JPH071381B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, high light fastness is imparted without deteriorating whiteness and dark fading is improved. And a silver halide photographic light-sensitive material.

[Background of the Invention]

Conventionally, a silver halide photographic light-sensitive material is imagewise exposed and color-developed to cause a coupling reaction between an oxidant of an aromatic primary amine color developing agent and a color-forming agent, such as indophenol, indoaniline and indamine. It is well known that azomethine, phenoxazine, phenazine and similar dyes are formed to form a dye image. In such a photographic method, a color reproduction method by a subtractive color method is usually adopted, and a blue sensitivity,
Green and red sensitive silver halide emulsion layers,
A silver halide photographic light-sensitive material containing a color-forming agent having a complementary color relationship, that is, a coupler capable of coloring yellow, magenta and cyan is used.

It is known that a silver halide photographic light-sensitive material having the above-mentioned dye image undergoes significant discoloration under certain storage conditions. For example, when exposed to light for a long period of time and stored, and when exposed to light for a short period of time, they often show different fading properties when stored in a dark place of high temperature and high humidity.
The former case is called light fading and the latter case is dark fading.In order to use a silver halide photographic light-sensitive material having a dye image as a recording material which can be semi-permanently stored, these fadings should be minimized. It is desired to be small. However, in the conventional silver halide photographic light-sensitive material, the fading property under the above-mentioned storage conditions is not sufficiently prevented, and the fastness of the dye image is not yet in a satisfactory state. Further, in recent years, the demand for the storability of dye images has only increased, and there is a strong demand for the development of a technique for dramatically improving the durability of dye images.

In order to improve the fastness of dye images, many methods have been conventionally proposed in two aspects. One is a method for improving the fastness of the dye image itself, which is an improvement in the design of the dye image itself or a compound (for example, a coupler) that forms the dye image in terms of molecular structure, or the presence state of the dye is changed. This is an improvement. The other one is a method using a dye image stabilizer. According to this method, many improvements in this aspect are proposed because of its small influence on the characteristics of the dye image such as color tone and high versatility. Has been done.

Regarding the method of using a dye image stabilizer, various methods for improving the light fading of a dye image by adding an ultraviolet absorber or providing an ultraviolet absorbing filter layer in a photographic element have been conventionally proposed. . However, in order to obtain satisfactory light fastness using this ultraviolet absorber, a large amount of ultraviolet absorber is required, and when a large amount of ultraviolet absorber is used, the photographic element may be colored due to the coloring of the ultraviolet absorber itself. Had a drawback that the dough portion was colored yellow, the solubility of the ultraviolet absorber in a high-boiling organic solvent was small, and the ultraviolet absorber was easily precipitated during the manufacturing process. Therefore, there is a limit to the amount of addition, and a sufficient effect for making the dye image fast can not be obtained. Further, there is a serious drawback that even if the light discoloration due to the ultraviolet rays can be prevented, it has no effect in preventing the light discoloration due to the visible light.

Therefore, in order to overcome these drawbacks, various dye image stabilizers have been proposed to replace the ultraviolet absorber. For example, as a compound having a phenolic hydroxyl group or a phenolic hydroxyl group which is hydrolyzed, Japanese Patent Publications No. 31256 and 48,
-31625 discloses bisphenols, U.S. Pat.
No. 262 describes pyrogallol, garlic acid, and esters or acyl derivatives thereof, U.S. Pat.
Nos. 432,300 and 3,574,627 disclose 5-hydroxychroman derivatives, and JP-B-49-20977 discloses 6,6'-dihydroxy-2,2'-bisspirochromans. . In addition, JP-A-52-35633 and JP-A-53-1
7729 and 54-48538 each propose a 6-alkoxychroman derivative, a 6,6'-dialkoxy-2,2'-bisspirochroman, a hydroquinone derivative and the like.

However, some of these compounds certainly have an effect on the photofading of the dye image, but have no effect on the dark fading, and, on the contrary, accelerate the dark fading. . Further, some compounds are effective for a certain period of time, but when stored for a long period of time, the effects are diminished or even completely absent, and, conversely, coloring and staining occur. Further, some compounds have an effect of preventing discoloration with respect to a magenta dye image, but some compounds remarkably accelerate discoloration with respect to a cyan dye image and a yellow dye image.

Further, the improvement effect is often limited only by using these compounds.

As a light stabilizer, U.S. Pat.No. 4,050,938, JP-A-56-99,340, JP-A-56-168,652, and JP-A-60-51,834.
And the metal complexes described in JP-A No. 60-97,353 are proposed. Certain of these compounds certainly give high light fastness when used alone or in combination with the dye image stabilizer described above, but the light stabilizer itself is colored because it is a metal complex. That the white background deteriorates,
High light fastness effect, including yellowing due to heat and humidity, low solubility of the light stabilizer in organic solvents, and negative effects on photographic performance such as reduced sensitivity and increased fog. It was difficult to apply it to a silver halide photographic light-sensitive material in order to achieve

As described above, at present, a dye image storability improving technology capable of imparting satisfactory fastness to a silver halide photographic light-sensitive material has not yet been found.

Also, US Pat. No. 4,555,477 and US Pat.
4,555,478 discloses a method for obtaining highly stabilized color masking dyes using a compound which releases a substantially colorless, immobile ligand in combination with a silver halide emulsion and a highly stabilized method. A method of obtaining a color image is disclosed. In the former method, specifically, the ligand is released in the developed part of the exposed part and flows out of the system, but the compound is complexed with the metal ion in the undeveloped part of the unexposed part. Is a technique for forming a stable masking dye complex. Therefore, in the exposed area after development, that is, in the area where the dye image is formed, the ligand is eluted out of the system, and the complex compound does not contribute. It is not disclosed at all that the ligand remains in some form and functions in the image forming unit.

Specifically, the latter method is a technique in which the ligand is released in the imagewise exposed and developed portion to form a stable metal complex dye image with the ligand and the metal ion. In the latter case, the source of the dye of the dye image is a metal complex, and as is generally said, the dye of the metal complex is excellent in light fastness, and thus a dye image having good light fastness is obtained. It is excellent in that it can be used. However, it is considered that there is a problem in that the metal complex dye cannot always be obtained in an arbitrary color and the selection range is narrow to some extent in terms of color tone and hue.

On the other hand, the present inventors have found a technique for producing an image stabilizer of a metal complex dye image stabilizer in the present situation, and in January 1986.
I filed a patent application on the 16th. According to this technique, it is possible to improve the light fastness of the dye image without deteriorating the whiteness.
The dye image storability in the dark place, that is, the dark fading property, has not been improved yet.For example, when aiming to improve the long-term storage property of general color prints, the overall progress of the dark fading property is desired.

In view of the above circumstances, the present inventors have found the present invention as a result of earnest research to improve the dark fading property in addition to the light fastness of a dye image without deteriorating the whiteness and yellowing due to light. It is a thing.

[Object of the Invention]

The first object of the present invention is to provide a silver halide photographic light-sensitive material which is provided with remarkably high light fastness and dark fading property at the same time.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which is provided with remarkably high light fastness without deteriorating the whiteness and has improved dark fading.

A third object of the present invention is to provide a silver halide photographic light-sensitive material which is provided with remarkably high light fastness without degrading photographic performance such as yellowing during storage and has improved dark fading. is there.

[Structure of Invention]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the halogenation contained in one layer containing at least a magenta coupler in the silver halide emulsion layer. A silver halide photographic light-sensitive material containing a compound represented by the following general formula [I] in combination with a silver emulsion in an emulsified and dispersed state using a high boiling point organic solvent having a dielectric constant of 6.0 or less. Achieved by

General formula [I] C _P T _n LIG ( _where C _P is a function of T _n as a function of development of silver halide)
Represents a group capable of leaving LIG, and T represents a group capable of releasing LIG when or after T _n LIG leaves,
Represents a ligand capable of forming a complex compound having a function of stabilizing a dye image by a complex formation reaction with a metal ion. n represents 0 or 1. In the present invention, as a result of the above constitution, the dye image-forming coupler develops color upon development, and-(T) _n -LIG is released. And LIG is released, because this LIG is capable of forming a complex compound having the function of stabilizing the dye image,
When the metal ion for forming such a complex compound is supplied, the complex compound having the stabilizing function can be formed at the same time as the dye image formation by the above-mentioned coupler or after the dye image formation. This complex compound is produced as a function of development, and is produced imagewise in the developed image forming portion, so that an effective image stabilizing function can be exhibited.

Various means can be used to supply the metal ions for forming the complex compound on the ligand. For example, as described later in detail, a means for supplying metal ions from outside the light-sensitive material can be adopted, or a metal ion or a metal ion-donating substance (including a substance capable of forming such a substance) can be previously added to the light-sensitive material. It may be configured to be contained.

The compound represented by the general formula [I] may be contained in combination with at least one of the silver halide emulsions contained in the silver halide emulsion layer, and is contained in the silver halide emulsion layer itself. However, it may be contained in a layer adjacent to the emulsion layer, or may be contained in a position capable of reacting with the silver halide emulsion of interest.

In the general formula, C _P is arbitrary and can be, for example, a coupler residue of a coupler capable of forming a dye image, or a coupler residue of a coupler which does not form a dye, or a coupling reaction. Then, a dye may be formed and eluted out of the system.

Further, a dye image-forming coupler can be used in combination with the compound of the general formula [1]. Without of course a combination of dye image-forming couplers may be configured so as to form a dye image only by C _P.

When a dye image-forming coupler is used in combination, and
When C _P is a coupler residue of a coupler capable of forming a dye image, both the dye image formed by the dye image-forming coupler and the dye image formed by C _P are formed. In this case, the image by the dye image-forming coupler can be configured in such a manner that the image is predominant, or the image by the C _P can be configured in such a manner that the image is predominant, or the contributions of both are equally divided. Can also be configured, and these are optional.

The complex compound formed by the reaction of LIG with the metal ion may be substantially colorless or colored.

The complex compound may be configured to exhibit a desired color and contribute to dye image formation.

Therefore, for dye image formation, a mode in which an image is formed only by the dye image-forming coupler (in this case,
C _P and LIG does not form a dye image. ) Can be taken.
Also, image formation by dye image-forming couplers is the main,
There can be a mode in which the image formation by C _P is subordinate, or a mode in which the master and subordinate are the opposite (in these cases, the mode in which LIG forms a dye image and the mode in which it does not form a dye image). C _P does not form a dye image, and the image formation by the dye image-forming coupler is mainly, and the image formation by LIG is secondary.

Since of course the combination of dye image-forming coupler is not essential, as described above, it is possible to form a dye image only on the C _P, LIG this case also may or may not form a dye image.

For example, as described above, the present invention can take various aspects.

When C _P and LIG form a dye image, C _P can be configured so that any color such as yellow, magenta, and cyan can be formed, and LIG can also be configured so that any color can be formed. For example, it is also possible to use a dye image-forming coupler in combination so that the color development by C _P and LIG (or the color development by two of the three) is the same. These colors are preferably magenta.

When a dye-forming coupler is preferably used, it is a case where the color development by this and the color development by C _P are the same or almost the same.

[Specific configuration of the invention]

 Next, the present invention will be specifically described.

In the compound represented by the general formula [I] according to the present invention, C _P is a function of the phenomenon of silver halide (T
Although _n LIG is also possible to take any structure as long as it is a group which is detached, dye image-forming coupler residue can be preferably used as the C _P, specific structure of the C _P which can be preferably used in the present invention Is the following general formula [I
It can be represented by I] to [IV].

That is, as the yellow dye image-forming coupler residue, a coupler residue represented by the following general formula [I] can be preferably used.

General formula (II) (In the formula, R ₁ is an alkyl group (for example, t-butyl group, adamantyl group, etc.), or an aryl group (for example, phenyl group,
p-methoxyphenyl group, etc.) and R ₂ represents an aryl group. Further, particularly preferable as the yellow dye image-forming coupler residue according to the present invention is represented by the following general formula [II-a].

General formula (II-a) In the formula, R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group,
R ₄ , R ₅ , R ₆ and R ₇ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a carbonyl group, a sulfonyl group, a carboxyl, an alkoxycarbonyl group, a carbamyl group, It represents a sulfone group, a sulfamyl group, a sulfonamide group, an acylamino group, a ureido group or an amino group.

These coupler residues are described, for example, in U.S. Pat.
No. 2, No. 2,875,057, No. 2,908,573, No. 3,227,15
No. 5, No. 3,227,550, No. 3,253,924, No. 3,265,5
No. 06, No. 3,277,155, No. 3,341,331, No. 3,369,
No. 895, No. 3,384,657, No. 3,408,194, No. 3,41
No. 5,652, No. 3,447,928, No. 3,551,155, No. 3,5
82,322, 3,725,072, 3,894,875 and other specifications, German Patent Publication No. 1,547,868, 2,057,941
No. 2,162,899, No. 2,163,812, No. 2,213,46
No. 1, No. 2,219,917, No. 2,261,361, No. 2,263,8
No. 75, Japanese Patent Publication No. 49-13,576, JP-A Nos. 48-29,432, 48-6
6,834, 49-10,736, 49-122,335, 50-28,83
No. 4, and No. 50-132,926.

As the magenta dye image-forming coupler residue, coupler residues represented by the following general formulas [III] and [III '] can be preferably used.

General formula (III) [In the formula, Ar represents an aryl group, R ₃₁ represents a hydrogen atom or a substituent, and R ₃₂ represents a substituent.

W represents -NH-, -NHCO- (N atom is bonded to carbon atom of pyrazolone nucleus) or -NHCONH-, and m is 1 or 2
Is an integer. ) The coupler residue represented by the general formula [III] will be described in detail.

Examples of the aryl group represented by Ar include a phenyl group and a naphthyl group, preferably a phenyl group,
Particularly preferred is a substituted phenyl group.

Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfonamide group, an acylamino group, and the like, and are represented by Ar. The phenyl group may have two or more substituents.

Specific examples of the substituent will be given below.

Halogen atom: chlorine, bromine, fluorine Alkyl group: methyl group, ethyl group, iso-propyl group,
A butyl group, a t-butyl group, a t-pentyl group and the like are preferable, and an alkyl group having 1 to 5 carbon atoms is particularly preferable.

Alkoxy group: methoxy group, ethoxy group, butoxy group,
sec-butoxy group, iso-pentyloxy group, etc.,
Particularly, an alkoxy group having 1 to 5 carbon atoms is preferable.

Aryloxy group: a phenoxy group, a β-naphthoxy group and the like, but this aryl portion may further have the same substituent as the phenyl group represented by Ar.

Alkoxycarbonyl group: A carbonyl group having an alkoxy group as described above, and one having 1 to 5 carbon atoms in the alkyl moiety such as methoxycarbonyl group and pentyloxycarbonyl group is preferable.

Carbamoyl group: Alkylcarbamoyl group such as carbamoyl group and dimethylcarbamoyl group Sulfamoyl group: Alkylsulfamoyl group such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group and ethylsulfamoyl group Sulfonyl group: methanesulfonyl group , Ethanesulfonyl group, butanesulfonyl group, etc., alkylsulfonyl group, sulfonamide group: methanesulfonamide group, toluenesulfonamide group, etc., alkylsulfonamide group, arylsulfonamide group, etc., acylamino group: acetamino group, pivaloylamino group, benzamide group, etc. A halogen atom is preferable, and chlorine is most preferable among them.

The substituent represented by R ₃₁ is a halogen atom, an alkyl group,
And an alkoxy group.

Specific examples are given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: methoxy group, ethoxy group, butoxy group,
An alkoxy group having 1 to 5 carbon atoms such as sec-butoxy group and iso-pentyloxy group is preferable.

Alkyl group: methyl group, ethyl group, iso-propyl group,
An alkyl group having 1 to 5 carbon atoms such as a butyl group, a t-butyl group and a t-pentyl group is preferable.

A halogen atom is particularly preferable, and chlorine is particularly preferable.

The substituent represented by R ₃₂ is a halogen atom, an alkyl group,
Amido group, imide group, N-alkylcarbamoyl group, N
An alkylsulfamoyl group, an alkoxycarbonyl group, an acyloxy group, a sulfonamide group, a urethane group or the like. Among these groups, an amide group (for example, a tetradecanamide group, a 3-t-butyl-4-hydroxyphenoxytetradecanamide group, etc.), an imide group (for example, a dodecylsuccinimide group, an octadecenylsuccinimide group, etc.), and a sulfonamide group (For example, a butyl sulfonamide group, a dodecyl sulfonamide group, etc.) can be preferably used.

W may be any of -NH-, -NHCO- (nitrogen atom bonded to carbon atom of pyrazolone nucleus) or -NHCONH-, but W
-NH- can be particularly preferably used.

Examples of the substituent capable of splitting off by the coupling reaction with the oxidation product of the aromatic primary amine color-developing agent represented by Y include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, (Z ₂ is a nitrogen atom together with a carbon atom, an oxygen atom, a nitrogen atom,
It represents a group of atoms required to form a 5- or 6-membered ring with an atom selected from sulfur atoms. ) And the like.

Specific examples are given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: ethoxy group, penzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc.Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group, etc. Acyloxy group : Acetoxy group, myristoyloxy group, penzoyloxy group, etc. Arylthio group: Phenylthio group, 2-Putoxy-5-
Octylphenylthio group, 2,5-dihexyloxyphenylthio group, etc.Alkylthio group: methylthio group, octylthio group, hexadecylthio group, penzylthio group, 2- (diethylamino) ethylthio group, ethoxycarbonylmethylthio group,
Etoxydiethylthio group, phenoxyethylthio group, etc. General formula [III ′] (In the formula, Z represents a group of metal atoms forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.
R represents a hydrogen atom or a substituent.

Of the groups represented by the general formula [III ′], the groups represented by the following general formulas [III-a] and [III-b] can be preferably used.

General formula (III-a) General formula (III-b) R'and R "represent an alkyl group, an aryl group or a heterocyclic group. It is particularly preferred that both R'and R" are an alkyl group.

The alkyl group represented by R'and R "has 1 carbon atom
Those of up to 32 are preferred. The alkyl group may be linear or branched.

The alkyl group represented by R ′ and R ″ is a substituent group such as aryl, cyano, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, acyl, Those substituted via a carbonyl group such as carboxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, and further substituted via a hetero atom {specifically hydroxy,
Substituted through an oxygen atom such as alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino , Those substituted through a nitrogen atom such as acylamino, sulfonamide, imide, ureido, those substituted through a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, phosphorus atoms such as phosphonyl And the like, which are substituted via the following).

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group,
1-hexylnonyl group, 1,1′-dipentylnonyl group,
2-chloro-t-butyl group, trifluorometer group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4 ′-{α- [4 ″ (p-hydroxybenzenesulfonyl) phenoxy] dodecanoylamino}
Phenylpropyl group, 3- {4 '-[α- (2 ", 4"-
Di-1-amylphenoxy) butanamide] phenyl}
-Propyl group, 4- [α- (o-chlorophenoxy) tetradecanamidophenoxy] propyl group, allyl group,
Examples thereof include cyclobenzyl group and cyclohexyl group.

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

Specifically, a phenyl group, a 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-
[Α- (4 ″ -t-butylphenoxy) tetradecanamide] phenyl group and the like.

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

Next, specific examples of R ′ and R ″ represented by the above general formula will be shown.

-C ₁₇ H ₃₅ -CH ₂ CH ₂ CH ₂ OC ₁₂ H ₂₅ -CH ₂ CH ₂ CONHC ₁₄ H ₂₉ Further, the group represented by the above general formula [III '] may be a so-called polymer coupler residue, which is disclosed in JP-A-59-2.
28,252 and 59-171,956, etc.

As the cyan dye image forming coupler residue, a coupler residue represented by the following general formula [IV] can be preferably used.

General formula (IV) (In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom, a halogen atom, an alkyl group, a carbamoyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, a phosphoramide group or a ureido group. , R ₉ and R ₁₀ may form a ring.) These coupler residues are described, for example, in US Pat.
No. 2,423,730, No. 2,434,272, No. 2,474,29
No. 3, No. 2,698,794, No. 2,706,684, No. 2,772,1
No. 62, No. 28011,171, No. 2,895,826, No. 2,908,5
No. 73, No. 3,034,892, No. 3,046,129, No. 3,227,
No. 550, No. 3,253,294, No. 3,311,476, No. 3,38
No. 6,301, No. 3,419,390, No. 3,458,315, No. 3,4
76,563, 3,516,831, 3,560,212, 3,
582,322, 3,583,971, 3,591,383, and
No. 3,619,196, No. 3,632,347, No. 3,652,286, No. 3,737,326, No. 3,758,308, No. 3,779,763,
Nos. 3,839,044 and 3,880,661, German Patent Publication Nos. 2,163,811, 2,207,468, and Japanese Patent Publication No. 39-2.
7,563, 45-28,836, JP-A-47-37,425, 50-
No. 10,135, No. 50-25,228, No. 50-112,038, No. 50-117,
422, 50-130,441, 53-109,630, 56-65,134
No. 56-99,341, Research Disclosure 14,853 (1976), and the like.

Further, the dye image-forming coupler residue represented by the general formulas [II], [III] and [IV] may be a polymer coupler residue, for example, JP-A-58-28745, 58-43,9.
55, 59-40,643, 59-65,844 and U.S. Pat.Nos. 3,451,820, 4,080,211 and British Patent No. 1,
It is described in each specification such as 104,658.

In addition, as a compound that can be used as Cp in the present invention, as contained in the above general formulas [II] to [IV], even if a dye is formed by a reaction with an oxidant of a color-developing main agent, elution or the like occurs. No dye image remains after processing. So-called Weiss coupler residues and the like are also included. Specific examples of these compounds are described in, for example, British Patent No. 861,132 and Japanese Patent Publication No. 49-77,635.

Specific examples of the group represented by C _P in the present invention are shown below, but not limited thereto.

Next, T in the general formula [I] in the present invention will be described in detail. In the general formula [I], T represents a group capable of releasing LIG when or after being separated by the reaction with the oxidant of the color developing agent by being bonded to the coupling position of Cp.

T is used to control the reaction rate during the reaction with the oxidized product of the developing agent, and it leaves LIG by an intramolecular substitution reaction after the coupling reaction or after the coupling reaction, or by electron transfer through a conjugated system. Those that leave LIG Further, those that cause coupling with the phenotype main drug and oxidant, or those that cross-oxidize to leave LIG, and the above reactions may be used in combination.

For example, U.S. Pat. No. 4,146,396 and Japanese Patent Publication No. 51-26039
No. 4, U.S. Pat.No. 4,248,962, Published Patent No. 56-114946,
57-154234, 57-188035, 57-111536 and other published patents 57-56873, 58-98728, 58-209736,
58-209737, 58-209738, 58-209739, 59-
206834, 60-7429, 60-213944, 60-214358
No. 60, No. 60-225156, No. 60-218645, No. 60-225844,
60-229030, 60-230139, 60-232549, 60-
It is a linking group described in 203943 and the like.

Preferred are those represented by the following general formula. In the formula, (L) is the binding hand for binding LIG.

General formula In the general formulas to, X ₁ ′ is a hydrogen atom, a nitro group, an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.),
Alkylsulfonyl group (eg, methanesulfonyl, butanesulfonyl, etc.), cyano group, alkoxy group (eg, methoxy, butoxy, etc.), chloro atom, bromine atom, alkyl group (eg, methyl group, ethyl group, i-propyl group, butyl group, etc.) ), A carboxy group, an acylamino group (eg, acetamino, benzoylamino, etc.), a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.) and the like.

X ₂ ′ represents the same group as X ₁ ′, but preferably a hydrogen atom,
An acylamino group and a sulfonamide group.

X ₃ ′ represents an alkyl group or an aryl group (eg, phenyl, naphthyl, etc.), and may have the group mentioned for X ₁ ′ as a substituent.

X ₄ ′ represents an atomic group forming a 5- or 6-membered nitrogen-containing heterocycle (eg, imidazole, pyridine, triazole, pyrazole, indole, etc.).

X ₅ 'represents a carbamoyl group (methylcarbamoyl, butylcarbamoyl, phenylalbamoyl, etc.) in addition to the same groups as X ₁ '.

W ₁ and W ₂ represent hydrogen, an alkyl group or the like, and W ₁ and W ₂ may be bonded to form a benzene ring to form a naphthalene ring.

Next, the LIG in the general formula [I] in the present invention will be described in detail. The released LIG may have any structure as long as it is a group which serves as a ligand capable of forming a complex compound having a function of stabilizing a dye image by forming a complexing reaction with a metal ion. ] And [VI] can be preferably used.

General formula [V] -X-A-Y (In formula, X is an oxygen atom, a nitrogen atom, or a sulfur atom, Y is an organic group couple | bonded with the oxygen atom, a nitrogen atom, or a sulfur atom, A is X-A-. It represents an associative group capable of forming a 5- to 6-membered cyclic chelate compound when coordinated to a metal by Y.) X, A and Y are as follows in more detail.

R ₅₁ : hydrogen, alkyl, aryl, alkylsulfonyl, arylsulfonyl A: alkylene, arylene, alkylene, arylene, It is a linking group in which 2 to 3 groups selected from are combined.

R ₅₂ : hydrogen, alkyl, aryl, amyl, sulfonyl R ₅₃ , R ₅₄ : hydrogen, alkyl, aryl, acyl, sulfonyl The alkyl group of R ₃ and R _{4 is} an alkyl group having 1 to 20 carbon atoms, preferably β or γ position is substituted with oxygen, sulfur or nitrogen atom What was done. Further, as the aryl group,
A substituted or unsubstituted phenyl group and a naphthyl group are preferable, and a phenyl group and a naphthyl group in which the o-position is substituted with oxygen, sulfur, or nitrogen atom are preferable.

Ligand X-A-Y is a group released during development processing.
However, in order to exert the effect in the dye image area, it is resistant to diffusion.
It is better to be To impart diffusion resistance, carbon
In terms of number, 8 or more, preferably 12 or more ballast groups
Should be contributed.

In order to improve the stability of the complex compound formed, X, Y
The coordination center atom contained in is required to have at least one or more sulfur and nitrogen atoms, and preferably two or more.

As a specific example of LIG, General formula [VI] (In the formula, R _{61 to} R ₆₅ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group.) In the general formula [VI], among the groups represented by R _{61 to} R ₆₅ At least one is preferably a heterocyclic group, and more preferably the heterocyclic group is a nitrogen-containing heterocyclic group.

Specific examples of the group represented by the general formula [VI] are shown below.

Next, specific examples of the compound represented by the general formula [I] are shown below.

Concrete example Exemplified compound No.36 LIG = -S-CH ₂ CH ₂ SC ₁₂ H ₂₅ No.38 LIG = -SCH ₂ CH ₂ NHC ₁₂ H ₂₅ No. 39 LIG = -OCH ₂ CH ₂ SCH ₂ CH ₂ SC ₁₂ H ₂₅ No. 40 LIG = -SCH ₂ CH ₂ SC ₁₂ H ₂₅ No. 41 LIG = -SCH ₂ CH ₂ NHC ₁₂ H ₂₅ No.43 LIG = -SCH ₂ CH ₂ SCH ₂ CH ₂ SC ₁₂ H ₂₅ No.44 LIG = -OCH ₂ CONHCH ₂ CH ₂ SC ₁₈ H ₃₇ No.46 LIG = -SCH ₂ CH ₂ SCH ₂ CH ₂ SC ₁₂ H ₂₅ No.47 LIG = -OCH ₂ CH ₂ SC ₁₂ H ₂₅ No.49 LIG = -SCH ₂ CH ₂ SC ₁₂ H ₂₅ No.50 LIG = -OCH ₂ CH ₂ SCH ₂ CH ₂ NHC ₁₂ H ₂₅ Synthesis Example 1 (Synthesis of Compound Example No. 2) Diethyl mercaptoacetal (Org Syn Col Vol IV 2
(Page 95) and commercially available laurylamine are heated to reflux in alcohol and reacted for 8 hours. After cooling to room temperature and adding sodium borohydride for reduction, the resulting mercaptan and epichlorohydrin are reacted according to the method described in Col Vol II, page 345, supra, to obtain a sulfide alcohol compound. The product was halogenated with phosphorus tribromide in chloroform at -5 ° C, and then alkylated according to the method described in Japanese Patent Laid-Open No. 117422/1975 to obtain the target compound (2) as solid crystals. Identification was performed by FD mass spectrum, NMR spectrum, and elemental analysis.

Synthesis Example 2 (Synthesis of Compound Example No. 26) Compound (26) was prepared according to the method described in the above-mentioned patent using the intermediate IV described in JP-A-54-145135, Preparation Example 4 and the intermediate of Synthesis Example 1. Obtained as a candy.

Identification was performed by FD mass spectrum and NMR spectrum, and the purity was 95% by liquid chromatography.

In the present invention, the high boiling point organic solvent that can be used for emulsifying and dispersing the compound represented by the general formula [I] will be described in detail below.

As the high boiling point organic solvent having a dielectric constant of 6.0 or less used in the present invention, the boiling point at atmospheric pressure is 150 ° C. or more and the dielectric constant is
Any compound can be used as long as it is an organic solvent having a pH of 6.0 or less, and examples thereof include esters such as phthalic acid ester and phosphoric acid ester having a dielectric constant of 6.0 or less, organic acid amides, ketones, and hydrocarbon compounds. . A high boiling organic solvent having a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure at 100 ° C. of 0.5 mmHg or less is preferable. More preferably, phthalic acid esters or phosphoric acid esters in the high boiling point organic solvent. Further, the high boiling point organic solvent may be a mixture of two or more kinds.

The dielectric constant in the present invention indicates the dielectric constant at 30 ° C.

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

General formula [d] In the formula, R _d5 and R _d7 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms of the groups represented by R ₁₆ and R ₁₇ is 8 to 32. More preferably, the total number of carbon atoms is 16 to 24.

In the present invention, the alkyl group represented by R _d6 and R _d7 in the general formula [d] may be linear or branched,
For example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group,
Examples thereof include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. The aryl group represented by R _d6 and R _d7 is, for example, a phenyl group, a naphthyl group or the like, and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an octadecenyl group or the like. These alkyl group, alkenyl group and aryl group may have a single or plural substituents, and examples of the substituent of the alkyl group and alkenyl group include a halogen atom, an alkoxy group, an aryl group and an aryloxy group. Group, an alkenyl group, an alkoxycarbonyl group, and the like. Examples of the substituent of the aryl group include a halogen atom, an alkyl group, an alkoxy group,
Examples thereof include an aryl group, an aryloxy group, an alkenyl group and an alkoxycarbonyl group.

Examples of the phosphoric acid ester advantageously used in the present invention include those represented by the following general formula [e].

General formula [e] In the formula, R _e8 , R _e9 and R _e0 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms represented by R _e8 , R _e9 and R _e0 is 24 to 54.

Examples of the alkyl group represented by R _e8 , R _e9 and R _e0 in the general formula [e] include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and tridecyl group. Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc., aryl groups such as phenyl group, naphthyl group, etc., and alkenyl groups, such as hexenyl group, heptenyl group. , Octadecenyl group and the like.

These alkyl group, alkenyl group and aryl group may have a single or a plurality of substituents. Preferably R _e8 , R _e9 and R _e0 are alkyl groups, for example, 2-ethylhexyl group, n-octyl group, 3,5,5-
Trimethylhexyl group, n-nonyl group, n-decyl group,
Examples thereof include sec-decyl group, sec-dodecyl group and t-octyl group.

Typical examples of the organic solvent used in the present invention are shown below, but the present invention is not limited thereto.

Exemplified organic solvent The amount of the high boiling point organic solvent added may be any amount, but generally 10 to 200% by weight based on the compound represented by the general formula [I] in the present invention.
It is used in a proportion of, preferably 20 to 150% by weight. Further, as described below, a dye image-forming coupler can be used in combination with the compound represented by the general formula [I],
In this case, 10 to 200% by weight based on the total amount of the compound represented by the general formula [I] and the dye image-forming coupler.
It is used in a proportion of, preferably 20 to 150% by weight.

In the present invention, a dye image-forming coupler can be used together with the compound represented by the general formula [I]. In this case, as the dye image-forming coupler, a coupler having any structure can be used, but as the dye image-forming coupler which can be preferably used in the present invention, the following compounds can be mentioned.

As the yellow dye image-forming coupler used in combination, a coupler represented by the following general formula [B] can be used.

General formula [B] In the formula, R _B1 represents an alkyl group or an aryl group, and R _B2
Represents an aryl group, and X represents a hydrogen atom or a group capable of leaving in the course of color development reaction. R _B1 is a linear or branched alkyl group (eg butyl group) or aryl group (eg phenyl group), preferably an alkyl group (particularly t-butyl group), and R _B2 is an aryl group ( Preferably a phenyl group), these R ₁ , R
The alkyl group and aryl group represented by ₂ also include those having a substituent, and the aryl group of R _B2 is preferably substituted with a halogen atom, an alkyl group or the like. X is preferably a group represented by the following general formula [C] or [D], and more preferably a group represented by the general formula [C '] in the general formula [C].

General formula [C] In the formula, Z ₁ represents a non-metal atom group capable of forming a 4- to 7-membered ring.

In the general formula [D] -O-R _D1 , R _D1 represents an aryl group, a heterocyclic group or an acyl group, and an aryl group is preferable.

General formula [C '] Where Z ₂ is Represents a non-metal atom group capable of forming a 4- to 6-membered ring together.

The yellow coupler according to the present invention, which is preferable in the general formula [B], is represented by the following general formula [B '].

General formula [B '] In the formula, R _B4 represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferable. Also R _B5 , R
_B6 , R _B7 and R _B8 are each a hydrogen atom, a halogen atom,
Represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, an alkylsulfonamide group, an acylamino group, a ureido group or an amino group, and R _B5 , R _B6 and R _B8 is preferably a hydrogen atom and R _B7 is preferably an alkoxycarbonyl group, an acylamino group or an alkylsulfonamide group. Also, X
Represents a group having the same meaning as that represented by the above general formula [B], preferably the above general formula [C] or [D] or [C], more preferably the above general formula [C ']. The groups represented may be mentioned.

In the silver halide photographic light-sensitive material of the present invention, the magenta dye image-forming coupler has the following general formula [a].
And the couplers represented by [aI] can be preferably used.

General formula [a] [In the formula, Ar represents an aryl group, R _a1 represents a hydrogen atom or a substituent, and R _a2 represents a substituent. Y represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent, W represents -NH-, -NHCO- (N atom is bonded to carbon atom of pyrazolone nucleus) or -NHCONH-, m is an integer of 1 or 2. ) Specific example of [a]: These are, for example, U.S. Patent Nos. 2,600,788 and 3,061,4.
No. 32, No. 3,062,653, No. 3,127,269, No. 3,311,
No. 476, No. 3,152,896, No. 3,419,391, No. 3,51
No. 9,429, No. 3,555,318, No. 3,684,514, No. 3,8
88,680, 3,907,571, 3,928,044, 3,
930,861, No. 3,930,866, No. 3,933,500, etc., JP-A-49-29639, 49-111631, 49-129538
No. 50, No. 50-13041, No. 52-58922, No. 55-62454, No. 55
-118034, 56-38043, 57-35858, 60-23855
Publications, British patent 1,247,493, Belgian patent 7
No. 69,116, No. 792,525, West German Patent No. 2,156,111, Japanese Patent Publication No. 46-60479, etc.

The general formula [aI] general formula [aI] In the magenta coupler represented by, Za represents a nonmetal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Za may have a substituent.

X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent.

Ra represents a hydrogen atom or a substituent.

As the substituent represented by Ra, for example, 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, heterocyclic oxy group, siloxy group, acyloxy Group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples thereof include an alkylthio group, an arylthio group and a heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, and a chlorine atom is particularly preferable.

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

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

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, bentadecyl group, heptadecyl group,
1-hexylnonyl group, 1.1'-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4 ′-{α- [4 ″ (p-hydroxybenzenesulfonyl) phenoxy] dodecanoylamino}
Phenylpropyl group, 3- {4 '-[α- (2 ", 4"-
Di-t-amylphenoxy) butanamide] phenyl}
-Propyl group, 4- [α- (o-chlorophenoxy) tetradecanamidophenoxy] propyl group, allyl group,
Examples thereof include a cyclopentyl group and a cyclohexyl group.

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

Specifically, a phenyl group, a 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-
[Α- (4 ″ -t-butylphenoxy) tetradecanamide] phenyl group and the like.

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

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

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

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

Examples of the phosphonyl group represented by Ra include 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. Arylphosphonyl groups such as

The carbamoyl group represented by Ra may be substituted with an alkyl group, an aryl group (preferably a phenyl group),
For example, N-methylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-pentadecyloctylethyl)
Carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-t-amylphenoxy)
Propyl} carbamoyl group and the like.

The sulfamoyl group represented by Ra may be substituted with an alkyl group, an aryl group (preferably a phenyl group),
For example, N-propylsulfamoyl group, N, N-diethylsulfamoyl group, N- (2-pentadecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group Groups and the like.

Examples of the spiro compound residue represented by Ra include spiro [3.3] heptan-1-yl.

As the bridged carbonized compound residue represented by Ra, for example, bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1
^3'7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.
2.1] Heptan-1-yl and the like.

The alkoxy group represented by Ra may be further substituted with those mentioned as the substituent for the alkyl group, for example, a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Pentadecyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group and the like can be mentioned.

As the aryloxy group represented by Ra, phenyloxy is preferable, and the aryl nucleus may be further substituted with any of the substituents or atoms for the aryl group.
For example, phenoxy group, p-1-butylphenoxy group, m
-Pentadecylphenoxy group and the like.

The heterocyclic oxy group represented by Ra is preferably one having a 5- to 7-membered heterocyclic ring, and the heterocyclic ring may further have a substituent, for example, 3,4,5,6-tetrahydropyrani Ru-2-oxy group, 1-phenyltetrazole-5
An oxy group.

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

Examples of the acyloxy group represented by Ra include, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, and the like, which may further have a substituent, and specifically include an acetyloxy group and an α-chloroacetyloxy group. , A benzoyloxy group and the like.

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

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

Examples of the acylamino group represented by Ra include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group) and the like, which may further have a substituent, specifically, an acetamide group, α- Ethylpropanamide group, N-phenylacetamide group,
Dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group and the like can be mentioned.

Examples of the sulfonamide group represented by Ra include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specifically, a methylsulfonylamino group, a bentadecylsulfonylamino group,
Examples thereof include a benzenesulfonamide group, a p-toluenesulfonamide group and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by Ra may be an open chain one, a cyclic one, or may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, Examples thereof include a glutarimide group.

The ureido group represented by Ra may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N-ethylureido group, N-methyl-N-decylureido group and N-phenylureido group. , Np-tolylureido group and the like.

The sulfamoylamino group represented by Ra is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group) and the like, and examples thereof include an N, N-dibutylsulfamoylamino group, an N-methylsulfamoylamino group and an N-phenylsulfamoylamino group. .

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

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

The alkoxycarbonyl group represented by Ra may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. Etc.

The aryloxycarbonyl group represented by Ra may further have a substituent, for example, a phenoxycarbonyl group,
Examples thereof include p-chlorophenoxycarbonyl group and m-pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by Ra may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group and a 3-phenoxypropylthio group.

The arylthio group represented by Ra is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples thereof 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, and may further have a condensed ring or may have a substituent. Examples thereof include a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of the substituent which can be removed by the reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), carbon atom, oxygen atom, sulfur atom or nitrogen atom. Groups which substitute by

Examples of the group substituting through a carbon atom include a carboxy group, for example, a general formula (R ₁ ′ has the same meaning as R above, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group). , A hydroxymethyl group, and a triphenylmethyl group.

Examples of the group substituting through an oxygen atom include an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, an alkoxyoxalyloxy group. Is mentioned.

The alkoxy group may further have a substituent, for example,
Examples thereof include an ethoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a phenethyloxy group and a 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-methanesulfonamide phenoxy group, 4- [α- (3'-pentadecylphenoxy) butanamide] phenoxy group, hexdecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group , 1-naphthyloxy group, p
-Methoxyphenoxy group and the like.

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. Specific examples thereof include a 1-phenyltetrazolyloxy group and a 2-benzothiazolyloxy group.

Examples of the acyloxy group include an acetoxy group, an alkylcarbonyloxy group such as a butanoloxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
An arylcarbonyloxy group such as a benzoyloxy group can be mentioned.

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 and the like.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group and the like.

Examples of the group substituting 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 and a benzylthio group.

Examples of the arylthio group include phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butyl. Examples thereof include a phenylthio group.

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

Examples of the alkyloxythiocarbonylthio group include dodecyloxythiocarbonylthio group.

Examples of the group substituting through the nitrogen atom include those represented by the general formula The items shown in are listed. Here, R ₄ ′ and R ₅ ′ represent a hydrogen atom, an alkyl group, 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 R ₄ ′ and R ₅ ′ may combine with each other to form a heterocycle. However, neither R ₄ ′ nor R ₅ ′ is a hydrogen atom.

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,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylamino group, arylamino group,
Acylamino group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group , A carboxyl group, a cyano group, and a halogen atom. Specific examples of the alkyl group include an ethyl group, an octyl group, a 2-ethylhexyl group, and a 2-chloroethyl group.

The aryl group represented by R ₄ ′ or R ₅ ′ has 6 carbon atoms.
To 32, especially a phenyl group and a naphthyl group are preferable, and the aryl group may have a substituent.
Examples of the substituent for the alkyl group represented by R ₄ ′ or R ₅ ′ and the alkyl group are mentioned. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R ₄ ′ or R ₅ ′ is preferably a 5- or 6-membered heterocyclic group, which may be a condensed ring or may have a substituent. Specific examples thereof include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2
-Villdyl group and the like.

The sulfamoyl group represented by R ₄ ′ or R ₅ ′ is N
-Alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group and the like can be mentioned, and these alkyl groups and aryl groups are the above-mentioned alkyl groups. And may have a substituent described for the aryl group. Specific examples of the sulfamoyl group include N, N-diethylsulfamoyl group, N-methylsulfamoyl group, N-dodecylsulfamoyl group, and Np-tolylsulfamoyl group.

The carbamoyl group represented by R ₄ ′ or R ₅ ′ is N-
Alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diaryl group carbamoyl group and the like can be mentioned. These alkyl group and aryl group are the substituents mentioned for the alkyl group and aryl group. May have. Specific examples of the carbamoyl group include, for example, N, N-diethylcarbamoyl group, N
-Methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, Np-
A trilylcarbamoyl group may be mentioned.

Examples of the acyl group represented by R ₄ ′ or R ₅ ′ include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, the alkyl group, the aryl group,
The heterocyclic group may have a substituent. Specific examples of the acyl group include, for example, a hexafluorobutanoyl group, a 2,3,4,5,6-pentafluorobenzoyl group,
An acetyl group, a benzoyl group, a naphthoyl group, a 2-furylcarbonyl group and the like can be mentioned.

Examples of the sulfonyl group represented by R ₄ ′ or R ₅ ′ include an alkylsulfonyl group, an arylsulfonyl group and a heterocyclic sulfonyl group, which may have a substituent, and specific examples thereof include ethanesulfonyl group. Group, benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl group, p-chlorobenzenesulfonyl group and the like.

The aryloxycarbonyl group represented by R ₄ ′ or R ₅ ′ may have the above-mentioned aryl group as a substituent, and specific examples thereof include a phenoxycarbonyl group.

The alkoxycarbonyl group represented by R ₄ ′ or R ₅ ′ may have the substituents described above for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group. Etc.

The heterocycle formed by combining R ₄ ′ and R ₅ ′ is 5 to
A 6-membered one is preferable, and it may be saturated or unsaturated,
Further, it may or may not have aromaticity, and may be a condensed ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxooxazolidinyl group, 2- N-1,1-dioxo-3-
(2H) -oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-
Pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1
-Indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1- (1,2,4
-Triazolyl) 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, 2-1H-pyridone group , A phthalazine group, a 2-oxo-1-piperidinyl group, and the like, and these heterocyclic groups are an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an acyl group, a sulfonyl group, an alkylamino group, an arylamino group, Substituted with an acylamino group, sulfoneamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imide group, nitro group, cyano group, carboxyl group, halogen atom, etc. May be.

The nitrogen-containing heterocycle formed by Z or Z'includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, and the like, and the substituent which the ring may have is the same as those described above for R. Is mentioned.

Further, the general formula [aI] and the general formulas described below [aII] to [aVIII]
On the heterocycle in (for example, R _a , R _{1a to} R _5a are Part (where R ″, X and Z ″ are R in the general formula [I],
Synonymous with X and Z. A), a so-called bis type coupler is formed, which is of course included in the present invention. Also, Z, Z ′,
The ring formed by Z ″ and Z ₁ described later may be condensed with another ring (for example, a 5- to 7-membered cycloalkene). For example, in the general formula [aV], R _5a and R _6a In the general formula [aVI], R _7a and R _8a may combine with each other to form a ring (for example, a 5- to 7-membered cycloalkene or benzene).

What is represented by the general formula [aI] is more specifically represented by, for example, the following general formulas [aII] to [aVII].

General formula (aII) General formula (aIII) General formula (aIV) General formula (aV) General formula (aVI) General formula (aVII) In the general formulas [aII] to [aVII], R _{1a to} R _8a and X
Is synonymous with R _a and X.

Among the general formula [aI], the one represented by the following general formula [aVIII] is preferable.

General formula (aVIII) In the formula, R _1a , X and Z _1a have the same meanings as R _a , X and Z in formula [aI].

Among the magenta couplers represented by the general formulas [aII] to [aVII], the magenta coupler represented by the general formula [aII] is particularly preferable.

Regarding the substituents on the heterocycle in the general formulas [aI] to [aVIII], R in the general formula [aI] and R ₁ in the general formulas [aII] to [aVIII] are the following condition 1 The following conditions 1 and 2 are more preferable, and the following conditions are particularly preferable.
This is the case when 1, 2, and 3 are satisfied.

Condition 1 The root atom directly connected to the heterocycle is a carbon atom.

Condition 2 Only one hydrogen atom is bonded to the carbon atom or none is bonded.

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

The most preferable substituents Ra and R _1a on the heterocycle are represented by the following general formula [aIX].

General formula [aIX] In the formula, R _9a , R _10a and R _11a are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group or a sulfinyl group. , Phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group , An acylamino group, a sulfonamide group, an imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and at least two of R _9a , R _10a and R _11a are not hydrogen atoms.

Also, two of R _9a , R _10a and R _11a , such as R _9a and R _10a
May combine to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), and R _11a may bond to the ring to form a bridged hydrocarbon compound residue. Good.

The group represented by R _{9a to} R _11a may have a substituent,
Specific examples and substituents which may be the base has a group represented by _9a to R _11a, include specific examples and substituents of the group represented by R in the general formula [aI] described above.

Further, for example, a ring formed by combining R _9a and R _10a and R _{9a to} R
Specific examples of the bridged hydrocarbon compound residue formed by _11a and the substituent which it may have include the cycloalkyl, cycloalkenyl and heterocyclic group bridged carbon atoms represented by Ra in the general formula [aI]. Specific examples of the hydrogen compound residue and its substituents are given.

Among the general formula [aIX], preferred is (i) when two of R _{9a to} R _11a are alkyl groups, (ii) one of R _{9a to} R _11a , for example, R ₁₁ is a hydrogen atom. And when the other two R _9a and R _10a combine to form a cycloalkyl with the root carbon atom.

Further preferred among (i) is 2 of R _{9a to} R _11a.
One is an alkyl group and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl, the cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl and the substituent thereof include the alkyl represented by Ra in the general formula [aI], the cycloalkyl and the substituent thereof. Specific examples of the group include:

Further, the ring formed by Za in the general formula [aI] and the substituent which the ring formed by Z _1a in the general formula [aVIII] may have, and the general formulas [aII] to [aVI]
As R _{2a to} R _8a , those represented by the following general formula [aX] are preferable.

The general formula [aX] -R ¹ -SO ^₂ -R ₂ Formula wherein R ¹ is alkylene, R ² represents alkyl, cycloalkyl or aryl.

The alkylene represented by R ¹ preferably has a straight chain portion having 2 or more carbon atoms, more preferably 3 to 6, and may be straight chain or branched. Further, this alkylene may have a substituent.

Examples of the substituent include Ra in the general formula [aI] described above.
When is an alkyl group, the examples of the substituent which the alkyl group may have are mentioned.

Preferred as the substituent is phenyl.

Preferred specific examples of the alkylene represented by R ¹ are shown below.

The alkyl group represented by R ² may be linear or branched.

Specifically, methyl, ethyl, propyl, iso-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, 2-
Hexyldecyl and the like can be mentioned.

The cycloalkyl group represented by R ² is preferably a 5- or 6-membered cycloalkyl group, and examples thereof include cyclohexyl.

The alkyl and cycloalkyl represented by R ² may have a substituent, and examples thereof include those exemplified as the substituent for R ¹ described above.

Specific examples of the aryl represented by R ² include phenyl,
Examples include naphthyl. The aryl group may have a substituent. Examples of the substituent include straight-chain or branched alkyl, and those exemplified as the substituent for R ¹ described above.

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

Among the compounds represented by the general formula [aI], particularly preferred are those represented by the following general formula [aXI].

General formula (aXI) Wherein, Ra, Xa has the same meaning Ra, and Xa in the general formula [aI], R ^1, R ² has the same meaning as R ^1, R ² in the general formula [aX].

Hereinafter, typical examples of the compound represented by the general formula [aI] will be shown.

As the cyan image forming coupler, the following general formula [E],
The coupler represented by [F] can be preferably used.

General formula [E] In the formula, R _1E represents an aryl group, a cycloalkyl group or a heterocyclic group. R _2E represents an alkyl group or a phenyl group. R _3E represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R _1E represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine type color developing agent.

General formula [F] In the formula, R _4F is an alkyl group (for example, a methyl group, an ethyl group,
Propyl group, butyl group, nonyl group, etc.). R _5F represents an alkyl group (eg, methyl group, ethyl group, etc.).
R _5F is a hydrogen atom, a halogen atom (for example, fluorine, chlorine,
Bromine etc.) or an alkyl group (eg methyl group, ethyl group etc.). Z ₂ represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine type color developing agent.

In the present invention, the aryl group represented by R _1E in the general formula [E] is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. The heterocyclic group represented by R _1E is, for example, a pyridyl group or a furan group. The cycloalkyl group represented by R _1E is, for example, a cyclopropyl group or a cyclohexyl group. The group represented by R _1E may have a single or a plurality of substituents. For example, a typical example of the substituent introduced into the phenyl group is a halogen atom (eg, fluorine, chlorine, bromine, etc.). ), An alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (eg, methoxy group, ethoxy group, etc.), alkyl sulfonamide group (eg, Methyl sulfonamide group, octyl sulfonamide group, etc.), aryl sulfonamide group (eg phenyl sulfonamide group,
Naphthyl sulfonamide group etc.), alkylsulfamoyl group (eg butylsulfamoyl group etc.), arylsulfamoyl group (eg phenylsulfamoyl group etc.), alkyloxycarbonyl group (eg methyloxycarbonyl group etc.), Aryloxycarbonyl group (for example, phenyloxycarbonyl group, etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfooxy group, sulfo group, aryloxy group, alkoxy group, carboxyl group, alkylcarbonyl group, An aryl carbonyl acid, an amino carbonyl group, etc. can be mentioned. Two or more of these substituents may be substituted with a phenyl group. The preferred group represented by R _1E is a phenyl group or a halogen atom, an alkylsulfonamide group, an arylsulfonamide group, an alkylflufamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, A phenyl group having one or more arylcarbonyl groups or cyano groups as substituents.

The alkyl group represented by R _2E is linear or branched and is, for example, a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group.

In the present invention, the cyan coupler represented by the general formula [E] is preferably a compound represented by the following general formula [E '].

General formula [E '] In the general formula [E ′], R _7E represents a phenyl group.

The phenyl group may have a single or a plurality of substituents, and typical examples of the introduced substituents include a halogen atom (eg fluorine, chlorine, bromine etc.), an alkyl group (eg a methyl group, Ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (eg methoxy group,
Ethoxy group, etc.), alkylsulfonamide group (eg methylsulfonamide group, octylsulfonamide group etc.), arylsulfonamide group (eg phenylsulfonamide group, naphthylsulfonamide group etc.), alkylsulfamoyl group (eg butylsulfur group) Famoyl group etc.), arylsulfamoyl group (eg phenylsulfamoyl group etc.), alkyloxycarbonyl group (eg methyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group etc.), etc. You can Two or more of these substituents may be substituted with a phenyl group. Preferable group represented by R _7E is phenyl or halogen atom (preferably fluorine, bromine, alkylsulfonamide group)
(Preferably o-methylsulfonamide group, p-octylsulfonamide group, o-dodecylsulfonamide group), arylsulfonamide group (preferably phenylsulfonamide group), alkylsulfamoyl group (preferably butylsulfamoyl group) Group), arylsulfamoyl group (preferably phenylsulfamoyl group), alkyl group (preferably methyl group, trifluoromethyl group)
It is a phenyl group having one or more alkoxy groups (preferably a methoxy group or an ethoxy group) as a substituent.

R _8E is an alkyl group or an aryl group. The alkyl group or aryl group may have a single or a plurality of substituents, and typical examples of the substituent include a halogen atom (eg, fluorine, chlorine, bromine), a hydroxyl group, a carboxyl group, an alkyl group. Group (for example, methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), aralkyl group, cyano group, nitro group, alkoxy group (for example, methoxy group, ethoxy group) aryloxy group, alkylsulfonamide group (Eg, methyl sulfonamide group, octyl sulfonamide group, etc.) Aryl sulfonamide group (eg, phenyl sulfonamide group, naphthyl sulfonamide group, etc.) Alkylsulfamoyl group (eg, butylsulfamoyl group, etc.), arylsulfamoyl group (Eg phenylsulfamoyl group etc.), alkylo Sicarbonyl group (eg, methyloxycarbonyl group), aryloxycarbonyl group (eg, phenyloxycarbonyl group), aminosulfonamide group (eg, dimethylaminosulfonamide group), alkylsulfonyl group, arylsulfonyl group, alkylcarbonyl group , An arylcarbonyl group, an aminocarbonylamide group, a carbamoyl group, a sulfinyl group and the like. Two or more kinds of these substituents may be introduced.

Preferred groups represented by R _8E are an alkyl group when n = o and an aryl group when n = 1 or more. R
A more preferred group represented by _8E is n = o
In this case, an alkyl group having 1 to 22 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group,
Dodecyl group), and when n = 1 or more, a phenyl group,
Or an alkyl group (preferably 1-butyl group, 1-amyl group, octyl group), an alkyl sulfonamide group (preferably a butyl sulfonamide group, an octyl sulfonamide group, a dodecyl sulfonamide group), an aryl sulfonamide group (preferably Phenylsulfonamide group), aminosulfonamide group (preferably dimethylaminosulfonamide group), alkyloxycarbonyl group (preferably methyloxycarbonyl group, butyloxycarbonyl group) as a substituent phenyl group having one or more Is.

R _9E represents an alkylene group. It represents a linear or branched alkylene group having 1 to 20 carbon atoms, and further having 1 to 12 carbon atoms.

R _10E represents a hydrogen atom or a halogen atom (fluorine, chlorine, bromine or iodine). It is preferably a hydrogen atom.

n is 0 or a positive integer, preferably 0 or 1.

X _E is -O -, - CO -, - COO -, - OCO-, SO 2 NR E '-,
_{NR E 'SO 2 NR E "} -, - S-, or -SO ₂ -. Represents a divalent group wherein R _E', R _E" represents a substituted or unsubstituted alkyl group. X _E is preferably -O-, -S-, -SO.
-, - group - SO _2.

Z ₃ represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.

Chlorine atom and fluorine atom are preferable.

In the present invention, the cyan coupler represented by the general formula [F] is more preferably represented by the following general formula [F '].

General formula [F '] In the formula, R ₁₁ and R ₁₂ are the same or different and each represent a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, dodecyl group, etc.), alkoxy group (eg, Methoxy group, ethoxy group, etc.).

However, the total number of carbon atoms of R ₁₁ and R ₁₂ is 8 to 16. More preferably, R ₁₁ and R ₁₂ are each a butyl group or an amyl group.

R ₁₃ is a hydrogen atom or an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, octyl group, etc.).

Preferred are a hydrogen atom, an ethyl group and a butyl group.

R ₅ ′ is an alkyl group (eg, methyl group, ethyl group, etc.).

m represents an integer of 0 to 2. Z ₄ represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.

In formulas [E], [F], [E '], and [F'], with an oxidized product of an aromatic primary amine type color developing agent represented by Z ₁ , Z ₂ , Z ₃ and Z ₄ . The group capable of splitting off upon reaction is well known to those skilled in the art, and modifies the reactivity of the coupler or splits off from the coupler to form a coating layer or other layer containing the coupler in the silver halide color photographic light-sensitive material. In the layer, it exerts an advantageous effect by fulfilling functions such as development suppression, bleaching suppression and color correction. Representative examples include alkoxy groups, aryloxy groups, arylazo groups, thioethers, carbamoyloxy groups, acyloxy groups, imide groups, sulfonamide groups, thiocyano groups or heterocyclic groups (eg, oxazolyl, diazolyl, triazolyl, tetrazolyl). Etc.) and the like. A particularly preferable example represented by Z is a hydrogen atom or a chlorine atom.

Typical representative examples of the cyan coupler represented by the formula [F] are shown below, but the cyan coupler is not limited to these.

The combination ratio of the compound represented by the general formula [I] to the dye image-forming coupler in the present invention can be any ratio depending on the case, but is preferably 10 ^{−3 with} respect to 1 mol of the color image-forming coupler. It can be used in the range of 10 mol to 10 mol, and particularly preferably in the range of 5 × 10 ^-2 mol to 5 mol.

Further, the complex compound formed by the complex formation reaction of the released LIG with the metal ion may be substantially colorless or colored, but when the molar extinction coefficient in the visible region is 10 ⁴ or more, the dye image forming coupler is used. It is preferable that the color of the dye image is substantially the same as that of the dye image obtained, and it is particularly preferable that the difference in the maximum absorption wavelength in the visible region is within 20 nm.

Also, Cp as a function of silver halide development may or may not form a dye image by reaction with an oxidant of a color developing agent, but when forming a dye image, it is obtained from the dye image-forming coupler. It is preferable that the color is substantially the same as that of the dye image, and it is particularly preferable that the difference in the maximum absorption wavelength in the visible region is within 20 nm, and it is particularly preferable that the same dye is used.

The complex compound having a function of stabilizing the dye image, which is produced by the complex formation reaction of the released LIG with the metal ion in the present invention, may be substantially colorless. Substantially colorless means that it does not have substantially strong absorption in the visible region, and more specifically, if it is desired to use a substantially colorless one, it does not show an absorption peak at 400 nm to 700 nm or 400 nm. The molar absorption coefficient at the maximum absorption wavelength at 700 to 700 nm is preferably 1,000 or less, 5
A value of 00 or less is particularly preferable.

The complex compound having the function of stabilizing the dye image represents a complex compound which is stabilized by any mechanism depending on the type of dye image, medium and existing state, but preferably the quenching rate constant of singlet oxygen is 3 or less. A complex compound of × 10 ⁷ M ^-1 · sec ^-1 or more, particularly a compound having an extinction rate constant of 1 × 10 ⁸ M ^-1 · sec ^-1 or more is preferably used.

The quenching rate constant of singlet oxygen described above is determined by the Journal of Physical Chemis
try) 83 , 591 (1979), etc., to determine the photobleaching of rubrene.

That is, a chloroform solution of rubrene and a chloroform solution of rubrene and a compound to be measured are irradiated with light of equal energy.

The initial concentration of rubrene in this and [R], the concentration of the compound to be measured as [Q], the concentration of rubrene rubrene single solution after the test and ▲ [R] ^O _F ▼, the rubrene after test Change the concentration of rubrene in the mixed solution of the measurement compound to ▲ [R] ^Q _F
Then, the quenching rate constant (kq) of singlet oxygen is Calculated by

Further, the complex stability constant of the complex compound according to the present invention can take any value, but generally, a compound having a range of 10 ^{10 to} 10 ³⁰ can be preferably used.

As a method of supplying metal ions for forming a complex compound with LIG in the general formula of the present invention, there are a method of supplying metal ions from outside the photosensitive material and a method of previously incorporating a metal ion or a metal ion donor. is there. As the former specific method, for example, a method of adding it as a water-soluble metal salt to a processing solution in the processing step of the photosensitive material to introduce it into the photosensitive material during the processing step can be mentioned. The processing solution may be any processing solution such as a color developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, a stabilizing solution, washing water, and a rinse solution, but it is preferably a step subsequent to the color developing. Further, it is preferably added to the processing liquid of the step subsequent to the bleaching or bleach-fixing step.

Specific examples of the water-soluble metal salt are shown below, but the present invention is not limited thereto.

・ Ni ₂ ⁺ … NiBr ₂ (+ 3H ₂ O) NiCl ₂・ 6H ₂ O Ni (NO ₃ ) ₂・ 6H ₂ O NiSO ₄・ 6H ₂ O ・ Cu ₂ ⁺ … CuCl ₂・ 2NH ₄ Cl ・ 2H ₂ O CuCl ₂・ 2H ₂ O Cu (NO ₃ ) ₂・ 3H ₂ O CuSO ₄・ 5H ₂ O ・ Zn ₂ ⁺ … ZnBr ₂ ZnCl ₂ Zn (NO ₃ ) ₂・ 6H ₂ O ZnSO ₄・ 7H ₂ O ・ Fe ^{2 +} … FeSO ₄・ (NH ₄ ) ₂ SO ₄・ 6H ₂ O FeBr ₂ FeCl ₂ (+ 4H ₂ O) Fe (NO ₃ ) ₂・ 9H ₂ O FeSO ₄・ 7H ₂ O ・ Co ₂ ⁺ … CoCl ₂・6H ₂ O CoSO ₄ .7H ₂ O The concentration of the water-soluble metal salt can be arbitrarily determined according to the composition of the treatment liquid to be added, the treatment temperature, etc., but is preferably a molar concentration of 10 ^{−4 to} 5 mol. It can be used in the range of.

As a specific method of the latter, a method of using a polymer complex formed from a polymer ligand and a metal ion as a metal ion donor compound is disclosed in JP-A-55-48,210 and JP-A-55-129,346. JP-A-56-126,529 and 60-206,537
No. 60-206,538, and Nos. 60-205,539, a method using a water-soluble organometallic complex is also disclosed.
No. 58-38,955, No. 58-105,146 and No. 58-129,429, the method using a water-insoluble organometallic complex, further JP-A-57-105,738 is reduced under alkali. Non-diffusible complexes having ligand exchange activity are disclosed respectively. Of these methods, they can be arbitrarily selected from the viewpoints of ease of introduction into a light-sensitive material and small influence on photographic performance, and speed of reaction such as ligand exchange, but preferably water-soluble. A method of using a water-soluble or water-insoluble organometallic complex as a metal ion donating compound can be used. This organometallic complex is produced, for example, by the following ligand and metal ion, and introduced into the photosensitive material by a conventionally known method. The metal ion may be any metal ion as long as it forms a complex compound having a dye image stabilizing function by undergoing a complex formation reaction with LIG in the above general formula of the present invention, but as described above, Ni
Transition metal ions such as ²⁺ , Cu ²⁺ , Zn ²⁺ , Fe ²⁺ and Co ²⁺ are preferable, and Ni ²⁺ , Cu ²⁺ and Fe ²⁺ are particularly preferable.

The specific examples of the ligands useful for producing the water-soluble and water-insoluble metal ion donor compounds which can be preferably used in the present invention are shown below, but the present invention is not limited thereto.

〔Water soluble〕

[Water insolubility] The complex compound-forming compound according to the present invention is contained in combination with the silver halide emulsion, and the term "combined" as used herein means that the complex compound is arranged so as to be formed as a function of the development of silver halide. It means that the silver halide emulsion and the complex compound-forming compound do not necessarily have to be in the same layer. The complex compound forming compound according to the present invention can be preferably added to the silver halide emulsion layer and the intermediate layer, and particularly preferably to the silver halide emulsion layer.

When the compound represented by the general formula [I] and the dye-forming coupler of the present invention are used in combination, the compound and the combined coupler may be added in any amount, but a preferable range is halogenation. 1 × 10 ^{−3 to} 2 mol, preferably 1 × 10 ⁻² mol, per mol of silver
It can be used in a range of 8 to 10 × ¹ mol.

The compound represented by the general formula [I] can be added by any method depending on the properties of the compound, the type of the light-sensitive material and the like. When the compound is a polymer coupler, it can be dispersed in the hydrophilic binder solution as it is. When the compound is a hydrophobic compound, known methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used, but the oil-in-water emulsion dispersion method is preferred.

The oil-in-water type emulsion dispersion method can be applied to a conventionally unknown method of dispersing a hydrophobic additive such as a coupler, and usually has a boiling point of about
High boiling point organic solvent of 150 ℃ or more, low boiling point, if necessary,
And / or a water-soluble organic solvent is used together to dissolve, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution and a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flowgit mixer, and a long-wave device is used. After emulsifying and dispersing, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

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

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

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

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

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

The grain size, grain shape, grain size distribution and grain growth rate of the silver halide grains can be controlled by using a silver halide emulsion, if necessary, during the production of the silver halide emulsion of the present invention.

The silver halide grains used in the silver halide emulsion of the present invention have a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt in the step of forming and / or growing the grain. , Iron salt or complex salt,
Can be incorporated into the inside of the particle and / or the surface of the particle by adding a metal ion to the inside of the particle, and by providing an appropriate reducing atmosphere, a reduction sensitizing nucleus is given to the inside of the particle and / or the surface of the particle. I can.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained therein. The salts can be removed by the method described in Research Disclosure 17643.

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

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

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal form, or may have an irregular crystal form such as a sphere or a plate. In these particles, any ratio of [1,0,0] plane to [1,1,1] plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

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

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

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

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

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

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

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

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

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

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

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

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer to prevent fog due to discharge due to the light-sensitive material being charged by friction or the like, and an ultraviolet absorber to prevent deterioration of the image by UV light. It may be included.

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

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

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

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

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

The light-sensitive material using the silver halide emulsion of the present invention is a photographic emulsion layer, the other layers are variter layer or α-olefrein polymer, laminated paper, flexible reflective support such as synthetic paper, cellulose acetate, It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, and rigid bodies such as glass, metal and pottery.

The silver halide material of the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, directly or (adhesiveness of the support surface, antistatic property, dimensional stability,
It may be applied via one or more subbing layers) to improve wear resistance, hardness, antihalation, frictional properties, and / or other properties.

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

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

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

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

The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known compounds widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds are generally used at a concentration of about 0.1 g to about 30 g for color developer 1, preferably at a concentration of about 1 g to about 15 g for color developer 1.

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

Particularly useful primary aromatic amino color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
The alkyl group and phenyl group may be substituted with any substituent. Among them, particularly useful compound examples are N,
N'-diethyl-p-phenylenediamine hydrochloride, N-
Methyl-p-phenylenediamine hydrochloride, N, N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5
-(N-ethyl-N-dodecylamino) -toluene, N
-Ethyl-N-β-methanesulfonamidoethyl-3-
Methyl-4-aminoaniline sulfate, N-ethyl-N-
β-hydroxyethylaminoaniline, 4-amino-3
-Methyl-N, N'-diethylaniline, 4-amino-N
Examples include-(2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate.

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

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

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

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotritri Sodium acetate salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide, a metal salt or a chelating agent. Further, borate, oxalate, acetate, carbonic acid support, pH buffers such as phosphates, alkylamines, polyethylene oxides and the like, which are known to be added to ordinary bleaching solutions, can be appropriately added. .

Further, the fixer and the bleach-fixer are ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid A single pH buffer or two or more pH buffers composed of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained.

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

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

〔Example〕

Examples of the present invention will be described below. It should be understood that the present invention is not limited to the examples below.

Example 1 A silver halide photographic light-sensitive material having a layer structure shown in Tables 1 and 2 below was prepared.

The coating amount was expressed in mg / 100 cm ² .

The composition of the coupler dispersion used in the green-sensitive emulsion layer is as shown in Table 2. In addition, as a water phase, each sample is a 5% gelatin aqueous solution 500 containing 3.0 g of alkanol B manufactured by DuPont.
After mixing with ml, the mixture was emulsified and dispersed by a homogenizer.

In the table, DBP is dibutyl phthalate and EA is ethyl acetate. The following dye image stabilizers were used, and the high boiling point organic solvent was kept constant at 25 ml.

The thus-prepared sample was exposed to white light through an optical wedge using a sensitometer (KS-7 type, manufactured by Konishi Rokusha Kogyo Co., Ltd.), and then treated according to the following treatment steps.

Samples 1 and 2 were processed in the process step A, and samples 3 to 13 were processed in the process step B.

[Color developer composition]

Pure water 700 ml Benzyl alcohol 15 ml Diethyl glycol 15 ml Hydroxylamine sulfate 2 g N-ethyl-N-β-methanesulfonamide ethyl-3
-Methyl-4-aminoaniline sulfate 4.4 g Potassium carbonate 30 g Potassium chloride 0.5 g Potassium bromide 0.4 g Potassium sulfite 2 g Pure water is added to make 1.

(Adjusted to pH = 10.2) [Complex forming liquid composition] 14.5 g of Ni (NO ₃ ) ₂ -6H ₂ O Pure water is added to make 1.

[Bleaching fixer composition]

Ethylenediaminetetraammonium iron acetate 61 g Ethylenediaminetetraacetate diammonium 5 g Ammonium thiosulfate 125 g Sodium metabisulfite 13 g Sodium sulfite 2.7 g Add water to make 1.

(Adjustment to pH = 7.2) Each sample thus treated was tested for white background, light fading and yellowing of white background due to light, and the obtained results are shown in Table 3.

(1) White background test The white area (unexposed area) of each obtained sample is JIS Z8722 and Z8.
The a ^* b ^* value was measured using a Hitachi Color Analyzer 607 type based on the object color measuring method defined in 727.

It shows that the redness increases as the a ^* value increases, and the greenness increases as the a ^* value decreases. Also, as the b ^* value increases, the yellowness increases,
It shows that the blue tint increases as it decreases.

(2) Light fastness test A Xenon fade meter Illuminance (lux) Irradiation time (H) 1 × 10 ⁵ 100 Light irradiation was performed under the conditions of A above, and the residual dye rate R and yellowing ΔD of the white background were as follows. I asked. The density of the unexposed area of the sample not irradiated with light is ▲ D ⁰ _min ▼, and the density of the color development area is D ₀ = 1.0.
And D _min and D after light irradiation respectively, It is represented by ΔD = D _min −ΔD ⁰ _min ▼ (blue density).

(2) Darkness storability test R and ΔD were obtained in the same manner as in (2) except that the condition B was left at 85 ° C, 60% RH in the dark for 10 days.

From the results shown in Table 3, it is clear from comparison between Comparative Samples 1 to 3 that Sample 3 has improved light fastness without deteriorating the whiteness, but the effect of improving the dark storage stability is can not see. On the other hand, it is clear that in Samples 4 to 13 according to the present invention, not only the light fastness is further improved, but also the storability in the dark is improved, and the high image storability is comprehensively imparted. .

Example 2 A multilayer silver halide color photographic light-sensitive material having the layer structure shown in Table 4 was prepared.

The stain inhibitor and the ultraviolet absorber used here are compounds having the structures shown below.

The sample prepared as described above is referred to as Sample 1, and the couplers and dye image stabilizers of the first layer, the third layer and the fifth layer in Sample 1 were changed as shown in Table 5 to prepare Samples 2 to 8. The result obtained by performing the same test as in Example 1 is also the fifth.
Shown in the table. However, Samples 1 and 2 are processing step A, Sample 3
Process steps B were applied to Nos. 8 to 8.

In Table 5, the numerical value in the lower row of the column for couplers and the like shows the coating amount, and the unit was × 10 ^-3 mol / m ² . However, the dye-forming coupler was changed equimolar.

In the magenta coupler-containing layer according to the present invention, the light fastness and the like are more remarkable than the other layers, and it can be seen that the effect of the present invention is exhibited. Further, in the multi-layer silver halide color photographic light-sensitive material, the same effect as in Example 1 was rather amplified, and a multi-layer silver halide light-sensitive material excellent in whiteness, light fastness and dark fading was obtained. I understand that

Example 4 Six kinds of samples Nos. 3 to 8 in Example 2 were used as the bleach-fixing solution 1 in the processing step A in Example 2.
The same process as in Process A was performed except that 15 g of Fe (NO ₃ ) ₂ .9H ₂ O was added, and the same test as in Example 2 was performed.

As a result, almost the same result as in Example 2 was obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion contained in one layer containing at least a magenta coupler in the silver halide emulsion layer. Compounds represented by the following general formula [I] in combination with
A silver halide photographic light-sensitive material characterized by being contained in a state of being emulsified and dispersed using the following high boiling point organic solvents. General formula [I] C _P T _n LIG ( _where C _P is a function of T _n as a function of development of silver halide)
Represents a group capable of leaving LIG, and T represents a group capable of releasing LIG when or after T _n LIG leaves,
Represents a ligand capable of forming a complex compound having a dye image stabilizing function by undergoing a complex formation reaction with a metal ion. n represents 0 or 1. )