JPH0216905B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to photographic elements, and more particularly, to photographic elements having robust dye images that do not discolor or fade even under long-term storage. It is known that photographic elements bearing dye images undergo significant discoloration under certain storage conditions. For example, when they are exposed to light for a long time and stored, and when they are exposed to light for a short time but are stored in a dark place with high temperature and humidity for a long time, they often exhibit different discoloration and discoloration. The former case is called light change fading (or photochange fading), and the latter case is called dark change fading.In order to use a photographic element containing a dye image as a recording material for semi-permanent preservation, these conditions must be met under any storage conditions. It is desired that discoloration and fading be as small as possible.
However, in conventional photographic elements, discoloration and fading under the storage conditions described above are not sufficiently prevented, and the fastness of dye images remains unsatisfactory. In order to improve the fastness of dye images, a number of methods have been proposed in the past on two fronts. One method is to improve the fastness of the dye image itself, which involves improving the molecular structure design of the dye image itself or the compound that produces the dye image (e.g., coupler, etc.), or changing the state of existence of the dye. This is an improvement. The other method is to use a dye image stabilizer, and many improvements in this aspect have been proposed because this method has little effect on dye image characteristics such as color tone and is highly versatile. has been done. Regarding the use of dye image stabilizers, various methods have been proposed in the past to improve photofading of dye images by adding ultraviolet absorbers or providing ultraviolet absorbing filter layers in photographic elements. . However, in order to obtain satisfactory light fastness using this UV absorber, a large amount of UV absorber is required, and if a large amount of UV absorber is used,
The fabric portion of the photographic element is colored yellow due to the coloring of the ultraviolet absorber itself. The drawbacks are that the solubility of the ultraviolet absorber in high-boiling organic solvents is low, and it tends to precipitate during the manufacturing process. Therefore, there is a limit to the amount of addition, and a sufficient effect for hardening the dye image cannot be obtained. Furthermore,
Although it was possible to prevent photofading due to ultraviolet rays, it had a serious drawback in that it was ineffective at preventing photofading due to visible rays. In order to overcome these drawbacks, various dye image stabilizers have been proposed to replace ultraviolet absorbers. For example, as compounds having phenolic hydroxyl groups or hydrolyzed phenolic hydroxyl groups, Japanese Patent Publication Nos. 48-31256 and 48-31625 disclose bisphenols, and U.S. Pat. No. 3,069,262 describes pyrogallol, garlicic acid, and Its esters or its acyl derivatives, U.S. Pat.
5-hydroxychroman derivatives according to the specifications of No. 3432300 and No. 3574627, and Japanese Patent Publication No. 1973
-20977 publication describes 6,6'-dihydroxy-2,
2'-bisspirochromans are disclosed. In addition, 6-alkoxychroman derivatives, 6,6'-dialkoxy-2,2'-bisspirochromans, , hydroquinone derivatives, etc. have been proposed. In addition, as light stabilizers, metal complexes described in US Pat. A hindered amine compound described in Japanese Patent No. 2126954 has been proposed. However, although some of these compounds are certainly effective against photochromic fading of dye images, they not only have no effect at all against dark pigment fading;
On the contrary, some promote darkening and fading. Furthermore, some compounds are effective for a certain period of time, but when stored for a long period of time, their effectiveness decreases or they become completely ineffective, and some even cause color staining. Furthermore, some compounds have an effect of preventing discoloration and fading on magenta dye images, but some compounds significantly accelerate discoloration and fading on cyan and yellow dye images.
Further, when looking at the individual substances, in the case of light stabilizers such as metal complexes and azomethine quenching substances, coloration of the light stabilizer itself becomes a serious problem, and the amount used is restricted. Hindered amine compounds also have low solubility in organic solvents and reduce color development when used in photographic elements that use dye image-forming couplers.
This had the fatal drawback of impairing image characteristics such as color tone. Furthermore, U.S. Patent No. 3112388, U.S. Patent No. 3206431,
Specifications of No. 3870680, U.S. Patent No. 1219205, and JP-A-54-48535 and U.S. Patent No. 54-147038
No. 55-84964 describes dye image stabilizers comprising 4-hydroxybenzoic acid ester compounds, but the compounds specifically described in these publications are difficult to apply to photographic elements. It had the following drawbacks. First, in a photographic element such as a silver halide color photographic light-sensitive material, an oxide of a color developing agent is produced by developing exposed silver halide grains using, for example, an aromatic primary amine compound as a color developing agent. A method is generally used in which a dye image is formed by a reaction between 4-hydroxybenzoic acid ester and a dye-forming coupler, but when these conventional 4-hydroxybenzoic acid ester compounds are used, the development efficiency is significantly reduced, and the image formation is difficult. This results in a decrease in maximum color density and deterioration in gradation. Second, due to its low solubility in high-boiling point organic solvents, a large amount of low-boiling point organic solvent is required to achieve sufficient dissolution, which places an excessive load on the removal and recovery equipment for low-boiling point organic solvents, resulting in high costs.・Connects to Atsupu. In addition, the high precipitation properties may cause coating failures during the manufacture of photographic elements, which is a problem. Furthermore, when various oil-soluble groups are introduced to improve solubility in high-boiling organic solvents, the molecular weight increases, and in this case, it is necessary to use equimolar amounts, which inevitably increases the amount used. This results in increased manufacturing costs. A primary object of the present invention is to provide a photographic element with hardened dye images without adversely affecting photographic properties. A second object of the present invention is to provide a photographic element having a dye image that does not discolor or fade even under long term storage conditions. A third object of the present invention is to provide a photographic element in which fastening of a dye image can be easily achieved by incorporating a compound that has excellent solubility in high-boiling organic solvents and does not adversely affect other photographic additives. Our goal is to provide the following. A fourth object of the present invention is to provide a photographic element in which fastening of a dye image can be easily and inexpensively achieved by incorporating a compound that has low precipitation and does not cause coating failure during production. be. Therefore, as a result of intensive research to achieve the above object, the present inventors have discovered that in a photographic element having at least one dye image-bearing layer, at least one of the dye image-bearing layers contains the following: It has been discovered that these objects can be achieved by incorporating a compound represented by the general formula [], and the present invention has been completed. General formula [] (In the formula, A represents a phenyl group substituted with at least one alkyl group. However, the total number of carbon atoms of the alkyl group that is a substituent is 9 to 36.) In the general formula [] Among the compounds represented (hereinafter referred to as "dye image stabilizer according to the present invention"), a particularly useful dye image stabilizer in the present invention is a compound represented by the following general formula []. General formula [] In the formula, R is an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, amyl group, nonyl group, decyl group, dodecyl group, octadecyl group, etc.)
represents. L is a halogen atom (fluorine, chlorine,
bromine or iodine), hydroxyl, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, amyl group, nonyl group, decyl group, dodecyl group, octadecyl group, etc.), alkenyl group (e.g. allyl group, etc.), cyclo Alkyl groups (e.g., cyclohexyl group, etc.), aryl groups (e.g., phenyl group, etc.), alkoxy groups (e.g., methoxy group, propyloxy group, etc.), alkylthio groups (e.g., ethylthio group, etc.), aryloxy groups (e.g., phenoxy group, etc.), arylthio group (e.g., phenylthio group, etc.), acyl group (e.g., benzoyl group, etc.), acylamino group (e.g., acetylamino group, etc.), alkylamino group (N-alkyl substituted or N,N-
dialkyl-substituted amino groups (e.g. N,N'-diethylamino), alkoxycarbonyl groups (e.g. ethoxycarbonyl), or alkylsulfonamide groups (e.g. ethylsulfonamide) or arylsulfonamide groups (e.g. phenyl). sulfonamide group, etc.). n
represents an integer from 0 to 4. However, substituent R
The total number of carbon atoms in the alkyl groups contained in and L is 9 to 36. Furthermore, among the dye image stabilizers represented by the general formula [], the most useful dye image stabilizer in the present invention is the compound represented by the following []. General formula [] In the formula, R' and L' each represent an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, etc.).
However, the total number of carbon atoms in the alkyl groups represented by R' and L' is 9 to 36. In the compound represented by the general formula [] or [], R and L, or R' and
As the alkyl group represented by L', R and L
or an alkyl group in which the alkyl group of at least one of R' and L' is branched at the α carbon, such as i-propyl, t-butyl, sec-butyl, t-amyl, sec-amyl, t-octyl,
or an alkyl group such as sec-nonyl, and further R
and L, or both R' and L' are preferably alkyl groups branched at the α carbon. Further, the total number of carbon atoms in the alkyl groups of R and L or R' and L' is preferably 9 to 18. Next, specific compounds of the dye image stabilizer according to the present invention are illustrated below, but the present invention is not limited to only these exemplified compounds. The dye image stabilizer according to the present invention can be synthesized by a conventionally known method. For example, 3,
It is easily synthesized as shown in the following synthesis example by the reaction of 5-di-t-butyl-4-hydroxybenzoic acid chloride and a phenol represented by AOH (A has the meaning described above). be able to. Synthesis example 1 Synthesis of 2,4-di-t-amyl phenyl-3',5'-di-t-butyl-4'-hydroxybenzoate [exemplified compound (1)] Stirrer, thermometer, dropping funnel, and hydrochloric acid gas 43.0 g (0.16 mol) of 3,5-di-t-butyl-4-hydroxybenzoic acid chloride, 2,4 into a 200 ml four-necked colben with a condenser equipped with a discharge tube.
-D-t-amylphenol 37.3g (0.16mol)
and 65 ml of toluene were added, and the reaction was carried out at 80°C for 10 hours. After the reaction is complete, cool to 60℃ and boil with 60ml of hot water.
twice, once with 90 ml of 5% sodium carbonate aqueous solution, and 60 times
ml of warm water three times, then toluene was distilled off under reduced pressure, and when 150 ml of ethanol was added to the oil phase and cooled, white crystals precipitated, which were collected by filtration at 0°C.
63.3g was obtained. The obtained crystals were confirmed to be the target compound from the following elemental analysis values. melting point
153-155℃. Yield 85%. Elemental analysis value (C ₃₁ H ₄₆ O ₃ ,%) Calculated value: C 79.8; H 9.9; O 10.3 Actual value: C 79.5; H 10.6; O 9.9 Synthesis example 2 2-t-butyl-4-n-nonylphenyl-
Synthesis of 3',5'-di-t-butyl-4'-hydroxybenzoate [exemplified compound (3)] 2-t-butyl-4-n-noel instead of 2,4-di-t-aminophenol Phenol 44.2
65 g of crystals were obtained in the same manner as in Synthesis Example 1 except that 65 g (0.16 mol) of the crystals were used. It was confirmed that the obtained crystal contained the target compound based on the elemental analysis values shown below. Melting point 120-124℃. Yield 80%. Elemental analysis value (C ₃₄ H ₃₂ O ₃ , %) Calculated value: C 80.3; H 10.2; O 9.5 Actual value: C 80.9; H 9.7; O 9.4 Synthesis example 3 2-t-butyl-4-n-dodecylph enil
Synthesis of 3,5-di-t-butyl-4-hydroxybenzoate [exemplified compound (20)] 2-t-butyl-4-n-dodecylphenol instead of 2,4-di-t-amylphenol
65 g of crystals were obtained in the same manner as in Synthesis Example 1 except that 50.9 g (0.16 mol) was used. The obtained crystals were confirmed to be the target compound from the elemental analysis values shown below. Melting point 100-104℃. Yield 74%. Elemental Analysis (C ₃₇ H ₅₈ O ₃ , %) Calculated: C 80.7; H 10.6; O 8.7 Observed: C 80.7; H 10.9; O 9.1 Photographic elements of the present invention have at least one dye image on a support. Any type of structure may be used as long as it is provided with a layer having . For example, non-silver salt photographic materials are also included, but silver halide photographic materials are particularly preferred.
This silver halide photographic light-sensitive material includes a black-and-white light-sensitive material using a dye image, a color negative film,
Examples include color paper, color reversal, motion picture color film, and color diffusion transfer photosensitive materials. Among these photographic elements, silver halide color photographic light-sensitive materials usually have three kinds of light-sensitive materials on a support that are selectively sensitized to be sensitive to blue light, green light, and red light, respectively. A silver halide emulsion layer is coated. For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and then a red-sensitive emulsion layer are coated in this order from the side to be exposed. A bleachable yellow filter layer is generally provided between the blue-sensitive emulsion layers to absorb the blue light transmitted through the blue-sensitive emulsion layers. Further, between each emulsion layer, an intermediate layer is provided for a special purpose, and a protective layer is generally provided as the outermost layer. Light-sensitive materials for color paper are usually coated in the order of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and then a blue-sensitive emulsion layer from the side to be exposed.Similar to color negative light-sensitive materials, a UV absorber layer and an intermediate layer are coated. A non-photosensitive layer such as a protective layer is provided. Alternatively, it is known that each of the photosensitive emulsion layers is provided in a different layer order, and it is also known that two emulsion layers each having different photosensitive regions are used instead of one layer each. There is. In these silver halide color photographic light-sensitive materials, exposed silver halide grains are developed using, for example, an aromatic primary amine compound as a color developing agent, and the oxidation products of the color developing agent and the dye are produced. A dye image is formed by reaction with the forming coupler. This dye image usually includes phenol-based or naphthol-based cyan couplers, 5-pyrazolone-based couplers,
Pyrazolinobenzimidazole-based, pyrazolotriazole-based, indazolone-based, or cyanoacetyl-based magenta couplers, and acylacetamide-based or benzoylmethane-based yellow couplers are used. These dye-forming couplers are contained in the light-sensitive color photographic emulsion layer or in the developer solution. Various couplers can be used as the couplers that form the dye image used in the present invention, but the following general formulas (), (), or () can be used.
It is preferable that it is expressed by 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 ₁ 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.), R ₂ represents an aryl group,
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 having the following general formula ()' and general formula ()' In the formula, R ₃ represents a halogen atom, an alkoxy group or an aryloxy group, and R ₄ , R ₅ and R ₆ are
hydrogen atom, halogen atom, alkyl group, respectively.
represents an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a carbonyl group, a sulfonyl group, a carboxyl, an alkoxycarbonyl group, a carpamyl group, a sulfon group, a sulfamyl group, a sulfonamide group, an acylamide group, a ureido group, or an amino group; has the meaning given above. 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,
German Patent Publication No. 3725072, German Patent Publication No. 3894875, etc., German Patent Publication No. 1547868, German Patent Publication No. 2057941, German Patent Publication No. 2057941,
No. 2162899, No. 2163812, No. 2213461, No. 2219917, No. 2261361, No. 2263875,
Special Publication No. 13576, No. 48-29432, No. 48-
No. 66834, No. 49-10736, No. 49-122335, No. 50
-28834, and 50-132926, etc. 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 ₇ represents a hydrogen atom, a halogen atom, an alkyl atom, or an alkoxy group, and R ₈ represents an alkyl group, an amide group,
It represents an imide group, an N-alkylcarbamoyl group, an N-alkylsulfamoyl group, an alkoxycarbonyl group, an acyloxy group, a sulfonamide group, or a urethane group. Y is the same as in general formula (), W is -NH-, -NHCO-
(N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH-. ) These are, for example, US Pat. No. 2,600,788;
3061432, 3062653, 3127269, 3311476, 3152896, 3419391,
Same No. 3519429, Same No. 3555318, Same No. 3684514,
Same No. 3888680, Same No. 3907571, Same No. 3928044,
Specifications such as No. 3930861, No. 3930866, No. 3933500, JP-A-49-29639, No. 49-111631
No. 49-129538, No. 50-13041, No. 52-
No. 58922, No. 55-62454, No. 55-118034, No. 56
−38043, British Patent No. 1247493, Belgian Patent No. 769116, Belgian Patent No. 792525, West German Patent
It is described in the specifications of No. 2156111, Japanese Patent Publication No. 46-60479, 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 ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom, a halogen atom, an alkyl group, a carbamoyl group, a sulfamoyl group, an amide group, sulfonamide group, phosphoric acid amide group, or ureido group.) These are, for example, U.S. Pat.
Same No. 2698794, Same No. 2706684, Same 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,
3880661, German Patent Publication No.
No. 2163811, No. 2207468, Special Publication No. 39-27563,
45-28836, JP-A No. 47-37425, 50-
No. 10135, No. 50-25228, No. 50-112038, No. 50
−117422, No. 50-130441, No. 53-109603,
Publications No. 56-65134 and No. 56-99341 and Research Disclosure
Disclosure) 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)
-butyramide]-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)-butyramide]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-phthalimide-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-
Dimethyl-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-oxazoyl)-α-pivalyl-2-chloro-5-
[γ-(2,4-di-t-amylphenoxy)-
butylamide]-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)-
butylamide]-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-tetradecanamide-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-
(r-octadecynylsuccinimide)-propylsulfamoyl]-anilino-5-pyrazolone. (M-6) 1-(2,4,6-trichlorophenyl)-4
-acetoxy-5-(2-chloro-5-tetradecanamide)-anilino-5-pyrazolone. (M-7) 1-[γ-(3-pentadecylphenoxy)-
butylamide]-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-dicarboxy-
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-pentadecylphenyl)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-tetradecanamide)-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-dotecenylsuccinimide)-anilino-5-pyrazolone)]. (M-24) 1-(2,4,6-trichlorophenyl)-3
-[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone. (M-25) 3-ethoxy-1-4-[α-(3-pentadecylphenoxy)butyramide] 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)-butylamino]-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
- Milphenoxyacetamide) - Phenol. (C-6) 2,4-dichloro-3-methyl-6-[α-
(2,4-di-t-amylphenoxy)butyramide]-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)
-butyramide]-phenol. (C-10) 2-chloro-3-methyl-4-(1-phenyl-tetrazolyl-5-thio)-6-(2-dodecyloxyphenylacetamide)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)-butyramide]-phenol. (C-14) 2-perfluorobutyramide-5-[α-
(2,4-di-t-amylphenoxy)hexaneamide]-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)butyramide]-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) 2-chloro-5-(p-nitrobenzoyl-B
-O-hydroxyethylamino)-1-naphthol. (C-29) 5-(1,2,3,4-tetrahydronaphthalene-6-sulfamide)-1-naphthol. (C-30) 5-(quinoline-5-sulfamino)-1-naphthol. (C-31) 1-Hydroxy-4-acetoxy-N-[α-
(2,4-di-t-amylphenoxy)butyl-
2-Naphthamide. (C-32) 1-Hydroxy-4-thiocyano-N-[α-
(2,4-di-t-amylphenoxy)butyl]
-2- Naphthamide. (C-33) 1-hydroxy-4-(pentafluorophenoxy)-N-{β-{4-[α-(2,4-di-
t-amylphenoxy)acetamide]-phenyl}-ethyl}-2-naphthamide. (C-34) 1-Hydroxy-4-(4-chlorophenoxy)-2-tetradecyloxy-2-naphthamide. (C-35) 1-Hydroxy-4-phthalimide-N-[α
-(2,4-di-t-amylphenoxy)butyl-2-naphthamide. (C-36) 1-Hydroxy-4-(dodecenylsuccinimide)-N-[δ-2,4-di-t-amylphenoxy)butyl]-2-naphthamide. (C-37) 1-hydroxy-4-phenylthio-N-[α
(2,4-di-t-amylphenoxybutyl]-
2-Naphthamide. In the present invention, a particularly preferred dye image is one comprising a yellow dye represented by the following general formula [] or a cyan dye represented by the following general formula []. General formula [] [In the formula, R ₁ , R ₃ , R ₄ , R ₅ and R ₆ have the above-mentioned meanings. R ₁₃ represents a hydrogen atom or an alkyl group (for example, a methyl group). R ₁₄ and R ₁₅ are
respectively, an alkyl group, preferably an alkyl group substituted with a water-soluble group (e.g. hydroxyl, methanesulfonamido group, methoxy group, etc.) (e.g.
methyl group, ethyl group, propyl group, etc.). General formula [] [In the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and
R ₁₅ has the meaning given above. ] The color developing agent used to color develop the coupler forming the dye image contained in the photographic element of the present invention is not particularly limited, and commonly used color developing agents may be 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 inorganic acids such as sulfoethyl-p-phenylenediamine, o-aminophenol, p-aminophenol, and 5-amino-2-oxy-toluene, such as hydrochloric acid and sulfuric acid, or organic acids such as p-toluenesulfonic acid. . By incorporating the dye image stabilizer according to the present invention into a layer having a dye image, the effect of preventing photofading of cyan, magenta, or yellow dyes formed from dye image-forming couplers can be significantly improved. Furthermore, darkening and fading of the cyan dye can be prevented. In particular, when it is contained in the vicinity of the yellow dye, it exhibits an excellent effect in preventing photofading of the yellow dye. Furthermore, when used in combination with a conventionally used anti-fading agent, the effects of the anti-fading agent can be made permanent, and 2-
When used in combination with an ultraviolet absorber such as a (2'-hydroxyphenyl)benzotriazole compound, the effect of the ultraviolet absorber can be maintained for a long period of time without deterioration, so it can be preferably used. The method of incorporating the dye image stabilizer according to the present invention into a layer having a dye image is extremely simple. That is, it may be added in advance to any or all of the photographic emulsion layers in which cyan, magenta and yellow dyes are formed by color development in the constituent elements of a silver halide color photographic light-sensitive material. Furthermore, the compound of the present invention may be contained in other constituent elements, such as the intermediate layer, yellow filter layer, and ultraviolet absorbing layer. Furthermore, after or during development of the silver halide color photographic light-sensitive material, it may be contained in the resulting color photographic product. When the dye image stabilizer according to the present invention is contained in a dye-containing layer formed from a dye image-forming coupler that can be preferably used in the present invention, the effects of the present invention are extremely large and preferred.
Further, the effect is great even when it is contained in other constituent elements of the layer having the dye image (particularly in a layer adjacent to the layer having the dye image) and diffused into the layer having the dye image. For example, in order to incorporate silver halide into a photographic light-sensitive material in advance, gelatin is dissolved in an aqueous gelatin solution in a high-boiling organic solvent with a boiling point of approximately 175°C or higher, if necessary, in combination with a low-boiling solvent. They may be finely dispersed in an aqueous binder such as by using a surfactant, and this dispersion may be added to the layer to be used as a liquid. At this time, the coupler may be dispersed at the same time. Further, to explain in detail the method of adding the dye image stabilizer according to the present invention, the dye image stabilizer according to the present invention and a hydrophobic compound (a coupler, an ultraviolet absorber, an anti-fading agent, a fluorescent whitening agent, etc.) are added. , hydroquinone derivatives, etc.) and organic acid amides, carbamates, esters, ketones, urea derivatives, etc.
In particular, di-n-butyl phthalate, tri-cresyl phosphate, di-isooctyl acelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl, n- pentadecyl phenyl ether,
Triphenyl phosphate, di-octyl phthalate, n-nonylphenol, N,N-diethyl laurylamide, 3-pentadecyl phenylethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl-di-o - In a high boiling point solvent such as chlorophenyl phosphate or fluorine paraffin, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexanetetrahydrofuran, methyl alcohol, ethyl alcohol, acetonitrile, Dissolve in a low boiling point solvent such as dimethylformamide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, diethylene glycol, monoacetate, acetylacetone, nitromethane, nitroethane, carbon tetrachloride, chloroform (these high boiling point solvents and low boiling point solvents can be used alone). ) Also, anionic surfactants such as sodium alkylbenzenesulfonate and sodium alkylnaphthalenesulfonate, and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate. The agent is mixed with an aqueous solution containing a hydrophilic binder such as gelatin, and then mixed with a high-speed rotating mixer,
It can also be used by emulsifying and dispersing it using a colloid mill or an ultrasonic dispersion device, and adding it to a hydrophilic colloid. The amount of the dye image stabilizer according to the present invention to be added is not particularly limited, since these compounds are substantially colorless and do not cause any adverse effects such as color staining by themselves; however, per mole of the dye formed, 0.01
The amount is preferably 0.05 to 1 mol, more preferably 0.05 to 1 mol. In a color photosensitive material based on a color development method, the amount is preferably 0.01 mol or more, more preferably 0.05 to 1 mol, per mol of coupler used. There is no problem in using two or more of the dye image stabilizers according to the present invention in combination, and in this case as well, it is preferable to use them in the above-mentioned amounts. When the coupler used in the above-mentioned silver halide color photographic light-sensitive material is present in the silver halide color photographic light-sensitive material, it is generally used in an amount of 5 to 50 mol%, preferably 10 to 40 mol%, based on the silver halide. However, it may be used in an amount exceeding this range, for example, in a range of about 100 mol % based on silver halide. In addition, when it is present in the developer, it is generally 0.5 to 3.0 g/
, preferably used in an amount of 1.0 to 2.0 g/. In this case, the yellow, magenta, and cyan couplers may be used alone or each may be used in combination.
Two or more types may be used in combination, and when two or more types are used in combination, the amounts mentioned above are sufficient. The silver halide color photographic light-sensitive material may contain couplers other than the couplers mentioned above for special purposes, if necessary. For example, colored magenta couplers can be included for masking purposes. Further, the silver halide color photographic emulsion layer or the adjacent layer may contain a coupler that releases a development inhibitor depending on the density of the image during development, or a development inhibitor-releasing compound other than the coupler. In addition to the dye image stabilizer according to the present invention, thiazolidone, benzotriazole,
The use of acrylonitrile and benzophenone compounds is advantageous and preferable in terms of preventing discoloration due to short wavelength actinic rays. It is also advantageous to use hydroquinone derivatives which are antioxidants together with the dye image stabilizers according to the invention. Specific examples of hydroquinone derivatives are shown below. Hq-1 2,5-di-t-octylhydroquinone. Hq-2 2-t-octyl-5-methylhydroquinone. Hq-3 2,6-d-n-dodecyl-hydroquinone. Hq-4 2-n-dodecylhydroquinone. Hq-5 2,2'-methylenebis-5,5'-di-t-butylhydroquinone. Hq-6 2,5-d-n-octyl-hydroquinone. Hq-7 2-dodecylcarbamoylmethylhydroquinone. Hq-8 2-(β-n-dodecyloxycarbonyl)ethyl-hydroquinone. Hq-9 2-(N,N-dibutylcarbamoyl)hydroquinone. Hq-10 2-n-dodecyl-5-chloro-hydroquinone. Hq-11 2-(2-octadecyl)-5-methylhydroquinone. Hq-12 2,5-di-(p-methoxyphenyl)hydroquinone. Hq-13 2-t-octylhydroquinone. Hq-14 2-[β-{3-(3-sulfobenzamide)benzamide}ethylhydroquinone. Hq-15 2,5-dichloro-3,6-diphenylhydroquinone. Hq-16 2,6-dimethyl-3-t-octylhydroquinone. Hq-17 2,3-dimethyl-5-t-octylhydroquinone. Hq-18 2-{β-(dodecanoyloxy)ethyl}carbamoylhydroquinone. Hq-19 2-dodecyloxycarbonylhydroquinone. Hq-20 2-{β-(4-octanamidophenyl)ethyl}hydroquinone. Hq-21 2-methyl-5-dodecylhydroquinone. Hq-22 2,5-bis(1',1'-dimethylbutyl)hydroquinone. These hydroquinone derivatives may be used alone or in combination of two or more, and the amount added is usually 0.01 to 10 mol per 1 mol of coupler in silver halide color photographic light-sensitive materials containing couplers, particularly 0.1 ~3 mol is preferred. In addition, in the case of silver halide color photographic light-sensitive materials that do not contain couplers, 0.01
-1.0 mol is preferred, particularly 0.02-0.6 mol. The silver halide emulsion used in the photographic element of the present invention generally has silver halide grains dispersed in a hydrophilic colloid, and examples of the silver halide include silver chloride, silver bromide, silver iodide, and silver oxide, silver iodobromide, silver chloroiodobromide, or a mixture thereof;
These silver halides can be prepared using the ammonia method, neutral method,
It can be produced by various methods such as a conversion method or a simultaneous mixing method. Hydrophilic colloids for dispersing silver halide include gelatin,
Alternatively, gelatin derivatives such as phthalated gelatin and malonated 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 photosensitive wavelength range, and the sensitizing dyes include cyanine dyes, cyanine dyes,
Merocyanine dyes or complex cyanine dyes can be used alone or in combination of two or more.
Furthermore, if necessary, chemical sensitizers such as gold compounds, noble metal salts such as platinum, palladium, iridium, rhodium and ruthenium, sulfur compounds, reducing substances or thioether compounds, quaternary ammonium salt compounds or polyalkylene oxide compounds, Stabilizers such as triazoles, imidazoles, azaindenes, benzothiazolium salts, zinc compounds, cadmium compounds, mercaptans, etc.; chromium salts, zirconium salts, mucochloric acid, aldehyde series, triazine series, polyepoxy compounds, active halogens Hardening agents such as compounds, ketone compounds, acryloyl type, triethylene phosamide type, ethyleneimine type; glycerin, 1,5-
Various photographic additives such as dihydroxyalkane plasticizers such as pentanediol; fluorescent brighteners; antistatic agents; and coating aids may be used alone or in combination.
More than one species can be added and used in combination. The obtained silver halide emulsion layer is made to contain a dispersion in which the dye image stabilizer according to the invention described above is dispersed, and is further coated with a subbing layer, an antihalation layer, an intermediate layer, a yellow filter layer, and an ultraviolet ray as necessary. A dispersion of the dye image stabilizer according to the present invention is contained in an absorbing layer, a protective layer, etc., and a synthetic resin film such as cellulose acetate, cellulose nitrate, polycarbonate, polyethylene terephthalate, or polyethylene, baryta paper, polyethylene-coated paper, By coating on a support such as a glass plate,
A silver halide color photographic material is obtained. The above-mentioned silver halide color photographic light-sensitive material may be an internal silver halide color photographic light-sensitive material containing a coupler or an external silver halide color photographic light-sensitive material in which a coupler is contained in a developer, particularly an internal silver halide color photographic material containing a coupler. This is advantageous for photographic materials, and after exposure, color development is performed using a 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 silver halide color photographic materials where they can come into contact with each other after exposure, or silver halide colors containing couplers. A silver halide color photographic material in which a color developing agent is contained in a layer that does not contain the coupler, and when an alkaline processing solution is permeated, the color developing agent is moved and brought into contact with the coupler. It's okay. Furthermore, in a silver halide color photographic light-sensitive material for color diffusion transfer, the dye image stabilizer according to the present invention can be added to the light-sensitive element and/or the image-receiving element of the light-sensitive material, particularly in the image-receiving element. It is advantageous to have it present. In the reversal process, the image is developed in a black and white negative developer, then exposed to white light or treated in a bath containing a fogging agent such as a boron compound, and then color developed in an alkaline developer containing a color developing agent. At this time, there is no problem even if a fogging agent is included 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 silver halide color photographic light-sensitive material containing the dye image stabilizer according to the present invention is advantageously processed include, for example, color development, washing with water as necessary, bleach-fixing, washing with water, as necessary. This is a stabilization and drying step, and this treatment step is carried out at a high temperature of, for example, 30° C. or higher and within an extremely short period of 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, antifoggants, 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 complexes include metal lead salts of polycarboxylic acids such as malonic acid, tartaric acid, and malic acid, ferric chloride, and the like, 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. The silver halide color photographic light-sensitive material containing the dye image stabilizer according to the present invention is processed using a color developing solution containing both an aromatic primary amine color developing agent and an oxidizing agent for subjecting the metallic silver image to a redox reaction. It is also effective to treat using 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-
A preferred oxidizing agent for this purpose is a cobalt complex salt having a coordination number of 6, as disclosed in Japanese Patent No. 9729. 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 silver halide color photographic materials. Further, it contains a dye image stabilizer according to the present invention.
Silver halide color photographic light-sensitive materials are primarily aromatic
Development is carried out in a color developing solution containing a grade amine color developing agent, which is then preferably received in the photosensitive layer during the color development step and in an amplifying bath.
A color photographic processing method comprising the presence of a color developing agent, which is carried in a coloring bath), and brought into contact with an intensifying solution containing an oxidizing agent, such as a cobalt chain salt having a coordination number of 6, as described above. It is also useful to use Another preferred oxidizing agent for this purpose is an aqueous hydrogen peroxide solution. According to the photographic element of the present invention, the dye image stabilizer according to the present invention has excellent solubility in organic solvents, and does not easily precipitate when contained in the photographic element, resulting in precipitation failure. No inconvenience will occur. Furthermore, the storage stability of the dye image in terms of light fastness, heat resistance, moisture resistance, etc. can be significantly improved without impairing photographic properties such as sensitivity, gradation, and color development of the dye contained in the dye image layer. The present invention will be specifically described below with reference to Examples.
The embodiments of the present invention are not limited to this. Example 1 Photographic elements having the layer configurations shown in Tables 1 and 2 below were prepared.

[Table] The composition of the coupler dispersion used in the blue-sensitive emulsion layer was as shown in Table 2. For each sample, 500 ml of a 5% aqueous gelatin solution containing 3.0 g of Alkanol B manufactured by DuPont was used as the aqueous phase, and after mixing, the mixture was emulsified and dispersed using a homogenizer.

【table】

[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 15ml Diethylene glycol 15ml Hydroxyamine sulfate 2g 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) For each sample treated in this way, the relative sensitivity, maximum reflection density, and gamma (γ) value were measured using a photoelectric densitometer (PDA-60 manufactured by Konishiroku Photo Industry Co., Ltd.).
(type). The results are shown in Table 3. (3) Dye image storage test A dye image storage test was conducted on each photographic element under the following conditions. A. Bright and ^fading properties Illuminance (lux) Irradiation ^time (g) A. ℃ 80% RH for 14 days The obtained results are shown in Table 3 as the dye residual rate R. This dye residual rate R is defined as the initial concentration Do=1.0
It refers to the percentage (%) of the density D after the test against the yellowing of the white background ΔD, and was calculated using the following formula. R=Do−△D/Do×100

【table】

[Table] As is clear from the results shown in Table 3, when the comparative dye image stabilizer was used, there were the following drawbacks. That is, alkyl-3,5-di-t-butyl-
4-Hydroxybenzoate (B-2) does not provide satisfactory effects in terms of solubility, precipitation, sensitometric properties, and dye image stabilization effect. Furthermore, among 2,4-alkyl-substituted phenyl-3',5'-alkyl-substituted-4'-hydroxybenzoates, those in which the substituents at the 3' and 5' positions are not t-butyl [(B-4) and (B-
5)] cannot be said to be fully satisfactory in terms of solubility, precipitation and sensitometric properties, and is significantly inferior in terms of dye image stabilization effect. Furthermore, 2,4-alkyl substituted phenyl-3′,
Among 5'-t-butyl-4'-hydroxybenzoates, the total number of carbon atoms in the alkyl groups at the 2- and 4-positions is less than 9 [(B-1) and (B-
3)] is good in terms of dye image stabilization effect, but it cannot be said to be sufficient in terms of sensitometric properties, and is very poor in terms of solubility and precipitation. Compared to the cases using these comparative dye image stabilizers, the use of the dye image stabilizer according to the present invention is satisfactory in terms of solubility, precipitation, sensitometric properties, and dye image stabilizing effect. Demonstrate the desired characteristics. Example 2 Exemplary compound (1) of the dye image stabilizer according to the present invention
A photographic element identical to Example 1 was prepared except that exemplified compound (4), (7), (10), or (16) was used in place of (2). The thus obtained photographic element of the present invention was subjected to the same tests as in Example 1, and the results showed that it had satisfactory properties in all respects of solubility, precipitation, sensitometric properties, and dye image stabilizing effect. The object of the present invention was achieved. Example 3 Instead of the yellow coupler contained in layer 1,
A photographic element identical to Example 1 was prepared except that an edge-sensitive emulsion and an exemplary magenta coupler were used. The composition of the coupler dispersion used in the edge-sensitive emulsion layer was

[Table] Shown in the table. The dye image stabilizers (G-1) and (G-2) used here for comparison are the following compounds. (G-1) Exemplary compounds described in Japanese Patent Publication No. 40-20977 (G-2) Exemplary compounds described in US Pat. No. 3,432,300 Each photographic element obtained was subjected to the same sensitometric property test and dye image storage test as in Example 1. The results are shown in Table 5.

【table】

Table 5 As is clear from Table 5, the photographic elements of the present invention exhibit good properties in terms of sensitometric properties and dye image storage properties. In particular, it not only significantly improves the light resistance of the magenta dye, but also has a great effect of preventing yellowing of the white background due to photodecomposition of unreacted magenta coupler. Example 4 Instead of the yellow coupler contained in layer 1,
A photographic element identical to Example 1 was prepared except that a red sensitive emulsion and an exemplary cyan coupler were used. Table 6 shows the composition of the coupler dispersion used in the red-sensitive emulsion layer. Here, the dye image stabilizers (R-1) and (R-2) used for comparison are the following compounds. (R-1) Exemplary compounds described in JP-A-50-151149

[Table] (R-2) Exemplary compounds described in JP-A-50-151149 Each photographic element was subjected to the same sensitometric characterization tests as in Example 1. The results are shown in Table 7.

[Table] As is clear from the results in Table 7, when conventional dye image stabilizers are used, the sensitometric properties are degraded. Furthermore, in Comparative Samples 27 and 33, hydrophobic substances precipitated on the surface and became matte after the coating was dried. In comparison, when the dye image stabilizer according to the present invention is used, it exhibits satisfactory properties in terms of both sensitometric properties and dye image stabilizing effect, and in particular, the effect of preventing darkening and fading is remarkable. Are better. Moreover, no problems such as matting were observed, and it was found that the dye image stabilizer according to the present invention was excellent in terms of solubility and precipitation in organic solvents. Example 5 Photographic elements having the layer configurations shown in Table 8 were prepared.

[Table] Each photosensitive emulsion layer of layers 1, 3 and 5 has a 9th layer.
The dye image stabilizers listed in the table were added.

[Table] When each photographic element was subjected to the same sensitometric property test as in Example 1, photographic elements 35, 36, and 37 of the present invention showed almost the same properties as the unadded sample. Comparative Example Photographic Element 38 suffered from significant coloring defects in the yellow coloring layer and the cyan coloring layer. Exposure was then carried out to blue light, green light, and red light, respectively, to obtain yellow, magenta, and cyan three-color separation samples, which were subjected to the same dye image storage test as in Example 1. The results are shown in Table 10.

[Table] As is clear from Table 10, the photographic element of the present invention has very excellent dye image storage stability, and the improvement effect is particularly remarkable in the light fading property of yellow dyes and the dark fading property of cyan dyes.

Claims (1)

[Scope of Claims] 1. A photographic element having at least one dye image-bearing layer, wherein at least one of the dye image-bearing layers contains a compound represented by the following general formula []. A photographic element characterized by General formula [] (In the formula, A represents a phenyl group substituted with at least one alkyl group. However, the total number of carbon atoms of the alkyl group that is a substituent is 9 to 36.)