JPS62168157A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain high light fastness by incorporating a specified compound into a layer having a specified oxidation potential, contg. a fading inhibitor and forming a magenta dye image as at least one of silver halide emulsion layers. CONSTITUTION:The oxidation potential eOX of one of silver halide emulsion layers is regulated to 0.95-1.50 and a compound represented by a formula CP T nLIG [where CP is a group separating -T-nLIG as a function of the development of silver halide, T is a group capable of releasing LIG during or after the separation of -T-nLIG, LIG is a ligand capable of forming a complex compound having a dye image stabilizing function by a complex forming reaction with a metallic ion, and n=0 or 1] is incorpo rated into the emulsion layer. When development is carried out, T nLIG is separated and LIG is released. Since this LIG can form a complex compound having a dye image stabilizing function, such a complex compound can be formed during or after the formation of a magenta dye image by supplying a metallic ion for forming the complex compound. The complex compound is formed as a function of development, so it is imagewise formed on the developed image forming part and can show an effective image stabilizing function. Thus, a sensitive material provided with high light fastness without deteriorating the whiteness can be obtd.

Description

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

[Background of the invention]

Conventionally, by imagewise exposing a silver halide photographic light-sensitive material and performing color development, a coupling reaction occurs between an oxidized product of an aromatic primary amine color developing agent and a color former, such as indophenol, indophenol, etc. Aniline, indamine,
It is well known that azomethine, phenoxazine, phenazine, and similar dyes are produced to form dye images. In such photographic systems, a subtractive color reproduction method is usually adopted, and blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsions 11 are used.
In this method, 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 colors.

It is known that silver halide photographic materials containing the above-mentioned dye images undergo significant discoloration and fading under the storage conditions. For example, the former often exhibits different fading properties when exposed to light for a long period of time and when stored in a dark place with high temperature and humidity for a short period of time. The latter case is called light fading, and the latter case is called dark fading. In order to use a silver halide photographic light-sensitive material with a dye image as a recording material that can be stored semi-permanently, these fadings must be as small as possible under any storage conditions. is desired.

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 been increasing, and there is a strong desire for the development of a technology for dramatically increasing the hardness of dye images.

In order to improve the fastness of dye images, a number of methods have been proposed in the past on two fronts. One method is to improve the fastness of the dye image itself, which involves improving the molecular structure design of the dye image itself or the compound that produces the dye image (e.g., coupler, etc.), or changing the state of existence of the dye. This is an improvement. The other method is to use a dye image stabilizer; this method has little effect on the characteristics of the dye image such as color tone, and its versatility is questionable, so many improvements have been proposed in this aspect. has been done.

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. Ta.

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 solubility of ultraviolet absorbers in high boiling point organic solvents is low! It has the disadvantage that it tends to precipitate during the second manufacturing process. Therefore, there is a limit to the amount of addition, and a sufficient effect for solidifying the dye image cannot be obtained. Furthermore, even though it is possible to prevent photofading caused by ultraviolet rays, it has a serious drawback in that it does not show any effect in preventing photofading caused by visible rays.

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 when hydrolyzed, bisphenols are described in Japanese Patent Publication No. 4B-31256 and No. 4B-31625, and pyrogallol is described in US Pat. No. 3,069,262. Garlic acid and its esters or acyl derivatives thereof, 5”72, U.S. Patent No. 3.432.30
No. 0, and No. 3,574.627.
-Hydroxychroman derivatives, and Japanese Patent Publication No. 49-20
No. 977 discloses 6,6'-dihydroxy-2,2'-
Bisspirochromans are disclosed. In addition, 6-alkoxychroman derivatives, 6,6'-dialkoxy-2,2'-bisspirochromans, and , hydroquinone derivatives, etc. have been proposed.

However, although some of these compounds do show an effect on the brightness and fading of dye images, the effect is small if the amount added is not increased when only these compounds are used, and even if they are further increased, there is no sufficient improvement effect. was not obtained. In addition, when these compounds are used, there are generally problems with sensitometry such as a decrease in color development or softening of the tone, as well as discoloration when the dye image is exposed to light for a long period of time, and problems with high temperature and high humidity. There were some things that promoted yellowing at the bottom.

Also, as a light stabilizer, US Pat. No. 4,050,938
specification, JP-A No. 56-99.340, JP-A No. 56-11
38.652, 60-51,834 and 60
A metal complex described in Japanese Patent No. 97,353 has been proposed. 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. The brightness of the white background may deteriorate, some may yellow due to heat and humidity, and the presence of light stabilizers
? It is extremely difficult to apply to silver halide photographic materials in order to achieve high light fastness effects due to its low solubility in g media and its negative effects on photographic performance such as decreased sensitivity and increased capri. Met.

Furthermore, the hue of the image described in U.S. Pat. No. 4,555,478 is not suitable for use as a light-sensitive material for direct viewing, and the metallization rate of the dye is slow, making it difficult to process in recent years with simple and rapid processing and cost reduction. It has the problem of not meeting the trend, and is particularly difficult to apply to silver halide photographic materials for color photographic paper.

As described above, a technique for improving dye image storage stability that can impart satisfactory fastness to silver halide photographic materials without adversely affecting photographic performance such as hue and softening has not yet been found. is the current situation.

The inventors of the present invention have discovered the present invention in view of the current situation described below, and have conducted extensive research to achieve dramatically improved fastness of dye images without affecting photographic performance. .

[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 material having a magenta dye image which is imparted with extremely high light fastness without any deterioration in whiteness.

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

[Structure of the invention]

The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has an oxidation potential of E. , a layer for forming a magenta dye image containing an antifading agent in which (V) is 0.95≦EO)1≦1.50, and a silver halide emulsion contained in the layer for forming the magenta dye image. This was achieved by a silver halide photographic material characterized by containing a compound represented by the following general formula in combination with .

[General formula]

C2→T+F−LIG (where C2 is −(T
←Represents a group that leaves LIG, T is -fT)r-L
Represents a group that can release LIG when or after IG is released, and LIG represents a ligand that can form a complex compound having a dye image stabilizing function by performing a complex formation reaction with a metal ion. . n represents 0 or 1.

) In the present invention, as a result of the above structure, −+
T)-L I G leaves the child. and LIG is released,
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 dye image can be formed at the same time as the magenta dye image is formed. A complex compound having this stabilizing function can be formed after 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 described 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.

-a The compound represented by formula CI) may be contained in combination with a silver halide emulsion contained in at least one of the silver halide emulsion layers forming a magenta dye image; It may be contained in itself, in a layer adjacent to the emulsion layer, or in a position where it can react with the silver halide emulsion of interest.

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

Magenta dye image-forming couplers can also be used in combination with compounds of general formula (I).

Of course, the structure may be such that a dye image is formed only by CP without using a dye image-forming coupler in combination.

When a dye image-forming coupler is used in combination, and when CP is a coupler residue of a coupler capable of forming a dye image, both the dye image by the dye image-forming coupler and the dye image by this C1. is formed. In this case, it can be constructed in such a manner that the image is mainly produced by the dye image-forming coupler, or it can be constructed in such a manner that the image is mainly produced by C2, 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, CP and LIG do not form a dye image).

In addition, image formation is mainly performed using dye image-forming couplers.
Cps-, image formation by LIG
may take the form of forming a dye image or the form of not forming a dye image). Further, the CP may not form a dye image, and an embodiment may be adopted in which image formation is mainly performed by a dye image-forming coupler, and image formation by LtC is secondary.

Of course, as mentioned above, the combined use of a dye image-forming coupler is not essential, so a dye image can be formed only on C1, and in this case, LIG may or may not form a dye image.

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

When Cp and LIG form a dye image, CP may be configured to develop a magenta color.

Similarly, I and IG can be configured to produce magenta coloring. For example, a dye image-forming coupler can be used in combination, and the color produced by this and CPSLIG (or the color produced by two of the three) can all be the same magenta color.

Preferably, when a dye image-forming coupler is used, the color produced by this coupler and the color produced by CP are the same magenta color or substantially the same color magenta.

[Specific structure of the invention]

Next, the present invention will be specifically explained.

In the compound represented by the general formula [1] according to the present invention, CP is -(
T) Any structure can be used as long as it is a group that leaves r-LIG, but a magenta dye image-forming coupler residue can be preferably used as CP.

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

Ar [In the formula, Ar represents an aryl group, R31 represents a hydrogen atom or a substituent, and Ro represents a substituent.

W±'0- (N atom is bonded to carbon atom of pyrazolone nucleus)
or -NHCONH-, and m is an integer of 1 or 2. ) The coupler residue represented by the general formula (III) will be explained in detail.

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

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 resulting phenyl group may have two or more substituents.

Specific examples of substituents are listed below.

Halogen atom: chlorine, bromine, fluorine Alkyl group: Methyl group, ethyl group, 1so-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-natoxy group, etc., but this aryl moiety further has 71. It may have the same substituents as those listed for the phenyl group represented by r.

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: Alkylcarbamoyl group such as carbamoyl group, dimethylcarbamoyl group Sulfamoyl group: Alkylsulfamoyl group such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group Sulfonyl group: methanesulfonyl group , ethanesulfonyl group, methanesulfonyl 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 R31 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 5ec-butoxy group and 1so-pentyloxy group are preferred.

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

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

The substituent represented by R3□ is a halogen atom, an alkyl group, an amide group, an imido group, an N-alkylcarbamoyl group,
Examples include an N-alkylsulfamoyl group, an alkoxycarbonyl group, an acyloxy group, a sulfonamide group, and a urethane group. These groups include 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 may be either -NH-1-NHCO- (the nitrogen atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH-, but -NH- can be particularly preferably used for W.

Examples of substituents that can be separated by a coupling reaction with the oxidized product of the aromatic primary amine coloring agent represented by Y include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, and a (2g is a nitrogen atom). and represents an atomic group necessary to form a 5- or 6-membered ring with an atom selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms.

Specific examples are given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: ethoxy group, pendyloxy group, methyl
Aryloxy groups such as xyethylcarbamoylmethoxy group and tetradecylcarbamoylmethoxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group, etc. Acyloxy group: ace].xy 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-(diethylamine)ethylthio group, ethylthio group, ethylthio group, ethylthio group, ethoxyethyl group Thio group, fair 1xethylthio group, triazolyl group, tetrazolyl group general ring formula [■'
] (In the formula, Z represents a metal atom group forming a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent.R
represents a hydrogen atom or a substituent.

Among the groups represented by the general formula [■′], the following general formula (
Groups represented by III-a) and (III-b) can be preferably used.

General formula [l1llr-a] General formula (m-b) R' and R" represent an alkyl group, an aryl group, or a heterocyclic group. It is particularly preferable that both R' and R" are an alkyl group.

The alkyl group represented by R' and R'' has about 1 to 1 carbon atoms.
32 is preferred. Alkyl groups may be linear or branched.

The alkyl groups represented by R' and R'' include substituents [for example, aryl, cyano, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, acyl, Those substituted through a carbonyl group such as carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted through a hetero atom [specifically, hydroxy,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, etc. substituted via an oxygen atom, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, Those substituted via a nitrogen atom such as acylamino, sulfonamide, imide, and ureido, those substituted via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl. (e.g., a replacement).

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1' dibentynonyl! ,,
2-chloro-1-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2.4-di-1-alumiphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3 -4'-(α-(4" (p-hydroxybenzenesulfonyl)phenoxy) dodecanoylamino)phenylpropyl group, 3-(4'-(α-2', 4
Examples include '-di-1-amylphenoxy)butanamido]phenyl)-propyl group, 4-(α-(0-chlorophenoxy)tetradecanamidophenoxy)propyl group, allyl group, cyclopentyl group, and cyclohexyl group.

The aryl group represented by R' and R' is preferably a phenyl group, and a substituent (e.g. an alkyl group, an alkoxy group,
acylamino group, etc.).

Specifically, phenyl group, 4-1-butylphenyl group,
2.4-di-1-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-1-butylphenoxy)tetradecanamidophenyl group and the like.

R', I? The heterocyclic group represented by ' is preferably 5- to 7-membered, and may be substituted or fused. Specifically, 2-furyl group, 2-chenyl group,
Examples include 2-pyrimidinyl group and 2-benzothiazolyl group.

Next, R' represented by the above general formula, R' represented by R'',
A specific example of R' will be shown.

CH3 C+Jis -CHzCHzCIhOCtzHzs CHzCNtCONIIC+aHzq The magenta coupler residues represented by the previous general formula (III) and [■'] may be so-called polymer coupler residues, and they are described, for example, in JP-A-58-28-74
No. 5, No. 59-228.252 and No. 59-171.
It is also possible to use those described in Publication No. 956 and the like.

Other compounds that can be used as Cp in the present invention include those that do not form yellow, magenta or cyan dyes by reaction with the oxidized product of a color developing agent, or that do not remain as a dye image after development due to elution etc. Structures such as so-called Weiss coupler residues can also be used. Specific examples of these compounds are given in British Patent No. 8, for example.
It is described in the specification of No. 61.132 and Japanese Patent Publication No. 77.635/1983.

('1 Shi! To2 I Shi! I M-4 ■ I To5 ■ The following margins G9 ゛ca old, (L) G11 Next, T in the general formula (1) in the present invention will be explained in detail. In the general formula (1), T represents a group that is bonded to the camping position of Cp and is capable of releasing LIG when or after being separated by reaction with the oxidized product of the 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, ■ leaving LTG due to intramolecular substitution reaction, ■ electrons via conjugated system. Those that leave LIG by migration (2) Furthermore, they cause coupling between the active agent and the oxidant, or leave LIG through cross-oxidation, and the above-mentioned reactions may be used in combination.

For example, U.S. Patent No. 4,146.396, U.S. Pat. No. 51-26039, U.S. Pat.
No. 34, No. 57-188035, No. 57-11153
6 and other published patents No. 57-56873 and No. 58-98
No. 728, No. 5B-209736, No. 5B-20
No. 9737, No. 58-209738, No. 5B-20
No. 9739, No. 59-206834, No. 60-742
No. 9, No. 60-213944, No. 60-214358
No. 60-225156, No. 60-218645, No. 60-225844, No. 60-229030,
It is a linking group described in No. 60-230139, No. 60-232549, No. 60-203943, etc.

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

Margin below.

(♀・°2,
)! 1 tvl In the above general formulas (■ to ■), () represents a hydrogen atom, a nitro group, an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.),
Alkylsulfonyl groups (e.g. methanesulfonyl, butanesulfonyl, etc.), cyano groups, alkoxy 6<e.g. group), carboxy group, acylamino group (eg, acetamino, benzoylamino, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), and the like.

) (1 represents the same group as Xf, preferably a hydrogen atom, an acylamino group, or a sulfonamide group.

X113 is an alkyl group, an aryl group (e.g. phenyl,
naphthyl, etc.), and may have a group listed for Xf as a substituent.

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

X< represents a carbamoyl group (methylcarbamoyl, butylcarbamoyl, phenylalhamoyl, etc.) in addition to the same group as Xf.

W, , W represents hydrogen, an alkyl group, etc.
W2 may combine to form a benzene ring and a naphthalene ring. Next, LIG in general formula (1) in the present invention will be described in detail. The released LIG can have any structure as long as it is a group that can form a complex compound having the function of stabilizing a dye image by complex-forming reaction with a metal/ion. Stores represented by (V) and (VI) can be preferably used.

General formula (V) represents a combined group that can form a 5- to 6-membered cyclic chelate compound when coordinated to a metal.) X, A, and Y represent the following in more detail.

S1 .

R62: hydrogen, alkyl, aryl, amyl, R53,
R3: Hydrogen, alkyl, aryl, acyl, sulfonyl The alkyl group for R1 and R4 is an alkyl group having 1 to 20 carbon atoms, preferably substituted at the β or γ position with an oxygen, sulfur, or nitrogen atom. Further, as the aryl group, substituted or unsubstituted phenyl or naphthyl groups are preferred, and further preferred are phenyl groups and naphthyl groups in which the 0-position is substituted with oxygen, sulfur, or nitrogen atom.

The ligand eX-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. In this case, a ballast group having 8 or more carbon atoms, preferably 12 or more carbon atoms may be added.

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

Below is a specific example of the margin LIG: l -5CHCO5C4H9 CIJ! 5 SCIlzCIIzNC+ Jgs CHtCH□011 0M -5CHCOOH c+zozs -OCIItCHgSC+ dlgq (n)N -
CHgC1hSC+Jts SO□CH3 (In the formula, from R61 to s represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group.) In the general formula (Vl), represented by R□ to Ro At least one of the groups 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.

Below are blank spaces ゝ゛♀, °- Next, specific examples of compounds represented by the general formula [1] are illustrated below.

1hl Shingyo 10 '1' l Floor 11 I Floor 13 t Shi! 14 l N124 LIG= -5CHzCIl□
NHC salt zlhsN125 LIG = −
0(jlzcHxscIIzcHisct zHzs隘26 LIG -, 5C)1. CIl,
SI:, 211□5Na27 LIG
"-5CIIzCtlzNi(C+zihsnI
! Fish 29 LIG = , 5C1l, C1
l□5CHzCtlzSC+□Ls 30
LIG = ~QC1hC (1 layer) ICi! tcH
zsc+ 11IJt 31 Hz 32! , IG=-5CHzCHtSCH
tCHtSC+tutshh33 LIG=
-OCHgCHzSC+z! bsFh35L
IG--5CIhCHzSC+□)lzsm36
LIG= -OCII2CH2SCH2C1hNH
CI2H2SC1h C5) II l (t) 1h43 11 (2% 0=C-OClhClhSCIlzCIlzSCfiz
CHtSCt zHtsH C-s! l + + (t) 49 r# し1slIffl 隘51! lh52 patient 58 OI patient 59 pigeon 6O a61 In the synthesis of the compound of the present invention, the published patent No. 46-4
The coupler core can be easily synthesized by the methods described in No. 3447 and Japanese Patent Publication No. 171956/1983. Furthermore, the LIG portion can be synthesized according to the method described in Anti-12240, page 310. Next, a synthesis example will be described. Exemplified compound (36
), the synthesis of its LIG, the synthesis of the mother coupler,
The synthesis of exemplified compound (36) will be explained in order.

Synthesis Example LIG Synthesis City 11 Dodecyl mercaptan and ethylene chlorohydrin were reacted in alcohol under reflux under heating in the presence of 0.0 kg for 3 hours. The solvent is concentrated under reduced pressure, water is added to dissolve the salt, and the mixture is extracted with nickel acetate. Extract extract and pear in chloroform 3
Bromate with phosphorus bromide at -10°C. React for 2 hours and wash with water. Depressurize the solvent? m'l? and replace with alcohol solvent. Gas chromatography shows a reaction rate of 95% or more. Next, a calculated amount of thiourea is added and the mixture is heated under reflux and allowed to react for 3 hours. 1. Crystals precipitated after cooling. Calculate by adding 90% hydroalcohol immediately without drying.
Add 1.2 times as much NaOH and heat under reflux for 1 hour.

After the reaction, the solvent was distilled off, poured into an aqueous hydrochloric acid solution, and extracted with cyclohethiane. Yield: 70% (gas chromatography purity: 97%) Synthesis of coupler core Synthesis is performed by the method described in Japanese Patent Publication No. 1983-42045.

It is synthesized by the method described in Japanese Patent Publication No. 59-171956.

Synthesis of Exemplary Compound (36) The 4-equivalent coupler described in the above-mentioned patent and the above-mentioned LIG are stirred in chloroform at room temperature, and a calculated amount of FN-chlorosuccinimide is added thereto, followed by reaction under heating under reflux for 3 hours. After the reaction, the reaction mixture is washed with water and the solvent is concentrated. Separate and purify using a silica column. Colorless candy-like, yield 40% (purity 98%) Identification was done by F, mass spectrum, and NMR spectrum, and purity measurement was done by liquid chromatography.

Exemplary compound (54) was synthesized in the same manner and was obtained as a colorless candy-like substance in a yield of 38% (purity 94%).

In the present invention, a dye image-forming coupler can be used together with the compound represented by general formula (1). The dye image-forming coupler in this case may have any structure, but magenta dye image-forming couplers that can be preferably used in the present invention include those shown below.

As the Mazenk dye image-forming coupler, the general formula Ca
] and (alj) can be preferably used.

Ar [In the formula, Ar represents an aryl group, R□ represents a hydrogen atom or a substituent, and Ro represents a substituent.

Y is a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent, and the oath is -NH-1-NHCO-
(N atom is bonded to the carbon atom of the pyrazolone nucleus) or -N
It represents ICONH-, and m is an integer of 1 or 2.

) Below margin - Kasumi -5 Shi1 Shi! These include, for example, U.S. Patent Nos. 2,600,788, 3,061,432, 3,062,653,
3.127゜269, 3,311,476, 3,152.896, 3,419,391
No. 3,519.429, No. 3.555.31
No. 8, No. 3,684,514, No. 3,888.6
No. 80, No. 3.907.571, No. 3,928,
No. 044 4. Same No. 3.930.861, Same No. 3,93
No. 0,866, same'rj! 13. q33. ; oo issue, etc., JP-A-49-29639, JP-A-49-111
No. 631, No. 49-129538, No. 50-1304
No. 1, No. 5L58922.

No. 55-62454, No. 55-118034, No. 5
No. 6-38043, August 57-3585, No. 60-2
3855, British Patent No. 1,247,493, Belgian Patent No. 769,116, and British Patent No. 792.52.
5, West German Patent No. 2,156,111, Japanese Patent Publication No. 46-60479, etc.

In the magenta coupler represented by general formula (al) and general formula (al) χ, Za represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and glZa
The ring formed by may have a substituent.

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

Moreover, 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, ? IJ-ru group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group , heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine group, acylamino group, sulfonamide group, imide group,
ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Examples include an alkoxycarbonyl group, an 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.

The alkyl group represented by 11a has 1 to 32 carbon atoms.
, alkenyl group, alkynyl group has 2 carbon atoms
-32, cycloalkyl groups, and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl groups, alkenyl groups, and alkynyl groups may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted through a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted through a heteroatom (specifically, hydroxy, alkoxy, and aryloxy , heterocyclic oxy,
Substituents via an oxygen atom such as Those substituted via an N atom such as amide, imide, and ureido; those substituted via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl; and those substituted via a sulfur atom such as phospho; etc.)
].

Specifically, for example, methyl group, ethyl group, isopropyl group, L-butyl group, pentadecyl group, heptadecyl group,
-hexylnonyl group, 1.1'-dihenthylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, 1
-ethoxytridecyl group, ■-methoxyisopropyl group, methanesulfonyl ethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl L 3 -4'-<α-[4"(p-hydroxyhenzenesulfonyl)phenoxy] dodecanoylamino)phenylpropyl group, 3- (4' -(α-(2
",4"-di-t-amylphenoxy)butanamide]
phenyl)-propyl group, 4-[α-(0-chlorophenoxy)tetradecanamidophenoxy]propyl group,
Examples include allyl group, cyclopentyl group, and cyclohexyl group.

A phenyl group is preferable as the aryl group represented by Ra, and it may have a substituent (for example, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-dobutylphenyl group, 2
, 4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-
[α-(4#1-butylphenoxy)tetradecanamidophenyl group, etc.].

The heterocyclic group represented by Ra is preferably a 5- to 7-membered one, which may be substituted or fused. Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by Ra include acetyl group,
Alkylcarbonyl groups such as phenylacetyl group, dodecanoyl group, α-2,4-di-t-amylphenoxybutanoyl group, “1-aryl carbonyl group such as benzoyl group, 3-pentadecyloxybenzoyl group, p-chlorobenzoyl group, etc.” Examples include groups.

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 ethylsulfinyl group, octylsulfinyl group, alkylsulfinyl group such as 3-phenoxybutylsulfinyl group, phenylsulfinyl group, m-hentadecyl phenyl group.
Examples include arylsulfinyl groups such as rufinyl groups.

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

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 group, N,N-dibutylcarbamoyl group, N-(2-pentylcarbamoyl group). Examples thereof include decyl octylethyl) carbamoyl group, N-ethyl-N-dodecyl carbamoyl group, and N-(3-(2,4-di-t-amylphenoxy)propyl) carbamoyl group.

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

Examples of the spiro compound residue represented by Ra include spiro(3,3)hebutan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by Ra include bicyclo(2,2,1)hebutan-1-yl, tricyclo(
3,3,1,13°7]tecan-1-yl, 7,7-dimethyl-bicyclo(2,2,1)hebutan-1-yl, and the like.

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

The aryloxy group represented by Ra is preferably phenyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group, such as phenoxy group, p-1-butylphenoxy basis,
Examples include m-pendecyloxy group and the like.

The xy group represented by Ra is preferably one having a 5- to 7-membered heterocycle.The heterocycle may further have a substituent91, for example, 3,4゜5 .6-titrahydropyranyl, 2-oxy group, and 1-phenyltetrazole-5-oxy group.

1? The siloxy group represented by a may be further substituted with an alkyl group, etc., for example, a trimethylsiloxy group 1
．． Examples include triethylsiloxy group and dimethylbutylsiloxy group.

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

The carbamoyloxy group represented by Ra is an alkyl group,
It may be substituted with a teryl group, such as N-ethylcarbamoyloxy LN, N-diethylcarbamoyloxy, N-phenylcarbamoyloxy group, and the like.

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

The acylamino group represented by Ra includes an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, an α-
Examples include an ethylpropanamide group, an N-phenylacetamide group, a dodecaneamide group, a 2,4-sheet 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 a substituent.

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

The imide group represented by Ra may be open-chain or cyclic, and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarium group, etc. Examples include imide groups.

The ureido group represented by Ra may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group. , N-p-tolylureido group, and the like.

The sulfamoylamino group represented by Ra may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc. (e.g., N, N-dibutylsulfamoylamino group, N- Examples include methylsulfamoylamino group, N, and phenylsulfamoylamino group.

The alkoxycarbonylamino group represented by Ra may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like.

The aryloxycarbonylamino group represented by Ra is
(a) may have an A group, such as a fair-skid carbonylamino group and a 4-methylphenoxycarbonylamino group.

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

The -ruoxycarbonyl group represented by Ra may further have a substituent, such as phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, and the like.

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

The arylthio group represented by Ra is preferably a phenylthio group and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2 -carboxyphenylthio group, p-a7doaminophenylthio group, and the like.

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

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

Examples of the group substituted via a carbon atom include a carboxy group and, for example, the general formula (R1' is the same as the above R, Z' is the same as the above Z, R2 and R3 are a hydrogen atom, an aryl group , representing an alkyl group or a heterocyclic group), a hydroxymethyl group, and a triphenylmethyl group.

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

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

As the core aryloxy group, a phenoxy group is preferred, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-
Dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-[α-(3'-pentadecylphenoxy)butanamide]phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p-
Examples include methoxyphenoxy group.

The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include l-phenyltetrapryloxy group, 2-benzothiazolyloxy group, and the like.

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

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

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

1 aryloxycarbonyl Examples include oxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

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

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

Examples of the arylthio group include phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidophenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-1- Examples include butylphenylthio group.

Examples of the cough 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.

R4
・ and R3・ may be combined to form a heterocycle.

However, R4・ and R2・ are not both hydrogen atoms.

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

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

The aryl group represented by R, or R1. 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 the above R4. Alternatively, the substituents for the alkyl group represented by R1. include those listed above and an alkyl group. Specific examples of the nucleol group include phenyl group, 1-naphthyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R4 or R2 is 5 to 6
It is preferable that the ring is a membered ring, and it may be a condensed ring or have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2-pyrdyl group, and the like.

Examples of the sulfamoyl group represented by R4 or R2 include N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc. are mentioned,
These argyl groups and aryl groups may have the substituents listed above for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group, N-dodecylsulfamoyl group, and Np-1-dylsulfamoyl group.

The carbamoyl group represented by R4 or R6 includes N-alkylcarbamoyl group, N,N-dialkylcarbamoyl5, N-arylcarbamoyl group, N,N-
Examples include diarylcarbamoyl groups, and these alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group,
N-p-tolylcarbamoyl group is mentioned.

Examples of the acyl group represented by R4 or R3 include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You can leave it there. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4,5.6-bentafluorohenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. It will be done.

Examples of the sulfonyl group represented by R4 or R6 include an alkylsulfonyl group, an arylsulfonyl group, and a peterocyclesulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group, Examples include a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, and a p-chlorohenzenesulfonyl group.

The aryloxycarbonyl group represented by R4 or R1 may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like.

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

The heterocycle formed by R4 or R2 is preferably a 5- to 6-membered one, and may be saturated or unsaturated, and may or may not have aromaticity, or,
It may be a condensed ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxoxabridinyl group, 2- N-1,1-dioxo-
3-(211)-oxo-1,2-benzthiazolyl group, ■-pyrrolyl group, l-pyrrolidinyl group, l-pyrazolyl group, 1-pyrazolidinyl group, ■-piperidinyl group, ■
-pyrrolinyl group, l-imidazolyl group, l-imidazolinyl group, l-indolyl group, 1-isoindolinyl group,
2-isoindolyl group, 2-isoindolinyl group, 1-
Benzotriazolyl group, 1-benzimidazolyl group, 1
-(1,2,4-1-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 group, 2-IH-pyridone group, phthaladione group, 2-oxo-1-piperidinyl group, etc., and these heterocyclic groups include alkyl groups, group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group, sulfonamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imide group,
It may be substituted with a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like.

Examples of the nitrogen-containing heterocycle formed by Z or 2' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

Further, general formula (al) and general formula (aII) to be described later ~ [a
(2)] on the heterocyclic ring (e.g., R, R, ~R
When s) has a moiety (R'', X and Z'' have the same meanings as Ra, X and Za in general formula (r)), it forms a so-called screw-type coupler, but is of course not included in the present invention. Ru. Further, the ring formed by Za, Z', Z' and 21 described below may be further fused with another ring (for example, a 5- to 7-membered cycloalkene). For example, Ram and R1 in general formula (V) are R? in general formula (VI)? a
and Ram may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene).

(Margin below) ・tj　'-.

\,.

More specifically, what is represented by the general formula (ar) is represented by, for example, the following general formulas (aII) to [a■].

General formula (a II) General formula (a DI) General formula (a IV) General formula (aV) General formula (aVI) General formula [a■] In the above general formulas (a II) to [a■], RIM ~R
h and X have the same meanings as R1 and X above.

Also, preferred among the -8 formulas (al) are those represented by the following general formula [a].

General formula [a■] In the formula, RIm+χ and Zlm are R in the general formula (al)
, , has the same meaning as X and Z.

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

Regarding the substituents on the heterocycle in general formulas (a I) to [a■], in general formula Ca I), R1
However, in the general formulas (aI[) to [a■], it is preferable that Lm satisfies the following condition 1, more preferably the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following condition 1 is satisfied. ．． This is a case where conditions 2 and 3 are satisfied.

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

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

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

The most preferred substituents Ra and RIM on the heterocycle are those represented by the following general formula (a LX).

General formula (a IX) 4m ■ R+o-C- Story 11m In the formula, R911+ RIOa and R1111 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, Hetero Y1 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, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic group, and at least two of R9a + R1° and R11m are not hydrogen atoms.

In addition, RQm + R1゜ and two of RzaO, for example, R9a and RIO&, are combined to form a saturated or unsaturated ring (for example, cycloalkane, cycloalkene, heterocycle).
may be formed, and furthermore, R11m may be bonded to the ring to constitute a bridged hydrocarbon compound residue.

The groups represented by R11a to R11m may have a substituent<, and specific examples of the groups represented by R9- to R11m and the substituents that some groups may have include the above-mentioned general formula ( Specific examples of the group represented by Ra in al) and substituents are listed.

In addition, specific examples of the ring formed by bonding R9i and R1° and the bridged hydrocarbon compound residue formed by R91 to R1111 and the substituents that may have are as follows:
Specific examples of the cycloalkyl, cycloalkenyl, and heterocyclic group-containing bridged hydrocarbon compound residues represented by Ra in the aforementioned general formula (al) and their substituents are listed.

Among the general formulas (a IX), (1) R9
(ii) R where two of 1 to R1111 are alkyl groups
When one of 91 to R1111, for example R11, is a hydrogen atom, and the other two R11 and R1.3 combine to form a cycloalkyl together with the root carbon atom, the following is true.

Furthermore, preferred among (i) is the case where two of La-R111 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substituent represented by Ra in the general formula (al). Specific examples of the group are listed below.

In addition, the substituents that the ring formed by Za in the general formula (aI) and the ring formed by Zl & in the general formula [a] may have, and the following general formula (a X) The one represented by is preferable.

General formula (aX) -R'-5o□-R2 In the formula, R' represents alk; trene, and R2 represents alkyl, cycloalkyl or aryl.

The alkylene represented by R' preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and the straight chain portion has 1 or more carbon atoms.
Regardless of branching. Moreover, 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 above-mentioned general formula (a I) is an alkyl group.

Preferred substituents include phenyl.

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

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

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

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

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

Specific examples of the aryl group represented by R2 include phenyl and naphthyl. The nuclear Ryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R1 described above.

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

General formula [a! ] Among the compounds represented by the above, particularly preferred are those represented by the following general formula (aXl).

General formula (aXI) In the formula, Ra, Xa are Ra in general formula (a I),
It has the same meaning as Xa, and R1 and R2 are the general formula (a X)
R1. It has the same meaning as R2.

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

-15 H3 To16 To17 In the present invention, when a compound represented by the general formula (N) and a dye-forming coupler are used together, the ratio of the compound and the coupler used in combination to the dye image-forming coupler may be any ratio depending on the case. but preferably in the range of 10-'' moles to 10 moles, particularly 5xio-'' moles to 5 xio-'' moles per mole of color image-forming coupler.
It can be preferably used within a molar range.

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

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 dyes are within nm, and it is particularly preferable that they are the same dye.

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.
Does not show absorption peak at On+w or 40
The molar extinction coefficient at the maximum absorption wavelength from 0 nm to 700 nm is i, oo.

It is preferably less than or equal to SOO, particularly preferably less than or equal to SOO.

Also, a complex compound having the function of stabilizing a dye image.

represents a complex compound that is stabilized by any mechanism depending on the type of dye image, medium, state of existence, etc., but preferably has a quenching rate constant of - doublet oxygen of 3 XIO'M-'
・It is a complex compound of 5ec-' or more, especially IXIO"
A compound having a quenching rate constant of M-1·5ec-' or more is preferably used.

The above-mentioned quenching rate constant of heavyt oxygen was published in the Journal of Physical Chemistry.
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.

The initial concentration of rubrene at this time is (R), the concentration of the compound to be measured is (Q), and the concentration of luprene in a solution of rubrene alone after the test is [R)? Then, the concentration of rubrene in the mixed solution of rubrene and the test compound after the test is [R)? Then, the quenching rate constant (kq) of doublet oxygen is calculated by [Q] ([R] / (R)?).

Further, the complex stability constant of the complex compound according to the present invention can take any value, but generally it is 1010 to 1030.
It is possible to preferably use a chemical compound having a range of .

Next, the antifading agent used in the present invention (hereinafter referred to as the antifading agent according to the present invention) will be described in detail.

The oxidation potential (hereinafter referred to as EO) of the antifading agent used in the present invention
(represented by X) will be explained.

EOX can be easily measured by those skilled in the art.

The method is as described in the article “Naturwissenschaften” by A. 5tanienda, Volume 47, Sections 353 and 512 (1960), P. De
1 New Instrumental Methods in Electrochemistry by Lahay
Rumental Methods in Elect
roc-hemistry) (1954), In
“Polarographic Techniques” by Meites, published by Terscience Pulishers.
es) 2nd edition (1965) Interscience
e Publishers, etc.

E above. The value of X refers to the potential at which the compound has its electrons withdrawn at the anode in voltammetry, and it is linearly related to the highest occupied electron energy level in the ground state of the compound.

E in the present invention. X is a value determined from the half-wave potential of a polarographic graph under the conditions described below.

That is, acetonitrile is used as the solvent for the anti-fading agent, 0.1-layer sodium perchlorate is used as the supporting electrolyte, the concentration of the anti-fading agent is 10-' to 10-4 mol/l, and the reference electrode is Ag/Agcj! EOX was measured using a rotating platinum plate electrode at 25°C.

The oxidation potential obtained here is 0.95≦EOX≦1.
An anti-fade agent having a rating of 1.50 can be used in the present invention, but preferably a 1. Preferably, the antifading agent satisfies OO≦EOX≦1.45, and particularly 1.00≦EOX≦1.40.

Any compound can be used as the antifading agent according to the present invention as long as it has an oxidation potential within the above range, but in order to fully exhibit its original effect, it is preferably a water-insoluble compound.

Specific compounds of the antifading agent according to the present invention are shown below, but the present invention is not limited to these compounds.

th L;H3 (AO-3) (AO-6) ni 113 CIli (AO-13) OH c+Jzs (AO-14) OH c! I(ts (AO-15) Of( し+zlhs Ct)its (AO-16) OH (AO-17) 匡C! II, 5 OCsH+t ■ 0[;11111? (AO-20) 0+gHzs(n) (AO-23) H3Lu1lC)13 CL (AO-27) C)13CH3 (AO-28) The amount of the antifading agent according to the present invention to be added depends on the desired improvement effect, the type of antifading agent, and Any amount may be added depending on the type of dye to be produced, but in the present invention, a dye image can be formed from any or all of the C2 moiety and the I, I0 moieties in the dye image forming coupler in general formula (1). It can be preferably used in an amount of 0.05 to 3 mol, more preferably 0.1 to 2 mol, per mol of the total dye image formed by combining these dyes. I can do it.

In the present invention, the compound represented by the general formula (r) and the dye-forming coupler may be added in any amount, but the preferred range is 1 x 10-3 mol per mol of silver halide. It can be used in a range of 2 moles, preferably 1X10-" moles to 8X10" moles.

Further, the compound represented by the general formula (1) can be added by any method depending on the properties of the compound, the type of photosensitive material, etc.

If the compound is a polymer coupler, it can be directly dispersed in a hydrophilic binder solution. In the case of a hydrophobic compound, known methods such as a solid dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method can be used, and among them, an oil-in-ice emulsion dispersion method is preferred.

For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic compounds such as couplers can be applied, and the boiling point is usually about 15%.
Dissolve in an organic solvent with a high boiling point of 0°C or higher, if necessary, in combination with a low boiling point and/or a water-soluble organic solvent, and use a stirrer or homogenizer to mix a hydrophilic binder such as an aqueous gelatin solution with a surfactant. After emulsification and dispersion using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, 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.

Examples of high-boiling organic solvents include phenol derivatives, phthalate esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents are used.

The high boiling point organic solvent that can be preferably used in the present invention is a compound with a dielectric constant of 6.0 or less, such as esters such as phthalates and phosphates with a dielectric constant of 6.0 or less, organic acids, etc. These include amides, ketones, and hydrocarbon compounds.

Preferably, it is a high boiling point organic solvent having a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure of 0.5 mdg or less at 100°C. Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds.

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

Phthalate esters that can be advantageously used in the present invention include those represented by the following general formula (d).

In the formula, RI6 and R1'l each represent an alkyl group, an alkenyl group or an aryl group. However, Ro and R1? The total number of carbon atoms in the group represented by is 8 to 3
It is 2. More preferably, the total number of carbon atoms is 16
It is 24 to 24.

In the present invention, Ro and R1? of the general formula (d)?
The alkyl group represented by may be linear or branched, such as butyl group, pentyl group, hexyl group, -butyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group. group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. The aryl group represented by R16 and R11 is, for example, a phenyl group, a naphthyl group, etc.
Alkenyl groups include, for example, hexenyl group, heptenyl group,
Such as octadecenyl group. These alkyl groups, alkenyl groups, and aryl groups may have single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, and aryloxy groups. substituents for aryl groups include, for example, halogen atoms, alkyl groups, alkoxy groups, aryol groups, aryloxy groups, alkenyl groups,
Examples include alkoxycarbonyl groups.

Phosphate esters advantageously used in the present invention include those represented by the following general formula Ce).

General formula [e]0 RzoOP OR+s OR+9 where Rlg , Rt9 and . each represents an alkyl group, an alkenyl group or an aryl group.

However, the total number of carbon atoms represented by R+s s Rlg and Rt is 24 to 54.

The alkyl group represented by R(@, R19 and R7° in general formula (e) is, for example, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an I - Lysoyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc. Aryl groups include, for example, phenyl group, naphthyl group, etc., and alkenyl groups include, for example, hexenyl group, These include heptenyl group and octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably R111, R19 and Rlo are alkyl groups, such as 2-ethylhexyl group, n-octyl group,
3.5.5- Trimethylhexyl group, tomenyl group, dodecyl group, 98C-decyl group, 5ec-dodecyl group, t
-octyl group and the like.

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

Exemplary organic solvent ll3L; 11゜11S42 Czlls l 0-CIl□C1l (Cfh) zclbO・P-O
CIhCIl (CTo) *CH30czus CHzCll(C)lt) 3cL Js S-13 0-C*lI+q(f) 0・P-0-CJI+*(i) [0-CQHI 9 (i) 0=P-0- CqH+w(n) o-cqt+, (n) S-15 0-01°11□, (i) 0=P-0-C+oll□(i) 0-C+. Hat(i) S-16 0-C+oHg+(n) 0=P-0-C,, l2. (n) 0-CtoHz+(n) l5-17 0-C++Hg:+(i) 0・P-0-C11H2s(i) 0-C0Hzx(i) 0-C+zHzs(i) 0=P-0-CIJzs( i) 0-C+zHts(i) 15-20 Although any amount can be taken as the addition amount of these high boiling point organic solvents, generally the general formula (1
) 10 to 200% by weight based on the compound represented by
It is preferably used in a proportion of 20 to 150% by weight. Furthermore, as will be described later, a dye image-forming coupler can be used in combination with the compound represented by the -C formula [■]. In this case, the compound represented by the general formula (1) and the dye image-forming coupler can be used together. 10 to 200 for the total
It can be used in a proportion of 20 to 150% by weight, preferably 20 to 150% by weight.

As methods for supplying metal ions to form a complex compound with LAG 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.

・Ni”-NiBrg(+3HzO)pJ i C
1t・6Hz.

N 1 (NOz)z ・6 HzO NiS04・6H20 ・Cu2″″ −Cu Cl z ・2 N Ha C
l ・2 Hz 0CuC12・2H20 Cu(NOz)z ・38zO CuSO4'5HzO ・Zn” ... Zn13r2ZnC/2 Z n (N 0s)z ・6 HzOZnSOn7H
zO 'Fe' --- FeSO4' (NHn)zs
O4・6Hz.

FeBr.

F6CIZ(+4H20) F e (N 0s)z' 9 HzOFeSO4
・ 7HgO ・Co” ・・・ C0C1z・ 6HzOCO30
47HzO 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.

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.
-129,346, and JP-A No. 56-1
No. 26.529, No. 60-206.537, No. 60-
No. 206.538 and No. 60-205.539 describe methods using water-soluble organometallic complexes, and
Japanese Patent Publication No. 58-38.955, 5B-105,146
No. 58-129.429 discloses a method using a water-insoluble organometallic complex, and JP-A No. 57-1989 discloses a method using a water-insoluble organometallic complex.
No. 105,738 discloses non-diffusible complexes which become ligand exchange active when reduced in the presence of an alkali. Among these methods, any method can be selected from the viewpoints of small influence on the appearance and photographic performance of introduction into the photosensitive material, rapidity of reaction such as ligand exchange, etc., but preferably Alternatively, 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 the function of stabilizing a dye image by a complex formation reaction with IG in the above general formula of the present invention.
t”.

Transition metal ions such as Cu'', Zn''°, Fe'', Co'' are preferred, and among them Ni'', Cuz''
″, Fe!+ are particularly preferred.

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

〔Water soluble〕

S-1 H ■ CI, C00H s-i.

[Water-insoluble]

(n) HszC+6CIl CH2I NH, NH.

S-14 0H O The complex compound forming compound according to the present invention is contained in combination with a silver halide emulsion, and "in combination" as used herein means that the complex compound is formed as a function of development of silver halide. This means that the silver halide emulsion and the complex compound forming compound are not necessarily in the same layer. The complex compound forming compound according to the present invention 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.

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, silver 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 halogen ions may be mixed simultaneously, or one of them may be present while the other is mixed. 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, the halogen composition of the particles may be changed using the convergence method.

9. The present invention allows the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains to be controlled by using a silver halide emulsion as necessary during production of the silver halide emulsion of the present invention. The halides used in the silver halide emulsions are cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts in the process of grain formation and/or growth. 1. Iron salts or complex salts can be used to add metal ions to the interior of the particles and/or to the surface of the particles, and in a suitable reducing atmosphere (possibly to the interior of the particles and/or to the surface of the particles). Can provide reduction aggravation nuclei.

In the halogen monomer emulsion of the present invention, unnecessary soluble raw 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 a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. In other words, compounds containing sulfur that can react with 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 sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
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 advantageously used as a 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.

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

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other lignophilic 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 anti-capri agents are used to prevent deterioration and noticeable graininess.

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

In the color optical material using the silver halide emulsion of the present invention, an image stabilizer that prevents deterioration of the dye image can be used.

In the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention, an ultraviolet absorber is added to prevent fogging due to discharge caused by charging of the photosensitive material due to Pj rubbing, etc., and to prevent image deterioration due to UV light. May contain.

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

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention 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 wood-philic 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.).

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

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.
It may also be applied via one or more base coats N) 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 extruded sun 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 range in which the emulsion layer constituting the light-sensitive material of the present invention has intensity. 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, T-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. Since these compounds are more stable than the free state, -C is used in the form of a salt, such as a hydrochloride or a sulfate. Additionally, these compounds are generally used in concentrations of from about 0.1 g to about 30 g per 11 color developer, preferably from about 1 g to about 15 g per 11 color developer.

Examples of aminophenol-based developers include: -aminophenol, p-aminophenol, 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-phinidine diamine 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-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-3 −
Examples include 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. 1. Its composition is one in which metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic 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.

In addition, pH buffering agents such as borates, oxalates, acetates, carbonic acid supports, and F4 salts, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions may be added as appropriate. can.

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.
ζ may also be used, or a suitable oxidizing agent such as 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, ・,I.

°,,,t <Example 1> A silver halide photographic light-sensitive material having the layer structure shown in Tables 1 and 2 below was prepared.

The coating amount was expressed as Ig/100cm''.

*Amount of silver coated is 3.0mg/100cm for samples 1 to 3.
", Samples 4 to 13 were set to 1.5w+g/100cm".

The composition of the coupler dispersion used in the green-sensitive emulsion layer was as shown in Table 2. The aqueous phase used in each sample was Alkanol B 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, TCP represents tricresyl phosphate and EA represents ethyl acetate. The following comparative antifading agents X-1, X-2, and X3 were used.

(X-1) Hs Eox: 0.82 (v) Eox: 1.72 (v) The thus prepared sample was exposed to white light using a light-sensitive needle (KONISHIRoku Photo Industry Co., Ltd. model KST). After exposure through a light film, processing was performed according to the following processing steps.

[Processing process]

Note that Samples 1 to 5 were processed using Process A, and Samples 6 to 13 were processed using Process B.

[Color developer composition]

-Pure water 700
m1 benzyl alcohol 15m1 diethylene glycol 15a+j! 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 1, Potassium
Add 2g of pure water to make 11.

(Adjusted to pH-10.2) [Complex-forming liquid composition] Ni (N O2) 2 6 Hto 1
4.5 Add pure water to make 12.

[Bleach-fix solution composition]

Iron ammonium ethylenediaminetetraacetate 1 g Ethylenediaminetetraacetate diammonium g Ammonium thiosulfate 125 g Sodium metabisulfite L'g Sodium Atairo - 2.7 L Add water to make 11.

(Adjusted to pH = 7.2) For each sample treated in this way, whiteness, light fading,
Yellowing of white background due to light and photographic performance (γ) were tested and the results obtained 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 as-be value was measured using Hitachi Color Analyzer Model 607.

As the a' value increases, the redness increases, and as it decreases, the greenness increases. Also, as the b0 value increases, the yellowness increases, and as the b0 value decreases, the blueness increases.

(2) Light fastness test A, Kise, non-fade meter Teru Px (Lukunu) Irradiation time (H) I　XIO’　　　　to.

B. Fluorescent lamp fading tester Illuminance (lux) Irradiation time (11) 2X10' 500 Light irradiation was performed using the above two conditions A and B, and the dye residual rate R and white background yellowing ΔD were determined as follows (calculated). The density of the unexposed part of the sample before light irradiation is D IRi n + the density of the colored part Do = 1.0, and the density of the sample after light irradiation is D m i
If n and D, ΔD=Dmin −D! , 1 <blue density).

(3) Photographic performance The density of the obtained sample was measured and expressed as T, which indicates gradation.

From the results of Samples 1 to 6 in Table 3, the light fastness is improved by adding a conventionally known metal complex, but the whiteness deteriorates significantly, and the known antifading agent also has the disadvantage of softening the tone.
It can be seen that not only is it unsuitable for color printing, but yellowing also increases. On the other hand, the results of Samples 7 to 11 according to the present invention show that the light fastness is significantly improved compared to conventional metal complexes, without deterioration of whiteness or gradation, and furthermore, the light fastness is significantly improved compared to conventional metal complexes. It is clear that yellowing is also improved and overall significantly higher lightfastness is imparted. On the other hand, for Comparative Samples 12 and 13 in which the antifading agent whose Box value is outside the range of the present invention was used, no synergistic effect was obtained, but rather the fading property was promoted and sufficient light fastness effect was not achieved. I couldn't get it.

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

Below is the margin... Table 4 The numbers in parentheses indicate the amount of coating or addition.

*However, for samples 3 to 8, it was set to 0.16 g/+a2.

Table 4 (Continued) The stain inhibitor and ultraviolet absorber used here are compounds having the structures shown below.

(Stain inhibitor) (Ultraviolet absorber) H The yellow coupler and cyan coupler used here are compounds with the following structures.

[Yellow coupler]

(Y-1) [Cyan coupler] (C-2) The sample prepared as above was designated as sample 1, and the coupler and dye image stabilizer in the third layer of sample 1 were changed as shown in Table 5. Samples 2 to 8 were prepared and tested in the same manner as in Example 1, and the results obtained are also shown in Table 5. however,
Sample 1 was exposed using green light to produce a magenta colored sample.
For samples 3 and 2, treatment step A was used, and for samples 3 to 8, treatment step B was used.

Margin below 1 From the results in Table 5, although the light fastness of Sample 2 is improved in R compared to Sample 1, the degree of improvement is insufficient, and in particular, the decrease in gradation is significant. On the other hand, sample 3 according to the present invention
For 8 to 8, the light fastness has been improved to a higher level without any drop in gradation or deterioration of whiteness, and the multilayer halo Y
It is clear that the present invention is also effective in the production of photosensitive materials.

<Example 3> Using six types of samples from sample numbers 3 to 8 in Example 2, the processing steps were carried out except that 15 g of Fe (NO3) 2 .911tO was added to the bleach-fix solution 1' in the processing step of Example 2. The same treatment as that of Example 2 was carried out, and the same test as in Example 2 was conducted.

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

Patent applicant Konishi Roku Photo Industry Co., Ltd. Agent Patent attorney Takatsuki Shite Tsuzuki Juho Seisho (method) % formula % 1. Indication of the case 1985 Patent application No. 9807 2. Name of the invention Silver halide photographic photosensitive Material 3: Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Subject of amendment Specification

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has an oxidation potential E_O_X (V).
is a layer for forming a magenta dye image containing fading prevention in which 0.95≦E_O_X≦1.50, and is combined with a silver halide emulsion contained in the layer for forming the magenta dye image to form the following general formula: A silver halide photographic material containing a compound represented by: [General formula] C_P-(T)-_nLIG (where C_P is -(T) as a function of silver halide development
T)-_nLIG represents a group that leaves LIG, and T is -(T
)-_nRepresents a group capable of releasing LIG when or after LIG is detached, and LIG is a group that can form a complex compound having a dye image stabilizing function by performing a complex formation reaction with a metal ion. represent. n represents 0 or 1. )