JPH0544012B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a color photographic material containing a phenolic cyan coupler, and more particularly to a silver halide color photographic material having excellent color reproducibility. [Prior Art] As is well known, subtractive color photography uses oxidation products of a color developing agent produced by reducing exposed silver halide grains with an aromatic primary amine color developing agent, and yellow and cyan color developing agents. A dye image is formed by oxidative coupling of a magenta dye-forming coupler in a silver halide emulsion layer. As a yellow coupler that forms a yellow dye, a compound having an open chain methylene group is generally used, and as a magenta coupler that forms a magenta dye, compounds such as pyrazolone, pyrazolinobenzimidazole, and imidazolone are used. . As cyan couplers that form cyan dyes, compounds having phenolic or naphtholic hydroxyl groups are used. Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent or in combination with an auxiliary solvent if necessary, and added to the silver halide emulsion;
Alternatively, it is dissolved in an aqueous alkaline solution and added to the emulsion. The former is an oil drop dispersion method, and the latter is an alkali dispersion method, but the former is generally considered to be superior to the latter in terms of light resistance, heat resistance, moisture resistance, granularity, and color sharpness. . The basic properties required for each coupler are:
In addition to simply forming a dye, it must also have high solubility in high-boiling organic solvents or alkaline aqueous solutions, good dispersibility and stability in silver halide photographic emulsions, and good spectral absorption characteristics. Furthermore, it is desired that the obtained dye image has various properties such as good color reproducibility and fastness. In particular, cyan couplers are required to have improved spectral absorption characteristics and color reproducibility. In view of the above circumstances, Japanese Patent Application Laid-Open No. 59-102234 describes the use of a specific diacylamino type phenolic cyan coupler in combination with a phenolic high-boiling solvent,
No. 139031 discloses that the above-mentioned two
Attempts have been made to improve the color reproducibility of cyan color-forming dyes obtained from various cyan couplers. These attempts aimed to shift the maximum absorption wavelength (λ _nax ) of the absorption spectrum of the cyan coloring dye to the longer wavelength side and reduce the absorption of the cyan coloring dye in the undesirable green region (500 to 600 nm). It is something. Through these attempts,
Although it was recognized that the color reproducibility of the cyan coloring dye obtained from the cyan coupler was considerably improved, it was still not satisfactory. [Object of the Invention] Therefore, the object of the present invention is to provide a silver halide emulsion layer which has a good spectrum of a cyan color-forming dye formed from a phenolic cyan coupler and which has excellent color reproducibility. Our objective is to provide color photographic materials. [Structure of the Invention] The object of the present invention is to provide, on a support, a silver halide emulsion layer containing at least one phenolic cyan dye image-forming coupler represented by the following general formulas [] and []; This can be achieved using a color photographic material containing at least one compound represented by the general formula []. General formula [] General formula [] In the formula, R ₁ , R ₂ and R ₄ each represent an aliphatic group, an aryl group or a heterocyclic group, R ₃ and R ₆ each represent a hydrogen atom, a halogen atom, an alkyl group or an acylamino group, and R ₅ represents an alkyl group. Further, R ₂ and R ₃ may be combined with each other to form a 5- to 6-membered nitrogen-containing heterocycle. Z ₁ and Z ₂ each represent a hydrogen atom or a coupling-off group. n is 0 or 1. General formula [] In the formula, R ¹ and R ³ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, or a sulfone group. Represents an amide group, cycloalkyl group or alkoxycarbonyl group, ^R2 is a hydrogen atom, a halogen atom, an alkyl group,
alkenyl group, aryl group, aryloxy group,
Represents an acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group. Y represents an atomic group necessary to form a chroman or coumaran ring. The present invention will be explained in more detail below. First, the cyan couplers represented by the general formulas [] and [] according to the present invention will be explained in more detail. In the present invention, the "aliphatic group" may be linear, branched, or cyclic, and may be an alkyl group,
It includes saturated and unsaturated groups such as cycloalkyl groups, alkenyl groups, and alkynyl groups. Also,
May be replaced. In the general formulas [] and [], R ₁ ,
R ₂ and R ₄ are aliphatic groups having 1 to 31 carbon atoms (for example,
methyl group, butyl group, octyl group, tridecyl group, hexenyl group, i-hexadecyl group, cyclohexyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), heterocyclic group (e.g. 2-
pyridyl group, 2-thiazolyl group, 2-imidazolyl group, 2-furyl group, 6-quinolyl group, etc.), and these represent an alkyl group, aryl group, heterocyclic group, alkoxy group (e.g. methoxy group, 2- methoxyethoxy group, tetradecyloxy group, etc.),
Aryloxy group (e.g., 2,4-di-t-amylphenoxy group, 2-chlorophenoxy group, 4
-cyanophenoxy group, 4-butanesulfonamidophenoxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., ethoxycarbonyl group, 2,4-di-t-amylphenoxycarbonyl group) group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g.
acetylamino group, butanesulfonamide group, dodecylbenzenesulfonamide group, dipropylsulfamoylamino group, etc.), carbamoyl group (e.g. dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (e.g. butylsulfamoyl group, etc.) , imide group (e.g.
succinimide group, hydanthonyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), sulfonyl group (e.g., methanesulfonyl group, carboxymethanesulfonyl group,
(e.g., phenylsulfonyl group), aliphatic or aromatic thio groups (e.g., butylthio group, phenylthio group, etc.), hydroxyl group, cyano group, carboxyl group, nitro group, sulfo group, halogen atom, etc. may be replaced with .
When there are two or more substituents, they may be the same or different. In addition, in the general formula [], R ₃ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Represents an acylamino group or a group of nonmetallic atoms that together with R form a nitrogen-containing 5- to 6-membered ring. Furthermore, in the general formula [], R ₅ represents an alkyl group, which is preferably an alkyl group having 1 to 24 carbon atoms and may have a substituent. Specific substituents include aliphatic groups, aryl groups, heterocyclic groups, aliphatic oxy groups, aliphatic thio groups, aryloxy groups, arylthio groups, and acylamino groups. More preferably, _R5 is an alkyl group having 1 to 14 carbon atoms, particularly preferably a lower alkyl group having 1 to 4 carbon atoms. In the general formula [], R ₆ is a hydrogen atom,
Halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, etc.), lower alkyl groups (e.g., methyl group, ethyl group, i-propyl group, butyl group, etc.),
Aryl group (e.g. phenyl group, naphthyl group)
Alternatively, it represents an acylamino group (eg, acetylamino group, benzamide group, etc.). Z ₁ in the general formula [] and Z ₂ in the general formula [] represent a hydrogen atom or a coupling-off group, such as a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy groups (e.g., ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group,
Tetradecanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group) group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), aliphatic or aromatic group. Examples include thio groups (eg, ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide groups (eg, succinimide group, hythantoynyl group, etc.), aromatic azo groups (eg, phenylazo group, etc.), and the like. These leaving groups may include photographically useful groups. Furthermore, preferred examples of the cyan coupler represented by the general formula [] or [] are as follows. In the general formula [], R ₁ is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group; an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, or a sulfonyl group. , a sulfamide group, an oxycarbonyl group, or an aryl group substituted with a cyano group is more preferable. In the general formula [], when R ₂ and R ₃ do not form a ring, R ₂ is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group,
R ₃ is preferably a hydrogen atom. In the general formula [], R ₄ is preferably a substituted or unsubstituted alkyl group, particularly preferably an alkyl group substituted with substituted aryloxy. In the general formula [], preferred R ₅ is an alkyl group having 1 to 4 carbon atoms, as described above. In the general formula [], preferred R ₆ is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. In the general formula [], it is particularly preferable that R ₆ is a chlorine atom and R ₅ is a lower alkyl group having 1 to 4 carbon atoms. Preferred Z ₁ in general formulas [] and []
and Z ₂ are each a hydrogen atom, a halogen atom, an alkoxy group which may have a substituent, an aryloxy group or a sulfonamide group. In the general formula [], Z ₂ is preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom. In the general formula [], when n=0, Z ₁ is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom. In the present invention, it is recognized that the compound represented by the general formula [] of the present invention exhibits a greater effect on the coupler represented by the general formula [] than the coupler represented by the general formula []. . Specific examples of cyan coupler compounds represented by the general formulas [] and [] are listed below,
The present invention is not limited to these. (-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-10) (−11) (−12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) (-20) (-21) (-22) (−23) (-24) (-25) (-26) (-27) (-28) (-29) (-30) (-31) (-32) (-33) (-34) (-35) (-36) (-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-10) (−11) (−12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) (-20) (-21) (-22) (−23) (-24) These cyan couplers represented by the general formulas [] and [] of the present invention (hereinafter referred to as the couplers of the present invention) are disclosed in U.S. Pat.
Same No. 2895826, No. 3311476, No. 3446622, Same No.
No. 3758308, No. 3880661, No. 3996253, Tokko Akira
No. 49-11572, No. 56-65134, JP-A-55-163537
No. 56-29235, No. 56-80045, No. 56-
No. 104333, No. 56-116030, No. 57-136650, No.
No. 57-157246, No. 57-204543, No. 57-204544
No. 57-204545, No. 58-105229, No. 59-
No. 31953, No. 59-31954, No. 59-69755, No. 59
-166956, etc., and can be synthesized according to the described synthesis method. In order to incorporate the coupler of the present invention into a silver halide emulsion, conventionally known methods may be followed. For example, the coupler of the present invention is dissolved in a mixture of a known high-boiling point solvent and a low-boiling point solvent such as butyl acetate or butyl propionate, and then mixed with an aqueous gelatin solution containing a surfactant, followed by a high-speed rotary mixer or colloid mill. Or after emulsifying with an ultrasonic disperser,
Silver halide emulsions can be prepared. Known high-boiling point solvents include phthalate esters (e.g., dibutyl phthalate, etc.), phosphoric acid esters (e.g., tricresyl phosphate, etc.), N-substituted acid amides (e.g., N,N-diethyl lauryl amide, etc.). etc.), phenols (for example, 2,5-di-t-amylphenol, etc.), and the like. The couplers of the present invention are generally 1 x 10 ^-3 mol to 5 x 10 ^-1 mol per mol of silver halide, preferably 1 x
It can be used in a range of 10 ^-2 mol to 5 x 10 ^-1 mol. The coupler of the present invention can also be used in combination with other types of cyan couplers. Furthermore, when the silver halide photographic material according to the present invention is used as a multicolor photographic material, in addition to the coupler of the present invention, yellow couplers and magenta couplers commonly used in this industry are used in the usual manner. be able to. Furthermore, a colored coupler having a color correction effect may be used if necessary. Two or more types of the above couplers can be used together in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different types. The compound used in conjunction with the cyan coupler of the present invention is a 7-hydroxychroman or 6-hydroxycoumaran compound represented by the general formula []. General formula [] In the formula, R ¹ and R ³ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, cycloalkyl group or alkoxycarbonyl group, R ² is a hydrogen atom, a halogen atom, an alkyl group,
alkenyl group, aryl group, aryloxy group,
Represents an acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents. Examples of substituents include alkyl groups, alkenyl groups, alkoxy groups, aryloxy groups, hydroxy groups, alkoxycarbonyl groups,
Aryloxycarbonyl group, acylamino group,
Examples include carbamoyl group, sulfonamide group, sulfamoyl group, and the like. Y represents an atomic group necessary to form a chroman or coumaran ring. This chroman or coumaran ring may be substituted with a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, etc., and may further be substituted with a spiro ring. may be formed. Among the compounds represented by the general formula [], the compounds particularly useful in the present invention are those represented by the general formula [a], [b],
It is included in the compounds represented by [c] and [d]. General formula [a] General formula [b] General formula [c] General formula [d] R ¹ , R ² and R ³ in general formulas [a], [b], [c], and [d] have the same meanings as in the above general formula [], and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and
R ⁹ each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or a heterocyclic group. Furthermore, R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ may be bonded to each other to form a hydrocarbon ring, and The ring may be substituted with an alkyl group. The general formulas [a], [b], [c] and [
d], R ¹ and R ³ are hydrogen atoms, alkyl groups,
Alkoxy group, hydroxy group or cycloalkyl group, R ² is a hydrogen atom, alkyl group, cycloalkyl group, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, alkyl group, or cycloalkyl Particularly useful are compounds that are radicals. Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby. (-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-10) (-11) (−12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) (-20) (-21) (-22) (−23) (-24) (-25) (-26) (-27) (-28) (-29) (-30) (-31) (-32) (-33) (-34) (-35) (-36) (-37) (-38) (-39) (−40) The compound of the present invention represented by the general formula [] is described in Tetrahedron, 1970,
vol26, pages 4743-4751, Journal of the Chemical Society of Japan, 1972, No.
10, pp. 1987-1990, Chemical Letters (Chem.
Lett), 1972(4), pp. 315-316, JP-A-55-139383
It includes the compounds described in this issue and can be synthesized according to the methods described therein. The amount of the compound represented by the general formula [] of the present invention used is preferably 5 to 300 mol%, more preferably 5 to 300 mol% based on the cyan coupler according to the present invention.
It is 10 to 200 mol%. Patent applications No. 59-280486 and No. 60-85195 include:
It has been described that the compounds represented by the general formula [] according to the present invention are effective as photofading inhibitors for color-forming dyes obtained from pyrazoloazole magenta couplers. ] There is no suggestion whatsoever that the phenolic cyan coupler shown in the above is significantly effective in improving the color reproducibility of coloring dyes obtained. As a result of extensive studies, the present inventors have determined that the compound represented by the general formula [] of the present invention is the compound represented by the general formula [] of the present invention.
It has been discovered that the phenolic cyan coupler represented by or [ ] has a completely unexpected favorable effect on the tone adjustment of the coloring dye obtained. The color photographic materials of the present invention include, for example, color negative and positive films, and color photographic paper. The silver halide photographic materials of the present invention, including this color film, may be monochromatic or multicolor. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction,
Usually, it has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. The number of layers and the order of layers may be changed as appropriate depending on the important performance and purpose of use. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver emulsions can be used. The silver halide grains used in the silver halide emulsion of the present invention 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 the presence of the other. Alternatively, growth may be carried out by sequentially and simultaneously adding halide ions and silver ions while controlling the PH and pAg in the mixing pot, taking into consideration the critical growth rate of silver halide crystals. After growth, a conversion method may be used to change the silver halide composition of the grains. When producing the silver halide of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary. The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. Metal ions can be added inside the particles and/or on the surface of the particles by adding iron salts or complex salts, and by placing them in an appropriate reducing atmosphere, reduction can be increased inside the particles and/or on the surface of the particles. It can give a sensitive core. In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, use a research disk closure.
It can be carried out based on the method described in No. 17463. The silver halide grains used in the silver halide emulsion of the present invention may consist of uniform layers inside and on the surface, or may consist of different layers. The silver halide grains used in the silver halide emulsion of the present invention 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 grains. The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical or 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. The silver halide emulsion of the present invention may be a mixture of two or more silver halide emulsions that have been separately formed. The silver halide emulsion of the present invention is chemically sensitized by a conventional method. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination. The silver halide emulsion of the present invention is produced using a dye known as a sensitizing dye in the photographic industry.
Can be optically sensitized to a desired wavelength range. 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. The silver halide emulsion of the present invention may be used during chemical ripening and/or for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or to maintain stable photographic performance. and/or after chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added. As the binder (or protective colloid) for the silver halide emulsion of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins,
Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as monopolymers or copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention can be formed by using a hardening agent alone or in combination to crosslink binder (or protective colloid) molecules and increase film strength. It is hardened. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention. A dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer may be included in the photographic emulsion layer or other hydrophilic colloid layer of the photosensitive material using the silver halide emulsion of the present invention for the purpose of improving dimensional stability. I can do it. The emulsion layer of the silver halide color photographic light-sensitive material of the present invention contains a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) during color development treatment. A dye-forming coupler is used that performs the following steps to form a dye. The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler for the blue light-sensitive emulsion layer. However, a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer.
However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. Yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides); magenta dye-forming couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazoles, and open-chain acylacetanilides. cyan dye-forming couplers include naphthol couplers and phenol couplers other than those of the present invention. These dye-synthesizing 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 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either equivalence is acceptable. For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water type emulsification dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher and, if necessary, a low boiling point and/or a high boiling point organic solvent. Or, by dissolving it in combination with a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, After being emulsified and dispersed, 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. Examples of high-boiling oil agents include organic solvents with a boiling point of 150°C or higher, such as phenol derivatives, phthalates, phosphates, citric esters, benzoic esters, alkylamides, fatty acid esters, and trimesic esters that do not react with the oxidized form of the developing agent. is used. Anionic surfactants, nonionic surfactants, and cationic surfactants are used as dispersion aids when hydrophobic compounds are dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using machines or ultrasound. Surfactants can be used. Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers),
Color antifoggants are used to prevent color turbidity, deterioration of sharpness, and noticeable graininess due to migration of oxidized products of developing agents or electron transfer agents. The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers. A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain. Color photosensitive materials using the silver halide emulsion of the present invention include a filter layer, an antihalation layer,
And/or auxiliary layers such as anti-irradiation layers can be provided. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the color light-sensitive material during development. The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material using the silver halide emulsion of the present invention is used to reduce the gloss of the photosensitive material and increase the retouchability of the photosensitive material. A matting agent can be added for prevention purposes. A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention. An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in colloid layers. The photographic emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention may be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification dispersion, prevent adhesion, and (promote development, Various surfactants are used for the purpose of improving photographic properties (such as increasing contrast and sensitization). The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, and other layers include a baryta layer or an α-olefin polymer, a flexible reflective support such as paper laminated with a synthetic paper, cellulose acetate, nitric acid, etc. Cellulose, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyamide, and rigid bodies such as glass, metal, and ceramics. The silver halide light-sensitive material of the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, and then directly or on the surface of the support to improve adhesion, antistatic properties, dimensional stability, and durability. It may be applied through one or more subbing layers to improve friction, hardness, antihalation, friction properties, and/or other properties. When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously. 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 microseconds to 1 microsecond can be used, and longer exposures of 1 second or more are also possible. The exposure may be performed continuously or intermittently. An image can be formed using the silver halide photographic material of the present invention by color development as known in the art. The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than in the free state. In addition, these compounds generally have a concentration of about 0.1 g to about 30 g per color developer,
Preferably about 1 g to 1.5 g for 1 color developer
Use at a concentration of g. Examples of aminophenol-based developers include -
Aminophenol, p-aminophenol, 5-
Amino-2-oxytoluene, 2-amino-3-
Oxytoluene, 2-oxy-3-amino-1,
Includes 4-dimethylbenzene and the like. A particularly useful primary aromatic amino color developer is an N,N'-dialkyl-p-phenylenediamine compound, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride,
p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,
N'-diethylaniline, 4-amino-N-(2-
(methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. As the bleaching agent used in the bleaching process, a metal complex salt of an organic acid is used, and the metal complex salt is
It has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. Its composition is aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. Coordinated with metal ions such as iron, cobalt, and copper. The most preferred organic acids used to form such metal complexes of organic acids include:
Mention may be made of polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid Sodium Acetate Salt The bleaching agent used contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.
In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, and borax. , sodium hydroxide, potassium hydroxide,
It may contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. [Examples] The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 Gelatin (13.0 mg/100 cm ² ), cyan coupler-18 of the invention (4.3 mg/100 cm ² ) and 2,5-di-t-octylhydroquinone ( 0.4mg/ ^100cm2 )
was dissolved in dibutyl phthalate (3.0 mg/100 cm ² ), emulsified and dispersed, and mixed to coat a silver chlorobromide emulsion (containing 80 mol% silver bromide) to give a silver amount of 3.5 mg/100 cm ² .
After drying, monochromatic color photosensitive material sample 1 was prepared. Samples 2 and 3 were obtained by adding Comparative Compound a and Compound-34 of the present invention in 1/2 moles of cyan coupler to Sample 1 above. Samples 4, 5 and 6 were obtained by replacing the cyan coupler -18 in Samples 1, 2 and 3 with equimolar -10.
Similarly, cyan couplers of the present invention -21, -1,
Samples 7, 8, 9, 10, 11, 12,
13, 14 and 15 were obtained (equimolar amounts of each coupler were used as -18). Comparative compound a (compound described in JP-A-59-102234) The sample obtained above was exposed to light through an optical wedge according to a conventional method, and then processed in the following steps. [Processing process] Processing temperature Processing time Color development 33°C 3 minutes 30 seconds Bleaching Fixing 33°C 1 minute 30 seconds Washing 33°C 3 minutes Drying 50-80°C 2 minutes The ingredients of each treatment are as follows. It is. [Color developer] Benzyl alcohol 12ml Diethylene glycol 10ml Potassium carbonate 25g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxylamine sulfate 2.5g N-ethyl-N-β-methanesulfone Amidoethyl-3-methyl-4-aminoaniline sulfate Add 4.5g of salt to make 1 and adjust the pH with sodium hydroxide.
Adjusted to 10.2. [Bleach-fix solution] Ammonium thiosulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to 1 and adjust the pH to 6.7 to 6.8. For samples 1 to 15 treated above, the maximum spectral absorption wavelength (λ _nax ) and the reflection density at λ _nax are
The reflection density (D〓 ₅₅₀ ) at 550 nm at a value of 1.0 was measured, and the spectral absorption characteristics and color reproducibility were examined.
The smaller the value of _D〓550 , the less false absorption occurs in the green region, indicating that the color reproducibility is excellent. The results are shown in Table 1.

[Table] From Table 1, the samples containing the compound according to the present invention (3, 6, 9, 12 and 15) have a small D〓 ₅₅₀ ,
It can be seen that λ _nax is also shifted to the long wavelength side, and the color reproducibility of cyan is extremely good. On the other hand, samples to which comparative compound a was added (2, 5,
8, 11 and 14), the color reproducibility was only slightly improved. Next, the absorption spectra of samples 4, 5, and 6 (wavelength -
The concentration curve) is shown in FIG. 1, and the absorption spectra of Samples 7, 8, and 9 are shown in FIG. That is, curves a, b, and c in FIG. 1 represent the absorption spectra of samples 4, 5, and 6, respectively, and curves d, e, and f in FIG. 2 represent the absorption spectra of samples 7, 8, and 9, respectively. ing. As is clear from FIGS. 1 and 2, in the color photographic materials a and f of the present invention, the absorption maximum in the red region is shifted to the long wavelength side, and the absorption maximum in the green region ( 550nm), resulting in extremely favorable color reproducibility. Example 2 Sample 16 was coated in the same manner as in Example 1, except that the coupler and additive compounds were changed as shown in Table 2.
~35 created. Each sample was processed in the same manner as in Example 1, and the color reproducibility of the cyan coloring dye was examined. The results are shown in Table 2. Comparative compound b (compound described in JP-A-59-102234)

【table】

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilo Triacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1 and adjust the pH to 10.6 using sodium hydroxide. [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make 1, and use ammonia water to pH
Adjust to 6.0. [Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1, and adjust to PH6.0 using acetic acid. [Stabilizing liquid] Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1. Spectral absorption maximum wavelength (λ _nax ) of each processed sample
The transmission density at 590 nm (D〓 ₅₉₀ ) when the transmission density at λ nax and λ _nax was 1.0 was measured, and the spectral absorption characteristics and color reproducibility were examined. D〓 The smaller _{the 590} , the
This shows that there is less irregular absorption in the green region and excellent color reproducibility. The results are shown in Table 3.

【table】

〔Effect of the invention〕

According to the color photographic material containing the cyan coupler of the present invention and the hydroxychroman or hydroxycoumaran compound of the present invention, the absorption of the cyan color-forming dye in the green region is extremely reduced, and the maximum absorption in the red region is prolonged. A very favorable result can be obtained in terms of color reproduction by shifting to the wavelength side.

[Brief explanation of the drawing]

Figures 1 and 2 show the absorption spectra of the color photographic material of the present invention (curves c, f) and comparative color photographic materials (curves a, b, d, e), with wavelength on the horizontal axis and wavelength on the vertical axis. Reflection density is plotted on the axis.

Claims (1)

[Claims] 1. On a support, the following general formulas [] and []
A color photographic light-sensitive material comprising a silver halide emulsion layer containing at least one phenolic cyan dye image-forming coupler represented by: and at least one compound represented by the following general formula [] . General formula [] General formula [] [In the formula, R ₁ , R ₂ and R ₄ are each an aliphatic group,
Represents an aryl group or a heterocyclic group, R ₃ and R ₆
each represents a hydrogen atom, a halogen atom, an alkyl group or an acylamino group, and R ₅ represents an alkyl group. Further, R ₂ and R ₃ may be combined with each other to form a 5- to 6-membered nitrogen-containing heterocycle. Z ₁ and Z ₂ each represent a hydrogen atom or a coupling-off group. n is 0 or 1. 〕 General formula 〕 [In the formula, R ¹ and R ³ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, Represents a sulfonamide group, cycloalkyl group, or alkoxycarbonyl group, and R ² is a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cyclo Represents an alkyl group or an alkoxycarbonyl group. Y represents an atomic group necessary to form a chroman or coumaran ring. ]