromatic or heterocyclic amino group (e.g., anilino group, naphthylamino group, 2-benzothiazolyl amino group, 2-pyridylamino group, etc.),
These groups further include alkyl groups, aryl groups,
Heterocyclic groups, alkoxy groups (e.g. methoxy groups,
2-methoxyethoxy group, etc.), aryloxy group (e.g., 2,4-di-tert-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (e.g.,
2-propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, trienesulfonyloxy group) group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g.,
dipropylsulfamoylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group, (e.g., phenylsulfonyl group), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxyl group, cyano group, carboxy group, nitro group, sulfo group, halogen atom, etc. may have been done. In this specification, the "aliphatic group" may be linear, branched or cyclic, and may also be an alkyl group,
The meaning includes both saturated and unsaturated groups such as alkenyl groups and alkynyl groups (typical examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, icosenyl group, iso
-propyl group, tert-butyl group, tert-octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, 2-hexadecenyl group, propargyl group, etc.). R ₂ is a hydrogen atom, preferably an acylamino group having 1 to 36 carbon atoms (e.g., acetylamino, butyrylamino, tetradecanoylamino, benzoylamino group, etc.), or a fatty acid having 1 or more carbon atoms, preferably 1 to 20 carbon atoms. Represents a family group. These groups are
R ₁ may be substituted with a permissible substituent; for example, R ₂ includes a methyl group and a methyl group having a substituent, and the substituent includes an alkyloxy group (e.g., methoxy group, butoxy group, benzyloxy group, etc.), aryloxy group (e.g., phenoxy group, 4-chlorophenoxy group, 4-cyanophenoxy group, 4-tert-amylphenoxy group, etc.), alkylthio group (e.g.,
methylthio group, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, 4-chlorophenylthio group, 4-dodecylphenylthio group, etc.), alkyl or arylsulfonyl group (e.g., methanesulfonyl group, phenylsulfonyl group) , 4-chlorophenylsulfonyl group, etc.),
Preferred are acylamino groups (eg, acetylamino groups, benzoylamino groups, etc.), imide groups (eg, succinimide groups, phthalimide groups, hydantoinyl groups, etc.), ureido groups (eg, phenylureido groups, methylureido groups, etc.), and cyano groups. X represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), preferably an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or an acylamino group; The basis of
R ₁ may be substituted with a permissible substituent. Furthermore, R ₂ and X may be linked to each other to form a saturated or unsaturated 5- to 7-membered ring (excluding a benzene ring), in which case R ₂ together with an acylamino group forms a nitrogen-containing heterocycle. It is preferable to do so. Z represents a hydrogen atom or a coupling-off group, such as a halogen atom (e.g.
fluorine atom, chlorine atom, bromine atom, etc.), alkoxy groups (e.g., ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy groups (e.g., 4
-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tekiladecanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., amide groups (e.g., dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.),
Alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy, benzyloxycarbonyloxy, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy, etc.), aliphatic, aromatic or heterocyclic thio groups (e.g., Examples include ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide groups (eg, succinimide group, hydantoinyl group, etc.), and aromatic azo groups (eg, phenylazo group, etc.).
These leaving groups may include photographically useful groups. General formula () is preferably a cyan coupler represented by general formula () or general formula ().

【formula】

[Formula] In the general formula () and the general formula (), X and Z are as defined in the general formula (). R ₃ , R ₄ and R ₅ are each a substituted or unsubstituted aliphatic group having 1 to 36 carbon atoms or a C 6 to
36 substituted or unsubstituted aromatic groups,
R ₆ represents a hydrogen atom, an aliphatic group having 1 to 20 carbon atoms, or a substituted aliphatic group having 1 to 20 carbon atoms;
R ₄ or X and R ₆ may be linked together to form a saturated or unsaturated 5- to 7-membered ring (excluding a benzene ring). Preferred substituents for these groups include the substituents allowed for R ₁ . Preferred R ₃ is a substituted alkyl group or a substituted or unsubstituted aryl group, and particularly preferred as a substituent for the alkyl group is an optionally substituted phenoxy group or a halogen atom, and the aryl group has at least one halogen atom. Particularly preferred are phenyl groups substituted with atoms, alkyl groups, sulfonamido groups, or acylamino groups. Preferred R ₄ is a substituted alkyl group or a substituted aryl group, and a phenoxy group which may be substituted is particularly preferred as a substituent of the alkyl group. In the general formula (), preferable X is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, or an acylamino group. It is also preferable that X and R ₄ form a 5- to 7-membered ring, and in that case, forming a 5- or 6-membered ring is particularly preferable. In the general formula (), Z is preferably a hydrogen atom or a halogen atom, with a chlorine atom being particularly preferred. Preferred R ₅ is an optionally substituted alkyl group or a substituted aryl group, and particularly preferred is a substituted or unsubstituted alkyl group. Preferred R ₆ is an alkyl group having 1 to 15 carbon atoms or a substituted methyl group, and among them, an ethyl group is particularly preferred. In the general formula (), preferable X is a halogen atom. In the general formula (), Z is preferably a halogen atom. When R ₆ is a hydrogen atom, X is preferably an acylamino group. The cyan coupler represented by the general formula () is
They can be used alone or in combination with other known couplers (not limited to cyan). Further, couplers of general formula () and general formula () can be used (single or plural) in combination. The mixing ratio of these is 5 to 95 mol% each.
It can be used effectively in a wide range of areas.

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【formula】

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【formula】

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embedded image Next, the compound represented by the general formula [ ] will be explained in detail. A is a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, benzyl group, allyl group, cyclohexyl group, octyl group,
hydroxymethyl group, hexanoyloxymethyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, octadecenyl group, etc.), aryl group (e.g., phenyl group, 4-tert-butylphenyl group, 3-pentadecylphenyl group, 3-(2-
(ethylhexanamide) phenyl group, 3-naphthyl group, etc.), heterocyclic group (e.g. furfuryl group,
pyridyl group, etc.), acyl group (e.g., acetyl group, heptanoyl group, 2-ethylhexanoyl group, benzoyl group, dodecanoyl group, etc.), alkoxy group (e.g., methoxy group, hexyl group, 2-ethylhexanoyl group, etc.),
-ethylhexyl group, dodecyloxy group, hexadecyloxy group, 2-dodecyloxyethoxy group, 2-(2-octyloxy-5-tert-octylbenzenesulfonamido)ethoxy group, etc.),
Aryloxy group (e.g. phenyloxy group,
2,4-di-tert-amylphenoxy group, 3-pentadecylphenoxy group, cholestane-3-oxy group, etc.), heterocyclic oxy group (e.g., 3-pyridyloxy group, 2-furfuryloxy group, etc),
Alkylthio groups (e.g. ethylthio group, hexylthio group, dodecylthio group, benzylthio group, cyclohexylthio group, octylthio group, etc.), arylthio groups (e.g. phenylthio group, 4-octyloxyphenylthio group, 4-tert-butylthio group, etc.) nylthio group, 3-pendadecyl phenylthio group, etc.), amino group (e.g., amino group, N-methylamino group, N,N-diethylamino group, N,
N-dihexylamino group, anilino group, 2-chloroanilino group, 4-anisidinyl group, 4-cyanoanilino group, 2-(dodecyloxy)ethylamino group, 4-(2,4-di-tert-amylphenoxy)butylamino group , 2-pyridylamino group,
2,6-pyrimidylamino group, N-dodecylamino group, etc.). The compound of general formula () is A
A dimer may be formed via _R21 , _R22 ,
The substituted or unsubstituted alkyl group or aryl group of R ₂₃ and R ₂₄ has the same meaning as explained for the substituted or unsubstituted alkyl group or aryl group of A above. P represents an oxygen atom or a sulfur atom, with an oxygen atom being particularly preferred. A is preferably a substituted or unsubstituted alkoxy group. Also A
It is preferable that the substituent defined in (1) does not contain an acid group such as carboxylic acid or sulfonic acid. Next, specific examples of typical compounds represented by the general formula [] according to the present invention will be shown, but the present invention is not limited thereto.

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[Chemical formula] The coupler represented by the general formula () is from 1×10 ^-3 mol per mol of silver halide present in the same layer.
It is preferable to add it to the emulsion layer in a proportion of 1 mole,
More preferably, the proportion is 2×10 ⁻³ mol to 3×10 ⁻¹ mol. The compound of general formula () may be added in an amount of 1 mol% to 200 mol%, particularly preferably 2 mol% to 30 mol%, relative to the coupler represented by general formula ().
The range is mole %. In carrying out the present invention, it is preferable that the lipophilic coupler represented by the general formula () and the compound represented by the general formula () be dissolved or impregnated in the lipophilic fine particles. The substances constituting the lipophilic fine particles include oily solvents (including those that are solid at room temperature such as wax) for additives such as couplers, latex polymers, couplers, etc., depending on the needs of the above-mentioned compounds. Additives such as color mixing inhibitors and ultraviolet absorbers are substances that also serve as oily solvents. Here, the lipophilic fine particles mean fine particles that are not substantially dissolved in the gelatin aqueous solution and exist as a separate phase in the gelatin aqueous solution. The lipophilic fine particles according to the present invention are usually prepared by combining a coupler of the general formula () and a compound of the general formula () in a high boiling point solvent (oil) with a boiling point of 170°C or higher at atmospheric pressure.
It can be used alone, or dissolved in a low boiling point solvent alone (if no oil is required as mentioned above), or in a mixed solvent of the oil and a low boiling point solvent, and this solution is emulsified and dispersed in an aqueous solution of a hydrophilic colloid such as gelatin. prepared. There is no particular restriction on the particle size of lipophilic particles, but
It is preferably 0.05μ to 0.5μ, particularly preferably 0.1μ to 0.3μ. The oil/coupler ratio is preferably 0.00 to 2.0 by weight. Specific examples of the oil include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.). ate, dioctylbutyl phosphate, monophenyl-
pt-butylphenyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide, dibutyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate,
diethyl azelate), trimesates (e.g. tributyl trimesate), compounds containing epoxy rings (e.g. the compounds described in US Pat. No. 4,540,657), phenols (e.g.

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[Chemical formula] Ethers (eg, phenoxyethanol, diethylene glycol monophenyl ether) can be mentioned. In addition, latex polymers include acrylic acid methacrylic acid and its esters (e.g. methyl acrylate, ethyl acrylate, butyl methacrylate, etc.), acrylamide, methacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate, etc.), acrylonitrile, Styrene, divinylbenzene, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters (e.g. maleic acid methyl ester), N-vinyl-2-pyrrolidone,
Latex polymers produced using monomers such as N-vinylpyridine, 2- and 4-vinylpyridine alone or in combination of two or more are used. Further, as the low boiling point solvent used to prepare the lipophilic fine particles according to the present invention, organic solvents having a boiling point of about 30°C to 150°C at atmospheric pressure, such as lower alkyl acetates such as ethyl acetate, isopropyl acetate, and butyl acetate; Ethyl propionate, methanol, ethanol, secondary butyl alcohol, cyclohexanol, fluorinated alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
Examples include methyl cellosolve acetate, acetone, methyl acetone, acetonitrile, dioxane, dimethyl formamide, dimethyl sulfoxide, chloroform, and cyclohexane. In the present invention, magenta and yellow couplers can be used in addition to the cyan couplers. Typical examples of these include pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these magenta and yellow couplers that can be used in the present invention are available from Research Disclosure (RD).
17643 (December 1978) - Section D and Section 18717 (1979)
(November 2013). The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler whose coupling active position is a hydrogen atom. Couplers in which the coloring dye has adequate diffusivity, colorless couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used. A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. Specific examples thereof are described in US Pat. No. 2,407,210, US Pat. No. 2,875,057, and US Pat. No. 3,265,506. The use of two-equivalent yellow couplers is preferred for the present invention;
U.S. Patent No. 3408194, U.S. Patent No. 3447928, U.S. Patent No.
Oxygen atom separation type yellow couplers described in No. 3933501 and No. 4022620, Japanese Patent Publication No. 58-10739, U.S. Patent No. 4401752, U.S. Pat.
No. 4326024, RD18053 (April 1979), British Patent No.
No. 1425020, West German Published Application No. 2219917, same no.
Typical examples thereof include nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2261361, 2329587, and 2433812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density. Magenta couplers that can be used in the present invention include oil-protected indazolone-based or cyanoacetyl-based couplers, preferably pyrazoloazole-based couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone 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 coloring dye. Representative examples thereof include U.S. Pat.
No. 2600788, No. 2908573, No.
It is described in No. 3062653, No. 3152896, No. 3936015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat.
or the nitrogen atom leaving group described in U.S. Patent No.
The arylthio group described in No. 4351897 is particularly preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73636 provides high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3,061,432, preferably pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Pat. No. 3,725,067; Research Disclosure
24220 (June 1984) and pyrazolotetrazoles and research described in JP-A-60-33552.
Examples include the pyrazolopyrazoles described in Disclosure 24230 (June 1984) and JP-A-60-43659. Imidazo[1,2-b]pyrazoles described in U.S. Pat. No. 4,500,630 are preferred from the viewpoint of low yellow side absorption and light fastness of coloring dyes, and pyrazolo[1,5-b]s described in U.S. Pat. No. 4,540,654 are preferable. -b][1,2,4]triazole is particularly preferred. The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide, sodium chloride, potassium iodide alone or a mixture thereof) solution with gelatin. It is produced by mixing in the presence of a water-soluble polymer solution such as The silver halide grains may have different layers inside and on the surface, may have a multiphase structure such as a bonded structure, or may have a uniform phase throughout the grain. Moreover, they may be mixed.
For example, silver chlorobromide grains having different phases may have a core or single or multiple layers within the grain that are richer in silver bromide than the average halogen composition. Furthermore, the grains may have a core or single or multiple layers that are richer in silver chloride than the average halogen composition. The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain size is taken as the grain size, and in the case of cubic grains, the grain size is taken as the ridge length, and expressed as an average based on the projected area) is 2μ or less.
0.1 μ or more is preferable, but 1 μ or less is particularly preferable.
It is 0.15μ or more. The particle size distribution may be narrow or wide. So-called monodisperse silver halide emulsions can be used in the present invention. The degree of monodispersity is 15%, which is the coefficient of variation obtained by dividing the standard deviation derived from the grain size distribution curve of silver halide by the average grain size.
It is preferably at most 10%, particularly preferably at most 10%. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use. The silver halide grains used in the present invention may have regular crystal shapes such as cubes, octahedrons, dodecahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical shapes. It may have an irregular crystal form, or it may have a composite form of these crystal forms. Further, tabular grains may be used, and in particular, an emulsion in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more, account for 50% or more of the total projected area of the grains may be used. It may also be an emulsion consisting of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the grains. The photographic emulsion used in the present invention is described in "Chimie et Physique" by P. Grafkides.
Photographique) (Paul Montel Publishing, 1967)
2003), “Photographic Emulsion Chemistry” by GF Duffin
(Photographic Emulsion Chemistry) (published by Focal Press, 1966), “Making and Coating of Photographic Emulsions” by VL Zelikman et al.
It can be adjusted using the method described in Coating Photographic Emulsion (Focal Press Co., Ltd., 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). It is also possible to use a conversion method in which a halide salt is added to form a less soluble silver halide. As one of the simultaneous mixing methods, it is also possible to use a method in which pAg in the liquid phase in which silver halide is produced is kept constant, that is, a so-called controlled double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating. Known silver halide solvents (for example, ammonia, rhodankali or U.S. Pat.
−144319, JP-A-54-100717 or JP-A-Sho
54-155828 etc.) can be used in precipitation, physical ripening, and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, washing with water, flocculation sedimentation, ultrafiltration, etc. are used. The photographic emulsion used in the present invention can be spectrally sensitized with methine dyes or the like, if necessary. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. The photosensitive material produced using the present invention contains hydroquinone derivatives, aminophenol derivatives, amines,
It may contain gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, and the like. In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer (protective layer, intermediate layer, etc.). The ultraviolet absorber can be either solid or liquid at room temperature. As a specific example of a liquid ultraviolet absorber, see
No. 57-142975, Special Publication No. 55-36984, US Patent
2- described in No. 3794493, No. 4518686, etc.
Examples include (2'-hydroxyphenyl)benzotriazole compounds. The 2-(2'-hydroxyphenyl)benzotriazole compound preferably has a melting point of 15°C or lower. Other examples of ultraviolet absorbers that can be used in the photosensitive material of the present invention include US Pat.
Aryl-substituted benzotriazoles described in U.S. Pat. No. 3553794, U.S. Pat. No. 4236013, U.S. Pat. U.S. Patent No. 3705805 and U.S. Pat.
Cinnamic acid esters described in US Patent No. 3707375, benzophenones described in US Patent No. 3215530 and UK Patent No. 1321355, US Patent No. 3761272
Polymer compounds having ultraviolet-absorbing residues such as those described in No. 1 and No. 4431726 can be used. Ultraviolet absorbing fluorescent brighteners described in US Pat. No. 3,499,762 and US Pat. No. 3,700,455 may be used. A typical example of UV absorber is RD24239
(June 1984), etc. Various anti-fading agents can be used in the light-sensitive material of the present invention. Specific examples of anti-fading agents include compounds represented by the following general formula () or ().

[ka]

[Chemical formula] In the formula, R ₃₃ is a hydrogen atom, an aliphatic group, an aromatic group,
Heterocyclic group or substituted silyl group

Represents [formula]. Here, R ₄₃ , R ₄₄ or R ₄₅ may be the same or different and each represents an aliphatic group, an aromatic group, an aliphatic oxy group or an aromatic oxy group, and these groups are allowed in R ₁ . may have other substituents. R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a mono- or dialkylamino group, an imino group and Represents an acylamino group. R ₃₃ and R ₃₄ may be combined with each other to form a 5- or 6-membered ring. R ₃₉ , R ₄₀ , R ₄₁ and R ₄₂ may be the same or different and represent a hydrogen atom and an alkyl group, respectively. X ₀ represents a hydrogen atom, an aliphatic group, an acyl group, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic sulfinyl group, an oxy radical group, and a hydroxyl group. A ₀ is 5 members,
Represents a group of nonmetallic atoms necessary to form a 6- or 7-membered ring. Representative examples are shown below.

【formula】

【formula】

【formula】

[ka]

【formula】

【formula】

[ka]

【formula】

[ka]

【formula】

【formula】

【formula】

[ka]

【formula】

【formula】

[ka]

[ka]

[ka]

【formula】

【formula】

[Chemical] The photosensitive material of the present invention contains one or more types of surfactants for various purposes such as a coating aid, antistatic property, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (for example, development acceleration, high contrast, and sensitization). It may also contain an agent. In addition to the above-mentioned additives, the photosensitive material of the present invention includes:
Furthermore, various stabilizers, antifouling agents, developing agents or their precursors, development accelerators or their precursors,
Lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. A representative example of these additives is Research Disclosure 17643 (December 1978).
18716 (November 1979). The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Further, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity. In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a back layer. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic light-sensitive materials. be done. Among the supports used in the present invention, baryta paper and paper supports laminated with polyethylene containing a white pigment (for example, titanium oxide) in polyethylene are preferred. The present invention can be applied to various photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper. The present invention is also applicable to black-and-white light-sensitive materials using a mixture of three color couplers as described in Research Disclosure 17123 (July 1978). The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p
-Toluenesulfonate and the like. Color developers contain preservatives such as alkali metal sulfites and hydroxylamines, as well as PH buffers such as alkali metal carbonates, borates, or phosphates; bromides, iodides, and vanzimidazole. It generally contains development inhibitors or antifoggants such as benzothiazoles or mercapto compounds. In addition, organic solvents (eg, benzyl alcohol, diethylene glycol, etc.), polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, etc. may be included. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron () or cobalt (); amino acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid; Complex salts of polycarboxylic acids or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; manganates; nitrosophenols, and the like can be used. Among these, ethylenediaminetetraacetic acid iron() salt and persulfate are preferable from the viewpoint of rapid processing and environmental pollution. Furthermore, iron ethylenediaminetetraacetate ()
Complex salts are particularly useful in both stand-alone bleach solutions and single bath bleach-fix solutions. If necessary, various accelerators may be used in combination with the bleaching solution and bleach-fixing solution. After the bleach-fixing process or the fixing process, a washing process is usually performed. Various known compounds may be added to the water washing process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, disinfectants and anti-fungal agents that prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum. A hardening agent typified by salt, a surfactant for preventing drying load and unevenness, etc. can be added as necessary. Or LE
West “Water Quality Judgment Standards”
Criteria), “Science and Engineering of Photography” (Phot.Sci.
Eng.), Vol. 6, pp. 344-359 (1965), etc. may be added. The addition of chelating agents and anti-bacterial agents is particularly effective. In the washing process, two or more tanks are generally used for countercurrent washing to save water. Furthermore, instead of the water washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be performed. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image.
For example, various buffers (e.g., borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, Typical examples include monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. (used in combination) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (benzisothiazolinone,
irithiazolone, 4-thiazolinebenzimidazole, halogenated phenols, etc.), surfactants,
Various additives such as fluorescent brighteners and hardeners may be used, and two or more compounds for the same or different purposes may be used in combination. Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a membrane PH regulator after treatment. The silver halide photosensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development. Typical compounds of these are JP-A No. 56-64339,
No. 57-144547, No. 57-211147, No. 58-50532
No. 58-50536, No. 58-50533, No. 58-
It is described in No. 50534, No. 58-50535, No. 58-115438, etc. Various processing solutions in the present invention are used at a temperature of 10°C to 50°C, but it is preferable to develop at a temperature of 33°C to 38°C. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed. A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary. EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Example 1 A multilayer color photographic paper having the layer structure shown in Table 1 was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. Preparation of first layer coating solution: 10 g of yellow coupler (a) and 2.3 g of color image stabilizer (b), 10 ml of ethyl acetate and solvent.
(c) 4 ml was added and dissolved, and this solution was emulsified and dispersed in 90 ml of a 10% aqueous gelatin solution containing 5 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the blue-sensitive dye shown below was added to a silver chlorobromide emulsion (containing 80 mol% silver bromide, 70 g/Kg of Ag) at 2.0 ×
10 ^-4 mol was added to make 90 g of a blue-sensitive emulsion. The emulsified dispersion and the emulsion were mixed and dissolved, and the concentration was adjusted with gelatin to give the composition shown in Table 1 to prepare a coating solution for the first layer. The fifth layer contains couplers I-4 and I-4 of the present invention.
36 was used as a 1:1 (mol/mol) mixture. The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. The following spectral sensitizers were used in each emulsion.

【table】

【table】 Blue-sensitive emulsion layer;

[Formula] (2 x 10 ^-4 mol added per mol of silver halide.) Green-sensitive emulsion layer;

[Chemical] (2.5 x 10 ^-4 mol added per 1 mol of silver halide.) Red-sensitive emulsion layer;

[Chemical formula] (2.5×10 ^-4 mol added per mol of silver halide.) The structural formulas of the compounds used in this example, such as couplers, are as follows. (a) Yellow coupler

[ka] (b) Color image stabilizer

[C] (c) Solvent (isoC ₉ H ₁₉ O) - ₃ P=O

[ka]

[ka]

[ka]

【table】 (h) Ultraviolet absorber

【formula】

【formula】

[ka] 1:5:3 mixture (molar ratio) of (i) Color mixing prevention agent

[Formula] (j) Solvent (isoC ₉ H ₁₉ O) - ₃ P=O The following dyes were used as anti-irradiation dyes in each emulsion layer. Green-sensitive emulsion layer;

【formula】 red-sensitive emulsion layer;

[C] Next, photosensitive material (B) for comparison and the present invention ~
(I) was created. Photosensitive material [B] Photosensitive material [A] except that the fifth layer of the photosensitive material [A] further contains 30 mol% of the exemplary compound [-1] of the general formula () of the present invention based on the coupler.
The same photosensitizer material. Photosensitive material [C] Photosensitive material [A] except that the fifth layer of the photosensitive material [A] further contains 30 mol% of the exemplary compound [-5] of the general formula () of the present invention based on the coupler.
The same photosensitive material. Photosensitive material [D] Photosensitive material [A] except that the fifth layer of the photosensitive material [A] further contains 30 mol% of the exemplary compound [-8] of the general formula () of the present invention based on the coupler.
The same photosensitive material. Photosensitive material [E] Photosensitive material [A] except that the fifth layer of the photosensitive material [A] further contains 30 mol% of the exemplary compound [-12] of the general formula () of the present invention based on the coupler.
The same photosensitive material. Photosensitive material [F] Photosensitive material [A] except that the fifth layer of the photosensitive material [A] further contains 30 mol% of the exemplary compound [-24] of the general formula () of the present invention based on the coupler.
The same photosensitive material. Photosensitive material [G] Photosensitive material [A] except that the fifth layer of the photosensitive material [A] further contains 30 mol% of the exemplary compound [-25] of the general formula () of the present invention based on the coupler.
The same photosensitive material. Photosensitive material [H] The same photosensitive material as photosensitive material [A] except that the fifth layer of photosensitive material [A] further contains 30 mol% of Exemplified Compound-35 based on the coupler. Photosensitive material (I) Same as photosensitive material [A] except that the fifth layer of photosensitive material [A] further contains 30 mol% of the following compound R-1 described in U.S. Pat. No. 3,241,967 based on the coupler as a comparative compound. Same photosensitive material.

[Formula] Photosensitive material [J] Photosensitive material [A] except that the fifth layer of the photosensitive material [A] further contains 30 mol% of the following compound R-2 described in JP-A-57-211147 based on the coupler as a comparative compound. The same photosensitive material as material [A].

[Formula] Photosensitive material [K] In the fifth layer of the photosensitive material [A], except that the following structure R-3 described in JP-A No. 57-211147 is further contained in an amount of 30 mol% based on the coupler. The same photosensitive material as photosensitive material [A].

[Formula] The photosensitive materials (A) to (K) obtained as described above were exposed to light through an optical wedge, and then color developed according to the following processing method. However, in order to clarify the effects of the present invention, the processing method described below is formulated so that the developing agent and other processing solution components tend to remain and stains are likely to occur. Processing process temperature and time Color development 33°C 3 minutes 30 seconds Bleach-fixing 33°C 1 minute 30 seconds Washing 20-25°C 1 minute (no stirring) Drying 50°-80°C 2 minutes The components of each processing solution are as follows: It is as follows. Color developer Nitrilotriacetic acid/3Na 2.0g Benzyl alcohol 15ml Diethylene glycol 10ml Sodium sulfite 0.2g Potassium bromide 0.5g Hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-ethyl-N-
[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate 6.5g Sodium carbonate (monohydrate) 30g Add water to 1000ml (PH10.1) Bleach-fix solution Color developer mentioned above 400ml Ammonium thiosulfate ( 70wt%) 150ml Sodium sulfite 12g (EDTA) Sodium iron 36g (EDTA) Disodium 4g Water was added and 1000ml Adjusted to pH 7.0 with 1N sulfuric acid The above composition solution was aerated for 1 hour and used. Note) The above bleach-fix solution is formulated to be used in cases where the color developer adheres to the photosensitive material during running and the composition of the solution changes due to a large amount being brought into the bleach-fix solution. be. Next, the developed photographic material [A] ~
For each of [K], after processing, the cyan reflection density of the non-image area was measured using a Fuji type self-recording densitometer under red light, and then left at 80°C and 70% RH for 3 days;
The cyan reflection density of the non-image area was measured in the same manner again for each case where the samples were left at 80° C. dry (10 to 15% RH) for 5 days. Table 2 shows the increase in cyan density from the density immediately after treatment.

[Table] As is clear from Table 2, when the cyan coupler of the general formula () according to the present invention is used, staining due to moist heat can be significantly prevented by using the additive of the general formula () of the present invention. Recognize.
On the other hand, no stain suppression effect was observed in the comparative light-sensitive materials [I] to [K]. Example 2 Photographic material (A) prepared in Example 1
After exposing (K) through an optical wedge,
Color development was carried out according to the following processing method. After exposing the above photosensitive material through an optical wedge, it was processed in the following steps. Processing steps (33°C) Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing with water 3 minutes Drying (50-80°) 2 minutes The components of each processing solution are as follows. Color developer Benzyl alcohol 12ml Diethylene glycol 5ml Potassium carbonate 25g Sodium chloride 0.1g Sodium bromide 0.5g Anhydrous sodium sulfite 2g Hydroxylamine sulfate 2g Fluorescent brightener 1g N-ethyl-N-β-methanesulfonamidoethyl-3- Methyl-4-aminoaniline sulfate
Add 4g water to 1 and add NaOH to adjust the pH to 10.2. Bleach-fixing solution Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Anhydrous sodium sulfite 2.7g EDTA ferric ammonium salt 65g Color developer (above) 100ml Adjust the pH to 6.7-6.8 and add water 1. A roller transport type developing processor was used in which the developing process was carried out with normal replenishment, and the composition of the processing solution was approximately at equilibrium. Next, for each of the above-mentioned photosensitive materials that had been developed, the non-image area was measured for red light 1 hour after processing, and then the results were measured for red light when left at 80°C - 70% RH for 3 days and when dried at 80°C. (10~15%
RH) After being left for 5 days, the cyan reflection density of the non-image area was measured again. Table 3 shows the increase in stain from 1 hour after treatment.

[Table] As is clear from Table 3, when using the cyan coupler of the general formula () according to the present invention, by using the additive of the general formula () of the present invention, staining caused by heat and moist heat can be significantly reduced. It turns out that it can be prevented. On the other hand, comparative photosensitive materials [I] ~
In [K], no stain suppression effect was observed. Example 3 Photographic materials (A) to (K) according to Example 1
was prepared, exposed to light through an optical wedge, and then processed according to the following steps. In this processing, the photographic materials (A) to (K) of Example 1 were processed using a rapid processing step and a processing solution assuming a running equilibrium state of rapid processing. Processing step C Temperature Time ^* Color development 37℃ 1 minute 40 seconds Bleach fixing 33℃ 1 minute 00 seconds Washing 1 30℃ 20 seconds Washing 2 30℃ 20 seconds Washing 3 30℃ 20 seconds Drying 80℃ 1 minute 00 seconds *However Includes 10 seconds of transfer time between baths. *Water washing should be done in a countercurrent flow from 3 to 2 to 1. Color developer Water 800ml Diethylenetriaminepentaacetic acid 3.0g Benzyl alcohol 15ml Diethylene glycol 10ml Sodium sulfite 2.0g Potassium bromide 0.5g Potassium carbonate 30.0g N-ethyl-N-(β-methanesulfamidoethyl)-3-methyl-4-amino Aniline sulfate
5.5g Hydroxylamine sulfate 4.0g Fluorescent brightener (stilbene type) 1.0g Add water to 1000ml Bleach-fix solution Ammonium thiosulfate (70%) 200ml Sodium sulfite 18g Iron ethylenediaminetetraacetate () Ammonium 65g Ethylenediaminetetraacetic acid, 2Na 5g of the above color developer 350ml Add water 1000ml Bleach-fixer Ammonium thiosulfate (70%) 200ml Sodium sulfite 18g Iron () ammonium ethylenediaminetetraacetate
65g Ethylenediaminetetraacetic acid/2Na 5g 350ml of the above color developer Add 1000ml of water PH7.00 Next, for each of the above developed photosensitive materials, measure the non-image area with red light one hour after processing. and then left at 80℃-70%RH for 3 days and 80℃ dry (10-15%RH)5
After being left for a day, the non-image area was again measured using red light. Table 4 shows the increase in stain from 1 hour after treatment.

[Table] As is clear from Table 4, when the cyan coupler of the general formula () according to the present invention is used, staining due to moist heat can be significantly prevented by using the additive of the general formula () of the present invention. I understand.
On the other hand, no stain suppression effect was observed in the comparative light-sensitive materials [I] to [K]. Example 4 A comparative photographic material was prepared as shown below. A color photographic material was prepared by coating the following layers 1 to 11 in multiple layers on a paper support laminated on both sides with polyethylene. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye. (Photosensitive layer composition) The components and the coating amount in g/m ² are shown below. Regarding silver halide, the coating amount is shown in terms of silver. 1st layer (antihalation layer) Black colloidal silver ……0.01 Gelatin ……0.2 2nd layer (low sensitivity red sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (*5 and 4) (Silver iodide 3.5 mol%, average grain size
0.7μ) ...Silver 0.15 Gelatin ...1.0 Cyan coupler (*3) ...0.30 Anti-fading agent (*2) ...0.15 Coupler solvent (*15 and *1) ...0.06 3rd layer (high sensitivity red sensitivity Layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (*5 and *4) (silver iodide 8.0 mol%, average grain size 0.7μ)...Silver 0.10 Gelatin...0.50 Cyan coupler (* 3) ...0.10 Anti-fading agent (*2) ...0.05 Coupler solvent (*15 and *1) ...0.02 4th layer (intermediate layer) Yellow colloidal silver ...0.02 Gelatin ...1.00 Anti-color mixing agent (*14 ) ...0.08 Color mixture inhibitor solvent (*13) ...0.16 Polymer latex (*6) ...0.40 5th layer (low-sensitivity green-sensitive layer) Iodine spectrally sensitized with green sensitizing dye (*12) Silver bromide emulsion (silver iodide 2.5 mol%, average grain size 0.4μ)
…Silver 0.20 Gelatin …0.70 Magenta coupler (*11) …0.40 Anti-fading agent A (*10) …0.05 Anti-fading agent B (*9) …0.05 Anti-fading agent C (*8) …0.02 Coupler solvent (*18) ...0.60 6th layer (high sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) (silver iodide 3.5 mol%, average grain size 0.9 μ)
…Silver 0.20 Gelatin …0.70 Magenta coupler (*11) …0.40 Anti-fading agent A (*10) …0.05 Anti-fading agent B (*9) …0.05 Anti-fading agent C (*8) …0.02 Coupler solvent (*18) ...0.60 7th layer (yellow filter layer) Yellow colloidal silver ...0.20 Gelatin ...1.00 Color mixing prevention agent (*14) ...0.06 Color mixing prevention agent solvent (*13) ...0.24 8th Layer (Low sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (*16) (silver iodide 2.5 mol%, average grain size 0.5μ)
...Silver 0.15 Gelatin ...0.50 Yellow coupler (*15) ...0.20 Coupler solvent (*18) ...0.05 9th layer (high sensitivity blue sensitive layer) Spectral sensitized with blue sensitizing dye (*16) Silver iodobromide emulsion (silver iodide 2.5 mol%, average grain size 1.4μ)
...Silver 0.20 10th layer (ultraviolet absorption layer) Gelatin ...1.50 Ultraviolet absorber (*19) ...1.0 Ultraviolet absorber solvent (*18) ...0.30 Color mixture prevention agent (*17) ...0.08 11th layer (Protective layer) Gelatin...1.0 The compounds used here are as follows: *1 Dioctyl phthalate *2 2-(2-hydroxy-3-sec-butyl-
5-t-butylphenyl)benzotriazole *3 2-[α-(2,4-di-t-amylphenoxy)butanamide]-4,6-dichloro-5-ethylphenol *4 5,5'-dichloro-3, 3'-di(3-sulfobutyl)-9-ethylthiacarbonyl cyanine sodium salt *5 Triethylammonium-3-[2-{2-
[3-(3-sulfopropyl)naphtho(1,
2-d) Thiazolin-2-ylidenemethyl]-1-butenyl}-3-naphtho(1,2
-d) Thiazolino]propanesulfonate *6 Polyethyl acrylate *7 Trioctyl phosphate *8 2,4-di-t-hexylhydroquinone *9 Di-(2-hydroxy-3-t-butyl-
5-methylphenyl)methane*10 3,3,3',3'-tetramethyl-5,6,
5′,6′-tetrapropoxy-1,1′-bisspiroindane*11

[Chemical] *12 5,5'-diphenyl-9-ethyl-3,
3'-Disulfopropyloxacarbocyanine Na salt *13 Phosphoric acid-o-cresyl ester *14 2,4-di-t-octylhydroquinone *15 α-pivaloyl-α-[(2,4-dioxo-1- benzyl-5-ethoxyhydantoin-3-yl)-2-chloro-5-(α-
2,4-dioxo-t-amylphenoxy)butamino]acetanilide*16 Triethylammonium 3-[2-(3-benzylrhodanin-5-ylidene)-3-benzoxazolinyl]propanesulfonate*17 2,4-di -sec-octylhydroquinone *18 Trinonyl phosphate *19 5-chloro-2-(2-hydroxy-3-
t-Butyl-5-t-octyl)phenylbenztriazole Photosensitive materials (B) for comparison and of the present invention
(J) was created as follows. Photosensitive material (B) Photosensitive material (A) except that the second and third layers of the photosensitive material (A) further contain exemplified compound-1 of the general formula [] of the present invention in the same lipophilic fine particles as the 30 mol% coupler. ) is the same photosensitive material. Photosensitive material (C) In the second and third layers of the photosensitive material (A), 30 mol% of exemplified compound-5 of the general formula [] of the present invention is contained as a comparative compound based on the coupler, and further, in the same lipophilic fine particles as the coupler. The same photosensitive material as photosensitive material (A) except for the following. Photosensitive material (D) In the second and third layers of the photosensitive material (A), 30 mol% of exemplified compound-8 of the general formula [] of the present invention is further contained in the same lipophilic fine particles as the coupler. The same photosensitive material as photosensitive material (A). Light-sensitive material (E) In the second and third layers of the light-sensitive material (A), the exemplified compound-12 of the general formula [] of the present invention is further contained at 30 mol% relative to the coupler in the same lipophilic fine particles as the coupler. is the same photosensitive material as photosensitive material (A). Photosensitive material (F) In the second and third layers of the photosensitive material (A), 30 mol% of exemplified compound-24 of the general formula [] of the present invention is contained relative to the coupler in the same lipophilic fine particles as the coupler. The same photosensitive material as photosensitive material (A). Photosensitive material (G) In the second and third layers of the photosensitive material (A), 30 mol% of the exemplified compound-25 of the general formula [] of the present invention is contained in the same lipophilic fine particles as the coupler. , the same photosensitive material as photosensitive material (A). Photosensitive material (H) Same as photosensitive material (A) except that in the second and third layers of photosensitive material (A), 30 mol% of Exemplary Compound-35 is contained in the same lipophilic particles as the coupler. photographic material. Photosensitive material (I) In the second and third layers of the photosensitive material (A), the following compound R-1 described in U.S. Pat. The photosensitive material is the same as photosensitive material (A) except for the content.

[Formula] Photosensitive material (J) In the second and third layers of the photosensitive material (A), 30 mol% of the following compound R-2 described in JP-A-57-211147 was added to the coupler as a comparative compound, and The same photosensitive material as photosensitive material (A) except that it is contained in the same lipophilic fine particles.

[Formula] Photosensitive material (K) In the second and third layers of the photosensitive material (A), the following structure R-3 described in JP-A No. 57-211147 is further contained as a comparative compound in an amount of 30 mol% based on the coupler. is the same photosensitive material as photosensitive material (A).

[Processing process]

First development (black and white development) 38℃ 1′15″ Water washing 38℃ 1′30″ Reverse exposure 100Lux or more 1″ or more Color development 38℃ 2′15″ Water washing 38℃ 45″ Bleach fixing 38℃ 2′00″ Washing with water 38℃ 2′15″ [Processing solution composition] First developer Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt 0.6g Diethylenetriaminepentaacetic acid, pentasodium salt
4.0g Potassium sulfite 30.0g Potassium thiocyanate 1.2g Potassium carbonate 35.0g Hydroquinone monosulfonate potassium salt
25.0g Diethylene glycol 15.0ml 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0g Potassium bromide 0.5g Potassium iodide 5.0mg Add water 1 (PH9.70) Color developer Benzyl alcohol 15.0ml Diethylene glycol 12.0ml 3,6-dithia-1,8-octanediol
0.2g Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt 0.5g Diethylenetriaminepentaacetic acid, pentasodium salt
2.0g Sodium sulfite 2.0g Potassium carbonate 25.0g Hydroxylamine sulfate 3.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g Potassium bromide 0.5g Iodide Potassium 1.0mg Add water 1 (PH10.40) Bleach-fix solution 2-mercapto-1,3,4-triazole
1.0g Ethylenediaminetetraacetic acid, disodium, dihydrate 5.0g Ethylenediaminetetraacetic acid, Fe(), ammonium hydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate (700g/liquid) 160.0ml Glacial acetic acid 5.0ml Add water 1 (PH6.50) Next, for each of the above-mentioned photosensitive materials that had been developed, the non-image areas were measured using red light from 1 hour after processing, and then left at 80°-70% RH for 3 days. The non-image area was again measured using green light for both the case and the case of leaving it at 80° dry (10 to 15% RH) for 5 days. Table 5 shows the increase in stain from 1 hour after treatment.

[Table] As is clear from Table 5, when the cyan coupler of the general formula () according to the present invention is used, staining due to moist heat can be significantly prevented by using the additive of the general formula () of the present invention. Recognize.
On the other hand, no stain suppression effect was observed in the comparative photosensitive materials [] to [K]. Example 5 The same photosensitive material 1 as the photosensitive material [A] of Example 1 and the exemplified compounds of the general formula [] of the present invention as shown in Table 6 below in the fifth layer of the photosensitive material [A] or Photosensitive materials 2 to 17 were prepared which were the same as photosensitive material [A] except that the comparative compound was further contained in the lipophilic fine particles in an amount of 30 mol % based on the cyan coupler. <Preparation method of emulsified dispersion of cyan coupler in the fifth layer> 10.0 g of cyan coupler (k), 3.84 g of color image stabilizer (l), and ethyl acetate to an exemplary compound of the general formula [] of the present invention or a comparative compound. Add 100 ml and 13 ml of solvent (m) and dissolve this solution containing 20 ml of 10% sodium dodecylbenzenesulfonate.
Emulsify and disperse in 100ml of 10% gelatin aqueous solution. The photosensitive materials 1 to 17 thus obtained were exposed to light through an optical wedge, and then color developed according to the same processing method used in Example 1. However, the washing time was shortened to 50 seconds. Next, the cyan reflection density (stain) of the non-image area was measured for each of the developed photosensitive materials 1 to 17 under the same conditions as in Example 1. The results obtained are shown in Table 6.

[Table] As is clear from the above results, the generation of cyanstein can be significantly suppressed by using the compound of the general formula [] in combination with the cyan coupler of the present invention. By the way, the effect of combined use with the compound of general formula [] is compound (-9) where A in general formula [] is an aryl group, compound (-34) where A is an acyl group, and compound (-2) where A is an aryloxy group. , a compound that is a heterocyclic oxy group (-21), a compound that is an alkylthio group (-15), a compound that is an arylthio group (-14), a compound that is an amino group (-16), a compound where P is a sulfur atom (-10)
Also, compounds in which A is an alkoxy group (-1,
−27, −31, −33).

Claims (1)

[Scope of Claims] 1. An emulsified dispersion obtained by dissolving or impregnating lipophilic fine particles with at least one cyan image-forming coupler represented by the following general formula () and at least one compound represented by the following general formula (). A silver halide color photographic material characterized by having a layer containing. General formula () [Chemical formula] In the formula, R ₁ is a substituted or unsubstituted aliphatic group,
represents an aromatic group, a heterocyclic group, an aromatic amino group, or a heterocyclic amino group, R ₂ represents a hydrogen atom, or a substituted or unsubstituted aliphatic group having 1 or more carbon atoms or an acylamino group, and X represents hydrogen atoms, halogen atoms, substituted or unsubstituted aliphatic groups,
It represents an aromatic group or an acylamino group, and Z represents a hydrogen atom or a group that can be separated upon oxidative coupling with a developing agent. Here, R ₂ and X may be connected to each other to form a 5- to 7-membered ring (excluding a benzene ring),
Further, one group among R ₁ , R ₂ , X, and Z may form a dimer or more multimeric coupler. General formula [Chemical formula] In the formula, A represents a substituted or unsubstituted alkyl group, aryl group, acyl group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, or amino group. Representation,
R ₂₁ and R ₂₂ each independently represent a hydrogen atom or an unsubstituted or substituted alkyl group, R ₂₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group, and R ₂₄ represents a substituted or unsubstituted alkyl group. It represents an aryl group, and P represents an oxygen atom or a sulfur atom.