JPH043542B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material which contains a cyan coupler having excellent dispersion stability and which provides a dye image formed with good long-term storage stability. Regarding materials. To form a dye image using a silver halide color photographic light-sensitive material, an aromatic primary amine color developing agent is usually used to reduce the silver halide grains in the exposed silver halide color photographic light-sensitive material. In this process, the silver halide is itself oxidized, and this oxidized product reacts with a coupler previously contained in the silver halide color photographic light-sensitive material to form a dye. Generally, three types of couplers are used that form three dyes, yellow, magenta, and cyan, in order to perform color reproduction by the subtractive color method. Each coupler is usually dissolved in a substantially water-insoluble high-boiling organic solvent or in this solvent, if necessary, in combination with an auxiliary solvent, and added to the silver halide emulsion. The basic properties required for each coupler are:
First of all, it has high solubility in high-boiling organic solvents, has good dispersibility and dispersion stability in silver halide emulsions, does not easily precipitate, and has good photographic properties. , have robustness against heat, moisture, etc. In particular, in cyan couplers, improvement of heat-humidity resistance (fading resistance) has become an important issue in recent years. Conventionally known cyan couplers include 2,5-diacylaminophenol cyan couplers in which the 2- and 5-positions of phenol are substituted with acylamino groups; for example, as disclosed in U.S. Pat.
Specification No. 2895826, Japanese Unexamined Patent Application Publication No. 112038/1983, No. 53-
No. 109630 and No. 55-163537. These 2,5-diacylaminophenol cyan couplers are frequently used because they provide cyan dye images with good dark fading resistance, but they generally have the drawback of extremely poor photofading resistance. Therefore, as a means to improve the photofading property of 2,5-diacylaminophenol cyan couplers, it has been proposed to use a benzotriazole compound in combination, as described in JP-A-50-151149. . However, this compound is not practical because it has a large precipitation property and is only effective against photofading against ultraviolet rays. It is also known to increase the amount of a conventionally used high-boiling organic solvent such as dibutyl phthalate, which slightly improves photobleaching properties, but reduces photographic properties such as color tone. Problems such as adverse effects and deterioration of fading properties have arisen. JP-A No. 57-173835 discloses that a 2,5-diacylaminophenol cyan coupler in which the 2-position of the phenol is substituted with an orthosulfonamidophenylacylamino group is used in a high-boiling organic solvent having a specific dielectric constant. By dispersing the
Although methods have been proposed to improve color tone and dye fastness, it has been found that these methods significantly impair the photobleachability of cyan dye images. The first object of the present invention is to use halogen-based dyes that can form dye images that have well-balanced improvements in light fastness, heat resistance, and moisture resistance, and exhibit excellent image storage stability over a long period of time even under high temperature and high humidity conditions. The purpose of the present invention is to provide a silver oxide photographic material. A second object of the present invention is to provide a silver halide photographic material in which the fastness of a cyan dye image is improved in light fading without deteriorating dark fading. A third object of the present invention is to provide a silver halide photographic material capable of forming a dye image with improved image storage stability without adversely affecting photographic properties. A fourth object of the present invention is to contain a cyan coupler dispersed using a high boiling point organic solvent that can be dispersed extremely stably, so that the dispersion stability of the cyan coupler is good and no precipitation failure occurs. An object of the present invention is to provide a silver halide photographic material. The present inventors have proposed that in a silver halide photographic material having at least one silver halide emulsion layer provided on a support, at least one of the silver halide emulsion layers is represented by the following general formula []. at least one cyan coupler and at least one high boiling point organic solvent represented by the following general formula []
The present inventors have discovered that the above object can be achieved by a silver halide photographic material characterized by containing seeds, and have completed the present invention. General formula [] [In the formula, R ₁ represents an alkyl group or an aryl group. R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group,
cyano group, alkyl group, alkoxy group, alkylsulfamoyl group, arylsulfamoyl group,
Represents a group selected from an alkyloxycarbonyl group and an aryloxycarbonyl group. Z ₁ is a hydrogen atom, a halogen atom, or an aromatic primary
Represents a group that can be separated by reaction with an oxidized product of a class amine color developing agent. ] General formula [] [In the formula, R ₇ , R ₈ and R ₉ each represent an alkyl group, alkenyl or aryl group. however,
The total number of carbon atoms in the groups represented by R ₇ , R ₈ and R ₉ is 24 to 48. ] In the present invention, the alkyl group represented by R ₁ in the general formula [] is a linear or branched one, such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group. , octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. These alkyl groups may have a single or multiple substituents, and a typical substituent is a phenoxy group (this phenoxy group may further have a substituent, and this substituent Typical examples include halogen atoms (e.g. fluorine, chlorine), hydroxyl groups, nitro groups, cyano groups, alkyl groups (e.g. methyl, butyl, dodecyl), and alkoxy groups (e.g. methoxy, ethoxy). , aryl group (e.g. phenyl group, tolyl group), aryloxy group (e.g. phenoxy group, naphthoxy group),
Aralkyl group (e.g. benzyl group), alkylsulfamoyl group (e.g. butylsulfamoyl group), arylsulfamoyl group (e.g. phenylsulfamoyl group), alkyloxycarbonyl group (e.g. n-octyloxycarbonyl group) ,
Aryloxycarbonyl group (e.g. phenoxycarbonyl group), alkylsulfonamide group (e.g. butylsulfonamide group), arylsulfonamide group (e.g. phenylsulfonamide group)
), an alkylacylamino group, an arylacylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxy group, an alkyloxycarbonyl group, and an aryloxycarbonyl group.
Two or more of these substituents may be introduced into the alkyl group. The aryl group represented by R ₁ is
For example, phenyl group, naphthyl group, etc. These aryl groups may have a substituent, and typical examples of this substituent include halogen atom (for example, chlorine, fluorine), hydroxyl group, and nitro group. ,
cyano group, alkyl group (e.g. methyl group, butyl group, dodecyl group), alkoxy group (e.g. methoxy group, ethoxy group), aryl group (e.g. phenyl group), aryloxy group (e.g. phenoxy group),
Alkylsulfamoyl groups (e.g. butylsulfamoyl group), arylsulfamoyl groups (e.g. phenylsulfamoyl group), alkyloxycarbonyl groups (n-octyloxycarbonyl group), aryloxycarbonyl groups (e.g. phenylsulfamoyl group), cyclocarbonyl group), an alkylsulfonamide group (eg, butylsulfonamide group), an arylsulfonamide group (eg, phenylsulfonamide group), an alkylsulfonyl group (eg, dodecylsulfonyl group), and the like. Preferred groups represented by R ₁ include phenoxy-substituted alkyl groups (e.g., 2,4-di-t-butylphenoxypentyl group, 2,4-di-t-pentylphenoxypropyl group, 2,4-di-t-pentylphenoxypropyl group, di-t-butylphenoxybutyl group, 2,4-di-t-pentylphenoxypentyl group), arylsulfonyl-substituted alkyl group (e.g., 2,4-di-t-butylphenylsulfonyl group), Aryl group, (e.g. 2,4-
di-t-butylphenyl group, 2,4-di-t-pentylphenyl group), arylthio-substituted alkyl group (for example, 2,4-di-t-butylphenylthio group), and the like. In the present invention, R ₁ is preferably a group represented by the following general formula []. General formula [] R ₁₀ -X-R ₁₁ - In formula [], R ₁₀ is an alkyl group (e.g. n
-butyl group, n-paytyl group, n-octyl group,
n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, sec-pentadecyl group, sec-tridecyl group, 5-octyl group, t-nonyl group, etc.) or phenyl group. The phenyl group may have a single or multiple substituents, and typical substituents include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), hydroxyl, cyano,
Nitro, alkyl groups (e.g. methyl, ethyl, butyl, pentyl, octyl, dodecyl, etc.), alkoxy groups (e.g. methoxy,
ethoxy group, butoxy group, octoxy group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, octylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, xylylsulfamoyl group, etc.) group, tolylsulfamoyl group, mesitylsulfamoyl group,
), alkyloxycarbonyl groups (e.g. methyloxycarbonyl group, butyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g. phenyloxycarbonyl group, xylyloxycarbonyl group, tolyloxycarbonyl group, mesityloxycarbonyl group) , etc.), alkylsulfonamide groups (e.g. methylsulfonamide group, ethylsulfonamide group, butylsulfonamide group,
benzylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group, xylylsulfonamide group, tolylsulfonamide group, mesitylsulfonamide group, etc.), or aminosulfonamide group (e.g. N, N -dimethylaminosulfonamide group, etc.). Two or more types of these substituents may be introduced into the phenyl group. Preferred groups represented by R ₁₀ include phenyl or a phenyl group having a hydroxyl group, an alkyl group, or an alkylsulfonamide group as a substituent. R ₁₁ represents an alkylene group. It preferably represents a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms. (For example, α−
Butylmethylene group, α-ethylmethylene group, α-
dodecylmethylene group) X represents a divalent group such as -O-, -S-, -SO- or _-SO2- group. In the general formula [], R ₂ and R ₆ each represent a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, etc.), a hydroxyl group, a nitro group, a cyano group, an alkyl group (e.g., a methyl group, an ethyl group, a propyl group, etc.). group, butyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), alkylsulfamoyl group (e.g., methylsulfamoyl group, butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, xylylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, butyloxycarbonyl group,
), or an aryloxycarbonyl group (eg, phenyloxycarbonyl group, xylyloxycarbonyl group, tolyloxycarbonyl group, mesityloxycarbonyl group, etc.). Preferred groups represented by R ₂ and R ₆ include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and the like. R ₃ , R ₄ and R ₅ are each a hydrogen atom, a halogen atom (e.g. fluorine, chlorine, bromine, etc.), a hydroxyl group, a nitro group, a cyano group, an alkyl group (e.g. a methyl group, an ethyl group, a propyl group, butyl group, octyl group, decyl group, dodecyl group, trifluoromethyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, octoxy group, etc.),
Alkyl sulfamoyl group (e.g., butyl sulfamoyl group, octyl sulfamoyl group, etc.),
Arylsulfamoyl groups (e.g. phenylsulfamoyl group, xylylsulfamoyl group, tolylsulfamoyl group, mesitylsulfamoyl group, etc.), alkyloxycarbonyl groups (e.g.
methyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, xylyloxycarbonyl group, tolyloxycarbonyl group, mesityloxycarbonyl group, etc.) , represents a group selected from . Preferred groups represented by R ₃ , R ₄ and R ₅ include a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an alkyl group, and an alkyloxycarbonyl group. The group represented by Z ₁ that can be released by reaction with the oxidized product of an aromatic primary amine color developing agent is well known to those skilled in the art, and can modify the reactivity of the coupler or can be released from the coupler. Therefore, in the coating layer or other layer containing the coupler in the silver halide color photographic light-sensitive material, it acts advantageously by performing functions such as development inhibition, bleaching inhibition, and color correction. Typical examples include halogen atoms (e.g. fluorine, chlorine, bromine), alkoxy groups (e.g. methoxy, ethoxy, octoxy, etc.), aryloxy groups (e.g. phenyloxy, etc.), cyclohexyloxy groups, Aryl azo group (e.g. phenylazo group etc.), thioether (e.g. benzylthio group etc.),
or a heterocyclic group (eg, oxazolyl, diazolyl, triazolyl, tetrazolyl, etc.), an aralkylcarbonyloxy group, and the like. A particularly preferred example of Z is a hydrogen atom or a halogen atom (preferably a chlorine atom). Typical specific examples of the cyan coupler represented by the formula [] are shown below, but the invention is not limited thereto. In the present invention, the cyan coupler represented by the general formula [] can be used in combination with conventionally known cyan couplers as long as it does not contradict the purpose of the present invention. When the cyan coupler according to the present invention represented by the general formula [] is contained in a silver halide emulsion layer, it is usually about 0.05 to 2 cyan couplers per mole of silver halide.
It is used in moles, preferably in the range of 0.1 to 1 mole. In the present invention, the total number of carbon atoms represented by R ₇ , R ₈ and R ₉ in the general formula [] is 24 or less.
The reason why it is 48 is that if it is less than 24, it will not exhibit the improvement effect aimed at by the present invention, and if it exceeds 48, its function as a coupler solvent will decrease and the coupler precipitation will deteriorate. be. Examples of the alkyl group represented by R ₇ , R ₈ or R ₉ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl, nonyl, decyl, undecyl group, dodecyl group, tridecyl group. groups, such as tetradecyl group, pentadecyl group, hesadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc. Aryl groups are phenyl group, naphthyl group, etc., and alkenyl groups are butenyl group, pentenyl group, hexenyl group, heptenyl group. group, octadecenyl group, etc.
These alkyl groups, alkenyl groups, and aryl groups may have single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, Examples of the substituent for the aryl group include an alkenyl group and an alkoxycarbonyl group. Examples of substituents for the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group. Preferably _R7 and _R8 are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, sec-
Examples include decyl group, sec-dodecyl group, t-octyl group, and the like. In the present invention, the high boiling point organic solvent generally refers to an organic solvent having a boiling point of 175° C. or higher at 1 atm. In the present invention, the amount of the high boiling point organic solvent according to the present invention represented by the general formula [] may be any amount depending on the type and amount of the cyan coupler according to the present invention represented by the general formula []. but preferably a cyan coupler according to the invention
It is preferably 0.1 to 1×10 ³ parts by weight, more preferably 10 to 200 parts by weight, per 100 parts by weight. Further, the high boiling point organic solvent according to the present invention represented by the general formula [] can be used in combination with other conventionally known high boiling point organic solvents within the range that does not contradict the purpose of the present invention. Examples of these high boiling point organic solvents include phthalate esters such as dibutyl phthalate, dimethyl phthalate, and dibenzyl phthalate; phosphate esters such as tricresyl phosphate and trihexyl phosphate; N,N-diethyl laurylamide, 3-
Pentadecyl phenylethyl ether, 2,5-
Di-sec-amyl phenyl butyl ether, 2-
Examples include ethylhexanol. High boiling point organic solvent to low boiling point organic solvent: 1:0.1-1:
50, more preferably 1:1 to 1:20. Typical specific examples of the high boiling point organic solvent represented by the general formula [] are shown below, but the invention is not limited thereto. (-1) O=P [-OC ₈ H ₁₇ (n)] ₃ (-3) O=P [-OC ₉ H ₁₉ (n)] ₃ (-12) O=P [-OC ₁₀ H ₂₁ (n)] ₃ (-15) O=P [-OC ₁₁ H ₂₃ (n)] ₃ (-21) O=P [-OC ₁₂ H ₂₅ (n)] ₃ (-23) O=P [-OC ₁₃ H ₂₇ (n)] ₃ (-25) O=P [-OC ₁₄ H ₂₉ (n)] ₃ (-28) O=P [-OC ₁₅ H ₃₁ (n)] ₃ (-29) O=P [-OC ₁₆ H ₃₃ (n)] ₃ (-32) O=P [-OCH=CHC ₁₆ H ₃₃ ] ₃ (-34) O=P [-OCH ₂ COOC ₈ H ₁₇ (n)] ₃ The silver halide photographic material of the present invention is one in which at least one silver halide emulsion layer is provided on a support. Any layer may be used, and there are no particular limitations on the number and order of the silver halide emulsion layer and the non-photosensitive layer. Typical examples include color positive or negative films, color photographic paper, color slides, and black and white photographic materials using dye images, and are particularly suitable for color photographic paper. Usually, most of the silver halide emulsion layer and the non-photosensitive layer are hydrophilic colloid layers containing a new aqueous binder. This new aqueous binder includes gelatin,
Alternatively, gelatin derivatives such as acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin are preferably used. The cyan coupler according to the present invention represented by the formula [] (hereinafter referred to as the cyan coupler according to the present invention) and the high boiling point organic solvent represented by the formula [] (hereinafter referred to as the high boiling point organic solvent according to the present invention),
The method used for ordinary cyan dye-forming couplers can be similarly applied, and a silver halide emulsion layer containing the cyan coupler according to the present invention dispersed using a high boiling point organic solvent according to the present invention is prepared on a support. A silver halide photographic light-sensitive material is formed by coating. In the case of this silver halide photographic light-sensitive material, whether it is a single-color silver halide photographic light-sensitive material or a multi-color silver halide photographic light-sensitive material, the cyan coupler according to the present invention is usually used in a red-sensitive silver halide emulsion layer. However, it may be contained in a non-sensitized emulsion or an emulsion layer sensitive to the three primary color regions of the spectrum other than red. Each structural unit forming a dye image in the present invention is a single emulsion layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum. In order to incorporate the cyan coupler according to the present invention into an emulsion, a conventionally known method may be followed. for example,
The high boiling point organic solvent according to the present invention, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane, tetrahydrofuran, methyl alcohol, ethyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, methyl isobutyl According to the present invention, the present invention can be used as a single solvent with a low-boiling organic solvent represented by ketone, diethylene glycol monoacetate, acetylacetone, nitromethane, nitroethane, carbon tetrachloride, chloroform, etc., or as necessary, a mixture of these solvents. After dissolving the cyan coupler,
Mixed with an aqueous gelatin solution containing a surfactant,
Next, stirrer, homogenizer, colloid mill,
After emulsifying and dispersing using a dispersion means such as a flow jet mixer or an ultrasonic dispersion device, the silver halide emulsion used in the present invention can be prepared in addition to the silver halide emulsion. At the same time, a step of removing the low boiling point organic solvent may be included. In the present invention, the ratio of the high boiling point organic solvent and the low boiling point organic solvent according to the present invention is 1:0.1 to 1:50,
More preferably, the ratio is 1:1 to 1:20. Examples of surfactants that can be used in the present invention include alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl polyesters. Anionic surfactants such as oxyethylene alkyl phenyl ethers, nonionic surfactants such as steroidal saponins, alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkylsulfonic acids and alkyl betaines, etc. Cationic surfactants such as amphoteric surfactants and quaternary ammonium salts can be used. Specific examples of these surfactants can be found in "Surfactant Handbook" (Sangyo Tosho, 1966)
and ``Emulsifier/Emulsifier Research/Technical Data Collection'' (Science Panroner, 1978). The cyan coupler and high boiling point organic solvent according to the present invention may contain other hydrophobic compounds such as hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, optical brighteners, coloring dyes, etc., as necessary.
Can be added at the same time. When the silver halide color photographic material of the present invention is a multicolor element, the necessary layers of the photographic element, including the layers of the image-forming units described above, may be added in various orders as known in the art. Can be arranged.
A typical multicolor photographic element consists of a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having cyan dye-forming couplers (at least one of the cyan dye-forming couplers is represented by the formula at least one light-insensitive silver halide emulsion having at least one magenta dye-forming coupler; It consists of a magenta dye image-forming structural unit consisting of a layer and a yellow dye image-forming structural unit consisting of at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler supported on a support. Photographic elements can have additional layers such as non-light sensitive layers such as filter layers, interlayers, protective layers, antihalation layers, subbing layers, and the like. As the yellow dye-forming coupler used in the present invention, compounds represented by the following general formula () are preferred. General formula () In the formula, R ₁₂ is an alkyl group (for example, a methyl group,
R ₁₃ represents an aryl group,
Y represents a hydrogen atom or a group that is eliminated during the color development reaction. Furthermore, particularly preferred yellow couplers for forming the dye image according to the present invention are compounds represented by the following general formula (V'). General formula (V′) 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.
It represents an aryloxy group, a carbonyl group, a sulfonyl group, a carboxyl group, an alkoxycarbonyl group, a carpamyl group, a sulfon group, a sulfamyl group, a sulfonamido group, an acylamido 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,
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 ₁₈ represents a hydrogen atom, a halogen atom, an alkyl atom, or an alkoxy group, and R ₁₉ 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. Next, specific representative examples of yellow and magenta dye-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-amiphenoxy)
-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)acetamide]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)-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-(r-
octadecynylsuccinimide)-propylsulfamoyl]-anilino-5-pyrazolone. (M-6) 1-(2,4,6-trichlorophenyl)-4-
Acetoxy-5-(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-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-Nitroalinino-5-pyrazolone. Cyan coupler These yellow dye-forming couplers and magenta dye-forming couplers are contained in the silver halide emulsion layer in an amount of about 0.05 to 2 moles per mole of silver halide. Supports according to the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper; transparent supports with a reflective layer or a reflective material; glass plates; cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc. Examples include polyester film; polyamide film; polycarbonate film; polystyrene film. These supports are appropriately selected depending on the purpose of use of the silver halide photographic material of the present invention. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating are used for coating the silver halide emulsion layer and non-photosensitive layer used in the present invention. The silver halide used in the silver halide emulsion according to the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. Includes anything that These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100] planes to [111] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Furthermore, these silver halides may be produced by any of the neutral method, ammonia method, and acidic method, and may be produced by any of the simultaneous mixing method, forward mixing method, back mixing method, convergence method, etc. Silver halide grains manufactured by can also be applied. The silver halide emulsion according to the present invention contains sulfur sensitizers such as arylthiocarbamide, thiourea,
Also active or inactive selenium sensitizers, such as cystine, and reduction sensitizers, such as stannous salts, polyamines, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloride, etc. sensitizers of water-soluble salts such as ruthenium, rhodium, iridium, in particular ammonium chloroparadate,
Chemical sensitization can be carried out using potassium chloroplatinate, sodium chloroparadide, etc. alone or in combination as appropriate. Further, the silver halide emulsion according to the present invention can contain various known photographic additives. The silver halide according to the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range required for red-sensitive emulsions. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more. Spectral sensitizing dyes advantageously used in the present invention include, for example, US Pat. No. 2,270,378;
Typical examples include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in the specifications of No. 2442710 and No. 2454620. The silver halide emulsion layer and non-photosensitive layer of the silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives. For example, antifoggants, color stain inhibitors, optical brighteners, antistatic agents, hardeners, plasticizers, wetting agents, ultraviolet absorbers, and the like can be used as appropriate. The thus constructed silver halide color photographic material of the present invention can be subjected to various photographic processing methods for color development after exposure. A preferred color developing solution used in the present invention is one containing an aromatic primary amine color developing agent as a main component. Specific examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride.
p-phenylenediamine hydrochloride, 2-amino-5
-diethylaminotoluene hydrochloride, 2-amino-
5-(N-ethyl-N-dodecylamino)-toluene, 2-amino-5-(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate, 4-(N-ethyl-N-β) -methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-β-hydroxyethylamino)aniline, 2-amino-5-(N-ethyl-β-methoxyethyl)aminotoluene, and the like. These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone. Furthermore, color developing solutions generally contain alkaline agents such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and various additives such as alkali metal halides such as potassium bromide, or development regulators such as hydrazine acid. etc. may be included. The silver halide photographic light-sensitive material of the present invention may contain the above color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. The color developing agent precursor is a compound that can generate a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include a Shugar amine reactant precursor and a urethane type precursor. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat.
2695234, British Patent No. 3719492, British Patent No. 803783, Japanese Unexamined Patent Publications No. 53-135628 and 54-79035, Research Disclosure Magazine 15159
No. 12146, No. 13924. These aromatic primary amine color developing agents or their precursors need to be added in amounts that will provide sufficient color development during development. This amount varies considerably depending on the type of photosensitive material and is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of photosensitive silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the above compound into a photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc., and added. It can also be added as an emulsifier dispersion using a high-boiling organic solvent.
They can also be added by impregnation into latex polymers as described in US Pat. No. 14,850. The silver halide color photographic light-sensitive material of the present invention is usually subjected to bleaching and fixing, or bleach-fixing and water washing after color development. Many compounds are used as bleaching agents, among them polyvalent metal compounds such as iron (), cobalt (), tin (), and especially complex salts of these polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid. ,
aminopolycarboxylic acids such as nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid,
malonic acid, tartaric acid, malic acid, diglycolic acid,
Metal complex salts such as dithioglycolic acid, ferricyanates, dichromates, etc. are used alone or in appropriate combinations. According to the silver halide photographic material of the present invention,
Excellent dispersion stability of the cyan coupler contained,
In addition, the dye image formed maintains and exhibits good image storage stability over a long period of time without impairing photographic properties. In particular, light fastness, heat resistance, and humidity resistance are improved in a well-balanced manner, image storage stability is particularly improved under high temperature and high humidity conditions, and color fading resistance is significantly improved. The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 Monochrome photographic elements were prepared with the layer configurations shown in Table 1.

[Table] The cyan coupler dispersion used in Layer 1 was prepared in the following manner (a) to (c). (a) Exemplary cyan coupler (I-5) according to the present invention
33 g of 2,5-di-t-octylhydroquinone, 0.45 g of the high boiling point organic solvent shown in Table 2, and 60 g of ethyl acetate were mixed and heated to 60°C to dissolve. (b) Mix 40 g of photographic gelatin and 500 ml of pure water at room temperature and allow to swell for 20 minutes. Next, after heating to 60℃ and dissolving it, Alkanol B (manufactured by DuPont)
Add 50 ml of 5% aqueous solution of and stir evenly. (c) The solutions obtained in (a) and (b) were mixed and dispersed for 30 minutes using an ultrasonic disperser to obtain a dispersion liquid. For the 15 types of samples thus obtained, the following (1)
-(3) tests were conducted. The results are shown in Table 2. (1) Coupler dispersion stability test The turbidity of each dispersion obtained as described in (a) to (c) above (correlates with the particle size of the dispersed particles, the smaller the value, the smaller the particle size), And the particle precipitation property (precipitation start time) on the surface was measured. Storage conditions were 40° C. for 10 hours without stirring. (2) Sensitometric characteristic test 15 types of monochromatic photographic elements were exposed to white light through a light wedge using a sensitometer (KS-7 model manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following processing steps. (Processing process) Processing time Temperature Color development 3.5 minutes 33℃ Coagulation 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 Hydroxyl Amine sulfate 2g N-ethyl-N-β-methanesulfonamidomethyl-3-methyl-4-aminoaniline sulfate
4.4g Potassium carbonate 30g Potassium bromide 0.4g Potassium chloride 0.5g Potassium sulfite 2g Add pure water to make 1 (PH=10.2) (Bleach-fix solution composition) Iron ammonium ethylenediaminetetraacetate
61g Diammonium ethylenediaminetetraacetate
5g Ammonium thiosulfate 125g Sodium metabisulfite 13g Sodium sulfite 2.7g Add water to make 1 (PH = 7.2) For each sample obtained, measure the relative sensitivity, maximum reflection density, and gamma (γ) using a photoelectric densitometer (Roku Konishi photo) The results obtained by measurement using a PDA-60 model (manufactured by Kogyo Co., Ltd.) are shown in the table below. (3) Dye Image Preservability Test A dye image preservability test was conducted as described in (a) and (b) below on 15 types of monochrome photographic elements that had been subjected to the same treatment as in (2).

[Table] The dye image storage stability is based on the initial density (Do) = 1.0.
It is expressed as a percentage (%) of the concentration (D) after the test.

【table】

[Table] From the results in Table 2, the dispersion stability of the cyan coupler in the silver halide photographic material of the present invention is significantly improved compared to the conventional material. In addition, while maintaining the sensitometric properties at a high level, the long-term photofading property in particular is significantly improved, and the dark fading property is also maintained at an even higher level. Example 2 Exemplary compound (-4) according to the present invention was used as a high boiling point organic solvent, and the third compound was used as a cyan coupler.
Monochrome photographic elements identical to those in Example 1 were prepared except that those shown in the table were used. The same dye image storage test as in Example 1 was conducted on the 10 types of samples thus obtained. The results are shown in Table 3. In Table 3, the following compounds were used as comparative couplers 1 to 4.

[Table] The amount of cyan coupler applied is for samples 16 to 23.
is 7.0mg/100cm ² , sample 24 is comparative coupler 4 is 1.0
mg/100cm ² , (-5) is 5.6mg/100cm ² , 25 is comparative coupler 4 is 2.0mg/100cm ² , (-6) is 4.2mg/100cm 2
100cm ² . As is clear from Table 3, in the silver halide photographic material of the present invention, the long-term photofading resistance of the formed cyan dye image is significantly improved,
Moreover, the resistance to fading is maintained at a high level. Example 3 Multilayer photographic elements having the layer configurations shown in Table 4 were prepared.

[Table] In the table, the coating amount is expressed in mg/100cm ² , DBP is dibutyl phthalate, and TCP is tricresyl phosphate. As each coupler and ultraviolet absorber (UV agent) for M-1 and Y-1, the compounds shown below (UV-1) and (UV-2) were used in combination at a weight ratio of 1:1. After exposing the five samples thus obtained to blue light, fringe color light, and red light,
Yellow (Y),
Three color separation samples of magenta (M) and cyan (C) were obtained. These samples were subjected to the same dye image storage test as in Example 1. The results are shown in Table 5.

【table】

Table 5 As is clear from the results in Table 5, in the multicolor photographic elements of the present invention, the photofading resistance of cyan dye images and the dark fading resistance under high temperature and high humidity conditions are significantly improved. Example 4 Except that in Example 2, the exemplified compound (-2) of the present invention was used instead of the exemplified compound (-4) of the present invention as the high-boiling organic solvent, and the cyan couplers shown in Table 6 were used. A single color photographic element identical to Example 1 was prepared. Example 1 for the 17 types of samples thus obtained
The same dye image storage test was conducted. The results are shown in Table 6.

【table】

【table】

[Table] As is clear from the results in Table 6, the cyan coupler 39 of the present invention represented by the general formula [ ]
Photographic materials using 47 are superior to those using comparative cyan couplers (48 to 55) in photofading resistance of cyan dye images and in dark fading resistance under high temperature and high humidity conditions.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer provided on a support, at least one of the silver halide emulsion layers has the following general formula []. A silver halide photographic material comprising at least one cyan coupler represented by the following formula and at least one high boiling point organic solvent represented by the following general formula []. General formula [] [In the formula, R ₁ represents an alkyl group or an aryl group. R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group,
cyano group, alkyl group, alkoxy group, alkylsulfamoyl group, arylsulfamoyl group,
Represents a group selected from an alkyloxycarbonyl group and an aryloxycarbonyl group. Z ₁ is a hydrogen atom, a halogen atom, or an aromatic primary
Represents a group that can be separated by reaction with an oxidized product of a class amine color developing agent. ] General formula [] [In the formula, R ₇ , R ₈ and R ₉ each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms in the groups represented by R ₇ , R ₈ and R ₉ is 24 to 48. ]