JPS61156048A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the resistance to light and formalin and the color developability by incorporating a specified magenta coupler into a least one of emulsion layers. CONSTITUTION:A magenta coupler represented by general formula I is incorpo rated into at least one of silver halide emulsion layers. In the formula, R1 is H or a substituent, each of R2 and R3 is H, halogen, alkyl, aryl, alkoxy, carbonyl, aryloxycarbonyl, alkylaminocarboxyl or arylaminocaronyl. R4 is alkyl, aryl, alkoxy, aryloxy, amino, alkylamino, arylamino or a heterocyclic group contg. N; n=0, 1, 2 or 3; Z is a group of nonmetallic atoms capable of forming a heterocyclic ring contg. N. The amount of the magenta coupler incorporated is 1.5X1<-3>-7.5X10<-1>mol, preferably 1X10<-2>mol per 1mol silver.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a silver halide photograph containing a 7 zenta 7 plar that forms a magenta dye image with high color development and improved storage stability, especially light fastness. Regarding photosensitive materials. More specifically, the present invention relates to a silver halide color photographic material containing a novel magenta coupler.

(Prior art) In conventional silver halide color photosensitive materials, first, exposed silver halide grains are reduced with an aromatic 11fi amine color developing agent, and the color developing agent produced at this time is reduced. Dye images can be obtained by coupling the oxidant 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-mentioned drawbacks, various 1-biazolo[3,2-C]-3-triazole magenta couplers have been proposed.For example, U.S. Pat.
7, British Patent No. 1,252,418, British Patent No. 1.334,
It is described in No. 515. 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 image light resistance. .

Research [) 1 closure 124
The compound described in No. 43 cannot be put to practical use at all in terms of color development. ! The 1-day-virazolo[3,2-C]-8-triazole type magenta coupler described in Japanese Patent Publication No. 58-42045 has been significantly improved in terms of formalin resistance and color development, but it still has poor light resistance. Very few improvements have been made.

Also, JP-A-59-99437, JP-A No. 59-125732
Although the coupler described in the issue has also been improved in color development,
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, in the case of the former coupler, Compound Example 19 described in the specification, although the light resistance is slightly improved, it is still not sufficient. I can not say.

In other words, 1H-pyrazolo[3], which has attracted attention for its lack of side absorption and high formalin resistance,
, 2-C]-s-triazole type magenta couplers, it can be said that little improvement has been made in terms of 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 which 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 photographic light-sensitive 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: It is rapidly produced using a silver halide photographic material represented by [I] and containing an irises-magenta coupler.

General formula [I] In the formula, R1 represents a hydrogen atom or a W substituent, and specific examples of the substituent include 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, Amimu L acylamino group,
A sulfonamide group, an imide group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a furkylthio group, an arylthio group, or a heterocyclic thio group.

R2 and R3 may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, a monoaryl group, an alkoxy group (a carbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, or an aryl7minocarbonyl group); , R% is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amine L-alkyl amine group, or an M-containing element? I elementary ff1W
Represents W (bonded through a nitrogen atom). n represents a positive integer of O to 3.

2 represents a nonmetallic atomic group capable of forming a nitrogen-containing heterocycle. (However, the nitrogen-containing heterocycle represented by 2 does not further form a condensed ring.) This heterocycle may have a substituent. For convenience, the compound R shown below is simply represented by X.

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

Examples of the halogen atom represented by R in general formula [I] include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

The alkyl group represented by R7 has 1 to 32 carbon atoms.
, alkenyl group, alkynyl group has 2 carbon atoms
-32, cycloalkyl group, and cycloalkenyl group preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl group, alkenyl group, or alkynyl group may be straight 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, specific hydrocarbon compounds) In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom, specifically hydroxy, alkoxy, and aryloxy. , heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nido O, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, -, sulfonamide, Those substituted via a nitrogen atom such as imide and ureido, those substituted via a sulfur atom such as alkylthio, 7-arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted via a sulfur 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'-dibenthylnonyl group, 2-O-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)phenylpropyl group, 3-(4'-[α-(2")
, 4''-di-t-amylphenoxy)butanamido]phenyl)-propyl group, 4-[α-(0-chlorophenoxy)tetradecanamidophenoxy]butyl group, allyl group, cyclopentyl group, cyclohexyl group, etc. It will be done.

The aryl group represented by R/ is preferably a phenyl group, and this aryl group is ll! It may have a substituent (for example, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
2.4-di-t-amylphenyl group, 4-tetradecanamine phenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butylphenoxy)tetradecanamido]phenyl group and the like.

The hetero mM represented by R is preferably a 5- to 7-membered one, which may be substituted or condensed, specifically a 2-furyl group, a 2-chenyl group, etc. , 2-pyrimidinyl group, 2-benzothiazolyl group, and the like.

Examples of the acyl group represented by R1 include acetyl group, phenylacetyl group, dodecanoyl group, α-2,4-
Examples include furkylcarbonyl groups such as di-t-amylphenoxybutanoyl group, arylcarbonyl groups such as benzoyl group, 3-pentadecyloxybenzoyl group, and p-chlorobenzoyl group.

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

Examples of the sulfinyl group represented by R7 include alkylsulfinyl groups such as ethylsulfinyl group, octylsulfinyl group, and 3-phenoxybutylsulfinyl group;
Examples include arylsulfinyl groups such as phenylsulfinyl group and l-pentadecylphenylsulfinyl group.

Examples thereof include an alkoxyphosphonyl group such as a phenoxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and an arylphosphonyl group such as a phenylphosphonyl group.

The carbamoyl group represented by R/ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentylcarbamoyl group), etc. Examples thereof include decyl octylethyl) carbamoyl group, N-ethyl-N-dodecyl carbamoyl group, and N-(3-(2,4-di-t-amylphenoxy)propyl) carbamoyl group.

The sulfamoyl group represented by R/ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, N, N-
Examples include diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, .N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group.

Examples of the spiro compound residue represented by R include spiro[3,3]hebutan-1-yl.

Examples of the bridged carbonized compound residue represented by R2 include bicyclo[2,2,11hebutan-1-yl, tricyclo[3,3,1,1]]decan-1-yl 7,7-dimethylp Examples include cyclo[2,2°1]hebutan-1-yl.

The alkoxy group represented by R7 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-dodecyloxy group. Examples include ethoxy group and phenethyloxyethoxy group.

The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with W by any of the substituents or atoms listed above for the aryl group, such as phenoxy group, p-t- Examples include butylphenoxy group, -pentadecylphenoxy group, and the like.

The heterocyclic oxy group represented by R7 preferably has a 5- to 7-membered heterocycle, and the cough heterocycle may further have a '11 substituent, for example, 3.4.5 ．．
Examples include 6-tetrahydrobilanyl-2-oxy group and 1-phenyltetrazol-5-oxy group.

The siloxy group represented by R/ may be further substituted with an alkyl group, for example, a trimethylsiloxy group,
Examples include triethylsiloxy group and dimethylbutylsiloxy group.

Examples of the acyloxy group represented by R/ include an alkylcarbonyloxy group and an arylcarbonyloxy group, which may also have a substituent, specifically an acetyloxy group, an α-chloro group, etc. Examples include acetyloxy group and benzoyloxy group.

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-diethylthiolbamoyloxy group, an N-phenylcarbamoyloxy group, etc. Can be mentioned.

The amine group represented by R1 is an alkyl group, an aryl group (
(preferably a phenyl group), etc., for example, an ethylamime L anilino group, -monolyloranilim L
Examples include a 3-pentadecyloxyluponylanilino group and a 2-chloro-5-hexadecaneamideanilino group.

Examples of the acylamino group represented by R/ include an alkylcarbonylamino group (preferably a phenylcarbonylamino group), which may further have a substituent, specifically an acetamido group, an α-
Examples include ethylpropanamide group, N-7enylacetamide group, dodecanamide group, 2,4-di-t-7milphenoxyacetamide group, α-3-t-butyl-4-hydroxyphenoxybutanamide group, etc. .

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

The imide group represented by R may be open-chain or cyclic, and may have a substituent, such as a succinimide group, a 3-hebutadecylcohelic acid imide group, a phthalimide group, a glutaric acid group. Examples include imide groups.

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, an N-methyl-N-
Decylureido group, N-phenylureido I, N-D
-Tolylureido group and the like.

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 Amino group, N-7
Examples include enylsulfamoylamino group.

The alkoxycarbonylamino group represented by R/ 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/ may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonyl 7-mino group.

The alkoxycarbonyl group represented by R may further have a substituent, such as a methoxycarbonyl group,
Examples include butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxycarbonyl group, and the like.

The aryloxycarbonyl group represented by R7 may further have a substituent, and examples thereof include a dicarbonyl group, a dicarbonyl group, a dicarbonyl group, and a dicarbonyl group. It will be done.

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, etc.

The heterocyclic thio group represented by R7 is preferably a 5- to 7-membered heterocyclic thio group, which 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.

Further, examples of the nitrogen-containing heterocycle formed by 2 of general formula [I] include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, etc., and the substituents that the ring may have include the above-mentioned substituents. Those mentioned for R7 can be mentioned.

In addition, the substituents on the heterocycle in general formula [1] and general formulas [II] to [■ (for example, R/ to R77) described below are moieties (herein, R' and 2' are general formulas [ R/ in I]
%2, and X is as described above. ), it forms a so-called screw-type coupler, which is, of course, included in the present invention.

More specifically, what is represented by the general formula [I] is represented by, for example, the following general formulas [I[] to [■].

General formula En] General formula [IV] General formula [V] General formula [■] General formula [■] In the general formula NU ~ [■, Rt ~ R// and X are the general formula [I ] has the same meaning as R/ and X.

Moreover, among the general formula [1], the following general formula [
■].

General formula [■] In the formula, R,, X and z7 are R in the general formula [I],
, X and 2.

Among the magenta couplers represented by the general formulas [ff] to [■], particularly preferred are the magenta couplers represented by the general formula [1].

Regarding the substituents on the heterocycle in general formulas [I] to [■], R1 in general formula [E] and R/ in general formulas [I] to [■] meet the following conditions. It is preferable that condition 1 is satisfied, and more preferable that condition 1 is satisfied below.
and 2. Particularly preferred is the case where conditions 1.2 and 3 below are satisfied.

Condition 1: The root atom directly connected to the 'a cycle is a carbon atom.

Condition 2 Only one hydrogen atom is bonded to the carbon atom, or no hydrogen atom is bonded to the carbon atom.

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

The most preferred substituent R/ on the heterocycle is:
It is represented by the following general formula [IX].

General formula [IX] RI4C-! IM In the formula, Rtz, R/3, and R,≠ 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, and a sulfonyl group. , sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, Siam L spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, Amim L acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxylponylamino group, aryloxycarbonylamino group, alfkyl dicarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group At least two of Rii, R73 and R/4 are not hydrogen atoms.

Furthermore, two of the above R/2, Ri3 and Rz4t, for example R/2 and R/J, may be combined to form a saturated or unsaturated ring (for example, cycloalkane, cycloalkene, heterocycle). Often, Rz4t may be further bonded to the ring to constitute a bridged hydrocarbon compound residue.

The groups represented by R2 to R13 may further have a substituent. Specific examples of the groups represented by R/Z to R/4 and the substituents that the analogs may have include the above-mentioned substituents. Specific examples of the group represented by Ri in the general formula [I] and substituents are listed.

Also, for example, the ring formed by combining Ri2 and R/J and R
Specific examples of the bridged hydrocarbon compound residue formed by tz to Rttt and its optional substituents include cycloalkyl represented by R in the above general formula [E];
Specific examples of cycloalkenyl and heterocyclic groups and their substituents are listed.

Among the general formulas [IX], (1) R/2 to
If two of Rz4c are alkyl groups, (ii) R1
When one of z to R7μ, for example R/2, is a hydrogen atom and the other two, RiB and Ri4, combine to form a cycloalkyl group with the root carbon atom, the following is true.

Even more preferred among <i> is the case where two of R/Z to R19 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

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

R2 and R3 in the general formula [13 may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and an arylaminocarbonyl group. represents a group, and R% is a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amine group, an arylamino group, and an arylamino group.
JIIi represents a heterocyclic group.

Furthermore, these groups include halogen atoms, nitro groups, siam L
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, arylsulfonyl may be substituted with a group, an alkylsulfinyl group, an arylsulfinyl group, an alkylamino group, a ureido group, etc., and represents a positive integer from n&;to to 3.

Examples of the halogen atom represented by R2 and R3 in the general formula [I] include a chlorine atom and a bromine atom, and examples of the alkyl group include a methyl group, an ethyl group, a 1-propyl group, and a butyl group. Aryl groups include, for example, phenyl groups, alkoxycarbonyl groups include, for example, methoxycarbonyl groups, ethoxycarbonyl groups, etc., aryloxycarbonyl groups include, for example, phenoxycarbonyl groups, and alkylamine carbonyl groups include, for example. Examples of the arylaminocarbonyl group such as a methylaminocarbonyl group include an anilinocarbonyl group.

As the alkyl group of Rg represented by the general formula [E],
For example, aryl groups such as methyl group, ethyl group, 1-propyl group, butyl group, t-butyl group, dodecyl group, etc.
Examples of the alkoxy group include a phenyl group and a naphthyl group; examples of the alkoxy group include a methoxy group, an ethoxy group, and a propyloxy group; examples of the aryloxy group include a phenoxy group,
Alkylamino groups such as naphthoxy group and benzyloxy group include, for example, methylamim L ethylamino group and dimethylamim L diethylamino group; arylamino groups include, for example, anilino group and benzylamino group; nitrogen-containing heterocyclic groups include, Examples include a morpholino group, a piperazino group, a uradyl group, a hydantoyl group, a pyridyl group, and the like.

Examples of the alkoxy groups mentioned above as substituents of the general formulas R2, R3 and R4t include methoxy groups,
Examples of the above-mentioned aryloxy groups such as propoxy group and 2-ethoxyethoxy group include phenyloxy i, p-
As an acylamino group such as t-butylphenoxy group,
For example, an alkylcarbonyl group such as an arylcarbonylamino group, an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an aryloxycarbonyl group such as a phenoxycarbonyl group, and an N-ethyl group as a carbamoyl group. Carbamoyl group, N,N-diethylcarbamoyl group, N-phenylcarbamoyl group, etc.; examples of sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group, N-dodecylsulfamoyl group, etc. Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group; examples of the alkylthio group include an ethylthio group, a dodecylthio group, an octadecylthio group, and a phenethylthio group; and examples of the arylthio group include a phenylthio group, a phenylthio group, and the like. Examples of alkylsulfonyl groups such as -methoxyphenylthio group include ethanesulfonyl group and octanesulfone group; examples of arylsulfonyl groups include benzenesulfonyl group, naphthalenesulfonyl group, p-
Examples of alkylsulfinyl groups such as chlorobenzenesulfonyl group include ethylsulfinyl group, octylsulfinyl group, and 3-phenoxybutylsulfinyl group; examples of arylsulfinyl groups include phenylsulfinyl group, ■-pentadecyl phenylsulfinyl group, and alkylamino Examples of the group include methylamino group, ethylamino group, dimethylamim L diethylamino group, diethylamino group, etc.; examples of the ureido group include N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, etc. Each can be mentioned.

Next, specific examples of the magenta coupler represented by the general formula [I] of the present invention are shown below, but the third invention is not limited thereto.

C) 13 Ko C8H17 11] SaH3 C+o H2t ocH, caNH.

Next, a method for synthesizing the magenta coupler of the present invention will be described.
5ociety.

Perkln I 1977, 2047-2052, U.S. Patent No. 3,725,067, JP-A-59-99437
The synthesis was carried out with reference to JP-A No. 58-42045.

1H pyrazolo[3,2-C]-s-triazole 7
The method for introducing a hydroxy group into the position is described in US Patent No. 3,41
As shown in No. 9,391, it can be obtained by aminating the 7-position, diazotizing it, and heating it in an aqueous hydrochloric acid solution. 7-hydroxy-1 obtained here
The exemplified compound can be synthesized by reacting a -s-triazole compound with a substituted alkyl halide.

[In the formula, R/, R2, R3, and R4 are R, and n are
It is the same as that shown by the general formula [I[]. ] This reaction converts the 7-hydroxypyrazolo[3,2-C]-3-triazole compound into alcohol, acetone, benzene,
When reacted with a substituted alkyl halide in a solvent such as chloroform or DMF in the presence of a base such as sodium alcoholate, sodium hydroxide, sodium carbonate, sodium bicarbonate, pyridine, or triethylamine, the desired exemplary compound is obtained. . These exemplified compounds were synthesized with reference to Japanese Patent Publication No. 53-46453.

Next, a specific synthesis example will be shown.

Synthesis Example 1 [Said Exemplified Compound (11)] 3-(1-Methyl-2-dodecylsulfoethyl A/)
-6-tert-butyl-7-hydroxy-1H-pyrazolo[3,2-C]-s-triazole was dissolved in alcohol, an alcoholic solution of an equivalent amount of sodium alcoholate was added thereto, and nitrogen gas was filled. The alcohol heated above the aqueous solution was distilled off under reduced pressure, and the residue was mixed with DMF.
Add the separately prepared chloroacetone D while stirring.
A solution of MF was added dropwise. After further reacting at 40 to 50°C for 3 hours, the contents were poured into a mixture of ice water and dilute hydrochloric acid.

The resulting sticky substance was dissolved in ethyl acetate, the ethyl acetate solution was washed with water, and then dried with nitric oxide. Next, the solvent was distilled off under reduced pressure, and the remaining oil was purified by silica gel column chromatography.

The solvent was distilled off, and the remaining candy was confirmed to be Exemplified Compound (11) from the results of mass spectroscopy.

Synthesis Example 2 [Exemplary Compound (18)] According to the method shown in Synthesis Example 1, 3-[3-(4-octadecenylsuccinimidophenyl)propyl]-6-
Methyl-7-hydroxy-1H-pyrazolo[3,2-C
] -s-triazole replaced with 3-(1-methyl-2-dodecylsulfonityl)-6-tert-butyl-7- and droxy-1H-pyrazolo[3,2-C1-3-triazole, and Monochrome O-vinegar N2-methoxyethylamide was replaced with chloroacetone and the same reaction was performed to synthesize it. The crude product was purified by silica gel column chromatography, and the exemplified compound (18
).

The amount of the magenta coupler according to the present invention added to the photographic material of the present invention is preferably in the range of 1.5×10 mol to 7.5×10 mol, more preferably 1×10 mol to 5×10 −′ per mol of silver. It is in the molar range.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper. In particular, when a 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 light-sensitive materials of the present invention, including this color photographic paper, may be for single color or multicolor use.In the case of multicolor silver halide photographic materials, subtractive color reproduction is possible. To do this, it is usually used as a photographic coupler.
It has a structure in which silver halide emulsion layers containing magenta, yellow O-, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. The layer order may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of those used in 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 forming seed particles.The method for forming and growing seed particles may be the same or different.

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
The halogen composition of the particles may be changed by sequentially and simultaneously adding H and PAIJ while controlling, or by using a conversion method after growth.

When producing the silver halide emulsion 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 to the interior of the particles and/or on the surface of the particles using iron salts or complex salts, and can be reduced to the interior of the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can provide sensitizing nuclei.

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. Research Disclosure when removing such salts? This 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 a uniform layer inside and on the surface, or
It 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 [1,0,01 planes to [1,1,1] planes can be used. Further, 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 separately formed silver halide emulsions.

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

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range 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. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide emulsions are used during and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as anti-capri agents or stabilizers can be added before coating.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as synthetic hydrophilic polymer substances such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and single or copolymers can also be used.

For photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention, a hardening agent that crosslinks binder (° or protective colloid) molecules and increases film strength may be used alone or in combination. It is hardened by. The hardening agent is
Although it is desirable to add an amount of the photosensitive material that can be hardened to such an extent that it is not necessary to add a hardening agent to the processing solution, it is also possible to add a 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 HWl synthetic polymer may be included in the photographic emulsion layer or other hydrophilic colloid layer of a photosensitive material using the silver halide emulsion of the present invention for the purpose of improving dimensional stability. I can do it.

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). The dye-forming couplers are typically selected such that for each emulsion layer a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming dye is formed for the blue light-sensitive emulsion layer. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer.

However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), and magenta dye-forming couplers include 6-pyrazolone couplers, pyrazolobenzimidazole couplers, and pyrazolo couplers in addition to the couplers of the present invention. Examples include triazole, open-chain acylacetonitrile couplers, and cyan dye-forming couplers include naphthol couplers and phenol couplers.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are tetraequivalent, which requires reduction of four molecules of silver ions in order to form one molecule of dye, only two molecules of silver ions are reduced. Either good diisomerism is fine.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, a variety of methods can be used, including solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. It can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied to a previously unknown method of dispersing hydrophobic additives such as couplers. Usually, a high-boiling organic solvent with a boiling point of about 150"C or higher is mixed with a low-boiling point and /or Dissolved in combination with a water-soluble aWi medium, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, using a stirrer, homogenizer, colloid mill, flow jet mixer,
After emulsification and dispersion using a dispersion means such as a long sonic device, a step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion, which can be added to the desired hydrophilic colloid layer.

Examples of high boiling point oils include phenol ms form, which does not react with the oxidized form of the developing agent, phthalate ester, phosphate ester,
Boiling point 15 of citric acid ester, benzoic acid ester, alkyl amide, fatty acid ester, trimesine ester, etc.
An organic solvent having a temperature of 0° C. or higher is used.

Anionic active agents, nonionic surfactants, Cationic 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), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color anti-capri agents are used to prevent deterioration and noticeable graininess.

The color anti-capri agent may be used in the emulsion layer itself, or may be used in a film intermediate layer by providing an intermediate layer between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It may be included.

A 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 antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, improves the ease of writing, and prevents the photosensitive materials from sticking to each other. A matting agent can be added to achieve this goal.

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 of nails that are not laminated with the emulsion of the support, and are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Various surfactants are used for the purposes of preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitization).

The light-sensitive material using the silver halide emulsion of the present invention has a photographic emulsion layer, and other layers include a baryta layer or a flexible reflective support such as paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, nitric acid, etc. cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide material of the present invention can be used directly or (adhesiveness, antistatic property, dimensional stability, resistance The coating may be applied via one or more subbing layers (to improve abrasion, hardness, antihalation, frictional properties, and/or other properties).

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a layer adhesive may be used to improve coating properties. Particularly useful coating methods are ex-dulsion 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 electric lamps, fluorescent lamps, xenon arc lamps, carbon arc lamps,
xenon flash lamp, cathode ray tube flying spot,
Various laser lights, light emitting diode lights, electron beams, Xl, 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 commonly used in cameras, but also exposure times shorter than 1 microsecond, such as F
& 100 microseconds using polar ray tube Yaxenon flash lamp
Exposures of 1 microsecond can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide photographic material of the present invention can be used to form an image 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. Since these compounds are more stable than the free state, they are generally in the form of salts, such as salt i! ! Salt or sulfur! ! Used in salt form. These compounds generally have a color development W11 of about 0.1Q to about 30σ.
concentration, preferably 1 J of color developer! about 1rJ
Use at a concentration of ~1.5 g.

Examples of aminophenol-based developers include 〇-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-p-phenylenediamine compound, where the alkyl group and phenyl group can be at any position! Examples of particularly useful compounds that may be substituted include N,N'-diethyl-p-7enylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-diethyl-p-7enylenediamine hydrochloride,
'-Dimethyl-p-phenylenediamine salt I! salt, 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, 4-7minor N-(2-methoxyethyl)-N-ethyl-3-methyl7diphosphorus-ρ-
Examples include toluene sulfonate.

The color developing FLT solution used in the process of the present invention contains 1
, In addition to the M1 class aromatic amine color developer, various components normally added to color developers, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal sulfites, and alkalis. Metal bisulfite! ! Salts, alkali metal chlorides, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be contained. The pH value of this color developer is usually 7 or higher, most commonly about 10 to about 13.

In the present invention, after color development processing, a treatment II! having fixing ability is used! However, if the processing solution having the fixing ability is a fixing solution, a bleaching treatment is performed before that. The bleaching agent used in the bleaching process is a metal complex salt of II, and the gold B complex oxidizes the metallic silver produced by development and converts it into silver halide, and at the same time colors the uncolored part of the color former. Its structure is that metal ions such as iron, cobalt, and M are coordinated with aminopolycarboxylic acid or organic acids such as citric acid. Such an organic acid metal! The most preferred compounds used to form the i-salt include 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 [2conitrilotriacetic acid] [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid sodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [ 7] Nitrilotriacetic acid sodium salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid 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.

Also, borates, am salts, acetates, carbonate supports, phosphates, etc.
HII agents, alkylamines, polyethylene oxides, and other substances that are known to be added to clean liquids can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid A pea interim agent consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination.

When the process of the present invention is carried out while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the cough bleaching rate is 11! The (bath) may contain thiosulfate, thiocyanate or sulfite, or the bleach-fixing replenisher may contain these salts to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, sudden air blowing or severe blowing may be carried out in the bleach-fix bath and in the storage tank of the bleach-fix replenisher, or an appropriate method may be used. Oxidizing agents such as hydrogen peroxide, bromate 1,4 sulfate, etc. may be added as appropriate.

[Examples] Next, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

[Example-1] Take 0.1 mol of each of the magenta coupler of the present invention and the comparative coupler shown in Table 1 per 111 mol, and add tricresyl phosphate in an amount of 1 times the weight of the coupler and tricresyl phosphate in an amount of 3 times the weight of the coupler. of ethyl acetate was added and heated to 60°C to completely dissolve. This solution was mixed with 1 part of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
5% gelatin aqueous solution containing 20ml 1200Ill
and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was added to a 4ka green-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide) to give a hardening agent of 1.2
-Add 2% solution of bis(vinylsulfonyl)ethane 1 (water:methanol-1:1) 12h+M, coat on the subbed transparent polyester base and dry.
-1 to 1-9 were created. (Coated silver amount 20a + M100
cm) The thus obtained sample was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. Table 1 shows the results.

CfA image processing step 1 The composition of the processing solution used in each processing step is as follows.

[Color developing solution composition] [Bleaching solution composition] r constant x'a composition] [Stabilizing solution composition] Below is the margin 1) The specific sensitivity is the reciprocal of the exposure amount that gives a density of fog density + 0.1, and the comparative coupler 1) Sample No. 081 using the above was set as 100.

2) 0.9% temperature and humidity controlled to 30℃, 62%RH
After the sample was placed in a sealed container containing 6 cc of formalin aqueous solution for 3 days, color development was performed.For comparison, a sample not treated with formalin was also developed.

In addition, formalin resistance was calculated|required according to the following formula.

3) The sample after the color development process was irradiated with a xenon fade meter for 5 days, and the percentage of dye remaining at the initial @ft-1,0 was shown.

Comparative Couplers (2) Comparative Couplers (3)' (Exemplary Compounds of Japanese Patent Publication No. 53-46453) From Table 1, it is clear that the couplers of the present invention are excellent in color development, formalin resistance, and light resistance.

[Example 2] Samples (1) to (8) in Example 1 were similarly subjected to wedge exposure, and the following phenomenon treatment was performed.

These results are shown in Table 2. Insensitivity and light resistance were measured by the same method as in Example-1.

[Development processing step] The composition of the processing solution used in each processing step is as follows.

[Coloring Ring I Solution] [Bleach-Fix Solution] [Stabilizing Solution] From the results shown in Table 2, Samples 2-4 to 2-9 containing the magenta coupler of the present invention had high sensitivity 1 color density.

Moreover, it can be seen that it has excellent light resistance.

[Example 3] A silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on polyethylene resin-coated paper containing 7-natase type titanium oxide.

The amounts added below are per 100 cm.

(1) 20u of gelatin, 5 as silver amount! Layer (2) 12110 containing a blue-sensitive silver chlorobromide emulsion of .OMEGA. Interlayer comprising gelatin, 0.5 mg of 2,5-di-t-octylhydroquinone and 2 x Ω dibutyl phthalate UV absorber solvent in which 4:9 UV absorber was dissolved.

(3) 2.5 mg of 18 Q gelatin, a green-sensitive silver chlorobromide emulsion with a silver content of 4 to, and 51 g of magenta coupler and 0.2-〇 of 2.5-di-t-octylhydroquinone dissolved therein. layer containing dioctyl phthalate coupler solvent.

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

(5) 161 g of gelatin, a red-sensitive silver chlorobromide emulsion of 4aQ as the amount of silver, and 3.5*g of cyan coupler and 0.1 mg of 2.5-di-t-octylhydroquinone were dissolved in 2, Layer containing Oa+g tricresyl phosphate coupler solvent.

(6) Gelatin protective layer containing 9ma gelatin.

Coating aids are added to each layer (1) to (6), and (
A gelatin crosslinking agent was added to layers 4) and (6).

As the ultraviolet absorber (2) and (4), L of the following structure is used.
A mixture of IV-1 and UV-2 was used.

The above multilayer photosensitive material was treated 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.

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.

Margin below UV absorber IV-1 C4Hs(t) UV-2 Y-coupler t C-Kubler Procedural correction layer method) May 21, 1985

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a magenta coupler represented by the following general formula [I]. A silver halide photographic material comprising: General formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents a hydrogen atom or a substituent. R_2 and R_3 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, or an arylaminocarbonyl group, and R_4 is a hydroxyl group , alkyl group,
It represents an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkylamino group, an arylamino group, or a nitrogen-containing heterocyclic group (bonded through a nitrogen atom). n represents a positive integer from 0 to 3. Z represents a nonmetallic atomic group capable of forming a nitrogen-containing heterocycle. (However, the nitrogen-containing heterocycle represented by Z does not further form a condensed ring.)