JPH0514893B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material (hereinafter abbreviated as a color photographic light-sensitive material) which is provided with a high color mixing prevention effect and a color development fog prevention effect. ). (Prior art) Color photographic materials generally have three types of silver halide color photographic emulsion layers coated on a support that are selectively sensitized to have sensitivity to blue light, green light, and red light. has been done. For example, in a negative color photographic light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side, and between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. A bleachable filter layer is provided to absorb blue light transmitted through the blue-sensitive emulsion layer.
Furthermore, between each emulsion layer, another intermediate layer is provided for a specific purpose, and a protective layer is provided as the outermost layer. In addition, for example, in a color photographic light-sensitive material for photographic paper, generally a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are coated in this order from the side to be exposed. Intermediate layers such as ultraviolet absorbing layers, protective layers, etc. are provided for specific purposes. It is also known to provide these emulsion layers in a different arrangement from the above, and furthermore, instead of using a single layer of emulsion layers with different photosensitive ranges, it is known that the emulsion layers have sensitivities in substantially the same color sensitive range for each color light. It is also known to use two types of light-sensitive emulsion layers. In these color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine compound as a color developing agent, and the oxidation product of the color developing agent and the dye-forming coupler are combined. A dye image is formed by this reaction. This method typically uses phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indazolone or cyanoacetyl magenta couplers, and acyl to form cyan, magenta and yellow dye images, respectively. Acetamide or benzoylmethane yellow couplers are used. These dye-forming couplers are contained in the light-sensitive color photographic emulsion layer or in the developer. When color photographic materials obtained as described above are subjected to color development, there have conventionally been undesirable problems such as "color fog" and "color mixing." The former is mainly due to color development due to the coupling between the air-oxidized developing agent and the coupler, and as a countermeasure, a method of adding a color-forming capri inhibitor such as a hydroquinone derivative near the coupler is widely adopted. The latter type of "color mixing" occurs when a color developing agent oxidation product generated by color development of a certain silver halide emulsion layer diffuses to another silver halide emulsion layer during the color development processing process, and couples and develops color in that layer. As a countermeasure for this, an intermediate layer is provided between the two silver halide emulsion layers, and a non-diffusible hydroquinone derivative is added to this layer to prevent the color developing agent from diffusing. A method of reducing the oxidation product to eliminate the coupling ability is widely used. Regarding these non-diffusible hydroquinone derivatives that can be used for the purpose of preventing color fogging and color mixing, for example, US Pat.
No. 2384658, No. 2675531, No. 2675531, No. 2384658, No. 2675531, No.
Described in No. 2728659. However, in the conventional method, the emulsified dispersion containing the non-diffusible hydroquinone derivative is unstable, and storage for several hours causes coarsening of the dispersed particles and crystallization of the contained non-diffusible hydroquinone derivative. This means that the effect of suppressing color development fog and preventing color mixture is reduced, which has been a bigger problem than before from the viewpoint of quality stability during mass production of color photographic materials. Several methods for improving this problem have already been proposed, and they can be broadly classified into two types. 1
One is to change the physical properties of the non-diffusible hydroquinone derivative itself, and the other is to improve the technique of use. Regarding the former, for example, U.S. Patent No.
No. 3700453 describes a method using a mixture of two or more di-substituted hydroquinones having a secondary alkyl group having 9 to 20 carbon atoms. However, although this technique is very advantageous in terms of crystallization and precipitation of emulsified dispersions, it has little effect on improving the problem of reduced effectiveness due to coarsening of dispersed particles. Moreover, since the non-diffusible hydroquinone derivative is synthesized as a mixture, it is extremely difficult to maintain a constant composition of the many components it contains, and when the same weight is added, the effect varies;
This may cause a decrease in quality stability and performance consistency of color photographic materials. In addition, since the molecular weight is larger than conventional non-diffusible hydroquinone, the effect per weight is small, and the increase in the amount added increases the oil phase component relative to the gelatin in the added layer, resulting in a decrease in film strength and so-called sweating. This will cause a phenomenon. Another disadvantage is that the synthesis cost is high. 2-(1-ethyl-1,5-
A mixture of dimethylhexyl)hydroquinone and 2,5-bis(1-ethyl-1,5-dimethylhexyl)hydroquinone has been proposed. As for the latter method by improving the technology used, for example, Japanese Patent Publication No. 53-34043 discloses 2,5-bis1',
The combination of 1'-dimethylbutyl)hydroquinone with other aliphatic hydrocarbon-substituted hydroquinones has been proposed. However, this method is still insufficient in improving the precipitation properties and cannot suppress the coarsening of dispersed particles. Furthermore, two or more types of hydroquinone derivatives are required, leading to an increase in the number of man-hours in the manufacturing process and an increase in the overall cost. Furthermore, in JP-A No. 56-87040, an alkyl phosphate compound is proposed as a high boiling point organic solvent to be used when emulsifying and dispersing hydroquinone derivatives, but this method also has the effect of improving precipitation properties and coarsening of dispersed particles. The inhibitory effect is insufficient. Although this method is advantageous in that it is a simple improvement method, it has the disadvantage that it requires a significantly large amount of high-boiling organic solvent in order to improve the precipitation properties to a satisfactory level. This means an increase in the oil phase component per gelatin, which becomes a major hindrance in thin film coating technology. As described above, no satisfactory method for introducing non-diffusible hydroquinone derivatives into color photographic materials has yet to be found. (Object of the Invention) The first object of the present invention is to provide a color photographic material which is excellent in the effect of preventing color mixture and the effect of preventing color fogging. A second object of the present invention is to provide a color photographic material whose color mixing prevention effect does not decrease over time. Third aspect of the present invention
The purpose of the present invention is to provide emulsified dispersions of non-diffusible hydroquinone derivatives that are stable for long-term storage. A fourth object of the present invention is to provide a simple and inexpensive method for making an emulsified dispersion of a non-diffusible hydroquinone derivative a hit. Fifth aspect of the present invention
The object of the present invention is to provide an emulsified dispersion of non-diffusible hydroquinone derivatives in color photographic materials suitable for high-speed thin film coating. A sixth object of the present invention is to provide an emulsified dispersion of a non-diffusible hydroquinone derivative suitable for producing color photographic materials with high quality stability and quality consistency. (Structure of the Invention) As a result of intensive studies to improve the above-mentioned drawbacks, the present inventors have discovered that at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer are provided on a support. In the silver halide photographic light-sensitive material, at least one of the non-photosensitive hydrophilic colloid layers contains minute oil droplets comprising a non-diffusible hydroquinone derivative and a high boiling point organic solvent represented by the following general formula (). It has been found that the above object can be achieved by a silver halide photographic material characterized by the following characteristics. General formula () In the formula, R ₁ and R ₂ each represent an alkyl group, an alkenyl group, or _an aryl group;
The total number of carbon atoms in the group represented by R ₂ is 18 to
It is 36. In the general formula (), the groups represented by R ₁ and R ₂ include alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group). , straight chain and branched groups such as undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group), alkenyl group (e.g. allyl group, butenyl group, octenyl group, etc.) ), an aryl group (eg, phenyl group, tolyl group, xylyl group, etc.), or an aralkyl group (eg, benzyl group). Further, among the compounds represented by the general formula (), compounds that can be preferably used in the present invention are represented by the following general formula (). General formula () In the formula, R ₂ is a linear or branched nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group,
Represents a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group or an octadecyl group. More particularly preferred are compounds having a linear or branched R ₃ having 9 to 12 carbon atoms. The non-diffusible hydroquinone derivative used in the present invention is represented by the following general formula (). General formula () In the formula, R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R ₆ ,
R ₇ , R ₈ and R ₉ are each hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkylacylamino group, aryl Acylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, cyano group, alkyloxy Represents a carbonyl group, aryloxycarbonyl group, alkylacyloxy group or arylacyloxy group. However, R ₆ ,
When R ₇ , R ₈ and R ₉ are hydrogen atoms at the same time, R ₄
and R ₅ are never hydrogen atoms at the same time. Among the non-diffusible hydroquinone derivatives represented by the general formula () above, compounds represented by the following general formula () can be particularly preferably used in the present invention. General formula () In the formula, R ₁₀ and R ₁₁ each represent a hydrogen atom or an alkyl group, but R ₁₀ and R ₁₁ are not both hydrogen atoms. In the general formula (), at least one of the groups represented by R ₁₀ and R ₁₁ is a group (ballast group) that imparts diffusion resistance to this compound. Therefore, it is generally preferable that the total number of carbon atoms contained in R ₁₀ and R ₁₁ is 8 or more. Specific examples of non-diffusible hydroquinone derivatives that can be used in the present invention (hereinafter referred to as non-diffusible hydroquinone derivatives according to the present invention) are listed below, but of course the present invention is not limited thereto. These non-diffusible hydroquinone derivatives are described under the name antistain agents in Research Disclosure, No. 176 (1978), item 17643. Next, specific examples of the high-boiling point organic solvent represented by the general formula () (hereinafter referred to as the "high-boiling point organic solvent according to the present invention") will be given, but of course the present invention is not limited thereto. These compounds are made by the reaction of phthalic anhydride and the corresponding alcohol under an acid catalyst such as sulfuric acid. It is also made from phthalic acid and the corresponding alkyl halide in the presence of a tertiary amine. In the present invention, compounds similar to the high boiling point organic solvent represented by the general formula () are already known in the photographic field. For example, U.S. Patent No.
No. 4146398, JP-A-54-4125 and JP-A-54-
No. 106228 discloses only applications of dinonyl phthalate in which it is used as a high-boiling organic solvent for cyan couplers, magenta couplers, and ultraviolet absorbers. Furthermore, in JP-A-54-91325 and JP-A-54-118246, by incorporating a specific phthalate ester compound into a light-sensitive material, the amount of color developing agent remaining in the light-sensitive material after processing is reduced, resulting in a white background. However, nothing is known about the cumulative effect of the present invention which is synergistically produced by the combination of the hydroquinone derivative of the present invention and the high boiling point organic solvent of the present invention. Not yet. The main compound contained in the micro oil droplets containing the high-boiling organic solvent according to the present invention is the non-diffusible hydroquinone derivative according to the present invention, and the derivative is contained in the high-boiling organic solvent. Therefore, from this point as well, the contents of the above publication and the present invention should be clearly distinguished. The present invention was developed as a result of extensive research into stabilizing emulsified dispersions of color fog inhibitors and color mixing inhibitors. It was discovered that this compound has a surprising stabilizing effect. The non-diffusible hydroquinone derivative in the present invention is referred to as a color-forming fog suppressor in "Basics of Photographic Engineering - Silver Salt Photography Edition" (edited by the Photographic Society of Japan, published by Corona Publishing).
(1979), page 198. In addition, when the same compound is used for the purpose of preventing color mixing, it is called a color mixing inhibitor, and in the aforementioned Research Disclosure, it is called an antistain agent.
Its role is to prevent color mixing. The amount of the high boiling point organic solvent according to the present invention can be used in any amount depending on the type of the non-diffusible hydroquinone derivative according to the present invention, but preferably depending on the type of the non-diffusible hydroquinone derivative according to the present invention.
0.1 to 1000% by weight, especially 10 to 200% by weight
is preferred. Further, the high boiling point organic solvent according to the present invention may be used in combination with several other high boiling point organic solvents. In this case, any well-known high-boiling point organic solvent can be selected, such as dibutyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, dimethyl phthalate,
Dibenzyl phthalate, tricresyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, triisononyl phosphate, N,N-diethyl laurylamide, 3-pentadecyl phenylethyl ether, 2,5-di-sec-amyl Examples include phenyl butyl ether and 2-ethylhexanol. The non-diffusible hydroquinone derivative according to the present invention is dissolved in the high-boiling organic solvent according to the present invention, for example, using a low-boiling organic solvent as an auxiliary solvent, if necessary, and then added to an emulsifying agent in a dispersion medium such as an aqueous gelatin solution. to obtain an emulsified dispersion.
At this time, the non-diffusible hydroquinone derivative and the phthalate compound may be separately emulsified and dispersed, and then mixed in an aqueous gelatin solution. In addition to the non-diffusible hydroquinone derivative of the present invention, compounds (couplers, ultraviolet absorbers, anti-fading agents, fluorescent brighteners, colored dyes, and the non-diffusible hydroquinone derivatives of the present invention) may be added to the high-boiling organic solvent of the present invention. quinone derivative, etc.) can be added at the same time, but it is preferable that the amount does not exceed the amount of the non-diffusible hydroquinone derivative according to the present invention. Examples of low-boiling organic solvents that can be preferably used as auxiliary solvents in the present invention include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane, tetrahydrofuran, methyl alcohol, ethyl alcohol, acetonitrile, and dimethylformamide. , dioxane, methyl ethyl ketone, methyl isobutyl ketone, diethylene glycol monoacetate, acetylacetone, nitromethane, carbon tetrachloride, chloroform and the like. Examples of emulsifiers include alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl polyoxyethylene alkyl phenyl ethers. Anionic surfactants, steroidal saponins, nonionic surfactants such as alkylene oxide derivatives and glycidol derivatives, amphoteric surfactants such as amino acids, aminoalkylsulfonic acids and alkylpetaines, and quaternary surfactants. Cationic surfactants such as grade ammonium salts and the like can be used. Particularly preferred are anionic surfactants and nonionic surfactants. Specific examples of these surfactants are described in "Surfactant Handbook" (Sangyo Tosho, 1966) and "Emulsifiers and Emulsification Equipment Research and Technical Data Collection" (Science Panronsha, 1978). As the emulsifying and dispersing device, a simple stirrer, homogenizer/colloid mill, flow jet mixer, ultrasonic dispersing device, etc. are preferably used. After emulsification and dispersion, it can be added to a hydrophilic colloid for use, but a low boiling point organic solvent removal step may be included in the middle or simultaneously with the dispersion. In a preferred embodiment of emulsifying and dispersing the non-diffusible hydroquinone derivative according to the present invention, the non-diffusible hydroquinone derivative according to the present invention, the high boiling point organic solvent according to the present invention, and ethyl acetate are mixed and dissolved at about 60°C. let Separately, an aqueous gelatin solution as a dispersion medium and an emulsifier are mixed and dissolved at about 60°C. The two solutions thus obtained may be mixed with stirring and then emulsified and dispersed using a homogenizer or the like. The silver halide photographic material of the present invention has at least one silver halide emulsion layer having a dye image forming function on a support, preferably a non-photosensitive hydrophilic colloid layer. There is no particular restriction on the number and order of the silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer. Typical examples include color positive or negative films, color photographic paper, color slides, light-sensitive materials for color diffusion transfer, and monochrome or black-and-white light-sensitive materials using dye images. As the coupler for forming the dye image used in the present invention, various couplers can be used, but those represented by the following general formulas (), (), or () are preferred. That is, as the yellow dye image-forming coupler, a compound represented by the following general formula () is preferred. General formula () In the formula, R ₁₂ is an alkyl group (for example, a methyl group,
ethyl group, propyl group, butyl group, _etc. ) or an aryl group (e.g., phenyl group, p-methoxyphenyl, etc.);
Y represents a hydrogen atom or a group that is eliminated during the color development reaction. Further, particularly preferred yellow couplers for forming the dye image according to the present invention are those represented by the following general formula ()'. General formula ()′ In the formula, R ₁₄ represents a halogen atom, an alkoxy group or an aryloxy group, and R ₁₅ , R ₁₆ and R ₁₇
are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, respectively.
aryloxy group, carbonyl group, sulfonyl group, carboxyl group, alkoxycarbonyl group,
Carbamyl group, sulfonate group, sulfamyl group,
It represents a sulfonamide group, an acylamide group, a ureido group or an amino group, and Y has the above-mentioned meaning. These include, for example, U.S. Pat. No. 2,778,658;
No. 2875057, No. 2908573, No. 3227155, No. 3227550, No. 3253924, No. 3265506,
Same No. 3277155, Same No. 3341331, Same No. 3369895,
Same No. 3384657, Same No. 3408194, Same No. 3415652,
Same No. 3447928, Same No. 3551155, Same No. 3582322,
No. 3725072, No. 3894875, German patent publication
No. 1547868, No. 2057941, No. 2162899, No. 2163812, No. 2213461, No. 2219917,
No. 2261361, No. 2263875, Special Publication No. 1973-
No. 13576, JP-A-48-29432, JP-A No. 48-66834,
No. 49-10736, No. 49-122335, No. 50-28834
No. 50-132926. As the magenta dye image-forming coupler, a coupler represented by the following general formula () can be preferably used. General formula () In the formula, Ar represents an aryl group, R ₁₈ represents a hydrogen atom, a halogen atom, an alkyl group, or a alkoxy group, and R ₁₉ represents an alkyl group, an amide group, an imido group, an N-alkylcarbamoyl group, an N-alkyl sulfur group. Huamoyl group, alkoxycarbonyl group,
Indicates an acyloxy group, a sulfonamide group, or a urethane group. Y is the same as in general formula (), and W is -NH-, -NHCO- (the nitrogen atom is bonded to the carbon atom of the pyrazolone nucleus) or -
Represents NHCONH−. These include, for example, U.S. Pat. No. 2,600,788;
3061432, 3062653, 3127269, 3311476, 3152896, 3419391,
Same No. 3519429, Same No. 3555318, Same No. 3888680,
Same No. 3907571, Same No. 3928044, Same No. 3930861,
No. 3930866, No. 3933500, JP-A-49-
No. 29639, No. 49-111631, No. 49-129538, No. 49-129538, No. 49-111631, No. 49-129538, No.
No. 50-13041, No. 52-58922, No. 55-62454,
No. 55-118034, No. 56-38043, British Patent No.
1247493, Belgian Patent No. 769116, Belgian Patent No.
No. 792525, West German Patent No. 2156111, Special Publication No. 1979-60479
It is stated in the number etc. As the cyan dye image-forming coupler, a coupler represented by the following general formula () can be preferably used. General formula () In the formula, Y is the same as that shown in the general formula (), and R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are each a hydrogen atom, a halogen atom, an alkyl group, a carbamoyl group, a sulfamoyl group, and an amide group. , a sulfonamide group, a phosphoric acid amide group, or a ureido group. These include, for example, US Pat. No. 2,369,929;
No. 2423730, No. 2434272, No. 2474293, No. 2698794, No. 2706684, No. 2772162,
Same No. 2801171, Same No. 2895826, Same No. 2908573,
Same No. 3034892, Same No. 3046129, Same No. 3227550,
Same No. 3253294, Same No. 3311476, Same No. 3386301,
Same No. 3419390, Same No. 3458315, Same No. 3476563,
Same No. 3516831, Same No. 3560212, Same No. 3582322,
Same No. 3583971, Same No. 3591383, Same No. 3619196,
Same No. 3632347, Same No. 3652286, Same No. 3737326,
Same No. 3758308, Same No. 3779763, Same No. 3839044,
German Patent Publication No. 3880661, German Patent Publication No. 2163811, German Patent Publication No. 2207468, German Patent Publication No. 39-27563, German Patent Publication No. 45-28836
No., JP-A-47-37425, JP-A No. 50-10135, JP-A No. 50-
No. 25228, No. 50-112038, No. 50-117422, No.
No. 50-130441, No. 53-109630, No. 56-65134,
No. 56-99341 and Research Disclosure No. 148, Section 14853 (1976), etc. Next, specific representative examples of dye image-forming couplers preferably used in the present invention will be listed, but the invention is not limited thereto. Yellow coupler (Y-1) α-benzoyl-2-chloro-5-[α-(dodecyloxycarbonyl)-ethoxycarbonyl]-
Acetanilide. (Y-2) α-benzoyl-2-chloro-5-[γ-(2,
4-di-t-amylphenoxy)-butyramide]
Acetanilide. (Y-3) α-Fluoro-α-pivalyl-2-chloro-5
-[γ-(2,4-di-t-amylphenoxy)-
butylamide]-acetanilide. (Y-4) α-pivalyl-α-stearoyloxy-4-
Sulfamoyl-acetanilide. (Y-5) α-pivalyl-α-[4-(4-benzyloxyphenylsulfonyl)-phenoxy]-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butyramide] Acetanilide. (Y-6) α-(2-methoxybenzoyl)-α-(4-acetoxyphenoxy)-4-chloro-2-(4-t
-octylphenoxy)-acetanilide. (Y-7) α-pivalyl-α-(3,3-dipropyl-2,
4-dioxo-acetidin-1-yl)2-chloro-5-[α-(dodecyloxycarbonyl)-ethoxycarbonyl]-acetanilide. (Y-8) α-pivalyl-α-succinimide-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide. (Y-9) α-pivalyl-α-(3-tetradecyl-1-
succinimide) acetanilide. (Y-10) α-(4-dodecyloxybenzoyl)-α-
(3-methoxy-1-succinimide)-3,5-
Dicarboxyacetanilide - dipotassium salt. (Y-11) α-pivalyl-α-phthalimido-2-chloro-5-[γ-2,4-di-t-amylphenoxy)
butylamide] acetanilide. (Y-12) α-2-furyl-α-phthalimido-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide. (Y-13) α-3-[α-(2,4-di-t-amylphenoxy)butyramide]-benzoyl-α-succinimide-2-methoxyacetanilide. (Y-14) α-phthalimido-α-pivalyl-2-methoxy-4-[(N-methyl-N-octadecyl)-
sulfamoyl]-acetanilide. (Y-15) α-acetyl-α-succinimide-2-methoxy-4-[(N-methyl-N-octadecyl)sulfamoyl]-acetanilide. (Y-16) α-cyclobutyryl-α-(3-methyl-3-
ethyl-1-succinimide)2-chloro-5-
[(2,5-di-t-amylphenoxy)acetamido]acetanilide. (Y-17) α-(3-octadecyl-1-succinimide)
-α-propenoyl-acetanilide. (Y-18) α-(2,6-di-oxo-3-n-propyl-piperidin-1-yl)-α-pivalyl-2-
Chloro-5-[γ-(2,4-di-t-amylphenoxy)butylcarbamoyl]acetanilide. (Y-19) α-(1-Benzyl-2,4-dioxo-imidazolidin-3-yl)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy) butylamide] acetanilide. (Y-20) α-(1-benzyl-2-phenyl-3,5-
dioxo-1,2,4-triazin-4-yl)
-α-pivalyl-2-chloro-5-[γ-(2,4
-di-t-amylphenoxy)butyramide]-
Acetanilide. (Y-21) α-(3,3-dimethyl-1-succinimide)
-α-pivalyl-2-chloro-5-[α-(2,4
-di-t-amylphenoxy)butyramide]-
Acetanilide. (Y-22) α-[3-(p-chlorophenyl)-4,4-di-methyl-2,5-dioxo-1-imidazolyl]-α-pivalyl-2-chloro-5-[γ-(2 ，
4-di-t-amylphenoxy)-butyramide]
-acetanilide. (Y-23) α-pivalyl-α-(2,5-dioxo-1,
3,4-triazin-1-yl)-2-methoxy-5-[α-(2,4-di-t-amylphenoxy)-butyramide]-acetanilide. (Y-24) α-(5-benzyl-2,4-dioxo-3-
oxanezoyl)-α-pivalyl-2-chloro-
5-[γ-(2,4-di-t-amylphenoxy)
-butyramide]-acetanilide. (Y-25) α-(5,5-dimethyl-2,4-dioxo-
3-oxazoyl)-α-pivalyl-2-chloro-5-[α-(2,4-di-t-amylphenoxy)-butyramide]-acetanilide. (Y-26) α-(3,5-dioxo-4-oxazinyl)-
α-pivalyl-2-chloro-5-[γ-(2,4-
di-t-amylphenoxy)-butyramide]-acetanilide. (Y-27) α-pivalyl-α-(2,4-dioxo-5-
Methyl-3-thiazolyl)-2-chloro-5-[γ
-(2,4-di-t-amylphenoxy)-butyramide]-acetanilide. (Y-28) α-[3(2H)-pyridazon-2-yl]-α-
pivalyl-2-chloro-5[γ-(2,4-di-t
-amyl-phenoxy)-butyramide]-acetanilide. (Y-29) α-[4,5-dichloro-3(2H)-pyridazon-2-yl]-α-benzoyl-2-chloro-5
-[α-(dodecyloxycarbonyl)-ethoxycarbonyl]-acetanilide. (Y-30) α-(1-phenyl-tetrazol-5-oxy)-α-pivalyl-2-chloro-5-[γ-(2,
4-di-t-amylphenoxy)-butyramide]
-acetanilide. (Y-31) 4,4'-di-(acetoacetamino)-3,3-
Dimethyldiphenylmethane. (Y-32) P,P'-di-(acetoacetamino)diphenylmethane. Magenta coupler (M-1) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecylcarbamoyl-
anilino)-5-pyrazolone. (M-2) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-tetradecanamido-anilino)-5-pyrazolone. (M-3) 1-(2,4,6-trichlorophenyl)-3-
[2-chloro-5-γ-(2,4-di-t-amylphenoxy)butylcarbamoyl]-anilino-
5-Pyrazolone. (M-4) 1-(2,4,6-trichlorophenyl)-4-
Chloro-3-[2-chloro-5-γ-(2,4-di-t-amylphenoxy)butylcarbamoyl]
-anilino-5-pyrazolone. (M-5) 1-(2,4,6-trichlorophenyl)-4-
Diphenylmethyl-3-[2-chloro-5-(γ-
octadecynylsuccinimide)-propylsulfamoyl]-anilino-5-pyrazolone. (M-6) 1-(2,4,6-trichlorophenyl)-4-
Acetoxy-3-(2-chloro-5-tetradecanamido)-anilino-5-pyrazolone. (M-7) 1-[γ-(3-pentadecylphenoxy)-butyramide]-phenyl-3-anilino-4-(1
-phenyl-tetrazole-5-thio)-5-pyrazolone. (M-8) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecylsuccinimide)
-anilino-5-pyrazolone. (M-9) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecenylsuccinimide)-anilino-5-pyrazolone. (M-10) 1-(2,4,6-trichlorophenyl)-3-
[2-chloro-5(N-phenyl-N-octylcarbamoyl)]-anilino-5-pyrazolone. (M-11) 1-(2,4,6-trichlorophenyl)-3-
[2-chloro-5-(N-butylcarbonyl)-pyrazinylcarbonyl]-anilino-5-pyrazolone. (M-12) 1-(2,4,6-trichlorophenyl)-3-
[2-chloro-5-(2,4-di-carboxy-5
-phenylcarbamoyl)-benzylamide]-anilino-5-pyrazolone. (M-13) 1-(2,4,6-trichlorophenyl)-3-
(4-tetradecylthiomethylsuccinimide)-
Anilino-5-pyrazolone. (M-14) 1-(2,4,6-trichlorophenyl)-3-
[2-chloro-4-(2-benzofurylcarboxamide)]-anilino-5-pyrazolone. (M-15) 1-(2,4,6-trichlorophenyl)-3-
{2-chloro-4-[γ-(2,2-dimethyl-6
-octadecyl-7-hydroxy-chroman-4
-yl)-propionamide]}-anilino-5-
Pyrazolone. (M-16) 1-(2,4,6-trichlorophenyl)-3-
[2-chloro-5-(3-pentadecyl phenyl)
phenylcarbonylamide]-anilino-5-pyrazolone. (M-17) 1-(2,4,6-trichlorophenyl)-3-
{2-chloro-5-[2-(3-t-butyl-4-
hydroxyphenoxy)-tetradecanamide]-
Anilino}-5-pyrazolone. (M-18) 1-(2,6-dichloro-4-methoxyphenyl)-3-(2-methyl-5-tetradecanamido)-anilino-5-pyrazolone. (M-19) 4,4'-benzylidene bis[1-(2,4,6
-trichlorophenyl)-3-{2-chloro-4-
[γ-(2,4-di-t-amylphenoxy)-butyramide]-anilino}-5-pyrazolone]. (M-20) 4,4'-benzylidene bis[1-(2,3,4,
5,6-pentachlorophenyl)-3-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butyramide]-anilino-5-pyrazolone]. (M-21) 4,4'-(2-chloro)benzylidene bis[1
-(2,4,6-trichlorophenyl)-3-(2
-chloro-5-dodecylsuccinimide)-anilino-5-pyrazolone]. (M-22) 4,4'-Benzylidenebis[1-(2-chlorophenyl)-3-(2-methoxy-4-hexadecaneamide)-anilino-5-pyrazolone]. (M-23) 4,4'-methylenebis[1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-dodecenylsuccinimide)-anilino-5-pyrazolone)]. (M-24) 1-(2,4,6-trichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamido)bentusamide]-5-pyrazolone. (M-25) 3-ethoxy-1-{4-[α-(3-pentadecylphenoxy)butyramido]phenyl}-5
-Pyrazolone. (M-26) 1-(2,4,6-trichlorophenyl)-3-
[2-chloro-5-{α-(3-t-butyl-4-
hydroxy)-phenyl}-tetradecanamide]
-anilino-5-pyrazolone. (M-27) 1-(2,4,6-trichlorophenyl)-3-
(3-nitroanilino)-5-pyrazolone. Cyan coupler (C-1) 2-[α-(4-t-butylphenoxy)butyramide]phenol. (C-2) 2-[α-(4-t-amylphenoxy)-butyramido]-5-methylphenol. (C-3) 2-chloro-6-[α-(2,4-di-t-amylphenoxy)-butyramide]-phenol. (C-4) 2-phenyl-6-[α-(4-t-amylphenoxy)-butyramide]-phenol. (C-5) 2,4-dichloro-3-methyl-6-(di-t
-amylphenoxyacetamide)-phenol. (C-6) 2,4-dichloro-3-methyl-6-[α-
(2,4-di-t-amylphenoxy)butyramido]-phenol. (C-7) 2-chloro-3-methyl-4-ethylcarbamoylmethoxy-6-[α-(2,4-di-t-amylphenoxy)butyramide]phenol. (C-8) 2-chloro-3-methyl-4-propionyloxy-6-[α-(2,4-di-t-amylphenoxy)acetamido]-phenol. (C-9) 2-chloro-3-methyl-4-fluoro-6-
[α-(2,4-di-t-amyl)phenoxy)-
butylamide]-phenol. (C-10) 2-chloro-3-methyl-4-(1-phenyl-tetrazolyl-5-thio)-6-(2-dodecyloxyphenylacetamido)phenol. (C-11) 2,4-difluoro-3-methyl-6-[α-
(3-t-butyl-4-hydroxy-phenoxy)
-tetradecanamide]-phenol. (C-12) 2-(α,α,β,β-tetrafluoropropylamide)-4-acetoxy-6-(2,4-di-
t-Butylphenoxy)acetylamide-phenol. (C-13) 2,4-difluoro-3-methyl-6-[α-
(2,4-di-t-amylphenoxy)-butyramido]-phenol. (C-14) 2-perfluorobutyramide-5-[α-
(2,4-di-t-amylphenoxy)hexaneamido]-phenol. (C-15) 2-(α,α,β,β-tetrafluoropropionamide)-5-[α-(2,4-di-t-amylphenoxy)-butyramide]phenol. (C-16) 2-(α,α,β,β-tetrafluoropropionamide)-4-β-chloroethoxy-5-[α
-(2,4-di-t-amylphenoxy)butyramido]-phenol. (C-17) 2-(α, α, β, β, γ, γ, δ, δ-octafluoropentanamide)-5-[α-(2,4
-di-t-amylphenoxy)butyramide]-
Phenol. (C-18) 2-(4-t-amyl-3-phenoxybenzoylamino)-3,5-dimethylphenol. (C-19) 1-Hydroxy-N-[δ-(2,4-di-t-
amylphenoxy)butyl]-2-naphthamide. (C-20) 1-Hydroxy-4-(isopropylcarbamoyl)methoxy-N-[δ-(2,4-di-t-amylphenoxy)-butyl-2-naphthamide. (C-21) 1-hydroxy-4-[β-(methoxyethyl)
carbamoyl]-methoxy-N-dodecyl-2-
Naphthamide. (C-22) 1-hydroxy-4-(p-nitrophenylcarbamoyl)oxy-N-(δ-(2,4-di-t
-amylphenoxy)butyl]-2-naphthamide. (C-23) 1-Hydroxy-N-dodecyl-2-naphthamide. (C-24) 1-hydroxy-4-(4-nitrophenoxy)
-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide. (C-25) 1-hydroxy-4-(1-phenyl-5-tetrazolyloxy)-N-[δ-(2,4-di-t
-amylphenoxy)butyl]-2-naphthamide. (C-26) 5-(p-aminophenoxybenzenesulfonamino)-1-naphthol. (C-27) 5-(N-benzyl-N-naphthalenesulfonesulfonamino)-1-naphthol. (C-28) 5-(1,2,3,4-tetrahydronaphthalene-6-sulfamide)-1-naphthol. (C-29) 5-(quinoline-5-sulfamino)-1-naphthol. (C-30) 1-hydroxy-4-acetoxy-N-[α-
(2,4-di-t-amylphenoxy)butyl]-
2-Naphthamide. (C-31) 1-Hydroxy-4-thiocyano-N-[α-
(2,4-di-t-amylphenoxy)butyl]-
2-Naphthamide. (C-32) 1-hydroxy-4-(pentafluorophenoxy)-N-{β-{4-[α-(2,4-di-t-
amylphenoxy)acetamide]-phenyl}-
ethyl}-2-naphthamide. (C-33) 1-hydroxy-4-(4-chlorophenoxy)
-2-tetradecyloxy-2-naphthamide. (C-34) 1-hydroxy-4-phthalimide-N-[α
-(2,4-di-t-amylphenoxy)butyl-2-naphthamide. (C-35) 1-Hydroxy-4-(dodecenylsuccinimide)-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide. (C-36) 1-hydroxy-4-phenylthio-N-[α
(2,4-di-t-amylphenoxybutyl]-2
- Naphthamide. When the coupler used in the above-mentioned color photographic light-sensitive material is present in the color photographic light-sensitive material, it is generally used in an amount of 1 to 100 mol%, preferably 5 to 50 mol%, based on silver halide. If present, generally 0.5-30g/, preferably
Used at 1.0-20g/. In this case, each of the yellow, magenta, and cyan couplers may be used alone, or two or more of each may be used in combination, and when two or more are used in combination, the amounts mentioned above are sufficient. . The above color photographic material may contain couplers other than the above couplers for special purposes, if necessary. For example, colored magenta couplers can be included for masking purposes. In addition, the silver halide color photographic emulsion layer or its adjacent layer contains a coupler that releases a development inhibitor depending on the density of the image during development, and a development inhibitor-releasing compound other than the coupler (so-called DIR).
A coupler) may also be included. The color developing agent used for color developing the color photographic material of the present invention is not particularly limited;
Commonly used methods are used, including the following: Examples of useful aromatic primary amine compounds include primary phenylene diamines,
Representative examples of aminophenols and derivatives thereof include the following: N,N-dimethyl-p-phenylenediamine,
N,N-diethyl-p-phenylenediamine, N
-Carbamidomethyl-N-methyl-p-phenylenediamine, N-carbamidomethyl-N-tetrahydrofurfuryl-2-methyl-p-phenylenediamine, N-ethyl-N-carboxymethyl-
2-Methyl-p-phenylenediamine, N-carbamidomethyl-N-ethyl-2-methyl-p-phenylenediamine, N-ethyl-N-tetrahydrofurfuryl-2-methyl-p-aminophenol, 3- Acetylamino-4-aminodimethylaniline, N-ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline, N-ethyl-
N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline, N-methyl-N-β-
Examples include salts of sulfoethyl-p-phenylenediamine, o-aminophenol, p-aminophenol, and 5-amino-2-oxy-toluene with inorganic acids such as hydrochloric acid and sulfuric acid, or organic acids such as p-toluenesulfonic acid. . The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention generally has silver halide grains dispersed in a hydrophilic colloid, and the silver halide includes silver chloride, silver bromide, and silver iodide. , silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof, and these silver halides can be produced by various methods such as the ammonia method, neutral method, convergence method, or simultaneous mixing method. can do. The shapes of these silver halide grains are cubic, octahedral,
Any form such as tablet-like twin crystals or mixed crystal forms thereof may be used. Furthermore, the crystal structure of the silver halide grains may be uniform throughout the interior, or may have a layered structure with different interiors and exteriors. Hydrophilic colloids for dispersing silver halide include gelatin, phthalated gelatin,
Gelatin derivatives such as malonized gelatin are commonly used, but in place of some or all of this gelatin or gelatin derivative, albumin, agar,
Gum arabic, alginic acid, casein, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, imidized polyacrylamide, polyvinylpyrrolidone, or copolymers of these vinyl compounds can also be used.
Furthermore, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Examples of sensitizing dyes include cyanine dyes, merocyanine dyes, and complex cyanine dyes. The dyes can be used alone or in combination of two or more. Furthermore, if necessary, gold compounds, platinum, palladium, iridium, rhodium,
Noble metal salts such as ruthenium, sulfur compounds, reducing substances or thioether compounds, chemical sensitizers such as quaternary ammonium salt compounds or polyalkylene oxide compounds, triazoles, imidazoles, azaindenes, benzothiazoliums, zinc compounds , cadmium compounds, mercaptans, etc.; chromium salts, zirconium salts, mucochloric acid, aldehyde series, triazine series, polyepoxy compounds, active halogen compounds,
Hardeners such as ketone compounds, acryloyl, triethylenebisamide, and ethyleneimine; dihydroxyalkane plasticizers such as glycerin and 1,5-pentanediol; optical brighteners; antistatic agents; coating aids Various photographic additives such as these can be used alone or in combination of two or more. The obtained silver halide emulsion layer may contain minute oil droplets according to the present invention in which the non-diffusible hydroquinone derivative according to the present invention described above is dispersed in the high boiling point organic solvent according to the present invention, and the non-photosensitive hydrophilic At least one of the sexual colloid layers (antihalation layer, intermediate layer, yellow filter layer, ultraviolet absorbing layer, etc.) contains a dispersion of the non-diffusible hydroquinone derivative according to the present invention, and cellulose acetate, cellulose nitrate, polycarbonate, A silver halide photographic light-sensitive material is obtained by coating on a support such as a synthetic resin film such as polyethylene terephthalate or polyethylene, baryta paper, polyethylene-coated paper, or a glass plate. The emulsified dispersion of a non-diffusible hydroquinone derivative according to the present invention can be used by being added to any photographic layer as described above, and it is particularly advantageous to use it by adding it to an intermediate layer and a silver halide emulsion layer. It is. The above-mentioned silver halide photographic material may be a coupler-containing internal color photographic material or an external color photographic material containing a coupler in a developer, and is particularly advantageous for coupler-containing internal color photographic materials. , color development is carried out using the color development method. Furthermore, the coupler and the color developing agent are protected so that they do not come into contact with each other when unexposed and are present in the same layer, and can be used in color photographic materials where they can come into contact with each other after exposure, or in color photographic materials containing the coupler. It may also be a color photographic light-sensitive material in which a color developing agent is contained in a layer that does not contain a color developing agent, and when an alkaline processing solution is permeated, the color developing agent is moved and brought into contact with the coupler. Furthermore, the minute oil droplets according to the present invention can be used in a color photographic light-sensitive material for diffusion transfer, and it is particularly advantageous to have them present in the light-sensitive element of the light-sensitive material. When the color photographic light-sensitive material according to the present invention is used for color diffusion transfer, well-known dye image forming substances can be used.
For example, U.S. Patent Nos. 3227550, 3880658, 3765886, 3443940, 3751406,
Same No. 3725062, Same No. 3698897, Same No. 3728113,
Same No. 3928312, Same No. 3993638, Same No. 3932380,
Same No. 3932381, Same No. 3931144, Same No. 3929760,
British Patent No. 3942987, British Patent No. 904346, British Patent No.
No. 904365, No. 1038331, French Patent No.
Specifications of No. 2284140, JP-A-49-123032, same
No. 51-104343, No. 51-113624, No. 51-109928,
Publications No. 52-7727 and No. 52-8827 and Research Disclosure No. 130 (1975)
It is stated in Section 13024 of , Section 15157 of No. 151 (1976), etc. The reversal process involves development in a black and white negative developer, followed by white exposure or treatment in a bath containing a caprior such as a boron compound, and color development in an alkaline developer containing a color developing agent. At this time, there is no problem in including a capri agent in an alkaline developer containing a color developing agent. After color development, the silver image and residual halogen are bleached using a bleaching solution containing ferricyanide or ferric salt of aminopolycarboxylic acid as an oxidizing agent, and then fixed using a fixing solution containing a silver salt solvent such as thiosulfate. Removes silver oxide and leaves a dye image. Instead of using a bleaching solution and a fixing solution, bleach-fixing can also be carried out using a one-bath bleach-fixing solution containing an oxidizing agent such as a ferric salt of an aminopolycarboxylic acid and a silver salt solvent such as thiosulfate. Further, in combination with color development, bleaching, fixing, or bleach-fixing, various treatments such as pre-hardening, neutralization, water washing, termination, and stabilization may be performed. In particular, processing steps in which the color photographic light-sensitive material of the present invention is advantageously developed include, for example, color development, washing with water if necessary, bleach-fixing, washing with water, stabilizing if necessary,
This is a drying process, and this process is performed at a temperature of, for example, 30°
It is carried out at higher temperatures and in an extremely short time. In addition to the above-mentioned color developing agent, certain additives are added to the color developing solution as necessary. Main examples include alkali metal and ammonium hydroxides, alkaline agents such as carbonates and phosphates, buffers such as acetic acid and boric acid, PH regulators, development accelerators, anti-capri agents, stains, and These include anti-sludge agents, multilayer effect promoters, and preservatives. Bleaching agents used in bleaching include ferricyanide such as red blood salt, dichromate, permanganate, hydrogen peroxide, mustard powder, and aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and iminodiacetic acid. Metal complex salts, metal complex salts of polycarboxylic acids such as malonic acid, tartaric acid, malic acid, etc.
Examples include ferric chloride, and these may be used alone or in combination as necessary. Various additives such as bleaching accelerators can be added to this bleaching solution as needed. Fixing agents used in the fixing process include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, cyanide, urea, and derivatives, and various additives such as fixing accelerators may be added as necessary for this fixing process. You can also do it. It is also effective to process the color photographic material of the present invention using a color developing solution containing both an aromatic primary amine color developing agent and an oxidizing agent that subjects the metallic silver image to a redox reaction. When these color developing solutions are used, the color developing agent is oxidized by an oxidizing agent and then coupled with a photographic color coupler to form a dye image. Such a color developing solution is, for example, disclosed in Japanese Patent Application Laid-open No. 1986-
No. 9729, the preferred oxidizing agent for this purpose is a cobalt complex having a coordination number of 6. Color photographic processing using such a color developing solution is particularly effective for so-called silver-saving color photographic materials, which have a smaller amount of silver than ordinary color photographic materials. Further, the color photographic light-sensitive material of the present invention is developed in a color developing solution containing an aromatic primary amine color developing agent, and then, preferably, during the color development step, the color photographic material is received in the photosensitive layer and compensated. an oxidizing agent, as described above, in the presence of a color developing agent which is moved into an amplifying bath;
For example, it is also useful to use a color photographic processing method consisting of contacting with an intensifying solution containing a cobalt complex salt having a coordination number of 6. Another preferred oxidizing agent for this purpose is an aqueous hydrogen peroxide solution. (Example) Next, the present invention will be specifically explained with reference to Examples. Example 1 A precipitation test was conducted in the following manner using an oil phase solution having the composition shown in Table 1 below. After dissolving 1.0 g of a non-diffusible hydroquinone derivative in a mixed solution of 0.7 g of a high-boiling organic solvent and 2 g of ethyl acetate by heating to approximately 60°C, this solution was left at 5°C for 48 hours and filtered with a glass filter. The sample was quickly washed with 2 g of ethyl acetate at 0°C, filtered and dried, and then its weight was measured. The obtained results are also shown in Table-1.

[Table] In Table 1, DBP is dibutyl phthalate, DOP is di-2-ethylhexyl phthalate, TCP is tricresyl phosphate, TOP is tri-2-ethylhexyl phosphate, and DELA is diethyl laurylamide. From the results shown in Table-1, sample 1 according to the present invention
It can be seen that Samples -6 to 1-9 are significantly improved in precipitation properties compared to the comparative samples. Example 2 Various emulsified dispersions were prepared using the following emulsifying dispersion method, and their stability during storage was investigated. (a) Non-diffusible hydroquinone derivative according to the present invention
10 g of various high-boiling organic solvents and 20 g of ethyl acetate are mixed and heated to about 60°C to dissolve. (b) Mix 15 g of photographic gelatin and 20 ml of pure water at room temperature and allow to swell for 20 minutes. Next, after heating to about 60℃ and dissolving it, Alkanol B (manufactured by DuPont)
Add 20 ml of 5% aqueous solution of and stir evenly. (c) The solutions obtained in (a) and (b) were mixed and dispersed for 20 minutes using an ultrasonic disperser to obtain an emulsified dispersion. By the above method, five types of emulsified dispersions were obtained by changing the types of non-diffusible hydroquinone derivatives and high-boiling organic solvents as shown in Table 2 below.

[Table] DMP in Table 2 is dimethyl phthalate. The obtained emulsified dispersion was stoppered and kept at 40℃ for 24 hours, and the turbidity increase value ΔT was measured before and after keeping it warm.
The degree of crystal precipitation of the dispersion liquid after being left to warm was examined, and the obtained results are also shown in Table 2. Here, "turbidity"
shows a correlation with the particle size of the dispersed particles, and the smaller the value, the smaller the particle size. In other words, the smaller ΔT is, the more stable the dispersed particles are without coarsening. Turbidity is measured using a Poitzk integrating sphere turbidity meter (manufactured by Japan Precision Optical Co., Ltd., model SEP-PT-501D)
was used. In addition, the precipitation property was determined by 100% of the dispersion after being left warm.
ml was diluted with 100 ml of warm water, filtered with suction using No. 5A filter paper, washed and dried to determine the weight of the precipitate. From the results in Table 2 above, sample 2- according to the present invention
It can be seen that both the coarsening of the dispersed particles and the precipitation properties of Samples No. 4 and No. 2-5 were significantly improved. Example 3 A model experiment was conducted for the purpose of comparatively examining the ability to prevent color mixture in the color photographic material of the present invention. Sample 3-1 was prepared with the layer structure shown in Table 3 below.

[Table] Next, an emulsified dispersion of a non-diffusible hydroquinone derivative according to the present invention was added to layer 2 of Sample 3-1 so that the coating amount of non-diffusible hydroquinone was 1.5 mg/100 cm ³ . The emulsified dispersion was prepared in the same manner as in Example 2, and the ratio of the non-diffusible hydroquinone derivative to the high-boiling organic solvent was 1:1.

[Processing process]

Processing time Processing temperature Color development 3.5 minutes 33℃ Bleach-fixing 1.5 minutes 33℃ Washing with water 3 minutes 33℃ Drying - 80℃ [Color developer composition] Pure water 700ml Benzyl alcohol 715ml Diethylene glycol 15ml Hydroxylamine sulfate 2ml N-ethyl- N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
4.4g Potassium carbonate 30g Potassium chloride 0.5g Potassium bromide 0.4g Potassium sulfite 2g Add pure water to make 1. (Adjusted to PH=10.2) [Bleach-fix solution composition] Ethylenediaminetetraacetate iron ammonium
61g Diammonium ethylenediaminetetraacetate
5g ammonium thiosulfate 125g sodium metabisulfite 13g sodium sulfite 2.7g Add water to make 1. (Adjusted to PH = 7.2) The maximum reflection density of each sample thus treated was measured using a photoelectric densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.).
Measured using a PDA-60 model). Table 4 shows the results.
It was shown to.

[Table] From the above table, it can be seen that when a non-diffusible hydroquinone derivative is added to layer 2, the phenomenon in which the color developing agent oxidation product generated in layer 1 diffuses into layer 3 is suppressed. It is clear that this suppressing effect is significantly greater in the samples according to the invention. Example 4 A color photographic material having the layer structure shown in Table 5 was prepared and designated as Sample 4-1.

【table】

[Table] As ultraviolet absorbers used in layers 4 and 6, the following compounds (uv-1) and (uv-2) were used in combination at a weight ratio of 1:1. The high boiling point organic solvent used for layer 2 (HBS-2),
(HBS-10), (HBS-11) and (HBS-12)
Samples that changed to Sample 4-2 and Sample 4-
3, sample 4-4 and sample 4-5. Also,
Sample 4-6 was obtained by changing the high boiling point organic solvent of layer 1 and layer 3 to HBS-2 while keeping the high boiling point organic solvent of layer 2 unchanged. The five types of samples obtained were exposed and developed using an interference filter using blue light and green light in the same manner as in Example 3. The interference filters used had maximum transmittance at 470 nm and 550 nm, respectively. For the yellow colored sample, by comparing the magnitude of the green density (D _G ) at the point of the blue density (D _B ) of 2.0, the relative degree of color mixing from layer 1 to layer 3 can be determined. Similarly, for color mixing from layer 3 to layer 1, the magnitude of D _B is compared at the point of D _G =2.0 for magenta colored samples. The results thus obtained are shown in Table 6.

[Table] From the results in Table 6, it is clear that the samples according to the present invention exhibit a high color mixing prevention effect and have high monochromatic color purity. Example 5 The storage stability of the emulsified dispersion was investigated in the same manner as in Example 2 above. Except that the non-diffusible hydroquinone derivative according to the present invention was changed to (HQ-4),
When the experiment was conducted in the same manner as in Example-2,
Non-diffusible hydroquinone (HQ-
It was found that the sample according to the present invention using 4) also had excellent dispersion stability. (Effects of the Invention) The multiple objectives of the present invention described above were satisfied, and the present invention was effective in improving productivity and ensuring quality for users.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer each on a support, wherein the non-photosensitive hydrophilic colloid layer is A silver halide photographic material characterized in that at least one layer contains minute oil droplets comprising a non-diffusible hydroquinone derivative and a high boiling point organic solvent represented by the following general formula (). General formula () (In the formula, R ₁ and R ₂ are each an alkyl group,
It represents an aralkyl group, an alkenyl group, or an aryl group, and the total number of carbon atoms in the groups represented by R ₁ and R ₂ is 18 to 36. )