JPS62165654A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a remarkable high lightfastness by incorporating a color image forming coupler and a specific compd. together with a silver halide emulsion contd. in at least one layer of the silver halide emulsion layers. CONSTITUTION:The titled material comprises the color image forming coupler and the compd. shown by the formula together with the silver halide emulsion contd. in at least one layer of the sivler halide emulsion contd. in at least one layer of the silver halide emulsion layers in the titled material comprising at least one layer of the silver halide emulsion layers formed on a substrate. The compounding ratio of the compd. shown by the formula to the prescribed coupler is not specified, preferably 10<-3>-10mol, further preferably 5X10<-2>-5mol the compd. per 1mol the coupler.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material that is provided with extremely high light fastness without deteriorating whiteness. Regarding.

[Background of the invention]

Conventionally, when a silver halide photographic light-sensitive material is imagewise exposed and color developed, a coupling reaction occurs between the oxidized product of an aromatic primary amine color developing agent and a color former, resulting in formation of compounds such as indophenol, indoaniline, and indamine. It is well known that dyes such as , azomethine, phenoxazine, phenazine, and similar dyes are produced and dye images are formed. In this type of photography, a subtractive color method is usually used to reproduce colors, and blue sensitivity,
In the green-sensitive and red-sensitive photosensitive silver halide emulsion layers,
A silver halide photographic light-sensitive material is used which contains a color forming agent having an aftercolor relationship, that is, a coupler that develops yellow, magenta, and cyan.

It is known that silver halide photographic materials having the above-mentioned dye images undergo significant discoloration and fading under the storage conditions. For example, they often show different fading properties when they are exposed to light for a long time and when they are stored, and when they are exposed to light for a short time but are stored in a dark place with high temperature and humidity for a long time. The former case is called light fading, and the latter case is called dark fading.In order to use silver halide photographic materials with dye images as recording materials that can be stored semi-permanently, it is necessary to minimize these fading under any storage conditions. Desired to be small.

However, in conventional silver halide photographic materials, fading under the above-mentioned storage conditions has not been sufficiently prevented, and the fastness of dye images has not yet been satisfactory. Furthermore, in recent years, the demand for dye image storage stability has only increased, and the development of technology to dramatically increase the hardness of dye images has become increasingly important.
desired.

In order to improve the fastness of dye images, a number of methods have been proposed in the past from two aspects. One is a method of improving the fastness of the dye image itself, and Improvements are made in the molecular structure design of image-forming compounds (e.g., couplers, etc.) or by changing the state of existence of dyes.Another method is to use a dye image stabilizer; Many improvements in this respect have been proposed because the method has little effect on the characteristics of the dye image such as color tone and is highly versatile.

Regarding the use of dye image stabilizers, various methods have been proposed in the past to improve the photobleaching of dye images by adding ultraviolet absorbers to the photographic element or by providing a layer of ultraviolet absorbing filters. .

However, in order to obtain satisfactory light fastness using this UV absorber, a large amount of UV absorber is required. The fabric part is colored yellow.

The drawback is that the solubility of ultraviolet absorbers in high-boiling point a solvents is low, and they tend to precipitate during the manufacturing process.

Therefore, there is a limit to the amount that can be added, and a sufficient effect to harden the dye image cannot be obtained.Furthermore, even if it can prevent photofading caused by ultraviolet light, it is ineffective in preventing photofading caused by visible light. It also had the serious drawback of not showing

In order to overcome these drawbacks, various dye image stabilizers have been proposed to replace ultraviolet absorbers. For example, as compounds having a phenolic hydroxyl group or a phenolic hydroxyl group by hydrolysis, bisphenols,
U.S. Pat. No. 3,069,262 discloses Pirogar rJ
U.S. Pat. No. 3,432,300 and U.S. Pat. No. 3,574,627. No. 20977 discloses 6,6'-dihydroxy 2+2'-bisspirochroman.
6: No. 33, No. 53-17729, and No. 54-
48538, 6-alkoxychroman mR
6,6'-dialkoxy 2,2'-bisspirochromans, hydroquinone derivatives, etc. have been proposed.

However, while some of these compounds are certainly effective against photochromic fading of dye images, they have no effect at all on dark fading, and on the contrary, some promote dark fading. . Furthermore, some compounds are effective for a certain period of time, but their effectiveness decreases or becomes completely ineffective when stored for a long period of time, and some even cause color staining. Furthermore, some compounds have an effect of preventing discoloration and fading on magenta dye images, but some compounds significantly accelerate discoloration and fading on cyan and yellow dye images.

Furthermore, there are often limits to the improvement effect achieved by using only these compounds. Also, as a light stabilizer, US Pat.
Metal complexes described in JP-A No. 050,938, JP-A No. 56-99,340, JP-A No. 56-168,652, JP-A No. 60-51,834, and JP-A No. 60-97,353 have been proposed. There is. It is true that some of these compounds impart high light fastness when used alone or in combination with the above-mentioned dye image stabilizers, but because they are metal complexes, the light stabilizers themselves are colored. Some products may cause yellowing due to heat and humidity, low solubility of light stabilizers in organic solvents, and adverse effects on photographic performance such as decreased sensitivity and increased capri. However, it was difficult to apply it to silver halide photographic light-sensitive materials.

As described above, at present, no technique for improving the storage stability of dye images capable of imparting satisfactory fastness to silver halide photographic materials has yet been discovered.

Additionally, U.S. Pat. No. 4,555,477 and U.S. Pat. No. 4,555,478 disclose that substantially colorless, immobile ligand-releasing compounds are combined with silver halide emulsions. A method for obtaining highly stabilized color masking dyes and a method for obtaining highly stabilized color images is disclosed.

Specifically, in the former method, in the developed part of the exposed area, the ligand is released and flows out of the system, but in the undeveloped part of the unexposed area, the above-mentioned compound undergoes a complex reaction with the metal ion. This is a technology that causes the formation of stable masking dye complexes. Therefore, in the exposed area after development, that is, the area where the dye image is formed, the ligand is eluted out of the system, so that there is no contribution from the complex compound. There is no disclosure that the ligand remains in some form in the image forming area and functions.

Specifically, the latter method is a technique in which a ligand is released in an imagewise exposed and developed area, and the ligand and metal ion form a stable gold pA complex dye image. In the latter case, the source of the dye in the dye image is a metal complex, and as is commonly said, metal complex dyes have excellent light resistance, and therefore, dye images with good light resistance can be obtained. It is excellent in that it can be used. However, it is not always possible to obtain a desired color with metal complex dyes, and there is a problem in that the range of selection is somewhat narrow in terms of tone and hue.

Furthermore, in both specifications, one of the major features of the present invention, which will be explained in detail later, is that the ligand released as a function of development causes a complex formation reaction with metal ions and has a dye image stabilizing function. There is no description or even suggestion that a compound having the above compound can be obtained and that a silver halide photographic material using the same has excellent performance.

In view of the above-mentioned current situation, the present inventors have conducted intensive research to achieve dramatically improved fastness of dye images, and have discovered the present invention.

[Purpose of the invention]

A first object of the present invention is to provide a silver halide photographic material that is endowed with extremely high light fastness.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which is provided with extremely high light fastness without deteriorating whiteness.

A third object of the present invention is to provide a silver halide photographic light-sensitive material that is imparted with extremely high light fastness without deteriorating photographic performance such as yellowing during storage.

A fourth object of the present invention is to provide a method for introducing a metal complex dye image stabilizer into a silver halide photographic material without deteriorating whiteness.

[Structure of the invention]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which a small amount of the silver halide emulsion layer (both the silver halide emulsion contained in one layer and the silver halide emulsion contained in one layer) This was achieved by a silver halide photographic light-sensitive material characterized by containing a dye image-forming coupler and a compound represented by the following general formula [I] in combination.

General formula (1) % formula % (where CP is a function of silver halide development -+
T)-L E represents a group that leaves C, and 1゛ is →
T+, [, represents a group capable of releasing LIG when or after NG is detached; LIG is a ligand capable of forming a complex compound having the function of stabilizing a dye image by performing a complex-forming reaction with a metal ion; represents. Represents n=0 or 1. ) In the present invention, as a result of the above structure, the dye image forming coupler develops color upon development, and -(T), 1-L
IG leaves. In addition, LIG is released, and since this LIG can form a complex compound having the function of stabilizing a dye image, if a configuration is provided in which metal ions for forming such a complex compound are supplied, the above-mentioned coupler can be used. A complex compound having this stabilizing function can be formed simultaneously with dye image formation or after dye image formation. This complex compound is produced as a function of development, and is produced imagewise in the developed image forming area, so that it can exhibit an effective image stabilizing function.

Various means can be used to supply metal ions to form a complex compound with the ligand.

For example, as will be explained in detail later, it is possible to adopt a method of supplying metal ions from outside the photosensitive material, or to add metal ions or metal ion donating substances (including those that can form such substances) into the photosensitive material in advance. It is also possible to adopt a configuration in which it is contained.

The compound represented by general formula [I] only needs to be contained in a small amount (in combination with the silver halide emulsion contained in any one of the silver halide emulsion layers, and not contained in the silver halide emulsion layer itself). It may be contained in a layer adjacent to the emulsion layer, or it may be contained in a position where it can react with the silver halide emulsion of interest.

In the general formula, C7 is optional and can be, for example, a coupler residue of a coupler capable of forming a dye image, or can be a coupler residue of a coupler that does not form a dye, or can undergo a coupling reaction. The dye may be formed and eluted out of the system.

When C4 is a coupler residue of a coupler capable of forming a dye image, both a dye image due to the dye image-forming coupler and a dye image due to this C1 are formed. In this case, the image can be configured in such a manner that the image is mainly formed by the dye image-forming coupler, or it can be configured in such a manner that the image is mainly formed by C7, or the contribution of both can be equally divided. It can also be configured in certain ways, and these are arbitrary.

Moreover, the complex compound produced by the reaction of LIG with a metal ion may be substantially colorless or colored.

It is also possible to configure the complex compound to exhibit a desired color so as to contribute to the formation of a dye image.

Therefore, regarding dye image formation, an embodiment may be adopted in which an image is formed only by the dye image-forming coupler (in this case, C7 and LIG do not form a dye image). In addition, it is possible to adopt an embodiment in which the image formation by the dye image-forming coupler is main and the image formation by Cr is the secondary, or an embodiment in which the dominant and subordinate roles are reversed (in these cases, the embodiment in which LiG forms the dye image and the formation ). Further, C2 can be of type a, in which no dye image is formed and the image is mainly formed by the dye image-forming coupler, and the image is formed secondary by LIG.

For example, as mentioned above, the present invention can take various forms.

When CP and LIG form a dye image, C1 can be configured to develop an arbitrary color such as yellow, magenta, or cyan, and LIG can similarly be configured to develop an arbitrary color. For example, dye image-forming couplers C,
, color development by LIG (or color development by two of the three)
You can also make them all the same.

Preferably, the color developed by the dye imageable coupler and the color developed by C1 are the same color, or almost the same color.

[Specific structure of the invention]

Next, the present invention will be specifically explained.

In the compound represented by the general formula CI) according to the present invention, C1 is a function of the phenomenon of silver halide (Th
Although any structure can be used as long as it is a group that leaves -LIG, a dye image-forming coupler residue can be preferably used as the CP, and the specific structure of the CP that can be preferably used in the present invention is as follows. It can be represented by the general formula (n) anti-type (rV).

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 CI[) (wherein R7 represents an alkyl group (eg, t-butyl group, adamantyl group, etc.) or an aryl group (eg, phenyl group, p-methoxyphenyl group, etc.), and R2 represents an aryl group. ) Furthermore, particularly preferred as the yellow dye image-forming coupler residue according to the present invention are the following general formulas [
It can be expressed as -a).

General formula (na) In the formula, R3 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R4, Rs, Rh, and R'r each represent a hydrogen atom, a halogen atom, Alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, carbonyl group,
It represents a sulfonyl group, carboxyl, alkoxycarbonyl group, carbamyl group, sulfone group, sulfamyl group, sulfonamido group, acylamino group, ureido group, or amino group.

These coupler residues are described, for example, in US Pat. No. 2,778.
No. 658, No. 2.875,057, No. 2.908
．． No. 573, No. 3,227,155, No. 3.22
7.550, 3.253,924, 3.2
No. 65.506, No. 3,277.155, No. 3.
No. 341,331, No. 3.369.895, No. 3
．． 384,657, 3.408.194, 3.415.652, 3.447,928, 3,551.155, 3.582.322,
3.725.072, 3.894,875, etc., German Patent Publication No. 1, 547, 86
No. 8, No. 2.057,941, No. 2.162.8
No. 99, No. 2,163.812, No. 2.213,
No. 461, No. 2,219.917, No. 2,261
, No. 361, No. 2,263,875, Special Publication No. 1973-
No. 13.576, JP-A-48-29.432, JP-A No. 48
-66.834, 49-10,736, 49-
No. 122,335, No. 50-28,834, and No. 50-132.926.

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

General formula (Tll) Ar (wherein, Ar represents an aryl group, R3I represents a hydrogen atom or a substituent, and R3z represents a substituent.

W represents -NH-1-N) (CO- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -N HCON H-, m is an integer of 1 or 2) the general formula [11
The coupler residue represented by is explained in detail.

Examples of the aryl group represented by Ar include phenyl and naphthyl groups, preferably phenyl, and particularly preferably substituted) and enyl groups.

Examples of this 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 sulfonamido group, an acylamino group, etc. The phenyl group may have two or more substituents.

Put it below! #! Specific examples of groups are given below.

Halogen atom: chlorine, bromine, fluorine Alkyl group: Methyl group, ethyl group, tso-propyl group, butyl group, t-butyl group, t-pentyl group, etc., but alkyl groups having 1 to 5 carbon atoms are particularly preferred .

Alkoxy group: methoxy group, ethoxy group, butoxy group,
Examples include 5eC-butoxy group, 1so-pentyloxy group, and particularly preferred is an alkoxy group having 1 to 5 carbon atoms.

Aryloxy group: phenoxy group, β-naphthoxy group, etc., but this aryl moiety may further have the same substituents as listed for the phenyl group represented by Ar.

Alkoxycarbonyl group: The above-mentioned carbonyl group with an alkoxy group attached thereto, and those in which the alkyl moiety has 1 to 5 carbon atoms, such as a methoxycarbonyl group and a pentyloxycarbonyl group, are preferable.

Carbamoyl group z Alkylcarbamoyl group such as carbamoyl group and dimethylcarbamoyl group Sulfamoyl group: Alkylsulfamoyl group such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group Sulfonyl group: methanesulfonyl group , ethanesulfonyl group, butanesulfonyl group, etc., alkylsulfonyl group Sulfonamide group: alkylsulfonamide group such as methanesulfonamide group, toluenesulfonamide group, arylsulfonamide group, etc. Acylamino group: acetamino group, pivaloylamino group, benzamide group, etc. Preferred is a halogen atom, with chlorine being the most preferred.

The substituent represented by Rffl is a halogen atom, an alkyl group, an alkoxy group, etc.

Specific examples are listed below.

Halogen atoms: chlorine, bromine, fluorine alkoxy groups: methoxy group, ethoxy group, butoxy group,
Alkoxy groups having 1 to 5 carbon atoms such as 38C-butoxy group and 1so-pentyloxy group are preferred.

Alkyl group: An alkyl group having 1 to 5 carbon atoms is preferable, such as methyl group, ethyl i, iso-propyl group, butyl group, t-butyl75, t-pentyl group.

Particularly preferred is a halogen atom, with chlorine being particularly preferred.

The substituents represented by Rlg include a halogen atom, an alkyl moiety, an amide group, an imido group, a 4-alkylcarbamoyllkoxycarbonyl group, an acyloxy group, a sulfonamide group, and a pendant group. Among these groups, amide groups (e.g., tetradecanamide group, 3-t-butyl-4-hydroxyphenoxytetradecanamide group, etc.), imide groups (e.g., dodecylsuccinimide group, octadecenylsuccinimide group, etc.) and sulfonamide groups (For example, butylsulfonamide group, dodecylsulfonamide group, etc.) can be preferably used.

W is -NH-, -NHCO- (the nitrogen atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH
- may be used, but W is particularly preferably 1NH-.

A substituent which can be removed by a coupling reaction with the oxidized product of the aromatic primary amine coloring agent represented by Y, and C is, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a (Zz represents an atomic group required to form a 5- or 6-membered ring with a nitrogen atom and an atom selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms.

Specific examples are given below.

Halogen atoms: chlorine, bromine, fluorineAlkoxy groups: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc. -ruoxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group etc. Acyloxy group: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy-5-
Alkylthio groups such as octylphenylthio group, 2,5-dihexyloxyphenylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2-(diethylamino)ethylthio group, ethoxycarbonylmethylthio group,
Ethoxyethylthio group, phenoxyethylthio group, etc. "-11,-+-1,-...0" group, triazolyl group, tetrazolyl group General formula [m'
] (In the formula, 2 represents a metal atom group forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent and °ζ.

R represents a hydrogen atom or zmi.

-m formula [■'], the following general formula (
Groups represented by DI-all and (I[[-b) can be preferably used.

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

The alkyl group represented by R' and R' has a carbon number of 1
~32 are preferred, and the alkyl group may be straight chain or branched.

The alkyl group represented by R', rt:' includes a substituent [for example, aryl, cyano, halogen atom, petero ring, cycloalkyl, cycloalkenyl, spiro compound residue, bridged carbide wood compound residue, and acyl group] , carboxy, carbamoyl, alkoxycarbonyl, ``aryloxycarbonyl'', which are substituted via a carbonyl group, and furthermore, ``zeta'' substituted via a hetero atom (specifically, hydroxy, alkoxy, aryl phosphorus ('oxy, Heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, etc. that form Fl h'4 through an oxygen atom, nitro, amimino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, and
&J
Those substituted via a sulfur atom such as alni-1-ruthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., or via a phosphorus atom such as phosphonyl? ZIn, etc.)] may be used.

Specifically, for example, methyl group, ethyl group, isopropyl 1
5, t-butyl group, pencudecyl group, heptadecyl group,
1-hexylnonyl group, 1.1'-dibentynonyl group, 2-chloro-1-butyl group, trifluoromethyl group,
1-Ethoxytridecyl group, l-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-1-amylphenoxymethyl group, anilino group, 1-phenylisopropyl i, 3-m-butanesulfonaminophenoxyprobyl group ,3-4'-(α-(4"(p-hydroxybenzenesulfo;,le)phenoxy]dodecanoylamino)phenylpropyl5.3i4'-[α-(2",
Examples thereof include a 4''-di-1-amylphenoxy)butanamido)phenyl)-propyl group, a 4-[α-(0-chlorolephenoxy)tetradecanamidophenoxypropyl group, an allyl group, a cyclopentyl group, a cyclohexyl group, and the like.

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

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

The heterocyclic group represented by R' and R# is preferably a 5- to 7-membered one, and may be [1] or fused. Specifically, 2-furyl group, 2-chenyl group,
Examples include 2-pyrimidinyl group and 2-benzothiazolyl group.

Next, specific examples of R' and R# shown in the above general formula will be shown.

■ C11゜l783S -CIIzGHzCl(zOc+ titsCHzCH
zCONIIC+Jzq CH.

Also, the group represented by the above general formula [■'] may be a so-called polymer coupler residue, and they are
It is described in No. 228.252 and No. 59-171.956.

The cyan dye image-forming coupler residue has the following general formula (
A coupler residue represented by rV) can be preferably used.

General formula (IV) (wherein Rq, R+., R1+ and R, t are each a hydrogen atom, a halogen atom, an alkyl group, a carbamoyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, a phosphoric acid amide group, or represents a ureido group,
A ring may be formed by R1 and R1°. ) These coupler residues are described, for example, in U.S. Pat.
, No. 929, No. 2.423.730, No. 2,43
4.272, 2.474,293, 2.6
No. 98,794, No. 2.706.684, No. 2,
No. 772.162, No. 2801.171, No. 2,
No. 895,826, No. 2.908,573, No. 3
．． 034.892, 3,046,129, 3.227,550, 3.253,294, 3,311,476, 3.386.301,
No. 3,419,390, No. 3,458,315, No. 3.476.563, No. 3,516,831
No. 3,560,212, No. 3,582,32
No. 2, No. 3,533,971, No. 3.591,3
No. 83, No. 3,619.196, No. 3.632.
No. 347, No. 3,652,286, No. 3,737
．． No. 326, No. 3.758, 308, No. 3.77
No. 9,763, No. 3,839.0=14, No. 3,
880,661, German Patent Publication No. 2,
No. 163,811, No. 2,207,468, Japanese Patent Publication No. 39-27,563, No. i5-28.836, Japanese Patent Publication No. 37-425, No. 50-10.135 , No. 50 25.228, No. 50-112.038, No. 50-117. / No. 122, 50-130, 4
No. 41, No. 53-109.630, No. 56-65, 1
No. 34, No. 56-99.341 and Research Disclosure + - (Research n1s
c1osure) 14, 853 (1976), etc.

Further, the dye image-forming coupler residues represented by the general formulas (n), ([[] and (IV) may be polymer coupler residues, for example, as described in JP-A-58-28-745
No. 58-43,955, No. 59-40.643, No. 59-65,844, and U.S. Patent No. 3.
451,820, British Patent No. 4.080.211, and British Patent No. 1,104,658.

In addition, compounds that can be used as Cp in the present invention include those contained in the general formula [■] and inverse type IV), which can be eluted even if they form a pigment by reaction with an oxidized product of a coloring agent. etc., it does not remain as a dye image after processing. Also included are so-called Weiss coupler residues. Specific examples of these compounds are, for example, British Patent No. 861,
It is described in the specification of No. 132 and Japanese Patent Publication No. 49-77.635.

Specific examples of the group represented by Cp in the present invention are listed below, but the invention is not limited thereto.

1M I 5 H3 I 9 ■ 11 Shi+4 (Shi lh Nonoz) T in the general formula (1) in the present invention will be explained in detail. In the general formula (1), T is bonded to the camping position of Cp. represents a group capable of releasing LIG when or after it is released by reaction with an oxidized form of a coloring agent.

T is used to control the reaction rate during the reaction with the oxidized form of the main drug, and after leaving during or after campling, ■ leaves LIG due to intramolecular substitution reaction, and ■ electrons via conjugated system. Those that translocate and release LIG by migration (2) Furthermore, those that cause campling with the active agent and the oxidant or cross-oxidize and release LIG, and the above-mentioned reactions may be used in combination.

For example, U.S. Pat. L/16,396, Published Patent No. 1986-2 (IO39, U.S. Patent No. 4.248,96)
2 No. 0, Published Patent Publication No. 114'146, No. 57-
No. 154234, No. 57-188035, No. 57-1
Ike Publication Patent No. 11536 No. 56873, No. 5
No. 8-98728, No. 58-209736, No. 58-
No. 209737, No. 53-209738, No. 58-2
No. 09739, No. 59 206834, No. 60-74
No. 29, No. 60-213944, No. 60-21435
No. 8, No. 60-225156, No. 60-218645
No. 60-225844, No. 60-229030, No. 60-230139, No. 60-232549,
It is a linking group described in No. 60-203943 and the like.

Preferred examples include those represented by the following general formula. In the formula, (L) represents the bond that connects LIG.

Below is the margin general formula ■ -〇C,H,-(L) ■ -〇〇〇 -(
L) In the above general formulas ■ to ■, Xf is a hydrogen atom, a nitro group, an alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, methoxycarbonyl, etc.)
, alkylsulfonyl group (e.g. methanesulfonyl, pukunsulfonyl, etc.), cyano group, alkokene group (e.g. methoxy, butoxy), chlorine atom, bromine atom,
Alkyl groups (e.g. methyl, ethyl, l-propyl, butyl, etc.), carboxy groups, acylamino groups (
Examples include acetamino, benzoylamino, etc.) sulfonamide groups (for example, methanesulfonamide, benzenesulfonamide, etc.).

xl represents the same group as Xl, but preferably a hydrogen atom,
They are an acylamino group and a sulfonamide group.

Xi represents an alkyl group or an aryl group (for example, phenyl, naphthyl, etc.), and may have one of the groups listed above as a substituent.

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

×≦ represents a carbamoyl group (methylcarbamoyl, butylcarbamoyl, phenylalbamoyl, etc.) in addition to the same group as Xf.

W, , W represent hydrogen, alkyl group, etc., and WI,
Wt may combine to form a benzene ring and form a naphthalene ring.

Next, LIG in general formula (1) in the present invention will be explained in detail. The released LIG is a group that becomes a ligand that can form a complex compound having the function of stabilizing a dye image by a complex formation reaction with a metal ion! Although any structure can be used, groups represented by the following general formulas [■] and (Vl) can be preferably used.

General formula [11] -X -A -Y (In the formula, χ is an oxygen atom, a nitrogen atom or a sulfur atom, Y is an oxygen atom, a nitrogen atom or a q group bonded to an sulfur atom, and A is a When coordinated to metal with X-A-Y 5
It represents an association group capable of forming a 6-membered cyclic chelate compound. ) XSA, Y indicate the following in more detail.

5I It is a linking group.

R52; hydrogen, alkyl, aryl, amyl, RS3,
R, 4: hydrogen, alkyl, aryl, acyl, sulfonyl The alkyl group for R1 and R4 is an alkyl group having 1 to 20 carbon atoms, preferably oxygen at the β or γ position, -(
O, substituted with a nitrogen atom. Furthermore, the aryl group is preferably a substituted or unsubstituted phenyl group or naphthyl group, and more preferably a phenyl group or naphthyl group substituted at the 0-position with an oxygen, sulfur, or nitrogen atom.

The ligand θX A Y is a group released during development processing, but in order to exhibit its effect in the dye image area, it is better to have diffusion resistance. To provide diffusion resistance,
It is sufficient to contribute ballast groups having 8 or more carbon atoms, preferably 12 or more carbon atoms.

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

Below - white, 1 1゜ゝ) ■, As a specific example of IG, H -5CIICOSC*I* Clgllzs SCHgCH! NCtt cap I ■ CHzCIhOH H -5CHCOOH Cl1182!1 -OCH2CIIzSC+aHzv(n)-N C
HzCToSC+zLs ■ 5O2CI+3 (In the formula, R61 to R represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group.) In the general formula (Vl), the group represented by R61 to R6% At least one of them is preferably a heterocyclic group, and more preferably the heterocyclic group is a nitrogen-containing heterocyclic group.

Specific examples of the group represented by general formula (Vl) are listed below.

Next, specific examples of compounds represented by the formula (I) are illustrated below.

Concrete example Kan 1 Hidden 2 0 to HzCHzSCHgCHJHCt zHzsArashi 3 (J UI; 12HχS 11h6 し2 隘7 ('IH k8 し 2 suffer lO し! 1h13 I し1 1'k16 !l&l17 しl 隘18 I I Vh1 9H? h20 Warm C=O 0CHzC1bSCHzCHzSCHtCHzSC+J
zs~II L; U to +13 hidden 26 NOk magnetic 27 p ■ t hindrance 28 C! Exemplary compound 11h36 LIU knee 5-CHzcH! SCl
z)l z sO) 38 LIG = SC, HzCHtNtlC
＋□h.

N139 LIG = QC)lzcHzscH
zclhsc+ zllrsmagnetic 41 LIG--
5CII□CHzNHC+JzsH CoHl? (t) lh43 LIG--5CHzCHtSCHzC
IhSC+Jts patient 44 LIG-0CHzC
ONHCHzCHzSC+sH,, fish 46
LiG” 5CIIzCtfzSCLCHtSC+□
H□Magnetic 47 LIG = -0Cjl□CH,
SC,,II□.

49 LTG = -5CIIzCi (□S
CI□L5N[L50 LIG =-OC112
C11,5CIlzCl! ,NHC,2! (2,.

Hs [;+sth+ CH3 magnetic 58 ni 59 Arashi 6O 63 a64 1lL65 C1 66 shi 2 1h67 1'1h70 71 l demon 72 l shildhl yang 74 kan 75 sho 76 sho 77 s 79! 1h81 H a82 Floor 83 C=O OCHzCHzSCHgCHzSCHtCLSCtti
Synthesis Example 1 (Synthesis of Compound Example 2) Diethyl mercaptoacetal (Org Syn Co
IVol IV, page 295) and commercially available laurylamine are heated to reflux in alcohol and reacted for 8 hours. Cool to room temperature, add sodium borohydride for reduction, and combine the obtained mercaptan and epichlorohydrin with Co1Vol.
The reaction is carried out according to the method described on page 345 to obtain a sulfide alcohol. Phosphorus tribromide in chloroform
Halogenated at 5°C, then published patent No. 117-1983
Alkylation was performed according to the method described in No. 422 to obtain the target compound (2) as a solid crystal. Identification was performed by FD mass spectrum, NMR spectrum, and elemental analysis.

Synthesis Example 2 (Synthesis of Compound Example 26) Compound (26) was synthesized in a candy form according to the method described in the above patent using Intermediate 1 described in Preparation Example 4 of Published Patent Publication No. 145135/1982 and the intermediate of Synthesis Example 1. I got it as a thing.

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

In the present invention, the dye image-forming coupler used together with the compound of the present invention represented by the general formula [I] may have any structure, but as the dye image-forming coupler that can be preferably used in the present invention, , the following are listed.

As the yellow dye image-forming coupler, a coupler represented by the following general formula CB) can be used.

General formula CB) In the formula, R represents an alkyl group or an aryl group, and R
B2 represents an aryl group, and X represents a hydrogen atom or a group that is eliminated during the color development 1 reaction.

R+11 is a straight-chain or branched alkyl group (for example, butyl group) or an aryl group (for example, Fe, R group), and < is preferably an alkyl group (especially t-butyl group); ? oz represents an aryl group (preferably a phenyl group), and the alkyl group and aryl group represented by R1 and R7 include those having a substituent,
It is preferable that the aryl group of R and lz has 746 halo Y atoms, alkyl groups, etc. As X, a group represented by the following general formula (C) or CD) is preferable, and a group represented by general formula (C') among general formula [c] is particularly preferable.

General Formula (C) In the formula, Z represents a nonmetallic atomic group capable of forming a 4- to 7-membered ring.

General formula CD) -0-RD.

In the formula, R□ represents an aryl group, a heterocyclic group or an acyl group, with an aryl group being preferred.

General formula [C'] Represents a group of nonmetallic atoms that can form .

A preferred yellow coupler according to the present invention in the general formula (B) is represented by the following general formula [B'].

General Formula [B'] In the formula, R114 represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferred.

Also R33, R1 or R11? , R□ are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, carboxy groups, alkoxycarbonyl groups, carbamyl groups, sulfone groups, sulfamyl groups,
represents an alkylsulfonamide group, acylamino group, ureido group or amino group, hl, R11 and Ro
are each a hydrogen atom and I? Preferably, s't is an alkoxycarbonyl group, an acylamino group, or an alkylsulfonamide group.

Further, X represents a group having the same meaning as that shown in the above general formula (B), preferably the above general formula (C) or [D],
or (C), more preferably the general formula [C
' ] is mentioned.

(y-1) (y-2) (y-3) (y-4) O-=C-C)+3 (y-6) 逼H3 :y-7) (y-8) ν' (y- 9) (y-10) (y-11) In the silver halide photographic light-sensitive material of the present invention, the magenta dye image-forming coupler is represented by the following general formula (a):
Couplers represented by and [a1] can be preferably used.

General formula [1] r [In the formula, Δr represents an aryl group, and RlI is a hydrogen atom or V! Represents a substituent, and R13 represents a substituent.

Y is released by a reaction with a hydrogen atom or an oxidized product of the color-forming ring α-main ios.
14 [fCt'1- (N atom is bonded to carbonitrous atom of pyrazolone) or -) represents ICONI+-, R is 1
t, or an integer of 2. )I s+-5 し! These include, for example, U.S. Pat. No. 2,600,788;
Same No. 3,061,432, Same No. 3,062.653, Same No. 3.127゜269, Same No. 3,311.476
No. 3.152.896, No. 3.419,39
No. 1, No. 3.519.429, No. 3.555, 3
No. 18, No. 3,684.514, No. 3,888,
No. 680, No. 3.907.571, No. 3.928
．． No. 044, No. 3,930.861, No. 3.93
0.866, 3.933.500, etc., JP-A-49-29639, JP-A-49-111631, JP-A-49-129538, JP-A-50-13043, JP-A-52-58922 , No. 55-62454, No. 55-
118034, No. 56-3R043, No. 57-35
858, t30-23855, British Patent No. 1.247,493, Belgian Patent No. 769,11
No. 6, No. 792, 525, West German Patent No. 2,156. l
It is described in the specifications of No. 11, Japanese Patent Publication No. 46-60479, etc.

In the magenta coupler represented by the general formula (al) (aN), Za represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by za is a disubstituted group. may exist.

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

Moreover, Ra represents a hydrogen atom or a substituent.

Examples of the substituent represented by Ra include a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heteroff
l 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 , an alkylthio group, an arylthio group, and a heterocyclic thio group.

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

I? The alkyl group represented by a is 1. Carbon number 1
-32, alkenyl group, alkynyl 11 preferably has 2 to 32 carbon atoms, cycloalkyl group, cycloalkenyl group preferably has 3 to 12 carbon atoms, especially 5 to 7 carbon atoms, alkyl group, alkenyl The alkynyl group may be straight or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups and substituent groups [
For example, Ali-R1. In addition to cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compound residues, acyl, carboxy, carbamo-fluor, alkoxycarbonyl, and monoyloxycarbonyl. Those substituted via a carbonyl group, such as those substituted via a carbonyl group, and those substituted via a hetero atom (specifically, hydroxy, alko, I-cy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbakiyl) Substitution through an oxygen atom such as oxy, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, etc. Those substituted through a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted through a phosphorus atom such as phosphonyl.
vague, etc.)].

Specifically, for example, methyl group, ethyl group, isopropyl 4
, t-butyl group, pentadecyl group, heptadecyl &, 1
-hexylnonyl &, 1.1'-dibenthylnonyl group,
2-chloro-[-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, l-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenyl 1' soprobyl N, 3-m-butanesulfonaminophenoxo proyl i, 3-4'-(α(4'(p-hydroxybenzenesulfonyl)phenoxy)dodecanoylamino)phenylpropyl group, 3-(4'-Cα-(2
#, 4#-di-t-amylphenoxy)butanamide]
phenyl)-propyl group, 4-[α-(0-chlorophenoxy)tetradecanamidophenoxypropyl group,
Examples include allyl group, cyclopentyl group, and cyclohexyl group.

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

Specifically, phenyl group, 4-t, butylphenyl group, 2.4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group,
4', (α-(4'-1-butylphenoxy)tetradecanamide) phenyl group, and the like.

The hetero 1M represented by P is preferably 5□-7'f4, which may be substituted, or a fused carbon
Good too. Specifically, 2-furyl group, 2-chenyl group, 2
-pyrimidinyl group, 2-benzothiazolyl group, etc.

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

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

Examples of the sulfinyl group represented by Ra include alkylsulfinyl groups such as ethylsulfinyl group, octylsulfinyl i, 3-7e, and dibutylsulfinyl group,
Examples include arylsulfinyl groups such as phenylsulfinyl group and -bencdecylphenylsulfinyl group.

The phosphonyl group represented by Ra includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an oxyphosphonyl group such as a phenoxyphosphonyl group,
Examples include arylphosphonyl groups such as f, c-nylphosphonyl groups, and the like.

The carbamoyl group represented by Ra may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl N, N-dibutylcarbamoyl &, N-(2.pentadecyl octyl). Examples include ethyl)carbamoyl 1k, N-ethyl-Nrdecylcarbamoyl group, N-(3-(2.4-di-t-amylphenoxy)propyl)carbamoyl group, and the like.

The sulfyl moyl group represented by Ra may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-propylsulfamoyl i, N,N-diethylsulfamoyl 77tadecyl Examples include JiS (oxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group.

Examples of the spiro compound residue represented by Ra″7! include spiro L3.3J heptan-1-yl.

As a bridged carbonized compound residue represented by Ra, "ζ" is, for example, bicyclo(2.2.1)hezokun-1-yl, tricyclo(3.3.1.1"'")tethenone-1.yl7
,7-dimethyl-bicyclo(2.2.1)hebutane-1
-il etc.

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

The aryloxy group represented by h is preferably phenyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group,
Examples include phenoxy group, p-1-butylphenoxy group, and pentadecylphenoxy group.

The heterocyclic oxy group represented by Ra preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3 or 4.

Examples include 5,6-tetrahydrobilanyl-2-oxy group and 1-phenyltetrazole-5-oxy group.

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

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

The carbamoyloxy group represented by Ra is a convex alkyl group,
゛? It may be substituted with a lyl group or the like, such as N-ethylcarbamoyloxy L N 1 14-diethylcarbamoyloxy group, N-phenylcarbamoyl ookine group, and the like.

The amino group represented by Ra is a
(preferably a phenyl group), for example, an enal/mino group, anilino group, l@-chloroanilino group, 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecanamidoanilino group. Examples include groups.

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

Examples of the sulfonamide group represented by Ra include an alkylsulfonylamino group and an arylsulfonylamino group, and may further have an IA stem.

Specific examples include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a ρ-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by Ra may be open-chain or cyclic, and may have a W substituent, such as a succinimide group, 3-. , phthal 1° mido group, glutar/f mido group ring/)<.

[Cow 1゛d tod represented by ia is 1. Substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-ethylureido group, N-methyltodecylureido group, N-phenylureido group,
Examples include N-p-tolylureido group.

The sulfamoylamino group represented by 11a is
may be substituted with an aryl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamolylamino L, N-methylsulfamoylamino, N
-Soenylsulfamoylamino group and the like.

The alkoxycarbonylamino group represented by L may have one substituent, and examples thereof include a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like.

The aryloxycarbonylamino group represented by Ra is
;11 substituents may be present (for example, phenoxycarbo 1.-lyamino group, 4-notylphenoxycar'J
Examples include ζnylamino group.

The alkoxycarbonyl group represented by Ra may further have a radical conversion (for example, a methoxycarbonyl group,
Examples include butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxycarbonyl group, and the like.

The aryloquine group represented by R,i may further have a substituent (e.g., phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-/, "
Examples include tadecyloxyphenoxycarboxylic acid group and the like.

! The alkylthio group represented by <11 may further have a substituent (for example, ethylthio group, dodecylthio group, octadecylna group, phenethylthio group, 3-phenoxypropyl group, The stem is mentioned.

I? The arylthio group represented by n is preferably a phenylthio group L <It may further have a substituent, for example, a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group ,2
-carboxyphenylthio group, p-acetaminophenylthio group, etc.

The heterocyclic thio group represented by R, J-71, is preferably a 5- to 7-membered heterocyclic thio group, which may have a fused ring or a substituent. Examples include 2-pyridylthio group, 2-hendithiazolylthio group, and 2,4-diphenoxy-1+3+5-) lyazole-6-thio group.

Examples of the substituent which can be separated by reaction with the oxidized product of the color developing agent represented by Examples include groups substituted via.

In addition to the carboxy group, examples of the group substituting 7 through a carbon atom include, for example, the general formula % (R+. has the same meaning as the above R, 2' has the same meaning as the above 2, R2. and R3. ) representing an atom, an aryl group, an alkyl group, or a heterocyclic group, a hydroxymethyl group, a triphenyl group, and a methyl group.
゜Through oxygen atoms! tr! Examples of the group include alkoxy group, aryloxy group, -terocyclicoxy group, acyloxy group, sulfo group, alkoxy carbonyloxy group, aryloxycarbonyloxy group, alkyloxalyloxy group, alkoxyoxalyloxy group; can be mentioned.

The alkoxy group is further expressed as
21 For example, ethoxy I, 2-pheno L.
-chlorobenzyloxy group, etc.

The aryloxy group is preferably a phenoxy group, and the aryl group may further have M or a substituent.

Specifically, phenoxy group, 3-methylphenoxy group, 3
-Dodecylphenoxy group, 4-methanesulfonamidophenoxyH14-(α-(3'-pe)/tadecylphenoxy)bucunamido]phenoxy group, hexydecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-natatyloxy group,
Examples include p-methoxyphenoxy group.

The cough heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a fused ring or may have a substituent, specifically, 1-phenyltetra Examples include a zolyluoxy group and a 2-benzothiazolyloxy group.

Examples of the acyloxy group 7 include alkylcarbonyloxy groups such as an acetoxy group and a butazuroxy group, alkenylcarbonyloxy groups such as a cinnamoyloxy group, and arylcarbonyloxy groups such as a benzoyloxy group.

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

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

Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkyloxalyloxy group include ethoxyoxalyloxy group.

Examples of groups that form Wm via a sulfur atom include alkylthio groups, arylthio groups, heterocyclic thio groups, and alkyloxythiocarbonylthio groups.

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

The arylthio bottle includes a phenylthio group, a 4-methane J lephonamide phenylthio group, a 4-dodecylphenethylthio group, a 4-nonafluorobencunamidophenethylthio group, a 4-carboxyphenylthio group, and a 2-ethoxy-5- Examples include 1-methylphenylthio group.

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

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

group, aryl group, heterocyclic group, sulfamoyl group, carbamoyl group, acyl group, sulfonyl group, aryloxycarbonyl group, alkoxycarbonyl group 4i: represents,
R4. and Is. may be combined to form a petero ring. However, R4. and R3. are not both hydrogen atoms.

The alkyl group may be linear or branched, preferably
It has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group). , sulfone °1 mido group, imino group,
Acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, ryoroxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group, carbonyl group, cyano group, Examples include halogen atoms.

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

The aryl group represented by 1 or R3 is,
The aryl group has 6 to 32 carbon atoms, and is particularly preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent such as R4 or I? Examples of substituents for the alkyl group represented by S. include those listed above and an alkyl group. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 4-mer≠sulfonylphenyl group.

R9 or! ? 5. The heterocyclic group represented by 5.
It is preferably 6-membered, may be a condensed ring, and may have a substituent. Specific examples include 2-furyl group, 2
-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2-pyrdyl group and the like.

The sulfupmo.f group represented by R4 or R2.・Irukyo etc., and these alkyl groups and aryl groups may have the substituents listed for the above-mentioned alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N, N-
Examples include diethylsulfamoyl group, N-methylsulfamoyl group, N-dodecylsulfamoyl group, and N-tolylsulfamoyl group.

The carbamoyl group represented by R4. or R3.
Diaryl groups, carbamoyl groups, etc. may be mentioned, and these alkyl groups and aryl groups may have the substituents listed for the above-mentioned argyl groups and aryl groups, and may also be ζ. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl5, N-dodecylcarbamoyl &, N-p-cyanophenylcarbamoyl group, and N-p-)lylcarpamoyl group.

Examples of the acyl group represented by R# or R3 include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group.
The heterocyclic group may have a substituent. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. .

Examples of the sulfonyl group represented by R4 or R6 include an alkylsulfonyl group, an irisulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, such as ethane. Examples include a sulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphculenesulfonyl group, and a p-chlorobenzenesulfonyl group.

The aryloxy carbonyl group represented by R4 or R1 may be substituted with the groups listed above for the aryl group (specific examples include phenoxycarbonyl group, etc.).

The alkoxycarbonyl group represented by R4 or R2 may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. Can be mentioned.

The heterocycle formed by R1 or R6 is preferably a 5- to 6-even ring, and may be saturated or unsaturated, and may or may not be aromatic. Alternatively, it may be a condensed ring. Examples of the heterocycle include N-phthalimide group, (!, succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-
Dioxooxazolidinyl group, 2-N-1,1-dioxo-3-(28)-oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, ■-pyrrolidinyl group, 1-pyrazolyl group, 1- Pyrazolidinyl group, 1-piperidinyl group,
l-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group,
1-benzotriazolyl group, l-benzimidazolyl group, 1-(1,2,4-)riazolyl) group, 1-(1,2
, 3-1-riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, .N-morpholinyl group, 1.2.3.
4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl L 2-IH-pyridone group, phthaladione group, 2
-oxo-1-piperidinyl groups, etc., and these heterocyclic groups include alkyl groups, aryol groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, alkylamino groups, and aryamino groups. , acylamino group, sulfonamide, ? group, carbamoyl group, sulfamoyl group,
It may be substituted with an alkylthio group, an arylthio group, a ureido group, an alkoxycarbonyl group, an aryloxycarbonyl group, an imido group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like.

Also nitrogen-containing 'ui'gf formed by 2 or 2':
Examples of the ring include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituent that the ring may have include those described for H above.

In addition, substituents on the heterocycle (for example, R, R) in the general formula (1> and the general formula (■) described below).

~Rs), where R', X and Z'' are the general formula (I in H
? , X, and Z. ), it forms a so-called screw-type coupler, which is of course included in the present invention.

Further, the ring formed by Z, Z', Z" and 21 described below may be further fused with another ring (for example, a 5-7's cycloalkene). For example, -m formula [■ ] In the general formula (V[), R1 and R
, and may be combined with each other to form a ring (eg, 5- to 7-membered urochloroalkene, benzene).

(・yut゛,・l (da,',:,/') What is represented by the general formula (aI) is more specifically represented by the following general formula (a Iri～[a■]) .

General formula (aII) General formula (a III) General formula [a■] General formula (a V) General formula (aVI) ・General formula Ca'''M] In the above general formula [a■] to [a■] R1s~R8&
and X have the same meanings as R1 and X above.

Moreover, among the general formulas (31), those represented by the following general formula 1:aII) are preferable.

General formula [a■] In the formula, R,,, X and Z+s 't, E General formula (al)
It has the same meaning as R, , X and 2 in .

Among the magenta couplers represented by the general formulas (aII) to [a■], particularly preferred is the magenta coupler represented by the general formula (a II).

Also, regarding the water exchange on the heterocycle in general formulas (al) to [a■], R in general formula (al) or L in general formulas (a n) to [a■] is It is preferable that condition 1 is satisfied, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1.2 and 3 are satisfied.

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

conditions? - Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom.

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

Preferred substituents Ra and R1& on the heterocycle are those represented by the following general formula (a IX ).

General formula (alX) 1m R3°, -〇- 11m In the formula, R9, I n+. 1 and RIls+ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group,
Alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfthimoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue , alkoxy l, aryloxy group, heterocyclic oxy group, siloxy group, acyl group, carlevamoyl 1, amino group, acylamino group, sulfonamido group, f-mido group, ure, ido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycar, carbonyl group, alkylthio group, arylthio group, heterocyclic thio group, La + R1゜1
and at least two of R11m are not hydrogen atoms.

Also, two of the above R11m r R111# and RIl&, for example, l? ,, ,g,. , may be combined to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, hexagonal ring). You may.

The groups represented by R9a to R18 may have a W substituent. Specific examples of the groups represented by R9- to RRa and the W substituents that the cough group may have include the above-mentioned W substituents. General formula [
a! Examples of groups represented by R in ] and! ! I can't find the base I wanted.

Also, for example, specific examples of U-containing hydrocarbon compound residues formed by the ring formed by bonding R, and R1゜1, and RQ, ~R0, and the residues it may have. Specific examples of the cycloalkyl, cycloargenyl, and heterocyclic group-containing one-layer hydrocarbon compound residues represented by Ra in the general formula (al) described in Section 7iil include substituents thereof.

Among the general formula CafX), (i) Ra
- When two of R11m are alkyl groups (ii) One of R, s to R11m, for example Ro, is a hydrogen atom, and the other two R1 and R1@a are bonded to the root carbon When forming cycloalkyl together with atoms,

Furthermore, among (1), R9, ~island, is preferable.

Two of them are alkyl groups, and the other one is a hydrogen atom or an argyl group.

Here, the alkyl and cycloalkyl may further have a substituent. Specific examples of the cycloalkyl and its substituents include Ra in the general formula (al).
Argyl, cycloalkyl and their att'x represented by
A specific example of a is given.

In addition, the ring formed by Za in i6 in the general formula Ca)l and the substituents that the ring formed by zo in the general formula [avIJ may have, and the general formula %formula% Preferably.

General formula (aX) -R'--So, -R'' In the formula, 1?' represents alkylene, and RZ represents alkyl, cycloalkyl or aryl.

The alkylene represented by RI is preferably carbon T in the straight chain portion.
The number of 5 losses is 2 or more, more preferably 3 to 6, and it does not matter whether the alkylene is a straight chain or one branched, and this alkylene may have a substituent.

Examples of the substituent include those shown as substituents that the alkyl group may have when Ra in the general formula [a1] described by Mil is an alkyl group.

Preferred substituents include phenyl.

Preferred examples of alkylene represented by 1?1 are shown below.

-C)ltCHgCIlt-, -CHC)! tCIls
−, −(JCHtCII*−, −+Jtl*CR−(:
Ih CJi The alkyl group represented by CJ+sR2 may be a straight chain or monobranched.

Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, 2-hexyldecyl, and the like.

The cycloalkyl group represented by R1 is preferably a 5- to 6-membered one, such as cyclohexyl.

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

Specific examples of the aryl group represented by are phenyl and naphthyl. The aryl group may have a substituent, and the substituent includes, for example, chain-forming or branched alkyl, as well as those shown in the above-mentioned substituent for R1.

Further, when there are two or more substituents, their substituents may be the same or different.

Represented by the general formula (aN)・1. Particularly preferred among the arsenic compounds are those represented by the following general formula [aχl].

General formula (a Xll in a H human, h a 1 in Ra +
IXZRK, which is synonymous with X and 1, is -1 immersion type (aX
It has the same meaning as A, R', and R2 in ;.

Hereinafter, representative examples of compounds represented by the formula Cal C are shown in Example 2.

m-8 master-12 C! 1゜7CJ17(t): 1iCH2c, If□5O2C+uH coretit, L shilliillll As the cyan image forming coupler, the following general formula (E), C
Couplers represented by F) can be preferably used.

General Formula (E) H In the formula, RIM represents an aryl group, a cycloalkyl group, or a heterocyclic group. R■ represents an alkyl group or a phenyl group eR1! represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

211 represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

In the formula, R4F represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R.S.
F represents an alkyl group (e.g. methyl group, ethyl group, etc.) *R11F represents a hydrogen atom, a halogen atom (e.g. fluorine, chlorine, bromine, etc.) or an alkyl group (e.g. methyl group,
(ethyl group, etc.).

Zt represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

In the present invention, the aryl group represented by RIM of the general formula (E) is, for example, a phenyl group or a naphthyl group,
Preferably it is a phenyl group. The heterocyclic group represented by RIM is, for example, a pyridyl group or a furan group. R1,
The cycloalkyl group represented by is, for example, a cyclopropyl group or a cyclohexyl group. These groups represented by RIM may have single or multiple substituents, and typical substituents for phenyl groups include halogen atoms (e.g. fluorine, chlorine, bromine, etc.). ), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.),
Arylsulfonamide group (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxy Carbonyl group (e.g. methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group, etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfoxy group, sulfo group, ruoxy group, alkoxy group, carboxyl group,
Examples include an alkylcarbonyl group, an arylcarbonyl group, and an aminocarbonyl group. Two or more of these substituents may be substituted with a phenyl group. R8
Preferred groups represented by include a phenyl group or a halogen atom, an alkylsulfonamide group, an alkylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and an alkylcarbonyl group. , an arylcarbonyl group, or a phenyl group having one or more cyano groups as substituents.

The alkyl group represented by R2 is linear or branched, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, and octyl group.

In the present invention, preferred cyan couplers represented by the general formula (E) are compounds represented by the following general formula [E'].

In the general formula [E'] 0M IJtsuto-m formula [E'], R7□ represents a phenyl group.

This phenyl group may have a single or multiple substituents, and typical substituents to be introduced include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, octyl group, etc.) sulfonamide group, etc.),
Arylsulfonamide group (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxy Examples include a carbonyl group (eg, methyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenyloxycarbonyl group, etc.). Two or more of these substituents may be substituted with phenyl groups *R? ! Preferred groups represented by are phenyl or halogen atoms (preferably fluorine, bromine, alkylsulfonamide groups) (preferably 0-methylsulfonamide groups, p-octylsulfonamide groups, O-dodecylsulfonamide groups) , arylsulfonamide group (preferably phenylsulfonamide group), alkylsulfamoyl group (preferably butylsulfamoyl group), arylsulfamoyl group (preferably butylsulfamoyl group)
Preferably phenylsulfamoyl group), alkyl group (
It is preferably a phenyl group having one or more alkoxy groups (preferably methoxy or ethoxy groups) as a substituent (methyl group, trifluoromethyl group).

R11t is an alkyl group or an aryl group. The alkyl group or aryl group may have a single or multiple substituents, and typical examples of these substituents include:
Halogen atoms (e.g. fluorine, chlorine, bromine, etc.), hydroxyl groups, carboxyl groups, alkyl groups (e.g. methyl, ethyl, propyl, butyl, octyl, dodecyl, etc.), aralkyl groups, cyano groups, nitro groups, Alkoxy group (e.g. methoxy group, ethoxy group), aryloxy group, alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group,
naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.),
Alkyloxycarbonyl group (e.g. methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group, etc.), aminosulfonamide group (e.g. dimethylaminosulfonamide group, etc.), alkylsulfonyl group, arylsulfonyl group, alkylcarbonyl group group, arylcarbonyl group, aminocarbonylamide group, carbamoyl group, sulfinyl group, etc. Two or more types of these substituents may be introduced.

A preferred group represented by R8 is n=a.

When , it is an alkyl group, and when it is n-1 or more, it is an aryl group. A more preferable group represented by Re is 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, or a dodecyl group) when n"o. Yes, when n = 1 or more, phenyl group, or alkyl group (preferably 1-butyl group, 1-amyl group, octyl group), alkylsulfonamide group (preferably butylsulfonamide group, octylsulfonamide group, dodecyl group) sulfonamide group), arylsulfonamide group (preferably phenylsulfonamide group), aminosulfonamide group (preferably dimethylaminosulfonamide group), alkyloxycarbonyl group (preferably methyloxycarbonyl group, butyloxycarbonyl group). It is a phenyl group having one or more substituents.

R'lE represents an alkylene group. It represents a straight chain or branched alkylene group having 1 to 20 carbon atoms, and further having 1 to 12 carbon atoms.

R3° represents a hydrogen atom or a halogen atom (fluorine, chlorine, bromine or iodine). Preferably it is a hydrogen atom.

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

X is -O-, -CO-1-coo-, -oco-9S
OtNR'*-1N R' is OtNR", -1
-S-1-SO- or -sog- represents a divalent group, where R''H and R' y represent a y1-substituted or unsubstituted alkyl group, and X is preferably -0-1 -S-
It is a 1-8O-1-3Oz- group.

2 represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

Preferred are chlorine atom and fluorine atom.

The cyan coupler represented by the following margin 0I (in the present invention, the general formula CF) is more preferably the following general formula % general formula [F'] H where R11 and RI! are the same or different, and include a hydrogen atom, an alkyl group (e.g. 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 Ro, R, and t is 8 to 16. More preferably, Rl 1 and R32 are each a butyl group or an amyl group.

R1 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.

Rj is an alkyl group (eg, methyl group, ethyl group, etc.).

m represents an integer from O to 2. Z4 represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

In formulas (E), (F), (E'), and [F'], 2. ．． 22, Z, and Z4
Groups that can be released by reaction with the oxidized form of amine-based color developing agents are well known to those skilled in the art, and can modify the reactivity of the coupler or can be released from the coupler to improve silver halide color photographic sensitization. In the coating layer or other layer containing the coupler in the material, it acts advantageously by performing functions such as development inhibition, bleaching inhibition, and color correction. Typical examples include alkoxy groups, aryloxy groups, arylazo groups, thioethers, carbamoyloxy groups, acyloxy groups, imido groups, sulfonamide groups, thiocyano groups, or hetero-r, di-groups (e.g., oxy→tozolyl, diazolyl). , triazolyl, tetrazolyl, etc.). A particularly preferred example of Z is a hydrogen atom or a chlorine atom.

Typical specific examples of the cyan coupler represented by formula (F) are shown below, but the invention is not limited thereto.

I H Shil H C-10 Shil Shi I In the present invention, the ratio of the compound represented by the general formula [I] to the dye image-forming coupler can be any ratio depending on the case, as long as they are used in combination. is preferably used in the range of to-' moles to 10 moles per mole of color image-forming coupler, especially 5X1
A range of 0-'' mol to 5 mol is preferred.

Furthermore, the complex compound formed by the complex-forming reaction of the released LIG with a metal ion may be substantially colorless or colored, but if the molar extinction coefficient in the visible region is 104 or more, the complex compound formed by the complex-forming reaction of the released LIG with a metal ion can be removed from the dye image-forming coupler. It is preferable that the dye image has substantially the same color as the obtained dye image, and it is particularly preferable that the difference in maximum absorption wavelength in the visible region is within 20 nw+.

Also, if Cp forms a dye image as a function of development of the silver halide, which may or may not form a dye image by reaction with an oxidized form of a color developing agent, then Cp can be obtained from said dye image forming coupler. It is preferable that the color is substantially the same as that of the dye image, and in particular, the difference in maximum absorption wavelength in the visible region is 20%.
It is preferable that the number is within no+, and it is particularly preferable that the dyes are the same.

In the present invention, the substantially colorless complex compound produced by the complex-forming reaction of separated LIG with metal ions and having the function of stabilizing a dye image will be described in detail.

Substantially colorless means that it does not have substantially strong absorption in the visible range, and more specifically, from 400 nm to 70 nm.
No absorption peak at 0 nm or 400 nm
It is preferable that the molar extinction coefficient at the maximum absorption wavelength from nm to 700 nm is 1,000 or less, 5
It is especially preferable that it is 00 or less.

In addition, the complex compound having the function of stabilizing a dye image refers to a complex compound that stabilizes by any mechanism depending on the type of dye image, medium, state of existence, etc., but preferably, the quenching rate constant of doublet oxygen is 3 X 10'M-'-5e
It is a complex compound with a complex compound of more than C, especially I
- A compound having a quenching rate constant of 5ee-' or more is preferably used.

The above-mentioned quenching rate constant of heavyt oxygen is based on the Journal of Physical Chemistry (Journal of Phys.
sical Chemistry ) 83.591 (
It is determined by the method of measuring photobleaching of luprene described in (1979) et al.

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

Let the initial concentration of rubrene at this time be (R), the concentration of the compound to be measured be (Q), and the concentration of rubrene in the solution of luprene alone after the test be [R)? After closing and testing, determine the concentration of rubrene in the mixed solution of luprene and the test compound [R)? Then, the quenching rate constant (kq) of doublet oxygen is calculated as follows.

Further, the complex stability constant of the complex compound according to the present invention can take any value, but generally IQ+6 to 1030.
Compounds having the following range can be preferably used.

As methods for supplying metal ions to form a complex compound with LIG in the general formula of the present invention, there are two methods: a method of supplying metal ions from outside the photosensitive material, and a method of incorporating metal ions or metal ion donating substances in advance. be. A specific example of the former method is, for example, a method in which the metal salt is added as a water-soluble metal salt to the processing solution in the processing step of the photosensitive material, and thereby introduced into the photosensitive material during the processing step. The processing solution includes a color developing solution, a bleaching solution, a bleach-fixing solution,
Any processing solution such as a fixing solution, stabilizing solution, washing water, rinsing solution, etc. can be used, but it is preferably added to the processing solution in the step that follows the color development step, and is further added to the processing solution in the step that follows the bleaching or bleach-fixing step. It is preferable.

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

・N iZo −N t B r z (+ 3 H2O
)Nl(1g・6H,O Ni(NOs)z・6H2O NiSOn・6Ht.

-Cu"-'CuC1z'2NHaCIA"2
HzOCuCj! g '2HzO Cu (NOri! ・3 H2O' Cu S Oa ・5 Ht0 ・Zn” -ZnBr= nCIM Z n (N 0i)z ・6 HIO2n S Oa
・7 Ht0 “Fe” −Fe5Oa・ (NH*)gsOi・
6HzOFeBrFeClg(4HzO) Fe(NOx)z ・9 HzO FeSO4・7HtO・Co"... CoC1!-6H, OCo
S O4 7H20 The concentration of the water-soluble metal salt can be arbitrarily determined depending on the composition of the treatment liquid to be added, the treatment temperature, etc., but it is preferably used in a molar concentration range of 10 −4 mol to 5 mol. can.

As a specific method of the latter, a method using a polymer complex formed from a polymeric ligand and a metal ion as a metal ion donating compound is described in JP-A-55-48.210 and JP-A-55-55-2.
129.346, and also JP-A No. 56-12
No. 6,529, No. 60-206.537, No. 60-2
06.538 and 60-205.539 disclose methods using water-soluble organometallic complexes, and JP-A-58-38.955, JP-A-58-5B-105,146, and JP-A-58-105,146. No. 58-129 and No. 429 disclose a method using a water-insoluble organometallic complex, and Japanese Patent Application Laid-Open No. 57-57
No. 105.738 discloses non-diffusible complexes which become ligand exchange active upon reduction in the presence of an alkali. Among these methods, any method can be selected from the viewpoints of ease of introduction into the photosensitive material, small influence on photographic performance, rapidity of reaction such as ligand exchange, etc., but preferably, A method 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, from the following ligands and metal ions, 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 reacting with LIG in the above general formula of the present invention, but as mentioned above, N
i” ”+Cu zZ Z n ”+ F e
Transition metal ions such as "Z Co " are preferred, especially N i ", 011!e, F13 g+
is particularly preferred.

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

The following margin [Water-soluble] S-1 H C3zCOOH (Water-insoluble) (n) HitC+ h CH Ctlz)
I NlI□ NHt S-14 0H The complex compound-forming compound according to the present invention is contained in combination with a silver halide emulsion, and "combined" as used herein means that the complex is formed as a function of the development of silver halide. 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 is It can be preferably added to a silver halide emulsion layer or an intermediate layer, and is particularly preferably added to a silver halide emulsion layer.

In the present invention, the compound represented by the general formula [I] and the dye-forming coupler may be added in any amount, but the preferred range is 1XIO-3 mol to 2 mol per mol of silver halide. It can be used preferably in a molar range of 1X10-' moles to 8X10-1' moles.

Further, the compound represented by the general formula [I] can be added by any method depending on the properties of the compound and the type of photosensitive material. .

If the compound is a polymer coupler, it can be directly dispersed in a wood-philic binder solution. When the compound is a hydrophobic compound, known methods such as solid dispersion, latex dispersion, and oil-in-ice emulsion dispersion can be used, but oil-in-water emulsion dispersion is particularly preferred.

The oil-in-water emulsion dispersion method can be applied to a previously unknown method of dispersing hydrophobic additives such as couplers, and is usually used in a high boiling point organic solvent with a boiling point or <150°C or higher, and if necessary, with a low boiling point or a high boiling point organic solvent. Alternatively, it is dissolved using a water-soluble organic solvent, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution, using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or long sonic device. After emulsification and dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper. In particular, when a color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. The order may be changed as appropriate depending on the important performance and purpose of use.

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

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

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. Alternatively, hydride ions and silver ions may be generated by sequentially and simultaneously adding hydride ions and silver ions while controlling the PH and PAg in the mixing pot, taking into account the critical growth rate of silver halide crystals. After growth, a conversion method may be used to change the halogen composition of the particles.

During the production of the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a halide v&solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. Metal ions can be added to the inside of the particles and/or on the surface of the particles using iron salts or complex salts, and by placing them in an appropriate reducing atmosphere, metal ions can be added to the inside of the particles and/or on the surface of the particles. Can provide reduction-sensitized nuclei.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

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

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

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

The silver halide emulsion of the present invention may be prepared by mixing separately formed silver halide emulsions of 2fi or more at °C.

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

The silver halide emulsion of the present invention can be chemically enhanced to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes may be used singly or in combination of two or more. Together with the sensitizing dyes, they may be dyes that themselves do not have a spectral sensitizing effect, or compounds that do not substantially absorb visible light. However, a super sensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion.

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

Gelatin is preferably used as the binder (or protective colloid) for the silver halide emulsion of the present invention, but
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 single or copolymers can also be used. .

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

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

A dispersion of a water-insoluble or sparingly soluble synthetic polymer (
latex).

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

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

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

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

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an anti-irradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention is added to reduce the gloss of the photosensitive material and improve the addability.
A matting agent can be added to prevent the sensitive materials from sticking together.

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

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.).

The photosensitive TJA material G using the silver halide emulsion of the present invention is a photographic emulsion layer, and the other layers are a baryta layer or an a-olefin layer.
Paper laminated with inpolymer, etc., synthetic paper, etc. (
reflective supports, films made of semi-synthetic or synthetic polymers such as cellulose acetate, sucrose nitrate, polystyrene, polyvinyl chloride, polyethylene L, -terephthalate 1-, polycarbonate, polyamide, etc., and films made of glass, metal, ceramics, etc. Can be applied to rigid bodies, etc.

The silver halide material of the present invention can be prepared directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
The coating may be applied via one or more subbing layers (to improve wear resistance, hardness, antihalation properties, 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 to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser beams, emitting diode light, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide photographic material of the present invention can be used to form an image by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally used at a concentration of about 0.18 to about 30 g for color developer lβ, preferably about 1 g to about 15 g for color developer 11.

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

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-dimethyl-p-phenylenediamine hydrochloride;
N-methyl-p-phenylenediamine hydrochloride, N,N'
-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4- Aminoaniline sulfate, N-ethyl-N-β, hydroxyethylaminoaniline, 4-
Amino-3-methyl-N,N'-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-p-toluenesulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
Alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. This color developer p
The H value is usually 7 or higher, most commonly about 10 to about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as diconic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5]
] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid sodium salt The bleaching agent used contains a metal complex salt of an organic acid as mentioned above as a bleaching agent, and various may contain additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also contains borate, oxalate, acetate, carbonate support, phosphate, etc.
Those known to be added to ordinary bleaching solutions, such as H buffering agents, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid It may contain one or more pH buffers consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

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

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or 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. Note that, as a matter of course, the present invention is not limited to the following examples.

Margin below: ゛2 (Example 1) A silver halide photographic window optical material having the layer structure shown in Tables 1 and 2 below was prepared.

Table 1 The composition of the coupler dispersion used in the green-sensitive emulsion layer was as shown in Table 2. The aqueous phase for each sample was Alkanol B3. manufactured by DuPont. After mixing, 500 cal of a 5% aqueous gelatin solution containing Og was emulsified and dispersed using a homogenizer.

In the table, DBP represents dibutyl phthalate and EA represents ethyl acetate. The following dye image stabilizers were used in the table.

The prepared sample was exposed to white light through a light film using a photosensitive needle (model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then processed according to the following processing steps. .

[Processing process]

Note that samples 1 to 3 were processed using the processing step, and samples 4 to 13 were processed using processing step B.

[Color developer composition]

Pure water 700
mj! Benzyl alcohol 15ml1 diethylene glycol 15ml! Hydroxylamine sulfate 2g N-ethyl-N-β-methanesulfonamidoethyl-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 Add pure water to make 11.

(Adjusted to pH=10.2) [Complex formation liquid composition] N i (N 0z)t 6 Hz OL 4.5 Add pure water to make 11.

[Bleach-fix solution composition]

Iron ammonium ethylenediaminetetraacetate 1 g Ethylenediaminetetraacetate diammonium g Ammonium thiosulfate 125 g Sodium metabisulfite 13 g Sodium sulfite 2.7 Add water to make up to 1 liter.

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

(1) White background test The white area (unexposed area) of each sample obtained was measured according to JIS Z872.
Based on the object color measurement method specified in 2 and Z8727,
The a"b" values were measured using Hitachi Color Analyzer Model 607.

As the a9 value increases, the redness increases, and as the a9 value decreases, the greenness increases. Further, as the b0 value increases, the yellowish tinge increases, and as the b0 value decreases, the blueish tinge increases.

(2) Light fastness test A, xenon fade meter illuminance (lux) Irradiation time ()l) IXIO' 100 B, fluorescent lamp fading tester illuminance (lux) Irradiation time (11) 2 XIO' 500 Above Δ and B Light irradiation was performed using the following two conditions, and the dye residual rate R and the yellowing ΔD of the white background were determined as follows. The density of the unexposed area of the sample irradiated with light is D 111M + YQ of the colored area
The degree is Do""1.0, and the value after light irradiation is D +++i
n and I], it is expressed as ΔD=D−t, D:+n (blue temperature).

The following margin is Table 3: 1'4; From the results of Samples 1 to 3, the addition of a conventionally known metal complex improves the light fastness, but the deterioration of the whiteness is significant, making the paper unsuitable for color printing, etc. It can be seen that burnishing and yellowing also increase.

On the other hand, the results of Samples 4 to 13 according to the present invention show that there is no deterioration of the white background, and the light fastness is significantly improved compared to conventional metal complexes, and furthermore, there is no yellowing of the white background. It is clear that the properties have also been improved, giving significantly higher overall light fastness.

<Example 2> A silver halide photographic light-sensitive material was prepared in the same manner as in Example 1, except that a blue-sensitive emulsion and a yellow coupler were used instead of the green-sensitive emulsion and magenta coupler contained in layer 1, and a coupler dispersion was prepared. The composition is shown in Table 4. Each sample obtained was subjected to the same treatments and tests as in Example 1, and the results are shown in Table 5. However, samples 1 and 2 were treated in process A.

Samples 3 to 7 were subjected to treatment step B.

From Table 5 in Table 5 below, it is clear that, similar to Example 1, in Samples 4 to 7 according to the present invention, the light fastness is significantly improved without any deterioration in whiteness and yellowing. It is.

<Example 3> A silver halide photographic material was prepared in the same manner as in Example 1 except that a red-sensitive emulsion and a cyan coupler were used instead of the green-sensitive emulsion and magenta coupler contained in layer 1. The composition is shown in Table 6. Each sample obtained was subjected to the same treatments and tests as in Example 1, and the results are shown in Table 7. However, samples 1 and 2 were subjected to treatment step A, and samples 3 to 7 were subjected to treatment step B.

Table 7 From Table 7, it is clear that, similar to Example 1, in Samples 4 to 7 according to the present invention, the light fastness is significantly improved without deteriorating whiteness and yellowing.

<Example 4> A multilayer silver halide color photographic light-sensitive material was prepared with the layer structure shown in Table 8.

Table 8 The numbers in parentheses indicate the amount of coating or addition.

Table 8 (Continued) The stain inhibitor and ultraviolet absorber used here are compounds having the structures shown below.

(Stain inhibitor) (Ultraviolet absorber) [111 The sample prepared as above is referred to as Sample 1, and the couplers and dye image stabilizers in the first, third and fifth layers of Sample I are shown in Table 9. Samples 2 to 8 were prepared with the changes shown, and the same tests as in Example 1 were conducted, and the results obtained are also shown in Table 9. For samples 8 to 8, treatment step B was applied. However, sample 1
and 2 indicate treatment step A, sample 3. In the following margins in Table 9, the numbers at the bottom of the Coupler, etc. column indicate the amount of coating, and the unit is X 10-'mol/m''.

From the results in Table 9, it can be seen that in the multilayer silver halide color photographic light-sensitive material, the same effects as in Example 1 are rather amplified, and the multilayer silver halide light-sensitive material has extremely excellent whiteness and light fastness. Obtained.

<Example 5> Six types of samples from sample numbers 3 to 8 in Example 4 were used, except that 15 g of Fa (NOl) t・9H20 was added to the bleach-fix solution 11 in Process A in Example 4. The same treatment as in Example 4 was performed, and the same test as in Example 4 was conducted.

As a result, almost the same results as in Example 4 were obtained.

Patent applicant: Roku Konishi Photo Industry Co., Ltd.
Physician Takatsuki Toru 1F Continued Shinichi”
3 Madon (Method) % formula % 1. Indication of the case 1986 Patent Application No. 8406 2. Name of the invention Silver halide photographic light-sensitive material 3. Relationship with the amended person case Patent applicant address Shinjuku, Tokyo Ward Nishi-Shinjuku 1-26-2 Name
(127) Konishiroku Photo Industry Co., Ltd. 4, agent name (8397) Patent attorney Takatsuki
9 “1 completed,゛・2

Claims (1)

[Scope of Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion contained in at least one of the silver halide emulsion layers is combined with the silver halide emulsion contained in at least one of the silver halide emulsion layers. , a dye image-forming coupler, and a compound represented by the following general formula [I]. General formula [I] C_p-(T)_n-LIG (where C_p is -( as a function of silver halide development)
T)_n-LIG represents a group that leaves off, and T is -(T
)_n-Represents a group capable of releasing LIG when or after LIG is detached, and LIG is a ligand capable of forming a complex compound having the function of stabilizing a dye image by performing a complex formation reaction with a metal ion. represents. n represents 0 or 1. )