JPS62291650A - Silver halide photographic sensitive material capable of forming stable coloring matter image against light - Google Patents

Abstract

PURPOSE:To obtain the titled material having an excellent spectral absorbing characteristics by incorporating one kind of the coupler selected from specific couplers and/or the polymer coupler derivated from said coupler, a specific compd. and a high boiling point org. solvent to one layer of a silver halide emulsion, and specifying a weight ratio of the coupler to the solvent to >=0.9. CONSTITUTION:The one kind of the coupler shown by formulas I-III, and/or the polymer coupler derivated from said coupler, and the one kind of the compd. selected from the compd. shown by formulas IV-V, and the high boiling point org. solvent are incorporated in one layer of the silver halide emulsion. The compounding wt. ratio (wt. ratio of B/A) of the high boiling point org. solvent A per the coupler A is >=0.9 in the titled material. In the formulas I-III, Za-Zc are each a non-metallic atom group necessary to forming a nitrogen contg. heterocyclic ring, Xa-Xc are each the group capable of releasing by reacting with hydrogen atom, etc., Ra-Rg are each hydrogen atom or a substituent. In formulas IV and V, R<1> is an aliphatic group, etc., Y is a hydrocarbon group such as a single bond, etc., necessary for forming a 5-7 membered heterocyclic ring together with nitrogen atom, R<2>-R<7> are each hydrogen atom, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material.
This invention relates to a silver halide photographic material in which a dye image is stable against light.

[Background of the Invention] Conventionally, a coupling reaction between an oxidized product of an aromatic primary amine color developer and a color former has been carried out by imagewise exposing a silver halide color photographic light-sensitive material and performing color development. It is well known that, for example, indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, and similar pigments are produced and color images are formed. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional colors, namely yellow, magenta and A silver halide color photographic material containing a coupler that develops cyan color is used.

Examples of couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, birazolotriazole, and indacylon couplers. Furthermore, as a coupler for forming a cyan image, for example, a phenol or naphthol coupler is generally used.

It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity. It is also desired that the uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) do not turn yellow (hereinafter referred to as Y-stain) by light or moist heat.

However, in the case of magenta couplers, fading by light in uncolored areas, Y-stain due to moist heat, and color fading in dye image areas due to light is extremely large compared to yellow couplers and cyan couplers, and often poses a problem.

1, which is widely used to form the magenta dye
In addition to the main absorption near 550 rv, the dye formed from magenta couplers of 2-pyrazolo-5-ones has an absorption of 430 n.
It has a sub-absorption near m, and various studies have been conducted to solve this problem.

Pyrazolobenzimidazoles as described in UK Patent No. 1.047.612, US Patent No. 3.770.4
The indacilones described in No. 47, and the indasilones described in No. 3.725.
061, British Patent No. 1,252,418, British Patent No. 1,
Magenta couplers such as the pyrazolotriazoles described in No. 334,515 have been proposed. Among these, U.S. Patent No. 3,725,067, British Patent No. 1,252,
No. 418, 1H described in No. 1.334.515
The dye formed from the -pyrazolo-[3,2-CI-s-triazole type magenta coupler has a small side absorption near 430ni, and the generation of Y-stin in the uncolored area when exposed to light, heat, and humidity is extremely small. It has favorable advantages.

Similarly, 43 of the dye formed from the above magenta coupler
British Patent No. 1 as a device with small sub-absorption near 0 nm
．． Pyrazolobenzimidazoles described in U.S. Pat. No. 047.612, imidazolones described in U.S. Pat. No. 3.770.447; Same No. 1,334,51
1H-pyrazolo[5,1-c]-]1 as described in No. 5.
2.4-triazole type coupler JP-A-59-1719
No. 56, Research Disclosure No. 245
1-pyrazolo[1,5-b]-]1 as described in 31.
2.4-Triazole type coupler 1-pyrazolo[1°5-c]-]1 as described in Research Disclosure t-NO, 24626 1.2.3-Triazole type coupler JP-A-59-162548; 1-Imidazo[1,2-b]pyrazole-type sicaplar described in Research Disclosure t-NO, 24531 JP-A-1982-
No. 43659, Research Disclosure N0.
1-day-pyrazolo[1,5-b]pyrazole type coupler described in JP-A No. 60-33552, Research Disclosure fsJ o, 1-day-pyrazolo[1,5-d]tetrazole type coupler described in 24220 Magenta couplers such as couplers have been proposed.

However, some of these azole couplers have problems in terms of color development.

On the other hand, in International Publication (WO) No. 86102461,
Similar to the above, a magenta coupler has been proposed that has small side absorption and excellent spectral absorption characteristics, as well as excellent coupler dissolution and dispersion characteristics and color development.

Although the magenta coupler proposed in the above-mentioned publication has excellent dissolution and dispersion characteristics and color development characteristics as compared to conventional azole couplers, it still has a drawback in light resistance.

We have developed a technique for improving the light resistance of the azole coupler, such as a technique using a phenol compound or a phenyl ether compound described in JP-A-59-125732, and JP-A-61-73152 and JP-A-61-61. 72
An attempt was made to apply the technique using a piperazine compound described in No. 246 to the coupler described in International Publication No. 86102467, but the light resistance could not be sufficiently improved.

Therefore, the present inventors investigated ways to improve the light resistance of dye images formed from these kaburani, which have excellent dissolution and dispersion characteristics and color development characteristics. It has been found that when a Takasu point-specific solvent is used as a dispersion medium in a specific ratio to the coupler, the color development and light resistance of the coupler are significantly improved.

Furthermore, we agree that these International Publications (WO) 86/624
In addition to the couplers described in No. 67, similar studies were conducted on couplers similar to these couplers, leading to the present invention.

[Object of the Invention] The present invention has been made in view of the above-mentioned problems, and the first object of the present invention is to provide a silver halide photographic photosensitive material that provides excellent spectral absorption characteristics and dye images with sufficiently high density. The purpose is to provide materials.

A second object of the present invention is to provide a silver halide photographic material having excellent fastness to light and having a dye image with little discoloration to light.

[Structure of the Invention] An object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one layer of the silver halide emulsion having the following general formula (a). , (b), at least one coupler selected from the couplers represented by (b) and/or a polymer coupler derived from the coupler, a compound represented by the following general formula [I], and a compound represented by the following general formula [II]
] and a high boiling point R solvent, and the content of the high boiling point R solvent relative to the coupler content (A)
) was achieved using a silver halide photographic material having an overlapping ratio (B/A) of 0.9 or more.

General formula (a) (Rd)n< General formula (b) General formula (c) (7a in general formulas (a), (b), and (b).

zb and ZC each represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle. Xa, Xb and XC each represent a hydrogen atom or a group that can be separated upon reaction with an oxidized product of a color developing agent.

Ra, Rb, Rc, Rd, Re, Rr and R(] each represent a hydrogen atom or a substituent. However, R(+ represents the reaction between the coupler represented by the general formula (C) and the oxidized product of the color developing agent. It is a substituent that does not undergo MJl12 when Yl represents a carbon atom or a nitrogen atom.Y2
represents a carbon atom or a heteroatom. = is Yl and Y2
This indicates that the bond between them may be a single bond or a double bond.

However, when Yl is a carbon atom and the bond between Yl and Y2 is a double bond, n3 is 1 and n4 is 0, and RC is the oxidation of the coupler represented by general formula (a) and the color developing agent. It is a substituent that does not leave when reacting with the compound, and when Yl is a carbon atom and the bond between Yl and Y2 is a single bond, both n3 and n4 are 1. Also, if Y1 is a nitrogen atom and the bond between Yl and Y2 is a double bond, n3 and n4 are both 0, and Y2 is a heteroatom, Yl is a nitrogen atom, and the bond between Yl and Y2 is a double bond. n3 for single bond
is 1 and n4 is O.

The couplers represented by general formulas (a), (b), and (C) have 9 bonds at the position where Xa is bonded, the position where xb is bonded, and the position where XC is bonded, respectively, and the color developing agent Coupling reaction with oxidized form of ) General formula [I] [In the formula, R1 represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y represents a group of nonmetallic atoms necessary to form a 5- to 7-membered heterocycle together with the nitrogen atom. represent. however,
At least two of the nitrogen-containing nonmetallic atoms forming the heterocycle must be heteroatoms, and the at least two heteroatoms are not adjacent to each other. ] General formula [II] In the E formula, R1 represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y is a simple bond necessary to form a 5- to 7-membered heterocycle with the nitrogen atom. Or represents a divalent hydrocarbon group. R2, R3°R4, R5, R+) and R7
each represents a hydrogen atom, an aliphatic group, a cycloalkyl group or an aryl group. However, R2 and R4 and R3 and R
5 combine with each other to form a simple bond to form a nitrogen atom,
Together with Y, it may form an unsaturated 5- to 7-membered heterocycle. Further, when Y is a simple bond, R5 and R7 may be bonded to each other to form a simple bond to form an unsaturated 5-membered heterocycle together with the nitrogen atom and Y. In addition, when Y is not a simple bond, R5 and Y, R' and Y, or Y itself form an unsaturated bond to form an unsaturated 6- or 7-membered heterocycle with the nitrogen atom and Y. Good too. ] [Movement rib 4f/:) Oval A'] jl, J-! 1 Next, the present invention will be specifically explained.

In the magenta coupler according to the present invention represented by the general formula (,), (b), (C) general formula (a) ■ (Rd)n< general formula (b) general formula (c), Za* zb and Zc are the clouds necessary to form a nitrogen-containing II ring.
Xa, Xb and Xc each represent a hydrogen atom or a substituent which can be separated by reaction with an oxidized product of a color developing agent.

Also, Ra, Rh, Rc, Rd, Ret Rf
and Rg each represent a hydrogen atom or a substituent.

However, Rg is a substituent that is not easily removed during the reaction between the coupler represented by the general formula (C) and the oxidized product of the color developing agent.

Y+ represents a carbon atom or a nitrogen atom; IIY2 represents a carbon atom or a heteroatom;

Even if the bond between Yl and Y2 is a single bond,
Indicates that it may be a double bond.

Y3. Y and Y5 each represent a carbon atom or a nitrogen atom.

n+e nzt niy n1m niy ni and n
, are O or 1, respectively.

However, when Yl is a carbon atom and the bond between Yl and Y2 is a double bond, n is 1, R4 is O, and
e is a substituent that does not leave during the reaction between the coupler represented by general formula (a) and the oxidized color developing agent, Y is a carbon atom, and the bond between Y and Y is a single bond. In this case, both n and n4 are 1. Further, when YI is a nitrogen atom and the bond between Yl and Yl is a double bond, n and n4 are both O, and Yl is a heteroatom,
When Y is a nitrogen atom and the bond between Y and Yl is a single bond, n3 is 1 and n4 is 0.

In addition, the couplers represented by the general formulas (,), (b) and (C) can be color developed only at the positions where Xa is bonded, xb is bonded, and Xc is bonded, respectively. Coupling reaction occurs with the oxidized form of the main drug.

Examples of the substituent represented by Ra, Rb, Re, Rd, Re or Rf include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an 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, carbamoyl group Oxy group, ami 7 group, acylami 7 group, sulfonamide group, imide group, frayed group,
Sul 7 Amoyl 7 Mi 7 groups, Alkoxycarbonyl amine 7
group, aryloxycarbonylamine group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

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

Examples of the furkyl group represented by Ra, Rb, Re, Rd, Re or Rf include those having 1 to 32 carbon atoms, alkenyl groups and alkynyl groups having 2 to 32 carbon atoms, cycloalkyl groups, and cycloalkenyl groups. has 3 or more carbon atoms
12, particularly those with 5 to 7 are preferred, and the alkyl group, alkenyl group, and alkynyl group may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups include substituents [e.g., aryl, cyano, halogen atoms, heterocycles, dichlorofurkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compound residues] In addition to groups, those substituted through a carbonyl group such as acyl, carboxy, carbamoyl, flufquin carbonyl, and aryloxycarbonyl, and those substituted through a hetero atom (specifically hydroxy, alkoxy, aryloxy , heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, ami/(including dialkylamino 7, etc.), sul7amoylamino, alkoxycarbonylamino/, 7yloxycarponylamino, acylamino, sulfonamide, Those substituted through a nitrogen atom such as imide and ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
(such as those substituted via a sulfur atom such as sulfamoyl, and those substituted directly via a phosphorus atom such as phosphonyl).

Specifically, for example, methyl group, ethyl group, isopINL/
1I--11:Number--/Sil-++-jf:++Egg A
Tseichiko, 1-1-=^-1゜tadecyl group, 1-hexylnonyl group, 1.1'-dipentyl7yl group, 2-chloro-t-butyl group, trifluoromethyl group, 1-ethoxy tridecyl group, 1-nodoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4'-(ff-(4"(p-hydroxybenzenesulfonyl)7e/xy]dodecanoylamino)phenylpropyl group, 3-(4'-(ff-(2")
, 4''-non-amyl7eth/xy)butanamide]phenyll-7''lopylt4-(α-(0-chlorophenoxy)tetradecanamidophenoxypropyl group, allyl group, cyclopentyl group, cyclohexyl group, etc.) It will be done.

The aryl group represented by Ra, Rh, Re, Rd, Re or Rf''' is preferably a phenyl group, which may have a substituent (for example, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-1-butylphninyl group,
2.4-di-t-7mylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4″
-(ff-(4″-t-butylphenoxy)tetradecanamidophenyl group, etc.).

The heterocyclic group represented by Ra, Rb, Re, Rd, Re or Rf is preferably 5- to 7-membered, and may be substituted or fused.

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

Examples of the acyl group represented by Ra, Rb, Re, Rd, Re or Rf include furkyl groups such as an acetyl group, a 7-enylacetyl group, a dodecanoyl group, and a Q-2,4-cy-1-amylphenoxybutanoyl group. Examples include 7-arylcarbonyl groups such as a carbonyl group, a benzoyl group, a 3-pentadecyloxybenzoyl group, and a p-chlorobenzoyl group.

The sulfonyl group represented by Ra, Rb, Re, Rd, Re or Rf includes methylsulfonyl group, furkylsulfonyl group such as dodecylsulfonyl group, benzenesulfonyl group, arylsulfonyl group such as p-)luenesulfonyl group, etc. ``It is done.''

The sulfinyl group represented by Ra, Rb, Re, Rd, Re or Rf includes alkylsulfinyl groups such as ethylsulfinyl group, octylsulfinyl group, 3-phenoxydibutylsulfinyl group, phenylsulfinyl group, m-pentadecylphenyl group. Examples include arylsulfinyl groups such as sulfinyl groups.

Phosphonyl groups represented by Ra, Rh, Re, Rd, Re or Rf''C include alkylphosphonyl groups such as butyloctylphosphonyl group, alkoxyphosphonyl groups such as octyloxyphosphonyl group, and phosphonyl groups such as phenoxyphosphonyl group. Examples thereof include arylphosphonyl groups such as aryloxyphosphonyl group and 7xylphosphonyl group.

The carbamoyl group represented by Rat Rb, Rcs Rd, Re or Rf''C may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, an N,N-dibutylcarbamoyl group , N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3-(2,4-di-t-7-milphenoxy)propyl)carbamoyl group, and the like.

The sulfamoyl group represented by Ra, Rh, Re, Rd, Re or Rf may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, N.

N-diethylsulfamoyl group, pJ-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-
Examples include N-dodecylsulfamoyl group and N-phenylsulfamoyl group.

The spiro compound residue represented by Rat Rb, Rct Rdt Re or RfC is, for example, spiro[3゜3
] Hebutan-1-yl and the like.

Examples of the carbonized compound residue represented by Ra, Rb, Re, Rd, Re or R include bicyclo r2-2
- 11hebutan-1-yl, tricyclo[3,3,
1,1''']decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The alkoxy group represented by Ra, Rb, Re, Rd, Re or Rft' may be further substituted with any of the substituents listed above for the alkyl group, such as a methoxy group,
Examples thereof include a propoxy group, a 2-di-containing jetoxy group, a pentadecyloxy group, a 2-dodecyloxyethoxy group, a 7-ethyloxyethoxy group, and the like.

The aryloxy group represented by Ra, Rb, Rat Rdr Re or Rf is preferably phenyloxy, and the 7-aryl nucleus is further substituted with any of the substituents or atoms listed above for the aryl group. Common examples include phenoxy group, pt-butylphenoxy group, m-pentadecyl 7-ethyl/oxy group, and the like.

The heterocyclic oxy group represented by Ra, Rb, Re, Rd, Re or Rf preferably has 5 to 7 heterocycles, and the heterocycle may further have a substituent, For example, 3,4,5°6-tetrahydrobilanyl-2-2*si, 1-phenyltetrazole-5-oxy groups are mentioned.

The siloxy group represented by Ra, Rb, Re, Rd, Re or Rf't' may be further substituted with an alkyl group, such as a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like.

Ra, Rh, Re, Rd, Re or Rf l! Examples of the acyloxy group to be treated include an alkylcarbonyloxy group, a 7-arylcarbonyloxy group, and the like.
It may further have a substituent, and specific examples include a 7-cetyloxy group, an a-chloroacetyloxy group, and a benzoyloxy group.

The carbamoyloxy group represented by Ra, Rh, Re, Rd, Re or Rf''t' may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N,N-diethylcarbamoyloxy Base, N
-phenylcarbamoyloxy group and the like.

The amide group represented by Raw Rh, Re, Rd, Re or Rf may be substituted with an alkyl group, an aryl group (preferably a 7enyl group), etc., such as an ethyl 7mino group, anilino group, -monochloroanilino group, etc. 7 groups of 3-pentadecyloxy group, 7 groups of 2-chloro-5-hexadecaneamide group, and the like.

Examples of the acylamide 7 groups represented by Raw Rb, Re, Rd, Re or Rf include alkylcarbonylamide 7 groups, 717-lcarbonylamide groups (preferably phenylcarbonylamide 7 groups), and further substituents. Specific examples include acetamido group, α-ethylpropanamido group, N-7 dinylacetamido group, dodecanamide group, 2,4-not-t-amylphenoxyacetamide group, a-3- Examples include t=dibutyl 4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by Ra, Rh, Re, Rd, Re or Rf include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent, specifically methyl Examples include a sulfonylamino group, a pentadecylsulfonylamide group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-7 milbenzenesulfonamide group.

The imide group represented by Ra, Rb, Re, Rd, Re or Rf't' may be open-chain or cyclic, and may have a substituent, such as a succinimide group, a 3- Examples include a heptadecylsuccinimide group, a 7-talimide group, a glutarimide group, and the like.

The ureido group represented by Ra, Rb, Re, Rd, Re or Rf may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylfreido group, an N-methyl-N -decylureido group,
Examples include N-phenylureido group and N-p-tolylureido group.

The sulfur T-moylamide 7 group may be substituted with a furkyl group, an aryol group (preferably a phenyl group), etc.
For example, N, N-dibutylsul7ammoyl7mi7 group, N-
Methylsul 7 amoyl 7 mi 7 groups, N7! Examples include Nilsul 77 moylamino group.

The alkoxycarbonyl amine 7 group represented by Ra, Rh, Rat Rd, Re or Rf further includes WtPA
Examples include 7 methoxycarbonylamide groups, 7 methoxyethoxycarbonylamide groups, and 7 octatecyloxycarbonylamide groups.

The aryloxycarbonylamino group represented by Ra, Rh, Re, Rd, Re or R may have a substituent, for example, phenoxycarbonylamino 7 group, 4-
Seven methylphenoxycarbonylamide groups are mentioned.

The alkoxycarbonyl group represented by Ra, Rh, Re, Rd, Re or Rf may further have a substituent (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group). , ethoxymethoxycarbonyloxy group, benzyloxycarbonyl group, and the like.

The aryloxycarbonyl group represented by Ra, Rh, Re, Rd, Re or Rf may further have a substituent, such as phenoxycarbonyl group, p-chlorophenoxycarbonyl group, l-pentadecyloxyphenoxycarbonyl group. Examples include groups.

The alkylthio group represented by Ra, Rb, Rat Rd, Re or Rf may further have a substituent, for example, an ethylthio group, a dodecylthio group, an octadecylthio group, a 7enethylthio group, a 3-phenoxypropylthio group, etc. Can be mentioned.

The arylthio group represented by Raw Rb, Rct Rd, Re or Rf is preferably a phenylthio group, and may further have a substituent, for example, a phenylthio group,
p-methoxyphenylthio group, 2--octadecylphenylthio group, 3-octadecylphenylthio group, 2-
Examples include carboxyphenylthio group and p-7 cetaminophenylthio group.

The heterocyclic thio group represented by Ra, Rh, Re, Rd, Re, and 1/Rf is preferably a 5- to 7-shell heterocyclic thio group, which may further have a fused ring, and may have a substituent. For example, 2-bilinorthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,
5-) lyazole-6-thio group.

When Rg and Y are carbon atoms and the bond between Y and Y2 is a double bond, the substituent that does not leave when the coupler represented by Re and the oxidized color developing agent reacts is as follows: For example, alkyl groups, aryl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, heterocyclic groups, acyl groups, sulfonyl groups, sulfinyl groups, ho, sulfonyl groups, carbamoyl groups, sulfamoyl groups, cyano groups, spiro compounds Examples thereof include a residue, a bridged hydrocarbon compound residue, a siloxy group, a carbamoyloxy group, an alphoxycarbonyl group, and an aryloxycarbonyl group.

As mentioned above, specific examples of each group include those shown as the above-mentioned specific example of Ra.

Examples of substituents that can be removed by reaction with the oxidized color developing agent represented by Xav , a group substituted via a nitrogen atom.

Examples of groups substituted via a carbon atom include a carboxyl group, a hydroxymethyl group, a )') 7 xnylmethyl group, and the formula (a') (Rd )n<'Formula(b'') R1 Formula (C'') (Rg')nF' 6 (Ra' is Ra, Rb' is Rb, Re'' is Re, Rd' is Rd, Re' is Re and Rf'
is Rf, RH' is Rg, 01' is Low, 1
2' is n2, n,'' is n, 04' is n, , l is n, and 1, l is n6, l is n, Y, ゛ is Yl, Y2'' is Y2 and Y,' are Y3
, Y4' is synonymous with Y, Ys' is Y, Za'' is synonymous with Za, zb' is synonymous with zb, Zc' is synonymous with Zc, and R,
-R represents hydrogen, an aryl group, an alkyl group, or a heterocyclic group.

Examples of the group substituted via an oxygen atom include an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, a 7-aryloxycarbonyloxy group, an alkyloxalyloxy group, and an alkoxyoxalyl group. An example is an oxy group.

The alkoxy group may further have a substituent, for example, an ethoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a 7enethyloxy group.

-chlorobenzyloxy group and the like.

The aryloxy group is preferably a 7e7oxy group,
The aryl group may further have a substituent, specifically a phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4-methanesulfonamidophenoxy! , 4-(α-(3′-pentadecylphenoxy)butanamide]phenoxy group, hexadecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p-nodoxyphenoxy group, etc. can be mentioned.

The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent, specifically, 1-phenyltetrazolyl. Examples include oxy group, 2-benzothiazolyloxy group, and the like.

The acyloxy group includes, for example, an acetoxy group, a fulkylcarbonyloxy group such as a pyloxy 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 alphkyloxy carbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

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

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a benzylthio group, and the like.

The arylthio group includes a phenylthio group, a 4-methanesulfonamidophenylthio group, a 4-dodecyl7enethylthio group, a 4-nonafluoropentanamide7enethylthio group, a 4-carboxyphenylthio group, a 2-ethyloxy-5-t -butylphenylthio group and the like.

Examples of the heterocyclic thio group include 1-722-1.
Examples include 2,3.4-tetrazolyl-5-thio group and 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group, which is substituted via the nitrogen atom. Here R1 and R
, is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
Represents a sulfamoyl group, carbamoyl group, acyl group, sulfonyl group, aryloxycarbonyl group, or alkoxycarbonyl group, and R1 and R6 may be combined to form a heterocycle, provided that R2 and R8 are both hydrogen atoms. Never.

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 a toryol group,
alkoxy group, 7-aryloxy group, alkylthio group, arylthio group, 7 alkylami groups, 7 arylami groups,
Acylamide 7 groups, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamide 7 group, 7lyloxycarbonylamide 7 groups, hydroxyl groups, carboxyl groups, 7 groups, and halogen atoms. Specific examples of the alkyl group include ethyl group, octyl group, 2-ethylhexyl group, and 2-chloroethyl group.

The aryl group represented by R1 or R6 has 6 to 32 carbon atoms, and is preferably a phenyl group or a naphthyl group, and the Tetsukoryl group may have a substituent. Examples of substituents for the represented alkyl groups include those listed above and alkyl groups. Specific examples of the aryl group include phenyl group, 1
Examples include -su7tyl group and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R7 or R3 is 5 to 6
Shellfish are preferred, and may be fused rings and may have substituents. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2- Examples include pyridyl group.

The sulfamo,yl group represented by Rγ or R1 includes N-furkylsulfamoyl i, N,N-noalkylsulfamoyl group, N-arylsulfamoyl group,
, N-diarylsulfamoyl group, etc., and these alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulf77moyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group,
Examples include N-)'7'silsulfamoyl group and N-p-)lylsul77moyl group.

The carbamoyl group represented by R2 or Rs is N
-furkylcarbamoyl group, N,N-1furkylcarbamoyl group, N-arylcarbamoyl group, N,N-Schiff 17-rucarbamoyl group, etc., and these alkyl groups and aryl groups are the same as those for the alkyl group and 7-aryl group. Specific examples of the carbamoyl group which may have the above-mentioned substituents include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group, N-p-)lylcarbamoyl group is mentioned.

Examples of the acyl group represented by R7 or R include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group may have a substituent. good. Specific examples of the acyl group include hexafluorobutanoyl group, 2.3,4,5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-furylcarbonyl group.

Examples of the sulfonyl group represented by R2 or R8 include an alkylsulfonyl group, a 7-arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group and a benzenesulfonyl group. group, octanesulfonyl group, naphthalenesulfonyl group, p-chlorobenzenesulfonyl group, and the like.

The aryloxycarbonyl group represented by R1 or R may have as a substituent any of the substituents listed for the 7-aryl group, and specific examples include a 7-ethyl/oxycarbonyl group.

The alkoxycarbonyl group represented by R or R1 is
It may have the substituents listed for the alkyl group,
Specific examples include methoxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, and the like.

The heterocycle formed by combining R7 and R3 is 5-
The heterocycle is preferably 6 in number, and may be saturated or unsaturated, may or may not have aromaticity, and may be a condensed ring. Examples of the heterocycle include N-7 talimide group, N-succinimide group, 4-N-urazolyl group, 1-
N-hyguntoynyl group, 3-N-2,4-dioxooxazolidinyl group, 2-N-1,1-:/oxo3-(
2H)-oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group, 1-virazolyl group, 1
-pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group,
1-indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-bencyimigzolyl group, 1- (1
,2,4-triazolyl) group, 1- (1,2,3-)
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, 7thalathion group, 2-oxo-
1-piperidinyl group, etc., and these heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, 7 alkylami groups, 7 arylami groups, 7 acylami groups, and sulfonamino groups. , carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imido group, nitro group, sia/group, carboxyl group, halogen atom, etc.

Also, Za, Zb, Zc, Za', Z
Examples of the nitrogen-containing i-element ring formed by b' or Zc' include a virole ring, a pyrazole ring, an imidazole ring, a triazole ring, a thiazoline ring, an oxazoline ring, and a tetrazole ring.

An example of the heteroatom represented by Y2 is nitrogen.

Za, Zb, Zc, Za', Zb'
Specific examples of the substituents that the nitrogen-containing heterocycle formed by Zc' may include include the substituents exemplified as Ra.
a 11) t(b 1)-(b-8), (e 1
)-(c-14) R sz tRs4tRsa
+Rsa 1is-Rts tRtyyRys 1R
a31RIS When the substituent is not present, such as the bonded position of tRll-RlG, the position having coupling ability is substituted with a group that does not leave due to the reaction between the coupler and the oxidized form of the color developing agent. do.

Furthermore, in the general formulas (a) to (e), substituents that do not leave off upon reaction with the oxidized product of the color developing agent (for example, R
a-RL Rz-R<zt Rs+-Rss bonded carbon or nitrogen) is (Rd")n,"(Rg"')Rho" amount (Ra" is Ra, Rb" is Rh, Re" is Re, Rd” is Rd, Re” is Re, Rf” is Rf
, Rg- is R, and n, # is n, and 12″ is n.
2, n, # is n, and n, ' is n4, n, # is n, and, n, " is n6 and n, " is n7 and Y1" is Y, and, Y2
″ is Y2, Y, ″ is Y, Y, ″ is Y4, Y,
” is Y, Za” is Za, Z is also zb, Zc
# is synonymous with Zc. ), and so-called screw-type couplers are of course included in the present invention.

Polymer couplers derived from couplers represented by the general formula (a), (b) or (c) include, for example, the formula (
A monomer having a coupler moiety represented by a), (b) or (e), preferably a monomer having an ethylenically unsaturated double bond, is homopolymerized or copolymerized with other monomers. Can be mentioned.

Specific examples of those represented by the general formula (a), (b) or (c) include the following.

General formula (a-1) General formula (a-
2) General formula (a-3) General formula (a
-4) General formula (a-5) General formula (
a-6) General formula (a-7) General formula (a-8) General formula (a9)
General formula (a-10) General formula (a-11) General formula (b-1) General formula (b-
2) General formula (b-3) General formula (
b-4) General formula (b-5) General formula (b-6) General formula (b-7) General formula (bs) General formula (c-1) General formula (c-2) General formula (c -3) General formula (c-4) General formula (c5) General formula (c-6) General formula (c-7) General formula (c8) General formula (c-9) General formula (clo) General formula (c -11)
General formula (c-12) General formula (c13)
In general formula (e-14) formula (a-1)-(c 14), Xa+-Xall is Xa, and xb, -xb, xb
, X c 1- X e I 4 is Xe, and R1
1-R2a is Ra, R5I-Ra3 is Rg, R
21-R2S is Re, R,, -R,, is Rg,
Rho-R42 has the same meaning as Rf, and Rts to R9° have the same meaning as Rg, and the same types are exemplified.

In addition, the compounds represented by each formula and the exemplified compounds described below each include tautomers. Among those represented by formulas (a) to (C), preferred are those represented by formulas (% formula %) (c-10) and (c-12),
Especially (a-3), (b-1), (c3), (c-9),
(c10).

Preferred substituents on the heterocycle (for example, Ra -Rg t R11-R4□t R5l-R9°) in the compounds represented by each formula are described below.

When the coupler according to the present invention is used for positive image formation, X
a-Xc, Xa, -Xa, ,Xb, -Xb, ,Xc.

As the substituent for the carbon atom +** to the carbon atom to which ~Xc is bonded, it is preferable that the following condition 1 is satisfied,
More preferred is the case where the following conditions 1 and 2 are satisfied, and particularly preferred is the case where the following conditions 1.2 and 3 are satisfied.

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

Condition 2: Only one hydrogen atom 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 on the heterocycle are those represented by the following general formula.

General formula % Formula % In the formula, R1゜1lR102 and R1゜ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, and an alshel $7
+1-le; Hesenguchi Takumi 7-rel certain-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, ami7 group, 7silami7 group, sulfonamide group, imide group, ureido group, sulfonamide group 7
group, alkoxycarbonylamide 7 groups, aryloxycarbonylamide 7 groups, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic O group, R1゜5. R1゜2 and R
8°, at least two of which are not hydrogen atoms.

Also, two of the above R3゜I*R102 and R1゜,
For example, R1°1 and R102 may be combined to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), and R3° may be added to the ring.

may be combined to form a bridged hydrocarbon compound residue.

The groups represented by R5° and ~R3° may have a substituent, and specific examples of the groups represented by RIOI to RI63 and the substituents that the iron group may have include the above-mentioned general formula ( Specific examples of the group represented by Ra in a) and substituents are listed.

In addition, specific examples of the ring formed by bonding R101 and R1゜, and the bridged hydrocarbon compound residue formed by R1゜, to R3゜, and the substituents thereof may include those mentioned above. Specific examples of the cycloalkyl, cycloalkenyl, heterocyclic group, and bridged hydrocarbon compound residue represented by Ra in the general formula (a) and their substituents are listed.

Among the general formulas mentioned above, preferred are: ) R+. 1 to R2°, when two are alkyl groups, (ii) R+0. ~R1°3, for example R1°.

is a hydrogen atom, and when the other two R1゜1 and R3゜2 combine to form a cycloalkyl together with the root carbon atom, the following holds true.

Furthermore, among (i), the preferred formula is %. ,~R3°.

Two of them 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. Specific examples of the alkyl, cycloalkyl and the substituent thereof include the alkyl, cycloalkyl and its substituent represented by Ra in the general formula (a). Specific examples of substituents are listed.

In addition, substituents on the heterocycle (e.g. Ra-Rgt Rz~R
4! l R5I~R,. ) is preferably represented by the following general formula.

General formula % Formula % In the formula, R' represents alkylene, and R2 represents alkyl, cycloalkyl or aryl.

The alkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and may be straight chain or branched, and this alkylene may have a substituent.

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

Preferred substituents include phenyl.

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

The alkyl group represented by R2 may be linear or branched.

Specifically, methyl, ethyl, propyl, iso-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-
Examples include hexyldecyl, and the dichlorofurkyl group represented by R2 preferably has 5 to 6 shells, such as cyclohexyl.

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

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

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

Moreover, when the coupler according to the present invention is used for negative image formation, Xa-Xct Xa, -Xa, +, Xb1-Xbm.

The substituent on the carbon atom adjacent to the carbon atom to which Xcl to Xc are bonded preferably satisfies Condition 1 below, and more preferably satisfies Conditions 1 and 2 below.

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

Condition 2: At least two hydrogen atoms are bonded to the carbon atom.

The most preferred substituents on the heterocycle are those represented by the following general formula.

General formula % formula % In the formula, R1゜4 is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group , phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamif group, alkoxycarbonylamide 7 groups, aryloxycarbonylamide 7 groups, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, Represents a heterocyclic thio group.

The group represented by R104 may have one substituent, and specific examples of the group represented by R2O3 and the substituents that the iron group may have include the group represented by Ra in the above general formula (a). Specific examples and substituents are listed.

Preferred as R1° is a hydrogen atom or an alkyl group.

Specific examples of compounds used in the present invention are shown below.

The numbers in the table represent the following groups, respectively.

- CH3C28s (i) C
3H.

−C<Hs −(t)C<Hs
-(i) C4HsCs H1l-Ca Hl 7
CIIH2slo
11 12-Cl2H2S
-CISH)l -CI? 8
3S-(CH2)3SO2CI2H2S(t) -
(CH2)3SO2C12H2S Sushi 1MB -CN -COCH3-COC,H
.

rθ -COOC2H, -COOC,H,, -COOC,,H
.

-COOC2H3r F CI
Br-NHCOC,,H,,-NHCO
C, IH3゜0 CHs OCz Hs
-OCl2H250COC2Hs
0COC(CH-)3-3C,,H
, 3-3CH2COOH The color tone of the coloring dye in the coupler of the present invention may vary depending on conditions such as the arrangement of the ring atoms of the coupler, the type of substituents, and even the type of color developing agent, but is mainly magenta. , can be used for multicolor color photography, but those with a red tone can also be used for monochromatic color photography because they have good light absorption characteristics.

The couplers of the present invention typically contain 1x per mole of silver halide.
10' mol to 1 mol, preferably 1 x 10-2 mol-8
It can be used in the range of X 10'' moles.

Further, the coupler of the present invention may be a compound represented by the general formula [11] and a compound represented by the general formula [111] contained in at least one of the silver halide emulsion layers in the silver halide photographic material of the present invention. At least one compound selected from the compounds (hereinafter referred to as the dye image stabilizer of the present invention) will be specifically explained below.

The aliphatic group represented by % R' in general formula [11] includes a saturated alkyl group which may have a substituent, and an unsaturated alkyl group which may have a substituent.

Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethynyl group, propenyl group, etc. It will be done.

Examples of the cycloalkyl group represented by R''t' include 5-7 cycloalkyl groups which may have substituents, such as cyclopentyl group, cyclohexyl group, and the like.

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

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R' include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, acylamino groups, sulfamoyl groups, sulfonamide groups, carbonyloxy groups, Examples include an alkylsulfonyl group, an arylsulfonyl group, a hydroxy group, a heterocyclic group, an alkylthio group, an arylthio group, and these substituents may further have a substituent.

In the general formula (1), Y is 5 to 7 together with the nitrogen atom.
Represents a group of nonmetallic atoms necessary to form the heterocycle of the shell ring, and at least two of the group of nonmetallic atoms including nitrogen atoms forming the heterocycle must be heteroatoms, and These at least two heteroatoms must not be adjacent to each other. In the compound ring of the general formula CI), when all the heteroatoms are adjacent to each other, the function as a magenta dye image stabilizer This is not preferable because it is not possible to demonstrate the

The 5- to 7-shell heterocycle of the compound represented by the general formula (1) may have a substituent, and examples of the substituent include a furkyl group, an aryl group, an acyl group, a carbamoyl group, and an alkoxycarbonyl group. , a sulfonyl group, a sulfamoyl group, etc., which may further have a substituent;
The heterocycle of the seven-shell ring may be saturated, but a saturated heterocycle is preferable, and a benzene ring or the like may be fused to the heterocycle to form a spiro ring.

Typical specific examples represented by general formula [1] are shown below.■-6
3 ■-66 Dyo-67 1-〇8 ■-70 ■-71 ■-72 Dyo-73 C,2II Yo- Among the compounds represented by the general formula (1), piperazine compounds and homopiperazine compounds Particularly preferred are compounds
More preferably, the following general formula CI-1) or (+-
This is a compound represented by 2).

General formula (1-1) General formula (1-2) In the formula, R2 and R3 each represent a hydrogen atom, an alkyl group, or an atomyl group, provided that R2 and R3 do not become hydrogen at the same time. , R4 to R+3 each represent a hydrogen atom, an alkyl group or an aryl group.

In the general formulas CI-1) and (1-23), R2 and R3 are each a hydrogen atom, an alkyl group, or a 717-
Examples of the alkyl group represented by R2 or R include a methyl group, an ethyl group, a butyl group,
Examples include octyl group, dodecyl group, tetradecyl group, hexadecyl group, and octadecyl group. R2 or R3
Examples of the aryl group represented by include a 7enyl group and the like.

The furkyl group and aryl group represented by R2 or R3 may have a substituent, and examples of the substituent include a halogen atom,
Examples thereof include an alkyl group, a 71)-l group, an alkoxy group, an aryloxy group, a heterocyclic group, and the like.

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

In the general formula (1-1) or (1-2), R4
~R'' each represents a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by R4~R'' include a methyl group and an ethyl group. R
Examples of the aryl group represented by 4 to R1' include a phenyl group.

Specific examples of the compound represented by the general formula CI-13 or (1-2) include the above-mentioned exemplary piperazine compound (1-2).
1) to (1-30) and exemplary homopiperazine compounds (
1-51) to (1-62).

Naruko Margin σ, d5t Φノ [talented] General formula [11] will be explained below.

In the general formula [■], the aliphatic group represented by RI"C" includes a saturated alkyl group which may have a substituent, and an unsaturated alkyl group which may have a substituent.

Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated furkyl groups include ethynyl group, propenyl group, etc. It will be done.

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

The aryl group represented by R1 is a phenyl group or a naphthyl group which may have a substituent.

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R1 include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, acylamide groups, sulfamoyl groups, sulfonamide groups, and carbonyl groups. Examples include an oxy group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy group, a heterocyclic group, an alkylthio group, an arylthio group, and these substituents may further have a substituent.

In the general formula Cff), Y is 5 to 5 along with the nitrogen atom.
It represents a simple bond or a divalent hydrocarbon group necessary to form a 7-shell heterocycle, but when Y is a simple bond, R5 and R7 further bond to each other to form a simple bond. to form an unsaturated pentagonal heterocycle,
In addition, when Y is a divalent monovalent hydrogen group, that is, when it is a methylene group, R5 and Y or R7 and Y form an unsaturated bond to form an unsaturated hexacyclic heterocycle. In the case of an ethylene group, R5 and Y, R' and Y or Y
The divalent hydrocarbon group may itself form an unsaturated bond to form an unsaturated heptad-ring heterocycle, and the divalent hydrocarbon group annihilated by Y may have a substituent, and this substituent Examples include an alkyl group, a carbamoyl group, an alkyloxycarbonyl group, an acylamide group, a sulfonamide group, a sulfamoyl group, an aryl group, and a heterocyclic group.

In the general formula [■], R2, R, R4゜R5,
R1 and R7 each represent a hydrogen atom, an aliphatic group, a cycloalkyl group, or a heptadyl group, and the aliphatic group represented by R2-R7 includes a saturated alkyl group that may have a substituent and a substituted Examples include unsaturated alkyl groups which may have a group.

Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethynyl group, propenyl group, etc. It will be done.

The cycloalkyl group represented by R2-R7 is a 5- to 7-shell cycloalkyl group that may have a substituent,
Examples include cyclopentyl group, cyclohexyl group, and the like.

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

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R2 to R7 above include a furkyl group, a 7-aryl group, an alkoxy group, a carbonyl group, a carbamoyl group,
Examples include an acylamino group, a sulfamoyl group, a sulfonamide group, a carbonyloxy group, an alkylsulfonyl group, a 7-arylsulfonyl group, a hydroxy group, a heterocyclic group, and an alkylthio group.

It is preferable that the compound represented by the general formula (I[) has 5 to 7 saturated heterocycles than the unsaturated one.6 Representative specific examples of the compound represented by the general formula CI[) Give an example.

■-35 II -36 ] [-37 1 [-39 [-40 , [-4i]
It is preferably used in a ratio of 5 x 10' to 5 mol, more preferably 1 x 10' to 3 el, per mole.

Further, the dye image stabilizer of the present invention may be contained in the same silver halide emulsion layer as the coupler of the present invention, but preferably the coupler of the present invention and the dye image stabilizer of the present invention are It is preferably contained in the oil droplets, preferably in the high boiling point In solvent according to the present invention.

In the silver halide photographic light-sensitive material of the present invention, the silver halide emulsion layer containing the coupler of the present invention and the dye image stabilizer of the present invention further has a high content of the coupler of the present invention relative to ♀(A). Content of boiling point organic solvent (B
) The light fastness and color development of the dye image formed by the coupler of the present invention can be greatly improved by setting the weight pressure (B/A> of 0.9 or more).

The effects of the present invention can be achieved as long as the weight ratio (B/A) of the content of the high boiling point g3 solvent to the content of the coupler is 0.9 or more, but preferably 1.0 to 3
．． The effect of the present invention is efficiently achieved when the value is 0, more preferably in the range of 1.0 to 2.0.

In the present invention, the coupler of the present invention and the dye image stabilizer of the present invention are dissolved in a high boiling point paid solvent according to the present invention described in detail below, and after emulsifying and dispersing in a hydrophilic binder, halogenated It can also be added to the silver emulsion layer.

Dissolve in a high boiling point organic solvent in combination with a low boiling point and/or water-soluble organic solvent if necessary, and use a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a stirrer, homogenizer, colloid mill, or flow jet. It may be emulsified and dispersed using a dispersion means such as a mixer or an ultrasonic device, and then 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 the high boiling point organic solvent according to the present invention include phenol derivatives, phthalate esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, trimesic acid esters, etc. that do not react with the oxidized product of the active ingredient. An organic solvent having a boiling point of 150° C. or higher is used.

In the present invention, the high boiling point organic solvent according to the present invention that can be preferably used when dispersing the coupler according to the present invention and the dye image stabilizer according to the present invention has a dielectric constant of 6.0.
The following compounds include, for example, esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds with a dielectric constant of 6.0 or less. Preferably, it is a high boiling point organic solvent with a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure of 0.5 mm 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 according to the present invention 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.

Phthalic acid esters advantageously used in the present invention include those represented by the following general formula [I[[].

General formula [1[[] In the formula, R16 and R47 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms in the groups represented by R16 and R17 is 8 to 32. More preferably, the total number of carbon atoms is 16 to 24.

In the present invention, the alkyl group represented by R16 and R17 in the general formula [1[] may be linear or branched, such as a butyl group, a pentyl group, a hexyl group,
These include 2-ethylhexyl group, 3.5.5-trimethylhexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and the like. R+
The aryl group represented by s and R+7 is, for example, a phenyl group, a naphthyl group, etc., and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an octadecenyl group, etc.

These alkyl groups, alkenyl groups, and aryl groups include those having single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, and aryloxy groups. Examples of substituents for aryl groups include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, and alkoxycarbonyl groups. .

In the above, R+s and R17 are preferably alkyl groups, such as 2-ethylhexyl group, 3.5.
Examples include 5-trimethylhexyl group, n-octyl group, n-nonyl M, and the like.

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

General formula [rV].

Yeah. OP ORl? OR+9 In the formula, R+a, R19 and R20 each represent an alkyl group, an alkenyl group or an aryl group.

However, the total number of carbon atoms represented by RI8, R+96 and R20 is 24 to 54.

The alkyl group represented by R+a, R+s and R20 in the general formula [IV] is, for example, a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a heptyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group. , octadecyl group, nonadecyl group, etc.; examples of the aryl group include phenyl group, naphthyl group, etc., and examples of the alkenyl group include hexenyl group, heptenyl group, octadecenyl group, etc.

These alkyl groups, alkenyl groups and aryl groups include those having single or multiple substituents. Preferably R+a, R+s and R20 are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3
, 5.5-trimethylhexyl group, n-nonyl group, n-
Decyl group, 5ec-decyl group, 5ec-dodecyl group, t
-octyl group and the like.

Typical specific examples of the high boiling point organic solvent according to the present invention are shown below, but the present invention is not limited thereto.

Exemplary high boiling point solvents ”’ C, 115C, H.

0-C,H,, (n) 0C+. H2+(i) o=p-o-c,. 02. ) 0 C,, H2, (i) 0-C1, H2, (n) ■ ○=P OC, flH2, (n) 0-C8°H21 (n) 0C0Has(ri0CIzH2i(i) 0"P OC12His (Rio-c, 2H2s) The silver halide photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but especially color prints that are provided for direct viewing. The effects of the present invention are effectively exhibited when paper is used.

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 silver halide emulsion layers containing magenta, yellow, and cyan couplers and a non-photosensitive 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.

When the silver halide photographic light-sensitive material of the present invention competes as a multicolor light-sensitive material, the specific layer structure includes a yellow dye image-forming layer, an intermediate layer, a magenta dye image-forming layer on the support, sequentially from the support side. Particularly preferred is an arrangement of a layer, an interlayer, a cyan dye imaging layer, an interlayer, and a protective layer.

As the yellow dye-forming coupler used in the present invention, compounds represented by the following general formula [Yl] are preferred.

General formula [Yl Yl 0 In the formula, R11 represents an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, etc.) or an aryl group (e.g. phenyl group, p-methoxyphenyl etc.), and R1
2 represents an aryl group, and Yl represents a hydrogen atom or a group that leaves during the color development reaction process.

These include, for example, U.S. Patent Nos. 2,778,658, 2,875,057, 2.908.573,
3,227.155, 3.227.550, 3.253.924, 3.265.506
@, No. 3,277, 155, No. 3.341.33
No. 1, No. 3.369.895, No. 3,384,6
No. 57, No. 3,408.194, No. 3.415.
No. 652, No. 3,447.928, No. 3.551
．． No. 155, No. 3.582.322, No. 3,72
5,072, 3,894,875, etc., German Patent Publication No. 1,547,868, German Patent Publication No. 2,057
, No. 941, No. 2.162499, No. 2,163
, No. 812, No. 2,213,461, No. 2,21
No. 9,917, No. 2,261,361, No. 2,2
No. 63,875, Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 4
No. 8-29432, No. 48-66834, No. 49-1
No. 0736, No. 49-122335, No. 50-288
No. 34, and No. 50-132926.

Specific examples of yellow couplers preferably used in the present invention are shown below, but the present invention is limited to these (Y-1) (Y-2) (Y-3) I-I3 (Y-4) (Y-5 ) (Y-6) (Y-7) (Y-8) (Y-9) (Y-10) (Y-11) (Y-12) t (Y-13) ('Y-14) This invention The cyan dye-forming couplers used in
Phenol-based and naphthol-based 4-equivalent or 2-equivalent cyan dye-forming couplers are typical, and specific examples thereof include U.S. Pat. No. 2,306,410 and U.S. Pat. No. 2,356.4.
No. 75, No. 2,362,598, No. 2.367,
531@, No. 2,369,929, No. 2.423
．． No. 730, No. 2,474,293, No. 2,47
6.008, 2.498, 466M, 2.5
No. 45.68γ, No. 2,728,660, No. 2.
No. 772.162, No. 2,895,826, No. 2
, 976.146, 3.002.836, 3,419,390, 3.446.622, 3,476.563, 3,737.316 ,
British Patent No. 3.758.308, British Patent No. 3.839.044, British Patent No. 478.991, British Patent No. 945,542, British Patent No. 1.084,480, British Patent No. 1,377.233.
No. 1,388,024 and No. 1.543.0
No. 40 winter m;a, as well as JP-A Nos. 47-37425, 50-10135, 50-25228, 5
No. 0-112038, No. 50-117422, No. 50
-130441, 51-6551, 51-37
No. 647, No. 51-52828, No. 51-10884
No. 1, No. 53-109630, No. 54-48237
No. 54-66129, No. 54-131931,
It is described in various publications such as No. 55-32071.

As the cyan image forming coupler, the following general formula [C-1
1, a coupler represented by [C-2] can be preferably used.

General formula [C-1] Z+ In the formula, R1 represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2 represents an alkyl group or a phenyl group. RaJ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

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

General formula [C-2] In the formula, R+ is an alkyl group (e.g. methyl group, ethyl group,
propyl group, butyl group, nonyl group, etc.). R5 represents an alkyl group (eg, methyl group, ethyl group, etc.).

R6 is a hydrogen atom, a halogen atom (e.g. fluorine, chlorine,
(bromine, etc.) or an alkyl group (eg, methyl group, ethyl group, etc.).

Z2 is converted to 1IIIB2 by reaction with a hydrogen atom, a halogen atom, or an oxidized product of an aromatic primary amine color developing agent.
Represents a group that can be obtained.

Typical specific examples of cyan image forming couplers used in the present invention are described below. Generally from 2 X 10-3 moles to 1 mole of silver per mole of silver in the emulsion layer.
It is used in moles, preferably in the range of 1×10 −2 moles.

Silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention)
Any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver iodochloride, silver chlorobromide, and silver chloride, can be used as the silver halide. Can be done.

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

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to the D
It may also be produced by sequentially and simultaneously adding Hl pAo while controlling it. After growth, a conversion method may be used to change the halogen composition of the particles.

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

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

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained. When removing the salts, please refer to Research Disc.
[)isclosure] It can be carried out based on the method described in No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of uniform layers on the inside and outside, 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 (100) plane to the (111) 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. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

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

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

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as 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 the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable to add lead to the hardening agent so that the photosensitive material can be hardened to such an extent that it is not necessary to add a hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution.

Halogen in the silver halide photographic material of the present invention. Plasticizers can be added to increase the flexibility of the silver emulsion layer and/or other hydrophilic colloid layers.

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

Between the emulsion layers of the 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 main ingredient or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifoggants are used to prevent deterioration and noticeable graininess.

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

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

The silver halide photographic material of the present invention may 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 are washed out or bleached from the light-sensitive material during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is intended to reduce the gloss of the light-sensitive material, to improve the ease of writing, to prevent the light-sensitive materials from sticking to each other, etc. A matting agent can be added as a matting agent.

A lubricant can be added to reduce the sliding friction of the silver halide photographic material of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the silver halide photographic material 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 the silver halide photographic light-sensitive material of the present invention
Or other hydrophilic colloid layers to improve coatability? ! For the purpose of preventing static electricity, improving slipperiness, emulsification dispersion, preventing adhesion, and improving page characteristics (promoting development, hardening, sensitization, etc.), etc.
Various surfactants are used.

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

The silver halide photosensitive material of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
Directly or one or more (to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties, and/or other properties of the support surface) It may also be applied through the lower Ni layer.

When coating the silver halide emulsion of the silver halide photographic material of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

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

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.

An image can be formed using the silver halide photographic material of the present invention by subjecting it to a color development treatment known in the art.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

These developers include amine phenol and p-phenylene diamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally present in a concentration of from about 0.1 g to about 30 g per color developer 12, preferably from about 1 g to about 15 g per color developer 12.
Use at a concentration of

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

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-〇-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N,N'-diethyl-p-phenylenediamine mF
IIPA, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine 21M
salt, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline@am
, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-o-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, known developer component compounds can be added to the color developer applied to the processing of the silver halide photographic material of the present invention. . For example, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites,
The pH value of the J color developing solution, which may optionally contain an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal scrap halide, benzyl alcohol, a water softener, a thickening agent, etc., is usually 7 or more. Most commonly from about 10 to about 13.

The silver halide photographic material according to the present invention may contain these color developing agents in the hydrophilic colloid layer either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. Color developing agent precursors are compounds that produce color developing agents under alkaline conditions, and include Schiff base type precursors with aromatic aldehyde derivatives, polyvalent metal ion complex precursors, phthalic acid imide derivative precursors, phosphoric acid amide derivative precursors, Examples include sugar amine reactant precursors and urethane type precursors.

These aromatic primary amine color developing main mulberry precursors are disclosed in, for example, U.S. Pat.
, No. 507, 114, No. 2,695,234@,
No. 3.719.492, British Patent No. 803.783
Specifications of each issue, JP-A-53-185628, JP-A No. 54-
No. 79035, Research Disclosure Magazine No. 15159, Research Disclosure No. 12146, and Research Disclosure No. 13924.

It is necessary to add enough of these aromatic primary amine color developing agents or their precursors to obtain sufficient color development during activation treatment. Although the amount varies depending on the type of photosensitive material, it is generally used in an amount of 0.1 to 5 mol, preferably 0.5 to 3 mol, per mol of silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate it into a photosensitive material, it can be dissolved in an appropriate solvent such as water, methanol, ethanol, acetone, etc. It can also be added as an emulsified dispersion.
They can also be added by impregnation into latex polymers as described in the above issue.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment. Many compounds are used as bleaching agents, among them iron (I[[), cobalt (■), copper (I
polyvalent metal compounds such as I), in particular complex salts of these polyvalent metal cations with oronic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid,
Metal complex salts such as tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromates, etc. may be used alone or in appropriate combinations.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, and dioether.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. The stabilizing liquid used in the stabilization treatment can contain a DH adjuster, a chelating agent, an anti-spill agent, and the like. These specific conditions are based on Japanese Unexamined Patent Publication No. 58-134636, etc. ・t"2 days ΦA6± [Specific effects of the invention] As explained above, in the present invention, deterioration due to fading and discoloration due to light Thus, it was possible to provide a silver halide photographic material that has excellent light fastness, excellent color development, and excellent spectral absorption characteristics.

[Specific Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 The magenta coupler 40 (l) shown in Table-1 below and the dye image stabilizer shown in Table-1 below at 100 mol % relative to the magenta coupler were mixed with a high boiling point organic solvent (Example No., S-2
) 280 [Ratio of content to magenta coupler (
B/A) is 0.7] or 60 g [the content ratio (B/A) to magenta coupler is 1.5] is dissolved in a mixed solvent of ethyl acetate 1001Q. After adding the solution to 300 TII; l of 5% gelatin solution containing sodium dodecylbenzenesulfonate,
The dispersion obtained by dispersing with an ultrasonic homogenizer was mixed with a silver chlorobromide emulsion (silver bromide 80 mol%) to prepare a coating solution, which was coated on a polyethylene-coated paper support, dried, and the surface was coated. 1
Samples shown in (No. 1 to No. 0.21) were obtained.

These samples 1 to 21 were subjected to optical wedge exposure with white light using a photosensitive needle (model Ks-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following treatments.

Standard treatment process (treatment temperature and treatment time) [1] Color development phenomenon 38℃ 3 minutes 30 seconds [2] Bleacher 33℃ 1 minute 30 seconds [3] Washing treatment 25
~30℃ 3 minutes [4] Drying 75-80℃
Approximately 2 minutes Processing solution composition (color developing solution) Benzine alcohol 15i12 nib-rangelicol 151Q potassium sulfite 2. OIJ potassium bromide 0.7g potassium chloride
2.09 potassium carbonate
300g hydroxylamine sulfate
3.0g polyphosphoric acid (TPPS) 2.
5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.017 hydroxylated Potassium 2.0 (1) Add water to bring total ω to 12 and adjust pH to 10.20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 Q Ethylenediaminetetraacetic acid 1 3 (1 Ammonium thiosulfate (70% solution) 100d Ammonium sulfite (40% solution) 27.5.fl Potassium carbonate or glacial acetic acid I) Adjust to 87.1 and add water to bring the total volume to 1.
Let it be t.

The magenta coloring maximum density was measured using an optical density needle (PDA-65 model manufactured by Konishi Roku Photo Industry Co., Ltd.) for the sample obtained by processing, and the coloring property of the magenta dye was investigated.Furthermore, the following test was conducted. carried out.

<Lightfastness test> Using an underglass outdoor exposure table, sunlight was irradiated for 10 days, and the residual rate of the concentration after 10 days of irradiation with respect to the initial concentration Qo = 1.0 was shown.

[Degree of color change] Under the same conditions as the light fastness test, calculate (yellow density) / (magenta density) before the light test from (yellow density) / (magenta dye) after the light test at an initial density of 1.0. This is the subtracted value, and the larger this value, the more likely it is to change the color tone from magenta to yellowish.

<Spectral Absorption Characteristic Test> The spectral reflection spectrum of the obtained colored sample was measured using Color Analyzer Model 607 (manufactured by Hitachi Seisakusho). At this time, the maximum concentration of the absorption spectrum in the visible region of multiple samples is set to 1.
The measurement was normalized to 0. The reflection density at 43 Or+m of each sample was taken as a sub-absorption and used as an index of color purity.

These results are shown in Table-1.

However, the comparative couplers (M-1) and (
M-2>, and the structural formula of the comparative dye image stabilizer (A-1) is as follows.

r: Saddle cuff °5-(H-22 α.

As is clear from Table 1, the samples using the couplers of the present invention (Nos. 3-7, 10-21) were compared to Compared to the sample using the M-2 coupler (No. 7.8), the sub-absorption concentration is smaller and the sample using the M-1 coupler (No. 1.2)
Just as good as n4'! It can be seen that it has 2-characteristics. On the other hand, among the samples using the coupler of the present invention, the light fastness deteriorated significantly in the sample without the dye image stabilizer (No, No), and compared with the sample using the comparative dye image stabilizer (A-1). Samples (NO96, 7) and samples in which the ratio (B/A) of the content (B) of the dye image stabilizer to the content (A) of the coupler is 0.9 or less even when using the dye image stabilizer of the present invention ( No. 3) has better light fastness and maximum concentration than the comparative sample (
No. 8.9). In contrast, a sample (NO6S-, 10 to 21 ) had significantly improved lightfastness and maximum density, which was not expected from the composition of the comparative samples.

<Example 2> Coating solutions for each layer were prepared so as to have the configurations shown in Tables 2 and 3 below, and the coating solutions were sequentially applied from the support side to produce a multilayer silver halide color photographic light-sensitive material. .

After the samples thus prepared were exposed to light according to the test, they were processed according to the processing steps described above, and the following tests were conducted.

Color development of magenta dye image> Evaluation was made at the maximum concentration in the same manner as in Example 1.

Light fastness> The magenta dye image was exposed to sunlight for 20 days using an underglass outdoor exposure table, and evaluated in the same manner as in Example-1.

<Spectral absorption characteristics> Evaluation was made in the same manner as in Example-1.

Table 2 Layer Structure Acid 7th layer Gelatin (1,0 (1/v2) (protective layer) 6th layer Gelatin (1,0 (1/f ”) (3rd intermediate FIJ) Ultraviolet absorber UV-1 ( 0,2(1/12) UV-2(0,IQ/v') HQ-1(0,02g/1') High boiling point solvent dinonyl phthalate(0,2(]/1') 5th layer Gelatin (1,2(1/v') (red sensitive layer) Silver chlorobromide emulsion [containing 70 mol% Aa Sr] (Silver lead 0.251J#) Cyan coupler [C-7/C-12] (Halogen 0.4 mol per mol of silveride) HQ −1(0
,01 (J/v') High boiling point solvent dioctyl phthalate (9,2q/possible 2) 4th layer Gelatin (1,5g/*') (3rd intermediate layer) Ultraviolet absorber UV-1 (0,5Q/ *2) UV-2 (0,2<1/v2) HQ-1 (0,030/1') High boiling point solvent dinonyl phthalate (0,3 (1/v') 3rd layer Gelatin (1,5o /f) (green sensing layer)
Silver chlorobromide emulsion [containing 70 mol% Alj 3r] (Amount of silver o, 2o/v2) (However, No. 32 is o, 4g/v2) Magenta coupler [Table-3] (0,4 (1/1 ) Dye image stabilizer (*O/i') High boiling point solvent (*g/i') 2nd layer Gelatin (1, OQ /v') (1st intermediate layer) HQ -1 (0,070/n ) High-boiling solvent diisodecyl phthalate (0,041 J/v') 1st layer Gelatin (2,0!] /v2) (blue-sensitive layer) Silver chlorobromide emulsion [contains 70 mol% A (lBr)] (Silver Amount 0.37f) Yellow coupler Y-2 (0,81j/1') HQ-1 (0,02i7/11") High boiling point solvent dinonyl phthalate (0,3a/w) Support Polyethylene coated paper () represents a coating base or an addition.

* is shown in Table-3.

In addition, the comparative magenta coupler (M-3) used in Table-3
, (M-4), comparative dye image stabilizer (A-2), ultraviolet absorber (LIV-1), (LIV-2), and HG-1 have the following structural formulas.

l: tR masse 7° error c-3) r-c comparison 7
As is clear from Table 3, the magenta colored dye image obtained from the silver halide photographic light-sensitive material having the structure of the present invention can also be obtained from the multilayer structure silver halide photographic light-sensitive material. It can be seen that, like the single-layer silver halide photographic light-sensitive material of Example 1, it had excellent color reproducibility, and the light fastness and maximum density were significantly improved.

Looking more closely, the effect is further enhanced by increasing the amount of the image stabilizer of the present invention added. Furthermore, it can be seen that among the types of high boiling point organic solvents, those with low dielectric constants achieve the effects of the present invention more efficiently.

Example 3 In samples 22 to 34 of Example 2, the fifth layer, the third layer,
Samples were prepared by coating in exactly the same manner as in Example 2, except that a silver halide emulsion containing 100 mol % of silver chloride was used for each of the first layer silver halide emulsions.

Each sample was treated in the manner shown below, and the same test as in Example-2 was conducted. The results were similar to those in Example-2.

[Processing process] Temperature Time Color development phenomenon 24.7±0.3℃ 50 seconds bleach fixing
34.7±0.5℃ Stabilized for 50 seconds 30~3
Dry at 4℃ for 90 seconds 60-80℃ for 60 seconds [Color developer] Pure water
800 vl ethylene glycol
10112N, N-diethylhydroxylamine 1
0 g Potassium chloride 2 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 59 Sodium tetrapolyphosphate 2 g Potassium carbonate
30 g optical brightener (4,4'
-Diaminostilbendisulfone M derivative) 1 (+Add pure water to make the total number of times 12, and adjust the pH to 10.08.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate dihydrate 60 Q ethylenediaminetetraacetate 'PJ3g Ammonium thiosulfate (70% solution) 100.2
Ammonium sulfite (40% solution) 27.511
Adjust the pH to 7.1 with potassium dicarbonate or glacial acetic acid, and add water to bring the pH to 12.

(Stabilizing solution) 5-chloro-2-methyl-4-isothiazolin-3-one 1Q 1-hydroxyethylidene-1゜1-diphosphonic acid 2Q Add water to make 1ffi, and add 1) H with sulfuric acid or hydroxide columnum. Adjust to 7.0.

Patent applicant: Konishiroku Photo Industry Co., Ltd., et al.
−: y+ ds i? Procedural amendment (voluntary) August 21, 1985 Director General of the Patent Office Uga Michibu-dono Tei 1, Indication of the case 1985 Patent NPt5135148 2, Name of the invention Halogen that can obtain a dye image stable against light Silver chemical photographic material 3, relationship with the amended person case Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1)
27) Konishi Roku Photo Industry Co., Ltd. Representative Director Keio Benko 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 2. Patent Claims in the Specification "Scope" and "2. Scope of Claims" of the Specification (I) will be amended as shown in the attached sheet.

(If) The column "3. Detailed Description of the Invention" of Book #I is amended as follows.

1, page 5, line 16 and line 17 of the specification [3,
Add a detailed description of the invention.

2. Correct the structural formula of general formula (c) in Book #lIl, $13, as follows.

3. The structural formula of general formula (e) on page 17 of the specification is corrected as follows.

4, Light 1mW'Js 34 RffK(e')f)M
Correct formula i as follows.

(Rg')nt' is 65, and the structural formula at the bottom of page 45 of Mei #I is corrected as follows.

6. The structural formula of general formula (c-9) on page 8150 of the specification is corrected as follows.

7. The structural formula of the general formula outside the table on page 61 of the specification is corrected as follows. In the silver halide photographic light-sensitive material, at least one layer of the silver halide emulsion has the following general formula (a), (
b), at least one coupler selected from the couplers shown in (b) and/or a polymer coupler derived from the coupler, the following general formula [I]
The high boiling point ara medium for (A) containing at least one compound selected from the compound represented by and the compound represented by the following general formula [I[ ], and a high boiling point organic solvent, and containing a coupler. mff1 of content CB)
A silver halide photographic material having a ratio (B/A) of 0.9 or more.

General formula (,) (Rd)n.

General formula (b) General formula (c) (In general formulas (a), (b), and (b), Za.

zb and ZC each represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle. Xa, Xb and XC each represent a hydrogen atom or a group that can be separated upon reaction with an oxidized color developing agent.

Ra, Rb, Rc, Rd, Re, Rf and Rg each represent a hydrogen atom or a substituent. However, R(+
aY+ represents a carbon atom or a nitrogen atom.

Y2 represents a carbon atom or a heteroatom. ＝：゛ is Y
Indicates that the bond between l and Y2 may be a single bond or a double bond.

However, when Yl is a carbon atom and the bond between Yl and Y2 is a double bond, n3 is 1 and nto is 0, and RC is the relationship between the coupler represented by general formula (a) and the color developing agent. It is a substituent that does not undergo M elimination upon reaction with an oxidant, and when Yl is a carbon atom and the bond between Yl and Y2 is a single bond, both n3 and n4 are 1. Also, if Y1 is a nitrogen atom and the bond between Yl and Y2 is a double bond, n3 and n,
are both 0, and Y2 is a heteroatom, Yl
If is a nitrogen atom and the bond between Yl and Y2 is a single bond, then n
3 is 1 and n4 is O.

In addition, the couplers represented by general formulas (a), (b), and (C) are only at the position where Xa is bonded, the position where Xbh (bonds), and the position where Xc/+ (1
Coupling reaction occurs with the oxidized form of one-color developing agent. ) General formula [I] [wherein R1 represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y1. represents a group of nonmetallic atoms necessary to form a 5- to 7-membered compound ring with a nitrogen atom.

However, at least two of the nitrogen atom-containing nonmetallic atoms forming the double ring must be heteroatoms (1);
The at least two heteroatoms are not in FA contact with each other. ] General formula [TI] fl'l

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 layer of the silver halide emulsion has the following general formula (a) or (b).
) and (c), and/or a polymer coupler derived from the coupler, represented by the following general formula [I
] and at least one compound selected from the compound represented by the following general formula [II] and a high-boiling organic solvent, and the ratio of the high-boiling organic solvent to the content (A) of the coupler is Weight ratio of content (B) (B
A silver halide photographic material characterized in that /A) is 0.9 or more. General formula (a) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (b) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (c) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (General formula (a) ), (b) and (c), Za, Zb and Zc each represent a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle.Xa, Xb and Xc each represent a hydrogen atom or an oxidized color developing agent. Represents a group that can be separated upon reaction with. Ra, Rb, Rc, Rd, Re, Rf and Rg each represent a hydrogen atom or a substituent. However, Rg is a group that can be separated from the coupler represented by general formula (c) and color development. It is a substituent that does not leave when reacting with the oxidized form of the main drug.Y_
1 represents a carbon atom or a nitrogen atom. Y_2 represents a carbon atom or a heteroatom. ■ indicates that the bond between Y_1 and Y_2 may be a single bond or a double bond. However, if Y_1 is a carbon atom and the bond between Y_1 and Y_2 is a double bond, n_3 is 1 and n_4 is 0,
and Rc is a substituent that does not leave when the coupler represented by general formula (a) reacts with the oxidized color developing agent, and when Y_1 is a carbon atom and the bond between Y_1 and Y_2 is a single bond; , n_3 and n_4 are both 1. If Y_1 is a nitrogen atom and the bond between Y_1 and Y_2 is a double bond, both n_3 and n_4 are 0, and
Y_2 is a heteroatom, Y_1 is a nitrogen atom, and Y_1
When the bond between and Y_2 is a single bond, n_3 is 1 and n_4 is 0. In addition, the couplers represented by general formulas (a), (b), and (c) are capable of binding to the color developing agent only at the positions where Xa is bound, Xb is bound, and Xc is bound, respectively. Coupling reaction with oxidant. ) General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^1 represents an aliphatic group, cycloalkyl group, or aryl group, and Y represents a 5- to 7-membered heterocyclic ring together with a nitrogen atom. Represents a group of nonmetallic atoms necessary to form . However, at least two of the nonmetallic atom group containing nitrogen atoms forming the heterocycle must be heteroatoms, and these at least two heteroatoms are not adjacent to each other. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables etc. Represents a simple bond or divalent hydrocarbon group necessary to form. R^2, R^3, R^4, R^5, R^
6 and R^7 each represent a hydrogen atom, an aliphatic group, a cycloalkyl group, or an aryl group. However, R^2 and R
^4, R^3 and R^5 may be combined with each other to form a simple bond to form an unsaturated 5- to 7-membered heterocycle together with the nitrogen atom and Y. In addition, when Y is a simple bond, R^5 and R^7 may be bonded to each other to form a simple bond, and together with the nitrogen atom and Y, an unsaturated 5-membered heterocycle may be formed. . Also, when Y is not just a bond,
R^5 and Y, R^7 and Y, or Y itself may form an unsaturated bond to form an unsaturated 6- or 7-membered heterocycle together with the nitrogen atom and Y. ]