JPS62291647A - Photographic sensitive material having improved coloring property and light fastness of coloring matter image - Google Patents

Abstract

PURPOSE:To obtain the titled material having improved light fastness by incorporating a specific coupler, a polymer coupler, a specific compd. and a anti- decoloring agent to one layer of a silver halide emulsion layer. CONSTITUTION:The silver halide photographic sensitive material is formed by incorporating one kind of the coupler shown by formulas I-III and/or the polymer coupler derivated from said coupler, one of the compd. selected from the compds. shown by formulas IV and V, and the anti-decoloring agent having an oxidation potential EOX of 0.95(V)<=EOX<=1.50(V). In formulas I-III, Za-Zc are each a non-metal atom group necessary for forming a nitrogen contg. heterocyclic ring, Xa-Xc is hydrogen atom, etc., Ra and Rg are each hydrogen atom, etc. In formulas IV and V, R<1> is a aliphatic group, etc., Y, together with a nitrogen atom, is a non-metal atom group necessary for forming a 5-7 membered nitrogen heterocyclic ring, R<2> and R<7> are each an aliphatic group. Said coupler is preferably incorporated to the titled material in an amount of 1X10<-2>-8X10<-1>mol per 1mol silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material with improved color development and light fastness of dye images.

"Background of the Invention" A method for forming a dye image using a silver halide color photographic light-sensitive material is to form a dye image using a reaction between a photographic coupler and an oxidized form of a color developing agent. ! Examples of photographic couplers for normal color reproduction include magenta, yellow, and cyan couplers, and examples of color developing agents include aromatic primary amine color-developing agents. are used, and dyes such as azomethine dyes are formed by the reaction of magenta and yellow couplers with oxidized products of aromatic primary amine color developing agents, and the reaction between cyan couplers and aromatic primary amine color developing agents forms dyes such as azomethine dyes. ,
A dye such as an indoaniline dye is formed by the reaction with an oxidized product of a color developing agent.

Of these, in order to form a magenta color image, 5
-Pyrazolone, cyanoacetophenone, indacilone,
Virazolobenzimidazole, pyrazolotriazole couplers, etc. can be used.

Conventionally, 5-pyrazolone couplers have been used practically as magenta color brass forming couplers.

Color images formed from 5-pyrazolone couplers have excellent fastness to light and heat, but the color tone of this dye is not sufficient, and there is unnecessary absorption with colored components around 430 nm, and The absorption spectrum of nearby visible light is also broad, causing color turbidity and photographic images lacking in sharpness.

U.S. Patent No. 3, 72 as a coupler without unnecessary absorption
No. 5.067, JP-A-59-162548, JP-A-Sho 5
1H-pyrazolo[3°2-a]-3-h riazole coupler, IH-
imidazo N, 2-b ]-pyrazole type coupler, 1
H-1t pyrazolo[1,5-h copyrazole couplers or IH-b pyrazolo[1,5-d]tetrazole couplers are particularly excellent.

However, the light fastness of magenta dye images formed from these couplers is significantly lower. When these couplers are used in photosensitive materials, especially photosensitive materials suitable for direct viewing, they impair the essential requirements of photographic materials, which are to record and preserve images, making them difficult to put into practical use. It was something.

Moreover, in JP-A-61-73152, by using a piperazine compound in combination with a 1-day-virazolo-[3,2-c]-s-triazole type magenta coupler,
Techniques have been proposed to improve light fastness.

Although this technology does improve light fastness,
The disadvantage is that the color development deteriorates.

In addition, according to studies conducted by the present inventors, it was found that by using a piperazine compound in combination with an azole magenta coupler having a specific structure, there is relatively little deterioration in color development. It was found that the degree of improvement in robustness was not that great.

[Object of the Invention] An object of the present invention is to provide a photographic light-sensitive material in which color development is not deteriorated and the obtained dye image has high light fastness. - [Structure of the Invention] The above object of the present invention is to provide a photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula (a).
), (b) and (c), respectively, and/or a polymer coupler derived from the coupler, selected from compounds represented by the following general formulas [1] and [II]. at least one, as well as an oxidation potential E. X%? 0.95
This was achieved by providing a silver halide photographic material containing an antifading agent satisfying (V)≦EOX≦1.50 (V).

General formula (a) General formula (c) (Rg)nfu (In general formulas (a), (b) and (c), Z.

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

R,, Rb, Ro, Rcl, R(, R (and R, 4 each represent a hydrogen atom or a substituent. However, R) is an oxidized product of a coupler represented by the general formula (c) and a color developing agent. It is a substituent that does not leave during the reaction.

Yl represents a carbon atom or a nitrogen atom. Y2 represents a carbon atom or a heteroatom. 2 represents that the bond between Yl and Y may be a single bond or a double bond.

However, if Yl is a carbon atom and the bond between Yl and Y2 is a double bond, n3 is 1, n4 is O, and R
, is a substituent that does not leave during the reaction between the coupler represented by the general formula (a) and the oxidized color developing agent, and when Yl is a carbon atom and the bond between Yl and Y2 is a single bond, , 03 and n4 are both 1. In addition, when Y1 is a nitrogen atom and the bond between Yl and Y2 is a double bond, n3 and n4 are both O, and Y2 is a heteroatom, Yl is a nitrogen atom, and the bond between Yl and Y2 is a double bond. In the case of a single bond, n3 is 1 and n4 is O.

The couplers represented by general formulas (a), (b), and (c) are capable of color development only at the position where X^ is bonded, the position where X) is bonded, and the position where Xc is bonded, respectively. Coupling reaction occurs with the oxidized form of the main drug. ) General formula [I] [In the formula, R1 represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y is an atomic group necessary to form a 5- to 7-membered polycyclic ring with a nitrogen atom. represents. However, at least two of the nonmetallic atom groups containing nitrogen atoms forming the heterocycle must be heteroatoms, and these at least two heteroatoms are not adjacent to each other. ] General formula [II] [In the formula, R1 represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y is a simple bond or lj necessary to form a 5- to 7-membered heterocycle with a nitrogen atom represents a hydrocarbon group. R2, R3°R+, R5, R6 and R7 each represent a hydrogen atom, an aliphatic group, a cycloalkyl group or an aryl group. However, R2 and R4 and R3 and R5
are bonded to each other to form a simple bond and form a nitrogen atom, Y
Together, they 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
It may form an unsaturated bond by itself to form an unsaturated 6- or 7-membered heterocycle together with the nitrogen atom and Y. ] [Specific structure of the invention] Next, the present invention will be specifically explained.

In the magenta coupler represented by the general formula (,), (b), (c) general formula (a) (Rd)n4 general formula (b) general formula (c) according to the present invention, Za.

Zb and Zc represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and Xa, Xb, and Xc each represent a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Further, Ra, Rb=Rc, Rd, Ret Rf and Rg each represent a hydrogen atom or a substituent.

However, RE is a substituent that does not leave when the coupler represented by the general formula (c) reacts with the oxidized product of the color developing agent.

Y represents a carbon atom or a nitrogen atom, and Y2 represents a carbon atom or a heteroatom.

Ni represents that the bond between Y, and Y2 may be a single bond or a double bond.

Ys, Y- and Y each represent a carbon atom or a nitrogen atom.

n++ nz+ nkov n4y ns+ ng and n
, are O or 1, respectively.

However, when Y is a carbon atom and the bond between Y and Y2 is a double bond, n is 1, n is 0, and R
e is a substituent that does not leave during the reaction between Kab2- represented by the general formula (,) and the oxidized product of a color developing agent, Yl is a carbon atom, and the bond between Y and Y2 is a single bond. In the case of , both 1 and n4 are 1. Also, if Y is a nitrogen atom and the bond between Yl and Y2 is a double bond, n,
and n are both O, and Y2 is a heteroatom, and when Y is a nitrogen atom and the bond between Y and Y2 is a single bond, n is 1, and n is O It is.

Note that the couplers represented by the general formulas (,), (b), and (c) can be 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, Rh, Ret Rd, Re or Rf include a halogen atom, an alkyl group, a dichlorofurkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, and a sulfonyl group. , sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group,
Aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, acylami 7 group, sulfonamide group, imide group, ureido group, sulfonamide group, 7 amoylami group, alkoxycarbonyl amide/group, 7 Examples include lyloxycarponylamine 7 groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylthio groups, arylthio groups, and heterocyclic thio groups.

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

The alkyl group represented by Ra, Rb, Rc+ Rd, Re or Rf''Ch is one with 1 to 32 carbon atoms, the alkenyl group, and the alkynyl group is one with 2 to 32 carbon atoms, cycloalkyl group, cycloalkenyl group. Those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, are preferable, and the alkyl group, alkenyl group, and alkynyl group may be linear or branched.

In addition, these alkyl groups, alkyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compound residues, 7-syl, carboxy , carbamoyl, alkoxycarbonyl, aryloxycarbonyl, which are substituted via a carbonyl group, and further substituted via a hetero atom (specifically, hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy) , those substituted via an oxygen atom such as carbamoyloxy, nitro, amino (
(including dialkyl amide 7, etc.), sulfamoyl amide/,
Substituents via a nitrogen atom such as 7-rukoxycarponylamino, aryloxycarbonylamino, acylamino, sulfone 7mido, imide, ureido, etc., via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc. (substituted through a phosphorus atom such as phosphonyl, etc.)
].

Specifically, for example, methyl group, ethyl group, isopro)/
Ishi 4 people Shi-Wku-Ma1-
--No ;-Ni former foot - Tadecyl group, 1-hexyl/nyl group, 1.1'-dibentynonyl group, 2-chloro-t--ythyl group, trifluoromethyl group, 1-ethoxytri Decyl group, 1-methoxyisopropyl group, methane-sulfonylethyl group, 2,4-di-t-amyl7ethyl/oxymethyl group, anilino group, 1-phenylisopropyl group, 3-ring-butanesl-lephonaminophenoxyproyl group group, 3-4'-[7-(4''(
p-hydroxybenzenesulfonyl) phenoxydodecanoylamino) phenylpropyl group, 3-+4″-
(ff-(2″,4″-di-t-amyl7eth/xy)butanamide] phenyl l-7′ lobil i, 4-(ff-
(o-chloro7e/xy)tetradecanamide72/xy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, and the like.

The aryl group to be attenuated by Ra, Rb, Rc, Rd, Re or Rf''Ch is preferably a phenyl group, and the substituent (
For example, it may have an alkyl group, an alkoxy group, an acylamide group, etc.).

Specifically, phenyl group, 4-t-butyl 7-enyl group,
2,4-nor-7milphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-7-butylphenoxy)tetradecanamideraphenyl group and the like.

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

Specific examples include 2-7lyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the 7-syl group that weakens Ra, Rb, Rc, Rd, Re or Rf'' include acetyl group, 7-enylacetyl group, dodecamyl group, α-2,4-not-t-amylphenoxybutanoyl fulkylcarbonyl group, benzoyl group, 3-pentadecyloxybenzoyl group, p
-7-aryl carbonyl groups such as chlorobenzoyl group, etc., and the like.

Ra, Rh, Re, Rd, Re or Rf''cR Wasahachiru sulfonyl groups include methylsulfonyl groups, alkylsulfonyl groups such as dodecylsulfonyl groups, benzenesulfonyl groups, arylsulfonyl groups such as p-)luenesulfonyl groups, etc. can be mentioned.

The sulfinyl group represented by Ra, Rb, Re, Rd, Re or Rf includes an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, a 3-7 dinoxybutylsulfinyl group, a phenylsulfinyl group, a -1pentylsulfinyl group, Examples include arylsulfinyl groups such as decylphenylsulfinyl groups.

The phosphonyl group substituted with Ra, Rb, Rc, Rd, Re or Rf''C'i includes an alkylphosphonyl group such as a methyloctylphosphonyl group, an arylphosphonyl group such as an octyloxyphosphonyl group, and a phenoxyphosphonyl group. Examples include aryloxyphosphonyl groups such as aryloxyphosphonyl groups, arylphosphonyl groups such as phenylphosphonyl groups, and the like.

The carbamoyl group represented by Ra, Rb, Rcy, Rd, Re or Rf is an alkyl group, an aryl group (preferably 7enyl), and S is ffmL.

For example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-13-(2,4-di-L- Examples include amylphenoxy)propyl)carbamoyl group.

The sulfamoyl group represented by Ra, Rh, Re, Rd, Re or Rffi may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, N.

N-Diethylsulfamoyl t N-(2-pentadecyloctyethyl)sulfamoylethyl-FJi-'f
Examples include decylsulfamoyl group, N-7enylsulfamoyl group, and the like.

Examples of the spiro compound residue represented by Ra, Rb, Re, Rd, Re or Rf''I'i include spiro[3.

3] heptane-1-yl and the like.

Ra. Rh, R'c, Rd, Re or RrC
Examples of the bridged carbonized compound residue to be Rb include bicyclo[2,2.1]hebutan-1-yl, dolicyclo[3
, 3,1,1'']decan-1-yl, 7,7-tumethyl-bicyclo[2,2,1]heptan-1-yl, and the like.

The alkoxy group to be substituted with Ra, Rb, Re, Rd, Re or Rf 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-ethoxyethoxy group, a pentadecyloxy group, a 2-dodecyloxyethoxy group, and a fewinteryloxyethoxy group.

Ra, Rb, Ray Rdt Re or Rf″ri
The aryloxy group to be substituted is preferably phenyloxy, and the aryl nucleus may be substituted with any of the substituents or atoms listed above for the aryl group, such as a 7eth/oxy group, a p-t -butyl 7eth/oxy group, m-
Examples include pentadecylphenoxy group.

The heterocyclic oxy group represented by Ra, Rb, Re, Rd, Re or Rf preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, Examples include 3,4,5°6-tetrahydrobilanyl-2-oxy group and 1-phenyltetrazol-5-oxy group.

The siloxy group represented by Ra, Rb, Re, Rd, Re or R' may be further substituted with an alkyl group, such as a trimethylsiloxy group, a triethylsiloxy group, a trimethylbutylsiloxy group, and the like.

Examples of the acyloxy group to be substituted with Ra, Rh, Re, Rd, Re or Rf't'fi include an alkylcarbonyloxy group, a 7-arylcarbonyloxy group, etc., and may further have a substituent, Specific examples include an acetyloxy group, an α-chloroacetyloxy group, a benzoyloxy group, and the like.

The carbamoyloxy group represented by Ra, Rb, Rc, Rd, Re or Rf may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N,N-noethyl Examples include carbamoyloxy group, N=phenylcarbamoyloxy group, and the like.

The ami7 group represented by Rat Rb, Re, Rd, Re or Rr may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, anilino group, -monolyroanily7 group, 3-bentatecyloxylponylani+7/i, 2-chloro-5
-hexadecaneamide aniline 7 groups and the like.

The 7 acyl amide groups represented by Ra, Rh, Re, Rd, Re or Rfr include 7 alkylcarbonyl amide groups,
Examples include 7 arylcarbonylamide groups (preferably 7 phenylcarbonylamide groups), which may further have a substituent, specifically an acetamido group, an α-ethylpropanamide group, an N-722 Examples thereof include an acetamido group, a dodecanamide group, a 2,4-not-t-amylphenoxy7cetamido group, and an a-3-t-butyl-4-hydroxy-7e/xybutanamide group.

Ra, Rb, Re, Rd, Re or Rf″C-represented by 7-V certain silfl+-7 lucylsulfonylaminogera 8, which may further have a substituent.Specifically, Examples include methylsulfonyl 7mi7 group, pentadecylsulfonyl 7mi7 group, benzenesulfonamyl' group, p-toluninsulfonamide group, 2-no)4C5-t-7 milbenzenesulfone 7mido group, etc. It will be done.

The imide group represented by Ra, Rb, Rct Rdt Re or Rf may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, 3-heptadecylsuccinimide group, etc. Examples include an acid imide group, a 7-talimide group, a glutarimide group, and the like.

Ra, Rb, Rcy Rdy Re or Rr-c
The unrepresented ureido group may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
Examples include N-ethylureido group, N-methyl-N-decylfreido group, N-phenylfreido group, N-p-tolylfreido group, and the like.

Ra, Rh, Rc, Rd. , Re or Rf15 wasahachiru sulfamoylamide 7 group may be substituted with an alkyl group, an aryol group (preferably a phenyl group), etc., for example, N,N-dibutylsulfamoyl 7 group, N
-Methylsul 77 moylami 7iLN-7, Nilsul 7
Examples include 7 amoylamides.

Ra+ Rh, Re, Rd, Re or Rfc The alphkyl carbonyl amine/group represented by c may further have a substituent, for example, methoxycarbonyl amine 7
group, methoxyethoxycarbonylamide 7 groups, octadecyloxycarbonylamide 7 groups, and the like.

The aryloxycarbonylamide 7 group represented by Ra, Rb, , Re, Rd, Re or Rf may have a substituent, for example, 7enoxycarbonylamide 7 group, 4
-methylphenoxycarbonylamide 7 groups.

The alkoxycarbonyl group depleted by Ra, Rb, Re, Rd, Re or Rf may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyl group. Examples include oxycarbonyl group, nitoxymethoxycarbonyloxy group, benzyloxycarbonyl group, and the like.

The aryloxycarbonyl group represented by Ra, Rb, Re, Rd, Re or Rf may further have a substituent, for example, a 7-ethyloxycarbonyl group, a p-chlorophenoxycarbonyl group, a l-pentadecyl group. Examples include oxyphenoxycarbonyl group.

The alkylthio group represented by Ra, Rh, Re, 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. can be mentioned.

The arylthio group represented by Ra, Rb, Rat Rd, Re or Rf'c2ij is preferably a phenylthio group, and may further have a substituent, for example, a phenylthio group,
p-methoxyphenylthio group, 2-t +.

Examples thereof include an octadecylphenylthio group, a 3-octadecylphenylthio group, a 2-carboxyphenylthio group, and a p-7doaminophenylthio group.

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

When Rg and Yl are carbon atoms and the bond between Yl and Y2 is a double bond, examples of the substituent that will not be separated upon the reaction of the coupler represented by Re with the oxidized product of the color developing agent include, for example. Alkyl group, 7-aryl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, sia/group, spiro compound residue group, bridged hydrocarbon compound residue, siloxy group, carbamoyl group ζ+je
++Pn-+ 4:, J-n J-+! -s
++, -+xdicarbonyl groups are listed.

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 product of the color developing agent represented by Xat Examples include groups substituted via a sulfur atom or a nitrogen atom.

Examples of groups substituted via a carbon atom include a carboxyl group, a hydroxymethyl group, and a triphenylmethyl group, corresponding to Xa, Xb, and Xc, respectively. b') R4 Formula (c') (R+r')n, · ■ K.

(Ra' is Ra, Rh' is Rb, Re' is Re
, Rd' is Rcl, Re' is Re, Rf
' is Rf, R8' is RE, 01' is n
l and , 1 with n2, , l with n, 04'
is n(, n%' is n5, 06' is n6,
T is n7, Y,' is Yl, Y2' is Y2, Y
,' is Y, Y4' is Y4, Y,' is Y, and Z
a' has the same meaning as Zg, Zb' has the same meaning as zb, Zc' has the same meaning as Ze, and R1 to R6 represent hydrogen, an aryl group, an alkyl group, or a heterocyclic group.

Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, fairoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyl groups. There are eight oxy groups.

The alkoxy group may further have a substituent, and examples thereof include an ethoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a 7enetheroxy group, and a p-chlorobenoloxy group.

The aryloxy group is preferably a phenoxy group,
The aryl group may further have a substituent, specifically a 7eth/oxy group, a 3-methylphenoxy group, a 3-1 decyl 7eth/oxy group, a 4-notanesulfone 7mid 7ethyl/oxy group, 4-[a-(3'-pentadecylphenoxy)butanamide]phenoxy group, hexadecylrubamoylnotoxy group, 4-cyano7yonoxy group, 4-methanesulfonylphenoxy group, 1-7thyloxy group, p -methoxyphenoxy group and the like.

The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a polycyclic group or may have a substituent, specifically, 1-furinylteY Examples include lazolyloxy group and 2-benzothiazolyloxy group.

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

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

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

Examples of the aryloxycarbonyloxy group include a fairoxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

#7I++-1st, :, + * →
11 Hada Suya:,X Shi 1 Zu-l+
Examples include toxyoxalyloxy group.

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

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

The arylthio group includes a phenylthio group, a 4-methanesulfone-7midophenylthio group, a 4-t-decyl-7enethylthio group, a 4-7fluoro-entanamide phenethylthio group, a 4-carboxyphenylthio group, and a 2-ethoxy-5 Examples include -t-butylphenylthio group.

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

The fulkyloxythiocarbonylthio includes a dodecyloxythiocarbonylthio group and the like.

The group substituting via the nitrogen atom is tilted. Here, R1 and R6 are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group,
It is an alkoxycarbonyl group, and R5 and R8 may be combined to form a heterocycle, provided that R7 and R5 are not both hydrogen atoms.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group,
alkoxy group, aryloxy group, alkylthio group, iri-ruthio group, alkylami 7 groups, arylami 7 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, aryloxycarbonylamino group, Examples include hydroxyl group, carboxyl group, cyano group, and halogen atom. Specific examples of the furkyl group include ethyl group, octyl group, 2-ethylhexyl group, and 2-chloroethyl group.

The aryl group represented by R2 or R1 preferably has 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group, and the 7-aryl group may have a substituent. Examples of substituents for the alkyl group include those listed above and the alkyl group. Specific examples of the aryl group include phenyl group, 1
Examples include -su7tyl group and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R1 or R is 5 to 6
Shellfish are preferable, and may be a fused ring or have a substituent. On the 14: body side, 2-furyl group, 2
-quinolyl group, 2-pyriminol group, 2-benzothiazolyl group, 2-bilinol group and the like.

As the sulfamoyl group represented by R1 or R1,
N-furkylsulfamoyl group, N, N-difurkylsulfamoyl group, N-7lylsulfamoyl group, N
, N-noarylsulfamoyl group, etc., and these furkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include: For example, N, N-noethylsulfamoyl group, N-methylsulfamoyl group,
Examples include N-dodecylsulfamoyl group and Np)lylsulfamoyl group.

The carbamoyl group represented by R or R8 is N
-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-noarylcarbamoyl group, etc., and these alkyl groups and aryl groups are the same as those mentioned above for the alkyl group and 7-aryl group. 3. Examples include N, N-ethyl, rubamoyl, N-methylcarbamoyl, N-
Examples include dodecylcarbamoyl Is, N-p-cyanophenylcarbamoyl group, and N-p-)lylcarbamoyl group.

Examples of the 7-syl group attenuated by R7 or R6 include an alkyl carbonyl group, a 7-aryl carbonyl group, and a heterocyclic carbonyl group. may have. 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 R7 or R include an alkylsulfonyl group, a 7-arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a monosubstituted sulfonyl group. Examples thereof include a sulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, and a p-chlorobenzenesulfonyl group.

The aryloxycarbonyl group attenuated by R1 or R8 may have as a substituent any of the substituents listed for the aryl group, and specific examples thereof include a 7e/xycarbonyl group and the like.

The alfkidicarbonyl group represented by R2 or R1 is
It may have the direct substituent groups listed for the alkyl group,
Specific examples include methoxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, and the like.

The heterocycle formed by combining R2 and R8 is 5-
A 6-membered heterocycle is preferred, and may be saturated or unsaturated, may or may not have aromaticity, and may be a condensed ring. Examples of the heterocycle include If N-7 talimide group. , N-succinimide group, 4-N-urazolyl group, 1-N-hyguntoynyl group, 3-N-2,4-dioxoxazolidinyl group, 2-N-1,1-dioxo-3
-(2H)-oxo-1,2-benzthiazolyl group, 1
-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperinonyl group, 1-pyrrolinyl group, 1-imidazolyl group, 2-imigzolinyl 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-triazolyl) group, 1-- (1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3.4
-tetrahydroquinolyl group, 2-oxo-1-pyrrolinonyl group, 2-IH-pyridone group, 7-taladion group, 2-
Oxo-1-piperinonyl group, etc. (de), these heterocyclic groups include alkyl group, aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group, Substituted with sulfonamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, carbonyl group, imido group, nitro group, cyano group, carboxyl group, etc. may have been done.

Also, Za, Zb, Zc, Za', Z
Examples of the nitrogen-containing heterocycle 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 substituent that the nitrogen-containing heterocycle formed by Zc' may include include the substituents exemplified as Ra, for example, the following formula (a-1)=
(a-11) f (b -1) - (b -8), (c -
1) R sz vRs4sR in -(c -14)
s*+Rs. , R6, ~Rts+RtttRts +
When the substituent is not present, such as the bonding positions of Rss +Rss +Rsa to Rse, a group that will not be separated by the reaction between the coupler and the oxidized form of the color developing agent is present at the position that has coupling ability. Replace.

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-R1+ R11-R42+ Ri+-carbon or nitrogen bonded to Rsm) are (Rd")n,"(Rg")nt- ■ (Ra" is Ra, Rb- is Rb, Re"I!Rc
, Rd'' is Rd, Re- is Re, Rf- is R
f and Rg'' are Rg, nl'' is nl, n2'' is n2, n,'' is n, and n4'' is n, and n,''
is 1%, ns" is n6 and n, " is n7 and Yl" is Y,
, Y2- is Y2, Y,' is Y, and Y4'' is Y4
, Ys” is Y, Za” is Za, Zb” is zb
and Zc″' is synonymous with Zc.), so-called screw-type couplers are of course included in the present invention.

Examples of polymeric couplers derived from couplers attenuated by the general formula (a), (b) or (e) include, for example, the formula (
A monomer having a coupler moiety represented by a), (b) or (c), 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 general formula (a), (b) or (c) include the following.

General formula (a-1) General formula (a-
2) General formula (a3) General formula (a4
) General formula (a5) General formula (a-
6) General formula (a-7) General formula (a
-8) General formula (a-9)
General formula (a-10) General formula (all) General formula (b-1) General formula (b-
2) General formula (b-3) General formula (
b-4) General formula (b-s) General formula (b-6) General formula (b-7) General formula (b-8) General formula (c-1) General formula (c2) General formula (c3) General Formula (c-4) General formula (e5) General formula (c-6) General formula (c7) General formula (c-8) General formula (c-9) General formula (c-10) General formula (all) General Formula (c-12) General formula (c13)
In general formula (c-14) formula (a -1)-(c -14), Xa and -χa++ are Xa, and xb and ~xb are Xb
, Xe+-Xe14 is Xc, R21~R2° is Ra, R51-Ra3 is Rr, R21~R2
, is Re, R54-R75 is Rg, Rso-R<
z has the same meaning as Rf, and R21 to R2° 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 (e-12),
Especially (a-3), (b-1), (c3), (c-9),
(c-10).

Preferred substituents on the polycyclic ring (for example, Ra -Rg+ Rz-R121Rs+-R3o) 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
The substituents for a-Xc, Xa, -Xa, , Xb, -Xb-, and It is preferable that conditions 1.2 and 3 below 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゜1. R1゜2 and R2゜, hydrogen atom, halogen atom, alkyl group, dichlorofurkyl ic, alkenyl group, cycloalkenyl group, al!&-
++, :1 length near goose 1+++1-jt-1==;=1M
Tni! Go=Shizuku-2 Ni++11: Sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulf7
Moyl group, sia/group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami7 group, acylamino group, sulfone Amide group, imide group, ureido group, 7 sul7amoylamino groups, 7 alkoxycarbonylamine groups, aryloxycarbonylamine group, alfkidicarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group,
Rewarding a heterocyclic thio group, R2゜3. R1゜2 and R3
At least two of ゜ and ゜ are not hydrogen atoms.

Also, the above R1°3. Two of R2゜2 and R3゜,
The side lights R1゜ and R8゜2 may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R103 may be further combined with the ring to form a bridged carbonized ring. It may also constitute a hydrogen compound residue.

The groups represented by R3゜, ~R5゜, may have a substituent, and specific examples of the group represented by Rlot ~R+03 and the substituents that the group may have include the above-mentioned general formula The specific side of the group represented by Ri in (,) and V
Examples include substituents.

Further, for example, specific examples of the ring formed by bonding R1゜1 and Ri02 and the bridged hydrocarbon compound residue formed by R1゜1 to R1113 and the substituents that it may have include those mentioned above. Specific examples of the cycloalkyl, cycloalkenyl, heterocyclic group, and bridged hydrocarbon compound residue represented by Ra in the general formula (,) and their substituents are listed.

Among the above general formulas, (i) when two of Rio1 to R1° are alkyl groups, (ii) R, is preferable. One of 1 to R, , for example, R1°.

is a hydrogen atom, and when the other 2R3゜l and R,,2 combine to form a cycloalkyl together with the root carbon atom, the following is true.

Furthermore, among (i), R+a+ to R103 are preferable.
Two of them are alkyl groups, and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl and the cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl and the substituent thereof include Ra in the general formula (IL)
Specific examples of alkyl, cycloalkyl and their substituents are mentioned.

In addition, substituents on the heterocycle (e.g. Ra-RFi+ Rll
~R421R%1~R1°) is preferably represented by the following general formula.

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

The alkylene represented by R' preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, regardless of whether it is 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 R- are shown below.

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

Specifically, examples of the cycloalkyl group represented by R2 include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-hexyldecyl, etc. Six-shell compounds are preferred, such as cyclohexyl.

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

Specific examples of the aryl represented by R2 include phenyl and naphthyl. The Tetsuko Ryl group may have a substituent. Examples of the substituent include those exemplified as the substituent for R1 described above, in addition to side-lighting, straight-chain or branched alkyl.

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-Xc, Xa, -Xa, , Xb, -Xba.

The substituent on the carbon atom adjacent to the carbon atom to which Xc, ~Xc, is 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 bicyclic ring are those represented by the following general formula.

General formula % formula % In the formula, R1゜ 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, sul77moyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, Amine group, acylamide 7 group, sulfonamide group, imide group, ureido group, sul7amoyl7mi7 group, alfkhidicarbonylamino group, aryloxycarbonylamino group 7, alfkhidicarbonyl group, aryloxycarbonyl group, alkylthio group , represents an arylthio group or a heterocyclic group.

The group represented by R8゜4 may have a substituent,
Specific examples of the group represented by R6゜4 and substituents that the iron group may have include R in the general formula (a) above.
Specific examples of the group represented by a 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.

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

CHs Cz Hs
(i) Cy HtC+ Hs
(L) C4H* (i) C4
H*-C, Hth -〇eH+1
-CIIH2coC+ 2H2S
Cls H) l -C
I 78 ) s13 l4 -CH,N(c,H5)2 -CH2CH,N
HSO,C,,H2ff-(cH,),So□C+2H
zs(t) (cH2)3SO2C+zHts
/'l し1 Q Cl 4 r12s -CN -COCH, -COC,H
.

-COOC,H, -COOC,H,, -COOC,2H
2SCOOC+ s H3+ F
CI B r-NHCOC, 3H,, -N
HCOC,,H,.

-OCH co-10C2H, -Q
C, □H25-OCH2CONHCH, CH, OCH,
-〇CH, CH, 5O2CH.

-OCOC2H, -0COC(cH,).

S Cl-Hs 3 - S CH
2COOHThe color tone of the coloring dye produced by the coupler of the present invention is as follows:
Although it can 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, it is mainly magenta, and can be used for multicolor color photography, but it is a red color. Colored ones also have good light absorption characteristics, so they can be used for monochromatic color photography.

The couplers of the present invention usually contain IXI O' mole per mole of halogenated fi, preferably 1 x 10-2
A range of -8 x 10'' moles can be used.

In addition, the coupler of the present invention is a compound represented by the general formula [1] contained in at least one of the silver halide emulsion layers in the silver halide photographic material of the present invention, and a compound represented by the general formula [R1] of other types of magenta. At least one compound selected from the compounds shown will be explained. General formula [
In +1, the aliphatic group represented by R1 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,
Examples of the unsaturated alkyl group include an octyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group. Examples of the unsaturated alkyl group include an ethynyl group and a propenyl group.

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

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

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

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

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 an alkyl group, a 717-l group, an acyl group, and a carbamoyl group. ,
These include an alkoxycarbonyl group, a sulfonyl group, a sulfamoyl group, and may further have a substituent. Also, said 5
Although the heterocycle of the ~7 shell ring may be saturated, a saturated heterocycle is preferable. Further, a benzene ring or the like may be fused to the heterocycle, or a spiro ring may be formed.

;p4. Nima T-63 ■-84 C,4H2tI N N \-y ■-65 Knee 6 Ro ■-69 ■ ■-72 ■ Import λH Among the compounds represented by the general formula (1), and veranone type compounds and homobiy2non thread compounds are particularly preferred,
More preferably, the following general formula (1-1 3 or C
I-2 ].

General formula (1-1 1 General formula [1-2] In the formula, R2 and R7 each represent a hydrogen atom, an alkyl group, or an aryl group. However, R1 and R' do not become hydrogen at the same time. R4 ~Rl) each represents a hydrogen atom, an alkyl group or an aryl group.

In the general formulas (r-1) and (1-2), R2 and R3 each represent a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by R2 or R3 include, for example, a methyl group, Examples of the aryl group represented by R4 or R3 include an ethyl group, a butyl group, an octyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group.

The alkyl group and aryl group represented by R2 or R3 may have a substituent, and examples of the substituent include /% lodene atom, alkyl group, aryl group, alkoxy group, aryloxy group, heterocyclic group, etc. Can be mentioned.

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), R″
~R1' each represents a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by R4~RIj include a methyl group, an ethyl group, etc. Examples of the group include a phenyl group, etc. 6 The above general formula (1-13 or (
[-2) Specific examples of compounds that are degraded include the above-mentioned exemplified biveranone compounds (1-1) to (1-30) and exemplified homobiperanone compounds (1-51) to (1-62). As described in.

The general formula [111] will be explained below.

The aliphatic group represented by % R' in the general formula [■] 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.

The cycloalkyl group represented by R'C includes 5 to 7 cycloalkyl groups which may have substituents, for example,
Examples include Schifbentyl group and cyclohexyl group.

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

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R1 include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, acylamide 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 ([), Y together with the nitrogen atom is 5 to 7
It represents a simple bond or a divalent hydrocarbon group necessary to form a bilobed shell ring, but when Y is a simple bond, R5 and R7 further bond to each other to form a simple bond. When Y is a divalent monovalent hydrogen group, that is, a methylene group, R5 and Y or R7 and Y may form an unsaturated bond. may form an unsaturated 6-membered heterocycle, and in the case of an ethylene group, R5 and Y, R' and Y, or Y itself may form an unsaturated bond to form an unsaturated 6-membered heterocycle. The divalent hydrocarbon group represented by Y that may form a heptagonal heterocycle may further have a substituent, and this substituent may include an alkyl group,
Examples include 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 (n), R2, R, R4°R5,
R' and R7 each represent a hydrogen atom, an aliphatic group, a cycloalkyl group, or an aryl group, and the aliphatic group represented by R2-R7 includes a saturated alkyl group that may have a substituent and a 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, dichlorofurkyl group, and aryl group represented by R2 to R7 above include an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbamoyl group,
Examples include acylamide 7 group, sulfamoyl group, sulfonamide group, carbonyloxy group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, heterocyclic group, and furkylthio group.

It is preferable that the compound represented by the general formula (II) has 5 to 7 saturated heterocycles than unsaturated ones.

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

L-38 [-39 ■-41 The compounds represented by the general formulas [I] and [II] are preferably used in an amount of 5X10 per mole of the coupler of the present invention.
-2 to 5 moles, more preferably 1×10°1 to 3 moles.

Next, the oxidation potential EOX used in the present invention is 0.
95 (V) 'i; EOX≦1.50 (V)
The alkali color inhibitor (hereinafter referred to as the fading inhibitor according to the present invention) will be described in detail.

The oxidation potential EOX of the anti-fading agent according to the present invention can be easily measured by those skilled in the art. The method is described, for example, in the paper "Naturwissenschaften" by A. Stanienda.
47, p. 353 and 512 (1960), P. Delahaye (P.
Delahay > “New Instrumental
"New Instrumental Method"
s inE electrochemistry)
(1954), Interscience Publishers
ers) and El Mides (L.

``Polarographic Techniques'' (Meit8S)
2nd edition (1965), Interscience Publishers
e Publishers), etc.

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

EOX in the present invention is a value determined from the half-wave potential of a polarograph under the conditions described below. That is, acetonitrile is used as the solvent for the anti-fading agent, 011N sodium perchlorate is used as the supporting electrolyte, and EOX is used as the solvent for the anti-fading agent. Concentration 10-3 to 10-4 mol/2, reference electrode is Ag/A
A 9C1 electrode was used, and a rotating platinum #i main electrode was used for EOX measurements at 25°C.

The anti-fading agent according to the present invention can be a compound of any structure as long as it has an oxidation potential within the above range, but
In particular, compounds represented by the following general formulas [Δ] to [T1] are preferred, and compounds represented by the general formulas [A], [8] and [G] are more preferred. Of course, it goes without saying that even compounds other than the above general formula can be used as the anti-fading agent according to the present invention, as long as the oxidation potential is within the above range.

General formula [A] In the formula, R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R2, R), Rs
, Rs each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group, R4 is an alkyl group,
Represents a hydroxy group, aryl group or alkoxy group.

Further, R and R2 may be ring-closed with each other to form a 5-membered or 6-shelled ring, in which case R4 represents a hydroxy group or an alkoxy group, or R3 and R4 may be ring-closed to form a 5-membered or 6-shelled hydrocarbon ring. A ring may be formed, in which case R1 represents an alkyl group, an aryl group, or a heterocyclic group, except when R1 is a hydrogen atom and R4 is a hydroxy group.

General formula [B] (wherein R6 and R1 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamide group, acyloxy group,
Represents a sulfonamide group, cycloalkyl or alfkyl dicarbonyl group, R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group, and R3 represents a hydrogen atom, a halogen atom, an alkyl group. group, alkenyl group, aryl group, aryloxy group, acyl group, acyloxy group, sulfonamido group, cycloalkyl group or alfkidicarbonyl group.

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

General formula [C] 2 General formula [D] In the formula, R5 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, It represents an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, or an alphkidicarbonyl group.

Y represents an atomic group necessary to form a dichroman or difuran ring together with a benzene ring.

General formula (E) l--, where R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R3 represents a hydrogen atom, a halogen atom, or an alkyl group. , alkenyl group, aryl group, aryloxy group,
It represents an acyl group, an acylamide group, a 7-syloxy group, a sulfonamide group, a cycloalkyl group, or an alphkyl dicarbonyl group.

R2 and R'' represent a hydrogen atom, 2, a rodene atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamide/group, a sulfonamide group, a cycloalkyl group, or an alphkidicarbonyl group.

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

In the general formula CF) R2R, R3 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R2 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group. group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfone 7mido group, cycloalkyl group, or alfkidicarbonyl group.

R1 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R1 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamine group, an acyloxy group, a sulfonamide group, or an alkoxycarbonyl group. represent.

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

General formula CG) In the formula, R1 and R3 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylami/group, an acyloxy group, and a sulfonamide, respectively. group, cycloalkyl group or alkoxycarbonyl group.

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

Y represents an atomic group necessary to form a kidney bean ring.

General formula (H) R'' In the formula, R' and R2 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxy Represents a carbonyl group.

R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alfukidyl group. Represents carbonyl M.

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

As the anti-fading agent according to the present invention, any compound can be used as long as it has an oxidation potential within the above range, but in order to fully exhibit the effects of the present invention, it is preferably a water-insoluble compound. The oxidation potential is 0.95 (V)≦EO
Although X≦1.50 (V), it is good! : Shikuha 1.00
(V) ≦[□×≦1.45 (V) Special 1. ．． 1.
, OO(V)≦EOX≦1.40(V) is preferable.

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

R (AO-26) (AO-27) (AO-28) (AO-2'?) The antifading agent according to the present invention is added to the silver halide emulsion layer containing the coupler of the present invention. The amount of the anti-fading agent according to the invention can be determined in any manner depending on the desired effect, the type of compound, etc.
It is preferably used in an amount of 0.05 to 3 mol, more preferably 0.1 to 2 mol.

As a method for adding the coupler of the present invention, the compound represented by the general formula [I] or [II] of the present invention, and the antifading agent of the present invention to a silver halide photographic light-sensitive material, a general hydrophobic compound can be added. Similar to the addition method, various methods can be used, such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc., and these methods are selected as appropriate depending on the chemical structure of the hydrophobic compound such as the coupler. be able to. The oil-in-water emulsion dispersion method can be applied to conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or The mixture is dissolved using a water-soluble organic solvent, and a surfactant is added to a hydrophilic binder such as an aqueous gelatin solution using dispersion means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, and an ultrasonic device. After being emulsified and dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point organic solvents include phenol derivatives, phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters, trimesates, etc. that do not react with the oxidized form of the developing agent.
An organic solvent having a temperature of 50° C. or higher is used.

In the present invention, the high boiling point organic solvent that can be preferably used when dispersing the antifading agent according to the present invention is a compound having a dielectric constant of 6.0 or less, for example, a dielectric constant of 6.0 or less.
, 0 or less esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds. Preferably, the dielectric constant is 6.0 or less and 1.9 or more and 1
It is a high boiling point organic solvent with a vapor pressure of 0.5 mmHo or less at 00°C. Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds.

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

Furthermore, in the silver halide photographic material of the present invention,
In the silver halide emulsion layer containing the coupler of the present invention, the compound represented by the general formula [I], [[], and the antifading agent of the present invention, the content of the coupler of the present invention (A> Further improving the light fastness and coloring properties of the dye image formed by the coupler of the present invention by adjusting the weight ratio (B/A) of the content (CB) of the high boiling point organic solvent to 0.8 or more. Can be done.

The weight ratio of the content of the high boiling point organic solvent to the content of the coupler (B/A>) is preferably in the range of 1.0 to 3.0, and more preferably in the range of 1.0 to 2.0. The effects of the present invention can be efficiently achieved in such cases.

The silver halide photographic material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but the method of the present invention is particularly effective when using color photographic paper that is intended for direct viewing. is effectively demonstrated.

When the silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material, the specific layer structure includes:
In order from the support side, a yellow dye image forming layer, an intermediate layer, a magenta dye image forming layer, an intermediate layer, a cyan dye image forming layer,
Particularly preferred is one in which an intermediate layer and a protective layer are arranged.

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

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

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
It may be generated by sequentially and simultaneously adding H and pAv while controlling them. 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 may be prepared from cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, or 4E rhodium salt or complex salt during the process of grain formation and/or grain growth. By adding extra pressure ions using iron salts or complex salts, it is possible to embed them inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, they can be encapsulated inside the particles and/or on the particle surfaces. Can give reduction sensitized cough.

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

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

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

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (1oo) 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 dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. 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,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide is added during chemical ripening, and/or at the end of chemical ripening, and/or after chemical ripening Compounds known in the photographic industry as antifoggants or stabilizers can be added before coating the emulsion.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention can be formed by using, alone or in combination, a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. It is hardened. It is desirable that the hardening agent be added to the processing solution to the extent that it is possible to harden the photosensitive material, but it is also possible to add the hardening agent to the processing solution.

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

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

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). The dye-forming couplers are typically selected such that for each emulsion layer a dye is formed that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler for the blue light-sensitive emulsion layer. However, a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

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

The halogen photographic material of the present invention may be provided with auxiliary layers such as a filter S, an antihalation layer, and/or an antiirradiation layer.

These layers and/or the emulsion may contain dyes that flow out of the light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material using the present invention reduces the gloss of the light-sensitive material, increases the ease of writing, prevents mutual sticking of the light-sensitive materials, etc. A matting agent can be added to achieve this goal.

A lubricant can be added to the photosensitive material of the present invention in order to reduce sliding friction.

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

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

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitizing). Surfactants are used.

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

The silver halide light-sensitive material of the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, and then directly or (adhesiveness, antistatic property, dimensional stability of the support surface). , one or more subbing layers) to improve abrasion resistance, hardness, antihalation properties, friction properties, and/or other properties.

In the photographic light-sensitive material of the present invention, a halogen emulsion (a thickener may be used to improve coating properties when coating the arsenic emulsion) is used as an extrusion method that allows two or more types of layers to be coated at the same time. Dollion coatings and curtain coatings are useful for 1 blue.

The light-sensitive material of the present invention can be exposed using electromagnetic 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, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, etc.

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

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

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds generally have a concentration of about 0.1 to about 30 g per color developer 11, preferably about 1 g to about 15 g per color developer 11.
(Use at + concentration.

Examples of the amine phenol developer include O-amine phenol, p-amine phenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N,N'-diethyl-〇-phenylenediamine salt M
salt, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine salt 1[,2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-meta, sulfonamide ediyl-3-methyl-4-aminoaniline sulfate, N
-ethyl-N-β-hydroxyethylaminoaniline,
4-Amino-3-methyl-N.

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

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention further contains various components that are normally added to color developers, such as sodium hydroxide and sodium carbonate. , an alkaline agent such as potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanine I[, an alkali metal halide, benzyl alcohol, a water softener, an S thickening agent, etc. can be optionally contained. . The l)H value of this color developer is usually 7 or more, most commonly about 10.
〜about 13.

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

Specific representative examples of these include the following.

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

In addition, I) H buffering agents such as boron PIi, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions are appropriately added. be able to.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabiite 5A acid.
1iiiIIIli salts such as cum, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate , acetic acid, sodium acetate, ammonium hydroxide, and the like can be contained alone or in combination.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, thiosulfur H is added to the bleach-fix solution (bath).
Salt, thiocyanine MfA or sub-1ii! ! An acid salt or the like may be included, or the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

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

[Effects of the Invention] The silver halide photographic light-sensitive material of the present invention can be obtained by using the coupler of the present invention together with the compounds represented by formulas [I] and [II] and the antifading agent of the present invention. The light fastness of the dye image obtained from the inventive coupler was significantly improved and thus has excellent light fastness.

On the other hand, the silver halide photographic light-sensitive material of the present invention can prevent the deterioration of color development that occurs when the coupler of the present invention and the compounds represented by the general formulas [I] and [I] are used together, and further prevents fading according to the present invention. Because it was prevented by using drugs together,
There is no deterioration in color development.

[Example] Examples of the present invention will be described in detail below.

<Example-1> 40 g of the coupler shown in Table 1, the compounds shown in Table 7 represented by the general formulas [1] f3 and [Eko] in equimolar amounts as the coupler, and the antifading agent shown in Table 1 in the equimolar amount as the coupler. , dissolved in a mixed solvent of 28 g of dioctyl phthalate and 100 g of ethyl acetate, added this solution to 5% gelatin solution 3001Q containing sodium dodecylbenzenesulfonate, and then dispersed with an ultrasonic homogenizer to obtain a dispersion liquid. 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 and dried to form the samples shown in Table 1 (No. 1 to No. 0. 20) was obtained.

(Comparative coupler M-1) A photosensitive needle (
After performing light pattern exposure with green light using a KS-7 model (manufactured by Roku Konishi Photo Industry Co., Ltd.), the following treatments were performed.

Standard processing steps (processing temperature and processing time) [1] Color development 38°C 3 minutes 30 seconds [2]
Bleach: 33°C, 1 minute 30 seconds [3] Washing: 25-30°C, 3 minutes [4] Drying: 75-
80℃ for about 2 minutes Processing solution composition (color developer) Benzyl alcohol 15-year old ethylene glycol 151N potassium sulfite 2.0 g Potassium bromide
0.7g sodium chloride
0.2 g potassium carbonate
3o, orJ hydroxylamine sulfate 3, Og polyline M (TPPS)
2.5 g3-methyl-4-amino-N
- Ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfone If M conductor) 1.0
g Potassium hydroxide 2.0 g
Add water to bring the total volume to 12 and adjust to pl-110, 20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 Q Ethylenediaminetetraacetic acid M 3(]thioiiiil
M Ammonium (10% solution) 100d Ammonium iacinite (40% solution) 27.5i β Adjust to pi-17.1 with potassium carbonate or glacial acetic acid, add water and bring the total amount to 1! shall be.

The maximum magenta color density of the sample obtained by the treatment was measured using an optical densitometer (Model PDA-65, manufactured by Konishiroku Photo Industry Co., Ltd.).

Light fastness test〉 Using an underglass outdoor exposure table, sunlight was irradiated through an ultraviolet absorption filter for 30 days to determine the initial density. =1
It is expressed as the fading rate of the density after irradiation for 30 days with respect to 0.

Fading rate=”’X100 Table 1 shows the results.

CFi, I CH3 As is clear from Table 1, from the results of Samples 17 to 20, when Compound I-1 is used as a comparative coupler, the surface T luminosity improves, but the coloring density deteriorates significantly, and Even if the antifading agent of the invention is used in combination, the deterioration of color density cannot be improved. Further, from the results of Samples 1 to 3, when Compound I-1 is used in the coupler of the present invention, the color density deteriorates, and the effect of improving fiJf optical properties is small.

On the other hand, in the sample of the present invention, the color density deteriorated and the l1iiT luminosity improved significantly. However, a sample (N 0.1'
1, No. 1, and No. 12>, there is a deterioration in the color density, and there is little synergistic effect in improving the iT luminosity.

<Example-2> The coating liquid for each layer was adjusted to have the composition shown in Table 2,
A multilayer silver halide color photographic material was prepared by sequentially coating from the support side.

After exposing the thus prepared samples 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 dye image> Evaluation is made at the maximum concentration in the same manner as in Example 1.

Light fastness> The magenta colored dye image was irradiated with sunlight for 30 days using an underglass outdoor exposure table, and evaluated in the same manner as in Example-1. The results are shown in Table 3.

Table 2 Layers 7 layers for configuration
Gelatin (1.0 g/-r) (protective layer) No. 61 Gelatin (1.0 g/f) (3rd intermediate @
) Ultraviolet absorber UV-1 (0,2 (1/l) tJV-2 (0,1 g/l') High boiling point solvent dinonyl phthalate (0,2 o/V) No. 51 Gelatin (1,2 g/l' ) (red sensitive layer)
Chlorobromide limited emulsion [70 mol% A2B)-containing] (Amount of silver 0.25 p/f) Cyan coupler [C-11 (04 mol/mol silver halide) High boiling solvent dioctyl phthalate (0.2Q/ f') 4th layer Gelatin (1,5 (1/v') second intermediate M) Ultraviolet absorber UV-1 (0,5 (1/v') IJV-2 (0,2 g/f) High Boiling point solvent dinonyl phthalate (0,3Q/v') 3rd layer Gelatin (1,5 (1/v') (green sensitive layer) FA silver bromide emulsion [containing 10 mol% A, p8 catties] (Silver Amount 0.2 (1/p) Coupler [Table-3] (0.4Ω/f) Compounds represented by general formula [I] δ and UH'J [Table-3] (Equimole m with coupler) Anti-fading Agent [Table 3] (Equimolar intoxication with coupler) High boiling point solvent dioctyl phthalate (0.25 mm/f) 2nd layer Gelatin (1.0 mm/f) (first intermediate layer) High boiling point solvent diisodecyl phthalate ( 0.04Mf) 1st layer Gelatin (2,OQ/f) (blue sensitive layer)
Silver chlorobromide emulsion [containing 70 mol% of A da B] (Silver jii O, 30/12) Yellow coupler [Y-1] (0,8 g/f) High boiling point solvent dinonyl phthalate (0,3 ( J/f) Support Polyethylene coated paper () The number in parentheses indicates the amount of coating or addition.

Below: n uA 2ψ Cyan coupler C-1 C/- Yellow coupler Y-1 C# Ultraviolet absorber (UV-1) CsH++ (t) Ultraviolet absorber (UV-2) E-car biao angler 2 Table As is clear from No. 3, in the sample of the present invention, there was no deterioration in color density and an image with good in-plane luminosity was obtained. Furthermore, the colored area of the sample of the present invention had a clear image with less yellow lumps.

<Example-3> Multilayer silver halide color photographic material sample N of Example 2
o. In 29, 100 mol% silver chloride was substituted for the silver chlorobromide emulsion containing 70 mol% A9B in the silver emulsion.
Sample 2 of Example VA-2 was used.
A sample was prepared by coating in exactly the same manner as No. 9. This sample is designated as sample 34. Next, the compound CI contained in the third layer, l/
Sample No. 3, which is the same as Sample 2, except that [π], the anti-fading agent, and the high-boiling organic solvent were replaced with the combinations shown in Table 4.
5 to N0.41 were prepared. Each sample (No, 34 to No.
, 41> was treated in the following manner, and the same test as in Example 2 was conducted. The results are shown in Table 4.

[Processing process] Temperature Time Color development phenomenon 34.7±0.3℃ 50 seconds bleach fixing
34.7±0.5℃ Stabilized for 50 seconds 30
~34℃ 90 seconds drying 60~
80"C, 60t) [color developer water
800 ethylene glycol
10i12N,N-diethylhydroxylamine
10 g potassium chloride
29N=Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 29 Potassium carbonate
30 Q Fluorescent brightener (4,4°-diaminostilbendisulfonic acid derivative) 1 g Add water to bring the total amount to 12, and adjust to I) Hlo, 08.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid let 3 (1 th) Ammonium 5A acid (70% solution) '10 (h
f Ammonium sulfite (40% solution) 27.5
142 Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 12.

(Stabilizing solution) Add 2 g of 5-chloro-2-methyl-4-isothiazolin-3-one 1Q1- and 2 g of droxyethylidene-1゜1-diphosphonic acid to make 12, and make 12 with [12 or potassium hydroxide]. ) H to 7
Adjust to 0.

11-co; As is clear from Table 4, in the sample of the present invention, the color density deteriorated and a magenta image with good light resistance was obtained.
In addition, the smaller the dielectric constant of the high-boiling organic solvent, the better the surface optical properties and the more robust images were obtained.

Further, the larger B/Δ (weight ratio of 8 boiling point solvent weight/coupler weight ratio) is, the better the light resistance is, which is more preferable.

Patent Applicant Roku Konishi Photo Industry Co., Ltd. Procedure 11 Official Book (Spontaneous) September 10, 1985 Patent Application No. 135i45/2, 1985 Name of the Invention Improvement in color development and light fastness of dye images Relationship with the amended photographic material 3 patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
No[te Keio 4, Agent 〒102 Address 4-1-1 Kudan Kita, Chiyo Eguchi-ku, Tokyo Kudan-
Rosaka Building Telephone 263-9524 6. Contents of Amendment (I) Section 11, [2. Scope of Claims], is amended as shown in the attached sheet.

(I) The column ``3. Detailed Description of the Invention'' in Section 11'I is supplemented as follows.

1. Amend the structural formula of general formula (c) on page 10 of Mei-aS as follows.

2. The structural formula of general formula (c) on page 14 of page 11'l is corrected as follows.

(Rg)nt! 3. The structural formula of general formula (c') on page 31 of the specification is amended as follows.

(Rg')nt' @4, and the structural formula at the bottom of page 42 of the specification is corrected as shown in F below.

(R+r”)nt- 5, light l1m, page 47 Structure of general formula (c-9))Fi
Correct the formula as follows.

Item 6. Correct the structural formula of the general formula in the margin of the table on page 58 of the Memorandum as follows.

Claims In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formulas (a), (b) and (c).
') and/or a polymer coupler derived from the coupler, the following general formulas [I] and [ff
] and an oxidation potential EQX or 0.95 (V)≦Eox≦1.
50 (V).

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

zb and zc each represent a group of nonmetallic atoms necessary to form a nitrogen-containing compound ring. Xe, Xb and Xc/
are respectively l1III! upon reaction with a hydrogen atom or an oxidized product of a color developing agent. Represents a group that yields 2.

R,, Rb, Ro, Rd, R,, R, and R
, > each represent a hydrogen atom or a substituent. however,
R is a substituent that does not leave when the coupler represented by the general formula (c) reacts with the oxidized color developing agent. Yl represents a carbon atom or a nitrogen atom. Y
l represents a carbon atom or a heteroatom. 2 represents that the bond between Yl and Yl may be a single bond or a double bond.

However, if Yl is a carbon atom and the bond between Yl and Yl is a double bond, n3 is 1, n4 is ○, and R
, is an apparatus yj1 that does not separate during the reaction between the coupler represented by the general formula (a) and the oxidized product of the color developing agent.
group, where Yl is a carbon atom and the bond between Yl and Yl is a single bond, both n3 and n4 are 1. Also Y1
If is a nitrogen atom and the bond between Yl and Yl is a double bond, then n3
and n4 are both O, and Yl is a heteroatom, and when Yl is a nitrogen atom and the bond between Yl and Yl is an li bond, port 3 is 1, and n is O.

The couplers represented by the general formulas (a>, (b), and (c) have the ability to act as a color developing agent only at the position where Xe is bonded, the position where Xb is bonded, and the position where XO is bonded, respectively. Coupling reaction with the oxidized product of the general formula [■CoE In the formula, R1 represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y forms a 5- to 7-membered heterocycle with the nitrogen atom. represents the atomic group necessary for . However, at least two of the redundant atoms containing nitrogen atoms forming the heterocycle must be heteroatoms, and these at least two heteroatoms are not adjacent to each other. General formula [I]

Claims (1)

[Scope of Claims] In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formulas (a), (b) and (c).
) and/or a polymer coupler derived from the coupler, each represented by the following general formulas [I] and [II]
At least one compound selected from the compounds represented by: and an oxidation potential E_o_x of 0.95 (V)≦E_o_x≦
A photographic material characterized by containing an anti-fading agent having a voltage of 1.50 (V). 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), Z_a, Z_
b and Z_c each represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle. X_a, X_b and X_
c each represents a hydrogen atom or a group that can be separated upon reaction with an oxidized product of a color developing agent. R_a, R_b, R_c, R_d, R_e, R_f and R_g each represent a hydrogen atom or a substituent. However, R_g is a substituent that does not leave when the coupler represented by the general formula (c) reacts with the oxidized product of the color developing agent. 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, when Y_1 is a carbon atom and the bond between Y_1 and Y_2 is a double bond, n_3 is 1, n_4 is 0, and R_c is the coupler represented by general formula (a) and the color developing agent. It is a substituent that does not leave when reacting with the oxidant of
If the bond between 2 is a single bond, n_3 and n_4 are both 1. Also, if Y_1 is a nitrogen atom and the bond between Y_1 and Y_2 is a double bond, n_3 and n_4 are both 0, and Y_2 is a hetero atom, Y_1 is a nitrogen atom, and the bond between Y_1 and Y_2 is a single bond. In the case of a bond, n_3 is 1 and n_4 is 0. In addition, the couplers represented by general formulas (a), (b), and (c) are bonded only at the position where X_a is bonded, the position where X_b is bonded, and the position where X_c is bonded, respectively.
Coupling reaction with oxidized color developing agent. ) 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. 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 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 bonded to 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. ]