JPH0476096B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide color photographic material containing a novel coupler, and more specifically,
The present invention relates to a silver halide color photographic material containing a novel coupler that has excellent solubility in high-boiling organic solvents and excellent color development. [Prior Art] Generally, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers on a support that are selectively spectrally sensitized to have sensitivity to blue light, green light, and red light. has been painted. for example,
In silver halide photographic materials for color negatives, generally a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated in this order from the exposed side. A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb blue light that passes through the blue-sensitive silver halide emulsion layer. ing. Further, each emulsion layer is provided with other intermediate layers for various special purposes, and a protective layer as the outermost layer. Furthermore, for example, in a silver halide photographic light-sensitive material for color photographic paper, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are generally arranged in this order from the exposed side. Similar to silver halide photographic materials for color negatives, intermediate layers such as an ultraviolet absorbing layer and protective layers are provided for special purposes. It is also known that these silver halide emulsion layers are provided in a different arrangement from the above, and each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use two photosensitive silver halide emulsion layers. In these silver halide color photographic materials, for example, an aromatic primary amine color developing agent is used as a color developing agent.
The exposed silver halide grains are developed, and a dye image is formed by reaction between the oxidation product of the color developing agent and the dye-forming coupler. In this method, phenolic or naphthol-based cyan couplers are typically used to form cyan, magenta and yellow dye images, respectively.
- Pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, pyrazoloimidazole, indazolone or cyanoacetyl magenta couplers and acylacetamide yellow couplers are used. Compounds are also known that react with the oxidation products of color developing agents in the same manner as these dye-forming couplers, but do not form dyes. This type of compound improves the photographic image by reacting competitively with the dye-forming coupler in reaction with the oxidation products of the color developing agent, thereby releasing photographically useful groups such as development inhibitors. This contributes to higher image quality. Various methods have been devised for adding these couplers into the silver halide emulsion layer, but generally, a lipophilic ballast group is introduced into the coupler molecule to make the coupler lipophilic. A method of dissolving this in an organic solvent, emulsifying and dispersing it, and adding it is useful. This lipophilic ballast group makes these couplers resistant to diffusion in order to keep them in the desired layer and prevent them from diffusing to other layers. characteristics are required. That is, (1) the coupler and the resulting dye have excellent solubility in a high-boiling organic solvent called a coupler solvent (for example, dibutyl phthalate, tricresyl phosphate, etc.) used for dispersing the coupler. (2) The coupler emulsified and dispersed with a high-boiling organic solvent is stable without agglomerating in the silver halide emulsion. (3) After coating a silver halide emulsion on a support and drying it, a stable coating film is formed without the coupler crystallizing. (4) The coupler has excellent reactivity with the oxidized form of the color developing agent, and the resulting dye has excellent spectral absorption characteristics and stability. (5) The coupler must be stable and not deteriorate against heat, humidity, light, etc. when stored over time. (6) The coupler is easy to synthesize and inexpensive. Up to now, many studies have been made on ballast groups to be introduced into couplers in order to improve these properties required of couplers. Examples are Special Publication No. 42-5582, Special Publication No. 5391, Special Publication No. 46-5391, and Special Publication No. 39 of Showa 39.
−27563, U.S. Patent No. 2589004, U.S. Patent No. 2908573,
Special Publication No. 44-3660, U.S. Patent No. 2474293, same
No. 2039970, U.S. Patent No. 2920961, Special Publication No. 1973-
No. 36078, US Patent No. 2589004, UK Patent No. 944838
No. 19026-19026, U.S. Patent No. 2659329, British Patent No. 1813832, Japanese Patent Publication No. 76834-1973, Japanese Patent Publication No. 1976-1902
-36856, JP-A-53-82411, OLS2707488
No., JP-A-53-139534, JP-A-53-141622,
JP-A-54-23528, JP-A-54-48541, JP-A-Sho
No. 54-65035, JP-A-54-99433, JP-A-54-
121126 and the like can be cited. However, hitherto known couplers having a ballast group have some drawbacks and do not fully satisfy all of the above-mentioned properties. Particularly in high-temperature rapid processing, which has recently become popular, the color-forming properties of couplers are important, and therefore the development of couplers with excellent color-forming properties is highly desired. JP-A No. 58-42045, No. 60-24547, No. 60-
No. 41042 and No. 60-55340 describe couplers having novel ballast groups, but although these couplers are superior to conventional couplers in terms of color development, they are still insufficient; It has the disadvantage of low solubility in high-boiling organic solvents for coupler dispersion. [Object of the Invention] The object of the present invention is to provide a silver halide color photographic light-sensitive material containing a coupler having a ballast group that has significantly improved solubility in a high-boiling organic solvent as a coupler solvent and having excellent color development properties. Our goal is to provide the following. [Structure of the Invention] The above object of the present invention has been achieved by a silver halide color photographic light-sensitive material containing a coupler having a cyclic ether group in the molecule represented by the following general formula []. General formula [] [In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a carbamoyl group, or an acyl group, and further, R ₁ and R ₂ or R ₂ and R ₃ may be bonded to each other to form a ring. ] Here, the coupler refers to anything that undergoes a coupling reaction with the oxidized form of a color developing agent. Yellow coupler residues include acylacetanilides, such as pivalyl acetanilide and benzoylacetanilide, and magenta coupler residues include pyrazolone, Pyrazolotriazole, pyrazoloimidazole, pyrazolobenzimidazole and indazolone, examples of cyan coupler residues include naphthol and phenol, and examples of coupler residues that form achromatic pigments include resorcinol and m-aminophenol. . Examples of coupler residues that react with oxidized color developing agents to form colorless compounds include indanone, oxazolinone, and acetophenone. Among the couplers characterized by having a cyclic ether group represented by the general formula [], preferred ones are represented by the general formula []. General formula [] In the above formula, coup represents the coupler residue described in the general formula [], L represents a divalent linking group,
R ₁ , R ₂ and R ₃ have the same meanings as in the general formula [].
Furthermore, R ₁ and L may form a ring. The divalent linking group represented by L may be any of the groups found in common ballast groups or groups that break off during coupling, such as alkylene groups having 1 to 10 carbon atoms, 6 to Arylene group with 10 carbon atoms, heterocyclene group with 5 to 10 atoms, -0-, -S-, -CO
−, −SO ₂ −, −COO−, −NR ₄ −, −CONR ₄ −, −
NR ₄ CO−, −SO ₂ NR ₄ −, −NR ₄ SO ₂ −, NR ₄
CONR ₄ − (where R ₄ represents a hydrogen atom, an alkyl group, or an aryl group), and any combination of these linking groups, such as an alkaline group,
aralkylene group, aminoarylene group, aminoalkylene group, amidoarylene group, amidoalkylene group, alkarylamide group, amidoarylsulfamoyl group, aminoarylamide group,
Aminoarylsulfamoylalkyl group, alkyleneoxycarbonylalkyleneoxycarbonyl group, alkoxycarbonylarylcarbamoyl group, alkoxyaryleneoxy group, heterocyclenearylamino group, alkyleneoxyarylsulfonylalkyleneamide group, alkyleneoxyarylsulfonamide group, etc. be. In addition, the alkyl group, alkylene group, aryl group, arylene group, and heterocyclene group in the linking group are the organic groups described below, such as a halogen atom, a nitro group, an amino group, a carboxy group, an alkyl group, an alkoxy group, and an aryl group. may be substituted with one or more groups such as aryloxy groups, heterocyclic groups, carbamoyl groups, amido groups, sulfonamido groups, sulfamoyl groups, etc. To describe each group represented by R ₁ , R ₂ and R ₃ in more detail, examples of the halogen atom include chloro, bromine and fluorine atoms. In addition, as the alkyl group, a straight chain or branched alkyl group, preferably a straight chain or branched alkyl group having 1 to 40 carbon atoms, such as methyl, ethyl, i
Examples include alkyl groups such as -propyl, 2-ethylhexyl, lauryl, and stearyl, as well as alkyl groups having substituents. Substituents for these alkyl groups include, for example, halogen atoms, alkoxy groups (such as methoxy,
butoxy, stearyloxy, etc.), aryloxy groups (e.g., phenoxy, etc.), aryl groups (e.g., phenyl, etc.), arylthio groups (e.g., phenylthio, etc.), aralkylthio groups (e.g., benzylthio, etc.), amino groups (e.g., piperidino, dimethylamino, etc.), ), acyloxy groups (e.g., acetoxy, benzoyloxy, furanoyloxy, cyclohexanoyloxy, etc.), alkoxycarbonyl groups (e.g., butoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), cycloalkoxycarbonyl groups (e.g., cyclohexyloxycarbonyl, etc.) , aryloxycarbonyl group (e.g. phenoxycarbonyl etc.), oxalyloxy group (e.g. ethoxyoxalyloxy etc.), carbamoyloxy group (e.g. hexylcarbamoyloxy etc.), amide group of sulfonyloxy group (e.g. phenylsulfonyloxy etc.) For example, benzoylamino group, etc.), ureido group (e.g., phenylureido, etc.), aminosulfamoyl group (e.g., dimethylaminosulfamoyl, etc.), etc. The cycloalkyl group preferably has 3 to 6 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclohexyl, etc., and this cycloalkyl group may further have a substituent, and examples of the substituent include the substituents for the alkyl group described above.Aryl Examples of the group include phenyl, and this aryl group may have the same substituent as the alkyl group. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, etc. The carbonyl group may further have a substituent similar to that of the alkyl group. Examples of the carbamoyl group include phenylcarbamoyl, and further examples of the acyl group include:
Examples include acetyl and p-methoxybenzoyl. In the present invention, the cyclic ether group represented by the general formula [ ] is preferably such that R ₁ and R ₂ are both hydrogen atoms, and R ₃ is an alkyl group or a hydrogen atom. Particularly preferred is the case where R ₁ , R ₂ and R ₃ are all hydrogen atoms. Among the coupler residues represented by coup in the general formula [], particularly preferred ones are represented by the following general formulas [] to []. In the above formula, at any position of the free bond of each coupler residue,

[Formula] [L, R ₁ , R ₂ , R ₃ are synonymous with the general formula []] can be combined. In addition, in the above formula, the * mark represents the coupling position of each coupler residue, and at this coupling position,

When [Formula] is bonded, it is preferably bonded through an oxygen atom, nitrogen atom or sulfur atom. In addition, the cup ring

[Formula] When the coupling position is not bonded, a hydrogen atom or a known coupling-off group is substituted at this coupling position. This coupling-off group is
A halogen atom or an atomic group bonded with an oxygen atom, nitrogen atom, carbon atom, or sulfur atom, specifically a chlorine atom, an alkoxy group, an acyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group , heterocyclic oxy group,
Sulfonamide group, nitrogen-containing 5- or 6-membered heterocyclic group (contains at least one nitrogen atom as a heteroatom and is bonded to the coupling position at the nitrogen atom. For example, imidazolyl group, pyrazolyl group, triazolyl group, 2,4-dioxoimidazolidinyl group, 3,5-dioxo-1,2,4-triazolidinyl group, etc.), benzene-fused ring heterocyclic group (e.g., benztriazolyl group, etc.), arylazo group, etc. . Furthermore, the above formula may also contain other substituents, such as halogen atoms,
Examples include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an acylamino group, a carbamoyl group, an alkoxycarbonyl group, a sulfonamide group, a sulfamoyl group, an anilino group, and a ureido group. Next, coupler compounds having a cyclic ether group in the molecule represented by the general formula [] of the present invention will be specifically shown, but the present invention is not limited thereto. Synthesis of compound (B) 35 g of n-octadecenyl succinic anhydride (A)
Dissolve in ml of methylene chloride and cool to 0°C. Add 18.9 g of m-chloroperbenzoic acid to this in methylene chloride.
Drop the solution dissolved in 100ml. After the dropwise addition, the reaction mixture was allowed to react for 3 hours, and then washed twice with cold water. After washing with water, dry in a sieve, and methylene chloride is distilled off under reduced pressure. N-hexane was added to the residue and recrystallization was performed to obtain 19.5 g of the target product (B). Synthesis of Exemplified Compound (15) 9.6 g of compound (B) and 10.1 g of 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-aminoanilino)-5-pyrazolone (C) were added in acetic acid. ethyl 200ml
Boil and stir for 2 hours. Then, concentrated sulfuric acid 1
ml and boil and stir for 3 hours. After cooling, the mixture is washed with water and dried in an oven, and then ethyl acetate is distilled off under reduced pressure. Acetonitrile was added to this to perform recrystallization to obtain 12.8 g of Exemplified Compound (15). The structure was confirmed using nuclear magnetic resonance spectroscopy and mass spectroscopy. The coupler of the present invention is preferably added in an amount of 1.times.10.sup. ^-4 mol to 5.times.10.sup.- ¹ mol per mol of silver in the layer to which the coupler is added. In order to add the coupler of the present invention into a silver halide color photographic light-sensitive material, various methods can be used, such as a solid dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method. It can be appropriately selected depending on the chemical structure and the like. The oil-in-water emulsion dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and usually involves dispersing the coupler in a high-boiling organic solvent with a boiling point of about 150°C or higher.
If necessary, use a stirrer, homogenizer, colloid mill, or flow mixer to dissolve a hydrophilic binder such as a gelatin solution using a surfactant in combination with a low-boiling point and/or water-soluble organic solvent. After emulsifying and dispersing it using a dispersing means such as an ultrasonic device, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion. The ratio of the high boiling point organic solvent to the low boiling point organic solvent used in the present invention is preferably 1:0.1 to 1:50, more preferably 1:1 to 1:20. Examples of high-boiling organic solvents include phenol derivatives, alkyl phthalates, esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, trimesic esters, etc. that do not react with the oxidized form of the developing agent, with a boiling point of 150°C.
The above organic solvents are used. Examples of high boiling point organic solvents that can be used in the present invention are U.S. Pat.
No. 2835579, No. 3287134, No. 2353262, No.
No. 2852383, No. 3554755, No. 3676137, No.
No. 3676142, No. 3700454, No. 3748141, No. 3748141, No. 3700454, No. 3748141, No.
No. 3779765, No. 3837863, British Patent No. 958441, No. 3837863, British Patent No. 958441,
No. 1222753, OLS2538889, JP-A-47-1031,
No. 49-90523, No. 50-23823, No. 51-26037,
No. 51-27921, No. 51-27922, No. 51-26035,
No. 51-26036, No. 50-62632, No. 53-1520,
No. 53-1521, No. 53-15127, No. 54-119921,
No. 54-119922, No. 55-25057, No. 55-36869
No. 56-19049, No. 56-81836, Special Publication No. 1977-
It is described in issues such as No. 29060. Low-boiling or water-soluble organic solvents that can be used with or in place of high-boiling organic solvents are disclosed in U.S. Pat.
Examples include those described in No. 2801171 and No. 2949360. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and examples of water-soluble organic solvents include acetone, Methyl isobutyl ketone, β-
Examples include ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol, and the like. Examples of surfactants used as dispersion aids include alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfonates,
Anionic surfactants such as alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl polyoxyethylene alkyl phenyl ethers, steroidal saponins, alkylene oxide derivatives, glycidol derivatives, etc. It is preferable to use nonionic surfactants, amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, and alkyl betaines, and cationic surfactants such as quaternary ammonium salts. Specific examples of these surfactants are described in ``Surfactant Handbook'' (Sangyo Tosho, 1966) and ``Emulsifiers, Emulsification Equipment Research, Technical Data Collection'' (Science Panronsha, 1978). As a latex dispersion method, for example, US Pat.
No. 4199363, No. 4214047, No. 4203716, No. 4203716, No. 4214047, No. 4203716, No.
4247627, JP 49-74538, JP 51-59942,
Preferred are the methods described in No. 51-59943, No. 54-32552, and the like. The silver halide emulsion used in the silver halide color photographic light-sensitive material (hereinafter referred to as light-sensitive material) of the present invention includes silver bromide, silver iodobromide, silver halide,
Any of those used in conventional silver halide emulsions can be used, such as silver iodochloride, silver chlorobromide, and silver chloride. The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the PH and/or pAg in the mixing pot. With this method,
Silver halide grains with a regular crystal shape and nearly uniform grain size can be obtained. After growth, a convergence method may be used to change the halogen composition of the particles. When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains. Silver halide grains can have metal ions added to them during the process of forming and/or growing the grains to contain metal elements inside the grains and/or on the grain surfaces. By leaving the particles in place, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (hereinafter abbreviated as RD) 17643
It can be carried out based on the method described in the item. Even if a silver halide grain has a uniform silver halide composition distribution within the grain, the core/silver halide composition differs between the inside and surface layer of the grain.
They may also be shell particles. The silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of {100} planes to {111} planes can be used. or,
The particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average particle size, the value is
0.20 or less. In the case of spherical silver halide, the grain size is the diameter thereof, and in the case of grains having a shape other than spherical, the grain size is the diameter when the projected image is converted into a circular image of the same area. ) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used. The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions. Silver halide emulsions can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too. Silver halide emulsions are used in the manufacturing process of photosensitive materials,
During chemical ripening, at the end of chemical ripening, and/or until the silver halide emulsion is applied after chemical ripening, for the purpose of preventing fog during storage or photographic processing, or to keep photographic performance stable. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added. It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention can be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. can. The hardening agent can be added to the processing solution in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. The emulsion layer of the photosensitive material contains a dye-forming compound that undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) to form a dye during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. The light-sensitive material of the present invention only needs to contain the coupler of the present invention in any one of its layers, and when the coupler is a dye-forming coupler, other dye-forming couplers may be used together with the coupler of the present invention. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either equivalence may be used. The dye-forming coupler has a color correction effect and, by coupling with an oxidized form of a developing agent, can be used as a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, and a toning agent. Compounds that release photographically useful fragments such as agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. Instead of the DIR coupler, a DIR compound that undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used. These DIR couplers and DIR compounds may or may not be the couplers of the present invention, but if they do not contain the couplers of the present invention as dye-forming couplers,
It is preferable to contain the coupler of the present invention as a DIR compound. The DIR couplers and DIR compounds used include:
one in which an inhibitor is directly bound to the coupling position;
The inhibitor is bonded to the coupling position via a divalent group, and the inhibitor is bonded in such a way that it is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron transfer reaction, etc. (referred to as timing DIR couplers and timing DIR compounds). Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler. As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. As a magenta dye-forming coupler, known 5
- Pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers, etc. can be used. Phenol or naphthol couplers are generally used as cyan dye-forming couplers. Among dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds are solids. Dispersion can be carried out using various methods such as a dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method, which can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler.
The oil-in-water type emulsification dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers. Usually, a high-boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low-boiling point and/or water-soluble additive as necessary. The mixture is dissolved in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and a dispersion method such as a stirrer, homogenizer, colloid mill, flow mixer, or ultrasonic device is used. After emulsification and dispersion, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion. As the high boiling point solvent, organic solvents such as phenol derivatives, phthalic acid alkyl esters, phosphoric esters, citric acid esters, benzoic esters, alkylamides, fatty acid esters, and trimesic esters that do not react with the oxidized form of the developing agent are used. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and water-soluble organic solvents include acetone, Examples include methyl isobutyl ketone, β-ethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, diethylene glycol monophenyl ether, phenoxyethanol, etc. Can be mentioned. Dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. are carboxylic acids,
When it has an acid group such as sulfonic acid, it can also be introduced into the hydrophilic colloid as an alkaline aqueous solution. Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used. The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity, deterioration of sharpness, and graininess. A color antifoggant can be used to prevent the color from becoming noticeable. The color antifoggant may be contained in the emulsion layer itself, or may be contained in an intermediate layer provided between adjacent emulsion layers. An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. A hydrophilic colloid layer such as a protective layer or an intermediate layer of a photosensitive material may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and deterioration of images due to ultraviolet rays. . In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material. When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes. The emulsion layer of the light-sensitive material contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholinic acid, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also contain quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and the like. A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process. Reducing the gloss of the photosensitive material in the silver halide emulsion layer and/or other hydrophilic colloid layer of the photosensitive material;
A matting agent can be added for the purpose of improving the ease of writing and preventing the light-sensitive materials from sticking to each other. A lubricant can be added to the photosensitive material to reduce sliding friction. An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. The silver halide emulsion layer and/or other hydrophilic colloid layer of the photosensitive material may contain coating properties, antistatic properties,
For the purpose of improving slipperiness, emulsifying and dispersing, preventing adhesion, improving photographic properties (promoting development, hardening, sensitization, etc.), etc.
A variety of surfactants can be used. The support used in the photosensitive material of the present invention includes α
- Flexible reflective supports such as paper laminated with olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymer), synthetic paper, etc., cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, Films made of semi-synthetic or synthetic polymers such as polyamide, flexible supports with reflective layers on these films, glass,
Includes metals, ceramics, etc. The hydrophilic colloid layer of the photosensitive material can be applied directly or after applying corona discharge, ultraviolet irradiation, flame treatment, etc. to the surface of the support as necessary, or to improve the adhesion, antistatic property, dimensional stability, and abrasion resistance of the support surface. The coating may be coated through one or more subbing layers to improve properties such as hardness, hardness, antihalation, friction properties, and/or other properties. When coating the photosensitive material, a thickener may be used to improve coating properties. Furthermore, for substances such as hardeners, which have quick reactivity and may cause gelation before coating if added to the coating solution in advance, it is recommended to mix them using a static mixer or the like immediately before coating. preferable. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.
Bucket coating is also used depending on the purpose. or,
The application speed can be selected arbitrarily. The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps,
Xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser lights, light emitting diode lights, electron beams, X-rays, γ
Any known light source can be used, such as light emitted from a phosphor excited by rays, alpha rays, or the like. Exposure times include not only exposure times of 1 millisecond to 1 second, which are normally used in cameras, but also exposure times shorter than 1 microsecond, such as those using cathode ray tubes or xenon flash lamps.
Exposures of 100 nanoseconds to 1 microsecond can be used, and exposures longer than 1 second are also possible.
The exposure may be performed continuously or intermittently. To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is performed after exposure. Color processing is
A color development process, a bleaching process, a fixing process, a water washing process and, if necessary, a stabilizing process are performed, but instead of the process using a bleaching solution and the process using a fixing solution, a one-bath process is performed. A bleach-fix treatment process can also be carried out using a bleach-fix solution,
It is also possible to carry out a monobath processing step using a one-bath development, bleach-fixing solution that allows color development, bleaching and fixing to be carried out in one bath. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in which the monobath process is performed using an activator solution. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are performed as a final step, one of a water washing process, a water washing process, and a stabilization process.) - Color development process - Bleach process - Fixing process - Color development process - Bleach-fixing process Process - Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process - Fixing process - Washing process - Post-hardening process Color development process - Washing process - Supplementary information Color development process - Stop process - Bleaching process -
Fixing treatment process / Activator treatment process - Bleach-fixing treatment process / Activator treatment process - Bleach treatment process - Fixing treatment process / Monobath treatment process The processing temperature is usually selected in the range of 10℃ to 65℃, but 65℃ is It is also possible to exceed the temperature. Preferably
Processed at 25°C to 45°C. If the light-sensitive material of the present invention is to be imaged by a reversal method, it is first subjected to a black-and-white negative development step, and then exposed to white light or processed with a bath containing a fogging agent to perform color development. Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods may also be used, such as a spray method in which the processing solution is supplied in the form of a spray, or a web method in which the material is brought into contact with a carrier impregnated with the processing solution. method, a method of performing viscosity phenomenon processing, etc. may be used. Examples of the present invention will be shown below and the present invention will be described in more detail, but the present invention is not limited thereto. The comparative couplers used in the present invention are the following exemplified compounds. Example 1 A coupler according to the invention or a coupler similar to a coupler according to the invention (listed in Table 1) is mixed with 2 x 10 ^-2 mol of tricresyl phosphate and ethyl acetate in an amount of 1 or 0.6 times the weight of the coupler. Heat and dissolve this solution in 30 ml of the mixed solution, and add 1.5 g of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
The mixture was mixed with 300 ml of a 5% aqueous gelatin solution containing 300 ml of gelatin, and emulsified and dispersed using a colloid mill. This coupler dispersion was mixed with 1 kg of a photographic emulsion containing 0.2 mol of blue-sensitive silver iodobromide (6 mol% silver iodide, 94 mol% silver bromide) with an average grain size of 1.6 μm and 40 g of gelatin. 20 ml of a 2% solution of 1,2-bis(vinylsulfonyl)ethane was added as an agent, and the mixture was coated on a cellulose triacetate film base and dried. Samples 1-1 to 1-10 of silver halide color photographic materials were prepared by coating this layer with a gelatin protective layer. The amount of silver applied to each sample at this time was 2 g/m ² . After each of these samples was wedge exposed in a conventional manner, they were processed using the following processing steps and the processing solution composition shown below. Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds [Color developer composition] 4-Amino-3- Ethyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous potassium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 3.75g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1, and use potassium hydroxide to
Adjust to PH=10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1, and adjust the pH using ammonia water.
= 6.0. [Fixer composition] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1, and adjust to PH=6.0 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 ml Add water to make 1. The obtained dye image was measured with complementary color light of the dye image using a densitometer (PD-7R, manufactured by Konishi Roku Photo Industry Co., Ltd.), and the obtained gamma and sensitivity are shown in Table 1. Gamma indicates the slope between concentration 0.3 and concentration 0.8 of each sample, and is given by the following formula. γ=0.5/logE _0.8 −logE _0.3 E _0.8 ; Exposure amount that gives a density of 0.8 E _0.3 ; Exposure amount that gives a density of 0.3 Sensitivity is expressed as the reciprocal relative amount of the exposure amount that gives a density of fog + 0.2. This is the value when the sample using is set as 100.

[Table] is small.
As is clear from Table 1, the color photosensitive material of the present invention has higher sensitivity and gamma value than the comparative color photosensitive material using a coupler with a similar structure that does not have the group of the general formula [] used in the present invention. shows,
Excellent color development. Example 2 6 x 10 ^-2 mol of the coupler of the present invention or a coupler similar to the coupler of the present invention (listed in Table 2) was mixed with 40 ml of dibutyl phthalate in an amount of 1 or 0.6 times the weight of the coupler and 100 ml of ethyl acetate. This solution was added to 300 ml of a 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate.
500g of green-sensitive silver chlorobromide emulsion (Ag amount
(containing 30g) and a coating aid was added thereto to prepare a coating solution. Next, this coating solution was coated on a polyethylene-coated paper support so that the coated silver amount was 0.3 g/m ² , and gelatin,
A coating liquid containing a spreading agent and a hardening agent was coated so that the gelatin coating amount after drying was 1.5 g/m ² to form a protective film, and a silver halide color photosensitive material sample 2 was prepared.
-1 to 2-8 were created. Measure each sample using a sensitometer (KS manufactured by Konishiroku Photo Industry Co., Ltd.).
After light wedge exposure for sensitometry was carried out using a 7-type (Model-7), the following processing was carried out. Standard processing steps (processing temperature and processing time) Processing process Processing temperature Processing time Color development 32.8℃ 3 minutes 30 seconds Bleach fixing 32.8℃ 1 minute 30 seconds Water washing 32.8℃ 3 minutes 30 seconds The composition of the processing solution used in the above processing step is It is as follows. (Color developer composition) 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5g Benzyl alcohol 15ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 18.5g Sodium bromide 0.7g Potassium bromide 0.5g Borax 39.1g Add water to make 1, and add sodium hydroxide Adjust the pH to 10.3 using (Bleach-fix tank solution) Iron ammonium ethylenediaminetetraacetate
61.0g Ethylenediaminetetraacetic acid diammonium 2
Water salt 5.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.5g Anhydrous sodium sulfite 2.7g Add water to make 1. The obtained dye image was measured using a densitometer (PD-7R, manufactured by Konishi Roku Photo Industry Co., Ltd.) using complementary color light to the dye image, and the obtained gamma and sensitivity are shown in Table 2.
(Gamma and sensitivity are measured using the same method as in Table 1.)

[Table] As is clear from Table 2, the color photosensitive material of the present invention has a high It exhibits high sensitivity and gamma value, and has excellent color development. Example 3 Table 3 shows the solubility of the coupler of the present invention.
DOP stands for dioctyl phthalate and TCP stands for tricresyl phosphate. Solubility is given as the solvent layer required to dissolve 10 g of coupler at 60°C.

【table】

[Table] As is clear from Table 3, the couplers of the present invention have better solubility than the comparative couplers.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material characterized by containing a coupler having a cyclic ether group in its molecule represented by the following general formula []. General formula [] [In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom,
halogen atom, alkyl group, cycloalkyl group,
It represents an aryl group, an alkoxycarbonyl group, a carbamoyl group, or an acyl group, and R ₁ and R ₂ or R ₂ and R ₃ may be bonded to each other to form a ring. ]