JPH0621946B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material containing a magenta coupler capable of forming a magenta dye image having high color-forming property and improved storability, especially light fastness. Regarding materials. More specifically, it relates to a silver halide color photographic light-sensitive material containing a novel magenta coupler.

[Prior art]

Usually, in a silver halide color photographic light-sensitive material, the exposed silver halide grains are reduced by an aromatic primary amine type color developing agent, and the oxidation product of the color developing agent and yellow, magenta and A dye image can be obtained by coupling with a coupler forming each cyan dye.

In order to form the magenta dye, a coupler which has been conventionally put into practical use is a pyrazolone type coupler,
This has the disadvantage of having unfavorable side absorption and poor storage stability, in particular resistance to formalin gas (formalin resistance).

In order to improve the above-mentioned drawbacks, various 1H-pyrazolo [3.2-c] -s-triazole type magenta couplers have been proposed so far. For example, U.S. Patent 3,725,067,
It is described in British Patents 1,252,418 and 1,334,515. The compounds described in any of the patents are, of course, superior to the pyrazolone-based magenta couplers in terms of side absorption, but the improvement in formalin resistance is insufficient, and the improvement in color development and light fastness of the image is almost shown. Absent.

Research Disclosure 1
The compound described in 2443 cannot be put to practical use in terms of color forming property. The 1H-pyrazolo [3,2-c] -s-triazole type magenta coupler described in JP-A No. 58-42045 is remarkably improved in terms of formalin resistance and color development, but it is still lightfast. Little improvement has been made.

Further, the couplers described in JP-A-59-99437 and JP-A-59-125732 have also been improved in color forming property, but in terms of light resistance of a dye image based on the described coupler, the improvement cannot be seen.

In the latter case, the light fastness of the image is improved only by the additive used in combination therewith. However, the coupler of Compound Example 19 described in the former specification is slightly improved in light resistance, but is still insufficient.

That is, the 1H-pyrazolo [3.2-c] -s-triazole type magenta coupler, which has hitherto been noted as having no side absorption and high formalin resistance, has almost been improved in light resistance of dye images. It can be said that it has not come.

[Object of the Invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material having good light resistance and formalin resistance and high color development.

[Structure of Invention]

The above-mentioned object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is represented by the following general formula [I]. And a silver halide color photographic light-sensitive material containing a magenta coupler.

General formula [I] In the formula, R ₁ and R ₂ each represent a hydrogen atom or a substituent, R ′ and R ″ may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group or a heterocyclic group. R ′ and R ″ may combine with each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or the 6-membered ring may form a condensed ring with a benzene ring or a heterocycle. X represents an oxygen atom or a sulfur atom.

Hereinafter, unless otherwise specified, a compound represented by the general formula [I] For convenience, the group represented by is represented here simply by Q.

The substituent represented by R is specifically a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, 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, 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,
It is an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group.

Next, the magenta coupler represented by the general formula [I] of the present invention will be described in more detail.

Next, in the general formula [I] of the present invention, examples of the halogen atom represented by R ₁ and R ₂ include a chlorine atom and a bromine atom, and a chlorine atom is particularly preferable.

The alkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and the alkynyl group have 2 to 32 carbon atoms.
The cycloalkyl group or cycloalkenyl group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms is preferable, and the alkyl group, alkenyl group or alkynyl group may be linear or branched.

Further, these alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group are substituents [for example, aryl, cyano, halogen atom, heterocycle,
In addition to cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, those substituted through carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, and further through hetero atom Substituents (specifically those substituted through an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfa Substituted through a nitrogen atom such as moylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfoneamino, sulfonamide, imide, and ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfini , Those that substitute through the sulfur atom of the sulfamoyl may have something like}] replacing through a phosphorus atom such as phosphonyl.

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-butanesulfoneaminophenoxypropyl group, 3-4 '-{α- [4 "(p-hydroxybenzenesulfonyl) phenoxy] dodecanoylamino} phenylpropyi 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, etc. Can be mentioned.

The aryl group represented by R ₁ and R ₂ is preferably a phenyl group and may have a substituent (for example, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, a phenyl group, a 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4 '
Examples thereof include-[α- (4 "-t-butylphenoxy) tetradecanamide] phenyl group.

The heterocyclic group represented by R ₁ and R ₂ is preferably a 5- to 7-membered heterocyclic group, which may be substituted or may be condensed. Specifically, 2-furyl group, 2-thienyl group, 2
Examples include -pyrimidinyl group and 2-benzothiazolyl group.

Examples of the acyl group represented by R ₁ and R ₂ include an acetyl group, a phenylacetyl group, a dodecanoyl group, α-2,
Examples thereof include an alkylcarbonyl group such as a 4-di-t-amylphenoxybutanoyl group, a benzoyl group, a 3-pentadecyloxybenzoyl group, an arylcarbonyl group such as a p-chlorobenzoyl group, and the like.

Examples of the sulfonyl group represented by R ₁ and R ₂ include an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group and a p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R ₁ and R ₂ include an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, a 3-phenoxybutylsulfinyl group, a phenylsulfinyl group, and an arylsulfinyl group such as an m-pentadecylphenylsulfinyl group. Etc.

The phosphonyl group represented by R ₁ and R ₂ is an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group,
Examples thereof include an aryloxyphosphonyl group such as a phenoxyphosphonyl group and an arylphosphonyl group such as a phenylphosphonyl group.

The carbamoyl group represented by R ₁ and R ₂ is an alkyl group,
An aryl group (preferably a phenyl group) and the like may be substituted, and examples thereof include an N-methylcarbamoyl group, N, N-dibutylcarbamoyl group, 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 ₁ and R ₂ is an alkyl group,
Aryl group (preferably phenyl group) and the like may be substituted, for example, N-propylsulfamoyl group, N, N
-Diethylsulfamoyl group, N- (2-pentadecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group and the like can be mentioned.

Examples of the spiro compound residue represented by R ₁ and R ₂ include spiro [3.3] heptan-1-yl and the like.

Examples of the bridged hydrocarbon compound residue represented by R ₁ and R ₂ include bicyclo [2.2.1] heptan-1-yl and tricyclo [3.3.1.1 ^3,7 ] decane-1-. Ill,
7,7-Dimethyl-bicyclo [2.2.1] heptane-
1-yl and the like can be mentioned.

The alkoxy group represented by R ₁ and R ₂ may be further substituted with the above-mentioned substituents for the alkyl group, for example, a methoxy group, a propoxy group, a 2-ethoxyethoxy group, a pentadecyloxy group. , 2-dodecyloxyethoxy group, phenethyloxyethoxy group and the like.

The aryloxy group represented by R ₁ and R ₂ is preferably a phenyloxy group, and the aryl nucleus may be further substituted with a substituent or an atom described above for the aryl group, for example, a phenoxy group, p Examples thereof include -t-butylphenoxy group and m-pentadecylphenoxy group.

The heterocyclic oxy group represented by R ₁ and R ₂ is 5 to 7
Having a membered heterocycle is preferred, and the heterocycle may further have a substituent, for example, 3,4,5,6-
Examples thereof include a tetrahydropyranyl-2-oxy group and a 1-phenyltetrazole-5-oxy group.

The siloxy group represented by R ₁ and R ₂ may be further substituted with an alkyl group or the like, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group and a dimethylbutylsiloxy group.

Examples of the acyloxy group represented by R ₁ and R ₂ include an alkylcarbonyloxy group, an arylcarbonyloxy group and the like, which may further have a substituent, specifically, an acetyloxy group, α- Examples thereof include a chloroacetyloxy group and a benzoyloxy group.

The carbamoyloxy group represented by R ₁ and R ₂ may be substituted with an alkyl group, an aryl group or the like, and examples thereof include N-
Examples thereof include an ethylcarbamoyloxy group, an N, N-diethylcarbamoyloxy group and an N-phenylcarbamoyloxy group.

The amino group represented by R ₁ and R ₂ may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include an ethylamino group, anilino group, m-chloroanilino group and 3-pentadecyloxy. Examples thereof include a carbonylanilino group and a 2-chloro-5-hexadecanamide anilino group.

Examples of the acylamino group represented by R ₁ and R ₂ include an alkylcarbonylamino group and an arylcarbonylamino group (preferably a phenylcarbonylamino group), which may further have a substituent. Group, α-ethylpropanamide group, N-phenylacetamide group, dodecane amide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group and the like. .

Examples of the sulfonamide group represented by R ₁ and R ₂ include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specific examples thereof include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R ₁ and R ₂ may be open chain,
It may be cyclic and may have a substituent, and examples thereof include a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group and a glutarimide group.

The ureido group represented by R ₁ and R ₂ may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N-ethylureido group and N-methyl-
N-decylureido group, N-phenylureido group, N-
p-tolyl ureido group etc. are mentioned.

The sulfamoylamino group represented by R ₁ and R ₂ may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N, N-dibutylsulfamoylamino group and N- Methylsulfamoylamino group, N
-Phenylsulfamoylamino group and the like.

The alkoxycarbonylamino group represented by R ₁ and R ₂ may further have a substituent, and examples thereof include a methoxycarbonylamino group, a methoxyethoxycarbonylamino group and an octadecyloxycarbonylamino group.

The aryloxycarbonylamino group represented by R ₁ and R ₂ may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R ₁ and R ₂ may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, Examples thereof include a benzyloxycarbonyl group.

The aryloxycarbonyl group represented by R ₁ and R ₂ may further have a substituent, and examples thereof include a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and a m-pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R ₁ and R ₂ 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 ₁ and R ₂ is preferably a phenylthio group and may further have a substituent, for example, phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenyl group. Thio group,
Examples include 2-carboxyphenylthio group and p-acetaminophenylthio group.

The heterocyclic thio group represented by R ₁ and R ₂ is 5 to 7
Membered heterocyclic thio group is preferable, and may further have a condensed ring or may have a substituent. Examples thereof include a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring, and examples of the substituent that the ring may have include those described for R above. .

Further, the substituent R ₁ or R ₂ on the heterocycle in the general formula [I] is Moiety (wherein R ₁ 'and R ₂ ' are R in the general formula [I]
_{1 has} the same meaning as R ₂ and Q has the same meaning as described above. Regarding the substituents on the heterocycle in the general formula [I], it is preferable that R ₁ satisfies the following condition 1, and it is more preferable that R ₁ satisfies the following conditions 1 and 2.
Particularly preferable is the case where 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 is bonded to the carbon atom or none is bonded.

Condition 3 All the bonds between the carbon atom and the adjacent atom are single bonds.

The most preferable substituent R ₁ on the heterocycle is represented by the following general formula [IX].

General formula [IX] In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, 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 , An acylamino group, a sulfonamide group, an imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and at least two of R ₉ , R ₁₀ and R ₁₁ are not hydrogen atoms.

Also, two of R ₉ , R ₁₀ and R ₁₁ such as R ₉ and R ₁₀
May combine to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), and R ₁₁ may bond to the ring to form a bridged hydrocarbon compound residue. Good.

The groups represented by R _{9 to} R ₁₁ may have a substituent,
Specific examples of the group represented by R _{9 to} R ₁₁ and the substituent which the group may have include R in the above general formula [I].
Specific examples of the group represented by ₁ and substituents can be given.

Further, for example, a ring formed by combining R ₉ and R ₁₀ and R _{9 to} R ₉
Specific examples of the bridged hydrocarbon compound residue formed by ₁₁ and the substituents which it may have include specific examples of the cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R ₁ in the above formula [I]. Examples and their substituents are mentioned.

Preferred are among the general formula [IX], there in (i) if two are alkyl groups in _{R 9 ~R 11, (ii)} 1 one example R ₁₁ in R ₉ to R ₁₁ is a hydrogen atom And when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further preferred among (i) is 2 of R _{9 to} R _11.
One is an alkyl group and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl, the cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl and the substituent thereof include the alkyl represented by R ₁ in the general formula [I], the cycloalkyl and the Specific examples of the substituents are given.

The substituent represented by R'and R "in the general formula [I] is an alkyl group (for example, methyl group, ethyl group, i
-Propyl group etc.), aryl group (eg phenyl group etc.), cycloalkyl group (eg cyclohexyl group etc.)
Alternatively, a heterocyclic group (eg, imidazolyl group, thiazolyl group, etc.) can be mentioned. Further, these groups are halogen atom, hydroxy group, nitro group, cyano group, sulfo group, carboxy group, alkoxy group, aryloxy group, amino group, acylamino group, alkylamino group, alkoxycarbonyl group, aryloxycarbonyl group, It may be substituted with a carbamoyl group, a sulfamoyl group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, and a ureido group.

When R ′ and R ″ are bonded to each other to form a 5-membered ring or 6-membered ring with a nitrogen atom, a cyclic amide compound, a cyclic imide compound, a cyclic urea compound, an imidazole, a pyrazole, a triazole, a lactam compound, Examples include cyclic amines such as piperidine, pyrrolidine, pyrroline, pyrrole, morpholine, pyrazolidine, and pyrazoline.

Next, specific examples of the magenta coupler represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

(1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) (33) (34) 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 Tran
s.I), 1977, 2047-2052, U.S. Pat. No. 3,725,067.
Synthesis was carried out with reference to JP-A No. 59-99437, JP-A No. 58-42045 and the like.

For example, a method of introducing a hydroxy group at the 7-position of a 1H-pyrazolo (3,2-c) -s-triazole compound is a method in which a 7-position is aminated and then diazotized as shown in US Pat. No. 3,419,391. It can be obtained by heating in a hydrochloric acid aqueous solution. Exemplified by the reaction of the 7-hydroxy-1H-pyrazolo (3,2-c) -s-triazole compound obtained here with an N-substituted carbamyl chloride or N-substituted thiocarbamyl chloride obtained by the formula below. Coupled couplers can be synthesized. The N-substituted carbamyl chloride was synthesized with reference to the method described in Organic Synthesis, Volume 2 (Org. Synth Coll. 2), p.

In the formula, R ′ and R ″ have the same meanings as those represented by the general formula [I].

The N-substituted thiocarbamyl chloride can be synthesized using thiophosgene instead of phosgene as in the above case.

In the formula, R ′ and R ″ have the same meanings as those represented by the general formula [I].

The reaction of N-substituted carbamyl chloride or N-substituted thiocarbamyl chloride with 7-hydroxy-1H-pyrazolo (3,2-c) -s-triazole compound is
It is carried out in a solvent such as acetone, benzene, toluene, carbon tetrachloride, chloroform, hexane and ether in the presence of a base such as sodium carbonate, sodium hydrogen carbonate, pyridine and triethylamine.

When one of R'or R "in the general formula [I] is a hydrogen atom, the corresponding isocyanate or thioisocyanate and 7-hydroxy-1H-pyrazolo (3,2-c)
The target compound can be synthesized by reacting the -s-triazole compound in a solvent such as benzene, toluene, xylene, or dioxane.

In the formula, R ′, R ₁ , R ₂ and X have the same meanings as shown in formula [I] or formula [II]. For the synthetic method by this reaction, refer to Japanese Patent Publication No. 53-34733.

Next, a specific synthesis example will be shown.

Synthesis Example 1 (Exemplified Compound 3) Dry ether is cooled and allowed to absorb a phosgene in a 3 molar ratio. An ether solution of monomethylaniline having a molar ratio of 1 is added dropwise under ice cooling. After stirring for 1 hour, the methylaniline hydrochloride that had come out was filtered off and the filtrate was concentrated under reduced pressure to completely remove excess phosgene and then dissolved in ether.

Separately 3- (1-methyl-2-dodecylsulfoethyl)-
6-Methyl-7-hydroxy-1H-pyrazolo [3,2
-C] Dissolve 0.5 mole ratio of triazole in alcohol,
To this, 0.5 mol ratio of sodium alcoholate was added and heated in a water bath under a nitrogen atmosphere. Next, the alcohol is completely distilled off under reduced pressure, and the remaining solid is thoroughly broken down to give a powder. To this, dry ether was added and the ether solution of N-phenyl-N-methylcarbamyl chloride prepared above was added dropwise while stirring at room temperature. After reacting at room temperature for 5 hours, the mixture is gently refluxed on a water bath for 1 hour. Ethyl acetate is added to this, and the mixture is stirred, then the resulting inorganic substances are filtered, and the filtrate is concentrated under reduced pressure. The brown candy is purified by silica gel column chromatography. It was confirmed from the results of mass spectrum that the pale yellow candy-like substance obtained by removing the solvent was Exemplified Compound (3).

Synthesis Example 2 (Exemplified Compound 7) 3- [3- {4- (2,4-ditert-pentylphenoxyacetamido) phenyl} propyl] in dry toluene
-6-Methyl-7-hydroxy-1H-pyrazolo [3,
2-c] -s-triazole is dissolved by heating, and a toluene solution of p-nitrophenylisocyanate in a calculated amount of 10% excess is added thereto while stirring at 80 ° C. Next, pyridine is added and the mixture is refluxed for 10 hours. Toluene is distilled off under reduced pressure, the residue is dissolved in ethyl acetate, washed with dilute hydrochloric acid and then with water, and then dried over sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and the candy-like substance was recrystallized from alcohol to obtain a pale yellow amorphous solid. From the result of mass spectrum, it was confirmed that the compound was Exemplified compound (7). Melting point 148-150 ° C.

Synthetic Example 3 (Exemplified Compound 26) Except that phosgene was replaced with thiophosgene, the same reaction and treatment as in Synthetic Example 1 were carried out, and the result was confirmed by mass spectrum to obtain Exemplified Compound (26).

Synthetic Example 4 (Exemplified Compound 29) Reaction exactly the same as in Synthetic Example 2 except that p-nitrophenyl isocyanate was replaced by p-nitroisothiocyanate,
Treatment was performed to obtain a pale yellow amorphous powder having a melting point of 175 to 179 ° C. From the result of mass spectrum, it was confirmed that the compound was Exemplified compound (29).

The magenta coupler according to the present invention is added to the photographic light-sensitive material of the present invention in an amount of 1.5 × 10 ⁻³ mol to 1 mol of silver.
The range of 7.5 × 10 ^-1 mol is preferable, and 1 × 1 is more preferable.
It is in the range of 0 ^-2 mol to 5 x 10 ^-1 mol.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative and positive film, and a color photographic paper. Especially, when the color photographic paper used for direct viewing is used, the method of the present invention can be used. The effect of is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, may be monochromatic or polychromatic. In the case of a multi-color silver halide photographic light-sensitive material, a silver halide emulsion layer and a non-light-sensitive layer usually containing magenta, yellow and cyan couplers as photographic couplers in order to perform color reduction method color reproduction. Has a structure in which it is laminated on the support in an appropriate number of layers and layer order, but the number of layers and layer order may be appropriately changed depending on the priority performance and the purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes, as a silver halide, a conventional halogenated silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and the like. Any of those used for silver emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or one of them may be present while the other is mixed. In addition, while considering the critical growth rate of silver halide crystals, the halide ion and silver ion are mixed in the p
It is possible to grow by adding H and pAg simultaneously while controlling them. After growth, the conversion method may be used to change the silver halide composition of the grains.

During the production of the silver halide of the present invention, a silver halide solvent may be used, if necessary, to control the grain size, grain shape, grain size distribution and grain growth rate of the silver halide grains.

The silver halide grains used in the silver halide emulsion of the present invention have a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt in the step of forming and / or growing the grain. , Iron salt or complex salt,
Can be added to the inside of the grain and / or included in the surface of the grain, and a reduction sensitizing nucleus can be imparted to the inside of the grain and / or the surface of the grain by placing in a suitable reducing atmosphere.

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 may be contained therein. When removing the salts,
It can be performed based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may be composed of a layer having a uniform inside and surface,
It may consist of different layers.

The silver halide grain used in the silver halide emulsion of the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal form, or may have an irregular crystal form such as a spherical shape or a plate shape. In these grains, any ratio of {100} faces to {111} faces can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more kinds of silver halide emulsions formed separately.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions, a sulfur sensitizing method using active gelatin, a selenium sensitizing method using a selenium compound, a reduction sensitizing method using a reducing substance,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye in the emulsion. Good.

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
Silver halide during chemical ripening and / or after chemical ripening for the purpose of preventing fog during storage or photographic processing and / or for maintaining stable photographic performance, and / or after chemical ripening. By the time the emulsion is coated, compounds known in the photographic art as antifoggants or stabilizers can be added.

As the binder (or protective colloid) of the silver halide emulsion of the present invention, it is advantageous to use gelatin,
Other than that, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, and other hydrophilic colloid layers can be obtained by crosslinking the binder (or protective colloid) molecules to increase the film strength. It is dura. The hardener is preferably added in an amount such that the light-sensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

A plasticizer may be added for the purpose of enhancing the flexibility of the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. You can

In the color development processing, the emulsion layer of the silver halide color photographic light-sensitive material of the present invention is subjected to a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative or aminophenol derivative). Dye-forming couplers are used that do the above to form dyes. The dye-forming couplers are usually selected so that for each emulsion layer a dye is formed which absorbs the light in the light-sensitive spectrum of the emulsion layer, and the blue-light-sensitive emulsion layer contains a yellow dye-forming coupler. 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, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

Examples of yellow dye-forming couplers include acylacetamide couplers (for example, benzoylacetanilides and pivaloylacetanilides). There are triazoles, open-chain acylacetrinitol couplers and the like, and as cyan dye forming couplers, there are naphthol couplers, phenol couplers and the like.

It is desirable that these dye-synthesizing couplers have a group having a carbon number of 8 or more which makes a coupler called a ballast group non-diffusible in the molecule. Also, these dye-forming couplers need only reduce 4 molecules of silver ion in order to form 1 molecule of dye, but they need only reduce 2 molecules of silver ion even if they are 4 equivalence. Either of two equivalence may be used.

For the hydrophobic compound such as a dye-forming coupler which does not need to be adsorbed on the surface of the silver halide crystal, a solid dispersion method, a latex dispersion method, an oil-in-water type emulsion dispersion method and various methods can be used. It can be appropriately selected depending on the chemical structure of the hydrophobic compound. The oil-in-water emulsification dispersion method can be applied to a conventionally known method of dispersing a hydrophobic additive such as a coupler, usually, a high boiling point organic solvent having a boiling point of about 150 ° C. or higher, a low boiling point if necessary, and / or Alternatively, a water-soluble organic solvent is used in combination to dissolve, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution to emulsify using a dispersing means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As a high-boiling point oil agent, a phenol derivative that does not react with an oxidized product of a developing agent, a phthalic acid ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150 ℃
The above organic solvents are used.

A hydrophobic compound is dissolved in a solvent having a low-boiling point solvent alone or in combination with a high-boiling point solvent, and as a dispersion aid when dispersed in water using a machine or ultrasonic waves, an anionic surfactant, a nonionic surfactant, a cationic Surfactants can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (same color-sensitive layers and / or different color-sensitive layers), an oxidant of a developing agent or an electron transfer agent moves to cause color turbidity or sharpness. An anti-foggant is used to prevent deterioration and conspicuous graininess.

The color antifoggant may be used in the emulsion layer itself, or may be used in the intermediate layer by providing an intermediate layer between adjacent emulsion layers.

An image stabilizer which prevents deterioration of a dye image can be used in the color light-sensitive material using the silver halide emulsion layer of the present invention.

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer is provided with an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction or the like and to prevent deterioration of an image by UV light. May be included.

The color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an anti-halation layer, and / or an anti-irradiation layer. In these layers and / or in the emulsion layer, a dye which flows out or is bleached from the color light-sensitive material during the development processing may be contained.

A silver halide emulsion layer of a silver halide light-sensitive material using the silver halide emulsion of the present invention, and / or other hydrophilic colloid layer to enhance the writing property for reducing the gloss of the light-sensitive material,
A matting agent can be added for the purpose of preventing sticking of the photosensitive materials to each other.

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 antistatic can be added to a light-sensitive material using the silver halide emulsion of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used for protection of the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. It may be used for the colloid layer.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention, the coating property is improved,
Various surfactants are used for the purpose of antistatic, improvement of slipperiness, emulsion dispersion, prevention of adhesion, and improvement of photographic properties (such as acceleration of development, hardening, and sensitization).

A photographic emulsion layer of a light-sensitive material using the silver halide emulsion of the present invention, and other layers include a baryter layer or a paper laminated with an α-olefin polymer or the like, a flexible reflective support such as synthetic paper, cellulose acetate, cellulose nitrate. ,polystyrene,
It can be applied to a film made of a semi-synthetic polymer such as polyvinyl chloride, polyethylene terephthalate, polycarbonate or polyamide, or a rigid body such as glass, metal or pottery.

The silver halide light-sensitive material of the present invention, if necessary after subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc.,
Directly or on the surface of support, antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, friction property,
And / or 1 or 2 for improving other properties
It may be applied via the above-mentioned undercoat layer.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam,
Any known light source such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays or the like can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and it is also possible to use exposure shorter than 1 microsecond, for example, 100 microsecond to 1 microsecond using a cathode ray tube or a xenon flash lamp. However, an exposure longer than 1 second is possible. The exposure may be performed continuously or intermittently.

The silver halide photographic light-sensitive material of the present invention can form an image by performing color development known in the art.

The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Further, these compounds are generally used in a concentration of about 0.1 g to 30 g for the color developer 1, preferably about 1 g to 1.5 g for the color developer 1.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amino color developing agents are N, N '.
It is a -dialkyl-p-phenylenediamine compound, and the alkyl group and the phenyl group may be substituted with any substituents. Among them, examples of particularly useful compounds include N, N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-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-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N, N'-diethylaniline, 4,
-Amino-N- (2-methoxyethyl) -N-ethyl-
Examples thereof include 3-methylaniline-p-toluenesulfonate.

The color developer used in the processing of the present invention contains various components which are usually added to the color developer in addition to the primary aromatic amine color developer, such as sodium hydroxide and sodium carbonate. Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
An alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softening agent, a thickening agent and the like can be optionally contained. PH of this color developer
The value is usually 7 or higher, most commonly about 10-13.

In the present invention, after color development processing, processing is carried out with a processing solution having fixing ability. When the processing solution having fixing ability is a fixing solution, bleaching processing is carried out before that. As the bleaching agent used in the bleaching step, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes the metal silver produced by development to convert it to silver halide, and at the same time, acts to color the uncolored part of the color former. And has a structure in which a metal ion such as iron, cobalt, or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be given as specific representative examples of these.

[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] Nitrilotritri Sodium acetate salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide, a metal salt or a chelating agent. In addition, borate, oxalate, acetate, carbonate, phosphate and other pH buffers, alkylamines, polyethylene oxides and the like, which are known to be added to ordinary bleaching solutions, can be appropriately added. . Further, fixers and bleach-fixers include ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, and other sulfites, boric acid, and borax. PH buffers consisting of various salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc., alone or in combination. The above can be included.

When the processing of the present invention is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate or sulfite. The bleach-fixing replenisher may contain these salts and be replenished to the processing bath.

In the present invention, in order to increase the activity of the bleach-fixing solution, air may be blown in, or oxygen may be blown in the bleach-fixing bath and the storage tank of the bleach-fixing replenisher, if desired, or a suitable oxidizing agent, For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

Example 1 0.1 mol of each of the magenta coupler and the comparative coupler of the present invention as shown in Table 1 was taken with respect to 1 mol of silver.
The tricresyl phosphate in an amount 1 times the weight of the coupler and ethyl acetate in an amount 3 times the weight of the coupler were added, and the mixture was heated to 60 ° C. to completely dissolve it. This solution was added to 120 m of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
Was mixed with 1200 m of a 5% gelatin aqueous solution containing and was emulsified and dispersed by an ultrasonic disperser to obtain an emulsion. Thereafter, this dispersion was added to a green-sensitive silver iodobromide emulsion (containing 6 mol% of silver iodide).
A 2% solution of 1,2-bis (vinylsulfonyl) ethane as a hardening agent added to Kg (water: methanol = 1: 1)
After adding 1200 m, it was coated and dried on a transparent polyester base which was subbed to prepare Samples 1-1 to 1-10.
(Amount of coated silver: 20 mg / 100 cm ² ) The sample thus obtained was subjected to wedge exposure according to a conventional method and then subjected to the following development treatment.

[Development process] The composition of the treatment liquid used in each treatment step is as follows.

[Color developer composition] [Bleaching composition] [Fixer composition] [Stabilizing liquid composition] Comparison coupler (1) Comparison coupler (2) Comparison coupler (3) (Exemplified compounds of JP-B-48-30895) From Table 1, it is clear that the coupler of the present invention is excellent in color forming property and formalin resistance and light resistance.

[Example-2] Samples 1-1 to 1-10 in Example-1 were similarly wedge-exposed and subjected to the following development processing. The results are shown in Table 2. In addition, insensitivity and light resistance were measured in Example-1.
The same method was used.

[Development process] The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] [Bleaching fixer] [Stabilizing liquid] As is clear from the results in Table 2, Samples 2-4 to 2-10 containing the coupler of the present invention are superior in sensitivity, color developability and light resistance to the comparative sample.

Example 3 A silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on a polyethylene resin-coated paper containing anatase type titanium oxide.

The following addition amounts are based on 100 cm ² .

(1) 20 mg of gelatin, 5 mg of silver-sensitive silver chlorobromide emulsion as silver content, and 8 mg of yellow coupler * and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved.
Layer containing 2 mg of di-octyl phthalate coupler solvent (2) 12 mg of gelatin, 0.5 mg of 2,5-di-t-octyl hydroquinone and 4 mg of UV absorber * dissolved in 2 mg of dibutyl phthalate UV absorber solvent. Including middle layer.

(3) 18 mg of gelatin, 4 mg of silver-sensitive silver chlorobromide emulsion as silver content, and 5 mg of magenta coupler and 0.2 mg of 2,5-di-t-octylhydroquinone were dissolved 2.
Layer containing 5 mg of dioctyl phthalate coupler solvent.

(4) An intermediate layer containing the same composition as (2).

(5) 16 mg of gelatin, 4 mg of silver-sensitive silver chlorobromide emulsion as silver content, 3.5 mg of cyan coupler * and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved 2.
Layer containing 0 mg of tricresyl phosphate coupler solvent.

(6) A gelatin protective layer containing 9 mg of gelatin.

A coating aid was added to each of the layers (1) to (6), and a gelatin crosslinking agent was added to each of the layers (4) and (6).

The UV absorbers (2) and (4) include UV-1 having the following structure.
And UV-2 were mixed and used.

The above-mentioned multilayer photosensitive material was processed in the same manner as in Example-2. Table 3 shows the yellow coupler, magenta coupler, and cyan coupler used in each layer and the results thereof.

Each sample was measured for magenta density after white exposure.

The specific sensitivity and light resistance were measured in the same manner as in Example 1.

From Table 3, it is clear that the dye image of the coupler of the present invention is excellent in light fastness, and that it is further improved by using an ultraviolet absorber.

UV absorber UV-1 UV-2 Yellow coupler Y-1 Y-2 Cyan coupler C-1 C-2 C-3 C-4 [Specific effects of the invention] When the present invention is applied to a color photographic light-sensitive material for printing, a magenta dye has excellent spectral absorption characteristics, a color tone is good, and a clear dye image having a wide color reproduction range is formed, and The light fastness of the magenta dye can be improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuko Matsubara 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Industrial Co., Ltd. Kenji Hara (56) Reference JP-A-51-117032 (JP, A) Kai 61-156048 (JP, A) JP 61-160743 (JP, A)

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein magenta represented by the following general formula [I] is contained in at least one of the silver halide emulsion layers. A silver halide color photographic light-sensitive material comprising a coupler. General formula [I] [In the formula, R ₁ and R ₂ each represent a hydrogen atom or a substituent, R ′ and R ″ may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group or a heterocyclic group. R ′ and R ″ may combine with each other to form a 5-membered ring or a 6-membered ring.
The member ring or 6-membered ring may form a condensed ring with a benzene ring or a heterocycle. X represents an oxygen atom or a sulfur atom. ]