JPS61267049A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an excellent light fastness and sharpness without destroying a whiteness in a white part by incorporating one of a specific magenta coupler, one of the metal complex having >=3X10<7>M<-1>.sec<-1> the extinction rate constant of the singlet oxygen and one of an oil soluble dyestuff to the material. CONSTITUTION:The titled material is composed of at least one of the magenta coupler shown by the formula, at least one of the metal complex having >=3X10<7>M<-1>.sec<-1> the extinction rate constant of the singlet oxygen, and at least one of the oil soluble dyestuff. In the formula, Z is a non-metallic atom group necessary to forming a nitrogen contg. a heterocyclic ring, a ring capable of forming together with Z may be substituted, X is a hydrogen atom or a substituent capable of cleaving with a reaction of an oxidation product of the developing agent, and R is a hydrogen atom or a substituent. The metal complex has the extinction rate constant of the singlet oxygen having >=3X10<7>M<-1>.sec<-1>, preferably >=1X10<8>M<-1>.sec<-1>. The center metal contd. in the metal complex is preferably, each metallic atoms composed of Fe, Co, Ni, Pd and Pt.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material.
The present invention relates to a silver halide color photographic material that has excellent fastness to light, does not impair the whiteness of white areas, and has excellent sharpness. [Background of the Invention] A method of forming a dye image using a silver halide color photographic light-sensitive material includes a method of forming a dye image by a reaction between a photographic coupler and an oxidized color developing agent. Magenta, yellow and cyan couplers are used as photographic couplers for color reproduction.
In addition, aromatic primary amine color developing agents are used as color developing agents, and azomethine dyes are produced by the reaction of magenta and yellow couplers with oxidized products of aromatic primary amine color developing agents. By the reaction between the cyan coupler and the oxidized product of the aromatic primary amine color developing agent, dyes such as indoaniline dyes are formed. Of these, in order to form a magenta color image, 5
-Pyrazolone, cyanoacetophenone, indacilone,
Pyrazolobenzimidazole, pyrazolotriazole couplers, etc. are used. Most of the magenta color image-forming couplers that have been put to practical use in the past have been 5-pyrazolone 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 a yellow component around 430 rv. The absorption spectrum of nearby visible light is also broad, which causes color turbidity and results in photographic images lacking in vividness. U.S. Patent No. 3.72 as a coupler that does not have this unnecessary absorption
No. 5,067, JP-A-59-162548, JP-A-5
1-pyrazolo[3°2-c]-s-triazole type coupler, 1H-, described in No. 9-171956 etc.
imidazo[1,2-b]-pyrazole coupler, 1
H-b pyrazolo[1,5-b]-pyrazole type couplers or IH-b pyrazolo[1,5-d]tetrazole type couplers are excellent for bees. 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 can be used as photographic materials for recording and preserving images.

This would impair the essential requirements for
However, there were some difficulties in putting it into practical use. To improve the robustness of these six-element images to light.
Many methods have been proposed so far. A typical method is to use dyes formed from couplers.
How to make it solid and by adding various anti-fading agents
Methods are being used to improve robustness. Anti-fading agent
The method of adding
ing. A compound that improves the fastness of dye images to light.
For example, U.S. Pat. No. 2,360,290;
, No. 418,613, No. 2,675,314, No. 2,675,314, No.
Hydrokino described in 2,7Of, No. 197, etc.
derivatives, U.S. Pat. No. 3,432,300;
No. 573,050, No. 3,574,627, No. 3
, No. 764,337, No. 3,574.626, No. 3,574.626, No. 3,574.626, No.
No. 3,698,909 and No. 4,015,990.
Derivatives such as chromans and coumarans listed, US patents
No. 3,457,079, No. 3,069,262,
p-Alkoxy described in Japanese Patent Publication No. 43-13496 etc.
Examples include cyphenols, etc. However, these compounds are not sufficiently effective.
It wasn't. On the other hand, JP-A-56-99340, JP-A No. 56-99340,
No. 6-168652, No. 60-51834, etc. contain metals.
Techniques for improving light fastness using complexes have been described. these
metal complexes are effective as lightfasteners, but gold
Some complexes themselves are highly colored, resulting in a white color in the photographic image.
A defect in which parts of the body appear yellow, yellow-green, or green.
It has points. Therefore, we used metal complexes in combination to improve light fastness and produce white color.
It was desired to improve the whiteness of the area. Conventionally, two types of methods have been used to improve whiteness.
It is being One is described in JP-A-53-19021 etc.
A method of improving the whiteness of the base paper support itself on which it is mounted.
Yes, the other one is described in JP-A-55-93150 etc.
This method uses oil-soluble dyes. The base paper itself
The improvement in whiteness is due to the properties of titanium oxide contained in the base paper.
It is difficult to significantly improve whiteness. Improvement of whiteness with oil-soluble dyes is easily achieved with silver halide dyes.
It can be used in photographic materials, and also during whiteness improvement.
It is more effective because it is larger. As a result of various studies, the inventors of the present invention found a surprising result.
and at least one of certain magenta couplers.
, at least one certain metal complex, and an oil-soluble dye
By using in combination with at least one of
Lightfastness of dye images without compromising the whiteness of the white areas of the image
In addition, the sharpness of the dye image is improved.
I found out. In particular, the particular magenta used in the above combination of the present invention
Light fastness to dye images obtained from couplers and
The sharpness improvement effect can be achieved by using it in combination with a conventional fogger.
This significantly exceeds the prediction of the improvement effect achieved by
This could not be predicted from any of the conventional techniques described above.
. [Object of the Invention] Therefore, the first object of the present invention is to improve the light fastness of dye images.
Excellent, with even greater sharpness without compromising the whiteness of white areas.
Our goal is to provide excellent silver halide photographic materials.
. The second object of the present invention is to improve the color reproducibility of magenta dye images.
Excellent and improved lightfastness of magenta dye images.
An object of the present invention is to provide a silver halide photographic material. [Structure of the Invention] The above object of the present invention is to provide a maze represented by the following general formula CI].
at least one of the intercoupler and - heavy '7-1 -
The quenching rate constant of 1-term oxygen is 3X10 M −1・se
at least one metal complex of c-1 or higher and an oil-soluble dye
A silver halide photographic photosensitive material containing at least one of
This is achieved through materials. General formula [I] [wherein Z is a nonmetallic element necessary to form a nitrogen-containing heterocycle
represents a child group, and the ring formed by Z has a substitution or substituent.
You may. X is formed by a reaction with a hydrogen atom or an oxidized product of a color developing agent.
Represents a substituent that can be removed. Also, R is a hydrogen atom or! F represents a substituent. ] [Invention
Specific Configuration] The present invention will be specifically described below in the blank space. General formula (I) General formula CI) according to the present invention! In the magenta coupler represented by
Represents a group of nonmetallic atoms necessary to form a ring, and by Z
The ring formed may have a substituent. X is formed by a reaction with a hydrogen atom or an oxidized product of a color developing agent.
represents a substituent that can be removed. Moreover, R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include a halogen atom, a
Alkyl group, cycloalkyl group, alkenyl group, cycloa
alkenyl group, alkynyl group, aryl group, heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group
group, carbamoyl group, sulfamoyl group, cyano group,
Pyro compound residue, bridged hydrocarbon compound residue, alkoxy
Group, Ally+L1 Toko-S/M:, A-amf”lqto
A-8ix, X1f-+4-F/jc maciloxy group,
Carbamoyloxy group, amino group, acylamino group, sulphate
sulfonamide group, imide group, ureido group, sulfamoyl group
Ruamino group, alkoxycarbonylamino group, aryl
Oxycarbonylamino group, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylthio group, aryl
Examples thereof include a ruthio group and a heterocyclic thio group. Examples of halogen atoms include chlorine atoms and bromine atoms.
Among them, a chlorine atom is particularly preferred. The alkyl group represented by R includes those having 1 to 32 carbon atoms.
The alkenyl group and alkynyl group have 2 to 3 carbon atoms.
2, cycloalkyl group, cycloalkenyl group
It is preferable to have 3 to 12 carbon atoms, especially 5 to 7 carbon atoms.
Alkyl, alkenyl, and alkynyl groups can be linear or branched.
But that's fine. In addition, these alkyl groups, alkenyl groups, alkynyl groups
, cycloalkyl group, and cycloalkenyl group are substituents [e.g.
For example, aryl, cyano, halogen atom, heterocycle, cyclo
loalkyl, cycloalkenyl, spiro compound residues,
In addition to bridge hydrocarbon compound residues, acyl, carboxy, and carboxyl
Bamoyl, alkoxycarbonyl, aryloxycal
Those substituted via a carbonyl group such as carbonyl, and
substitutes through a heteroatom (specifically, a hydro
xy, alkoxy, aryloxy, heterocyclic oxy,
Oxygen such as siloxy, acyloxy, carbamoyloxy
Substitution via atoms, nitro, amino (dialky)
), sulfamoylamino, alkoxy
Cycarbonylamino, Aryloxycarbonylamino
, acylamino, sulfonamide, imide, ureido, etc.
substituted through the nitrogen atom, alkylthio, ali
ruthio, heterocyclic thio, sulfonyl, sulfinyl,
Those that substitute through the sulfur atom such as sulfamoyl,
Substituted through a phosphorus atom such as sulfonyl)
You can leave it there. Specifically, for example, methyl group, motyl group, isopropyl group
, t-butyl group, pentadecyl group, heptadecyl group, l
-hexylnonyl group, 1.1-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group
, methanesulfonylethyl group, 2,4-di-t-amyl
phenoxymethyl group, anilino group, 1-phenylisoprop
Lopyl group, 3-m-butanesulfonaminophenoxypyl group
Lopyl group, 3-4・-(α-[4・・(p-hydroxy
benzenesulfonyl) phenoxyfudodecanoylamino
) phenylpropyl group, 3-(4・-[α-(2LL,
4...-di-t-amylphenoxy)butanamide]
phenyl)-propyl group, 4-[α-(0-chlorophenol)
xy)tetradecanamidophenoxypropyl group, a
Examples include lyl group, cyclopentyl group, cyclohexyl group, etc.
It will be done. The aryl group represented by R is preferably a phenyl group.
, substituents (e.g., alkyl groups, alkoxy groups, acyl groups)
amino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group,
2.4-di-t-amylphenyl group, 4-tetradecane
amidophenyl group, hexadecyloxyphenyl group, 4.
-[α-(4...-t-butylphenoxy)tetradeca
and amidophenyl groups. The heterocyclic group represented by R is preferably 5- to 7-membered.
may be substituted, or may be fused. Specifically, 2-furyl group, 2-chenyl group, 2-pyrimi group
Examples include a diinyl group and a 2-benzothiazolyl group. Examples of the acyl group represented by R include an acetyl group and a fluoride group.
Phenylacetyl group, dodecanoyl group, α-2,4-di-
Alkyl carbo such as t-amylphenoxybutanoyl group
Nyl group, benzoyl group, 3-pentadecyloxybenzo
Aryl carbonyl group, p-chlorobenzoyl group, etc.
and the like. The sulfonyl group represented by R is a methylsulfonyl group
, an alkylsulfonyl group such as a dodecylsulfonyl group,
Such as benzenesulfonyl group, p-toluenesulfonyl group
Examples include arylsulfonyl groups and the like. As the sulfinyl group represented by R, ethylsulfinyl
Nyl group, octylsulfinyl group, 3-phenoxybutyl group
Alkylsulfinyl group such as rusulfinyl group,
Nilsulfinyl group, m-pentadecyl phenyl sulfate
Examples include arylsulfinyl groups such as finyl groups.
Ru. The phosphonyl group represented by R is butyl octyl phosphor.
Alkylphosphonyl group such as honyl group, octyloxy
Alkoxyphosphonyl group such as phosphonyl group, phenoxy
Aryloxyphosphonyl group such as cyphosphonyl group,
Arylphosphonyl groups such as phenylphosphonyl group, etc.
can be lost. The carbamoyl group represented by R is an alkyl group, an aryl group,
It may be substituted with a group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group,
Rubamoyl group, N-(2-pentadecyl octylethyl
) Carbamoyl group, N-ethyl-N-dodecylcarbamo
yl group, N-(3-(2,4-di-t-amylphenokyl group)
ci)propyl)carbamoyl group, and the like. The sulfamoyl group represented by the margin R below is an alkyl group, an aryl group.
It may be substituted with a group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-diethyl group
Rusulfamoyl group, N-(2-pentadecyloxye
thyl) sulfamoyl group, N-ethyl-N-dodecyl group
Examples include rufamoyl group, N-phenylsulfamoyl group, etc.
can be lost. Examples of spiro compound residues represented by R include spiro [
3,3] Hebutane-! -il etc. Examples of the bridged carbonized compound residue represented by R include Bisic.
ro[2,2,1]heptan-1-yl, tricyclo[3
,3,1,1'°7]decane-1-yl, 7,7-sime
Chirubicyclo[2,2,1]hebutan-1-yl, etc.
Can be mentioned. The alkoxy group represented by R further has a linkage to the alkyl group.
Those listed as substituents may be substituted, for example,
methoxy group, propoxy group, 2-ethoxyethoxy group,
Pentadecyloxy group, 2-dodecyloxyethoxy group
, phenethyloxyethoxy group, and the like. The aryloxy group represented by R is phenyloxy
is preferable, and the aryl nucleus is further substituted with the aryl group.
Optionally substituted with those listed as groups or atoms,
For example, phenoxy group, p- is -butylphenoxy group, m
-pentadecylrefpentoxy group and the like. The heterocyclic oxy group represented by R is a 5- to 7-membered heterocyclic group.
Preferably, the heterocycle has a substituent.
For example, 3°4.5.6-tetrahydrogen
Drobyranyl-2-oxy group, l-phenyltetrazo
-5-oxy group is mentioned. The siloxy group represented by R is further substituted with an alkyl group, etc.
For example, trimethylsiloxy group, trimethylsiloxy group,
Examples include ethylsiloxy group, dimethylbutylsiloxy group, etc.
It will be done. As the acyloxy group represented by R, for example, alkyl
Carbonyloxy group, arylcarbonyloxy group, etc.
and may further have a substituent, specifically
Acetyloxy group, α-chloroacetyloxy group, ben
Examples include zoyloxy group. The carbathyloxy group represented by R is an alkyl group, an alkyl group,
The lyl group may be substituted, for example, N-ethyl
Carbamoyloxy group, N,N-diethylcarbamoyl
Oxy group, N-phenylcarbamoyloxy group, etc.
It will be done. . The amino group represented by R is an alkyl group or an aryl group (preferably
or phenyl group), etc., for example,
ethylamino group, anilino group, -monochloroanilino group,
3-pentadecyloxycarbonylanilino group, 2-k
Examples include lor-5-hexadecaneamide anilino group, etc.
Ru. The acylamino group represented by R is an alkyl carboxyl group.
nylamino group, arylcarbonylamino group (preferably
is a phenylcarbonylamino group), and furthermore,
It may have a substituent, specifically an acetamide group, an α-ethyl group, etc.
Tylpropanamide t hT -t--11, Ma J
-zL? SL? anus VS-h”/?-nido group, 2,4-
Di-t-amylphenoxyacetamide group, α-3-t
-Butyl 4-hydroxyphenoxybutanamide group, etc.
can be mentioned. The sulfonamide group represented by R is an alkyl sulfonamide group.
Honylamino group, arylsulfonylamino group, etc.
and may further have a substituent. Specifically, methylsulfonylamino group, pentadecyl group
sulfonylamino group, benzenesulfonamide group, p-
Toluenesulfonamide group, 2-methoxy-5-t-a
Examples include milbenzenesulfonamide group. The imide group represented by R may be open-chain or cyclic.
It may also have a substituent, for example, amber.
Acid imide group, 3-heptadecyl succinimide group, lid
Examples thereof include a limide group and a glutarimide group. The ureido group represented by R is an alkyl group, an aryl group (
(preferably a phenyl group) etc. may be used as a substitution source (
, for example, N-ethylureido group, N-methyl-N-decyl
Luureido group, N-phenylureido group, N-p-tri
Examples include a leureido group. The sulfamoylamino group represented by R is an alkyl group,
Substituted with an aryl group (preferably a phenyl group), etc.
For example, N,N-dibutylsulfamoylamide
group, N-methylsulfamoylamino group, N-phenylamino group
Examples include rusulfamoylamino group. As the alkoxycarbonylamino group represented by R,
Furthermore, it may have a substituent, for example, methoxycarboxylic
nylamino group, methoxyethoxycarbonylamino group,
Examples include octadecyloxycarbonylamino group, etc.
. The aryloxycarbonylamino group represented by R is
It may have a substituent, for example phenoxycarbonyl
Amino group, 4-methylphenoxycarbonylamino group
Can be mentioned. The alkoxycarbonyl group represented by R further has a substituent.
For example, methoxycarbonyl group, butyl
Oxycarbonyl group, dodecyloxycarbonyl group,
tadecyloxycarbonyl group, ethoxymethoxycal
Bonyloxy group, benzyloxycarbonyl group, etc.
It will be done. The aryloxycarbonyl group represented by R further has a substituent
For example, phenoxycarbonyl group,
p-chlorophenoxycarbonyl group, m-pentadecyl
Examples include oxyphenoxycarbonyl group. The alkylthio group represented by R further has a substituent.
For example, ethylthio group, dodecylthio group,
tadecylthio group, phenethylthio group, 3-phenoxy
Propylthio group is mentioned. The arylthio group represented by R is preferably a phenylthio group.
Furthermore, it may have a substituent, for example, a phenylthio group,
p-methoxyphenylthio group, 2-t-octylphenyl
ruthio group, 3-octadecylphenylthio group, 2-cal
Boxyphenylthio group, p-acetaminophenylthio
Examples include groups. The heterocyclic thio group represented by R is a 5- to 7-membered heterocyclic thio group.
A locyclic thio group is preferred, and may further have a fused ring, or
It may have a substituent. For example, 2-pyridylthio group
, 2-benzothiazolylthio group, 2,4-diphenoxy
-1,3,5-triazole-6-thio group is mentioned.
. It may be released by reaction with the oxidized form of the color developing agent represented by X.
Examples of substituents include halogen atoms (chlorine atoms, odor
low carbon atoms, oxygen atoms, sulfur
Examples include groups substituted via an atom or a nitrogen atom. As a group substituting via a carbon atom, a carboxyl group
In addition, for example, in the general formula (R, . is the same as the above R, and Z is the same as the above Z)
Yes, R2 and R3 are hydrogen atoms, aryl groups, and alkyl groups.
Represents a kill group or a heterocyclic group. ) are listed.
Ru. Examples of groups substituted via an oxygen atom include alkoxy
group, aryloxy group, peterocyclic oxy group, acyloxy group
cy group, sulfonyloxy group, alkoxycarbonyloxy group
cy group, aryloxycarbonyloxy group, alkyl group
Examples include xalyloxy group and alkoxyoxalyloxy group.
can be lost. The alkoxy group may further have a substituent, for example,
Ethoxy group, 2-phenoxyethoxy group, 2-cyanoe group
Toxy group, phenethyloxy group, p-chlorobenzyl group
Examples include xy group. The aryloxy group is preferably a phenoxy group.
, the aryl group may further have a substituent. Ingredients
Physically, phenoxy group, 3-methylphenoxy group, 3
-dodecylphenoxy group, 4-methanesulfonamide
phenoxy group, 4-[α-(3-pentadecyl phenoxy)
c) Butanamide] phenoxy group, hexidecyl carba
Moylmethoxy group, 4-cyanophenoxy group, 4-meta
Examples include methoxyphenoxy group and the like. The heterocyclic oxy group is a 5- to 7-membered heterocyclic oxy group.
A cy group is preferable, and it may be a condensed ring or have a substituent.
You may do so. Specifically, l-phenyltetrazoly
2-benzothiazolyloxy group, etc.
It will be done. Examples of the acyloxy group include acetoxy group, butane
Alkylcarbonyloxy groups such as trunoxy groups, thinner
alkenylcarbonyloxy groups such as moyloxy groups,
Arylcarbonyloxy groups such as benzoyloxy groups
can be mentioned. The sulfonyloxy group is, for example, butanesulfonyloxy group.
Examples include fluoroxy group and methanesulfonyloxy group. As the alkoxycarbonyloxy group, for example, ethyloxy
xycarbonyloxy group, benzyloxycarbonyloxy group
Examples include xy group. The aryloxycarbonyl group is a phenoxycarboxyl group.
Bonyloxy group etc. are mentioned. As the alkyloxalyloxy group, for example, methyl
An example is an oxalyloxy group. As the alkoxyoxalyloxy group, ethoxy
Examples include xalyloxy group. Examples of groups substituted via a sulfur atom include alkyl
Thio group, arylthio group, heterocyclic thio group, alkylthio group
Examples include xythiocarbonylthio group. As the alkylthio group, butylthio group, 2-cyano
Ethylthio group, phenethylthio group, benzylthio group, etc.
Can be mentioned. As the arylthio group, phenylthio group, 4-methane
Sulfonamidophenylthio group, 4-dodecylphenethyl group
ruthio group, 4-nonafluoropentanamidophenethyl
Thio group, 4-carboxyphenylthio group, 2-ethoxy
-5-t-butylphenylthio group and the like. Examples of the heterocyclic thio group include l-phenyl-1,
2,3,4-tetrazolyl-5-thio group, 2-benzothi
Examples include azolylthio group. As the alkyloxythiocarbonylthio group, dode
Examples include syloxythiocarbonylthio group. Examples of the group substituted via the nitrogen atom include R
4' Examples include those represented by the general formula -N.
group, heterocyclic group, sulfamoyl group, carbamoyl group
, acyl group, sulfonyl group, aryloxycarbonyl
group, represents an alkoxycarbonyl group, and R4 and Rs are
They may be combined to form a petero ring. However, R4 and R3
・ cannot both be hydrogen atoms. The alkyl group may be straight chain or branched, preferably carbon
It is a prime number of 1 to 22. In addition, an alkyl group is a substituent
The substituent may include, for example, an aryl group.
, alkoxy group, aryloxy group, alkylthio group,
Arylthio group, alkylamino group, arylamino group
, acylamino group, sulfonamide group, imino group, acylamino group,
group, ad, a, 11-9+1. J+++11. Te?
III+, "yl+, -8--+L! 2 → 1 rubamoyl
group, sulfamoyl group, alkoxycarbonyl group, ali
Alkyloxycarbonyl group, Alkyloxycarbonyl group
mino group, aryloxycarbonylamino group, hydroxy
Examples include syl group, carboxyl group, cyano group, and halogen atom.
can be lost. Specific examples of the alkyl group include, for example, ethyl group.
, oxytyl group, 2-ethylhexyl group, 2-chloroethyl group
Examples include ru groups. The aryl group represented by R4 or Rs' is carbon
Number 6 to 32, particularly phenyl group and naphthyl group are preferable,
The aryl group may have a substituent, and examples of the substituent include
Substituent to the alkyl group represented by R4 or R5 above
and alkyl groups. The ant
Specific examples of the metal group include, for example, a phenyl group.
, 1-naphthyl group, 4-methylsulfonylphenyl group
Can be mentioned. The heterocyclic group represented by R4 or R6 is 5 to 6
A membered ring is preferable, and it may be a fused ring, and the substituent is
May have. Specific examples include 2-furyl group, 2-kyl group,
Noryl group, 2-pyrimidyl group, 2-benzothiazolyl group
, 2-pyridyl group and the like. The sulfamoyl group represented by R4 or R6 is
, N-alkylsulfamoyl group, N,N-dialkyl
Sulfamoyl group, N-arylsulfamoyl group, N
, N-diarylcarbamoyl group, etc., and these
The alkyl group and aryl group are the aforementioned alkyl group and aryl group.
About the group. It may have the substituents listed above. sulfamoyl group
Specific examples include N,N-diethylsulfamoyl
group, N-methylsulfamoyl group, N-dodecylsulf
Ammoyl group, N-p-tolylsulfamoyl group, etc.
It will be done. The carbamoyl group represented by R4 or R6 is,
N-alkylcarbamoyl group, N,N-dialkylcar
Bamoyl group, N-arylcarbamoyl group, N,N-di
Examples include arylcarbamoyl groups, and these alkyl
The alkyl group and aryl group are the same as the alkyl group and aryl group.
It may also have the substituents listed above. Carbamoyl
Specific examples of the group include N,N-diethylcarbamoy.
group, N-methylcarbamoyl group1. N-dodecylcal
Bamoyl group, N-p-cyanophenylcarbamoyl group,
N-p-tolylcarbamoyl group is mentioned. Examples of the acyl group represented by R6・ or Rs・
Alkylcarbonyl group, arylcarbonyl group, hetero
Examples include ring carbonyl groups, such alkyl groups, and aryl groups.
The heterocyclic group may have a substituent. Asil
Specific examples of the group include hexafluoro.
Butanoyl group, 2゜3.4.5.6-pentafluorobe
nzoyl group, acetyl group, benzoyl group, naphthonyl group
, 2-furylcarbonyl group, and the like. The sulfonyl group represented by R4・ or Rs・
Rukylsulfonyl group, arylsulfonyl group, heterocycle
Examples include sulfonyl groups, which may have substituents, and specifically
For example, ethanesulfonyl group, benzene
Sulfonyl group, octanesulfonyl group, naphthalene sulfonyl group
Honyl group, p-chlorobenzenesulfonyl group, etc.
It will be done. Aryloxycarbonyl represented by R4 or R6
The group has the substituents listed for the aryl group above.
may have a phenoxycarbonyl group, specifically a phenoxycarbonyl group, etc.
can be mentioned. The alkoxycarbonyl group represented by R4 or R6 is
, may have the substituents listed for the alkyl group above.
, specific examples include methoxycarbonyl group and dodecyl group.
oxycarbonyl group, benzyloxycarbonyl group, etc.
can be mentioned. The heterocycle formed by combining R4 and R5 is
A 5- to 6-membered one is preferable, and it may be saturated or unsaturated.
, and may or may not have aromaticity;
It may be a fused ring. Examples of the heterocycle include N-phthal
imido group, N-succinimide group, 4-N-urazolyl
group, 1-N-hydantoynyl group, 3-N-2,4-dio
xoxazolidinyl group, 2-N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolidinyl group, l-pyrazolyl
group, 1-pyrazolidinyl group, l-piperidinyl group, 1-
pyrrolinyl group, l-imidazolyl group, l-imidazolinyl group
Le group,! -i, indolyl group, l-isoindolinyl group,
2-isoindolyl group, 2-isoindolinyl group, 1-
Benzotriazolyl group, 1-benzimidazolyl group, 1
-(1,2,4-triazolyl) group, 1-(1,2,3
-) riazolyl) group, 1-(1,2,3,4-tetrazo
(lyl) group, N-morpholinyl group, 1,2,3,4-tet
lahydroquinolyl group, 2-oxo-1-pyrrolidinyl group
, 2-IH-pyridone group, phthaladione group, 2-oxo
-1-piperidinyl group, etc., and these heterocyclic groups
is an alkyl group, aryl group, alkylamino group, aryl group,
hydroxyl group, acyl group, sulfonyl group, alkylamino
group, arylamino group, acylamino group, sulfonamide
- group, carbamoyl group, sulfamoyl group, alkyl group
o group, arylthio group, ureido group, alkoxycarbo group
Nyl group, aryloxycarbonyl group, imide group, nitro group
By group, cyano group, carboxyl group, halogen atom, etc.
may be replaced. In addition, as a nitrogen-containing heterocycle formed by Z or Z.
, pyrazole ring, imidazole ring, triazole ring or
may include a tetrazole ring, etc., and the Fuki ring may have
Examples of the substituent include those described for R above.
. In addition, general formula CI) and general formula (II) to [■] described below
Substituents (for example, R9R1 to R1) on the heterocycle in the moiety (herein, R..., X and Z... are general formula CI)
It has the same meaning as R, X, and Z. ), the so-called bi
Forming a solid coupler is, of course, included in the present invention. Also, formed by Z, Z・, Z... and Z described later
The ring may further include other rings (e.g. 5-7 shell cycloalkenes)
may be condensed. For example, in general formula (V)
R6 and R, are R7 and R8 in general formula (Vl)
are bonded to each other to form a ring (for example, a 5- to 7-membered cycloalke).
benzene). Below is the general formula for the margin (the one represented by l is more specifically, for example,
It is represented by general formulas (II) to [■]. General formula (II) General formula (III) N -N -N General formula (1'l/) N -H-NH General formula [V] General formula (Vl) N N -811 General formula [■] NN The above general In formulas [■] to [■], R5 to R and X are
It has the same meaning as R and X above. Also, among the general formula (1), the following general formula [
■]. General formula [■] In the formula, Rr, X and Z+ are Rl in the general formula (1)
It is synonymous with X and Z. Magenta coupler represented by the general formula (II) ~ [■]
Among these, particularly preferred ones are represented by general formula (II)
It is a magenta coupler. In addition, the substituents on the heterocycle in general formulas (1) to [■]
For that matter, in the general formula [■], R is also the general
In formulas (n) to [■], R. It is preferable and more preferable that the condition 1 is satisfied below.
is a case where the following conditions 1 and 2 are satisfied, and is particularly preferable.
In this case, 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 is bonded to the carbon atom
, or not bonded at all. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.
This is the case. Most preferred as substituents R and R on the heterocycle
is represented by the following general formula (IX). General formula (IX) e ■ R+oC- In the formula, Re, R+o and RII are hydrogen atoms and halo, respectively.
Gen atom, alkyl group, cycloalkyl group, alkenyl
group, cycloalkenyl group, alkynyl group, aryl group,
Heterocyclic group, acyl group, sulfonyl group, sulfinyl group
, phosphonyl group, carbamoyl group, sulfamoyl group,
Cyano group, spiro compound residue, bridged hydrocarbon compound residue
, alkoxy group, achnoloxy group, peterocyclic oxy
group, siloxy group, acyloxy group, carbamoyloxy
group, amino group, acylamino group, sulfonamide group,
Mido group, ureido group, sulfamoylamino group, alkoxy
oxycarbonylamino group, aryloxycarbonylamino group
Mino group, alkoxycarbonyl group, aryloxycal group
Bonyl group, alkylthio group, arylthio group, heterocycle
represents a thio group, and at least RIIIRIG and RII
Two are not hydrogen atoms. Also, two of the above Rs, R+o and RII, for example R6
and RIG are bonded to form a saturated or unsaturated ring (e.g. cyclo
alkanes, cycloalkenes, heterocycles).
Furthermore, R1 is bonded to the ring to form a bridged hydrocarbon compound residue.
may be configured. The group represented by R8-R11 may have a substituent
, Specific examples of the group represented by R8-R1 and the group having
As optional substituents, in the above general formula (I),
Specific examples of the group represented by R and substituents are listed. Also, for example, a ring formed by bonding R, and RIG, and R,
-Bridged hydrocarbon compound residue formed by R11
Examples of compounds and substituents that they may have include the above-mentioned general
cycloalkyl, cycloalkyl represented by R in formula CI)
Specific examples of bridged hydrocarbon compound residues with kenyl and heterocyclic groups
and its substituents. Among the general formulas (IX), (i) Re-R
When two of 11 are alkyl groups, (ii) Rs to R
One of II, for example Rol, is a hydrogen atom, and the other
Two R9 and RIG combine to form a cyclo with the root carbon atom.
When forming an alkyl, Furthermore, among (i), preferred are R9-R11.
Two are alkyl groups and the other one is a hydrogen atom or
is for an alkyl group. Here, the alkyl and cycloalkyl further have a substituent.
The alkyl, the cycloalkyl and their substitutions may be
As a specific example of the group, R in the above general formula (I) represents
Specific examples of alkyl, cycloalkyl and their substituents are listed.
can be lost. In the following margins, the ring formed by Z in the general formula CI) and the
Even if the ring formed by Zl in the general formula [■] has
Good substituents and R in general formulas (n) to (VI)
As 1-R8, those represented by the following general formula (X) are preferred.
Delicious. General formula (X) -R'-So! -R", where R1 is alkylene, R" is alkyl, cycloal
Represents kill or aryl. The alkylene represented by R1 is preferably a straight chain carbon
The number is 2 or more, more preferably 3 to 6, and the linear
Regardless of branching. Also, this alkylene has a substituent
Good too. Examples of the substituent include R in the general formula CI) described above.
is an alkyl group, a substituent that the alkyl group may have
The following can be mentioned. Preferred substituents include phenyl.
Ru. Preferred specific examples of alkylene represented by R1 are shown below.
show. <HxCfbCHt-9"'CHCHtCHt-,"C
lICl1. CHy-, “CLCLCTOCIl,”
C, Il, C, If
,. <HxCH2C, -cHxCLCH2CH2-1'C
HrCIltCHzCH-. The alkyl group represented by lI R3 may be linear or monobranched. Specifically, methyl, ethyl, propyl, 1so-propyl
butyl, 2-ethylhexyl, octyl, dodecyl
, tetradecyl, hexadecyl, octadacil, to 2-
Examples include xyldecyl. The cycloalkyl group represented by R1 includes a 5- to 6-membered cycloalkyl group.
is preferred, such as cyclohexyl. Alkyl and cycloalkyl represented by R3 have a substituent.
For example, the substituent to R1 described above and
The following are examples. Specifically, the aryl represented by R2 is phenyl.
, naphthyl. The aryl group has a substituent
It's okay. Examples of the substituent include linear or branched atom groups.
In addition to Rkyl, those exemplified as substituents for R1 mentioned above
can be mentioned. In addition, if there are two or more substituents, those substituents must be the same.
They may be the same or different. Among the compounds represented by the general formula CI), particularly preferred are
is represented by the following general formula (XI). General formula (XI) In the formula, R and X have the same meanings as R and X in general formula (1).
Rl, R! is R1°R1 in general formula (X)
is synonymous with Margin C, lI below. c,ns tzlhs C,lI! I C2111 Below margin 2H5 C, US I HICB1 ctolltt ttnzs CJ@ctzllti Below margin C2H. 2H5 CaH+y(t) yl14 Cs1Ly(1 C,ll. C,l1% OCJ+t C1l. C1+. ■ C1HI. C76 Below margin C,H-kotlls tL 0CIlhCONIICIhC1hOCHiC11tUC,lIUC,H@C![l . lll5 C,U= C!IItsuC,R. CI!. Below margin tHs c, n. C,H. 12H25 5llti Below margin I11 OC!a. NIISOtCtsllll! CII= Call+t(L) CaH+t(L) 1ls ll5 cH3C0lI+, (1) CH3CJ++(t) ■ C1l.
sN -N N Ca1ls C8゜)□ N -N -8N
-N -N NN□Ryu N N NH Shiyama cII
, N −N Ni1N N
811 C, 8% C21I! cu (,H. Between NN □ N N NH N -N NH N N NH NH@ N -N -N C1l+21 ” ”
"N -N -N C, 8% (, H, N N
Michal Society, Barkinye (Journal
of the Chemical 5ociety,
Perkinl) (1977), 2047-2
052, U.S. Patent No. 3,725,067, Japanese Patent Application Publication No. 1983-
Referring to No. 99437 and Japanese Unexamined Patent Publication No. 58-42045, etc.
The synthesis was performed using The couplers of the invention are usually 1X1 per mole of silver halide.
0' mole to 1 mole preferably 1X10°2 mole to 8
It can be used in a range of ×10 mol. Moreover, the coupler of the present invention is different from other types of magenta couplers.
They can also be used together. Further, the silver halide photographic light-sensitive material according to the present invention can be used in a multicolor manner.
- When used as a photographic light-sensitive material, the method of the present invention
In addition to pullers, there are yellow couplers and seals commonly used in this industry.
The uncoupler can be used in normal usage. Ma
In addition, colored couplers have the effect of color correction if necessary.
, or a coupler that releases a development inhibitor during development.
- (DIR coupler) may also be used. The coupler above is
, in the same layer to satisfy the characteristics required for photosensitive materials.
Two or more types can be used together, or the same compound can be used in combination with R
It can also be added to two or more layers. Cyan coupler and yellow coupler used in the present invention
- are phenolic or naphthol, respectively.
cyan couplers and acylacetamide or base couplers.
An zoylmethane yellow coupler is used. These yellow couplers include, for example, US Pat.
, No. 778,658, No. 2,875,057, No. 2,
908.573, 3,227,155, 3
, No. 227,550, No. 3.253,924, No. 3
, No. 265,506, No. 3,277.155, No. 3
, No. 341,331, No. 3,369,895, No. 3,
No. 384,657, No. 3,408.194, No. 3,4
No. 15,652, No. 3,447.928, No. 3,55
No. 1,155, No. 3,582,322, No. 3.725
, No. 072, No. 3,894,875, etc., German Patent Publication
lj11,547,868, lj2,057,941
, No. 2,162,899, No. 2,163,812,
2,218,461@, 2,219.917, 2,218,461@, 2,219.917,
No. 2,261,361, No. 2,263,875, Special Publication
No. 49-13576, JP-A No. 48-29432, same
No. 48-86834, No. 49-10736, No. 49-
122335@, Nos. 50-28 & 34 and No. 50-1
It is described in No. 32926, etc. As a cyan coupler, for example, U.S. Patent No. 2.369
, No. 929, No. 2,423,730, No. 2,43
No. 4,272, No. 2,474,293, No. 2,698
, No. 794, No. 2,706.684, No. 2,772,
No. 162, No. 2,801,171, No. 2,895.8
No. 26, No. 2,908,573, No. 3,034,
No. 892, No. 3.046, 129, No. 3,227,
No. 550, No. 3,253,294, No. 3,311,
No. 476, No. 3,386,301, No. 3,419,3
No. 90, No. 3,458,315, No. 3,476.56
No. 3, No. 3,516.831, No. 3,560,212
No. 3,582,322, No. 3,583,971
, No. 3,591,383, No. 3,619,198,
3,632,347%, 3,652,286, 3,652,286,
No. 3,737,326, No. 3,758,308, No. 3
, 779,763%, No. 3,839.044, No. 3,
No. 880,661, German Patent Publication 2,163.811
No. 2,207,468, Special Publication No. 39-27563
No. 45-28836, JP-A No. 47-37425
, No. 50-10135, No. 50-25228, No. 50-25228, No. 50-10135, No. 50-25228, No.
No. 50-112038, No. 50-117422, No. 50-117422, No.
No. 5G-130441, No. 53-109630, No. 5
B-65134, No. 56-99341 and research
・Disclosure (Research D 1scl
osure ) 14,853 (197B) etc.
has been done. The metal complex according to the present invention has - quenching rate constant of doublet oxygen
is a metal complex of 3×107 M −5ea or more
. Above - The quenching rate constant of heavyt oxygen is given in the Journal of Fluid Oxygen.
Physical Chemistry (Journal of Ph.
(chemical chemistry) 83. 591
(1979) etc., photobleaching of rubrene was performed.
Determined by the method of measurement. i.e. chloroform solution of rubrene and
isoenergetic in a chloroform solution containing the compound to be measured.
Irradiate with ghee light. The initial concentration of luprene at this time is [R], and the compound to be measured is
The concentration of the substance is [Q], and the rubrene solution after the test is
Let the concentration of Brene be [R]F, and the luprene and the
The concentration of rubrene in the mixed solution of the test compound is [R]:
Then, the quenching rate constant (ka) of deuterated acid is calculated by: The metal complex according to the present invention has a singlet oxygen defined by the above formula.
The quenching rate constant of 3 × 10 M-sec”?
-1-1 or more, preferably lX10 M -5ea
This is a compound that has a quenching rate constant of the above. Also, metal complexes
The central metal of the body is preferably a transition metal, more preferably a transition metal.
Preferably, Fe, Go, Ni, and Pd. each metal atom of pt, particularly preferably N+ metal atom
It is a child. The quenching rate constant of singlet oxygen according to the present invention is 3×10
M-5ea IJ, the above metal complexes are as follows:
Those represented by general formulas [XII] to [XV] are preferred
. Below are the margins General formula [XI[] General formula [XI[[] O ↓ General formula [XIV] [General formula [Xn], General formula [XI] and General formula [Xr
V], M represents a metal atom. X and X are an oxygen atom, a sulfur atom or
is -NR (R is a hydrogen atom, an alkyl group, an aryl group or
represents a hydroxyl group). X is hydroxy
Represents a syl group or a mercapto group. Y is an oxygen atom or
or represents a sulfur atom. R, R, R and R are that
hydrogen atom, halogen atom, cyano group or directly
or an alkyl bonded to a carbon atom via a divalent linking group
group, aryl group, cycloalkyl group or heterocyclic group
represent. Also, the combination of R3 and R4 and R5 and R is small.
at least one with carbon atoms connected and bonded to each other
A 5- or 6-membered ring may be formed. zo represents a compound capable of coordinating with M or a residue thereof
vinegar. Below is the general formula [XV] [In the formula, R21N R)2, R3 and R24 are respectively
Hydrogen atom, halogen atom, hydroxy group, cyano group or
directly or indirectly through a divalent linking group
Alkyl groups, aryl groups, and cylindrical groups bonded to carbon atoms on the ring.
Represents a chloroalkyl group or a heterocyclic group. Also R2/
and R,12, R2□doR)3 or R1□ and R,4
They may be combined with each other to form a 6-membered ring. No. 82 represents a hydrogen atom, an alkyl group or an aryl group.
Was. A is a hydrogen atom, an alkyl group, an aryl group, or a hydrogen atom
Represents a roxy group. M represents a metal atom. ] The general formula [XI[], the general formula [XI[] and the general formula [
XIV], X' and X2 may be the same or different.
Good, but oxygen atom, sulfur atom or -NR7
-(R7 is a hydrogen atom, an alkyl group (e.g. methyl group,
thyl group, n-propyl group, 1-propyl group, n-butyl group
group, t-butyl group, l-butyl group, benzyl group, etc.), a
lyl group (e.g. phenyl group, tolyl group, naphthyl group, etc.)
) or represents a hydroxyl group. ), preferably
is an oxygen atom or a sulfur atom, more preferably
It is an oxygen atom. X in the general formula [XrV] is a hydroxyl group or a mer
represents a capto group, preferably a hydroxyl group
. General formula [XII], general formula [XI [[] and general formula [
XIV] 'l, (in general formula [XrV], T is 2 pieces
(Y present may be the same or different) Oxygen
represents a sulfur atom or a sulfur atom, preferably a sulfur atom
It is a child. General formula [X■], general formula [XlIr] and general formula [X
IV] (F) R3, R', R' O, J:tFR'
may be the same or different, and hydrogen atoms
child, halogen atom (fluorine, chlorine, bromine, iodine), sia
- group, direct or divalent linking group [e.g. -〇-17'- -S-1-NH-1-NR, (R'' is a hydroxyl group,
Alkyl groups (e.g. methyl, ethyl, n-propyl)
group, 1-propyl group, n-butyl group, t-butyl group, 1
-butyl group, etc.), aryl group (e.g. phenyl group, tri-butyl group, etc.),
Represents a monovalent group such as a hydroxyl group, a naphthyl group, etc. ), -0
CO-1-CO-1-NHCO-1-CONH-1-C
OO-1-8O2NH-1-NH8O2-1-8O2-
alkyl W bonded to the carbon atom (e.g.
Tyl group, ethyl group, propyl group, butyl group, hexyl group
, octyl group, dodecyl group, hexadecyl group, etc.
These alkyl groups may be straight chain alkyl groups or branched alkyl groups.
It may also be a kill group. ), aryl group (e.g. phenyl group,
naphthyl group, etc.), cycloalkyl group (e.g. cyclopene), cycloalkyl group (e.g. cyclopene),
methyl group, cyclohexyl group) or heterocyclic group (e.g.
Pyridyl group, imidazolyl group, furyl group, chenyl group,
Pyrrolyl group, pyrrolidinyl group, quinolyl group, morpholinyl group
(e.g.). Among these, via a divalent linking group
Alkyl group, a, aryl group, cyclyl group bonded to a carbon atom
A loalkyl group or a heterocyclic group together with the divalent linking group
The group to be formed includes, for example, an alkoxy group (for example, meth)
Oxy group, ethoxy group, n-butyloxy group, octyloxy group
linear or branched alkyloxy groups such as xy groups),
Koxycarbonyl group (e.g. methoxycarbonyl group,
Toxycarbonyl group, n-hexadecyloxycarbonyl group
Straight chain or branched alkyloxycarbonyl groups such as
), alkylcarbonyl M (e.g. acetyl group, valeryl group),
Straight chain or branched alkyl groups such as
carbonyl group), arylcarbonyl group (e.g. benzoyl group), arylcarbonyl group (e.g. benzoyl group),
), alkylamino! I (e.g. N-n-butyl
Amino group, N, N-di-n-butylamino group, N, N-
Straight chain or branched alkyl groups such as di-n-octylamino group
Ruamino 1, alkylcarbamoyl group (e.g. n-butyl
carbamoyl group, n-dodecylcarbamoyl group, etc.
chain or branched alkylcarbamoyl group), alkyl group
rufamoyl group (e.g. n-butylsulfamoyl group,
Straight chain or branched atom such as n-dodecylsulfamoyl group
(rukylsulfamoyl group), alkylacylamino group (
For example, acetylamino group, valmitoylamino group, etc.
chain or branched fulkylcarbonylamino group), aryl
ruoxy group (e.g. phenoxy group, naphthoxy group, etc.),
Aryloxycarbonyl group (e.g. phenoxycarbo
nyl group, naphthoxycarbonyl group, etc.), aryl 7mino
groups (e.g. N-phenylamino group, N-phenyl-N-
methylamino group, etc.), arylcarbamoyl group (e.g.
phenylcarbamoyl group, etc.), arylsulfamoyl
group (e.g. phenylsulfamoyl group, etc.), aryl group
Examples include cylamino groups (e.g. benzoylamino groups, etc.).
can be given. Also, general formula [XIr], general formula [XIII] #yohi3
+ R, R, R and R' in general formula [XIV] are R3 and R
4 and at least one of the combinations of R' and R6 are mutually
A 5- or 6-membered ring with connected carbon atoms
may be formed. In this case, R3 and R and R5 and R'
' at least one of the combinations is connected and combined with each other.
As a 5- or 6-membered ring formed with a carbon atom,
, e.g. cyclopentene ring, cyclohexene ring, benzene ring
(However, this benzene ring has a fused benzene ring, i.e.
For example, naphthalene ring, anthracene ring), etc.
hydrocarbon ring with at least one unsaturated bond, hetero
rings (e.g. nitrogen-containing 5- or 6-membered heterocycles), etc.
It will be done. These 5-membered or 6JI rings have substituents
In this case, this substituent is, for example, a halogen atom (fluorine atom).
chlorine, bromine, iodine), cyano group, alkyl group (e.g.
Methyl group, ethyl group, n-propyl group, n-butyl group
, n-octyl group, t-octyl group, n-hexadecyl
Straight chain or branched alkyl groups having 1 to 20 carbon atoms, etc.
), aryl groups (e.g. phenyl group, naphthyl group, etc.)
), alkoxy groups (e.g. methoxy group, n-butoxy group)
, straight chain or branched fulkyloxy such as t-butoxy group
group), aryloxy group (e.g. phenoxy group, etc.), a
Rukoxycarbonyl Jl (e.g. n-pentyloxycarbonyl
carbonyl group, t-pentyloxycarbonyl group, n-o
Cutyloxycarbonyl group, t-octyloxycarbo
Straight chain or branched alkyloxycarbonyl such as nyl group
group), aryloxycarbonyl group (e.g. phenoxy
carbonyl group, etc.), acyl group (e.g. acetyl group,
Straight chain or branched alkylcarbonyl groups such as aroyl groups
etc.), acylamino groups (e.g., straight chain such as acetamide groups)
or branched alkylcarbonylamino group, benzoyl
7-aryl carbonylamino group such as amino group), aryl
Amino group (e.g. N-phenylamino group, etc.), alkyl
Amino groups (e.g. N-n-butylamino group, N,N-di
Straight chain or branched alkylamino groups such as ethylamino groups
), carbamoyl group (e.g. n-butylcarbamoyl group)
linear or branched alkylcarbamoyl groups, etc.),
rufamoyl group (e.g. N,N-di-n-butylsulf
Amoyl group, N-n-dodecylsulfamoyl group, etc.
chain or branched alkylsulfamoyl group, etc.), sulfonate
amide groups (e.g. straight chain methylsulfonylamino groups)
or branched alkylsulfonylamino group, phenyl group
Arylsulfonylamino groups such as sulfonylamino groups),
Sulfonyl groups (e.g. straight chain or branched alkyl groups such as mesyl groups)
7-arylsulfonyl group such as a rkylsulfonyl group and a tosyl group
group), cycloalkyl group (e.g. cyclohexyl group, etc.)
etc. can be mentioned. General formula [XII], general formula [XI[] and general formula [X
IV] preferably represents R, R4, R5'' and R.
an alkyl group, an aryl group, or R3 and R and R'
At least one of the combinations of R6 is connected and bonded to each other.
When forming a 5- or 6-membered ring with a carbon atom
More preferably, R3, R4 and
and the combinations of R' and R' are connected to each other and combined.
a 6-membered ring, particularly preferably a benzene ring
This is the case when forming . Also, general formula [Xπ], general formula [XIII] and -general formula
M in [XIV] represents a metal atom, preferably a transition
Metal atoms, more preferably nickel atoms, copper atoms,
Iron atoms, cobalt atoms, palladium atoms, platinum atoms.
most preferably a nickel atom. Can be coordinated with M represented by 2 in the general formula [XI[[]
The compound preferably has a straight or branched alkyl group.
particularly preferably an alkylamine having an alkyl
The total number of carbon atoms in the group is 2 to 36, and even 3 to 24.
is a dialkylamine, a trialkylamine,
Specific examples of these include butylamine and octylamine.
(e.g. t-octylamine), dodecylamine (e.g.
(ban-dodecylamine), hexadecylamine, octane
Monoalkylamines such as Tatouramine, diethylamine
dibutylamine, dioctylamine, didodecylar
diamine, jetanolamine, jetanolamine, etc.
Alkylamines, and triethylamines, tributyl
amine, trioctylamine, triethanolamine,
Tributanolamine, trioctatoolamine, etc.
Realkylamines and the like can be mentioned. General formula [XII], general formula [XIII] and general formula [
) NV] More preferable metal complexes according to the present invention are represented by
The potato has the following general formula [XI[a], general formula [XI[[
a] and a metal complex represented by the general formula [XIVa]
be. General formula [X[a] General formula [XIIIa] O ↓ General formula [XIVa] General formula [XIIa], general formula [XIl[a] and
In the general formula [XIva], M, X', X'',
X'Y and Zo each have the same meanings as above. General formula [XIIa], General formula [XI[[a]o]
Yohi General Formula XIVa] 1cc15iT, R11, R
12, R13, and 1t-R are each an alkyl group (e.g., methyl group, ethyl group,
n-propyl group, n-butyl group, n-octyl group, t-
1 to 2 carbon atoms such as octyl group and n-hexadecyl group
0 straight-chain or branched alkyl groups), aryl groups (e.g.
(e.g. phenyl group, naphthyl group, etc.), alkoxy group (e.g.
For example, methoxy group, n-butoxy group, t-butoxy group, etc.
chain or branched alkyloxy group), aryloxy group
(e.g. phenoxy group etc.), alkoxycarbonyl wb
<For example, n-pentyloxycarbonyl group, t-pentyl group
oxycarbonyl group, n-octyloxycarbonyl group
group, straight chain or branched t-octyloxycarbonyl group, etc.
alkyloxycarbonyl group), aryloxycarbonyl group)
carbonyl group (e.g. phenoxycarbonyl group, etc.), acyl
group (e.g. straight chain or acetyl group, stearoyl group, etc.)
is a branched alkylcarbonyl group, etc.), acylamino group (
For example, a straight or branched alkyl group such as an acetamide group.
Alkyl groups such as rubonylamino group and benzoylamino group
Rubonylamim 1, arylamino group (e.g. N-phenylamino group)
nylamino group), alkylamino group (e.g. N-n-
Straight chain or butylamino group, N, N-diethylamino group, etc.
or branched alkylamino group), carbamoyl group (e.g.
Straight chain or branched alkali such as n-butylcarbamoyl group
carbamoyl group, etc.), sulfamoyl group (e.g. N
, N-di-n-butylsulfamoyl group, N-n-dode
Straight chain or branched furucyl group such as silsulfamoyl group
rufamoyl group, etc.), sulfonamide group (such as methyl
Straight chain or branched alkyl sulfonyl groups such as sulfonylamino groups
Ants such as honylamino group, phenylsulfonylamino group, etc.
sulfonylamino group), sulfonyl group (e.g.
linear or branched alkylsulfonyl groups such as
7-arylsulfonyl group such as
Represents a group (for example, a cyclohexyl group). Teng and n
each represents an integer from O to 4. General formula [XIIa], [XI[[a], [XIVa]
] Among these, more preferable compounds have the general formula [XIIIa ]
This is a compound represented by Represented by the general formula [Xl1ra]
The most preferable compound among the compounds represented by the formula % is the compound having the general formula [XII[b]IcOTM,
Y. R'', R'', I, and n are the same as above, and R'',
R'' and R'7 are hydrogen atoms, alkyl groups (e.g. butyl
aryl group, octyl group, stearyl group, etc.) or aryl group
Represents a group (for example, phenyl group, naphthyl group, etc.). However, at least one of R, R, R"'
Two represent an alkyl group or an aryl group. Said general formula [XV]l:t+ite, R211Rt*
t The halogen atoms represented by R23 and R24 are
Examples include elementary atom, chlorine atom, bromine atom, and iodine atom. Rt+t R22t A represented by R23 and R24
The alkyl group preferably has 1 to 19 carbon atoms.
group, either a straight-chain alkyl group or a branched alkyl group.
may exist, and may have a substituent. ky Aryl represented by R2□, R2, and R24
The group is preferably a 7-aryl group having 6 to 14 carbon atoms.
Yes, and may have a substituent. Heterocycle represented by Rz+*R2□, R23 and Rt4
The group is preferably a 5-membered or 6-membered ring, with substituents
May have. R21t R22t The series represented by R23 and R24
The chloroalkyl group is preferably a 5-membered ring group or a 6-membered ring group.
Yes, and may have a substituent. 6 shells formed by combining R21 and R2□, etc.
can be mentioned. R2□ and R2 or R23 and R24 are bonded to each other
The 6-membered ring formed is preferably a benzene ring.
This benzene ring may have a substituent, and the benzene ring may have a substituent.
It may be something that has been done. Rx + + R22t Represented by R23 and R24
Examples of the alkyl group include methyl group and ethyl group.
, propyl group, butyl group, t-butyl group, hexyl group,
Octyl group, decyl group, dodecyl group, tetradecyl group,
Examples include hexadecyl group and octadecyl group.
. RlIt R22t R2! and a represented by R24
Examples of the lyl group include phenyl group and naphthyl group.
can be given. R21t R22f Complex represented by R and R24
The cyclic group preferably contains at least one heteroatom in the ring.
also contains one nitrogen atom, oxygen atom or sulfur atom
A 5- to 6-membered heterocyclic group, such as a 7lyl group,
Hydro7lyl group, chenyl group, pyrazolyl group, pyrrolidi
group, pyridyl group, imidazolyl group, pyrazolyl group,
Noryl group, indolyl group, oxacylyl group, thiazolyl group
You can list the basics etc. R2 eyes R22? cyclo represented by R23 and R24
Examples of alkyl groups include cyclopentyl group, cyclopentyl group,
Chlorhexyl group, cyclohexenyl group, cyclohexano
Examples include enyl groups. Rz+* R2z* 'R23 and R24 are connected to each other.
The 6-membered ring formed by combining is, for example, a benzene ring.
, naphthalene ring, isobenzothiophene ring, isobenzo
Examples include furan ring and isointone ring. The above kt R2□, R23 and R24 are
alkyl group, cycloalkyl group, aryl group or double chain′
The gA group is a divalent linking group, for example, an okyne group (-0-)
, thio group (-s-), ami7 group, oxycarbonyl group,
carbonyl group, carbamoyl group, sulf77 moyl group, carbonyl group, carbamoyl group,
7 rubonylamide groups, 7 sulfonylamide groups, sulfonyl group
or on the benzene ring via a carbonyloxy group, etc.
may be bonded to a carbon atom in which a preferred group is present.
There are some things. Alkyl represented by R2,, R2□, R, and R24
The carbon group on the benzene ring via the above divalent linking group.
Examples of bonds to atoms include alkoxy groups (and
For example, methoxy, ethoxy, butoxy, propoxy
cy group, 2-ethylhexyl oligooxy group, n-decyloxy
group, n-dodecyloxy group, or n-hexadecyloxy group
xy group), alkoxycarbonyl group (e.g. meth),
Oxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group
carbonyl group, n-decyloxycarbonyl group or n-
(hexadecyloxycarbonyl group, etc.), acyl group (such as hexadecyloxycarbonyl group),
For example, acetyl group, valeryl group, stearoyl group,
(e.g., toluoyl or toluoyl groups)
groups (e.g. acetoxy or hexadecyl carbonyl)
(e.g., n-
Butylamino M, N, N-diethylamide 7 groups or N,
N-didecylamine 7 groups, etc.), alkylcarbamoyl group
(For example, butyl carbamoyl group, N, N-y ethyl
Carbamoyl group or n-dodecylcarbamoyl group
etc.), alkylsul77 moyl group (e.g., butylsul),
77 moyl group, N,N-diethylsul 77 moyl group,
or n-dodecylsulf77 moyl group), sulfonyl
Amino groups (for example, methylsulfonyl amine 7 groups, or
(butylsulfonyl amine 7 groups, etc.), sulfonyl groups (such as
for example, mesyl group or ethanesulfonyl group),
or acylamide 7 groups (e.g., acetylamide 7 groups,
Valeryl 7mi7 group, valmitoylamino group, benzoyl
amino group or toluoyl amino group), etc.
be able to. R2+t Rz2t The system represented by Rts and R24
The chloroalkyl group connects to the carbon on the ring via the above divalent linking group.
An example of bonding to an elementary atom is cyclohexyloxy
cy group, cyclohexylcarbonyl group, cyclohexyl group
oxycarbonyl group, cyclohexyl 7tano
Number 7 nyl 6 ruzenyl calculation infrared is cyclohexenyloxy group
I can give you things like. Itt+t R2! t Represented by R23 and R24
An aryl group connects to a carbon atom on the ring via the above divalent linking group.
An example of a bond to a child is an aryloxy group (and
(e.g., phenoxy group or 7-toxy group), aryl
phenoxycarbonyl group (for example, phenoxycarbonyl group)
ole group or 7-toxycarbonyl group), acyl group (
For example, benzoyl group or 7toyl group),
nilino group (e.g. phenylamino group, N-methylae
ary group or N-7 cetylanily7 group), acyl
Oxy groups (e.g. benzoyloxy or toluo)
yloxy group), arylcarbamoyl group (such as
phenylcarbamoyl group, etc.), arylsulfamo
yl group (for example, phenylsul 77 moyl group, etc.), a
arylsulfonylamino group (e.g. 7enylsulfonate)
nylamino group, p-)'J sulfonyl amine 7 group, etc.)
, arylsulfonyl group (e.g., benzenesulfonyl group)
(e.g., tosyl group, tosyl group), or acylami-7 group (e.g.,
examples include benzoylamino groups). Represented by R, , R, 2, R, and R24 above
Alkyl group, aryl group, heterocyclic group, cycloalkyl group
Or R21 and R2□, RZZ and R13 or R23
The 6-membered ring formed by combining and R24 with each other is a halo
Gen atoms (e.g. chlorine, bromine or fluorine atoms)
), sia7 group, alkyl group (for example, methyl group,
Ethyl group, i-propyl group, butyl group, hexyl group,
cutyl group, decyl group, dodecyl group, tetradecyl group,
xadecyl group, heptadecyl group, octadecyl group, and
(methoxyethoxyethyl group, etc.), aryl group (such as methoxyethoxyethyl group),
For example, phenyl group, tolyl group, naphthyl group, chloro7
Nyl group, methoxyphenyl group or acetylphenyl group
), alkoxy groups (e.g., methoxy, ethoxy),
cy group, butoxy group, propoxy group or methoxyethoxy group
), aryloxy group (such as phenoxy group), aryloxy group (such as phenoxy group),
, triloxy group, naphthoxy group or methoxyphenoxy group
cy group), alkoxycarbonyl group (e.g. methoxycarbonyl group),
oxycarbonyl group, butoxycarbonyl group or phenol group
(oximethoxycarbonyl group, etc.), 7-aryloxycarpo
Nyl group (e.g., phenoxycarbonyl group, triloyl group)
Cycarbonyl group or methoxyphenoxycarbonyl group
), acyl groups (e.g., formyl group, acetyl group),
, valeryl group, stearoyl group, benzoyl group, toluo group
yl group, naphthoyl group or p-nodoxybenzoyl group
), acyloxy groups (e.g., acetoxy groups or
(such as acyloxy group), acylamino group (such as
Acetamide group, benzamide group, or methoxyacetyl group
(e.g. toamide group), anilino group (e.g. phenyl atom),
Mino group, N-methylanilino group, N-phenylamino group
, or N-7 cetyl 7 dilino group, etc.), alkylamino
group (e.g. n-butylami7 group, N,N-noethyl
ami7 group, 4-methoxy-n-butylamino group, etc.),
Carbamoyl group (e.g. n-butylcarbamoyl group)
, N, N-diethylcarbamoyl group, n-butylsulfur
amoyl group, N,N-diethylsulfamoyl group, n-
dodecylsulfamoyl group, or N-(4-methoxy
-n-butyl) sulf77 moyl group, etc.), sulfonyla
7 groups (e.g., methylsulfonyl 7 groups, phenyl 7 groups,
Rusulfonyl 7mi7 group, or methoxymethylsulfonyl
7 groups), or sulfonyl groups (such as
Syl group, tosyl group or methoxymethanesulfonyl group
etc.) may be substituted. The alkyl group represented by R21 and A has a substituent.
moyo(, can be either straight chain or branched.
These alkyl groups, excluding the carbon atoms in the substituent moieties, are
Preferably, it is an alkyl group having 1 to 20 carbon atoms, and
For example, methyl group, ethyl group, propyl group, butyl group,
xyl group, octyl group, decyl group, dodecyl group, tetra
Decyl group, hexadecyl group, heptadecyl group or octyl group
Examples include tadecyl group. R2 and A″Ch represent a substituent.
may have, and excluding carbon atoms in the substituent moiety, preferably
is a 7-aryl group having 6 to 14 carbon atoms, for example,
, phenyl group, tolyl group or s7tyl group, etc.
be able to. Also, two ligands are linked via A.
You can leave it there. In the formula, M represents a metal atom. Preferably a transition metal atom
be. More preferably Cut Ca2 N1yPd,
Fet! or pt, particularly preferably Ni
. A preferred group for A is a hydroxy group. In addition, among the complexes represented by the above general formula (XV),
, those preferably used include those in which R21 is an oxy group or a thio group.
group, alkyl group via carbonyl group, cycloalkyl
group, aryl group or heterocyclic group, hydroxy group or 7
7 elements, represented by R22, R2, * or RX<
At least one of the groups is a hydrogen atom, a hydroxy group, or an alkyl group.
or alkoxy group. Even more preferable among them
A type of potato is one in which R=s is a hydrogen atom, and the Rz
RzztThe number of carbon atoms in the group represented by R23 or R24
A complex whose total number is at least 4 or more. Specific examples of the metal complexes according to the present invention are shown below.
The invention is not limited to these compounds. Below are the blank examples of metal complexes H (4) NHzCsHly (su↓ H (6) NH2CIIH1?↓ (7) NH2C1zHz@↓ (8) NHzCtsHsy↓ C5Htdt) C5Hty (t) (10) NH
2C8 Akira,) ↓ (12) NH@H17(t) ↓ NH(C4H110H)2 ↓ C5H1y(t) C5Ht(14) N(C4HsOH)s↓ C5Hsdli Cs111t(su(17) NH(C4H11) 2
↓ -Ni-0 (18) N) ((.4Ha)2↓ 0-N1-0 (19) N(C2)1s)s↓ C3H1 Paris 0 company (ty(t) (21) 02H5 H-N- csH, Tae (29) NH (C8H17)・■ SaH3 CtJNtlCsHlt(+soJ (g2)
(96) (11B)
(122) Metal complexes represented by the above general formulas [XII] to [XIV] in the following margins
The body is British patent 858490@, German patent application publication 2
, 042, 652jJ, etc.
can be achieved. The metal complex represented by the above general formula IXV] is
- Cox, F. Double Pinkard, Double W.
Draw and G.C. Webster, Journal
・Op Chemical Society (E, G, Cox
, F.W., Pinkard, W. Wa-rdlaw and K., C., Webste.
r, J, Chew. Soc, , ) 1935. Listed in 459
It can be synthesized by the following method. The gold a complex according to the present invention is characterized by the type of gold III body used.
It also depends on the type of coupler used, but in general
Ne201Q/12 to 500mg/Fake 2 coating
Preferably used in cloth weight, 50ag/va27
') It is used at a coating amount of up to 3001g/lR2.
Even more preferred. The metal complex according to the present invention can be prepared using the oil-in-water FiII type dispersion method.
The color of silver halide photographic light-sensitive materials is
in the puller-doped layer and/or the layer adjacent to the coupler-doped layer.
However, the metal complexes according to the present invention are coupler-added.
It is preferable to add it to the same layer. Furthermore, Kap
It is preferable to add it to the same oil droplet as the oil. Furthermore, in JP-A No. 55-93150, copper phthalo
Although cyanine-based compounds are cited, these compounds
The product is used in a very small amount to adjust the whiteness of the white part.
Yes, the gold according to the present invention is used for dye image fastening.
The genus complexes have physical properties (quenching rate constant of singlet oxygen),
They have completely different usage amounts, usage methods, and purposes. The oil-soluble dye according to the present invention refers to a dye that dissolves in water at 20°C.
Degree [0/1000 of water] (Weight of substance soluble in 100g of water)
refers to organic dyes with a degree of 1×10 or less,
Compounds include anthraquinone compounds, azo compounds, etc.
can be mentioned. The oil-soluble dye according to the present invention has a wavelength of 400 nm or more.
The molecular extinction coefficient of the maximum absorption wavelength is (solvent chloroform)
It is preferably 5,000 or more, and 20,000 or more.
It is even more preferable to The oil-soluble dye according to the present invention has 0. Old -〇／ I”～
Preferably used at a coating weight of 10 B/m2,
is 0.0511)/■ to 5mg/a+
things are more preferable. The oil-soluble dye according to the present invention can be used in any of the photographic emulsion layers.
Can be used, but non-photosensitive layers other than coupler-containing layers
More preferably, it is added to the layer. A particularly preferred method of using the oil-soluble dye according to the present invention is as follows:
The molecular extinction coefficient of the maximum absorption wavelength at a wavelength of 400 nm or more is
, oil-soluble dyes that are more than 20,000
/m” to 51M1” (7) Application amount Tekafura
It is to be contained in a non-photosensitive layer other than the additive layer. Preferred oil-soluble dyes in the present invention include the following general dyes:
It is a compound represented by formula [XVI] or [X■]. Below is the general formula [X[, where R, -R,, are hydrogen atoms and hydroxy atoms, respectively]
represents a group, an amino group, or a halogen atom. General formula ExvIJ In the formula, Rq'''R20 is a hydrogen atom and a halogen atom, respectively.
Atom, nitro group, human oxy group, alkyl group, alkoxy group
cy group, aminocarbonyl group, amino group or -N-N-
represents an R group, where R is an aryl group. Halogen base represented by R1 to R2 of general formula [XVI]
Examples of the child include chlorine atom, bromine atom, etc.
. Furthermore, the amino groups represented by R1 to R3 have a W1 substituent.
The M substituent may be an alkyl group (for example,
methyl group, butyl group, etc.), aryl group (e.g. phenyl group)
groups), acyl groups (e.g. methoxy groups, benzoyl groups, etc.)
) etc. -I[[X■] halogen atom represented by R~R2°
For example, chlorine atom, bromine atom, etc.
Examples of alkyl groups include methyl group, ethyl group, and propylene group.
Examples of alkoxy groups include pyru groups, and examples of alkoxy groups include pyru groups.
Examples include toxy group, ethoxy group, propoxy group, etc.
Examples of the minocarbonyl group include, for example, methylaminocarbonyl group.
Examples thereof include a nyl group, a phenylaminocarbonyl group, and the like. Furthermore, the amino group represented by R9-R20 has the general formula [XV
It may have the same substituents as [ ]. Typical examples of oil-soluble dyes used in the present invention are shown below.
These include, but are not limited to: Exemplary oil-soluble dye ONH. Using a combination of the metal complex and oil-soluble dye according to the present invention
The method to use is singlet #! The elementary quenching rate constant is 3
xlOM -1・sec-1 or more metal complexes 2
ol1g/I to 5001M II (D coating amount
and oil-soluble dye at 0.01 mg/m
It can be used with a coating amount of 10111111/12.
preferable. Furthermore, the quenching rate constant of singlet oxygen is 3X107M-5e
A metal complex of 20s+o/m to 50
Used in the coupler-containing layer at a coating weight of 0.011 J/l.
, and oil-soluble dye from 0.01 FaQ/wear to 10 ■
At a coating weight of g/12, it can be applied to non-photosensitive layers other than coupler-containing layers.
The method used is more preferred. A coupler represented by the general formula [1] used in the present invention
- Dispersion method of metal complex and oil-soluble dye according to the present invention
Methods include so-called alkaline aqueous dispersion method and solid dispersion method.
method, latex dispersion method, oil-in-water emulsion dispersion method, etc.
This method can be used to coupler, metal complex
and can be selected appropriately depending on the chemical structure of the oil-soluble dye.
can. In the present invention, latex dispersion method and oil-in-water emulsification method are used.
The dispersion method is particularly effective. These distribution methods have traditionally been
The latex dispersion method and its effects are well known.
JP-A No. 49-74538@, No. 51-59943, No. 51-59943,
54-32552 publications and Research Discology
-(Research D +sc+osure)
Magazine, August 1916, No. 14850177-79
It is described in. As a suitable latex used in latex dispersion method
For example, sutylene, ethyl acrylate, n-butyl
Acrylate, n-butyl methacrylate, 2-aceto
Acetoxyethyl methacrylate, 2-(methacryloyl)
(oxy)ethyltrimethylammonium methosulfate
3-(methacryloyloxy)propane-1-su
Sulfonic acid sodium salt, N-isopropylacrylamide
do, N-[2-(2-methyl-4-oxypentyl)]
Acrylamide, 2-acrylamide-2-methylpro
heptad homopolymers such as pansulfonic acid,
Mention may be made of copolymers and terpolymers. oil droplet type
As an emulsification dispersion method, hydrophobic additives such as couplers are dispersed.
Conventionally known methods can be applied, and the boiling point is usually about 150.
'C or higher boiling point organic solvent, low boiling point and
and/or a water-soluble organic solvent.
Dissolves soluble dyes, couplers, and hydrophilic buffers such as gelatin.
Homogenize with a stirrer using a surfactant in the inder.
colloid mill, flow jet mixer, ultrasonic equipment
After emulsifying and dispersing using a dispersion method such as a
It may be added to the hydrophilic colloid layer. dispersion or min.
It is also possible to add a step to remove the low boiling point organic solvent at the same time as dispersion.
stomach. The following margins have a high boiling point that can be preferably used in the present invention.
w11s is a compound with a dielectric constant of less than 6.0, which is about the lower limit.
Although there is no particular limitation, if the mwt ratio is 1.9 or more,
preferable. For example, heptatalic acid ester with a dielectric constant of less than 6.0.
esters, phosphoric acid esters, organic acid amides,
These include ketones and hydrocarbon compounds. Further, in the present invention, preferably evaporation at 100°C
A high boiling point organic solvent with an atmospheric pressure of 0.5s+el-1g or less.
Ru. More preferably, phthalate in the high-boiling organic solvent
They are acid esters or phosphoric esters. In addition, there is
The organic solvent may be a mixture of two or more types; in this case,
1 of the mixture! It is sufficient if the electric rate is less than 6.0. still,
The dielectric constant indicates the dielectric constant at 30°C. As a phthalate ester advantageously used in the present invention,
Examples include those represented by the following general formula [X■]
. General formula [X■] In the formula, R30 and R31 each represent an alkyl group
Represents a kenyl group or an aryl group. However, R30 and
The total number of carbon atoms in the groups represented by R and 1 is 9 to 3.
It is 2. More preferably, the total number of carbon atoms is 16
It is 24 to 24. In the present invention, R31) of the general formula [X■] and
The alkyl group represented by R3I can be linear or branched.
For example, butyl group, pentyl group. Hexyl group, heptyl group, octyl group, nonyl group. Decyl group, undecyl group, dodecyl group, tridecyl group,
Tetradecyl group, pentadecyl group, hexadecyl group,
llR? which is a ptadecyl group, an octadecyl group, etc. 6 and
The aryl group represented by and R3 is. For example, phenyl group, naphthyl group, etc., and alkenyl group
For example, hexenyl group, heptenyl group, octadecenyl group
etc. These alkyl groups, alkenyl groups and
and aryl groups have single or multiple substituents.
may be used as a substituent for alkyl and alkenyl groups.
For example, halogen atoms, alkoxy groups, aryl groups
, aryl 1 oxy group, alkenyl group, alkoxy
Carbonyl group etc. are mentioned, and as a substituent of aryl group
is, for example, a halogen atom, an alkyl group, an alkoxy group,
Aryl group, aryloxy group, alkenyl group, alco
Examples include xycarbonyl group. Phosphate esters advantageously used in the present invention
Examples include those represented by the following general formula [XrX]
. General formula [XIX] R,,0-P-OR,. R33 In the formula, R, R and R each represent an alkyl group, an alkenyl group or an aryl group. However, carbon atoms represented by R 1, R and R34
The sum of the numbers is 24-54. General formula [Represented by R3□, R33 and R91F of XIX
Examples of the alkyl group used include butyl group, pentyl group,
Hexyl group, heptyl group, octyl group, nonyl group, decyl group
group, undecyl group, dodecyl group, tridecyl group, tetyl group
Radecyl group, pentadecyl group, hexadecyl group, hepta
These include decyl group, octadecyl group, nonadecyl group, etc. These alkyl, alkenyl and aryl groups are
, may have single or multiple substituents. Like
Or R3□, R, yo and R34 are alkyl groups
, for example, 2-ethylhexyl group, n-octyl group, 3
．． 5.5-trimethylhexyl group, n-nonyl group, rho
Decyl group, 5ea-decyl group, 5eC-dodecyl group, t
-octyl group and the like. The organic solvents preferably used in the present invention are as follows:
An example is shown. Below are examples of organic compounds in the margins: 18 medium C2Hs C2H. I O-Cs H1-(i) 0 CeH+5(n) 0-C,, Il,, (i) ■ 0 C+oH2+(n) Bright silver halide photographic materials can be
can be difilm, color, etc.
, especially when using directly applied color photographic paper.
The effect of water droplets is effectively demonstrated. Halogen photographic materials of the present invention including color photographic paper
The material may be of a single color or of multiple colors. Multicolor halogen
In the case of silver oxide photography, in order to perform subtractive color reproduction,
As a true coupler, magenta, yellow, and ann are available.
A silver halide containing a coupler and a non-photosensitive layer are
It has a structure in which layers are laminated in an appropriate order on a support.
, the order of the layers may be changed as appropriate depending on the important performance and purpose of use.
. When bright silver halide photographic light-sensitive materials are multicolor color materials,
In this case, the specific layer structure is 1, sequentially from the support side.
, yellow dye layer image-forming intermediate layer, magenta dye image-forming layer of the present invention
Layering, interlayer containing absorber, cyan dye image forming layer
, an intermediate layer containing an ultraviolet absorber, and a protective layer.
is particularly preferred. Halogen used in the silver halide photographic material of the present invention
silver halide emulsion (hereinafter referred to as the silver halide emulsion of the present invention)
Silver halides include silver bromide, silver iodobromide, and silver iodochloride.
, silver chlorobromide, and silver chloride.
Any used can be used. Silver halide grains used in the silver halide emulsion of the present invention
The particles can be obtained by either the acidic method, neutral method, or ammonia method.
It may also be something that has been removed. The particles may be grown all at once, or
, seed particles may be produced and then grown. Seed particle
Even if the method of harvesting and the method of growing are the same, they are different.
Also good. The silver halide emulsion of the present invention contains halide ions and silver ions.
Even if they are mixed at the same time, if one is present, the other
You may mix both. In addition, the critical formation of silver halide crystals
Mixing halide ions and silver ions while considering long velocity
Sequentially while controlling l) H, I) AQ in the pot
They may be generated by adding them at the same time. after growth
Change the halogen composition of particles using the conversion method
You can let me. When producing the silver halide emulsion of the present invention, if necessary,
By using a silver halide solvent, silver halide grains can be
Particle size, particle shape, particle size distribution, particle growth
You can control the speed. Silver halide grains used in the silver halide emulsion of the present invention
In the process of particle formation and/or growth,
, cadmium salt, dust lead salt, lead salt, thallium salt, iridium
aluminum salt or complex salt, adium salt or complex salt, iron salt or complex salt,
Add metal ions to the interior of the particles and/or
It can be encapsulated on the surface and create an appropriate reductive atmosphere.
By leaving the particle inside and/or on the particle surface, reduction sensitization can be achieved.
Liquid can be applied. The silver halide emulsion of the present invention is characterized by the growth of silver halide grains.
After the completion of the process, unnecessary soluble salts may be removed or
Otherwise, it may be left as is. When removing the salts,
, those listed in Research Disclosure No. 17643
It can be done according to the law. Silver halide grains used in the silver halide emulsion of the present invention
The child may consist of a uniform layer inside and on the surface,
It may consist of different layers. Silver halide grains used in the silver halide emulsion of the present invention
A particle is a particle whose latent image is mainly formed on the surface.
may be formed mainly inside the particles.
Particles may also be used. Silver halide grains used in the silver halide emulsion of the present invention
The crystals may have regular crystal shapes, spherical or plate shapes.
It may also have an irregular crystal shape such as a shape. these
In a particle, the ratio of (1oo) plane to (111) plane is arbitrary.
You can use whatever you want. Also, it may have a composite form of these crystal forms, and various crystal forms may be used.
Crystalline particles may also be mixed. The silver halide emulsion of the present invention comprises two or more types formed separately.
A mixture of silver halide emulsions may be used. The silver halide emulsion of the present invention is chemically sensitized by a conventional method.
Ru. That is, compounds containing sulfur that can react with silver ions,
Sulfur sensitization method using activated gelatin, using selenium compound
selenium sensitization method using reducing substances, reducing layer sensitization method using reducing substances,
Noble metal sensitization method using other noble metal compounds can be used alone or
can be used in combination. The silver halide emulsion of the present invention is widely used in the photographic industry for sensitization.
Using pigments known as dyes, the desired wavelength range is
Can be optically sensitized. Sensitizing dyes may be used alone, but
, two or more types may be used in combination. sensitizing dye and
dyes that do not themselves have spectral sensitizing properties or
A compound that does not substantially absorb visible light, and is a compound that does not substantially absorb visible light and is a compound that does not absorb visible light.
A supersensitizer that enhances the sensitizing effect may be included in the emulsion.
stomach. The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
Preventing fog during storage or photo processing and/or
During chemical ripening and to maintain stable photographic performance.
and/or at the end of chemical ripening and/or at the end of chemical ripening.
After that, by the time silver halide emulsion was applied, the photographic industry
Compounds known as anti-capri agents or stabilizers
can be added. The binder (or protective coating) of the silver halide emulsion of the present invention
It is advantageous to use gelatin as the id), but
In addition, gelatin derivatives, gelatin and 6 other molecular groups
Raft polymer, protein, sugar i-conductor, cellulose derivative
, synthetic hydrophilic polymer substances such as single or copolymers, etc.
Hydrophilic colloids can also be used. Photographic emulsion of a light-sensitive material using the silver halide emulsion of the present invention
layer, other hydrophilic colloid curves are coated with a binder (or
A hardening agent that cross-links (protective colloid) molecules and increases film strength.
It is hardened by using alone or in combination. 1i! The membrane agent
, to the extent that it is not necessary to add a hardening agent to the processing solution.
It is desirable to add enough amount of material to harden the film, but
It is also possible to add a hardening agent. Halogen in photosensitive materials using the silver halide emulsion of the present invention
Increasing the flexibility of the silver emulsion layer and/or other hydrophilic colloid layers
Plasticizers can be added to increase the strength. Photographic emulsion of a light-sensitive material using the silver halide emulsion of the present invention
Improved dimensional stability of other hydrophilic colloid layers
For this purpose, dispersions of water-insoluble or sparingly soluble synthetic polymers (
latex). Using a hydrophobic compound alone or in combination with a low-boiling point solvent
Dissolved in a solvent and dispersed in water using mechanical or ultrasonic waves.
Anionic surfactants, nonionic surfactants are used as dispersion aids when
Ionic surfactants and cationic surfactants can be used.
I can do it. Between emulsion li1 of the color photographic light-sensitive material of the present invention (same-sensitivity
between chromatic layers and/or between different color-sensitive layers), between developing agents.
The oxidant or electron transfer agent may migrate, causing color turbidity or brightness.
Color caps are applied to prevent sharpness deterioration and graininess from becoming noticeable.
Reinhibiting agents are used. The color anti-capri agent may be used in the emulsion layer itself or in the middle.
An interlayer may be provided between adjacent emulsion layers and used as the intermediate layer.
. Color photosensitive materials using the silver halide emulsion of the present invention include
It is possible to use image stabilizers to prevent the deterioration of dye images.
come. Image stabilizers preferably used in the present invention include
, the following general formulas [A1-[H] and [J][K] are listed.
be able to. The following is a general formula [A] in which R1 is a hydrogen atom, an alkyl group, an alkenyl group, or an alkyl group.
Represents a lyl group or a heterocyclic group, R2, Rs, Ri, R
6 is a hydrogen atom, a halogen atom, a hydroxy group,
Alkyl group, alkenyl group, aryl group, alkoxy group
or a 7-syl amino group, R1 is an alkyl group,
Represents a hydroxy group, an aryl group, or an alkoxy group. Also, R+ and R1 close each other to form a 5-shell or 6-shell ring.
In that case, ■(, is a hydroxy group or an alkali group.
Koxy group is added, and ■ (3 and R4 are ring-closed, and 5 shells are formed.
may form a hydrocarbon ring, in which R is an alkyl ring.
aryl group, aryl group, or heterocyclic group, provided that
When Rt is a hydrogen atom and R1 is a hydroxy group,
In the general formula [A], RI is a hydrogen atom, an alkyl
group, alkenyl group, aryl group or heterocyclic group.
However, among these, examples of alkyl groups include ethyl group.
, ethyl group, propyl group, n-sctyl group, t, ec
Direct magnetic or branched groups such as t-octyl group and hexadecyl group
Fist the alkyl group of
The alkenyl group represented by f+ is 2, for example allyl,
Examples include hexenyl and octenyl groups. moreover,
[(As the aryl group in 1, phenyl, naphthyl
Each store is listed. Furthermore, as a polycyclic group represented by R3,
In this case, tetrahydropyranyl group, pyrimidyl group, etc.
Physically mentioned. Each of these groups may have a substituent.
For example, as an alkyl group with a substituent, pencil
aryl group, nidoxymethyl group, or a substituent.
methoxy 7-ethyl group, chlor 7-enyl group,
4-Hydroxy3,5-dibutylphenyl group etc.
can be lost. In the general formula [AI, R7, R5, R, and R6 are
Hydrogen atom, halogen atom, hydroxy group, alkyl group,
alkenyl, aryl, alkoxy or acyl
There are 7 amide groups, among which alkyl groups and alkylene groups.
Nyl group, 7. Regarding the lyl group, it is described in relation to R8 above.
Same as alkyl group, alkenyl group, aryl group
can be mentioned. Further, as the halogen atom, for example,
Examples include fluorine, chlorine, and bromine. moreover
Examples of the alkoxy group include methoxy group, ethoxy group, etc.
I will end by listing specifically. In addition, the Asilua
The mino group is denoted by R'C0NI (-, where R
' is an alkyl group (e.g. methyl, ethyl, n-propyl
, n-butyl, n-octyl, tert-octyl, pen
groups such as acyl), alkenyl groups (e.g. allyl,
groups such as ctenyl and oleyl), aryl groups (e.g.
each group such as phenyl, methoxyl, naphthyl),
or heterocyclic groups (e.g. pyridyl, pyrimidyl groups)
). In addition, in the general formula [AI, R4 is an alkyl group,
Represents a droxy group, aryl group or alkoxy group,
Among these, for alkyl groups and aryl groups, the above R1
The same alkyl group and aryl group shown in
can be mentioned. Also, regarding the alkenyl group of R4
As mentioned above, R2, R3, Rs and R1 are described above.
The same group as an alkoxy group can be included. R1 and R2 combine with each other to form a benzene ring.
As a ring, for example, chroman, coumaran, methylene diode
Examples include xybenzene. Also, if Ra and R1 form a ■ ring together with a beni/cene ring,
Examples of such rings include French bean. these
The ring contains a substituent (e.g. alkyl, alkoxy, aryl)
). Also, RI and R...! or formed by R3 and R4 joining together
Spiro compounds are formed by using atoms in the ring as spill atoms.
It is also possible to form a bis body by using R2, R4, etc. as a linking group.
may be completed. The phenolic compound represented by the general formula [AI or
Among the phenyl ether compounds, preferred are R
〇-group (R is an alkyl group, an alkenyl group, an aryl group,
or biindalation having 4 ) representing a heterocyclic group
It is a compound represented by the following general formula IA-11.
can be done. General formula [A-1] In the formula, 1 is an alkyl group (e.g. methyl, ethyl, propylene
n-octyl, tart-octyl, pencil, hexyl
xadecyl), alkenyl groups (e.g. allyl, octetyl),
aryl groups (e.g., phenyl, oleyl), aryl groups (e.g., phenyl, oleyl),
phthyl) or heterocyclic groups (e.g., tetrahydripyra)
(nyl, pyrimidyl), R1 and
and RtO each represent a hydrogen atom, a halogen atom,
(fluorine, chlorine, bromine), alkyl groups (e.g. methyl, ethyl
n-butyl, benzyl), alkoxy groups (e.g. 7
lyl, hexenyl, octenyl) or alkoxy group
(e.g. ponodoxy, ethoxy, penciloxy)
, R8 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl
, n-butyl, benzyl), alkenyl groups (e.g., t,
2-7'ropenyl, hexenyl, octenyl), or
Aryl groups (e.g. 7-el, methoxyphenyl, chloro)
(luphenyl, naphthyl). The compound represented by the general formula [A] is disclosed in U.S. Patent No. 3,
No. 935,018, No. 3,982,944, No. 4
No. 1254.216, Special No. 55-21004, No. 5
No. 4-145530, British Patent Publication No. 1j112,077.
No. 455, No. 2,062, No. 888, U.S. Patent No. 3,
764,337, same No. 3.432300, same No. 3.5
No. 74,627, plS3,573.050, JP
No. 52-152225, No. 53-20327, No. 5
No. 3-17729, No. 55-6321, British Patent No. 1
, No. 341,556, Kokan No. 2.066.975, Special
Publication No. 54-12337, Publication No. 48-31825, United States
Also includes compounds described in Patent No. 3,700,455 etc.
nothing. The amount of the compound represented by the general formula IAI is mazen.
It is preferably 5 to 300 mol% based on Takafufu, and more
Preferably it is 10 to 200 mol%. Typical examples of the compound represented by the general formula [A] are shown below.
Give an example. Type (1) RI Type (2) Type (3) Type (4) Type (5) Type (6) Type (7) Type (5) Below margin type (6) Below margin A-7 Below margin General formula [B] (In the formula, R8 and R1 are hydrogen atoms and halogen atoms, respectively.
child, alkyl group, alkenyl group, alkoxy group, alke
Nyloxy group, hydroxy group, aryl group, "P 17
-ruoxy group, acyl group, acylamino group, acyloxy group
cy group, sulfonamido group, cyfuralkyl or alkyl group
represents a oxycarbonyl group, and R2 is a hydrogen atom or an alkyl group.
group, alkenyl group, aryl group, acyl group, cycloa group
alkyl group or heterocyclic group, R3 is a hydrogen atom
, halogen atom, alkyl group 1. alkenyl group, ary
group, aryloxy group, acyl group, acyloxy group,
Sulfonamide group, cycloalkyl group or alkoxy
Hail carbonyl group. Each of the groups listed above may be substituted with other substituents.
For example, an alkyl group, an alkenyl group, a hydroxy group,
Alkoxycarbonyl group, aryloxycarbonyl group
, acylamide 7 groups, acyloxy group, carbamoyl group,
Examples include sulfonami Y group, sulfonyl 77 moyl group, etc.
. Moreover, It and R3 are ring-closed with each other, and are 5-membered or 6Jl
! May form a ring, R3 and R5 are closed to form a benzene ring
For example, the ring formed with chroman ring, methylene
A dioxybenzene ring is mentioned. Y is necessary to form a chroman or coumaran ring
Hail atomic groups. Chroman or coumaran ring is a halogen atom, alkyl
group, cycloalkyl group, alkoxy group, alkenyl group,
Alkenyloxy group, hydroxy group, aryl group, aryl group
may be substituted with a ruoxy group or a hetero ring,
Furthermore, a spiro ring may be formed. Among the compounds represented by the general formula [B], those particularly suitable for the present invention
Compounds of general formula [B-IJ, [B-21, [B-3
], [B-4], [13-5]
Included. General formula [B-1] General formula [B-2] K' General formula [B-3] General formula [B-4] General formula [13-5] General formula [B-1], [I3-21, [B-3], [B
-4] and R1, R2, R3 in [I3-51
and R4 has the same meaning as in the general formula [B] above.
Has, Rs, Rs, R6, R8, Rs and R,. is hydrogen atom, halogen atom, alkyl group, alkoxy group
, hydroxy group, alkenyl group, alkenyloxy group,
Aryl group, aryloxy group or heterocyclic group
It will be. Furthermore, Rs and R, Rs and R7, R1 and R1, R1 and R
- and Rs and R++ cyclize with each other to form a carbocycle
Furthermore, the carbocycle may be substituted with an alkyl group.
Good too. The general formula [B-1], [B-21, [B-3], [
B-4] and [B-51, R1 and R4 are
Hydrogen atom, alkyl group, alkoxy group, hydroxy group or
or cycloalkyl group, Rs, Ra, Rt, Ra, Ra
and Rho is a hydrogen atom, an alkyl group, or a cycloatom
Particularly useful are compounds that are alkyl groups. The compound represented by the general formula [B] is tetrahedron (Te
trahedron), 19F O, vo126*4F
43-4751 Shin, Journal of the Chemical Society of Japan, 1972. No1
0, pp. 0987-1990, Chemical (chess, L.
ett, ), 1972 (4) pp. 315-316, JP
Represents the compound described in No. 55-139383
, and synthesized according to the methods described in these
can do. The amount of the compound represented by the general formula [B] to be used is as follows.
5 to 300 for the magenta coupler according to the emulsion of the present invention.
Mol% preferably, more preferably 10-200mol%
It is. Typical specific examples of these compounds are shown below. Below is the blank general formula [CI R+ general formula [D] where R1 and R1 are a hydrogen atom, a halogen atom, an alkyl atom,
group, alkenyl group, alkyl group, alkenyloxy
group, hydroxy group, aryl group, aryloxy group, a
nru group, acylami 7 group, acyloxy group, sulfonate group
Contains a mido group or an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents.
For example, halogen atom, alkyl group, alkenyl group,
Alkoxy group, aryloxy group, hydroxy group, alkoxy group, aryloxy group, hydroxy group,
Koxycarbonyl group, aryloxycarbonyl group,
sil7mi7 group, carnozumoyl group, sulfonamide group,
Examples include sulfamoyl group. Y is fuchroman or dikumara with benzene ring]/
Hail the atoms necessary to form a ring. The chroman or coumaran ring is a herogen atom, an alkyl
group, cycloalkyl group, fluoroxy group, alkenyl group
, alkenyloxy group, hydroxy group, aryl group, a
May be substituted with a lyloxy group or a heterocyclic group (
, may further form a spiro ring. Among the compounds represented by the general formula [CI Oori [DJ], this
Compounds particularly useful in the invention have the general formula IC-11, [C-2
], [D-11 and [D-2]
Included. General formula [C-1] General formula [C-21 General formula [D-1] General formula [D-21 General formula [C-11, [C-21, [D-41 and [D
-2]) where R r and 512 are the general formula [
has the same meaning as in CI and [131, R,
, R4, R3, R6, R2 and R3 are hydrogen atoms, halo
Gen atom, alkyl group, alkoxy group, hydroxy group,
Alkenyl group, alkenyloxy group, aryl group, aryl group
R represents a group or a heterocyclic group, and further R
5 and R4, R4 and Rs, Rs and R R6 and R2 and R
? and R1 may be cyclized with each other to form a carbocycle,
Furthermore, the carbocycle may be substituted with an alkyl group. The general formula [C-1], [C-2], [D-11 and
[D-21 is loaded, R3 and R5 are 1 m of water, and
alkyl group, alkoxy group, hydroxy: M or cyclo
Alkyl group, Rs, R4, Rs%Rs, R7 and Ra
is a hydrogen atom, an alkyl group, or a cycloalkyl group.
Particularly useful are compounds such as Compounds represented by the general formula [CI, [DJ] are those of the Chemical Society of Japan.
Magazine (J, Chew, Soc, part C) 1
968. (14), pp. 1937-18, Organic Media Chemistry
Association Journal 1970.2B(1), pp. 60-65, Tetra
Hedron (Tetrahcdron Letters)
19f3. (29), pp. 2707-271G.
Compound & also A+tsu, fu^◆ pattern and here phantom one-year-old pattern -1,
It can be synthesized in a variety of ways. The amount of the compound represented by the general formula [CI, [DJ] is
, 5 to 30 for the magenta coupler according to the present invention.
0 mol % is preferable, more preferably 10 to Zoo mol
%. Specific representative examples of these compounds are shown below. Below is the general formula (E) in which R' is a hydrogen atom, an alkyl group, an alkenyl group,
- group, acyl group, cycloalkyl group or heterocycle
represents a group, R3 is a hydrogen atom, a halogen atom, an alkyl
group, alkenyl group, aryl group, aryloxy group, a
Cyl group, acylamino group, acyloxy group, sulfona group
Mido group, cycloalkyl group or alkoxycarbonyl group
represents a group. R” R4 is a hydrogen atom, a halogen atom, an alkyl group
, alkenyl group, aryl group, acyl group, acylami 7
group, sulfonamide group, cycloalkyl group or alkyl group.
Represents a koxycarbonyl group. The groups listed above each have other substituents r! 1 exchanged
Examples include alkyl groups, alkenyl groups, alco
xy group, aryl group, aryloxy group, hydroxy group
, alkoxycarbonyl group, aryloxycarbonyl group
group, acylamino group, carbamoyl group, sulfonamide
group, sulfamoyl group, etc. In addition, R1 and R2 are mutually polycyclic, forming a 5- or 6-shell ring.
may be formed. At that time, R3 and t'R' are water atoms, halogen
Atom, alkyl group, alkenyl group, alkoxy group, alkyl group
thenyloxy group, hydroxy group, aryl group, aryl
Oxy group, ゛r acyl group, acylamino group, acyloxy
group, sulfonamide group or alkoxycarbonyl group
represents. Y is necessary to form a chroman or coumaran ring
Represents a group of atoms. Chroman or coumaran ring is a halogen atom, alkyl
group, cycloalkyl group, alkoxy group, alkenyl group,
Alkenyloxy group, hydroxy group, aryl group, aryl group
may be substituted with a hydroxyl group or a heterocyclic group.
Furthermore, a spiro ring may be formed. Among the compounds represented by the general formula (E),
The compound used is general formula (E-1). (E-2), (E-3)t(E-4) and (E-53
It is included in the compound represented by. General formula (E-1) flR+ General formula (E-23 OR+ General formula (E-3) !tI11'%1vOR1 General formula (E-4) a General formula (E-5) General formula (E-13~( R' in E-5). R2, R'' and R' are the same as in the above general formula (E).
R'', R1, Rte, R', R'' and V have the same meaning.
Rl O is a hydrogen atom, a halogen atom, an alkyl group, an atom
Rukoxy group, hydroxy group, alkenyl group, alkenyl
Oxy group, aryl group, aryloxy group or hetero group
Representing a ring group, further RII and R6, R6 and R'r,
Ry and R", R- and ll@, and R" and 1(+. may be cyclized with each other to form a carbocycle, and furthermore,
Carbocycles may be substituted with alkyl groups. In the general formulas (E-1) to (E-5), R1, R
2, R' and R' are hydrogen atoms, alkyl groups, or
Chloalkyl group, in the general formula (E-5), % R
' and f/R4 are hydrogen atoms, alkyl groups, alkoxy groups
, a hydroxy group or a cycloalkyl group;
In general formulas (E-1) to (E-5), R, R', R
', R-rich, R-kai and R1'' are hydrogen atoms, alkyl groups,
or cycloalkyl groups are particularly useful.
. The compound represented by the general formula [E] is tetrahetocune (
Tetrahcdron 1. 198
5. j8) y457-4QO pages Journal of the Chemical Society of Japan (J, C
bem, Soc, part (:) 196B. (22), pp. 2013-2018, (Zh,
Org, nihim) 19f0f(6). 1230 to IZ37,
and be synthesized according to the methods described therein.
I can do it. The usage amount of the compound represented by the general formula [1, 13]
is 5 to 3 for the magenta turnip according to the present invention.
00 mol% is preferable, more preferably 10 to 200 mol%
%. Specific representative examples of these compounds are shown below. Below is the general formula (F) in which R1 is a hydrogen atom, an alkyl group, an alkenyl group, an ali
group, acyl group, cycloalkyl group or heterocycle
represents a group, R2 is a hydrogen atom, a halogen atom, an alkyl group
, alkenyl group, aryl group, aryloxy group, acyl
group, acylamino group, acyloxy group, sulfonamide
group, cycloalkyl group, or alkoxycarbonyl group
Hail to you. R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group
aryl group, acyl group, acylamino group, sulfonate group, aryl group, acyl group, acylamino group,
amide group, cycloalkyl group or alkyl radical
Hail the Bonyl group. R9 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group.
group, alkoxy group, alkenyloxy jt: Shil/de
Cry 4. "jje"'PII-II, je"Fll-Il
, +4: no group, acyl group, acylamino group, acyloxy
cy group, sulfonamide group, or alkoxycarbonyl group
Hail to you. Each of the groups listed above may be substituted with other substituents.
6 For example, an alkyl group, an alkenyl group, an alkoxy group,
Aryl group, aryloxy group, hydroxy group, alco
oxycarbonyl group, aryloxycarbonyl group, acyloxycarbonyl group,
lamino group, carbamoyl group, sulfonamide group, sulfonamide group,
Examples include a 77 moyl group. Also, R1 and R6 are ring-closed with each other to form a 5jt or 6-shell ring.
(l and R4 are hydrogen atoms)
, halogen atom, alkyl group, alkenyl group, alkoxy
cy group, alknyloxy group, hydroxy group, aryl group
, arylokidi group, acyl group, acylamino° group, a
Syloxy group, sulfonamide group, or alkoxy group
Hail carbonyl group. Y is a glue that forms a chroman or coumaran ring, '#
Breath hawk? / Hara Koryu Nehonmu h+- Chroman or coumaran ring is a halogen atom, alkyl
group, cycloalkyl group, alkoxy group, alkenyl group,
Alkenyloxy group, hydroxy group, aryl group, aryl group
may be substituted with an oxy group or a heterocyclic group.
Furthermore, a spiro ring may be formed. Among the compounds represented by the general formula [F],
Useful compounds have general formulas [F-1], [F-2], [F
-3], [F-4] o, J, v [j'L indicated by F-51
It is included in the group compound. Below are the blanks General formula (F-1) General formula (F-23 General formula (F-3) General formula [F-4] General formula (F-53 R1 in general formulas [F-1] and [F-5] , R2
, R and R4 are the same as in the above general formula [F]
R3, R6, R2, R1, R, and R3
゜ is hydrogen atom, halogen atom, alkyl group, alkoxy
group, hydroxy group, alkenyl group, alkenyloxy group
, aryl group, aryloxy group or heterocyclic group
Hail. Furthermore, R5 and R8, R, and R1, R2 and R6, Ro and R
1 and R1 and LL,. are cyclized with each other to form a carbon ring.
furthermore, the carbocycle may be substituted with an alkyl group.
You may be Also, IF -31, [F -4] and [F'-5]
Come on, are the two Rt””RIGs the same or different?
You can leave it there. The general formula [F-11, [F-21, [F-3], [F
-4] and [I''-5], Rt-12 and
and It3 are hydrogen atoms, alkyl groups, cycloalkyl groups%
R4 is a hydrogen atom, an alkyl group, an alkoxy group, a hydro
xy group or cycloalkyl group, further R9, R6, R
2, R3, R1 and R3° are hydrogen atoms, alkyl groups,
or cycloalkyl groups are particularly useful.
. The compound represented by the general formula [F] is tetrahedron (
Tetrahedron Letters) 19F O
, Vol 2B, pp. 4743-4751, Chemical Society of Japan
Magazine 1972. No. 10e 1987-1990,
Synthesis 19f5. Vo
l L pages 392-393, (tlul 5oct Ch
ime Delg) 1975? VOI84(7)
, 747-759;
and be synthesized according to the methods described therein.
I can do it. The usage amount of the compound represented by the general formula [1''] is as follows.
5 to 300 mol for the magenta coupler according to the present invention C
%, more preferably 10 to 200 mol%.
Ru. Specific representative examples of compounds represented by general formula [F] are shown below.
show. The following is a blank general formula CG] R In the formula, R1 and R3 are a hydrogen atom and a halogen atom, respectively.
, alkyl group, alkenyl group, alkoxy group, hydroxy group
cy group, aryl group, aryloxy group, acyl group, acyl group,
lamino group, acyloxy group, sulfonamide group,
Represents a loalkyl group or an alkoxycarbonyl group. R1 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group
group, hydroxy group, aryl group, acyl group, acyl group
mino group, acyloxy group, sulfonamide group, cycloa group
represents an alkyl group or an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents.
Examples of substituents include alkyl groups, alkenyl groups,
Alkoxy group, aryl group, aryloxy group, hydro
Oxy group, alkoxy carbonyl group, aryloxycar
Bonyl group, acylamino group, carbamoyl group, sulfone
Examples thereof include an amide group and a sul77 moyl group. In addition, R2 and R' are ring-closed with each other, and 5-shell or 6-shell carbonization occurs.
This 5- or 6-membered hydrocarbon may form an aqueous ring.
Bare rings include halogen atoms, alkyl groups, cycloalkyl groups,
Alkoxy group, alkenyl group, hydroxy group, aryl
substituted with a group, an aryloxy group, a heterocyclic group, etc.
Good too. Y represents the atomic group necessary to form an indane ring,
The ring is a halogen atom, an alkyl group, an alkenyl group,
Alkoxy group, cycloalkyl group, hydroxy group, ali
Substituted with aryl group, aryloxy group, or heterocyclic group, etc.
or may further form a spiro ring. Among the compounds represented by general formula (G), particularly useful for the present invention
Compounds represented by general formulas CG-1) to (G-3)
included in the compound. Below are blank spaces General formula (G-1) h+ General formula (G-2) General formula CG-3) R l, R2 and
and R3 have the same meanings as in general formula CG), and R'
, R', R", Rte, R1 and (7R" are
atom, halogen atom, alkyl group, alkoxy group, alkyl
Kenyl group, hydroxy group, aryl group, aryloxy
R4 and R', R' and R'' represent a group or a heterocyclic group
, R" and R', R' and R" and f/R" and R1 are mutually closed.
may be combined to form a hydrocarbon ring, and further the hydrocarbon ring may be
may be substituted with an alkyl group. In the general formulas (a-i) to (G-3), R1 and
R3 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group
cy group or cycloalkyl group, R2 is hydrogen atom, alkyl
R group, hydroxy group or cycloalkyl group, R4, R
s, Ra, Ry, RI and R1 are hydrogen atoms
, a compound having an alcohol group or a cycloalkyl group is particularly
It is useful for The amount of the compound represented by the general formula [G]
It is preferably 5 to 300 mol% based on the zenta coupler,
More preferably, it is 10 to 200 mol%. Typical specific examples of compounds represented by general formula [G] are shown below.
show. The following is a blank general formula [11] R3 In the formula, R1 and R2 are a hydrogen atom and a halogen atom, respectively.
, alkyl group, alkenyl group, aryl group, acyl group,
Acylamino group, acyloxy group, sulfonamide group,
Represents a cycloalkyl group or an alkoxycarbonyl group
. R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group
group, alkoxy group, hydroxy group, aryl group, aryl group,
yloxy group, acyl group, acylamino group, acyloxy group
cy group, sulfonamide group, cycloalkyl group or alkyl group
Represents a koxycarbonyl group. Each of the groups listed above may be substituted with other substituents.
For example, furkyl group, alkenyl group, alkoxy group,
Aryl group, aryloxy group, hydroxy group, alco
oxycarbonyl group, aryl dicarbonyl group, acyl
lamino group, carbamoyl group, sulfonamide group, sulfonamide group,
Examples include famoyl group. Also, R' and R2 and (/R' and R'J! each other), ', rR
1iL, may form a 5- or 6-membered hydrocarbon ring
, the hydrocarbon ring is a halogen atom, an alkyl group, a cycloatom
alkyl group, alkoxy group, alkenyl group, hydroxy group
, 7-aryl group, aryloxy group, heterocyclic group, etc.
may be done. Y represents an atomic group necessary to form a kidney bean ring, and
Green bean ring is substituted with a substituent that can replace the above hydrocarbon ring
or may further form a spiro ring. Among the compounds represented by the general formula [1],
Compounds for use are represented by the general formulas [:H-1) to (II-2).
It is included in the compounds mentioned above. General formula (H-2) General formula (H-3) R', R mushroom in general formulas (H-1) to ()I-3)
and R'' have the same meaning as in general formula (H), and R
', R', R', R', I? “And 1.FR”+! ,+re
Sole hydrogen atom, halogen atom, alkyl group, alkoxy
group,) nitroxy group, alkenyl group, aryl group, aryl group
represents a group or a heterocyclic group. Also R' and R'
, R1 and R'', R' and R', I?'toR' and r7R
, I and R” may open to each other to form a hydrocarbon ring.
Furthermore, the M hydrocarbon ring may be substituted with a ?rukyl group.
stomach. In the general formulas (H-1) to (II-3), R1 and
and R2 are each hydrogen atom, alkyl group or cycloa
alkyl group, R3 is a hydrogen atom, an alkyl group, an alkoxy group
, hydroxy group or cycloalkyl group, R', R',
R・tR'is and R- are a hydrogen atom and an alkyl atom, respectively.
Compounds that are cycloalkyl or cycloalkyl groups are particularly useful.
be. The method for synthesizing the compound represented by the general formula [[11] is known.
No. 3,057,929, Chem. Ber, 1972. 95 (5L is) 3
~16th page 4, Chemist-ry Lett
ers, 1980e, pp. 739-742! of
Can be built. The compound magenta coupler represented by the general formula [H]
It is preferably 5 to 300 mol%, more preferably 1
It is 0 to 200 mol%. Specific representative examples represented by the general formula [H] are shown below. Below, the blank general formula (Jl −+, [wherein R' is an aliphatic group, cycloalkyl M or aliphatic group]
Y represents a heterocyclic ring with 5 to 7 shell rings together with a nitrogen atom
represents a group of nonmetallic atoms necessary to form a
2 or more nonmetallic atoms containing/containing nitrogen atoms forming a bare ring
If there are heteroatoms, at least two heteroatoms
are non-adjacent heteroatoms. ] The aliphatic group represented by R″? may have a substituent.
unsaturated alkyl groups, and unsaturated alkyl groups that may have substituents.
Examples include alkyl group. For example, as a saturated furkyl group,
For example, methyl group, ethyl group, butyl group, octyl group, dode
Examples include sil group, tetradecyl group, hexadecyl group, etc.
, unsaturated alkyl groups include, for example, ethynyl group,
Examples include a lopenyl group. The cycloalkyl group represented by R1 has a substituent.
For example, 5 to 7 cycloalkyl groups may be
Examples include a lopentyl group and a cyclohexyl group. As the oryl group represented by R1, each substituent is
7 R1 represents a phenyl group or a naphthyl group which may have P! FM that will be done! fj group group, cycloalkyl group,
Substituents for aryl groups include alkyl groups and aryl groups.
, alkoxy group, carbonyl group, carbamoyl group, acyl
lamino group, sulfamoyl group, sulfonamide group, carbon
Rubonyloxy group, alkylsulfonyl group, aryls
sulfonyl group, hydroxy group, heterocyclic group, alkylthio
group, arylthio group, etc., and these substituents are
It may further have a substituent. In the general formula (J), 1Y is 5 to 5 along with a nitrogen atom.
Lists the nonmetallic atoms necessary to form a 7-membered heterocycle.
However, the nonmetallic atomic group containing the nitrogen atom forming the heterocycle
at least two of must be heteroatoms, and
, the at least two heteroatoms are not adjacent to each other
In the heterocycle of the compound represented by the general formula (J),
If all the heteroatoms are adjacent to each other, then
It is difficult to perform the function as an image stabilizer.
I don't like it because there is no rice. of the 5- to 7-membered ring of the compound represented by the general formula (J)
The heterocycle may have a substituent, and the substituent includes
Kyl group, aryl group, acyl group, carbamoyl group,
Coxycarbonyl group, sulfonyl group, sulfonyl group
etc., and may further have a substituent, and 5 to 7
A membered heterocyclic ring may be saturated, but a saturated bicyclic ring may be saturated.
Preferably, a benzene ring or the like is fused to the bicyclic ring.
or may form a spiro ring. The amount of the compound represented by the general formula (J) of the present invention is
, a magenta coupler represented by the general formula (I) of the present invention
- is preferably 5 to 300 mol%, more preferably
is 10 to 200 mol%. Typical specific examples represented by general formula (J) are shown below. Below is a blank space J-63 J-64 J-F O ■ ■ C,2H
type compounds and homopiperazine type compounds are particularly preferred,
More preferably, the following general formula (J-1) or (J-
This is a compound represented by 2). General formula (J-1) General formula (J-2) In the formula, R2 and R'' are a hydrogen atom and an alkyl group, respectively.
or represents an aryl group, provided that R1 and R3 are simultaneously water
Each of R4 to RI'' is a hydrogen atom.
represents a child, an alkyl group, or an aryl group. In the general formulas (J-1) and (/(J-2)), R2 and
and R3 are each a hydrogen atom, an alkyl group, or an aryl group.
represents an alkyl group represented by R2* or R3
For example, methyl group, ethyl group, butyl group,
Cutyl group, Ydecyl group, Tetofdecyl group, Hexadecyl group
group, octadecyl group, etc. R2* or R3
Examples of the aryl group represented include a 7-el group, etc.
Ru. Rt or R''? Alkyl group, aryl group
may have a substituent, and the substituent is a halogen atom.
child, alkyl group, aryl group, flukoxy group, aryl
Examples include oxy group and heterocyclic group. The total number of carbon atoms in R2 and R' (including fl! substituents) is
6-40 is preferred. In the general formula (J-1) or (J-23), R4
~R1' is each a hydrogen atom, an alkyl group, or an ali
represents an alkyl group represented by R4 to R''
Examples thereof include a methyl group and an ethyl group. R
The aryl group represented by 4-R1'' includes phenyl group, etc.
can be mentioned. A compound represented by the general formula (J-1) or (J-23)
Specific examples of the compounds include the above-mentioned exemplified piperazine compounds (J
-1) to (J-30) and exemplary homopiperazine compounds
As described in (J-51) to (J-62)
. Next, a representative matrix of the present invention represented by the general formula (J)
An example of synthesis of a zenta dye image stabilizer is shown. Synthesis Example-1 (Synthesis of Compound J-2) 9.0 g of piperazine and 55 g of myristyl bromide
In 77 tons of dissolved 100ml, anhydrous potassium carbonate
15. was added, and the mixture was boiled and refluxed for 10 hours to react. After the reaction, the reaction solution was heated to 500mj! After soaking in water, add acetic acid ethyl
Extracted with Chill 500+mff1. ethyl acetate layer with sulfuric acid
After drying with magnesium and distilling off the ethyl acetate, a white
The desired crystalline product was obtained. Acetone 300@j! Reunited with
The crystals were crystallized to obtain 34 g of white scaly crystals (yield 70%).
. Melting point 55-58°C Synthesis Example-2 (Synthesis of Compound J-34)
Acetic anhydride 12mj! was added little by little. *After adding glacial acetic acid
After cooling with water and filtering off the precipitated crystals, filtrate with ethyl acetate.
Recrystallize to obtain 416.5 g (yield: 5%) of white powder.
Obtained. Melting point: 207-210°C or less General formula (K) In the formula, R1 is an aliphatic group, a cycloalkyl group, or an aryl group.
Y represents a 5- to 7-membered heterocycle together with a nitrogen atom.
Mere bonds or divalent hydrocarbons needed to form
represents a group. R2, IN3. R'tR9, R@, R? teeth,
hydrogen atom, aliphatic group, cycloalkyl group or
Represents an aryl group. However, R2 and R4 and R3 and R@
By combining with each other to form a simple bond, nitrogen atoms and Y
Together they may form an unsaturated 5- to 7-shell heterocycle, *
In addition, when Y is a simple bond, R5 and R7 are connected to each other.
together to form a simple bond, and together with the nitrogen atom and Y, it becomes unsaturated.
May form a 5-shell heterocycle of the sum, *, Y is simple
If it is not a bond, R' and Y, R' and Y, or Y self.
Forms an unsaturated bond with the nitrogen atom and Y together with the unsaturated bond.
It may form a heterocycle of 6 or 7j. The aliphatic group represented by R1 may have a substituent.
unsaturated alkyl groups, and unsaturated alkyl groups that may have substituents.
Examples include alkyl group. Examples of saturated alkyl groups include
For example, methyl group, ethyl group, butyl group, octyl group, dode
Examples include sil group, tetradecyl group, hexadecyl group, etc.
, unsaturated alkyl groups include, for example, ethynyl group,
Examples include a lopenyl group. The cycloalkyl group represented by R1 has a substituent.
For example, Schiff
Examples include pentyl group and cyclohexyl group. The aryl group represented by R1″? has a substituent and
It also represents a phenyl group or a naphthyl group. Aliphatic group, cycloalkyl group, aryl represented by R1
Substituents for groups include alkyl groups, aryl groups, and alkyl groups.
Imashi group, carbonyl group, carbamoyl group, acylamino group
group, sul77 moyl group, sulfonamide group, carbonyl
Oxy group, alkylsulfonyl group, arylsulfonyl group
group, hydroxy group, heterotetracyclic group, alkylthio group, ali
These substituents can be further substituted.
It may have a group. In the general formula (K), Y together with the nitrogen atom represents 5 to 7
A simple bond or
It represents a divalent hydrocarbon group, but when Y is just a bond,
, furthermore, R5 and R7 combine with each other to form a simple bond.
to form an unsaturated 5)l-ring heterocycle, or
When Y is a divalent monovalent hydrogen group, that is, when it is a methylene group,
In this case, Rs and Y or R1 and Y form an unsaturated bond.
However, it may form an unsaturated hexacyclic heterocycle, and
In the case of tyrene group, ls, YSR ma and Y or Y itself
to form an unsaturated bond and form an unsaturated heptad-ring heterocycle.
You may. Furthermore, the divalent hydrocarbon group represented by Y is
It may have a substituent, and this substituent includes an alkyl group, a carbon
Rubamoyl group, alkyloxycarbonyl group, acylua group
Mino group, sulfolyl pIIb2 Tsumugi-1 Moenon,
Examples include Toyoya 11-Tero ring group. RE-11 formula (K) NiHite, R", R3, R't
R'. R@ and R7 are hydrogen atom, aliphatic group, cyclo
Represents an alkyl group or an aryl group, but is represented by R2-R1
Examples of aliphatic groups include saturated aliphatic groups which may have substituents.
alkyl group and unsaturated alkyl group which may have a substituent
Can be mentioned. As a saturated alkyl group, for example, methyl
group, ethyl group, butyl group, octyl group, dodecyl group, tetra
Examples include tradecyl group, hexadecyl group, etc.
As the alkyl group, for example, ethynyl group, propenyl group
etc. R2~R? The cycloalkyl group represented by is substituted with
A 5- to 7-shell cycloalkyl group which may have a group, e.g.
For example, cyclopentyl group, cyclohexyl group, etc.
It will be done. The aryl group represented by R2-R1 has a substituent.
Examples include a phenyl group, a naphthyl group, and the like. Aliphatic group or cycloalkyl group represented by R2 to R4 above
, as substituents for aryl groups, alkyl groups, aryl
group, alkoxy group, carbonyl group, carbamoyl group,
cylamino group, sulfonyl moyl group, sulfonamyl group,
Carbonyloxy group, alkylsulfonyl group, aryl
Sulfonyl group, human mixi group, heterocyclic group, alkyl group
Examples include O groups. The compound represented by the general formula (K) has 5 to 7 shell rings.
It is preferable that the compound has the same heterocyclic ring as the unsaturated one.
stomach. The amount of the compound represented by the general formula (K) below is as follows:
Magenta turnip 2- represented by the general formula (1) of the present invention
It is preferably 5 to 300 mol%, more preferably
It is 10-200 mol%. Typical specific examples of the compound represented by the general formula (K) are shown below.
vinegar. In the margin below -34 to -35 to -36 to -37 to -38 to -39 to -40 to -41 Next, a representative synthesis of the compound represented by the above general formula (K)
Give an example. Synthesis Example-1 (Synthesis of compound-14) 9.0 g of piperazine and 28 g of myristyl bromide were added.
Dissolved 60. In 77 tons of Q, 6 anhydrous potassium carbonate
．． 08 was added, and the mixture was boiled and refluxed for 20 hours to react. After the reaction, the reaction solution was poured into 300.9% water, and then acetic acid was added.
Extracted with 300 tIll of ethyl. Ethyl acetate layer
After drying with magnesium sulfate, ethyl acetate is distilled off.
The desired product was obtained as white crystals. 100 ml of acetone
12g of white scaly crystals (yield 43%)
) was obtained. Melting point: 175-180°C or less Margin Hydrophilic colloid for protective layer, intermediate layer, etc. of the photosensitive material of the present invention
Discharge caused by the photosensitive material being charged in the layer due to friction, etc.
To prevent fogging and to prevent image deterioration due to U light.
may contain an ultraviolet absorber. Color photosensitive materials using the silver halide emulsion of the present invention include
, filter layer, antihalation layer and/or irradiation layer
An auxiliary layer such as an oxidation prevention layer can be provided. this
In the layers and/or emulsion layers, color is added during development.
Contains dyes that are leached from the photosensitive material or bleached.
You may be allowed to have one. Silver halide photosensitive material using the silver halide emulsion of the present invention
Silver halide emulsion layer and/or other hydrophilic coating
The id layer reduces the gloss of the photosensitive material, increases the ease of writing,
A matting agent is added to prevent the sensitive materials from sticking to each other.
I can do it. Sliding friction of photosensitive materials using the silver halide emulsion of the present invention
A lubricant can be added to reduce this. The photosensitive material using the silver halide emulsion of the present invention has antistatic properties.
Antistatic agents can be added to prevent static electricity. The antistatic agent prevents static electricity on the side of the support that is not laminated with the emulsion.
It is sometimes used in emulsion layers and/or supports.
Protective coatings other than the emulsion layer on the side where the emulsion layer is laminated
It may also be used as a lloid layer. Photographic emulsion of a light-sensitive material using the silver halide emulsion of the present invention
layer and/or other hydrophilic colloid layers may include coatability improvements,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion and (currently
For the purpose of improving photographic characteristics (image enhancement, contrast enhancement, sensitization, etc.)
Various surfactants are used. A photographic material using the silver halide emulsion of the present invention is a photographic emulsion.
The agent layer and other layers are coated with baryta paper or α-olefin.
Flexible paper such as paper laminated with embolimer, synthetic paper, etc.
Injection support, cellulose acetate, cellulose nitrate, polyethylene
Ren, polyvinyl chloride, polyethylene terephthalate,
Semi-synthetic or synthetic polymers such as polycarbonate and polyamide
films consisting of children, and rigid bodies such as glass, metal, and ceramics.
It can be applied to etc. The silver halide material of the present invention can be applied to the surface of the support as necessary.
After applying corona discharge, ultraviolet irradiation, flame treatment, etc. to
contact or (support surface adhesion, antistatic property, dimensional stability)
, wear resistance, hardness, antihalation properties, friction properties and
/ or to improve other properties) 1 or 2 or more
It may be applied through a subbing layer. Coating a photographic material using the silver halide emulsion of the present invention
A thickener may be used to improve coating properties.
stomach. The coating method involves applying two or more layers at the same time.
Ex-dollion coating and curtain coating available
coaching is particularly useful. The light-sensitive material of the present invention is an emulsion constituting the light-sensitive material of the present invention.
Uses electromagnetic waves in the f14M spectrum to which the layer is sensitive.
It can be exposed to light. Light sources include natural light (sunlight), tan
Gusten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, charcoal
Basic arc lamp, xenon flash lamp, gap pole tube fly line
light spots, various laser lights, light emitting diode lights, electronic
Is it a phosphor excited by radiation, X-rays, γ-rays, α-rays, etc.
Any known light source can be used, such as light emitted from a
I can do it. The exposure time is usually between 1 millisecond and 1 second, which is used in cameras.
Of course, exposure time is shorter than 1 microsecond, for example, in the shade.
100 microseconds to 1 using polar ray tube or xenon flash lamp
Microsecond exposures can be used, or even longer than 1 second.
Longer exposures are also possible. The exposure is carried out continuously.
It may also be performed intermittently. The silver halide photographic light-sensitive material of the present invention can be prepared using a silver halide photographic material known in the art.
An image can be formed by color development. Aromatic primary atom used in color developer in the present invention
Min color developing agents are used in various color photographic processes.
This includes well-known methods that are widely used. child
These developers are aminophenolic and p-phenylene
Contains diamine derivatives. These compounds are in free form
Salt forms, such as hydrochloride or sulfur salts, are generally used because they are more stable than their salt forms.
Used in acid salt form. Additionally, these compounds are generally
A concentration of about 0.1 g to about 30 g for the color developer 11;
Preferably about 1 g to about 15 o per color developer
Use in concentration. As an aminophenol developer, for example, 0-7min
Phenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1゜4-dimethylbenzene, etc.
is included. Especially useful Jl! The primary aromatic amino color developer is N,
With N'-dialkyl-p-phenylenediamine compounds
Yes, alkyl groups and phenyl groups can be substituted with any substituents.
may have been done. Among them, an example of a particularly useful compound is
is N,N'-diethyl-〇-7enylenediamine salt
acid salt, N-methyl-p-phenylenediamine hydrochloride, N
, N'-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N'-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamide
Doethyl-3-methyl-4-aminoaniline sulfate, N
-ethyl-N-β-hydroxyethylaminoaniline,
4-amino-3-methyl-N. N'-diethylaniline, 4-amino-N-(2-meth
xyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate. The color developing solution used in the processing of the present invention includes the above-mentioned
In addition to the primary aromatic amine color developer,
Various components normally added to imaging solutions, such as sodium hydroxide,
Alkalies such as thorium, sodium carbonate, and potassium carbonate
Reagents, alkali metal sulfites, alkali metal bisulfites
, alkali metal thiocyanate, alkali metal halogen
chemicals, benzyl alcohol, water softeners and thickeners, etc.
can also be optionally included. This color developer
The pH value is usually above 7, most commonly about 10-
It is about 13. In the present invention, after color development processing,
However, the processing liquid that has the fixing ability is used for fixing.
If it is a liquid, it is bleached first. The bleaching
Metal complex salts of organic acids are used as bleaching agents in the process.
The metal complex salt oxidizes the metallic silver produced by development.
At the same time, the uncolored part of the coloring agent is converted into silver halide.
It has the effect of producing color, and its composition is aminopolymer.
Carboxylic acids or organic acids such as IIM and citric acid to remove iron and cobalt.
It is coordinated with metal ions such as balt and copper. this
The most commonly used metal complex salts of organic acids such as
Preferred organic acids include polycarboxylic acids and amino acids.
Examples include nopolycarboxylic acids. These polycarbons
Acid or aminopolycarboxylic acid is an alkali metal salt, an
It may be a monium salt or a water-soluble amine salt. Specific representative examples of these include the following:
I can do it. [1] Ethylenediaminetetraacetic acid [2] Nitriotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethyl
ammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid sodium salt The bleaching agent used bleaches the metal complex salts of organic acids such as those mentioned above.
It is contained as a whitening agent and may also contain various additives.
can. As additives, especially alkali halides or
Ammonium halides, e.g. potassium bromide, sodium bromide
Re-halogenation of sodium chloride, ammonium bromide, etc.
It is desirable to contain a genifying agent, metal salt, and chelating agent.
Yes. Also borate, I! pH of salts, acetates, carbonates, phosphates, etc.
l1i agent, alkylamines, polyethylene oxide
Products known to be added to ordinary bleaching solutions such as
It can be added as appropriate. Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite
ammonium, sodium bisulfite, ammonium metabisulfite
, potassium metabisulfite, sodium metabisulfite, etc.
Sulfites, boric acid, borax, sodium hydroxide, potassium hydroxide
sodium carbonate, potassium carbonate, sodium bisulfite
um, sodium bicarbonate, potassium bicarbonate, acetic acid, acetic acid
Consists of various salts such as sodium and ammonium hydroxide
DH! Agent III may be contained alone or in combination of two or more types.
. While replenishing the bleach-fixing solution (bath) with bleach-fixing replenisher,
When performing brightening treatment, thiosulfuric acid is added to the bleach-fixing solution (bath).
It may contain salts, thiocyanates, sulfites, etc.
However, the bleach-fixing replenisher contains these salts.
The treatment bath may be replenished. In the present invention, bleaching is performed to increase the activity of the bleach-fix solution.
as desired in the fixing bath and in the bleach-fix replenisher storage tank.
Even if you blow air or oxygen into the
or a suitable oxidizing agent such as hydrogen peroxide, bromate
Salts, persulfates, etc. may be added as appropriate. [Specific Examples of the Invention] The present invention will be explained in more detail by showing specific examples below.
do. Example 1 Illustrated magenta on a support made of polyethylene coated paper
41i11/dl of puller 2, green-sensitive silver chlorobromide emulsion
Converted to silver, 211g/dl, dioctyl phthalate
4 ul/d of gelatin and 16 u/d of gelatin
It was coated so as to become the coated layer of i2. Furthermore, gelatin is added to the upper layer at 9 r;, g/di.
The coating was applied so that it looked like a clam. Sample prepared by
is sample 1 (comparison). Next, the coupler and metal were added to the coupler-containing layer of Sample 1.
The complexes and oil-soluble dyes were prepared as shown in Table 1.
Samples 2 to 16, which were the same as sample 1, except that sea urchin was added.
Created. A sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd., KS) was applied to these samples.
-7 type) to perform green light light mist light and then the following processing.
I did it. Standard processing steps (processing temperature and processing time) [1] Color development 38°C 3 minutes 30 seconds [2] Bleaching
Fixation 33℃ 1 minute 30 seconds [3] Washing area W! 2
5-30℃ 3 minutes [4] Drying 75-80℃
Approximately 2 minutes [Color developer] Benzyl alcohol 15m! Echiji
Ethylene 15m! potassium sulfite
2.0g potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30.0 g Hydroxylamine sulfate increase 3.0 g Polyline 11 (TPPS) 2.5a3
-Methyl-4-amino-N- (β-methanesulfonamidoethyl) -Aniline sulfate 5.5g Fluorescence enhancement
Whitening agent (4,4-diaminostilbenzsulfonic acid reading conductor> 1.0g hydroxy acid
Add 2.0g of water and dissolve
The amount is 1Q and adjusted to I) 810.20. [Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60!7 ethylene
diaminetetraacetic acid 3g ammonium thiosulfate
Ammonium (70% solution) 1oo-/Ammonium Mononitite
(40% solution) 27.5 ml potassium carbonate or
Make 11ml of p)47.1 with glacial acetic acid and add water to total volume.
Let be 1 no. After treatment, the obtained samples were tested for light resistance, whiteness measurement, and brightness.
Sharpness was measured using the following criteria. [Lightfastness test] Each dye image formed on each sample was exposed to underglass outdoors @
Fading rate (D) when exposed to sunlight for 30 days using an outdoor stand
o - D) / (Do) X 100, where DO
represents the initial density (1,0), and D represents the density after fading.
) was measured. [Measurement of whiteness] The white part (unexposed part) of each sample obtained was measured according to JIS Z872.
Based on the measurement method of object area specified in 2 and Z8727,
a *b *values using Hitachi Color Analyzer Model 607
It was measured by As the a* value increases, the redness increases; as the a* value decreases, the greenness increases.
Indicates an increase. Also, as the b* value increases, the yellowness increases.
The blue color increases as the value decreases. In addition, visual judgment of whiteness was performed. [Sharpness test] MTF (module) of photosensitive halogenated starved emulsion layer
tion transfer function) M T
F (M adulation transfer
Microdensitometer
and compare the MTF values at a spatial frequency of 5 lines/mm.
Ta. Note that the determination of image sharpness by MTF is performed by a person skilled in the art.
As is well known, The Theory of the
The Photographic Process, 3rd Edition (The
ory of the portrait+c
There is a description in Process, 3rd old tion).
Ru. The results of these measurements are shown in Table 1. However, the structure of the comparative magenta coupler used in Table 1
The formula is shown below. Comparative magenta coupler and below All white As is clear from Table 1, samples with coupler alone (1, 7,
9, 11, 13) have poor light fastness and poor sharpness.
bad. Sample 2 using only the metal complex related to the present invention
, the light resistance has improved, but the whiteness of the white area has deteriorated.
do. Samples of the present invention (3-6.8.10.12.14)
In addition to improving light fastness without deteriorating whiteness,
, sharpness is also improved. In addition, in the sample of the present invention, the comparative magenta
The light resistance of Tacoupler was improved compared to the sample (16) used.
The degree of improvement in sharpness and sharpness is greater. Example 2 The combination shown in Table 2 was added to the coupler-containing layer of Sample 1 of Example 1.
Except for adding gold 1 complex and oil-soluble dye in the experiment.
Samples 17 to 32, which were the same as Sample 1, were prepared. The sample thus prepared was subjected to the same exposure treatment as in Example 1.
became. For each sample obtained after treatment, a matrix was applied in the same manner as in Example 1.
Measures light fastness, whiteness and sharpness of Zenta dye images
did. The results are shown in Table 2. In the margin below, however, the structural formulas of the comparative metal complexes used in Table 2 are as follows:
It is. Comparative Metal Complex From Table 2 below, it is clear that the coupler of the present invention contains a metal complex.
(2, 17, 19, 21, 23, 25
, 27, 29), the whiteness deteriorates. of the present invention
A test of the present invention using a metal complex and an oil-soluble dye in the coupler
Fee (3, 18, 20, 22, 24, 26, 28, 30)
, there is no deterioration in whiteness, and both light fastness and sharpness are good.
A good image was obtained. In addition, using comparative metal complexes
This effect was not observed in our sample. Example 3 The following layers were deposited on a support made of polyethylene-coated paper.
Coating is applied sequentially from the support side, and silver halide photographic exposure for multicolors is applied.
The material was prepared. No. 111: α-pivalyl α-(1-ben
di-2,4-dioxo-imidaridin-3-yl)-
2-chloro-5-[γ-(2゜4-di-t-amylphene)
noxy)butyramide]-acetanilide at 811 J/
d Peng, 310/d in terms of silver of blue-sensitive silver chlorobromide emulsion
-,2,4-di-monobutylphenol-3',5'
-di-t-amyl-4'-human 0xybenzoate
31Md garden, dioctyl phthalate 3H/dl
Apply J5 and gelatin to a coating amount of 16-0/d-.
It was painted on. 2nd layer: Intermediate layer gelatin with a coating amount of 41111/dl
Painted. Third layer: green-sensitive silver chlorobromide emulsion layer containing the above exemplary magenta coupler (57) at 4117/dl,
The green-sensitive silver chlorobromide emulsion has a silver content of 2-g/da2, di
41Md■ octyl phthalate and 1Md■ gelatin
The coating was applied so that the coating amount was 61 Mdl. 4th layer: Intermediate layer UV absorber 2-hydroxy-3',5'-di-t
-amylphenol)-benzotriazole 3mg/
d+e 12- (2'-hydroxy-3'. 5'-di-t-butylphenol)-benzotriazo
3+eg/da of alcohol, 4 dioctyl phthalate
mg/dm” OJ: (F Seratin tr 14mo/d
The coating was applied so that the coating amount was +++2 (F). 5th layer: red-sensitive silver chlorobromide emulsion layer 2,4-dichloro-3-methyl- as cyan coupler
6-Ca-<2.4-G t-Afi /L/ Fe
1-g/d■
, 2-(2,3,4,5,6-pentafluoropheny
)acylamino-4-chloro0-5-[α-(2,4-
tert-amylphenoxy)pentylamide]
3 NQ/da and red-sensitive silver chlorobromide emulsion to silver
Apply the coating so that the coating amount is converted to 3sa/ds.
Ta. 6th layer: 2-(2'-hydroxy-3'
, 5'-di-t-amylphenol)-benztria
Sole at 2mg/d+a2.2- (2'-hydroxy
C-3', 5'-G [-butylphenol)-be
2 raQ/da”, diocchi
2111 Mdl of luphthalate and 6 of gelatin
The coating was applied so that the coating amount was 112 mQ/d. No. 711: Apply protective layer gelatin to a coating amount of 9 ml; l/da2.
It was painted on. The sample thus prepared is designated as sample 33. Next, the 311th sample of sample 33 is gold I! A complex (coupler
(applied at a ratio of 0.5 mol to
(applied at a ratio of 0.5 mol to the puller), oil-soluble in the fourth layer
Sample 33 except that the dyes were added in the combinations shown in Table 3.
Identical samples 34 to 46 were prepared. The sample thus prepared was subjected to the same exposure treatment as in Example 1.
became. For each sample obtained after treatment, a matrix was applied in the same manner as in Example 1.
The light fastness, whiteness, and sharpness of the Zenta color image were measured. Conclusion
The results are shown in Table 3. As is clear from Table 3 below, only the coupler of the present invention was used.
Sample 33 had poor light resistance and sharpness. In addition, sample 34 in which a gold m-complex was added to the coupler of the present invention
In this case, deterioration of whiteness is stopped and sharpness is not improved. of the present invention
A test of the present invention using a metal complex and an oil-soluble dye in the coupler
Colors (35 to 46) have good light fastness and sharpness.
In addition, there is no deterioration of whiteness, and a clear II image can be obtained.
Ta. In addition, samples containing antioxidants (39 to 46
, the light resistance has been further improved and a more robust color 1m image can be obtained.
It was. Example 4 In sample 35 of Example 3, the third layer metal complex and high
Except that boiling point mixed media were used in the combinations shown in Table 4,
Samples 47 to 52 were prepared in the same manner as sample 35. These samples were subjected to exposure treatment in the same manner as in Example 3 to produce magenta.
The light fastness, whiteness and sharpness of the yellow image were measured. the
The results are shown in Table 4. *Metal complex at a ratio of 0.5 mol to 1 mol of coupler
Added with. *POP Nidioctyl phthalate (11! Electricity rate 5.3
)*TNP nitriisononyl phthalate (dielectric constant 4.5) DEP nitriisononyl phthalate (dielectric constant 1.6) Table 4
As is clear from the above, the samples of the present invention have poor light resistance and whiteness.
, both have good sharpness. In addition, sample 35 using DOP and TNP with low dielectric constant
．． 47.50.51 uses DEP with higher dielectric constant
The degree of improvement in light resistance was particularly large compared to sample 48.52.
It is effective. Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent Patent attorney Ichinose Miyao procedural amendment August 12, 1985

Claims (1)

[Claims] At least one magenta coupler represented by the following general formula [I] and a singlet oxygen quenching rate constant of 3×10^
A silver halide photographic light-sensitive material characterized by containing at least one metal complex of 7M^-^1.sec^-^1 or more and at least one oil-soluble dye. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. You may. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ]