JPS626258A - Method for stabilizing dye image - Google Patents

Abstract

PURPOSE:To remarkably enhance light fastness of a conventional dye image, especially, a magenta dye image by processing a photographic product having a layer carrying at least one magenta dye image with a processing solution enhancing the specific rotation of a standard gelatin to >=-150 deg.. CONSTITUTION:The photographic product having a layer carrying at least one magenta dye image is processed with the processing solution enhancing the specific rotation of the standard gelatin to >=-150 deg.. This standard rotation is a value measured by using a light source for emitting the single color of the sodium D line of 589.3nm wavelength at 15 deg.C and represented by the left member of the equation shown on the right, and calculated in accordance with the right member, where alpha is rotation ( deg.), l (dm) is the length of the aqueous solution to be measured, and C is the concentration of the standard gelatin (g/100ml) in said aqueous solution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for stabilizing dye images, and more particularly to a method for stabilizing dye images that significantly improves the lightfastness of dye images.

[Background of the Invention W4] Generally, it is known that dye images of photographic products undergo significant discoloration and fading under various storage conditions. For example, when they are exposed to light for a long time and stored, and when they are stored in a dark place with high temperature and humidity for a long time even though they are exposed to light for a short time, they often show different discoloration and discoloration. The former case is called brightness fading (or photometric fading), and the latter case is called darkness fading. In order to use photographs with a layer carrying a pigment image as a recording material for semi-permanent preservation, it is necessary to It is desirable that these color changes be as small as possible under storage conditions.

Methods for improving the fastness of dye images in photographic products include, for example, U.S. Pat. No. 3,265,506;
i No. 3,894,875, No. 3,519,429, No. 2,895.826, No. 4,124,39
There is a method of improving the fastness of the dye image itself, as disclosed in Mei IllI, No. 6, No. 4,333,999, etc. Specifically, improvements may be made in the design of the molecular structure of the dye image itself or a compound (such as a coupler) that forms the dye image, or by changing the existing state of the dye. However, these methods have a large effect on photographic characteristics such as color tone,
Not only has it not been easily put into practical use due to its low versatility, but the degree of improvement has not yet been satisfactory.

Also, for example, U.S. Patent No. 3,253,921 #111
! ! i, Special Publication No. 11148-5496, No. 48-41
Ultraviolet absorbers described in each publication of No. 572, Special Publication No. 4
No. 8-31256, No. 49-20917, No. 56-2
No. 4257 and U.S. Pat. No. 3,432,30
0＠ノ明 [phenolic water described in m, etc.! ! i
Compounds with t or compounds whose hydroxyl groups are converted to alkoxy groups, nickel II salt compounds described in the specifications of U.S. Patent Nos. 4,050.938 and 4,346,165, etc.; Azomethine photo-performance compound described in Japanese Patent Publication No. 57-19413 and Japanese Patent Publication No. 1983-20
No. 973, No. 49-20074, No. 57-20617
Publications such as No. 1 and West German Patent Publication No. 2,126,954
There is a method using a dye image stabilizer such as a hindered amine compound described in the above publication, and this method is widely used because it has little effect on photographic properties and is highly versatile. It is being proposed.

However, although some of these compounds are effective against photofading of specific dye images, they have no effect at all on dark FF1 colors, and some even promote darkness fading. In addition, some dyes have an effect on photographic properties or cause coating failure due to precipitation as the amount added increases, and some dyes have a stabilizing effect on dye images that becomes saturated at a certain amount or more.

Furthermore, a method of surrounding photographic products with an oxygen-impermeable polymer film for the purpose of preventing oxidative fading has also been proposed; for example, Japanese Patent Application Laid-Open Nos. 49-11330, 50-57233, and 56
It is described in various publications such as No. 4145 and No. 56-59231. However, according to this method, not only one additional step is required when processing the support, but also lamination processing or an additional step of coating and drying is required in the case of silver halide photographic light-sensitive materials after development processing. None of these methods can be said to be suitable from the viewpoint of productivity for intensive intensive processing methods such as those used in recent photo labs. Furthermore, even if this method can suppress oxidative fading of one dye image, it promotes reductive fading of other dye images, which is undesirable from the viewpoint of color balance during fading.

Furthermore, as an improvement method from another aspect, there is a method in the C1 process. Specifically, for example, treatment with a zinc salt solution as described in U.S. Pat. No. 2,788,274, and U.S. Pat.
The specifications of British Patent No. 909,824 and British Patent No. 3,035,914 include treatment with a salt solution of magnesium, cadmium, zinc, and strontium and a polymeric nitrogen-containing cationic resin solution, British Patent No. 909,824, and British Patent No. 1! 1,001.446
Method of treatment with a solution containing monosaccharoid, disaccharoid, and hexitol, treatment with a solution containing formaldehyde and polycarboxylic acid, Japanese Patent Publication No. 4B-2128
Publication No. 9 describes 5-enhanced treatment using a solution containing lead compounds;
Japanese Patent Publication No. 42-19743 discloses a method of treating a silver dye bleaching sensitive material with a cobalt, nickel, or copper salt solution. However, these methods are techniques mainly aimed at improving the darkening and fading properties of dye images, and many of them do not show any effect on photometric fading. Furthermore, there are some that prevent fading of dye images but deteriorate the yellowing of white backgrounds. Furthermore, the technology using these metal salts runs counter to the recent trend toward low-load processing.

As is clear from the above description, many techniques have been known to improve the fastness of dye images in photographic products.
Some techniques are not only effective only for specific pigment images;
It has the fatal drawback of having an adverse effect on other dye images, white backgrounds, etc., and even if multiple techniques are used in combination, each with their own effects, the effect obtained is unlikely to be the sum total. It was difficult to break the standard.

On the other hand, social demands for the fastness of dye images in photographic products are increasing due to the expansion of demand for photos, changes in lifestyles and information transmission methods, etc., and the fastness of dye images has been dramatically improved. There is a strong desire to develop a means to do so.

OBJECTS OF THE INVENTION Accordingly, a first object of the present invention is to provide a stabilization method that dramatically improves the lightfastness of conventional dye images, particularly magenta dye images.

A second object of the present invention is to provide a method for stabilizing dye images without affecting any other photographic properties.

A third object of the present invention is to provide a dye image stabilization method using processing steps that is not only easy to implement but also has a low pollution burden and is socially acceptable.

[Structure of the Invention] As a result of intensive research to achieve the above object, the present inventors have discovered
A photographic product bearing at least a magenta dye image has a specific rotation of standard gelatin [α] of 1°-15
It has been found that one of the above objects can be achieved by a method for stabilizing a dye image, which involves processing with a processing solution that increases the dye density to 0 or more.

[Specific Structure of the Invention] In the present invention, standard gelatin refers to PL 6600 manufactured by Reiner Gelatin Company. The gelatin is FAG(I
nt13rnatlonale A rbeitsoo
meinschaft furp photogelat
It is registered and saved in ine).

In the present invention, the specific optical rotation is measured by the following method.

<Method for measuring specific rotation> (1) A test solution is prepared by adding a certain compound to a standard aqueous gelatin solution.

(2) Using the test solution obtained in (1), measure the specific optical rotation [α]7 of standard gelatin (15° C., using sodium D line as a light source).

+5 Specific optical rotation [α] in the present invention. What is sodium D line 589
This is the specific rotation at 15° C. when 3A monochromatic light is used as a light source, and is calculated using the following formula. Here, α is the optical rotation, l is the length of the liquid layer of the aqueous solution (dl), and C is the amount of standard gelatin in the aqueous solution 100<Q'). The above measurement method is based on Japanese Industrial Standard JIS K 0063.
(196B> can be referred to.

As a means for measuring the specific optical rotation, a commonly available polarimeter, such as a digital polarimeter DIP-4 manufactured by JASCO Corporation, can be used.

It is conventional knowledge that by processing a photographic product carrying a magenta dye image with a processing solution that increases the specific optical rotation of standard gelatin to -150 or higher, the light fastness of the magenta dye image is significantly improved. This was completely unexpected.

The photographic product having a lip carrying a magenta dye image according to the present invention may be any photographic product in which a magenta dye image is formed by a dye image-forming substance.

The dye image-forming material reacts with the oxidized form of the silver halide developer to form a dye image, or reacts with the oxidized form (e.g., through a redox reaction) to release a dye or its precursor that is diffusible under alkaline conditions. Generally known compounds such as compounds that can be used can be used.

A wide variety of compounds are known in the art as such dye image-forming substances, among which are (1) a substantially colorless compound that can form a dye image by a coupling reaction with the oxidized product of the silver halide developer described above; ■ A compound that can release a diffusible dye or its precursor as a result of a coupling reaction with the oxidant, and ■ A redox reaction (usually known as a redox reaction) with the oxidant, resulting in , compounds capable of releasing diffusible dyes or their precursors under alkaline conditions, etc. are advantageously used.

These dye image-forming substances are preferably non-diffusible and have a hydrophobic group commonly called a ballast group in the molecule.

In general, pigments that are included in the first group! ii The image-forming substance is
This is known as a so-called color-forming coupler. Such couplers may be either 4-equivalent or 2-equivalent to silver ion, but 2-equivalent couplers are particularly preferred. It may also be a colored coupler that has a color correction effect or a so-called DIR coupler that releases a development inhibitor upon reaction with the oxidized form of the developer.

As a DIR coupler, for example, U.S. Pat. No. 3,148
．． 062@, Id. No. 3,227,554, Id. i 3,7
01,783@, the specifications of British Patent No. 3,733,201, and British Patent No. 953,454, as well as the patent publication number 1
, 800, 420 and the like.

In particular, as magenta dye image-forming couplers, compounds such as pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indasilone couplers can be used.

As a magenta dye image-forming coupler, the following general formula [
A coupler represented by [I] or [Ial] can be preferably used.

General Formula II] [In the formula, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Further, R represents a hydrogen atom or a substituent. ] In the magenta coupler represented by the general formula (1) according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the Z The ring formed may have a substituent.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a 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, heterocyclicoxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group,
Acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group Can be mentioned.

Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

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

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted through a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted through a heteroatom [specifically, hydroxy, alkoxy, and aryloxy , heterocyclic oxy,
Those substituted through an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido Substituents via the nitrogen atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
(such as those substituted via a sulfur atom such as sulfamoyl, and those substituted via 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-dipendylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, l
-ethoxytridecyl group, l-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, l-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4.-(α-[4..(p-hydroxybenzenesulfonyl)phenoxydodecanoylamino)phenylpropyl group, 3-[4.-[α-(2..,
Examples thereof include 4...-di-t-amylphenoxy)butanamido]phenyl)-propyl group, 4-[α-(0-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group, cyclopentyl group, and cyclohexyl group.

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

Specifically, phenyl group, 4-t-butylphenyl group,
2.4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4I
-[α-(4...-t-butylphenoxy)tetradecanamide] phenyl group and the like.

The heterocyclic group represented by R is preferably 5- to 7-membered, and may be substituted or fused.

Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

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

The sulfonyl group represented by R includes an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group,
Examples include arylsulfonyl groups such as benzenesulfonyl group and p-toluenesulfonyl group.

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

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. Examples include arylphosphonyl groups such as.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarnomimoyl group, N-(3-(2,4- Examples include di-t-amylphenoxy)propyl)carbamoyl group and the like.

The sulfamoyl group represented by the margin R below may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group Examples include moyl group.

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

Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1]hebutan-1-yl, tricyclo[3
, 3,1,1'']decan-1-yl, 7,7-dimethyl-bicyclo[2,2,1cohebutan-1-yl, and the like.

The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Examples include pentadecyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group, and the like.

The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group,
For example, phenoxy group, p- is -butylphenoxy group, m
-pentadecylphenoxy group and the like.

The heterocyclic oxy group represented by R preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3゜4.5.6- Examples include tetrahydropyranyl-2-oxy group and -phenyltetrazole-5-oxy group.

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

The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloroacedeloxy group, etc. group, penzoyloquine group, and the like.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-phenylcarbamoyloxy group, etc. It will be done.

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as ethylamino group, anilino group, m-chloroanilino group,
Examples include 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamide anilino group, and the like.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, an α- Ethylpropanamide group, N-phenylacetamide group,
Examples include dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, and α-3-t-butyl 4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent.

Specific examples 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 may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutaric acid group. Examples include imide groups.

The ureido group represented by R is an alkyl group, an aryl group (
Preferably, it may be substituted with a phenyl group), and examples thereof include an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group, and an N-1)-tolylureido group.

The sulfamoylamino group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group, etc. .

As the alkoxycarbonylamino group represented by R,
It may further have a substituent, for example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group,
Examples include octadecyloxycarbonylamino group.

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

The alkoxycarbonyl group represented by R may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an etquinmethquinecarbonyloxy group, and a benzyloxycarbonyl group. Examples include groups.

The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group,
Examples include p-chlorophenoxycarbonyl group and m-pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R may further have a substituent, for example, an ethylthio group, do, decylthio group,
Examples include octadecylthio group, phenethylthio group, and 3-phenoxypropylthio group.

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

The heterocyclic thio group represented by R 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, 2.4-diphenoxy-i, and 3.5-triazole-6-thio group.

Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine, bromine, fluorine, etc.), as well as substituents that and substituent groups.

In addition to the carboxyl group, examples of the group substituted via a carbon atom include the general formula (R, . is the same as the above R, Z is the same as the above Z, R1 and R3 are hydrogen atoms, aryl group, an alkyl group, or a heterocyclic group), a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. can be mentioned.

The alkoxy group may further have a substituent, for example,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, and p-chlorobenzyloxy group.

The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-
Dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-[α-(3-bentadecylphenoxy)butanamide]phenoxy group, hexydecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, ■-naphthyloxy group, p-
Examples include methoxyphenoxy group.

The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. in particular,! -phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.

The acyloxy group includes, for example, an acetoxy group, an alkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include arylcarbonyloxy groups such as benzoyloxy groups.

Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group.

Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group.

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a phenethylthio group, a benzylthio group, and the like.

The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butyl Examples include phenylthio group.

Examples of the heterocyclic thio group include 1-phenyl-1,
Examples include 2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include dodecyloxythiocarbonylthio group.

For example, those represented by the general formula -N represent an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R4 and R5 are bonded. may be used to form a heterocycle. However, R4 and R6
・ cannot both be hydrogen atoms.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, alkylamino group, arylamino group, acylamino group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Examples include carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group, and halogen atom.

Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group.

The aryl group represented by R4 or R6 has preferably 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The aryl group may have a substituent, and examples of the substituent include those listed as substituents for the alkyl group represented by R4 or R6 above, and an alkyl group. Specific examples of the aryl group include phenyl group, 1-naphthyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R4 or R6 is 5 to 6
It is preferable that the ring is a membered ring, and it may be a condensed ring or have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, and 2-pyridyl group.

Examples of the sulfamoyl group represented by R4 or R6 include N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group,
Examples include N,N-diarylsulfamoyl groups, and these alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups.

Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group,
Examples include N-dodecylsulfamoyl group and N-p-tolylsulfamoyl group.

The carbamoyl group represented by R4 or R1 is,
Examples include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups can be substituted with the substituents listed above for the alkyl group and aryl group. It may have a group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-1)-cyanophenylcarbamoyl group,
N-p-tolylcarbamoyl group is mentioned.

Examples of the acyl group represented by R4 or R6 include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. It's okay. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. .

Examples of the sulfonyl group represented by R4 or R5 include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group, Examples include a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, and a p-chlorobenzenesulfonyl group.

The aryloxycarbonyl group represented by R4. or R6. may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like.

The alkoxycarbonyl group represented by R4 or R6 may have the substituents listed above for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. Can be mentioned.

The heterocycle formed by combining R4 and R6 is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity, or,
It may be a fused ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxoxazolidinyl group, 2- N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
l-pyrrolyl group, l-pyrrolidinyl group, l-pyrazolyl group, l-pyrazolidinyl group, ■-piperidinyl group, l-
Pyrrolinyl group, ■-imidazolyl group, l-imidazolinyl group, l-indolyl group, l-isoindolinyl group, 2
-isoindolyl group, 2-isoindolinyl group, ■-benzotriazolyl group, l-benzimidazolyl group, 1-
(1,2,4-1 riazolyl) group, 1-(1,2,3-
triazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1.2.3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group,
Examples include a 2-I H-pyridone group, a phthaladione group, a 2-oxo-1-piperidinyl group, and these heterocyclic groups include an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an acyl group, Sulfonyl group, alkylamino group, arylamino group, acylamino group, sulponamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imido group, nitro group, cyano group, Carboxyl group, halogen atom, etc.
7) The nitrogen-containing heterocycle formed by Z or Z. includes a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring. Examples of the substituents that may be used include those described for R above.

In addition, substituents on the heterocycle in general formula CI) and general formulas (II) to [■] described below (for example, RlR+-Ra)
but! When it has a moiety (R..., X, and Z... have the same meanings as R, X, and Z in general formula (1)), it forms a so-called screw type coupler, but is of course included in the present invention .

In addition, the ring formed by Z, Z., Z... and Zl described below may further include another ring (for example, a 5- to 7-membered cycloalkene).
may be condensed. For example, R5 and R8 in general formula (V), and R7 and R8 in general formula (VI), may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene).

What is represented by the general formula (1) below is more specifically represented by, for example, the following general formulas (II) to [■].

General formula (II) General formula (III) N -N -N General formula [■] N -N -NH General formula (V) General formula (Vl) N -N -N11 General formula [■] 18N The above general formula ( In I[) to [■], R1-R8 and X
has the same meaning as R and X above.

Also, among the general formula (1), the following general formula [
■].

General formula [■] In the formula, R+, X and Zl are Rl in general formula (1)
It is synonymous with X and Z.

Among the magenta couplers represented by the general formulas (I[) to [■], particularly preferred are those represented by the general formula (II)-7s vehicle driver button General formula CI) ~ [
Regarding the substituent on the heterocycle in [■], it is preferable that R in the general formula (I) and Ro in the general formulas [■] to [■] satisfy the following condition 1, and more preferably: This is a case where the following conditions 1 and 2 are satisfied,
Particularly preferred is the case where conditions 1.2 and 3 below are satisfied.

conditions! The root atom directly connected to the heterocycle is a carbon atom.

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

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

The most preferred substituents R and R8 on the heterocycle are those represented by the following general formula (IK).

General formula (IX) R.

R3゜-C- In the formula, R0, R, 0 and R11 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,
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 , represents a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, and Re

At least two of Rlo and R11 are not hydrogen atoms.

Moreover, two of the above Re, Rlo and R11, for example, R9
and R3゜ may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and RII may be further combined with the ring to form a bridged hydrocarbon compound residue. te (good)

The group represented by R9-R1 may have a substituent,
Specific examples of the group represented by R8 to R1I and substituents that the group may have include specific examples of the group and substituents represented by R in the aforementioned general formula (1).

Also, for example, a ring formed by combining R9 and R8゜ and R,
Specific examples of the bridged hydrocarbon compound residue formed by e to R1, and the substituents thereof that may have include cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the aforementioned general formula (1). Specific examples of bridged hydrocarbon compound residues and their substituents are listed.

Among general formulas (IX), (i) R11-
When two of R11 are alkyl groups, (ii) Rs
= Rr + For example, when one of R1 is a hydrogen atom and the other two, R9 and RIo, combine to form a cycloalkyl together with the root carbon atom, the following is true.

Furthermore, preferred among (i) is the case where two of R3 to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, cycloalkyl and their substituents include the alkyl, cycloalkyl and their substituents represented by R in the general formula (1). Specific examples of the group are listed below.

The following blanks also indicate the substituents that the ring formed by Z in general formula (1) and the ring formed by Z in general formula [■] may have, and the general formulas (If) to (V[) R3-R8 in is preferably represented by the following general formula (X).

General formula (X) -R'-5ot-R'' In the formula, R' represents alkylene, and R2 represents alkyl, cycloalkyl or aryl.

The alkylene represented by RI preferably has 2 or more carbon atoms in the linear part, more preferably 3 to 6 carbon atoms, and has 2 or more carbon atoms in the linear chain.
Regardless of branching. Moreover, this alkylene may have a substituent.

Examples of the substituent include R in the general formula CI) described above.
When is an alkyl group, the substituents that the alkyl group may have include those shown below.

Preferred substituents include phenyl.

Preferred specific examples of alkylene represented by R1 are shown below.

-CH2C1,CH,-,-CHCH,C1,-,-C
ICIl, CIl, -, -CIl, CIl, CH-CI
l, C, H, C, Il.

-CIl, CII□C11-, -C11□C111C1
12CH2-1 (112C112C112CH-.

The alkyl group represented by R2 may be a linear, monobranched group.

Specifically, methyl, ethyl, propyl, ISO''propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, 2-
Examples include hexyldecyl.

The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one, such as cyclohexyl.

The alkyl and cycloalkyl represented by R2 may have a substituent, and examples thereof include those exemplified as the substituent for R1 above.

Specific examples of the aryl represented by R1 include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R1 described above.

Moreover, when there are two or more substituents, those substituents may be the same or different.

Among the compounds represented by the general formula (1), particularly preferred are those represented by the following general formula (XI).

General formula (X[) In the formula, R and X have the same meanings as R and X in general formula CI), and R1 and R2 have the same meanings as R1°R2 in general formula (X).

Margin below C21+5 4Ili 12H25 C21+1 C2Hs Margin below C211゜ C4M.

H CHICIll art3 10H21 c+allts 04BI+ 11B15 Margin below -C, II.

C, l+5 cau+y(t) yLs C, I+,? (L) C, II? C,H- CJs QC-H1+ C+1Ls C211゜ Margin below C,1,.

C,11%C,lIself0ChCONIIICII2CIhOC)110CH,C
l12S02CH3 C2H C2H.

C,H.

C,H.

Js 0411g C.O.

C2H.

electric C1l.

Margin below C,H.

C4H.

c+111*s I2121 C,H.

C61113 Margin below l1 CM.

0C2H! 1 NHSO2CtJu C.I.

csH+t(1 ■ L CJ+t(L) Cll.

L CH.

CI, C5II++ (t1CH3 C11゜ Js C7U, U 13g HgCCH.

211s Below margin 0 (C1(a)*OC+Jts N -N N 15O N N N
Cu112sN N N C4■@C1゜l,, N -N -N
, N -N = N N □ to □N N N NH N -N -NH N N Nll N N 88 CJ! N N
M1Js C,lI.

sl+++(II N N NH N N N11 N N 88 N I'I N11
(,,l,.

HN M St N -N N N -N -H ICI The following margin also describes the synthesis of the coupler described in the Journal of the Chemical Society, Perkin 1.
of the Chemical 5oci
ety.

Perkin I) (1977), 2047~
2052, unclaimed patent 3.725,067%, JP-A-59
Synthesis was carried out with reference to No.-99437 and Japanese Patent Application Laid-open No. 58-42045.

The couplers of the invention are usually 1X1 per mole of silver halide.
It can be used in a range of 0 mol to 1 mol, preferably 1 x 10-2 mol to 8 x 10 mol.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

The following is a blank general formula [Ia] R1 Ar (wherein, Ar represents an aryl group, R1 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and R2 represents an alkyl group, an amide group, an imido group, It represents an N-alkylcarbamoyl group, an N-alkylsulfamoyl group, an alkoxycarbonyl group, an acyloxy group, a sulfonamide group, a urethane group, etc. Y represents a hydrogen atom or a group that is eliminated during the color development reaction process. , W is -NH, NHCO (N atom Gt H5 V D
> bonded to the carbon atom of M) or -N HCON H-
represents. ) These include, for example, U.S. Patent Nos. 2,600,788, 3,061,432, 3,062,653,
3,127.269, 3,311,476, 3,152,896, 3,419,391
No. 3,519,429, No. 3,555.31
No. 8, same No. 3,884,514 @, same $ 3,88
8,680, Wi 3,907,571, Wi 3,
No. 928,044, No. 3,930.861, No. 3
, No. 930,866, No. i 3,933,500, etc., JP-A-49-29639, No. 49-111
No. 631, No. 49-129538M, No. 50-1304
No. 1, No. 52-58922, No. 55-62454,
55-118034, 5B-38043M, British Patent No. 1,247,493@, Belgian Patent No. 769,116, Belgian Patent No. 792,525, West German Patent 2
, 156.111 @ 4) Each Mei 111! 11 special public service 1977-
It is described in Publication No. 60479 and the like.

Below is the margin, then the general formula [! a] Typical specific examples of magenta couplers indicated by the numbers in the middle are given below.

T CT IA -60T LA -10C1 CT LA -17CL IA -19 CT IA -21 L LA + 22 CZ LA -230 1A -25 CT IA -26 CT IA -27 CT IA -27 CT IA -28 CT IA 30 CT CT LA + 3 4 Ct Ct la -41 Ct Ct Ia -42 Ct Ia -43CL t la -45 L Ct la -48 Ia -49 1a -50 As the substance for forming a magenta dye image in the present invention, a magenta dye image forming coupler is preferable, Further, couplers represented by the general formulas [I] and [Ia] are preferred, particularly couplers represented by the general formula [I].

In order to add a substance that forms a magenta dye image to a photographic layer, it is common to use a solvent with a high boiling point.
As these high boiling point organic solvents, the following are preferred.

That is, the high boiling point organic solvent that can be preferably used in the present invention is a compound having a dielectric constant of 6.0 or less, such as esters such as 7-tal ester and phosphate ester having a dielectric constant of 6.0 or less. , organic acid amides, ketones, hydrocarbon compounds, etc. Preferably dielectric constant 6
．． Vapor pressure at 100℃ is 0.5 or less and 1.9 or more
--It is a high boiling point organic solvent below HO. Even more preferred are heptatarates or phosphoric acid esters in the high-boiling organic solvent. Furthermore, the high boiling point organic solvent is 2
It may be a mixture of more than one species.

Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C.

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula [a].

In the general formula [a], Rts and R16 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms in Rts and the group represented by Rts is 8 to 32. More preferably, the total number of carbon atoms is 1
6 to 24.

In the present invention, R+5 and R of the general formula [a ]
The alkyl group represented by ts may be linear or branched, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group. , pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. The aryl group represented by Rts and R+6 is, for example, a phenyl group, a naphthyl group, etc., and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an octadecenyl group, etc. These alkyl groups, alkenyl groups, and aryl groups may have single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, and aryloxy groups. Examples of substituents for aryl groups include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, and alkoxycarbonyl groups. .

Phosphate esters advantageously used in the present invention include those represented by the following general formula [b].

Margin below General formula [b] crane R,,0-P-OR+.

0R1° In the formula, R17, Rts and Rts each represent an alkyl group, an alkenyl group or an aryl group.

However, the total number of carbon atoms represented by R17, Rta (?J, and Rts) is 24 to 54.

The alkyl group represented by R17, Rts and Rts in the general formula [b] is, for example, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group. group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc. Aryl groups include, for example, phenyl group, naphthyl group, etc., and alkenyl groups include, for example, hexenyl group, heptenyl group, octadecenyl group. etc.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably RI7, R+a and R1° are alkyl groups, such as 2-ethyl I\xyl group, n-octyl group,
3.5.5-trimethylhexyl group, n-nonyl group, n
-decyl group, 5eC-decyl group, 5ec-dodecyl group,
[-Octyl group, etc. are mentioned.

The following are examples used in the present invention! Although typical examples of medium I are shown below, the present invention is not limited thereto.

The following margins illustrate organic solvents S-2C2Hs ■ C2Hs S''''12 C2H5 0Cs Hls (i) 0-C,H,, (n) 0-C3゜Hz+(i) ■ o-c+oHz+(n) () C+oti2+( n) S-17 S-18 These organic solvents are used in a proportion of 20 to 150% by weight based on the magenta coupler according to the present invention. Preferably, the amount is 40 to 100% by weight based on the coupler.

In addition to the magenta coupler [N, [Ia], an anti-fading agent that prevents fading of the dye image may be used, and the anti-fading agents that are preferably used are shown below.

The following is a blank general formula tAJ, where l (hydrogen atom, alkyl group, alkenyl group,
Represents an aryl group or a heterocyclic group,
(7, tt, respectively, are a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group,
The alkoxy group has 7 acylamide groups, and 1 (
4 represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group.

In addition, 1, and R2 may be ring-closed with each other to form a 5-shell or 6-shell ring, in which case I (A represents a hydroxy group or an alkoxy group. Also, 1 <, and L (4 is a closed ring). , 5
A shell hydrocarbon ring may be formed, in which case R+ may be an alkyl group, an aryl group, or a tow ring group. However, this excludes cases where 1<, is a hydrogen atom, or -], and R4 is a hydroxy group.

■Spring-stirrup flAH: j san; So, 1? , a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Among these, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-octyl group,
Straight chain or branched alkyl groups such as a jet-octyl group and a hexadecyl group can be mentioned. Also R5
Examples of the alkenyl group include allyl,
Examples include hexenyl and octenyl groups. moreover,
Examples of the aryl group for R+ include phenyl and naphthyl groups. Further, specific examples of the heterocyclic group represented by R1 include a tetrahydropyranyl group and a pyrimidyl group. Each of these groups can have a substituent, for example, an alkyl group having a substituent such as a benzyl group, an ethoxymethyl group, an aryl group having a substituent such as a methoxyphenyl group, a chlor-7enyl group,
-hydroxy-3,5-dibutyl 7enyl group and the like.

In general formula [A], R2, R1, Rs and kl
s is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group, and among these, the alkyl group, alkenyl group, and aryl group are the alkyl groups mentioned above for R1. , an alkenyl group, and an aryol group. Examples of the halogen atoms include fluorine, chlorine, and bromine. Further, specific examples of the alkoxy group include a methoxy group and an ethoxy group. Furthermore, the acylamino group is represented by R'CONI(-, where:
Ro is a furkyl group (e.g. methyl, ethyl, n-propyl, n-butyl, n-octyl, tert-octyl,
(pencil, etc.), alkenyl groups (e.g. allyl,
octenyl, oleyl, etc.), a 717-l group (eg, phenyl, methoxyphenyl, naphthyl, etc.), or a heterocyclic group (eg, pyrinol, pyrimidyl, etc.).

In addition, in the general formula [AI, R1 represents an alkyl group, a hydroxy group, an alkyl group, or an alkoxy group,
Among these, for the alkyl group and aryl group, the above R1
Specific examples include the same alkyl groups and aryl groups as shown in . The alkenyl group of tt can be the same as the alkoxy group described above for 2, R1, R5 and R6.

Examples of the ring formed by R1 and R2 together with a benzene ring by closing each other include chroman, coumaran, and methylenedioxybenzene.

Furthermore, examples of the ring formed by R3 and R4 together with a benzene ring include indane. These rings may have substituents (eg alkyl, alkoxy, aryl).

In addition, a spiro compound may be formed by using a spiro atom as an atom in the ring formed by R, and R2, or R3 and R9, or a bis compound may be formed by using R2, R4, etc. as a linking group. Good too.

Among the phenolic compounds or 7enyl-ester compounds represented by the general formula [AI], preferred are R
o-group (R is an alkyl group, alkenyl group, aryl group,
or represents a heterocyclic group. ), and is particularly preferably represented by the following general formula [A-1].

General formula [A-jl In the formula, R is an alkyl group (e.g., methyl, ethyl, propyl, n-octyl, tert-octyl, hensyl, hexadecyl), an alkenyl group (e.g., allyl, octenyl, oleyl), an aryl group (e.g., 7enyl, naphthyl) or a heterocyclic group (eg, tetrahydropyranyl, pyrimidyl). R3 and R10 each represent a hydrogen atom, a halogen atom, (e.g., fluorine, chlorine, bromine), an alkyl group (e.g., methyl, ethyl, n-butyl, pencil), an alkoxy group (e.g., allyl, hexenyl, octenyl), or alkoxy Group (
For example, methoxy, ethoxy, benzyloxy),
R's is a hydrogen atom, an alkyl group (e.g. methyl, ethyl,
11-butyl, benzyl), alkenyl group (Example L, 2
-7'lopenyl, hexenyl, octenyl), or aryl groups (e.g. phenyl, methoxyphenyl, chlorphenyl, naphthyl) eat.

The compound represented by the general formula IAI is disclosed in U.S. Patent No. 3.
No. 935.016, No. 3.982,944, No. 4
．． No. 254.216, JP-A No. 55-21004, No. 5
No. 4-145530, British Patent Publication No. 2,077.455
No. 2.062, No. 888, U.S. Patent No. 3,764
, 337, No. 3.43230(), No. 3,574
, No. 627, No. 3,573,050, Japanese Unexamined Patent Publication No. 1973-
No. 152225, No. 53-20327, No. 53-17
No. 729, No. 55-6321, British Patent No. L347t
No. 558, Publication No. 2.066.975, Special Publication No. 1973-
No. 12337, No. 48-31625, U.S. Patent No. 3,
700,455 and the like.

The amount of the compound represented by the general formula [A] used is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler.

Below is a representative of the compound represented by the general formula [AI^h
@ ikjM i Mayuzhi type (1) ORI type (2) type (3) type (4) type (5) type (6) type (7) ・ type (4) below margin type (5) below Margin A-7 The following margin is the general formula [B] (in the formula, R3 and R1 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group) , 7-ruami 7 groups, acyloxy group,
sulfonamide group, cycloalkyl or alkoxycarbonyl group, R2 is a hydrogen atom, an alkyl group,
alkenyl group, 71)-l group, acyl group, cycloalkyl group or heterocyclic group, R1 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group,
Aryloxy group, acyl group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, furkyl group, alkenyl group, alkoxy group,
Examples include an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylami 7 group, a 7 syloxy group, a carbamoyl group, a sulfonamide group, and a sul 77 moyl group.

Furthermore, R2 and R1 may be ring-closed with each other to form a 5-shell or 6-shell ring. Examples of the ring formed with a benzene ring when R2 and R1 are closed include a 1t chroman ring and a methylenedioxybenzene ring. .

Y represents the atomic group necessary to form a chroman or coumaran ring.

The chroman or coumaran ring is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
Alkenyloxy group, hydroxy group, aryl group, 71
It may be substituted with a 7-ruoxy group or a hetero ring, and may further form a spiro ring.

Among the compounds represented by general formula [B], compounds particularly useful in the present invention are general formulas [B-1], [B-23, [B
-3], [B-4], and [B-5].

General formula [B-1] General formula [B-2] 1 General formula [B-3] General formula [B-4] General formula [B-5] 8 General formula [B-1], [B- 2], [B-3], [B
-4] and [B-5], R3, R2, R1 and VF6 have the same meanings as in the general formula [Bl], and R5, R6, R7, R8, R1 and R3° are hydrogen atoms and halogen atoms. , an alkyl group, an alkoxy group, a roxy group, a fluorenyl group, an alkene group, a nyloxy group, an aryl group, an aryloxy group, or a heterocyclic group.

Furthermore, R6 and R, R6 and R7, R2 and R, R8 and R
3, VH2, and R7° may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

The general formula [B-1], [13-2], [[3-3]
, [B-4] and c/[B-51, R1 and R4 are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cycloalkyl groups, R6, R,, R7, R1
, R5 to R1° are hydrogen atoms, alkyl groups, or cycloalkyl groups, which are particularly useful.

The compound represented by the general formula [Bl is tetrahedron (Te
trahedron), 1970. vo126,474
3-4751, Journal of the Chemical Society of Japan, 1972. No.10.
pp. 0987-1990, Chemical (chem, Lett
, R19) 2(4) pp. 315-316, Japanese Patent Application Publication No. 1986-
Represents and includes a compound described in No. 139383,
and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [Bl] is 5 to 300% relative to the magenta coupler of the emulsion of the present invention.
Mol% preferably, more preferably 10 to 200 mol%
It is.

Typical specific examples of these compounds are shown below.

The following is a blank general formula [C] R1 to 2 General formula [Dl In the formula, R8 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, Acyl group, acylamino group, acyloxy group, sulfonamide group or alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents, such as a halogen atom, an alkyl group, an alkenyl group,
Examples include an alkoxy group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamide group, a carbamoyl group, a sulfonamide group, and a sulfonamide group.

Y represents the atomic group necessary to form a dichroman or nocoumaran ring with the benzene ring.

Chroman or coumaran ring has 0 halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkenyl group
, alkenyloxy group, hydroxy group, aryl group, 7
It may be substituted with a lyloxy group or a heterocyclic group, and may further form a spiro ring.

Among the compounds represented by the general formulas [C] and [Dl, the compounds particularly useful in the present invention are the compounds represented by the general formulas [C-1] and [C-2
], [D-1] and [D-2].

General formula [C-1] General formula [C-23 81 General formula [D-1] General formula [D-2] General formula [C-1], [C-2], [D-1] and [ D
R1 and R2 in -23 are the general formula [C] se7 r7rnl ke 1 + shigu 1, sound spitting or kakuko - R1, R
1, R9, R, R, and R6 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a heptadoxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or a heterocyclic group. Furthermore, R1 and R4, R1 and R1, R6 and R6, R8 and R2, and R7
and R1 may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

In the general formula [C-1], [C-2], -[D-1] and [D-2], R1 and R2 are a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or Particularly useful are compounds in which the cycloalkyl groups R1, R1, R2, R6, R1 and R6 are hydrogen atoms, alkyl groups, or cycloalkyl groups.

Compounds represented by the general formula [CI, [D] are described in the Journal of the Chemical Society of Japan (J, Chew, Soc, part C) 1
968. (14L, pp. 1937-18, Journal of the Kaisei Kagaku Kyokai 1970.28 (1), pp. 60-65, Tetrahedron Letters 1
973, (29), pages 2707-2710, and can be synthesized according to the methods described therein.

The usage amount of the compound represented by the general formula [CI, [D] is 5 to 30% relative to the magenta coupler according to the present invention.
It is preferably 0 mol%, more preferably 10 to 200 mol%.

Specific representative examples of these compounds are shown below.

The following is a general formula (E) in which R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group; group, aryl group, aryloxy group,
It represents an acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group.

R2 and R4 represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group, a sulfonamide group, a cycloalkyl group, or an alfkyl dicarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups,
7 silami 7 groups, carbamoyl group, sulfone 7 mido group,
Examples include a sulfyl moyl group.

Further, R1 and R2 may be ring-closed with each other to form a 5-shell or 6-shell ring.

At that time, R' and R4 are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, hydroxy groups, aryl groups, aryloxy groups,
It represents an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, or an alkoxycarbonyl group.

Y depletes the atomic group necessary to form a chroman or coumaran ring.

The chroman or coumaran ring is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
It may be substituted with an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group, and may further form a spiro ring.

Among the compounds represented by the general formula (E), the compound particularly useful in the present invention is the general formula (E-1).

(E-23, (E-3), (E-4) and (E-5)
It is included in the compound represented by.

General formula (E-1) OR+ General formula (E-2) OR+ General formula (E-3) K"K'"OR' General formula (E-4) G General formula (E-53 General formula (E-1) ) to (E-5), R', R2,
R3 and R4 have the same meanings as in the above general formula [E), and R', R', R', RI, R'' and RIG
is a hydrogen atom, a halogen atom, a furkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group,
Represents an aryl group, an aryloxy group or a heterocyclic group. Furthermore, R5 and R'%R6 and Rγ, R7 and R'', R
I, R'tJ, I/R'' and R10 may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with a furkyl group.

In the general formulas (E-1) to (E-5), RI,
l'(2, R3 and R4 are hydrogen atoms, alkyl groups,
or a cycloalkyl group, the above general formula (E-51, R3 up to R4 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a cycloalkyl group, and the above general formulas (E-1) to (E-5) In, R', R'
, 11γ, Rs, l(s and RIO are hydrogen atoms, alkyl groups, or cycloalkyl groups) are particularly useful.

The compound represented by the general formula [E] is tetrahedron (
Tetrahedron Letters) 1965
．． (8), pp. 457-460 Journal of the Chemical Society of Japan (J, C
he (Sac, part C) 1966° (22)
, pp. 2013-2016, (Zh, Org, nih
im) 19fuO, (a).

Compounds described on pages 1230 to 1237,
and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [E-1] is 5 to 30% relative to the magenta coupler of the water QBJ1.
It is preferably 0 mol%, more preferably 10 to 200 mol%.

Specific representative examples of these compounds are shown below. The blank formula CI'') 11 represents a heterocyclic group such as a hydrogen atom, an alkyl group, an alkynylyl group, an acyl group, or a cycloalkyl group,
R2 is a hydrogen atom, a halo atom, an alkyl group, an alkenyl group,
An arylaryloxy group, a 7-syl group, an acylaminosyloxy group, a sulfonamide group, a dichloro group, or an alphkidicarbonyl group.

A hydrogen atom, a halogen atom, an alkyl group, a nyl group, a 7-aryl group, an acyl group, an asyl group, a sulfonamide group, and a cycloalkyl group also refer to an alkoxycarbonyl group.

Hydrogen atom, halogen atom, alkyl group, nyl group, alkoxy group, alkenyloxydroxy group, aryl group,
Aryloxy group, acyl group, acylamide group, acyloxy group, sulfonamide group, or alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, alkyl groups, alkenyl groups, alkoxy groups,
Aryl group, aryloxy group, hydroxy group, alkoxycarbonyl group, carbonyl group,
Acylamino group, carbamoyl group, sulfone 7-mido group,
Examples include sulfamoyl group. .

Also, l< and R2 may be ring-closed with each other to form a 5-shell or 6H ring. In that case, 1 (3 and 1 (4) are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, hydroxy groups, aryl groups, aryloxy groups, acyl groups, acylamino groups, acyloxy groups, sulfonamide groups. , or an alkoxycarbonyl group.

Y represents the atomic group necessary to form a chroman or coumaran ring.

The chroman or coumaran ring is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
It may be substituted with an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group, and may further form a spiro ring.

Among the compounds represented by the general formula [F], compounds particularly useful in the present invention are those represented by the general formulas [1''-14, [['-2J, [F
-31, [F-4] and [F-5].

Below are the blanks General formula (F 1) General formula [F-23 General formula CF-3] General formula [F-4] General formula (F-5) General formula [1・”-1] and [F-5] l<
,, R2, R, and R have the same meaning as in the general formula [F], and R3, R6, R2, R8, R5
and R1° is a hydrogen atom, a halogen atom, an alkyl group,
It includes an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, a 7-aryl group, a 7-aryloxy group, or a heterocyclic group.

Furthermore, R9 and R6, R6 and R7, R7 and R6, R8 and R
4 and R3 and R+o may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

Further, in [F-3], [F'-4] and [F-.5], two R8-[o's may be the same or different.

The general formula [F-1], [F-2], [F-31,
jF -4] and [F-5], [(1,112
, and R are hydrogen atoms, alkyl groups, cycloalkyl groups, 1 is hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups, or cycloalkyl groups, and R9 and R6
, 12, R, , R9t-t Compounds in which o is a hydrogen atom, an alkyl group, or a cycloalkyl group are particularly useful.

The compound represented by the general formula [F] is tetrahedron (
Tetrahedron Letters) 1970
．． Vol 26, pages 4743-4751, Journal of the Chemical Society of Japan 1972. No. 10.1987-1990,
Synthesis 19f5. V
ol 6゜392-393, (Bul Soc,
Chin, Roe1g) 1975. V
o184(7), pages 747-759, and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [F] used is 5 to 300 mol% based on the magenta coupler according to the present invention.
is preferable, and more preferably 10 to 200 mol%.

Specific representative examples of the compound represented by the general formula [F] are shown below.

In the following margin general formula (G) R
Represents an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

The groups listed above may each be substituted with other substituents. Examples of substituents include alkyl groups, alkenyl groups,
Examples include an alkoxy group, an aryl group, an aryloxy group, a hydroxy group, an alkoxy group, an aryloxycarbonyl group, an acylamide group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.

Further, R2 and R3 may be ring-closed with each other to form a five-shell or six-shell hydrocarbon ring. These 5- or 6-shell hydrocarbon rings are halogen atoms, alkyl groups, dichlorofurkyl groups,
It may be substituted with an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, or the like.

Y represents an atomic group necessary to form an indane ring, an indane ring is a halogen atom, an alkyl group, an alkenyl group,
It may be substituted with an alkoxy group, a cycloalkyl group, a hydroxy group, an aryl group, a 7-aryloxy group, a heterocyclic group, or the like, and may further form a spiro ring.

Among the compounds represented by the general formula CG), compounds particularly useful in the present invention are included in the compounds represented by the general formulas (G-1) to (G-3).

Below, the margin General formula (G-1) 1 General formula (G-23 General formula (G-3) tz' in General formulas (G-1) to (G-3),
R2 and R3 have the same meaning as in general formula [G], and R', R', R', R? , R' and R9 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group,
Represents an alkenyl group, hydroxy group, aryl group, aryloxy group or heterocyclic group. (4 and R5, R5 and R6, R6 and R1, R) and [(8 and R'' and R' may be ring-closed with each other to form a hydrocarbon ring, and the hydrocarbon ring is an alkyl group. May be replaced.

In the general formulas (G-1) to (G-3), R1 and I3 are a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a dichlorofurkyl group, and R2 is a hydrogen atom, an alkyl group, a hydroxy group, or a cycloalkyl group. group, R',
Particularly useful are compounds in which R5, R', R', R' and R9 are hydrogen atoms, alkyl groups or cycloalkyl groups.

The amount of the compound represented by the general formula [G] is preferably 5 to 300 mol% relative to the magenta coupler,
More preferably, it is 10 to 200 mol%.

Typical sandwich examples of the compound represented by the general formula [G] are shown below.

The following is a blank general formula [H] R1 where R1 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a 7-syl group,
Acylamino group, 7-syloxy group, sulfonamide group,
Represents a cycloalkyl group or an alkoxycarbonyl group.

R3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, a 7-aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group .

The groups listed above may each be substituted with other substituents, such as alkyl groups, alkenyl groups, alkoxy groups,
Examples include aryl group, aryloxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, 7syl7mi7 group, carbamoyl group, sulfonamide group, and sulfamoyl group.

In addition, RI and R2 and R2 and 11' are ring-closed with each other, and 5
An N or hexashell hydrocarbon ring may be formed, and the hydrocarbon ring may include a halogen atom, a furkyl group, a cycloalkyl group,
It may be substituted with an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, or the like.

Y represents an atomic group necessary to form a bean ring, and the bean ring may be substituted with a substituent capable of substituting the hydrocarbon ring, and may further form a spiro ring.

Among the compounds represented by the general formula (11), compounds particularly useful in the present invention are included in the compounds represented by the general formulas (H-1) to (II-2).

General formula (H-2) General formula (11-3) General formula (1-1-1) -(11-3)llNtrul(
', 1<2 and 1-3 are synonymous with those in the general formula [Ill, R4, R5, group, hydroxy group, alkenyl group, aryl group, aryloxy group, or heterocyclic group. Also, R' and l('', R5 and R6, R' and R', [(7
and I? M and R'' and R9 may be ring-closed with each other to form a hydrocarbon ring, and the hydrocarbon ring may be further substituted with an alkyl group.

In the general formulas (II-1) to (II-3), R1
and 1 (2 is each a hydrogen atom, an alkyl group or a cycloalkyl group, R3 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, R', 1
Particularly useful are compounds in which R', R', R7, R' and R' are each a hydrogen atom, an alkyl group or a cycloalkyl group.

A method for synthesizing the compound represented by the general formula [trl is known, and is described in US Pat. No. 3,057,929, Chem.

Ber, 1972.95(5), '1673-1674
Page, Cbemist-ry Letters, 1
980*739-742 Follow the truth! ! Can be built.

It is preferably 5 to 300 mol%, more preferably 1% to the magenta coupler compound represented by the general formula [H].
It is 0 to 200 mol%.

Specific representative examples represented by the general formula [Ill] are shown below.

The following is a blank general formula (J) %+ [In the formula, R1 represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y is a non-containing compound necessary to form a 5- to 7-R polycyclic ring together with a nitrogen atom. Represents a metal atom group, provided that when there are two or more heteroatoms among the nonmetallic atoms containing nitrogen atoms forming the heterocycle, at least two heteroatoms are non-adjacent heteroatoms. ] Examples of the aliphatic group represented by R include a saturated alkyl group that may have a substituent and an unsaturated alkyl group that may have a substituent. Examples of the saturated alkyl group include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc.
Examples of the unsaturated alkyl group include ethynyl group and propenyl group.

The cycloalkyl group represented by R1 is a 5- to 7-shell cycloalkyl group that may have a substituent, such as a cyclopentyl group, a cyclohexyl group, and the like.

The aryl group represented by R1 represents a phenyl group or a naphthyl group, each of which may have a substituent.

Substituents for the aliphatic group, dichlorofurkyl group, and aryl group represented by R' include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, and acylamine groups.
group, sulfamoyl group, sulfonamide group, carbonyloxy group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, heterocyclic group, furkylthio group, arylthio group, etc., and these substituents further have a substituent. Good too.

In the general formula (J), Y together with the nitrogen atom is 5 to 7
jl represents a group of nonmetallic atoms necessary to form a bicyclic ring, and at least two of the nonmetallic atomic groups containing nitrogen atoms forming the bicyclic ring must be heteroatoms, and , the at least two heteroatoms must not be adjacent to each other. In the heterocycle of the compound represented by the general formula (J), it is not preferable if all the heteroatoms are adjacent to each other because the function as a magenta dye image stabilizer cannot be exhibited.

The 5- to 7-shell compound ring of the compound represented by the general formula (J) may have a substituent, and examples of the substituent include an alkyl group, a 7-aryl group, an acyl group, and a carbamoyl group. , an alkoxycarbonyl group, a sulfonyl group, a sulfamoyl group, etc., and may further have a substituent. Also, 5~
Although the heterocycle of ring 714 may be saturated, a saturated heterocycle is preferable. Further, a benzene ring or the like may be fused to the heterocycle, or a spiro ring may be formed.

The amount of the compound represented by the general formula (J) of the present invention to be used is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the magenta coupler represented by the general formula [1] of the present invention. It is 200 mol%.

A representative jl integral example represented by the general formula [J] is shown below.

The following margin J-63 J-64 /'-N C,4H,q-N,,,No-6low J-F O ■ ■ ■ I C12H, da In the compound represented by the above general formula (J) Piperazine compounds and homopiperazine compounds are particularly preferred.
More preferably, the following general formula (J-1) or (J-
This is a compound represented by 2).

General Formula (J-1) General Formula (J-2) In the formula, R2 and 1/R3 each represent a hydrogen atom, an alkyl group, or a 7-aryl group. However, R2 and R3 do not become hydrogen at the same time. R4 to R'3 each represent a hydrogen atom, an alkyl group or an aryl group.

In the general formulas (J-13 and (J-2)), R2 and R3 each represent a hydrogen atom, an alkyl group, or an aryl group, and the alkyl group represented by R2 or R3 includes, for example, a methyl group, an ethyl group, group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group,
Examples include octadecyl group. Aryl groups represented by R2 or R3 include phenyl groups, etc.
The alkyl group and aryl group represented by R2 or R3 may have a substituent, and examples of the substituent include a halogen atom,
Examples include a furkyl group, an aryl group, an alkoxy group, an aryloxy group, and a heterocyclic group.

The total number of carbon atoms in R2 and R3 (including substituents) is 6 to
40 is preferred.

In the general formula (J-1) or (J-2), R4
~R'' each represents a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by R4 to I?13 include a methyl group and an ethyl group.

Examples of the aryl group represented by R4 to R'' include a phenyl group.

Specific examples of the compound represented by the general formula (J-1) or (J-23) include the above-mentioned exemplary piperazine compounds (J-
1) to (J-30) and exemplary homopiperazine compounds (
J-51) to (J-62).

Next, a synthesis example of a typical magenta dye image stabilizer of the present invention represented by the general formula (J) will be shown.

Synthesis Example-1 (Synthesis of Compound J-2) Piveranone 9. 15 g of anhydrous potassium carbonate was added to 100 ml of acetone in which 55 g of Og and myristyl bromide were dissolved, and the mixture was boiled and refluxed for 10 hours to react.

After the reaction, the reaction solution was poured into 50 (b+1) water and extracted with 500 ml of ethyl acetate. The ethyl acetate layer was dried over magnesium sulfate, and the ethyl acetate was distilled off to obtain the desired product as white crystals. Recrystallization was performed with acetone 300111ffi to obtain 34 g of white scaly crystals (yield: 0%).

Melting point: 55-58°C Synthesis Example-2 (Synthesis of Compound J-34) 18 g of 4-morphora/aniline was dissolved in 100 m of ethyl acetate.
After dissolving the mixture in 1 liter of water, acetic anhydride was added little by little while stirring and keeping the reaction solution at 20'C. After adding acetic anhydride, cooling with water, filtering off the precipitated crystals, and recrystallizing with ethyl acetate, 16.5 g of white powdery crystals (yield 75%) were obtained.
I got it.

Melting point: 207-210°C General formula (K) In the formula, Rl represents an IJti aliphatic group, a cycloalkyl group, or an aliphatic group, and Y forms a polycyclic ring of 5 to 7 shell rings together with the nitrogen atom. represents a simple bond or a divalent hydrocarbon group necessary for R2+RkotRZR5, Ra, R'
C, Sofi f represents hydrogen, hydrogen, Jiff aliphatic group, cycloalkyl group, or aryl group. However, [(2 and R'' and R3 and 16 may be bonded to each other to form a simple bond to form an unsaturated 5- to 7-shell heterocycle together with the nitrogen atom and Y. When the bond is a river,
R5 and R7 may combine with each other to form a simple bond, and together with the nitrogen atom and Y, form an unsaturated pentagonal bicyclic ring. In addition, when Y is not a simple bond, 1 forms an unsaturated bond with 5 and Y, R' and Y, or Y itself to form an unsaturated 6-shell or 7-shell heterocycle with the nitrogen atom and Y. You may.

Examples of the aliphatic group represented by R''r include saturated alkyl groups which may have a substituent and unsaturated alkyl groups which may have a substituent. Examples of the saturated furkyl group include methyl Examples of the unsaturated alkyl group include ethynyl group, propenyl group, and the like.

The cycloalkyl group represented by R1 is a 5- to 7-shell cycloalkyl group which may have a substituent, and examples thereof include a schifbentyl group and a cyclohexyl group.

The aryl group represented by R' represents a phenyl group or a naphthyl group which may have a substituent.

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R1 include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, and acylamine groups.
group, sulfamoyl group, sulfonamide group, carbonyloxy group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, heterocyclic group, alkylthio group, arylthio group, etc., and these substituents further have a substituent. Good too.

In the general formula (K), Y together with the nitrogen atom is 5 to 7
It represents a simple bond or a divalent hydrocarbon group necessary to form the heterocycle of the shell ring, but when Y is a simple bond, R5 and R7 further combine with each other to form a simple bond. When Y is a divalent monovalent hydrogen group, that is, when it is a methylene group, R'- and Y or R7 and Y may form an unsaturated five-shell heterocycle. A saturated bond may be formed to form an unsaturated six-shell ring, and in the case of an ethylene group, an unsaturated bond may be formed between R5, Y%R7, and Y or Y itself. A saturated heptagonal heterocycle may also be formed. Furthermore, the divalent hydrocarbon group represented by Y″C′ may have a substituent (this substituent includes an alkyl group, a carbamoyl group, an alkyloxycarbonyl group, an acylamide group, a sulfonamide group, Examples include a sulfamoyl group, an aryl group, and a heterocyclic group.

In the general formula (K), R21R'tR41R'I
R6 and R7 each represent a hydrogen atom, an aliphatic group, a cycloalkyl group, or an aryl group, and the aliphatic group represented by R2-R7 includes a saturated alkyl group that may have a substituent and a substituent. Examples include unsaturated furkyl groups which may have . Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethynyl group, propenyl group, etc. It will be done.

The cycloalkyl group represented by R2 to R' is a 5- to 7-shell cycloalkyl group which may have a substituent,
Examples include cyclopentyl group and cyclohexyl group.

Examples of the aryl group represented by R2-R7 include a phenyl group and a naphthyl group which may have a substituent.

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R2 to R7 above include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, acylami 7 groups, sulf 7 moyl groups, and sulfone 7 groups. mido group,
Examples include carbonyloxy group, furkylsulfonyl group, arylsulfonyl group, humanmixy group, heterocyclic group, and alkylthio group.

It is preferable that the compound represented by the general formula (K) has a saturated ring at a' of 5 to 7 shells, rather than an unsaturated one.

The amount of the compound represented by the general formula (K) below is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the magenta coupler represented by the general formula (1) of the present invention. It is 200 mol%.

Representative specific examples of the compound represented by the general formula (K) are shown below.

In the margins below, -34 -35 -36 -37 -38 -39 -40 -41 Next, typical synthesis examples of the compound represented by the general formula (K) are shown.

Synthesis Example 1 (Synthesis of Compound -14) Anhydrous potassium carbonate 6.0 g was dissolved in 60 g of acetone in which 9.0 g of piperazine and 28 g of myristyl bromide were dissolved.
0 g was added, and the mixture was boiled and refluxed for 20 hours to react.

After the reaction, the reaction solution was poured into 300111I water,
Extracted with 300% of ethyl acetate. After drying the ethyl acetate layer over magnesium sulfate, the ethyl acetate was distilled off to obtain the desired product as white crystals. Recrystallization was performed with 100 mQ of acetone to obtain 12 g of white flaky crystals (yield: 43%).

Melting point: 175-180°C A UV absorber may be contained in the photographic layer containing the coupler of the present invention or in a photographic layer on a side farther from the support as viewed from the layer. Generally, the coating amount is 2-3 QI Q /1
000■2 can be used, especially from 3 to 20s a
It can be preferably used with a yoke of /100cc.

In the present invention, compounds represented by the following general formula [0] are particularly preferred.

General formula [0] In the above general formula [0], R+a, R17 and R1
8 each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group, or a hydroxyl group.

Examples of the halogen atom represented by R+s, Rt7, and R18 include a fluorine atom, a chlorine atom, a bromine atom, and the like, with a chlorine atom being particularly preferred.

an alkyl group represented by R+s, R+7 and R+a,
The alkoxy group preferably has 1 to 20 carbon atoms, and the alkenyl group preferably has 2 to 20 carbon atoms, and may be linear or branched.

Typical specific examples of the compound represented by the general formula (C) are shown below in the margins.

c4i-tg(t) 4M951 C1HII The dye image-forming substances included in the above-mentioned second group are known as so-called DDR couplers, and are generally combined with oxidized products of aromatic primary amine color developers. It is a compound that releases a diffusible dye or its precursor under alkaline conditions as a result of a coupling reaction.

Examples of this DDR coupler include a tI41 type DDR coupler which has a diffusible dye or its precursor moiety as a substituent that is released during the coupling reaction at the so-called active site of a non-diffusible coupler, and a diffusible coupler. The second type of DDR coupler has a ballast group at the so-called active site as a ms-binding group during the coupling reaction, and a phenol-based, α-naphthol-based, aniline-based or α-naphthylamine-based non-diffusible coupler. A diffusible dye or its precursor is bonded to a position adjacent to the active site via an amide bond (for example, a -NH8O2- bond, in which a nitrogen atom is bonded to a position adjacent to the active site). Three types of DDR couplers can be mentioned.

Specific examples of the above-mentioned DDR couplers include, for example,
Publication No. 1230324, Japanese Patent Publication No. 15471/1983,
U.S. Patent No. 3,227,550%, U.S. Patent No. 3,443,9
40@, same No. 3.751,406, same No. 3,880,
No. 658, No. 3,765,886, British Patent No. 90
No. 4,364 and No. 904,365, No. 1,03
It is described in No. 8,331, etc.

The dye image-forming substances included in the third group mentioned above are known as so-called DRR compounds, and the oxidized product of the DRR compound produced by a redox reaction is cleaved under alkaline conditions to form a diffusible dye or its precursor. Typical examples include those that release DRR compounds, or those that release diffusible dyes or their precursors through an intramolecular ring-closing reaction of an oxidized product of a DRR compound generated by a redox reaction.

Specific examples of DRR compounds include, for example, U.S. Patent No. 3.725.
, No. 062, No. 3,698,897, No. 3.72
8.113@, same No. 3,928,312, same No. 3,9
No. 93,638, No. 3,932,380, No. 3,
932,381@, same No. 3,931.144, same No. 3
, No. 929,760, No. 3,942,987, No. 3,443,943, No. 3,443,939, No. 3.443.940, No. 3,751,406 and French Patent No. 2,284,140, U.S. Patent Publication No. 351,673, Research Disclosure No. 13024 (1975), No. 15157 (
1976), JP-A-52-882γ, JP-A No. 51-10
No. 4343, No. 51-113624, No. 51-109
No. 928 and No. 52-7727.

Additionally, other dye image-forming materials include, for example, U.S. Pat.
So-called dye developers as described in the specifications of the above patents, compounds having a quinonoid nucleus as described in JP-A-56-184342, and other US Pat. No. 4,13
No. 9.379, No. 4,139,389, Special Publication No. 1979
-379, JP-A No. 51-63618, JP-A No. 56-14
Examples include compounds described in No. 2530 and the like, and azo dyes used in silver dye bleaching methods.

The compound for preparing the treatment liquid according to the present invention (hereinafter referred to as the compound according to the present invention) may be either an inorganic compound or an organic compound as long as it satisfies the specific optical rotation specified in the present invention. . Further, any of acids, bases, and salts can be used, but salts are preferred. Preferably, the salt is a salt consisting of an anion such as chloride ion, acetate ion, oxalate ion, bromide ion, sulfonate ion, benzoate ion, etc. and a cation such as lithium ion, sodium ion, potassium ion, ammonium ion, calcium ion, etc. However, salts formed from an anion selected from chloride and bromide ions and a cation selected from lithium, sodium and potassium ions are particularly preferred.

Furthermore, the specific conductivity of a 5 weight percent aqueous solution of the compound according to the present invention is 0.03 (Q-1·cyi-
' ) IJ, the above compound is preferred.

Specific examples of the compounds according to the present invention are listed below, but the invention is not limited thereto.

(X) Inorganic compound X-1 Lithium chloride X-2 Lithium bromide X-3 Lithium nitrate X-4 Sodium chloride X-5 Sodium bromide 9 Potassium nitrate x-10 Ammonium chloride X-11 Calcium chloride X-12 Calcium bromide x-13 Calcium nitrate X-14 Ferric chloride X-15 Barium chloride Sodium hydrogen talate Y-27 Potassium hydrogen talate Y-3 Sodium naphthalene sulfonate Y-4 Sodium benzoate In the stabilization method of the present invention, the concentration of the compound according to the present invention is [α]1' of standard gelatin - Any gap can be used as long as it is 150 or more, but it is preferably 0.1 to 50 weight percent, especially 0.5! IM percent to 20 weight percent is preferred.

The composition of the irises treatment liquid according to the present invention may be any composition as long as the treatment liquid contains at least the compound according to the present invention and the specific light application degree of standard gelatin is 1150 or more. can. For example, JP-A-57-8542
No. 57-58143, No. 57-97530, J
ilW No. 57-132146, No. 58-18831
It is optional to use treatment liquid stabilizers such as metal sequestering agents, anti-porous agents, and anti-settling agents described in Japanese Patent No. 5g-14834, No. 58-105145, and No. 58-134636. It is.

Further, the processing liquid according to the present invention may be used in any process as long as a magenta dye image is formed in all processing steps, but it is preferably used in the steps after the fixing step, and particularly preferably in the final bath.

Further, I)H of the treatment liquid according to the present invention can be used at any spacing, but generally EI H2.0 to 12.0 is used.
0 is preferred, and pH 2.5 to 9.0 is particularly preferred.

The processing temperature using the processing liquid according to the present invention is 0°C to 60°C.
, preferably in the range C of 10°C to 50°C.

The treatment time using the treatment liquid according to the present invention may be any time, but is preferably 5 seconds to 10 minutes, and more preferably 1 minute.
A time of 0 seconds to 5 minutes is preferable from the viewpoint of rapid processing.

Photographic products to which the dye image stabilization method of the present invention can be applied are preferably those using gelatin as a binder (or protective colloid), but in addition to gelatin, gelatin derivatives and grafts of gelatin and other polymers are preferred. It is also possible to use a mixture of hydrophilic colloids such as polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic molecular substances. The amount of these hydrophilic binders is generally 10 to 5001 (+/100 cm
2, but 30~30010/100CI"
It is preferable that the total amount of hydrophilic binder in all the layers on the far side from the support, including the magenta color patch-containing layer, is 2010/1000 or more.

In particular, the total amount of gelatin coated in all the photographic layers, including the magenta dye-containing layer, on the far side when viewed from the support is 201 (J
/100ca+” or more is preferable.

The following margins The layer structure of the silver halide photographic light-sensitive material used as a photographic product in the present invention can have any number of layers and any order of layers, but it is preferable that on the support: ■ silver halide emulsion layer containing yellow coupler, ■ silver halide emulsion layer containing magenta coupler. A silver halide emulsion layer and a cyan coupler-containing silver halide emulsion layer are coated from the support side in the order of ■-■-■. It is preferable to provide a non-photosensitive layer on the side further away from ■, and to contain an ultraviolet absorber in the intermediate layer between said ■ and ■ and the non-photosensitive layer adjacent to ■. When containing an ultraviolet absorber, it is preferable to further coat a protective layer adjacent to the layer.

The silver halide photographic light-sensitive material used as a photographic product in the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc., but especially when applied to color photographic paper for direct viewing. The effects of the present invention are effectively exhibited.

This color photographic paper and other silver halide photographic materials may be monochromatic or multicolor. In the case of multicolor silver halide color photographic materials, in order to perform subtractive color reproduction, silver halide emulsion layers containing magenta, yellow, and cyan couplers as photographic couplers and non-silver halide emulsion layers are usually used. Although the photosensitive layer has a structure in which the photosensitive layer is laminated on the support in an appropriate number and order of layers, the number and order of layers may be changed as appropriate depending on the important performance and the purpose of use.

Silver halide emulsions used in silver halide photographic materials include silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used can be used.

The silver halide grains used in the silver halide emulsion may be obtained by any one of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and trowel ions to the E
It may be produced by controlling and sequentially adding IH and 9AQ simultaneously. After growth, the halogen composition of the particles may be changed using the convergence method.

By using a silver halide solvent as necessary during the production of a silver halide emulsion, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled.

Silver halide grains used in silver halide emulsions are produced by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Metal ions can be added to the inside of the particles and/or on the surface of the particles using complex salts, etc., and by placing them in an appropriate reducing atmosphere, reduction can be increased inside the particles and/or on the surface of the particles. It can give you a feeling of emotion.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left as they are contained. When removing the salts, it can be carried out based on the method described in Research Disclosure 11643@.

The silver halide grains used in the silver halide emulsion may consist of uniform layers inside and on the surface, or may consist of uneven layers.

The silver halide grains used in the silver halide emulsion 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 may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, any ratio of the (100) plane to the (1113 plane) can be used. Also, particles having a composite form of these crystal forms may be used, or particles of various crystal forms may be mixed.

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

The silver halide emulsion is chemically sensitized by conventional methods. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing elements. 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.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, a silver halide emulsion is applied during and/or at the end of chemical ripening and/or after the end of chemical ripening for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable. By now, compounds known in the photographic industry as anticapri agents or stabilizers can be added.

The photographic emulsion layer and other hydrophilic colloid layers of silver halide photographic light-sensitive materials are formed into a W1 film by using alone or in combination with a hardening agent that frames binder (or protective colloid) molecules and increases 111 strength. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

Silver halide emulsion layer and/or silver halide photographic material
Alternatively, a plasticizer can be added for the purpose of increasing the flexibility of the hydrophilic colloid layer.

The photographic emulsion layer or other hydrophilic colloid layer of a silver halide photographic light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

In the emulsion layer of a silver halide color photographic light-sensitive material, an aromatic primary amine developer (for example, p
A dye-forming coupler is used that forms a dye through a coupling reaction with an oxidized product of (phenylenediamine derivative, aminophenol derivative, etc.). The dye-forming couplers are typically selected to form a dye for each emulsion layer that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming dye forming 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 photographic materials may be produced using different combinations from the above.

Typical yellow dye image-forming couplers are acylacetamido-type benzoylmethane-type 4-equivalent or 2-equivalent couplers, such as those disclosed in U.S. Pat. No. 2,186,
No. 849, No. 2,322,027, No. 2.728
, No. 658, No. 2,875,057, No. 3,26
No. 5,506, No. 3,277.155, No. 3,4
No. 08,194, No. 3,415,652%, No. 3,
No. 447,928, No. 3,864.841, No. 3
, 770,446, 3,778,277, 3,849.140, 3,894,875, British Patent No. 778,089, 808,276, British Patent No. Specifications of No. 875,476, No. 1,402,511, No. 1,421,126, and No. 1.513,832@, as well as Japanese Patent Publication No. 13576/1976, and Japanese Patent Publication No. 1977/1973
-29432, 48-66834, 49-10
No. 736, No. 49-122335, No. 50-288
No. 34, No. 50-132926, No. 50-1388
No. 32, No. 51-3631, No. 51-17438@,
No. 51-26038, No. 51-26039, No. 51
-50734, 51-53825, 51-75
No. 521, No. 51-89728, No. 51-10263
No. 6, No. 51-107137, No. 51-117031
No. 51-122439, No. 51-14331
No. 9, No. 53-9529, No. 53-82332,
No. 53-135625, No. 53-145619, No. 54-23528J! , No. 54-48541, No. 54-65035, No. 54-133329, No. 55
It is described in various publications such as No.-598.

Cyan dye image-forming couplers include phenolic,
Naphthol type 4-equivalent or 2-equivalent type cyan dye image-forming couplers are typical, and U.S. Patent No. 2,306,4
No. 10, No. 2,356,475, No. 2.362,
No. 598, No. 2,367.531, No. 2,369
, 929 Tan, Id. No. 2,423.730, Id. No. 2,47
No. 4,293, No. 2,476.008, No. 2,4
No. 98,466, No. 2.545.687, No. 2,
No. 728,660, No. 2,772,162, No. 2
, No. 895,826, No. 2.976, 146 Tan, No. 3,002.838, No. 3,419,390, No. 3,448,622, No. 3,476.563 ,
No. 3,737,316, No. 3,158.308, No. 3,839,044, British Patent No. 478,99
1 @, same No. 945,542, same * 1,084,48
No. 0, No. 1.377.233, No. 1,388.0
No. 24 and No. 1,543.040 for winter! II! I
, and Special IFI No. 47-37425, 5G-10
No. 135, No. 50-25228, No. 50-1120
No. 38, No. 50-117422, No. 50-13044
No. 1, No. 51-6551, No. 51-37647@, No. 51-52828, No. 51-408841, No. 5
No. 3-109630, No. 54-48237, No. 54-
No. 66129, No. 54-131931, No. 55-32
It is described in various publications such as No. 071.

As a colored coupler, for example, British Patent No. 937.
No. 621, No. 1,035,959, No. 1,255
, No. 111, JP-A-48-22028, JP-A No. 52-42
No. 121, Special Publication No. 38-22335@, 44-201
No. 5, No. 44-15754@, U.S. Patent No. 2.449,
966@, No. 2,521,908, No. 2,543,6
No. 91, No. 2,801,171, No. 2,9J13,6
No. 08, No. 3,005,712, No. 3,034,89
21! , No. 3,061,432, No. 3,419.39
No. 1, No. 3,476.580, No. 3,476.56
No. 3, 3,481,741M, 3,519,429
No. 3,583,971M, 3,622,328
No. 3,684,514, No. 4,004,92
No. 9, No. 4,070.191, No. 4.138,258
No. 4,138.264, jfl 4,163,
No. 670, No. 4,292,400, No. 4.369,
248J! You can use the ones described in .

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. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either 2-equivalence may be used.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be dispersed using various methods such as solid state dispersion, latex dispersion, and oil-in-water emulsion dispersion. , which 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 method of dispersing a hydrophobic compound such as a coupler. Usually, a high-boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low-point and/or water-soluble cloth is added. After dissolving using Ill solvent together and emulsifying and dispersing using a surfactant/agent in a hydrophilic binder such as an aqueous gelatin solution using a dispersing means such as a stirrer, homogenizer, colloid mill, 70-jit mixer, or ultrasonic device, It may be added to the target hydrophilic colloid body. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point organic solvents include phenol derivatives, phthalates, phosphates, citric esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic esters, etc., which have a boiling point of 150' and do not react with the oxidized form of the developing agent. Although all mediums having C or higher are used, the preferred high boiling point organic medium for dissolving the compound forming the magenta dye according to the present invention are as described above. .

Anionic surfactants and nonionic surfactants can be used as dispersion aids when dissolving a hydrophobic compound in a solvent used in combination with a high-boiling point WIIIL solvent or a low-boiling point solvent and dispersing it in water using mechanical or ultrasonic waves. , cationic world TIjJ8IF
Sex drugs can be used.

Emulsion ll@ of silver halide color photographic light-sensitive material (same-
(between color-sensitive layers and/or between different color-sensitive layers), to prevent color turbidity, deterioration of sharpness, and conspicuous graininess due to movement of acidified form of developing agent or electron transfer agent. A color anti-capri agent is used.

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

The silver halide color photographic light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer, if necessary. These layers and/or the emulsion layer may contain dyes that flow out of the light-sensitive material or are bleached during development.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer for the purpose of reducing the gloss of the light-sensitive material, increasing the elutriation property, and preventing the light-sensitive materials from sticking together.

A lubricant can be added to reduce the sliding friction of silver halide photosensitive materials.

An antistatic agent is added to the silver halide photosensitive material for the purpose of preventing static electricity. The antistatic agent protects the emulsion of the support.
It is sometimes used to prevent dust in non-pb cases, and it is also used for protection of layers other than the emulsion layer on the side where the emulsion layer is exposed to the emulsion layer and/or support = 1. 4 is also fine.

The photographic emulsion layer and/or other hydrophilic colloid layer of silver halide photographic light-sensitive materials are used to improve coating properties, prevent static electricity, improve slipperiness, emulsification and dispersion, prevent adhesion, and (promote development, P! toning, sensitization). Various surfactants are used for the purpose of improving photographic properties (such as).

The photographic emulsion layer of the silver halide photographic light-sensitive material, and other layers include the baryta layer or a flexible reflective support such as paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, polychloride, etc. vinyl,
Films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate, polycarbonate, polyamide,
It can be applied to rigid bodies such as glass, metal, and ceramics.

Silver halide photosensitive materials can be produced directly or (adhesiveness, antistatic properties, dimensional stability, abrasion resistance, etc. of the support surface) after corona discharge, ultraviolet irradiation, flame treatment, etc. The coating may be coated via one or more subbing layers (to improve properties such as hardness, hardness, antihalation properties, frictional properties, and/or other properties).

When coating the silver halide photographic light-sensitive material, a thickener may be used to improve coating properties. The application method is 2.
Particularly useful are ex-dulsion coatings and curtain coatings in which more than one layer can be applied simultaneously.

Exposure can be performed using electromagnetic waves in a spectral region to which the emulsion layer constituting the silver halide photographic light-sensitive material is sensitive.

Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, water lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, gamma rays,
Light emitted from a phosphor excited by alpha rays, etc.
Any known light source can be used.

The exposure time is not only 1 millisecond to 1 second, which is normally used with cameras, but also exposures shorter than 1 microsecond, such as exposures of 100 microseconds to 1 microsecond using a cathode ray tube or xenon flash lamp. , exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

A silver halide photographic light-sensitive material can form a color image by performing color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds are generally used in color developer 1.
It is used at a concentration of from about 1 g to about 30 g per 1 Jz of color developer, preferably from about 1 g to about 15 g per 1 Jz of color developer.

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 amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N,N'-diethyl-p-phenylenediamine salt Lm
, N-methyl-〇-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-
7 minnow 3-methyl-N.

Examples include N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methyl 7-niline-p-toluenesulfonate, and the like.

In addition to the aromatic primary amine color developer, the color developer further contains various components that are usually added to color developers, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate; Alkali metal sulfite I! salt,
Alkali metal bisulfite, alkali metal thiocyanine W1
1M, an alkali metal halide, benzyl alcohol, a water softener, a thickening agent, and the like may optionally be included.

The pH value of this color developing solution is usually 7 or more.

Most commonly from about 10 to about 13.

Generally, after color development processing, processing is performed with a processing liquid having fixing ability, but if the processing liquid having fixing ability is a fixing liquid, bleaching processing is performed before that. As the bleaching agent used in the bleaching step, a metal complex salt of 1/1 is used,
The metal complex salt has the effect of oxidizing the metallic silver generated by development and converting it into silver halide, and at the same time coloring the uncolored part of the coloring agent, and its composition is made of aminopolycarboxylic acid, oxalic acid, citric acid, etc. It is made by coordinating metal ions such as iron, cobalt, and copper with an organic acid. The most preferred organic acids used to form such organic acid gold WAR salts 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 [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used in the vinegar-sodium salt 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, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
1lii agents, alkylamines, polyethylene oxides, etc., which are known to be added to ordinary bleaching solutions, can be added as appropriate.

Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, sodium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, and boric acid. , borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. as pH buffering agents alone. Alternatively, two or more types can be included.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

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

The present invention will be described in more detail with reference to specific examples below, but the embodiments of the present invention are not limited thereto.

<Example 1> In order to examine the degree of improvement in light fastness by the dye image stabilization method according to the present invention, samples having the layer configurations shown in Table 1 below were prepared. Samples 1 to 12 were prepared by changing the contents of the coupler-containing layer as shown in Table 2.

Margin below <Table 1> *Application i is Takumi/100cn? It was expressed as

Table 2 Comparative coupler 1 Comparative coupler 2I Each sample obtained was tested with a sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd., K).
S-7 type) was used to expose green light through a light wedge.
1A to 1 were treated according to the following treatment steps A and B.
2A, 18-12B.

More sample 2? For I3 and 7, treatment steps C~■ were also applied, resulting in 20~2L7C~7■.

Table 3 [Processing liquid composition 1 [Color developer] Benzyl alcohol 15-ethylene glycol 15-potassium sulfite
2.0g potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30,017 hydroxylamine ram salt
3.0g polyphosphoric acid (TPPS) 2.
503-Methyl-4-amino-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5Q optical brightener (4,4'-diaminostilbenzsulfone I! derivative) 1,017
Add 2.0g of potassium hydroxide water and bring the total amount to 1i! Binding, I) Moisten with H10,20.

[Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 Q Ethylenediaminetetraacetic acid 30 Ammonium thiosulfate (70% solution) 1007d Ammonium sulfite (4
0% solution) 27,5ynj) Prepare 7.1 to 11 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 11.

A light fastness test was conducted on the sample thus obtained under the following conditions.

Illuminance (fuX) Irradiation time (H) a Xenon 1. OX 10ゝ 300
Fade meter b Fluorescent light fading 1.8X 10 1000
The results obtained by the tester are shown in Table 4 as the dye residual rate, and this "dye residual rate" is the percentage (%) of the density after irradiation with respect to the initial density Do -1,0.

From the results in Table 4, the light fastness of samples 1 to 10 that were subjected to treatments B to H according to the present invention was remarkable compared to the samples that were subjected to standard treatment step A. An improvement in the specific light intensity [α] of standard gelatin appears.

It can be seen that the light fastness is rather deteriorated in the treatment step using treatment solution (2) in which the value is less than -150.

Furthermore, when the concentration of the compounds in the stabilizing bath was increased in the order of C-B-D, the higher the specific light absorption, the better the results.

On the other hand, it is also clear that the improvement effect of the present invention is very small for Samples 11 and 12, which gave yellow and cyan dye images, respectively.

Furthermore, in Samples 2' and 7', not only the light fastness due to treatment step A was slightly lower, but the degree of improvement due to treatment step B was also slightly smaller, and the high boiling point 8 with a dielectric constant of 6.0 or less
The use of m solvent was more advantageous in terms of light fastness.

<Example 2> On a support made of polyethylene-coated paper, the following layers were sequentially coated from the support side to prepare a multicolor silver genide photographic light-sensitive material, which was designated as Sample 13.

1st W: Blue-sensitive silver halide emulsion layer Comparative coupler 1 of Example 1 was used as a yellow coupler.
113/drn", blue-sensitive silver chlorobromide emulsion was converted to silver at a coating weight of 31 (1/dtn"), dioctyl phthalate was applied at a coating amount of 31g/dm', and gelatin was coated at a coating amount of 16IO/dm'. Established.

Second layer: Intermediate layer gelatin was coated at a coating weight of 41 (J/drn).

Third layer: green-sensitive silver chlorobromide emulsion layer/d m', dioctyl phthalate 411Q/d
m'' and gelatin were coated in a coating amount of 16 sa/d Tl1t.

4th layer: 3 layers Q/d of intermediate layer UV absorber (LIV-16), (UV
-6) t3mMd-2, dit'; tchi) Irefta L/
- 41 (1/d v”) and 1411 gelatin
The coating was applied so that the coating amount was 0/dm.

5th layer: Red-sensitive silver chlorobromide emulsion layer Comparative coupler 2 of Example 1 was used as a cyan coupler at 11
0/d Tl+', 2-(2,3,4,5,6-pentafluorophenyl)acylamino-4-chloro-5
-[α-(2,4-di-t-amylphenoxy)pentylamide 1 to 311/dm'1 dioctyl phthalate to 2107 d y and red-sensitive silver chlorobromide emulsion to 31 g/dTIlf in terms of silver. The coating was applied so as to achieve the desired amount of coating.

6th layer: 2-g/d m' of (UV-16) as an intermediate layer ultraviolet absorber
, (UV 6) wo21 (1/d v", sit')
H) ItV tallate was coated at a coating amount of 210/d m" and gelatin was coated at a coating amount of 6 wa/d TIT".

Seventh layer: Protective layer Gelatin was coated at a coating amount of 9 sg/dm''.

Samples 14 to 22 were prepared in the same manner as Sample 13 except that the magenta coupler and antifading agent were changed as shown in Table 5. The obtained sample was exposed to light in the same manner as in Example 1, and subjected to treatment step A in Example 1 and treatment step J and C treatment in 1-1 below, and subjected to the same light fastness test as in Example 1. The results obtained are also shown in Table 5.

Standard gelatin when using the above stabilizing bath! 5′″ The specific optical rotation [α]D was as follows.

Stabilizing bath (J)-194 Stable@(H)-121 [Stabilizing bath prescription] Stabilizing bath LJ) Stabilizing bath (H) Fluorescent brightener 1. Og Doujin (Note 1) 1-Hydroxy 4. Og Same left Ethylidene-1,1-diphosphonic acid anti-pissing agent (Note 2) 0.050 laps Left Tog compound according to the present invention (X-
4) Add water to bring the total volume to 11, and adjust to I) 87.20.

(Note 1)...Keikoru PK-C manufactured by Shin Nisso Kako Co., Ltd. was used for fluorescent brightening agent binding.

(Note 2) 2-(4-thiazolyl)benzimidazole was used as the anti-piping agent.

Table 5 is shown in the margin below. From the results of Table 5 above, it can be seen that the effect of the stabilization treatment according to the present invention on multicolor silver halide photographic light-sensitive materials is also remarkable, as in Example 1, and the light fastness is dramatically increased. It can be seen that gender has been assigned.

Example 3 A silver halide photosensitive material for color diffusion transfer was prepared as shown below.

(1) Preparation of Photosensitive Element A photosensitive element was prepared by coating the following layers in the order listed on an opaque polyethylene terephthalate film support.

■Polymer Wi layer ■Timing layer ■Cyan DRR compound-containing layer ■Red-sensitive negative silver halide emulsion layer ■Medium layer where developer is introduced ■Magenta DRR compound-containing layer ■Green-sensitive negative silver halide emulsion Layer ■ Intermediate layer into which a developing agent has been introduced ■ Yellow DRR compound-containing layer [Co., Ltd.] Blue-sensitive negative-working silver halide emulsion ■ Matte protective layer Gold-white''/'DRR (IIs compound (, ). 5
□.

Cyan DRR Compound The polymeric acid layer and timing layer used here are described in Research Disclosure, Vol. 184, No. 18,452,
It is the same as that described on pages 1131-432 (August 1979).

The developer introduced into the intermediate layer is 1-phenyl-3-pyrazolidinone blocked at the 3-position. The matte protective layer is gelatin (8,9+e g 7100cm
), methacrylate beads (particle size 2-4μ, 0.17
10/10001), Ludox AM (L
udox AM) Silica (particle size 0.2μ, 4.5
mg/100 cm) and 2,5-didodecylhydroquinone (38 Q/100 cm”).

The total amount of coated gelatin from layer ■ to layer ■ is 81 I
Q /10001 and was hardened with 0.75% bis(vinylsulfonyl)methyl ether.

(2) Preparation of Image-Receiving Element Image-receiving by coating the following layers in the order listed on an opaque paper support! ! ! A base of 14 was made.

■Poly-1-vinyl-2-methylimidazole (321
1Q/100CI), gelatin (1111!I
I/100cm), sorbitol (2.7mg
/100cm) and formaldehyde (0,5m
Q /100cm ) image-receiving layer.

■Gelatin (a, at Q/100cm > , UV absorber (5,4gt Q/100c+a),
Interlayer of high-boiling organic solvent (3,2io/100cm) and formaldehyde (0.5IQ/100cs2).

■Protective layer of gelatin (6.5m O /100cm”).

(3) Preparation of activation solution An activation solution with the following composition was prepared.

Potassium hydroxide 0.6N5-methylbenzotriazole 3.0! J/I! 11-aminoundecanoic acid 2. h/I! potassium bromide
2. OQ/I! The photosensitive element was exposed as in Example 1, rinsed in activating solution for 15 seconds at 28°C, and then laminated to an image receiving element through nip rollers. After 10 minutes, the light-sensitive element and image-receiving element were peeled off to obtain a magenta dye image, and this sample 23 and sample 24, in which the stabilizing bath Bllllllll of Example 1 was applied to this sample, were subjected to the same light fastness test as in Example 1. The results obtained are shown in Table 6.

Table 6 From the results in Table 6, the effect of the present invention was confirmed also in silver halide photographic materials for color diffusion transfer.

Patent Applicant Roku Konishi Photo Industry Co., Ltd. Procedural Amendment (Akira Shisen @ August 1, 161 Commissioner of the Patent Office Academic Award Mr. Michibe ■31, Indication of the case 1985 Patent Case No. 126451 2, Name of the invention Pigment Image stabilization method 3, relationship with the case of the person making the correction Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1)
27) Konishi Roku Photo Industry Co., Ltd. Representative Director Keio Benko 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 Detailed explanation of the invention of Akira Jllf Correct the fields as follows.

Claims (1)

[Claims] A photographic product having at least a layer carrying a magenta dye image can be prepared with the specific optical rotation [α] of standard gelatin.
1. A method for stabilizing a dye image, comprising processing with a processing solution that increases D to -150 or more.