JPH0588457B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic material containing a magenta coupler that forms a magenta dye image with high color development and improved storage stability, especially light fastness. More specifically, the present invention relates to a silver halide color photographic material containing a novel magenta coupler. [Prior Art] Usually, in silver halide color photographic materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and the oxidized product of the color developing agent produced at this time is reduced. Dye images can be obtained by coupling with couplers that form yellow, magenta and cyan dyes. The coupler that has been put to practical use in the past to form the magenta dye is a pyrazolone type coupler, but this has unfavorable side absorption and is said to have poor storage stability, especially resistance to formalin gas (formalin resistance). It has its drawbacks. In order to improve the above drawbacks, various efforts have been made so far.
A 1H-pyrazolo[3,2-c]-s-triazole type magenta coupler has been proposed. For example, US Patent No. 3725067, British Patent No. 1252418,
Described in No. 1334515. The compounds described in both patents are, of course, superior to pyrazolone magenta couplers in terms of side absorption, but improvements in formalin resistance are insufficient, and little improvement has been shown in terms of color development and light fastness of images. do not have. Research Disclosure
The compound described in Disclosure) 12443 cannot be put to practical use at all in terms of color development. The 1H-pyrazolo[3,2-c]-s-triazole type magenta coupler described in JP-A No. 58-42045 has been significantly improved in terms of formalin resistance and color development, but it still lacks light resistance. Very few improvements have been made. Also, the couplers described in JP-A-59-99437 and JP-A-59-125732 have improved color development, but
There continues to be no improvement in the lightfastness of dye images based on the described couplers. In the latter case, the light resistance of the image is simply improved by the additive used in combination. However, regarding the former coupler of Compound Example 19 described in the specification,
Although the light resistance has been slightly improved, it is still not sufficient. In other words, 1H, which has attracted attention for its lack of side absorption and high formalin resistance,
-Pyrazolo[3,2-c]-s-triazole type magenta couplers also have little improvement in the light resistance of dye images. [Object of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material that has good light fastness and formalin resistance, and has high color development. [Structure of the Invention] The object of the present invention is to provide a silver halide color photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula [ This is achieved by a silver halide color photographic light-sensitive material containing a magenta coupler represented by the following formula. General formula []

[Formula] In the formula, R represents a hydrogen atom or a substituent,
R' represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Y represents a nonmetallic atom group necessary to form a 5- to 7-membered heterocycle together with the nitrogen atom, and Z represents 1H-pyrazolo[3,2-c][1,2,
4] Triazole, 1H-pyrazolo[2,3-c]
[1,2,3]triazole, 1H-pyrazolo[2,3-a]imidazole, 1H-pyrazolo[2,3-b]pyrazole or 1H-pyrazolo[2,3-d]tetrazole Represents a group of nonmetallic atoms. Below, unless otherwise specified, the compounds represented by the general formula []

For convenience, the group represented by the formula is simply represented by Q. Specifically, the substituent represented by R is a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, Phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, Acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, or heterocyclic thio group It is. Next, the magenta coupler represented by the general formula [] of the present invention will be explained in more detail. In the general formula [], examples of the halogen atom represented by R include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The alkyl group represented by R has 1 to 1 carbon atoms.
32, alkenyl groups, alkynyl groups with 2 to 32 carbon atoms, cycloalkyl groups, cycloalkenyl groups with 3 to 12 carbon atoms, especially 5 to 7 carbon atoms
The alkyl group, alkenyl group, or alkynyl group may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbons] In addition to compound residues, acyl, carboxy, carbamoyl,
Those substituted via a carbonyl group such as alkoxycarbonyl and aryloxycarbonyl, and those substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, etc. substituted through the oxygen atom, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamino, sulfonamide,
Those substituted via a nitrogen atom such as imide and ureido; those substituted via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl; those substituted via a phosphorus atom such as phosphonyl, etc. }]. Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1-hexylnonyl group, 1,1'-
Dipentylnonyl group, 2-chloro-t-butyl group, trifluoromethyl group, 1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group , anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4′-{α-[4″(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenyl Propyl group, 3-{4'-
[α-(2″,4″-di-t-amylphenoxy)butanamido]phenyl}-propyl group, 4-[α-
(o-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, and the like. The aryl group represented by R is preferably a phenyl group, and may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4
-tetradecanamide phenyl group, hexadecyloxyphenyl group, 4'-[α-(4''-t-butylphenoxy)tetradecanamide] phenyl group, etc. The heterocyclic group represented by R is 5- A 7-membered group is preferable, and may be substituted or condensed. Specific examples thereof include 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, α
-2,4-di-t-amylphenoxybutanoyl group and other alkylcarbonyl groups, benzoyl groups, 3
Examples include arylcarbonyl groups such as -pentadecyloxybenzoyl group and p-chlorobenzoyl group. Examples of the sulfonyl group represented by R include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-toluenesulfonyl group. Examples of the sulfinyl group represented by R include ethylsulfinyl group, octylsulfinyl group, 3-
Alkylsulfinyl group such as phenoxybutylsulfinyl group, phenylsulfinyl group, m-
Examples include arylsulfinyl groups such as pentadecyl phenylsulfinyl groups. The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group,
Examples thereof include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups. The carbamoyl group represented by R is an alkyl group,
Aryl groups (preferably phenyl groups) may be substituted, for example, N-methylcarbamoyl groups, N,N-dibutylcarbamoyl groups, N-(2
-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group,
N-{3-(2,4-di-t-amylphenoxy)
propyl}carbamoyl group, and the like. The sulfamoyl group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-
Examples include (2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group. Examples of the bridged hydrocarbon compound residue represented by R include bicyclo[2,2,1]heptan-1-yl, tricyclo[3,3,1,1 ^3.7 ]decane-1
-yl, 7,7-dimethyl-bicyclo[2,2,
1] heptane-1-yl and the like. The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group, 2-
Ethoxyethoxy group, pentadecyloxy group, 2
-dodecyloxyethoxy group, phenethyloxyethoxy group and the like. The aryloxy group represented by R is preferably a phenyloxy group, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as a phenoxy group, p
Examples include -t-butylphenoxy group and m-pentadecylphenoxy group. The heterocyclic oxy group represented by R is 5 to 7
Preferably, the heterocycle has a substituent, for example, 3,
Examples include 4,5,6-tetrahydropyranyl-2-oxy group and 1-phenyltetrazole-5-oxy group. The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like. The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloroacetyloxy group, etc. , benzoyloxy group, etc. The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-phenylcarbamoyloxy group, etc. Can be mentioned. The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, anilino group, m
Examples thereof include -chloroanilino group, 3-pentadecyloxycarbonylanilino group, and 2-chloro-hexadecaneamideanilino group. As the acylamino group represented by R, an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group)
etc., which may further have a substituent, specifically an acetamide group, an α-ethylpropanamide group, an N-phenylacetamide group, a dodecanamide group, a 2,4-di-t-amylphenoxylene group, etc. Examples include cyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group, and the like. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specifically, methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group, p-toluenesulfonamide group, 2-
Examples include methoxy-5-t-amylbenzenesulfonamide group. The imide group represented by R may be an open-chain one,
It may be cyclic and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, and the like. The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group,
Examples include N-methyl-N-decylureido group, N-phenylureido group, and Np-tolylureido group. The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoyl Examples thereof include an amino group and an N-phenylsulfamoylamino group. The alkoxycarbonylamino group represented by R may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like. The aryloxycarbonylamino group represented by R may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group. The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc. The aryloxycarbonyl group represented by R may further have a substituent, such as phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, etc. . The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group. The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2
-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-acetaminophenylthio group and the like. The heterocyclic thio group represented by R is 5 to 7
A membered heterocyclic thio group is preferable, and may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group. In addition, the general formula [] and the general formula [] ~
Substituents on the heterocycle in [] (for example, R,
_R1 to _R7 )

[Formula] Part (Here, R'' and Z' have the same meanings as R and Z in the general formula [], and Q is as described above.)
If it has, it forms a so-called screw-type coupler, but it is of course included in the present invention. What is represented by the general formula [] is more specifically represented by, for example, the following general formulas [] to []. General formula []

【formula】 General formula []

【formula】 General formula []

【formula】 General formula []

【formula】 General formula []

[Formula] In the above general formulas [] to [], R ₁ to R ₈ and Q have the same meanings as R and Q above. Also, preferred among the general formulas [] are those represented by the following general formula []. General formula []

[Formula] In the formula, R ₁ , Q and Z ₁ are R in the general formula [],
It is synonymous with Q and Z. Among the magenta couplers represented by the general formulas [] to [], particularly preferred are the magenta couplers represented by the general formula []. Regarding the substituents on the heterocycle in the general formulas [] to [], R in the general formula [] and R ₁ in the general formulas [] to []
It is preferable that the following condition 1 is satisfied, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1, 2 and 3 are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds. The most preferred substituents R and R ₁ on the heterocycle are those represented by the following general formula []. General formula []

[Formula] In the formula, R ₈ , R ₉ and R ₁₀ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group,
Aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocycle Oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group , represents an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group,
At least two of R ₈ , R ₉ and R ₁₀ are not hydrogen atoms. Also, two of the above R ₈ , R ₉ and R ₁₀ , for example R ₈ and
R ₉ may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R ₁₀ may be bonded to the ring to form a bridged hydrocarbon compound residue. It's okay. The group represented by P ₈ to _{P 10} may have a substituent, and specific examples of the group represented by P ₈ to _{P 10} and the substituents that the group may have are the same as those mentioned above. Specific examples of the group represented by R in formula [] and substituents are listed. Also, for example, a ring formed by combining R ₈ and R ₉ and
Specific examples of the bridged hydrocarbon compound residue formed by P ₈ to _{P 10} and its optional substituents include cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the above general formula []. Specific examples of and substituents thereof are listed. Among the general formulas [], (i) two of P ₈ to _{P 10} are alkyl groups, (ii) one of P ₈ to P ₁₀ , for example R ₁₁ , is a hydrogen atom and , when the other two P ₈ and P ₉ combine to form a cycloalkyl with the root carbon atom. Further preferred among (i) is the case where two of R ₈ to _{R 10} are alkyl groups and the other one is a hydrogen atom or an alkyl group. Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and the substituent thereof represented by R in the general formula []. Specific examples include: Examples of the halogen atom represented by R' include a chlorine atom and a bromine atom. Alkyl group represented by R′ (e.g. methyl group,
ethyl group, i-propyl group, etc.), cycloalkyl group (e.g., cyclohexyl group, etc.), aryl group (e.g., phenyl group, etc.), and heterocyclic group (e.g., imidazolyl group, thiazolyl group, etc.) may further include halogen atoms, nitro groups, Cyano group, hydroxy group, sulfo group, carboxy group, alkoxy group, aryloxy group, acylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonamide group, alkylthio group, arylthio group, alkylsulfonyl group , an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylamino group, or a ureido group. Examples of the 5- to 7-membered heterocycle formed by Y and a nitrogen atom include cyclic amide compounds, cyclic imide compounds, cyclic urea compounds, imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrroline, pyrrole, morpholine, Examples include cyclic amines such as pyrazolidine and pyrazoline. Next, specific examples of the magenta coupler represented by the general formula [] of the present invention are shown below, but the present invention is not limited thereto.

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embedded image Next, a typical method for synthesizing the magenta coupler of the present invention will be described. Journal of the Chemical Society, Perkin Edition I (J.Chem.Soc.,
Perkin Trans.
Synthesis was performed with reference to No. 42045. In addition, a method for introducing a hydroxy group at the 7-position of a 1H-pyrazolo[3,2-c]-s-triazole compound (general formula []) is to amate the 7-position as shown in U.S. Patent No. 3,419,391. After that, it can be obtained by diazotization and heating in an aqueous hydrochloric acid solution. 7-hydroxy- obtained here
The exemplified compounds can be synthesized by reacting a 1H-pyrazolo[3,2-c]-s-triazole compound with an α-substituted alkyl halide. The α-substituted alkyl halide was synthesized with reference to JP-A-52-90932.

[Chemical Formula] In the above reaction formula, Y and R' are the same as those shown in the general formula [], and Hal. represents a halide.
The obtained α-substituted alkyl halide was treated in a solvent such as alcohol, acetone, dioxane, tetrahydrofuran, ether, benzene, dimethylformamide, etc. in the presence of a base such as sodium alcoholate, sodium hydroxide, potassium carbonate, pyridine, triethylamine, etc. as described above. -Hydroxy-1H-pyrazolo[3,2-c]-s-triazole to obtain the desired exemplary compound. Next, a specific synthesis example will be shown. Synthesis Example 1 (Exemplary Compound 1) 5,5-dimethylhydantoin and formalin were heated on a water bath for 2 hours to form 5,5-dimethyl-3-
Hydroxymethylhydantoin was obtained. Next, this was reacted with thionyl chloride by heating, and excess thionyl chloride was distilled off under reduced pressure.
5-dimethyl-3-chloromethylhydantoin was obtained. Separately 3-[3-{4-(4-dodecyloxyphenylsulfonamido)phenyl}propyl]
-6-Methyl-7-hydroxy-1H-pyrazolo[3,2-c]-s-triazole was dissolved in alcohol, and an equivalent amount of sodium alcoholate was added and heated on a water bath under nitrogen atmosphere. Next, the alcohol was distilled off under reduced pressure, dimethylformamide was added, and while stirring at room temperature, the previously obtained 5,5-dimethyl-
A dimethylformamide solution of 3-chloromethylhydantoin was added dropwise. After stirring for 1 hour, 50
The reaction was allowed to proceed at ℃ for 2 hours, and the reaction mixture was poured into ice water, and the resulting brown viscous substance was dissolved in ethyl acetate. The ethyl acetate solution was washed with water, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. The oil was purified by silica gel column chromatography. The candy-like substance obtained by distilling off the solvent was confirmed to be Exemplary Compound (1) from the results of mass spectroscopy. Synthesis Example 2 (Exemplary Compound 11) 5,5-dimethylhydantoin in Synthesis Example 1 was replaced with morpholine, and 3-[3-{4-(4-dodecyloxyphenylsulfonamido)phenyl}propyl]-6-methyl-7 -Hydroxy-1H-pyrazolo[3,2-c]-s-triazole with 3-
(1-methyl-2-dodecylsulfoethyl)-6-
Methyl-7-hydroxy-1H-pyrazolo[3,
Synthesis was carried out in exactly the same manner as in Synthesis Example 1, except that 2-c]-s-triazole was used, to obtain a pale yellow candy-like substance. This product was confirmed to be Exemplified Compound (11) from the mass spectrum results. The amount of the magenta coupler according to the present invention to be added to the photographic light-sensitive material of the present invention is as follows:
The range is preferably from 1.5×10 ⁻³ mol to 7.5×10 ⁻¹ mol,
More preferably, the amount is in the range of 1×10 ⁻² mol to 5×10 ⁻¹ mol. The silver halide photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but in particular, when color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effects of this will be effectively demonstrated. The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually used. has a structure in which layers are laminated in an appropriate number and order of layers on a support, but the number and order of layers may be changed as appropriate depending on the important performance and purpose of use. The silver halide photosensitizer 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 material used in silver oxide 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. 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. 17643. 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 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. 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 uses 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 photosensitizing 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 edge color 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. Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides), and magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, and pyrazolo couplers. Examples include triazole and open chain acylacetrinitrol couplers, and examples of cyan dye-forming couplers include naphthol couplers and phenol couplers. 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, these dye-forming couplers have 4 molecules because one molecule of dye is formed.
Either the 4-isomerism, in which molecular silver ions need to be reduced, or the 2-isomerism, in which only 2 molecules of silver ions need to be reduced, may be used. Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the surface of silver halide crystals can be prepared using the solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc.
Various methods can be used, and 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, 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. Alternatively, 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 organic solvent may be included at the same time as the dispersion or dispersion. Examples of high-boiling oil agents include phenol derivatives, phthalate esters, phosphate esters, citric acid esters, and benign incense that do not react with the oxidized form of the developing agent. An organic solvent with a boiling point of 150°C or higher is used for acid esters, alkylamides, fatty acid esters, and trimesic acid esters. 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. In the color light-sensitive material using the silver halide emulsion layer of the present invention, an image stabilizer can be used to prevent deterioration of the dye image. Ultraviolet absorbers are 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. A coupler light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. 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 a flexible reflective support such as paper laminated with an α-olefin polymer, synthetic paper, cellulose acetate, cellulose nitrate, etc. , films made of semi-synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide;
Can be applied to rigid objects such as glass, metal, and ceramics. The silver halide photosensitive material of the present invention can be prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, water flame treatment, etc. as necessary, and then improving adhesion, antistatic properties, dimensional stability, etc. directly or on the surface of the support. It may be applied through one or more subbing layers to improve abrasion resistance, 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, since 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 about 1 g for 1 color developer
Use at a concentration of 1.5g. As the aminophenol developer, for example, o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-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 addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate,
Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, and the like may optionally be included. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. 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 added to normal bleaching solutions may be added as appropriate. can. 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. [Example] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. [Example 1] A magenta coupler of the present invention and a comparative coupler as shown in Table 1 were each added at a concentration of 0.1 to 1 mole of silver.
One mole of tricresyl phosphate and three times the amount of ethyl acetate were added to the coupler weight, and the mixture was heated to 60° C. to completely dissolve. This solution was added to a 5% solution containing 120ml of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont).
It was mixed with 1200 ml of gelatin aqueous solution and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was added to 4 kg of edge-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide), and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water: methanol) was added as a hardening agent. = 1:1) was added, coated on a subbed transparent polyester base and dried to prepare samples 1-1 to 1-14. (Coated silver amount 20mg/100
cm ² ) The samples thus obtained were subjected to wedge exposure according to a conventional method and then subjected to the following development treatment. Table 1 shows the results. [Development process] Color developer 38℃ 3 minutes 15 seconds Bleaching solution 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Fixing solution 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stabilizing solution 1 minute Drying for 30 seconds 47°C to 55°C 16 minutes and 30 seconds The composition of the processing liquid used in each treatment step is as follows. [Color developer composition] Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 5g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g Sodium diethylenetriaminepentaacetate 2.5g 4-Amino-3-methyl- N-ethyl-N-(β-hydroxyethyl) aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make 1, and adjust to PH10.06 using potassium hydroxide or 20% sulfuric acid. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminotetraacetic acid 10g Ammonium bromide 150g Glacial acetic acid 40ml Sodium bromate 10g Add water to make 1, and adjust to PH3.5 using ammonia water or glacial acetic acid. . [Fixer composition] Ammonium thiosulfate 180g Anhydrous sodium sulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetic acid 0.5g Sodium carbonate 10g Add water to make 1. [Stabilizing liquid composition] Formalin (37% aqueous solution) 2 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 5 ml Add water to make 1.

【table】

[Table] 1 Specific sensitivity is the reciprocal of the exposure amount that gives a density of fog density + 0.1.
No. 1 was set as 100. 2 Place 3 samples in a sealed container containing 6 c.c. of 0.9% formalin aqueous solution, temperature and humidity controlled at 30℃ and 62%RH.
After a day of exposure, color development is performed. For comparison, a sample not treated with formalin is also developed. In addition, formalin resistance was calculated|required according to the following formula. Formalin resistance = Color density of formalin-treated sample / Color density of non-formalin-treated sample x 100 (%) 3 The sample after color development treatment was irradiated with a xenon fade meter for 5 days, and the dye residual % at initial density = 1.0 showed that. Light resistance = Density after 5 days of xenon fade meter irradiation / 1.0 x 100

【formula】

【formula】

[Formula] It is clear from Table 1 that the couplers of the present invention are excellent in color development, formalin resistance, and light resistance. [Example 2] Samples 1-1 to 1-14 in Example 1 were similarly wedge exposed and subjected to the following development treatment. These results are shown in Table 2. The specific sensitivity and light resistance were measured by the same method as in Example-1. [Development process] Color development 38℃ 3 minutes 30 seconds Bleach fixing 33℃ 1 minute 30 seconds Stabilization treatment / or washing treatment 25-30℃ 3 minutes Drying 75-80℃ 2 minutes Treatments used in each processing step The liquid composition is as follows. [Color developer] Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-methyl-4-amino-N - Ethyl-N-(β-methanesulfone amidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diamino stilbene disulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total amount to 1, Adjust to PH10.20. [Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and water Add to make the total amount 1. [Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g Add water to make 1.

[Table] As is clear from the results in Table 2, Samples 2-4 to 2-14 containing the couplers of the present invention are superior in sensitivity, color development, and light resistance compared to the comparative samples. [Example 3] A silver halide color photographic material was prepared by sequentially coating the following layers on polyethylene resin-coated paper containing anatase-type titanium oxide. The amounts added below are per ^100cm2 . (1) 20 mg of gelatin, 5 mg of silver as a blue-sensitive silver chlorobromide emulsion, and 8 mg of yellow coupler*
and 0.1 mg of 2,5-di-t-octylhydroquinone dissolved in 3 mg of di-octyl phthalate coupler solvent (2) 12 mg of gelatin, 0.5 mg of 2,5-di-t-
Interlayer containing 2 mg of dibutyl phthalate UV absorber solvent in which octylhydroquinone and 4 mg of UV absorber were dissolved. (3) 18 mg of gelatin, 4 mg of silver edge-sensitive silver chlorobromide emulsion, and 2.5 mg of dioctyl phthalate coupler solvent in which 5 mg of magenta coupler and 0.2 mg of 2,5-di-t-octylhydroquinone were dissolved. Containing layers. (4) An intermediate layer containing the same composition as (2). (5) 16 mg of gelatin, 4 mg of red-sensitive silver chlorobromide emulsion as silver, and 2.0 mg of tricresyl phosphate dissolved in 3.5 mg of cyan coupler and 0.1 mg of 2,5-di-t-octylhydroquinone. Layer containing coupler solvent. (6) Gelatin protective layer containing 9 mg of gelatin. Coating aids are added to each layer (1) to (6), and (4)
A gelatin crosslinking agent was added to layer (6). The ultraviolet absorbers (2) and (4) have the following structure.
A mixture of UV-1 and UV-2 was used. The above multilayer photosensitive material was treated in the same manner as in Example-2. Yellow coupler used in each layer,
Table 3 shows magenta couplers and cyan couplers and their results. Each sample was measured for magenta density after exposure to white light. Further, measurements of specific sensitivity and light resistance were carried out in the same manner as in Example 1. It is clear from Table 3 that the light fastness of the dye image of the coupler of the present invention is excellent, and it is also clear that it can be further improved by using an ultraviolet absorber. * Ultraviolet absorber

【formula】

[ka] * Yellow coupler

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[Specific effects of the invention]

When the present invention is applied to a color photographic light-sensitive material for printing, it has excellent spectral absorption characteristics of magenta dye,
A clear dye image with good color tone and a wide color reproduction gamut is formed, and the light fastness of the magenta dye can be improved.

Claims (1)

[Scope of Claims] 1. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the following general formula [] A silver halide color photographic material characterized by containing a magenta coupler. General formula [] [Formula] [In the formula, R represents a hydrogen atom or a substituent,
R' represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Y represents a nonmetallic atom group necessary to form a 5- to 7-membered heterocycle together with a nitrogen atom, and Z represents 1H-pyrazolo[3,2-c][1,
2,4] triazole, 1H-pyrazolo[2,3
-c][1,2,3]triazole, 1H-pyrazolo[2,3-a]imidazole, 1H-pyrazolo[2,3-b]pyrazole or 1H-pyrazolo[2,3-d]tetrazole is completed Represents a group of nonmetallic atoms necessary for ]