JPS62289837A - Silver halide photographic sensitive material capable of giving coloring matter image having improvement light fastness - Google Patents

Abstract

PURPOSE:To obtain the titled material having the improved color fastness of a coloring matter image by dispersing a specific coupler and/or a polymer coupler derivated from said coupler and a specific anti-fading agent in a prescribed high boiling point org. solvent. CONSTITUTION:In the titled material, at least one layer of the silver halide emulsion layers contains one or more than one kinds of the couplers selected among the compds. shown by formulas I, II and III, and/or the polymer couplers derived from said couplers derived from said couplers, and the antifading agent having the oxidation potential of 0.95-1.50V for example, the compd. IV are dispersed in the high boiling point org. solvent having <=6.0 dielectric constant. In formulas I-III, Za-Zc are each a non-metallic atom group necessary for forming a nitrogen contg. heterocyclic ring, Xa-Xc are each H or a group capable of cleaving by reacting with the oxidant of the developing agent, Ra-Rg are each H or a substituent, Y1 is carbon or nitrogen atom, Y2 is carbon or a heterocyclic atom. In formula IV, R1 is H, alkyl or aryl group, etc., R2, R3, R5 and R6 are each H, halogen atom or hydroxyl group, etc., R4 is alkyl, hydroxy or aryl group, etc.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material.
It has excellent spectral absorption characteristics and light fastness of dye images.
A new technology that has been significantly improved and has improved the color development of modern poetry.
This invention relates to a silver halide photographic material. [Background of the Invention] Traditionally, silver halide color photographic materials have been subjected to imagewise exposure.
Aromatic primary amine coloring is achieved by color development.
The oxidized form of the developing agent and the color former undergo a coupling reaction.
For example, indophenol, indoaniline, inda
min, azomethine, phenoxazine, phenazine and
Pigments similar to those are generated and color images are formed.
This is a well-known fact. This kind of photography
In formulas, a subtractive color method is usually used to reproduce colors, and blue
Sensitive, green-sensitive and red-sensitive light-sensitive silver halide emulsions
Each layer contains a coloring agent that has an extra color relationship, that is, yellow.
- Contains couplers that produce magenta and cyan colors.
A solid silver halide color photographic sensitizer is used. The cartridge used to form the above yellow image
Examples of pullers include acyl azetanilide couplers.
It is also used as a coupler for magenta color image formation.
For example, pyrazolone, pyrazolobenzimidazole,
Lasolotriazole or indasilone couplers are known.
It is also used as a coupler for cyan image formation.
For example, phenolic or naphthol couplers
Commonly used. The dye image obtained in this way is exposed to light for a long time.
Even if stored under high temperature and high humidity, the color will not change or fade.
desired. In addition, silver halide color photographic materials
(hereinafter referred to as color photographic materials), the uncolored areas may be exposed to light or moisture.
Items that do not yellow due to heat (hereinafter referred to as Y-stain)
desired. However, in the case of a magenta coupler, the light in the uncolored area
, Y-stain due to moist heat, fading of dye image area due to light
is extremely large compared to yellow coupler and cyan coupler.
This is often a problem. 1, which is widely used to form magenta pigment.
Formed from magenta couplers of 2-pyrazol-5-ones
In addition to the main absorption near 550 nm, the dye that is
It has sub-absorption near m, and in order to solve this
Various studies have been conducted. Pyra as described in British Patent No. 1.047.612
Zolobenzimidazoles, U.S. Patent No. 3,770,4
The indacilones described in No. 47, and the indasilones described in No. 3.725.
067, British Patent No. 7,252,478, British Patent No. 1,
334,515, such as pyrazolotriazoles, etc.
A magenta coupler has been proposed. Of these, the U.S.
Patent No. 3.725.067, British Patent No. 1,252,
No. 418, the day stated in No. 1,334,515
-pyrazolo-[3,2-C]-s -t-lyazole type
The dye formed from the magenta coupler has 43 Onm
Low secondary absorption and no color development in response to light, heat, and humidity
The occurrence of Y-stin is also extremely small, which is a desirable advantage.
It is something that you have. Similarly, 43 of the element composed of the above magenta coupler
British Patent 1, which has small sub-absorption near 0 nm,
Virazolobenzimi described in No. 047,612
'Dazoles, as described in U.S. Pat. No. 3,770,447
Imidacylones, also No. 3,725,067, British Special
No. 1,252,418 and No. 1.334.515.
1H-pyrazolo[5,1-c]-]1.2.4-
Triazole type coupler JP-A-59-171956,
Recorded in Research Disclosure No. 24.531.
1H-pyrazolo[1,5-b]-]1.2.4-
Triangle type coupler research disclosure
- 1 day - Pyrazolo [1,
5-c]-]1.2.3-triazole type coupler special
No. 59-162548, Research Ice Clothes
1-Imidazo H,2 as described in Ya N 0.24531
-b] Pyrazole type coupler, JP-A-60-43659
No., Research Ice Closure NO, 24230
1H-pyrazolo N, 5-b] pyrazole type capacitor described in
Puller, Japanese Patent Publication No. 60-33552, Research Dis.
1 (-pyra) described in Closure NO, 24220
Zolo N, 5-d ] Mazen such as tetrazole type couplers
Takapura is proposed. However, some of these azole couplers
had a problem in terms of color development. On the other hand, in International Publication No. 86102467,
As mentioned above, the side absorption is small and the spectral absorption characteristics can be immersed.
Mazene has excellent coupler dissolution and dispersion characteristics and color development.
Takapura is proposed. The magenta coupler proposed in the publication is a conventional azo coupler.
The dissolution and dispersion characteristics and color development characteristics are better than that of the roll-type couplers.
Although it was excellent, it had a drawback in light resistance compared to t.
. We have developed a technology to improve the light resistance of the azole coupler.
, for example, as described in JP-A-59-125732.
Using phenolic compounds and phenyl ether compounds
technology, JP-A-61-73152 and JP-A-61-72
Using piperazine compounds described in No. 246
The technology is disclosed in the above-mentioned International Publication No. 86102467 (WO>86102467).
I tried applying it to the coupler described in
It was not possible to improve it in minutes. Therefore, the present inventors have developed a method that has excellent dissolution and dispersion properties and color development properties.
Dyes formed from these couplers have the advantages of
As a result of studying how to improve the light resistance of Odo, we found that an anti-fading agent and
using a specific compound as a coupler dispersion medium.
When certain high-boiling point organic solvents are used in
It was found that the color properties and light fastness were significantly improved.
. Furthermore, we have published these documents in International Publication No. 8610246.
In addition to the couplers listed in No. 7, these
Similar considerations were made for couplers similar to couplers.
This invention was arrived at without making the present invention. [Object of the invention] The present invention has been made in view of the above problems.
The first purpose of brightness is to have excellent spectral absorption characteristics and dye image
A silver halide photographic material with significantly improved light fastness.
The aim is to provide fees. The second object of the present invention is to improve the coloring property of the dye during development.
An object of the present invention is to provide a silver halide photographic material. The third object of the present invention is to improve spectral absorption characteristics, color development, and light hardness.
Silver halide photographic material with improved three properties at the same time:
The aim is to provide fees. The fourth object of the present invention is to improve spectral absorption characteristics and color development.
Our objective is to provide a method for improving light fastness without causing
Ru. [Structure of the Invention] The object of the present invention is to provide at least one layer of halogen on a support.
In a silver halide photographic light-sensitive material having a silver emulsion layer
, at least one layer of the silver halide emulsion has the following general formula:
Caps shown in (a), (b) and (c) respectively
at least one coupler and/or selected from
or polymer couplers derived from said couplers;
Oxidation potential E OX (V) is 0.95≦E0x≦1
50, an anti-fading agent with a dielectric constant of 6.0 or less and a high boiling point.
This was achieved by dispersion using several solvents. (Rd)n. General formula (b) General formula (C) (In general formulas (a), (b) and (c), 2cL. Z↓ and Zct each form a nitrogen-containing heterocycle.
Does not represent the required nonmetallic atomic group. XcL, X Anzu and ×
. are hydrogen atoms or reaction with oxidized color developing agent, respectively.
represents a group that can be separated upon reaction. R,,Rh, R,,R,(,R,,RJ and R
Each J represents a hydrogen atom or a substituent. However, R
V is a coupler represented by general formula (C) and a coloring agent.
A substituent that does not leave when reacting with an oxidant.
Ru. Yl represents a carbon atom or a nitrogen atom. Y2 is
Represents a carbon atom or a heteroatom. =- is Yl and Yl
The bond between may be a single bond or a double bond.
represents something. However, Yl is a carbon atom and the bond between Yl and Y2 is a double bond.
In this case, n3 is 1, n4 is O, and R6 is
A coupler represented by general formula (a) and a color developing agent
A substituent that does not leave when reacting with an oxidant.
Therefore, Yl is a carbon atom and the bond between Yl and Y2 is a single bond.
In this case, n3 and n are both 1. Also, Y1 is a nitrogen source
If the bond between Yl and Y2 is a double bond in the child, n3 and n4
are both O, and Y2 is a heteroatom, and Yl
If is a nitrogen atom and the bond between Yl and Y2 is a single bond, then
n3 is 1 and n4 is O. Note that caps represented by general formulas (a), (b) and (C)
RA is the position where X& is connected, and the position where X↓ is connected, respectively.
Color development occurs only at the positions where
Coupling reaction with oxidized image agent. ) [Specific structure of the invention] The silver halide photographic material of the invention has the general formula (a)
, (b) and (C), respectively.
at least one coupler selected from
A polymer coupler derived from a coupler (hereinafter referred to as a polymer coupler derived from a coupler)
A light coupler) is used. cPjIlU General formulas (a), (b), (e) according to the present invention
(,) (Rd)nq In the magenta coupler represented by the general formula (b) and the general formula (c), Zatzb and
and Zc are nonmetallic atomic groups necessary to form a nitrogen-containing heterocycle.
, and Xa, Xb and Xc are each a hydrogen atom or a color developer.
Represents a substituent that can be eliminated by reaction with the oxidized form of the image agent.
vinegar. Also, Rat Rb, RCt Rd, Ret Rf
and Rg each represent a hydrogen atom or a substituent. However, Rg is the coupler represented by the general formula (C) and the coloring
It will not be released when it reacts with the oxidized form of the developing agent.
It is a substituent. Y represents a carbon atom or a nitrogen atom, Y2 is a carbon atom
or represents a heteroatom. Koni believes that even if the open bond between Yl and Y2 is a single bond,
Indicates that it may be a double bond. Y, , Y, and Y each represent a carbon atom or a nitrogen atom.
represent. n+y nzt nfft net nst ns and V
nt is O or 1, respectively. However, Y is a carbon atom and the bond between Y and Y2 is a double bond.
If n3 is 1, n is O, and R
e is a coupler represented by the general formula (,) and a color developing agent
A substituent that does not leave when reacting with the oxidant of
Yes, Yl is a carbon atom and the bond between Y and Y2 is a single bond
In this case, both n and n4 are 1. Also, Y is nitrogen.
If the bond between Yl and Y2 is a double bond in an elementary atom, n3
and n4 are both O, and Y2 is a heteroatom
, if Yl is a nitrogen atom and the bond between Y and Y2 is a single bond,
If so, n is 1 and n is O. Note that the caps represented by general formulas (a), (b), and (e)
The puller is located at the position where Xa is bonded and where xb is bonded, respectively.
It is emitted only at the position where the
Coupling reaction with oxidized color developing agent. Table of the Rat Rh-RCt Rd, Re or Rf
Examples of substituents include halogen atoms and alkyl groups.
, cycloalkyl group, alkenyl group, cycloalkenyl
group, alkynyl group, aryl group, heterocyclic group, acyl group
, sulfonyl group, sulfinyl group, phosphonyl group, carbon
Bamoyl group, sulfamoyl group, sia/group, spiro compound
residues, bridged hydrocarbon compound residues, alkoxy groups, ants
ruoxy group, heterocyclic oxy group, siloxy group, acyl group
Oxy group, carbamoyloxy group, ami7 group, acyl group
Mi7 group, sulfonamide group, imide group, ureido group,
7 amoylamides, 7 alkoxycarbonylamides
, aryloxycarbonylamino group, alkoxylic
Zanyl group, aryloxycarbonyl group, alkylthio
group, arylthio group, and heterocyclic group. Examples of halogen atoms include chlorine atoms and bromine atoms.
Among them, a chlorine atom is particularly preferred. Ra, Rb, Rct Rd, Re or Rr'''C expressed
Examples of the alkyl group include those having 1 to 32 carbon atoms,
Kenyl group and alkynyl group have 2 to 32 carbon atoms.
, cycloalkyl group, cycloalkenyl group is carbon
Number 3 to 12, particularly preferably 5 to 7, and an alkyl group
, alkenyl group, alkynyl group may be straight chain or branched
. In addition, these alkyl groups, alkenyl groups, alkynyl groups
, cycloalkyl group, and cycloalkenyl group are substituents [e.g.
For example, aryl, sia/, halogen atom, heterocycle, cyclo
loalkyl, cycloalkenyl, spiro compound residues,
In addition to bridge hydrocarbon compound residues, acyl, carboxy, and carboxyl
bamoyl, alfkidicarbonyl, aryloxycal
Those substituted via a carbonyl group such as carbonyl, and
is exchanged via a heteroatom (specifically, hydrogen
Roxy, alkoxy, monoyloxy, heterocyclicoxy
, siloxy, acyloxy, carbamoyloxy and other acids
Those that substitute through elementary atoms, nitro, ami7 (dial)
(including Kirami 7, etc.), Suru 7 Amoyl 7 Mi/, Arco
Xycarbonylamide 7, aryloxycarbonylamide
No, acylamino, sulfone 7mide, imide, Waleido
Substituents via the nitrogen atom such as alkylthio, alkylthio, etc.
lylthio, heterocyclic thio, sulfonyl, sulfinyl
, those substituted via a sulfur atom such as sulfamoyl,
(e.g. those substituted via a phosphorus atom such as phosphonyl)
You may do so. Specifically, for example, methyl group, ethyl group, isopropyl group
, t-butyl group, pentadecyl group, heptadecyl group, 1
-Hexyl/Nil! , 1.1'-nobentyl/nyl group,
2-chloro-t-acyl group, tri7fluoromethyl group,
1-nitoxytridecyl group, 1-methoxyisopropyl
group, methanesulfonylethyl group, 2,4-not-amino
7ethyl/oxymethyl group, anilino group, 1-phenyliso
Propyl group, 3 rings, 1 butane, 7 lehon, 7 mino, 7 e, 7 k
ciprovir group, 3-4'-(α-[4''(p-hydro
xybenzenesulfonyl)7e/xy]dodeca/yrua
/) phenylpropyl group, 3-14'-(ff-
(2”, 4”-no 1-7 milphenoxy)butanami
[do]phenyl)-propyl group, 4-(α-(0-chloro
phenoxy)tetradecanamide 72/xy]propyl
group, allyl group, cyclopentyl group, cyclohexyl group, etc.
can be mentioned. Ra, Rb, Rat Rd, Re or Rf Tiwashare
As the aryl group, a phenyl group is preferable, and the substituent (
For example, alkyl group, alkoxy group, acylami 7 group, etc.
). Specifically, phenyl group, 4-t-butyl 7-enyl group,
2.4-sheet t-7 milphenyl group, 4-tetradecane
Amidophenyl group, hexadecyloxyphenyl group, 4″
-(ff-(4″-t-butylphenoxy)tetradeca
and amidophenyl groups. Represented by Ra, Rb, Rat Rd, Re or Rfr
The heterocyclic group preferably has 5 to 7 shells, and is unsubstituted.
They may be separated or condensed. Specifically, 2-furyl group, 2-chenyl group, 2-pyrimi group
Examples include a diinyl group and a 2-benzothiazolyl group. A represented by Ra, Rb, Rc, Rd, Re or Rf
Examples of the sil group include acetyl group, phenyl 7-cetyl group,
group, dodecanoyl group, a-294-cy-1-amylphene
Furkylcarbonyl group such as noxybutanoyl group, benzo
yl group, 3-pentadecyloxybenzoyl group, p-k
Examples include 7-aryl carbonyl groups such as lorbenzoyl group, etc.
It will be done. Represented by Ra, Rb, Rat Rdt Re or Rf
Examples of sulfonyl groups include methylsulfonyl group, dode
Alkylsulfonyl groups such as silsulfonyl groups, benzene
ants such as p-toluenesulfonyl group and p-toluenesulfonyl group.
Examples include lsulfonyl group. Represented by Ra, Rb, Re, Rd, Re or Rf″c
Also, as rufinyl i, ethylsulfinyl group, oc
Tylsulfinyl group, 3-phenoxybutylsulfini
Alkylsulfinyl group, phenylsulfinyl group, etc.
Nyl group, conjugate-bentate-silphenylsulfinyl group
Examples include arylsulfinyl groups such as. Represented by Ra, Rh, Rc, Rd, Re or RE"C'
As the phosphonyl group, butyloctylphosphonyl group is used.
Alkylphosphonyl groups such as octyloxyphosphonyl
Arylphosphonyl groups such as 7-enoxyphosphonyl
Group-like group-oxyphosphonyl group, phenylphosphonyl group
Examples include arylphosphonyl groups such as nyl groups. Represented by Ra, Rb, Re, Rd, Re or Rf″c
The carbamoyl group is an alkyl group, an aryl group (preferably
(phenyl group) etc. may be substituted (e.g. N-methyl
carbamoyl group, N,N-butylcarbamoyl group,
N-(2-pentadecyloctylethyl)carbamoyl
group, N-ethyl-N-dodecylcarbamoyl group, N-(
3-(2,4-di-t-7milphenoxy)propyl)
Examples include carbamoyl group. Ra, Rb, Rc, Rd, Re or Rf-r! It's been done
The sulfamoyl group is an alkyl group, an aryl group (preferably
or phenyl group), for example, N-
Propylsul 77 Moyl i, N. N-noethylsul7amoyl M, N-(2-pentadecyl
(oxyethyl) sulfamoyl group, N-ethyl-N-
Dodecylsulfamoyl M, N-phenylsul 77 mo
Examples include yl group. Ra, Rb, Rc, Rd, Re or Rf cffiwa
Examples of spiro compound residues include spiro[3゜3
] Hebutan-1-yl and the like. Ra, Rb, Rc, Rd, Re or Rrt'f<ゎ
Examples of bridged carbonized compound residues include bicyclo[2,
2,1] heptan-1-yl, tricyclo[3,3,1
, 13″71decane-1-yl, 7.mardimethyl-bi
Examples include cyclo[2,2,1]heptan-1-yl, etc.
Ru. Represented by Ra, Rb, Ray Rd, Re or Rf
The alkoxy group can further be used as a substituent to the alkyl group.
The listed ones may be substituted, for example, methoxy group,
Propoxy group, 2-ethoxynidoxy group, pentadecyl
Oxy group, 2-dodecyloxyethoxy group, 7enethyl
Examples include oxyethoxy group. Ray Rb, Re, Rd, Re or Rf['! Wasare
As the aryloxy group, phenyloxy is preferable.
In addition, the aryl nucleus may further include a substituent or an atom to the child aryl group.
It may be replaced by something listed as a child, e.g.
Phenoxy group, pt-butyl 7eth/oxy group, m-penta
Examples include decylphenoxy group. Represented by Ra, Rb, 'Re, Rd, Re or Rf''C
The heterocyclic oxy group has 5 to 7 heterocyclic rings.
It is preferable that the heterocycle further has a substituent.
For example, 3,4,5°6-tetrahydrobi
ranyl-2-oxy group, 1-phenyltetrazole-5
-oxy group. Represented by Ra, Rb, Rcw Rdt Re or Rf
The siloxy group is further substituted with an alkyl group, etc.
For example, trimethylsiloxy group, triethylsiloxy group, etc.
Examples include a roxy group and a dimethylbutylsiloxy group. Represented by Ra, Rh, Re, Rd, Re or Rf c
Examples of the acyloxy group include alkylcarbonyl groups.
xy group, arylcarbonyloxy group, etc.
may have a substituent, specifically acetyloxy
cy group, a-chloroacetyloxy group, benzoyloxy
Examples include groups. Calculator represented by Ra, Rh, Rc, Rd, Re or Rf
The rubamoyloxy group has an alkyl group, an aryl group, etc.
For example, N-ethylcarbamoyloxy
cy group, N, N-noethyl group, rubamoyloxy group, N-phthalate group,
Examples include phenylcarbamoyloxy group. A represented by Ra, Rb, Rc, Rd, Re or Rf
The group 7 is an alkyl group, an aryol group (preferably phenyl group)
group), etc., for example, ethylamino group
, anilino group, m-chloroanili 7 groups, 3-pentadecy
oxycarbonylanilino group, 2-chloro-5-hexyl
Examples include 7 groups of sadikanamide aniline. Represented by Ra, Rb, Re, Rd, Re or Rft'
As the 7 acyl amide groups, there are 7 alkyl carbonyl amide groups.
, arylcarbonylamine 7 groups (preferably phenylcarbonyl)
(7 groups), and further has a substituent.
Specifically, acetamido group, α-ethylpropane
Amide group, N-phenylacetamido group, dodecanamide group
do group, 2,4-di-t-7-milphenoxyacetamide
group, a-3-t-butyl-4-hydroxyphenoxy
Examples include butanamide group. Strain represented by Ra, Rb, Rc, Rd, Re or Rf
As a sulfonamide group, an alkylsulfonylamino group
, arylsulfonylamine/group, etc., and further substituted
may have a group, specifically methylsulfonylamine 7
group, pentadecylsulfonylamine 7 groups, benzene sulfonyl group,
amide group, p-toluenesulfonamide group, 2-methane amide group, p-toluenesulfonamide group,
Toxy-5-7-7-methylbenzenesulfonamide group etc.
Can be mentioned. Represented by Ra, Rb, Rct Rd, Re or Rf
The imide group may be open-chain or cyclic,
It may have a substituent, for example, a succinimide group,
3-heptadecylsuccinimide group, 7-talimide group,
Examples include glutarimide group. Ray Rb, Rct Rd, Re or Rf
The ureido group to be used is an alkyl group, an aryol group (preferably
(or phenyl group), etc., such as
N-ethylureido group, N-methyl-N-decylureido group
Ido group, N-phenylureido group, N-p-)lylure
Examples include ide groups. Represented by Ra, Rb, Rat Rd, Re or Rf
Sul 77 moylami 7 group is an alkyl group, an aryl group (
Preferably phenyl group) etc. may be substituted, e.g.
For example, N, N-dibutyl sulfur 77 moyl amine 7 groups, N-meth
Thirsul 7 amoylami 7 groups, N-7z Nilsul 77 moles
Examples include ylami 7 groups. A represented by Ra, Rb, Re, Rd, Re or RE
The alkoxycarbonylamine 7 group further has a substituent.
For example, methoxycarbonylamide 7 groups,
7 methoxyethoxycarbonylamide groups, octadecyloyl
Examples include oxycarbonylamide 7 groups. A represented by Ra, Rb, Re, Rd, Re or Rf
The 7 lyloxycarbonylamide groups have a substituent.
For example, phenoxycarbonylamide 7 groups, 4-
Seven methylphenoxycarbonylamide groups are mentioned. Ra, Rb, Re, Rd, Re or Rf? ! be ignored
Even if the alkoxycarbonyl group further has a substituent,
Often, for example, methoxycarbonyl group, butyloxycarboxylic group
Bonyl group, tosyloxycarbonyl group, octadecyl group
carbonyl group, ethoxymethoxycarbonyl group,
Examples include an xy group and a benzyloxycarbonyl group. Represented by Ra, Rb, Rc, Rd, Re or Rf″c
The aryloxycarbonyl group further has a substituent.
For example, phenoxycarbonyl group, p-chloro
Phenoxycarbonyl group, m-pentadecyloxy 7-ethyl group
/xycarbonyl group, etc. A represented by Ra, Rh, Rc, Rd, Re or Rf
The rukylthio group may further have a substituent, such as
Ethylthio group, dodecylthio group, octadecylthio group
, 7enethylthio group, 3-phenoxypropylthio group
Can be mentioned. Rat Rb, Re, Rd, Re or Rf Tiwasher
The arylthio group is preferably a phenylthio group, and further substituted
It may have a substituent, for example phenylthio group, p-
Methoxyphenylthio group, 2-t-octadecylphenyl
ruthio group, 3-octadecylphenylthio group, 2-cal
Boxyphenylthio group, p-acetami/phenylthio
Examples include groups. Ra, Rh, Re, Rd, Re and Rf ci
As the heterocyclic thio group, the heterocyclic thio group of 5-7 shells is
Preferably, it may further have a fused ring or a substituent.
For example, 2-pyridylthio group, 2-benzo
Thiazolylthio group, 2,4-di7-7xy1,3,5
-) lyazole-6-thio group. Rg and Yl are carbon atoms, and the open bond between Yl and Y2 is
Rclm in the case of a double bond i) With the coupler represented by
It is not released when the color developing agent reacts with the oxidized product.
Examples of substituents that are not present include alkyl groups, aryl groups,
Cycloalkyl group, alkenyl group, cycloalkenyl group
, alkynyl group, heterocyclic group, acyl group, sulfonyl group
, sulfinyl group, phosphonyl group, carbamoyl group,
Rufamoyl group, 7-cya group, spiro compound residue, bridge
Hydrocarbon compound residue, siloxy group, carbamoyloxy
group, alkoxycarbonyl group, aryloxycarbonyl group
Examples include ru groups. As mentioned above, as specific examples of each group, for example, the specific examples of Ra mentioned above include
The following are examples. Reaction with oxidized products of color developing agents represented by Xa, Xb, and Xc
Examples of substituents that can be removed by reaction include halogen atoms.
In addition to carbon atoms (chlorine atoms, bromine atoms, 7-noso atoms*),
through an oxygen atom, a sulfur atom, or a nitrogen atom.
Examples include groups such as As a group substituting via a carbon atom, a carboxyl group
, hydroxymethyl group, triphenylmethyl group, etc.
Xa, Xb, Xc l: Correspondingly, formula (a') (Rd)n,' formula (b') , Rb' is Rb, Rc' is Rc
, Rd' is Rd, Re' is Re, and Rf'
is Rf, Rg′ is Rg, n,′ is n, and 0
2' is R2, , l is n, 14' is n,
and , I is n, and 1, I is R6 and , l is n, and
, Y1' is Yl, Y2' is Y2, Y,' is Y, and
, Y4' is Y, Y,' is Y, Za' is Za,
zb' is synonymous with zb, Zc' is synonymous with Zc, and R5-
R6 is hydrogen, an aryl group, an alkyl group, or a heterocyclic group
The groups represented by ) are exemplified. Examples of groups substituted via an oxygen atom include alkoxy
cy group, 7 lyloxy group, heterocyclic oxy group, 7 syloxy group
Oxy group, sulfonyloxy group, alkoxycarbonyl group
xy group, aryloxycarbonyloxy group, alkyl group
Oxalyloxy group, alkoxyoxalyloxy group
Can be mentioned. The alkoxy group may further have a substituent, for example,
Toxy group, 2-7ethoxy group, 2-cya/ethoxy group
xy group, 7enethyloxy group, p-chlorobennoroxy group
Examples thereof include cy group. The aryloxy group is preferably a phenoxy group,
The aryl group may further have a substituent, specifically
contains 7 eth/oxy group, 3-methylphenoxy group, 3-dode
Silphenoxy group, 4-methanesulfonamidophenoxy group
cy group, 4-C(2-(3'-pentadecylphenoxy)
butanamide] phenoxy group, hexadecylcarbamoy
methoxy group 4-Schif/7eth/oxy group, 4-7 tansulf
Honylphenoxy group, 1-su7tyloxy group, p-metho
Examples include xyphenoxy group. The heterocyclic oxy group includes 5 to 7 true heterocyclic oxy groups.
A cy group is preferable, and it may be a condensed ring or have a substituent.
Specifically, 1-phenyltetrazoly
2-benzothiazolyloxy group, etc.
It will be done. Examples of the acyloxy group include acetoxy group, buto
Alkylcarbonyloxy groups such as sulfoxy groups, thinner
Flukenylcarbonyloxy group such as moyloxy group,
Arylcarbonyloxy groups such as benzoyloxy groups
can be mentioned. The sulfonyloxy group is, for example, butanesulfonyloxy group.
Examples include fluoroxy group and methanesulfonyloxy group. Examples of the alfkidicarbonyloxy group include etho
xycarbonyloxy group, benzyloxycarbonyloxy group
Examples include xy group. The aryloxycarbonyloxy group is phenoxy
Examples include cycarbonyloxy group. 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
Nitylthio group, 7enethylthio group, benzylthio group, etc.
Can be mentioned. As the ruthio group, phenylthio group, 4-methane
Sulfonamidophenylthio! , 4-)' decil 7 energy
Tylthiotanami Y7enethylthio group, 4-carboxyphenyl
Thio group, 2-ethoxy-5-t-butylphenylthio group
etc. Examples of the heterocyclic thio group include 1-phenyl-1.
2,3.4-tetrazolyl-5-thio group, 2-benzothi
Examples include azolylthio group. As the alkyloxythiocarbonylthio group, dode
Examples include syloxythiocarbonylthio group. The group substituting via the nitrogen atom is tilted. child
Here, R1 and R1 are a hydrogen atom, an alkyl group, an aryl group
, heterocyclic group, sul77 moyl group, carbamoyl group, a
Syl group, sulfonyl group, aryloxycarbonyl group,
represents an alphkidicarbonyl group, and R7 and R6 are bonded together.
may form a heterocycle, provided that Rt and R8 are both
It is never a hydrogen atom. The alkyl group may be straight chain or branched, preferably carbon
These are numbers 1 to 22. In addition, an alkyl group has a substituent.
Examples of the substituent include an aryl group,
Alkoxy group, aryloxy group, alkylthio group,
lylthio group, 7 alkylamides, 7 arylamides,
Acylamide 7 groups, sulfonamide group, imino group, acyl
group, alkylsulfonyl group, arylsulfonyl group, carbon
Rubamoyl group, sulfamoyl group, alkoxycarbo2
-Benzothiazolyl group, 2-bilinol group, etc.
. As the sulfamoyl group represented by R7 or R8,
N-alkylsulfamoyl group, N,N-dialkyl group
rufamoyl group, N-arylsulfamoyl group, N,
N-diarylsul 77 moyl group, etc., and these
The alkyl group and aryl group are the aforementioned alkyl group and aryl group.
may have the substituents listed for the group. Sur
Specific examples of famoyl groups include, for example, N,N-diethyl
Rusul 77 moyl group, N-methylsulfamoyl i, N
-)'f silsulfamoyl i, Np) rilusul 7 amo
An example is an yl group. The carbamoyl group represented by R1 or R8 is N
-furkylcarbamoyl group, N,N-dialkylcarba
Moyl group, N-7 arylcarbamoyl group, N,N-Schiff
17-carbamoyl group, etc., and these alkaline
Kyl group and aryl group are the above-mentioned alkyl group and 7-aryl group.
It may have the substituents listed above. Karbamoi
Specific examples of Nyl groups, aryloxycarbonyl groups,
Kyloxycarbonylamine 7 groups, aryloxycarbo
Nylamino group, hydroxyl group, carboxyl group, sia
and a halogen atom. Specifics of the alkyl group
For example, ethyl group, octyl group, 2-
Examples include ethylhexyl group and 2-chloroethyl group. The aryl group represented by R2 or R8 has a carbon number of
6 to 32, especially 7enyl group and naphthyl group are preferable, and
The aryl group may have a substituent, and examples of the substituent include those listed above.
As a substituent to the alkyl group represented by R7 or R8
Examples include those listed above and a furkyl group. the aryl
Specific examples of the group include phenyl group, 1
-su7tyl group, 4-methylsulfonylphenyl group are mentioned.
La eightru. The heterocyclic group represented by R7 or R8 is 5 to 6
A simple ring is preferable, and a fused ring may also be used, and a substituent is
May have. Specific examples include 2-furyl group, 2-kyl group,
7lyl group, 2-pyrimidyl group, examples include N,
N-diethylcarbamoyl group, N-methylcarbamoyl
group, N-dodecylcarbamoyl i, N-p-cyanophe
Nylcarbamoyl group, N-p-)lylcarbamoyl group is
Can be mentioned. Examples of the acyl group annihilated by Rt or R8 include acyl groups such as
alkylcarbonyl group, arylcarbonyl group, heterocycle
Examples include carbonyl groups, such alkyl groups, and aryl groups.
, the heterocyclic group may have a substituent. Acyl group
For example, hexafluorob
Tameyl group, 2,3,4,5,6-pentafluoroben
Zoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-7lylcarbonyl group. As the sulfonyl group represented by R or R6,
Kylsulfonyl group, arylsulfonyl group, heterocyclic group
Examples include sulfonyl group, which may have a substituent, and specifically
For example, ethanesulfonyl group, benzene
sulfonyl group, octane sulfonyl group, naphthalene sulfonyl group
Nyl group, p-chlorobenzenesulfonyl group, etc.
It will be done. Aryloxycarbonyl group represented by R7 or R,C
is the substituent listed for the above-mentioned ori-ru group.
It may have a phenoxycarbonyl group, specifically, a phenoxycarbonyl group, etc.
Can be mentioned. The alfkidicarbonyl group represented by R2 or R3 is
It may have the substituents listed for the alkyl group,
Specifically, methoxycarbonyl group, dodecyl group
Oxycarbonyl group, benzyloxycarbonyl group, etc.
Can be mentioned. The heterocycle formed by combining R2 and R8 is 5-
It is preferable that there are 6, and it may be saturated or unsaturated, or
It may or may not have aromaticity, and it may be a condensed ring.
The heterocycle may include, for example, an N-7 talimide group.
, N-succinimide group, 4-N-urazolyl group, 1-
N-hyguntoynyl group, 3-N-2,4-nookinyl group
sazolidinyl group, 2-N-1,1-dioxo-3-(2
H)-oxo-1,2-benzthiazolyl group, 1-pyro
Lyle group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-
Pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group
group, 1-imidazolyl group, 1-imigzolinyl group, 1
-indolyl group, 1-isoindolinyl group, 2-isoyl group
indolyl group, 2-″″isoindolinyl group 1-benzoto
Liazolyl group, 1-pencyimigzolyl group, 1-(
1,2,4-triazolyl) group, 1- (1,2,3
-) riazolyl) group, 1- (1,2,3,4-tetra
zolyl) group, N-morpholinyl group, 1,2,3,4-te
trahydroquinolyl group, 2-oxo-1-pyrrolidinyl
group, 2-IH-pyridone group, 7-talathion group, 2-oxy
So-1-piperinonyl group, etc., and these heterocycles
Groups include alkyl groups, aryl groups, alkyloxy groups, and aryl groups.
group, acyl group, sulfonyl group, alkylamino group
7 groups, arylamino group 7 groups, acylamino group, sulfonate group
Mi7 group, carbamoyl group, sulfamoyl group, alkyl group
Thio group, arylthio group, ureido group, alkoxyl
Bonyl group, aryloxycarbonyl group, imide group,
Toro group, sia/group, carboxyl group, halogen atom, etc.
It may be replaced by more. Also, Za, Zb, Zc, Za', Z
As a nitrogen-containing heterocycle formed by b' or Zc'
is a virol ring, pyrazole ring, imidazole ring, tri-
Azole ring, thiazoline ring, oxazoline ring or tet
Examples include lazole rings. An example of the heteroatom represented by Y2 is nitrogen. Za, Zb, Zc, Za', Zb'
or the nitrogen-containing heterocycle formed by Zc' may have
Examples of substituents include the substituents exemplified as Ra.
As an example, if there are few examples, the formula (a-1)-(
a-11) = (b-1)-(b8), (c-1)-
R s z in (c-14), Rs < t R
s ay Rs. , R@, ~R751R7'7tR7
91Rs 3+ Ras r Ras -R90
When the substituent is not present, such as at the bonding position,
is a coupler and color development at the position that has coupling ability.
A group is placed that does not leave due to reaction with the oxidized form of the active ingredient.
exchange. In addition, in the general formulas (a) to (c), oxidized products of color developing agents
Substituents that do not leave off upon reaction with (e.g. R
a= Rit Rz-R421R51-Rss is bonded
carbon or nitrogen) is (Rd")n, "(Rg")n 7"(Ra'" is Ra, Rb- is Rb, Rc" is Rc
, Rd" is Rd, Re- is Re, Rr" is
Rf, Rg" is R8, nl" is nl, 02''
is R2 and n, ″ is n, and n, ″ is n, and n, ″ is
n, ng" is R6 and n7" is R7 and Y, - is Y,
, Y2″ is Y2, Y3″ is Y, and Y,″ is Y
, Ys'' is Y, Za- is Za, zb- is zb
and Zc” is synonymous with Zc.) may have a part.
Of course, so-called screw-type couplers are also included in the present invention. Coupler represented by general formula (a), (b) or (c)
Examples of polymer couplers derived from the formula (
having a coupler part represented by a), (b) or (C)
a monomer having an ethylenically unsaturated double bond, preferably an ethylenically unsaturated double bond.
homopolymerized monomer or copolymerized with other monomers
can be mentioned. Ingredients represented by general formula (a), (b) or (c)
Examples include the following: General formula (a-1) General formula (a-
2) General formula (a-3) General formula (a
-4) General formula (a-5) General formula
(a-6) General formula (a-7) General
Formula (a-8) General formula (a-9) General formula (a-10) General formula (a-11) General formula (b-1> General formula (b-
2) General formula (b-3) General formula
(b-4) General formula (b-s) -
General formula (b-6) General formula (b-7)
General formula (b-8) General formula <C-1)
General formula (c-2) General formula (c3)
General formula (c-4) General formula (c5)
General formula (c-6) General formula (c-7)
General formula (c8) General formula (c9)
General formula (c-10) General formula (c-11)
General formula (c12) General formula (c13)
General formula (c-14) Formula (a 1)-(c-14)
In the middle, Xal−Xa++ is Xa and X b + −X b
s is xb, Xc+-Xcz is Xc, Rl
l -R20 is Ra, R5I-R8) is Rg,
R21-R29 are Re and R64-R71 are Rg
, Rho-R42 is Rf, R76~R3° is Rg
They have the same meaning and are examples of the same kind. In addition, the compounds represented by each formula and the exemplified compounds shown below are
Each also includes tautomers. Expressed by formulas (,) to (c)
Among those, preferred are those represented by the formula (%) (c-10), (c-12),
Especially (a-3), (b-1), (c3), (c-9)
, (c-10). In the compound represented by each formula, substituents on the heterocycle (example:
Ra -Rg r Rz-R42t R51-Rso)
The preferred ones are described below. When the coupler according to the present invention is used for positive image formation, X
a-Xc, Xa, -Xa,, Xb, -Xbs, X
c. of the carbon atom adjacent to the carbon atom to which ~X c, 4 is bonded
As a substituent, it is preferable that the following condition 1 is satisfied.
, more preferable is when conditions 1 and 2 below are satisfied.
Particularly preferred is one that satisfies conditions 1.2 and 3 below.
This is the case. 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. The most preferred substituents on the heterocycle are the following:
It is expressed by the general formula. General formula % formula % In the formula, R3゜1lR102 and R1゜ are hydrogen atoms, respectively.
child, halogen atom, alkyl group, cycloalkyl group,
alkenyl group, cycloalkenyl group, alkynyl group,
-ru group, heterocyclic group, acyl group, sulfonyl group, sulfur group
finyl group, phosphonyl group, carbamoyl group, sulfamoyl group
yl group, cyano group, spiro compound residue, bridged hydrocarbonization
Compound residue, alkoxy group, aryloxy group, heterocycle
Oxy group, siloxy group, acyloxy group, carbamoyl
Oxy group, amine 7 group, acylamino group, sulfone 7 amide
group, imide group, thureido group, sul7amoylami7 group,
7 alkoxycarbonylamide groups, aryloxycarbo
Nylamino group, Alfkidicarbonyl group, Aryloxy group
cycarbonyl group, alkylthio group, arylthio group,
RIOIIR+ represents a terocyclic thio group. 2 and R1゜
, at least two of which are not hydrogen atoms. Moreover, the above R1°1. Two of R1゜2 and R1゜,
For example, Rlot and R1゜2 combine to create a saturated or unsaturated
Sum rings (e.g. cycloalkanes, cycloalkenes, hetero
R1° may be formed in the ring. may be combined to form a bridged hydrocarbon compound residue. The group represented by R1°, ~R10) has a substituent
of the group represented by R1゜l'-R1゜,
Specific examples and substituents that the group may have include the above-mentioned
Specific examples and substitutions of the group represented by Ra in general formula (,)
Examples include groups. Also, for example, the ring formed by combining R3゜ and R1゜2,
Bridged hydrocarbonization formed by and R1゜1~R3゜
Specific examples of compound residues and substituents they may have include:
, Diclofur represented by Ra in the above general formula (a)
Kyl, cycloalkenyl, heterocyclic group, bridged hydrocarbonization
Specific examples of compound residues and their substituents are listed. Among the general formulas mentioned above, (i) where two of R1o1 to R1° are alkyl groups,
(ii) R=. 1 to R3°, for example R1°
. is a hydrogen atom, and the other 2R3゜1 and Ro. 2 is the conclusion
together with the root carbon atom to form a cycloalkyl
If so, then . Furthermore, among (i), R1°1 to R4° are preferable.
Two of them are alkyl groups and the other one is a hydrogen atom
Or in the case of 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, Ra in the above general formula (,) is
Specifics of alkyl, cycloalkyl and their substituents
An example is given. Also, a substituent on a bicyclic ring (e.g. Ra-Rgr R+ 1
~R421R5l~R1゜) is one of the following:
Those represented by the general formula are preferred. General formula % formula % In the formula, R' is alkylene, R2 is alkyl, cycloa
Represents rukyr or aryl. The alkylene represented by R1 is preferably a carbon of the straight chain portion.
The prime number is 2 or more, more preferably 3 to 6, and a straight chain
, regardless of branching. Also, this alkylene has a substituent.
You may. Examples of the substituent include R in the above general formula (,)
When a is an alkyl group, any substitutions that the alkyl group may have
Those shown as substituents may be mentioned. Preferred substituents include phenyl.
Ru. Preferred specific examples of alkylene represented by R1 are shown below.
show. The alkyl group represented by R2 may be linear or branched. Specifically, methyl, ethyl, propyl, iso-probi
butyl, 2-ethylhexyl, octyl, dodecyl
, tetradecyl, hexadecyl, oftagyl, 2-to
Examples include xyldecyl. The cycloalkyl group represented by R2 includes 5 to 6 shellfish.
is preferred, such as cyclohexyl. Alkyl and cycloalkyl represented by R2 have a substituent.
For example, the substituent to R' mentioned above and
The following are examples. Specifically, the aryl represented by R2 is phenyl.
, naphthyl. The aryl group has a substituent
It's okay. As the substituent, for example, a straight chain or branched
In addition to alkyl, the above-mentioned substituents for R'
The following can be mentioned. In addition, if there are two or more substituents, those substituents are the same
They may be the same or different. Furthermore, when the coupler according to the present invention is used for negative image formation
, Xa-Xcs Xa, -Xa, , Xb, -Xb,. The carbon that is in contact with the carbon atom to which Xc, ~Xc, , is bonded
As a substituent for an elementary atom, there are cases where the following condition 1 is satisfied.
Preferably, and more preferably, it satisfies conditions 1 and 2 below.
This is the case. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 At least two hydrogen atoms are bonded to the carbon atom.
ing. The most preferred substituents on the heterocycle are the following:
It is expressed by the general formula. General formula % formula % In the formula, RIo< is a hydrogen atom, a halogen atom, a furkyl group
, dichlorofurkyl group, alkenyl group, cycloalkenyl
group, alkynyl group, aryol group, heteroat7yl group
, sulfonyl group, sulfinyl group, phosphonyl group, carbon
Bamoyl group, sul77moyl group, cyano group, spiro compound
residues, bridged hydrocarbon compound residues, alkoxy groups, ants
ruoxy group, heterocyclic oxy group, siloxy group, acyl group
Oxy group, carbamoyloxy group, amide 7 group, acyl 7
Mi7 group, sulfonamide group, imide group, t-raid group, sulfonamide group,
77 moylamino groups, 7 alkoxycarbonylamino groups
, 7 groups of monoyloxycarbonylamide, alf-kidical
Bonyl group, aryloxycarbonyl group, alkylthio
group, arylthio group, and heterocyclic thio group. The group represented by R+04 may have a substituent,
Specific examples of the group represented by R101 and
Examples of substituents that may be used include R in the general formula (,) described above.
Specific examples of the group represented by a and substituents are listed. Preferred as R4゜4 is a hydrogen atom or an alkyl group
It is. Specific examples of compounds used in the present invention are shown below. The numbers in the table represent the following groups, respectively. -CH, -C2H5-(i)C3H7 -C4H9-(t)C+Hs -(i)C1
t(sCs H+ 1Cs H+ ,C+ + H23
CI 282 s C+ s H! I
Cl7H) S20
2l -CH,N(C2H,)2 -CH,C)(2NH
3○2 CIGH23-(CHzhSOzC+zHzs
(t) −(CHz)ssOzc+2His sushi,
, M2゜-CN-COCH,-COC,H
. 100 1JI
102COOC2Hs C00C
sH1, C00C12H2s- COOC1s H31
F C(l B r-NHCO
C,,H,,-NHCOC,,H3)-OCH,-○C
2H-OC, 2H2S-OCH, CONHCH2CH,
OCH, -OCH, CH2SO, CH. 0COC2Hs 0COC(C
Hs)s-SC,,H,,-5CH,C00H
Arrangement of ring atoms, types of substituents, and color developing agent
Although it may change depending on the type of color and other conditions, it is mainly magenta.
It can be used for multicolor photography, but red-ish
The light absorption properties are also good, so it is easy to use
It can be used for color photographs, etc. The couplers of the present invention typically contain 1X per mole of silver halide.
10"' mol - 1 mol, preferably 1 x 10 -2 mol -
It can be used in a range of 8×10 −1 mol. The coupler of the present invention may also be used with other types of magenta oak:
Souichi LpJ1+II Next, the oxidation potential EOX used in the present invention is 0.
95(V)≦E0x≦C50(V)rAnti-fading agent
(hereinafter referred to as the anti-fading agent according to the present invention)
do. The oxidation potential EOX of the antifading agent according to the present invention can be measured by a person skilled in the art.
can be determined. For example, Ei Stani
The paper “Nato” written by A.
47
Vol. 353 and 512 (1960), P.D.
Written by Elahay (P. Elahay)
Instrumental Methods in Electrochemi
Story” (New Instrumental Method
s inE electrochemistry)
(1954), Interscience Publishers
(1ntersciencePublisher)
``Polarographic Techniques'' by L. Mites, published by S.
” (polarographic Tech
2nd edition (1965), Intersci
1nterscience Publishers
Publishers), etc.
Ru. The above EOX value indicates that the compound is voltammetrically
means the potential at which the electrons are extracted at the anode, and
Therefore, it is the highest occupied electron electron in the ground state of the compound.
Primarily related to energy level. EOX in the present invention is a port under the conditions described below.
This is the value obtained from the half-wave potential of the Rallograph. That is, acetonitrile is used as the solvent for the anti-fading agent, and
Discoloration using 0.1N sodium perchlorate as electrolyte
Concentration of inhibitor 10-3 to 10-4 mol/2, reference electrode
is AQ /At; l C1 electrode is used to measure EOX.
was measured at 25°C using a rotating platinum plate electrode. The antifading agent according to the present invention has an oxidation potential within the above range.
As long as a compound with any structure can be used,
Particularly preferred are compounds represented by the following general formulas [A] to [H].
Preferably, more preferably general formulas [A], [8] and [
G]. Of course, the general formula
Even if the compound is outside the range, if the oxidation potential is within the above range,
Needless to say, it can be used as an anti-fading agent according to the present invention.
not. General formula [A] In the formula, R5 is a hydrogen atom, an alkyl group, an alkenyl group, 7
'J-represents a group or a heterocyclic group, R2, R,, R5
, R, are hydrogen atoms, halogen atoms, and hydroxy atoms, respectively.
group, alkyl group, alkenyl group, aryl group, alkoxy
represents a cy group or an acylami 7 group, R1 is a furkyl group,
Represents a hydroxy group, aryl group or alkoxy group. Also, R1 and R2 close each other to form a 5-shell or 6-shell ring.
In that case, R4 is a hydroxy group or an alkoxy group.
It represents a cy group, and R1 and R4 are ring-closed, and the hydrocarbon of s.
A bare ring may be formed, in which case R1 is an alkyl group, a
Represents a aryl group or a heterocyclic group, provided that R8 is a hydrogen atom
So, gah, R. except when is a hydroxy group. In the general formula [A], R1 is a hydrogen atom, an alkyl
group, alkenyl group, aryl group or heterocyclic group.
Among these, examples of alkyl groups include methyl group and ethyl group.
thyl group, propyl group, n-octyl group, tert-octyl group
Straight chain or branched alkyl groups such as thyl group and hexadecyl group
can be mentioned. In addition, the alkene represented by R1
Examples of the group include allyl, hexenyl, octenyl
Examples include groups. Furthermore, as the aryl group of R2,
, phenyl, and naphthyl groups. Furthermore, R
As the heterocyclic group represented by 3, tetrahydropyranyl
Specific examples thereof include a group, a pyrimidyl group, and the like. Each of these groups
may have a substituent, for example, an atom having a substituent may have a substituent.
Benzyl group, ethoxymethyl group, substituent as alkyl group
represents a methoxyphenyl group as a radical having
, chlor7enyl group, 4-hydroxy-3,5-dibutylene
and 7enyl group. In general formula [A], R2, R, , R, and R6 are water
Elementary atoms, halogen atoms, hydroxy groups, alkyl groups,
alkenyl group, aryl group, alkoxy group or acylamide
It represents 7 groups, among which alkyl groups and alkenyl groups
, for the aryl group, the alkyl group mentioned above for R1
The same groups as alkenyl, alkenyl, and aryl groups are listed.
It will be done. Further, as the halogen atom, for example, fluorine,
Examples include chlorine and bromine. Furthermore, the alkaline
Specific examples of koxy groups include methoxy groups, ethoxy groups, etc.
can be mentioned. Furthermore, the 7 groups of 7-silamis are
R' is represented by C0NH-, where R' is an alkyl
Kyl groups (e.g. methyl, ethyl, n-propyl, n-butyl
chill, n-octyl, jerk-octyl, benzyl, etc.
), alkenyl groups (e.g. allyl, octenyl,
each group such as oleyl), 7-aryl group (e.g. phenyl, methane),
groups such as toxyphenyl and naphthyl), or heterocyclic groups
(e.g. pyridyl, pyrimidyl groups)
can. In addition, in the general formula [A], R1 is an alkyl group,
Represents a droxy group, aryl group or alkoxy group,
Among these, for the alkyl group and aryl group, the above R3
Specifically, the same alkyl group and aryol group as shown in
can be mentioned. Also, regarding the alkenyl group of R1
As mentioned above, R2, R, , R5 and R6 are described above.
The same groups as alkoxy groups can be mentioned. R1 and R2 close each other to form a benzene ring
As a ring, for example, chroman, coumaran, methylene diode
Examples include xybenzene. In addition, a ring formed by R1 and R4 together with a benzene ring
Examples include green beans. These rings may contain substituents (e.g. alkyl, alkoxy,
aryl). Also, a ring formed by R1 and R2 or R3 and R4 being closed
Even if a spiro compound is formed by using the atom inside as a spiro atom,
Yes, R,, R, etc. are used as linking groups to form a bis body.
You may. A heptadol compound represented by the general formula [A] or
Among the phenyl ether compounds, preferred are R
O- group (R is an alkyl group, alkenyl group, aryl group or
represents a heterocyclic group. )
It is particularly preferably represented by the following general formula [A-1].
can be done. General formula [A-1] In the formula, R is an alkyl group (e.g. methyl, ethyl, propylene
terl, n-octyl, terl-octyl, benzyl, hel
xadecyl), alkenyl groups (e.g., 7lyl, octyl),
aryl groups (e.g., phenyl, oleyl), aryl groups (e.g., phenyl, oleyl),
phthyl) or heterocyclic groups (e.g., tetrahydropyrani)
represents a group represented by (ru, pyrimidyl). R3 and
Rto is a hydrogen atom, a halogen atom, (for example, 7
), chlorine, bromine), alkyl groups (e.g. methyl, ethyl
n-butyl, pencil), alkenyl groups (e.g. aryl, n-butyl, pencil),
lyl, hexenyl, octenyl), or alkoxy group (
For example, methoxy, ethoxy, benoloxy)
, RI+ is a hydrogen atom, an alkyl group (e.g. methyl, ethyl
(l, n-butyl, pencil), alkenyl groups (for example,
2-propenyl, hexenyl, octenyl) or ali
group (e.g. phenyl, methoxyphenyl, chlorophenyl)
phenyl, naphthyl). The compound represented by the general formula [A] is disclosed in U.S. Patent No. 3,
No. 935,016, No. 3.982.944, No. 4
, 254. No. 216, JP-A-55-21004, JP-A No. 54-145
No. 530, British Patent Publication No. 2,077.455, No. 2,
No. 062,888, U.S. Patent No. 3,764,337;
Same No. 3.432300, Same No. 3゜574.627,
No. t4 & 3,573,050, JP 52-1522
No. 25, No. 53-20327, No. 53-17729
, No. 55-6321, British Patent No. 1,347,556
No., Publication No. 2,066.975, Special Publication No. 54-12
No. 337, No. 48-31625, U.S. Patent No. 3,70
It also includes compounds described in No. 0,455 and the like. General formula [B] (In the formula, R1 and R4 are a hydrogen atom and a halogen atom, respectively.
child, alkyl group, alkenyl group, alkoxy group, alke
Nyloxy group, hydroxy group, aryl group, aryl group
xy group, acyl group, acylami 7 group, acyloxy group,
Sulfonamide group, cycloalkyl or alkoxylic
Represents a bonyl group, R2 is a hydrogen atom, an alkyl group, an alkyl group,
Kenyl group, aryl group, acyl group, cycloalkyl group or
represents a heterocyclic group, R3 is a hydrogen atom, a halogen atom
, alkyl group, alkenyl group, aryl group, aryl group
Oxy group, acyl group, acyloxy group, sulfonamide group
, represents a cycloalkyl group or an alphkidicarbonyl group
vinegar. Each of the groups listed above is substituted with other substituents.
Examples of substituents include alkyl groups and alkenyl groups.
group, alkoxy group, aryl group, aryloxy group,
Hydroxy group, alkoxycarbonyl group, aryloxy group
cycarbonyl group, acylami 7 group, acyloxy group, carbonyl group,
Rubamoyl group, sulfonamide group, sulfamoyl group, etc.
can be mentioned. In addition, R2 and R3 close each other to form a 5-shell or 6-shell ring.
may form, R2 and R3 are ring-closed together with a benzene ring.
Rings formed include, for example, chroman rings, methylene diode rings, etc.
Examples include xybenzene rings. 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
Useful compounds have general formulas [B-1], [B-2], [B
-3], [B -41, [B -51]
included in General formula [B-1] General formula [B-2] to 1 General formula [B-3] General formula [B-4] General formula [B-51 to' General formula [B-1], [B-2] ], [B-3], [B-
4] and (7[B-5] R+, R2, R3 and
and R4 have the same meanings as in the general formula [B] above.
, Rs, Rs, R2, Re, Rs and R2° are water
Elementary atoms, halogen atoms, alkyl groups, alkoxy groups,
droxy group, alkenyl group, alkenyloxy group, ali
aryl group, aryloxy group or heterocyclic group.
vinegar. Furthermore, R1 and Re, Re and R,, R, and R8, R, and
R9 and Rs and R1゜ are cyclized with each other to form a carbon ring.
Furthermore, the carbocycle may be substituted with an alkyl group.
It's okay. The general formula [B-1], [B-21, [B-3],
R2 and R in [B-4] and [B-5]
1 is hydrogen atom, alkyl group, alkoxy group, hydroxy
group or cycloalkyl group, R3, R6, R7, Rs
, R9 and lLo are hydrogen atoms, alkyl groups, or
Particularly useful are compounds that are loalkyl groups. The compound represented by the general formula [B] is tetrahedron (Te
traheclron), 1970. vo126,47
pp. 43-4751, Journal of the Chemical Society of Japan, 1972. Nol0
, pp. 1987-1990, Chemical Letters (che
M, Lett, ), 1972(4), pp. 315-316.
, a compound described in JP-A-55-139383
represents, contains, and in accordance with the manner described therein.
It can be synthesized by General formula IC] General formula [D] R' In the formula, R1 and R2 are a hydrogen atom, a halogen atom, an alkali
Kyl group, alkenyl group, alkoxy group, alkenyloxy
cy group, hydroxy group, aryl group, aryloxy group,
Acyl group, acylamide 7 group, acyloxy group, sulfone
Represents an amide group or an alphkidicarbonyl 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,
Fukidicarbonyl group, aryloxycarbonyl group, a
Silami 7 groups, carbamoyl group, sulfonamide group, sulphate
Examples include rufamoyl group. Y is a benzene ring and a dichroman or dicoumaran ring
represents the atomic group necessary to form . Chroman or coumaran ring is a halogen atom, alkyl
group, cycloalkyl group, alkoxy group, alkenyl group,
Alkenyloxy group, hydroxy group, aryol group, aryl group
may be substituted with a ruoxy group or a heterocyclic group,
Furthermore, a spiro ring may be formed. Among the compounds represented by general formulas [C] and [D], the present invention
Particularly useful compounds for this purpose are the general formulas [C-1] and [C-2]
, [D-1] and [D-2]
be done. General formula [C-1] General formula [C-2] R4 to 1 General formula [D-1] General formula [D-2] General formula [C-13, [C-2], (D-1) and [D-
R1 and R2 in [2] are the general formulas [C] and [D
] has the same meaning as in R3, R4, R3, R
6, R7 and R6 are hydrogen atoms, halogen atoms, alkyl
group, alkoxy group, hydroxy group, alkenyl group, alkyl group, alkoxy group, hydroxy group, alkenyl group,
Kenyloxy group, aryl group, aryloxy group or
represents a heterocyclic group. Furthermore, R1 and R,, R4 and Rs, Rs and R6, R6 and
R7, R1 and R8 are cyclized with each other to form a carbocycle;
Furthermore, the carbocycle may be substituted with an alkyl group.
good. The general formulas [C-1], [C-2], [D-11 and [
D-2], R1 and R2 are hydrogen atoms, alkyl
group, alkoxy group, hydroxy group or cycloalkyl group
group, R3, R4, R1, R6, R7 and R8 are hydrogen atoms
, an alkyl group, or a cycloalkyl group.
It is useful for Compounds represented by general formulas [C] and [D] are journal
・Of the Chemical Society (J)
Chem, Soc, C) 1968. (14),
1937-18, Journal of the Society of Synthetic Organic Chemistry 1970.28
(1), pp. 60-65, Tetrahedron (Tetra
hedron) 1973. (29), 2707-2
Contains the compounds listed on page 710, and
It can be synthesized according to the method described. General formula (E) In the formula, R' is a hydrogen atom, an alkyl group, an alkenyl group, an
lyl group, 7syl group, cycloalkyl group or hetero
Represents a ring group, R3 is a hydrogen atom, a halogen atom, an alkyl
group, alkenyl group, aryl group, aryloxy group,
Acyl group, acylamide 7 group, acyloxy group, sulfone
Amide group, cycloalkyl group or alkoxycarbo
Represents a nyl group. R2 and R4 are hydrogen atoms, halogen atoms, alkyl groups
, alkenyl group, aryl group, acyl group, acylami 7
group, sulfonamide group, cycloalkyl group or alkyl group.
Represents a fukdicarbonyl group. Each of the groups listed above is substituted with another substituent group.
It's okay. For example, alkyl groups, alkenyl groups, alkoxy
cy group, aryl group, aryloxy group, hydroxy group,
Alkoxycarbonyl group, aryloxycarbonyl group
, 7 acylamide groups, carbamoyl group, sulfonamide group
, sulfamoyl group, etc. Also, R' and R2 close each other to form a 5-shell or 6-shell ring.
may be formed. At that time, R3 and R4 are hydrogen atoms, halogen atoms, alkali atoms,
Kyl group, alkenyl group, alkoxy group, alkenyloxy
cy group, hydroxy group, aryl group, aryloxy group,
Acyl group, acylamide 7 group, acyloxy group, sulfone
Represents an amide group or an alphkidicarbonyl group. Y is necessary to form taloman 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),
Useful compounds have general formulas (E-1), (E-2), (E-3
), (E-4) and (E-5)
be done. General formula (E-1) OR' General formula (E-2,1 OR+ General formula (E-33 General formula (E-43 R@ General formula (E-5) General formula (E-1) to (E- R1, R2, R in 5)
3 and R4 have the same meaning as in the general formula (E) above.
Hold, R', R', R', R@. R9 and Rto are hydrogen atom, rhodene atom, alkyl
group, alkoxy group, hydroxy group, alkenyl group, alkyl group, alkoxy group, hydroxy group, alkenyl group,
Kenyloxy group, ryol group, 7-arylokyne group or
represents a heterocyclic group. Furthermore, R5 and R@, R@ and R
', R' and R'', R' and R3 and R1 and 'R
I O may be cyclized with each other to form a carbocycle, and
Furthermore, the carbocycle may be substituted with an alkyl group. In the general formulas (E-11 to (E-53), R',
R2, Rco and R4 are hydrogen atoms, alkyl groups, or
Cycloalkyl group, in the general formula [E-5], R
3 and R4 are hydrogen atoms, alkyl groups, alkoxy groups,
a drooxy group or a cycloalkyl group, and further the above general formula
In (E-1) to [E-5], R5, R6, R',
R”・R9 and R” are hydrogen atoms, alkyl groups, or
Particularly useful are compounds that are chloroalkyl groups. The compound represented by the general formula [El is tetrahedron]
・Tetrahedron Letters
) 1965. (8), pp. 457-460 Journal of Chemistry
J.Chem.So
c. part C) 1966, (22), 2013
-2016 pages, (Zh, Org. Khim) 197
0. (6), pages 1230-1237
containing products and combining them according to the methods described therein.
can be achieved. General formula CF) R2 R co ・In the formula, R is a hydrogen atom, an alkyl group, an alkenyl group, or an alkyl group.
Ryl group, acyl group, cycloalkyl group or hetero
Represents a ring group, R2 is a hydrogen atom, a halogen atom, an alkyl
group, alkenyl group, ryol group, aryloxy group,
Acyl group, acylami/group, acyloxy group, sulfone
Amide group, cycloalkyl group, or alkoxyl group
Represents a bonyl group. R is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group.
group, aryol group, acyl group, acylamino group, sulfonate group,
amide group, cycloalkyl group or alf-kidical
Represents a bonyl group. R4 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group.
group, alkoxy group, alkenyloxy group, hydroxy
group, aryl group, aryloxy group, acyl group, acyl
Amino group, acyloxy group, sulfonamide group, or
represents an alkoxycarbonyl group. Each of the groups listed above is substituted with other substituents.
Examples of substituents include alkyl groups and alkenyl groups.
group, alkoxy group, aryl group, aryloxy group,
Hydroxy group, alkoxycarbonyl group, aryloxy group
Cycarbonyl group, acylami 7 group, carbamoyl group, carbonyl group,
Examples include a sulfonamide group and an amoyl group. Also, R1 and R2 are ring-closed with each other to form a 5-shell or 6-shell ring.
may be completed. At that time, R1 and R1 are hydrogen atoms, halogen
atom, alkyl group, alkenyl group, alkoxy group,
lekenyloxy group, hydroxy group, aryl group, aryl group
oxy group, acyl group, acylami 7 group, acyloxy
group, sulfonamide group, or alfkidicarbonyl
represents a group. 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 hydroxyl group or a heterocyclic group.
Furthermore, a spiro ring may be formed. Among the compounds represented by the general formula [F], those particularly suitable for the present invention
Compounds with general formulas [F-1], [F-2], [F-
3], [F-4] and [F-5]
CF-3) General formula (F-4) General formula CF-51 R1, R2 in general formulas [F-1] and [F-5],
R- and R4 have the same meaning as in the above general formula [F]
and R3, R,, R,, Ra, R9 and IR1° are water.
Elementary atoms, halogen atoms, alkyl groups, alkoxy groups,
droxy group, alkenyl group, alkenyloxy group, 7-ri group
represents an aryl group, an aryloxy group or a heterocyclic group
. Furthermore, R1 and Rs, Rs and R,, R, and R8, R8
and R9 and R9 and R10 are cyclized with each other to form a carbocyclic ring.
Furthermore, the carbocycle may be substituted with an alkyl group.
It's okay. Also, [F-31, [F-4] and [/'[F-5]
and two R, -R,. are both the same and different
It's okay. The above general formula [F-1], [F-2], [F-3], [F
-4] and [F-5], R1, R2, and R
3 is a hydrogen atom, a furkyl group, a cycloalkyl group, R1 is
Hydrogen atom, alkyl group, alkoxy group, hydroxy group or
or a cycloalkyl group, further R5, R, SR,, R,
, R, and RIO are hydrogen atoms, alkyl groups, or cyclo
Particularly useful are compounds that are alkyl groups. The compound represented by the general formula [F] is tetrahedron
e-letters (Tetrahedron Letters)
) 1970tVo126, pages 4743-4751, Japan
Journal of the Chemical Society of Japan 1972. No. 10, pp. 1987-1990, Synth
hesis) 1975, Vol 6, 392-39
Page 3, (Bul Soc, Chimt Be1g) 1
975, Vo184(7), 747-759
Contains the listed compounds and is listed in these
General formula CG) In the formula, R' and R3 are each a hydrogen atom, and El'/
/X child, furkyl group, alkenyl group, alkoxy group, hydrogen
Droxy group, aryl group, aryloxy group, acyl group
, acylami 7 group, acyloxy group, sulfone 7 mido group
, represents a cycloalkyl group or an alphkidicarbonyl group.
Was. R2 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 alfkyl dicarbonyl group. Each of the groups listed above may be substituted with an Ike substituent.
stomach. Examples of substituents include alkyl groups, alkenyl groups,
Alkoxy group, aryl group, aryloxy group, hydro
xy group, alfkidicarbonyl group, aryloxycar
Bonyl group, 7 acylamide groups, carbamoyl group, sulfone
Examples include amide group and sulfamoyl group. In addition, R2 and R3 are ring-closed with each other, and 5-shell or 6-shell carbon
A hydrogen ring may also be formed. Carbonization of these 5 or 6 shellfish
Hydrogen ring is halogen atom, alkyl group, cycloalkyl group
, alkoxy group, alkenyl group, hydroxy group, aryl group
substituted with an aryl group, an aryloxy group, a heterocyclic group, etc.
It's okay. Y represents an atomic group necessary to form a kidney bean ring. Green bean ring has halogen atom, alkyl group, alkenyl group
, alkoxy group, cycloalkyl group, hydroxy group,
Substituted with aryl group, aryloxy group, heterocyclic group, etc.
may be substituted, and may further form a spiro ring. Among the compounds represented by the general formula CG), particularly useful for the present invention
Compounds having the general formulas (G-1) to (G-3)V, -11
Japan/E7J Structure General Formula (G-1) K'' General Formula (G-2) General Formula (G-3) R l in General Formulas CG-11 to CG-3). R2 and R3 are General Formula (G-3). ) is synonymous with
, R', R5, R', R', R'' and 17R' are
hydrogen atom, halogen atom, alkyl group, alkyl group, respectively.
xy group, alkenyl group, hydroxy group, 7-aryl group, a
Represents a lyloxy group or a heterocyclic group. R4 and R5,
R5 and Ra, Ra and Rf, R' and R'' and R8 and R
9 may be ring-closed with each other to form a hydrocarbon ring, and further
The hydrocarbon ring may be substituted with an alkyl group. In the general formulas (G-1) 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
group, hydroxy group or cycloalkyl group, R', R5
, R', R7, R@ and R' are hydrogen atoms, alkyl groups
or cycloalkyl groups are particularly useful. General formula (H) In the formula, Rl and R2 are a hydrogen atom and a halogen atom, respectively.
child, alkyl group, alkenyl group, aryl group, 7-syl group
, acylamino group, acyloxy group, sulfonamide group
, represents a cycloalkyl group or an alphkidicarbonyl group
vinegar. R3 is a hydrogen atom, a halogen atom, an alkyl group, 7
Nyl group, alkoxy group, hydroxy group, aryl group, a
lyloxy group, acyl group, 7-syl amino group, acyl group
xy group, sulfonamide group, cycloalkyl group or alkyl group
Represents a koxycarbonyl group. Each of the groups listed above is substituted with other substituents.
Substituents include, for example, alkyl groups and alkenyl groups.
group, alkoxy group, 71-nol group, aryloxy group
, hydroxy group, alkoxycarbonyl group, aryl group
oxycarbonyl group, 7 silami 7 groups, carbamoyl group,
Examples include a sulfonamide group and a sulfamoyl group. In addition, R1 and R2 and R2 and R3 are ring-closed with each other, and five shells are formed.
Alternatively, a six-shell hydrocarbon ring may be formed, and the hydrocarbon
The ring is a halogen atom, an alkyl group, a cycloalkyl group, or an alkyl group.
Rukoxy group, alkenyl group, hydroxy group, aryl group
, may be substituted with an aryloxy group, a heterocyclic group, etc.
. 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 general formula (H), particularly useful for the present invention
Compounds represented by general formulas (H-1) to (H-2) are
included in the compound. General formula (H-1) General formula (H-2) General formula (H-3) R l +R in general formulas [G-1] to (H-3)
2 and R have the same meanings as in general formula (H),
R', R', R', R', R' and R9 are
Hydrogen atom, halogen atom, alkyl group, alkoxy group respectively
cy group, hydroxy group, alkenyl group, aryl group,
Represents a lyloxy group or a heterocyclic group. Also, with R4
R', R' and Ra, R' and R7, R7 and R6 and
Even if R” and R5 close each other to form a hydrocarbon ring,
Often, the hydrocarbon ring may also be substituted with an alkyl group.
stomach. In the general formula (H-13 to (H-33), R1 and
R2 is a hydrogen atom, an alkyl group or a cycloalkyl group, respectively
The group %R' is a hydrogen atom, an alkyl group, an alkoxy group, a hydrogen atom,
Droxy group or cycloalkyl group, R', R5, R'
, R', R@ and Rg are a hydrogen atom and an alkali atom, respectively.
Compounds that are kill or cycloalkyl groups are particularly useful.
be. The method for synthesizing the compound represented by the general formula [H] is known.
No. 3,057,929, Chemish
Berichte (CheIIIl, Ber,) 1972.9
5(5)-1673-1674, Journal of
The American Chemical Society (J, Am
, Chevn, Soc, ) 1973.95
(5), pp. 1673-1674, Chemistry Letters
Chemistry Letters (19)
80+, pages 739-742. The antifading agent according to the present invention has an oxidation potential within the above range.
Although any compound can be used as long as the present invention
It must be a water-insoluble compound to fully exhibit its effects.
is preferable. The oxidation potential is 0.95 (V)≦E0
x≦1.50(V), preferably 1.00(V
)≦E0x≦ 1.45 (V) especially 1.00 (V)≦E
0x≦1.40 (V) is preferable. Specific compounds of the antifading agent according to the present invention are shown below.
, the present invention is limited to these compounds CH3CH3 0H (AO-26) (AO-27) (AO-28) The antifading agent according to the present invention has the general formula (a). Select from the couplers shown in (b) and (C), respectively.
at least one coupler and/or said coupler
Polymer couplers derived from
In the silver halide emulsion layer containing a bright coupler)
However, the anti-fading agent according to the present invention may be added in some places.
Depending on the desired effect and type of compound, etc.
However, O, OS per mole of the coupler of the present invention
~3 mol is preferred, more preferably 0.1-2 mol
Can be used within a range. The high boiling point organic solvent according to the present invention has a dielectric constant of 60
The following compounds, such as phthalate with a dielectric constant of 6.0 or less
Esters such as acid esters and phosphate esters, organic acid esters, etc.
These include amides, ketones, hydrocarbon compounds, etc. preferably
is the vapor pressure at 100°C with a dielectric constant of 60 or less and 19 or more.
is a high boiling point organic solvent with a pressure of 0.5 mmHg or less. See you again
More preferably, the phthalate ester in the high-boiling organic solvent
or phosphoric acid esters. Furthermore, high boiling point organic solvents
The medium may be a mixture of two or more types. Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C.
It shows the electric rate. Phthalate esters used in the present invention
Examples include those represented by the general formula [I]
. General formula [I] In the formula, R1 and R2 are an alkyl group and an alkyl group, respectively.
Nyl group represents an aryl group. However, R1 and
The total number of carbon atoms in the group represented by R2 is 8 to 32.
be. More preferably, the total number of carbon atoms is 16.
To 24. In the present invention, R1 and R2 of the general formula [I]
The alkyl group represented may be linear or branched.
, for example, butyl group, pentyl group, hexyl group, 2-ethyl group
hexyl group, 3.5.5-trimedhexyl group,
cutyl group, decyl group, dodecyl group, tetradecyl group,
These include a xadecyl group and an octadecyl group. R1 and R
The aryl group represented by 2 is, for example, a phenyl group, a naphyl group,
thyl group, etc., and alkenyl group is, for example, hexenyl group.
, heptenyl group, octadecenyl group, etc. These alkyl, alkenyl and aryl groups are
, including those with single or multiple substituents,
Examples of substituents for the kill group and alkenyl group include ha
rogen atom, alkoxy group, aryl group, arylox
Examples include cy group, alkenyl group, alkoxycarboxyl group, etc.
Examples of substituents on the aryl group include halogen atoms.
child, alkyl group, alkoxy group, aryl group, aryl
Oxy group, alkenyl group, alkoxycarbonyl group, etc.
can be mentioned. In the above, R1 and R2 are preferably alkyl groups
, for example, 2-ethylhexyl group, 3.5.5-
Trimethylhexyl group, n-octyl group, n-nonyl group
etc. Phosphate esters advantageously used in the present invention
Examples include those represented by the following general formula [11]. General formula [1] %Formula% In the formula, R3, R4 and R5 are each an alkyl group,
Represents an alkenyl group or an aryl group. However, the number of carbon atoms represented by R3, R4 and R5
The total sum is 24-54. A represented by R3, R4 and R5 of the general formula [I[]
The alkyl group is, for example, a butyl group, a pentyl group, a hexyl group.
, 2-ethylhexyl group, heptyl group, nonyl group, decyl group
group, dodecyl group, tetradecyl group, hexadecyl group,
Octadecyl group, nonadecyl group, etc., and aryl group
For example, phenyl group, naphthyl group, etc.
Examples of alkenyl groups include hexenyl group, heptenyl group,
and octadecenyl groups. These alkyl, alkenyl and aryl groups are
, those having single or multiple substituents are also included. Like
Alternatively, R3, R4 and R5 are alkyl groups, e.g.
For example, 2-ethylhexyl group, n-octyl group, 3.5.
5-trimethylhexyl group, n-nonyl group, n-decyl group
group, 5ec-decyl group, 5ec-dodecyl group,
Examples include chill group. Typical examples of high boiling point organic solvents used in the present invention are as follows:
Examples are shown, but the invention is not limited to these.
. I-4'! #t= , N2, ,,,,,, I Ftj tip example Takaxiang point is a solvent, 5-1 Summer C2+ (s 0C=H, 5(i) ■ 0=P-0-C, H1! (i) 0 C=H1, (i) 0C5H1t(n) 0"P 0-C-H,, (n) ■ 0 C=H,-(n) O-C,.H,, (i) 0 =p-o-c,.Hzl(i) O-C,.H21(i) 0-Ci,H2,(n) 0=P OC7-H21(n) 0 C1,H)1(n) 0C, , H2, (i) These high boiling point organic solvents are suitable for couplers of the present invention.
It is generally used in a proportion of 10 to 400% by weight. Like
Or, it is 40 to 300% by weight based on the coupler. Hydrophobic compounds such as couplers can be mixed with high boiling point solvents alone or with low boiling points.
Dissolved in a solvent used in combination with a solvent, and using a mechanical or ultra-rich wave.
Various surfactants are used as dispersion aids when dispersing in water.
agent, can be used. Couplers of the present invention, antifading agents, high boiling point organic solvents, etc.
There is one method for adding silver halide to photographic light-sensitive materials.
[General politics] Similar to the addition method of aqueous compounds, solid dispersion method
, latex dispersion method, oil-in-water emulsion dispersion method, etc.
method can be used for hydrophobic compounds such as couplers.
It can be appropriately selected depending on the chemical structure of the substance. water
The medium oil drop emulsion dispersion method separates hydrophobic additives such as couplers.
Conventionally known methods for dispersing can be applied, and if necessary, low boiling
gelatin by dissolving it in combination with a water-soluble organic solvent and/or a water-soluble organic solvent.
Using a surfactant in a hydrophilic binder such as an aqueous solution of
Stirrer, homogenizer, colloid mill, flowage
Ultrasonic wave! Using a dispersion means such as A8,
After emulsifying and dispersing, add it to the desired hydrophilic colloid layer.
do it. Low boiling point paid solvent at the same time as dispersion or dispersion
A step of removing may be included. Preservation area, intermediate layer, and thickness of photosensitive material 1 of the present invention
Ultraviolet rays are applied to the silver emulsion layer for the purpose of stabilizing the dye image.
3. Absorbent may be used. Purple that can be used for right handedness
External radiation absorbers are 2- (2'-human

Examples include [:1xiflnyl)benzo1-lyazole compounds, and compounds represented by the following general formula [III] are particularly preferred. General formula [I[11] In the above general formula [111], R+6, RI7 and R18 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryl711 di group,
Represents an alkenyl group, a 21-ro group or a water M group. Furthermore, among the compounds represented by the general formula [IIL],
Compounds that are liquid at room temperature can be used even with high boiling point solvents such as the couplers of the present invention, so the oil ratio in the illumination can be lowered; It can be advantageously used in terms of precipitation properties.The term "liquid at room temperature" refers to the temperature conditions of the step of incorporating the compound represented by the general formula [D] into the silver halide photographic light-sensitive material according to the present invention. In this case, if it is liquid under the above conditions, it is preferable to use a compound whose melting point is 30°C or lower. More preferably, it is a compound whose melting point is 15°C or lower. − (
Any compound among the 2'-hydroxyphenyl)benzotriazole compounds can be used, and it may be a single compound or a mixture. As a mixture, one composed of a group of structural isomers can be preferably used. Typical specific examples of the compound represented by the general formula (m) are shown below, but the present invention is not limited thereto. As the addition port for these 2-(2'-hydroxyphenyl)benzotriazole compounds, any base may be used, but it is preferably used at a ratio of 1 to 50 mMd, 2, particularly preferably 2 to 30 ml. /
It is d12. The silver halide photographic material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but the method of the present invention is particularly effective when using color photographic paper that is intended for direct viewing. is effectively demonstrated. The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. The order may be changed as appropriate depending on the important performance and purpose of use. When the silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material, the specific layer structure includes:
In order from the support side, a yellow dye image forming layer, an intermediate layer, a magenta dye image forming layer, an intermediate layer, a cyan dye image forming layer,
Particularly preferred is one in which an intermediate layer and a protective layer are arranged. Silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention)
As the silver halide, any silver halide used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride can be used. The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to I
) H, OA (+) may be produced by sequentially and simultaneously adding them while controlling. After growth, a conversion method may be used to change the halogen composition of the grains. By using a silver halide solvent as necessary during production, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled.Used in the silver halide emulsion of the present invention Silver halide grains are produced by using metals such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, iron salt or complex salt in the process of forming and/or growing grains. Ions can be added and encapsulated inside the particles and/or on the particle surfaces, and reduction sensitization can be imparted to the insides and/or the particle surfaces by placing them in an appropriate reducing atmosphere.This invention After the growth of silver halide grains is completed, unnecessary soluble salts may be removed from the silver halide emulsion, or they may be left in the silver halide emulsion.If the salts are removed, please refer to Research Disclosure No. 17643. The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers. The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions. The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination. The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. Along with the sensitizing dye, the agent contains a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye. You can let me. The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide is added during chemical ripening, and/or at the end of chemical ripening, and/or after chemical ripening Compounds known in the photographic industry as antifoggants or stabilizers can be added before coating the emulsion. Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable that the hardening agent be added to the processing solution to the extent that it is possible to harden the photosensitive material, but it is also possible to add a hardening agent to the processing solution. A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. The emulsion layer of the silver halide photographic light-sensitive material of the present invention is subjected to a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivative, amine phenol derivative, etc.) in the color development treatment. A dye-forming coupler is used that performs the following steps to form a dye.The dye-forming coupler is typically selected for each emulsion layer so that a dye is formed that absorbs light in the emulsion layer's sensitive spectrum. A yellow dye-forming coupler is used in the blue light-sensitive emulsion layer, a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. Depending on the situation, silver halide photographic materials may be prepared using different combinations from the above combinations.The cyan dye-forming couplers used in the present invention include:
Phenol-based and naphthol-based 4-equivalent m or 2-equivalent Φ-type cyan dye-forming couplers are typical, and specific examples thereof include U.S. Pat. Nos. 2,306,410 and 2,356,4.
No. 75, No. 2.362.598, No. 2.367,
No. 531, No. 2.369.929, No. 2.423
．． No. 730, No. 2,474,293, No. 2,47
6.008, 2,498, 466, 2.5
No. 45.687, No. 2.728.660, No. 2.
No. 772,162, No. 2.895.826, No. 2
．． 976, 446, 3.002.836, 3,419,390, 3.446.622, 3.476, 563@, 3,737, 316,
British Patent No. 3.758.308, British Patent No. 3.839.044, British Patent No. 478,991, British Patent No. 945.542, British Patent No. 1, 084.480, British Patent No. 1.377, 233.
No. 1.388.024 and No. 1, 543.
Each specification of No. 040, as well as JP-A Nos. 47-37425, 50-10135, 50-25228, and 5
No. 0-112038, No. 50-117422, No. 0-112038, No. 50-117422, No.
No. 50-130441, No. 51-6551, No. 51-
No. 37647, No. 51-52828, No. 51-108
No. 841, No. 53109630, No. 54-48237
No. 54-66129, No. 54-131931, and No. 55-32071. The cyan image-forming coupler has the following general formula [C-1
], [C-2] can be preferably used. General Formula EC-1] In the formula, R1 represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2 represents an alkyl group or a phenyl group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Zl represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. General formula [C-21 Z2 In the formula, rLl represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R5
represents an alkyl group (eg, methyl group, ethyl group, etc.). R6 represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.) or an alkyl group (eg, methyl group, ethyl group, etc.). Z2 represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. tC-11CsH+
t(t) As the yellow dye-forming coupler used in the present invention, a compound represented by the following general formula [Yl is preferred. General formula [Yl OY'0 In the formula, R11 represents an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, etc.) or an aryl group (e.g. phenyl group, p-methoxyphenyl etc.), and R1
2 represents an aryl group, and Yl represents a hydrogen atom or a group that leaves during the color development reaction process. These include, for example, U.S. Patent Nos. 2.778.658@, 2.875.057, and 2.908.573,
3,227.155, 3.227.550, 3.253.924, 3.265.506
No. 3,277.155, No. 3.341.33
No. 1, No. 3.369.895, No. 3.3EI4,
No. 657, No. 3.408.194, No. 3,415
, No. 652, No. 3.447.928, No. 3,55
No. 1,155, No. 3.582.322, No. 3.7
25.072@, 3.894.875, etc. specifications,
German Patent Publication No. 1,547,868, German Patent Publication No. 2,05
No. 7,941, No. 2.162.899, No. 2.1
No. 63.812, No. 2.213,461, No. 2,
No. 219,917, No. 2,261,361, No. 2
．． 263.875, JP 49-13576, JP 48-29432, JP 48-66834, JP 49
-10736, 49-122335, 50-2
No. 8834 and No. 50-132926. Specific examples of yellow couplers preferably used in the present invention are shown below, but the present invention is not limited thereto. (Y-1) (Y-2) (Y-31 O-C-CH3 CH3 (Y-4) (Y-5) (Y-6) (Y-7) C/ (Y-8) (Y- 9) (Y-10) (Y-11) (Y-12) t + Y-13) ('Y-14) The zero-density forged photographic light-sensitive material of the present invention includes a filter layer, an antihalation layer, And/or an auxiliary layer such as an anti-irradiation layer can be provided. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development. The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is used to reduce the gloss of the light-sensitive material, to improve its roughness, to prevent the light-sensitive materials from sticking to each other, etc. A matting agent can be added. A lubricant can be added to reduce the sliding friction of the silver halide photographic material of the present invention. An antistatic agent for the purpose of preventing static electricity can be added to the silver halide photographic material of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer. The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitizing). Surfactants are used. The silver halide photographic light-sensitive material of the present invention has a photographic emulsion layer, and other layers include a flexible reflective support such as baryta paper or paper laminated with α-olephne polymer, synthetic resin, cellulose acetate, cellulose nitrate, polystyrene, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics. The silver halide photographic light-sensitive material of the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or Silver halide photographs of the present invention may be coated via one or more T11 to improve properties such as hardness, abrasion resistance, hardness, antihalation properties, friction properties, and/or other properties. When coating a photosensitive material, a thickener may be used to improve coating properties. Exdolsion coating and curtain coating, which allow two or more layers to be coated at the same time, are particularly useful coating methods. The photosensitive material of the present invention can be exposed using electromagnetic waves in the spectral range to which the emulsion layer constituting the photosensitive material of the present invention is sensitive.As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, Mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like. Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently. The silver halide photographic material of the present invention can be used to form an image by color development as known in the art. The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones that are widely used in various color photographic processes. These developers include amine phenol and p-phenylene diamine derivatives. These compounds are 'i
Since it is more stable than the t tin state, it is generally used in the form of a salt, such as a hydrochloride or a sulfate. Further, these compounds are generally used in an amount of about 0.1 g to about 3 g per color developer 12.
0a concentration, preferably about 1 g for color developer 12
Use at a concentration of ~15 g. Examples of the amine phenol developer include O-amine phenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like. Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine salt Mm, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N. N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in processing the silver halide photographic light-sensitive material of the present invention further contains various components that are usually added to the color developer solution. For example, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanides? 1! Salts, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developer is usually 7 or higher, most commonly about 10 to about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3 Koiminodiacetic acid [4 Coethylenediaminetetraacetic acid disodium salt] [5 Coethylenediaminetetraacetic acid tetra(trimethylammonium) salt] [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used as a sodium salt contains a metal complex salt of an organic acid as mentioned above as a bleaching agent, and may also contain divine additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. In addition, pH buffering agents such as 531 acid salts, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions may be added as appropriate. can. Further, the fixing solution and the bleach-fixing solution include ammonium acetate, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, metabisulfite III! Sulfites such as sodium I-acid, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. 1) H buffering agent consisting of a salt may be contained alone or in combination. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanine M salt, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. , for example, hydrogen peroxide, bromate, persulfate, etc. [Effects of the Invention] The silver halide photographic material of the present invention has excellent color reproducibility and color development, and the light fastness of dye images is improved. Significantly improved. [Examples] Hereinafter, specific examples of the present invention will be described in detail, but the present invention is not limited to these embodiments. <Example 1> Various coupler dispersions were prepared with the compositions shown in Table 1 by the methods shown below, and the resulting dispersions were mixed with a green-sensitive silver chlorobromide emulsion SOOG and applied to a polyethylene-coated paper support. Samples 1 to 29 were obtained by coating and drying. (Preparation of coupler dispersion) Coupler 40 (l) shown in Table 1 and the antifading agent shown in Table 1 (50 mol % based on the coupler) were combined with 40 g of the high boiling point organic solvent shown in Table 1 and 100 d of ethyl acetate. This solution was added to a 5% gelatin aqueous solution (h12) containing sodium dodecylbenzenesulfonate, and then dispersed with an ultrasonic homogenizer to obtain a coupler dispersion. After wedge exposure, the following processing was performed according to the method. Standard processing steps (processing temperature and processing time) [1] Color development @ 38°C 3 minutes 30 seconds [2] Bleach fixing 33°C 1 minute 30 seconds [3] Washing process
25-30℃ 3 minutes [4] Drying 75-80℃
Approximately 2 minutes Processing solution composition (color developer) Benzyl alcohol 15d ethylene glycol 151g Potassium sulfite 2.0g Potassium bromide
0.7 (sodium monochloride
o, 2g potassium carbonate
300g hydroxylamine lii! tFli salt
3. og polyphosphoric acid (TPPS)
2.5! ;13-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline monoacid s, sg optical brightener (
4,4'-Diaminostilbendisulfonic acid derivative) 109 Potassium hydroxide 2.0 g Add water to set d to 1y, and adjust the pH to 10.20. (Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate dihydrate 609 ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100d Ammonium sulfite (40% solution) 27.5d Potassium carbonate or glacial acetic acid to pl-171 Adjust and add water to make a total of 12. After processing, the light fastness of the resulting magenta dye image was tested using the following method. The results are shown in Table 1. <Light fastness test> The residual rate was shown as the initial concentration Qo = 1.0 when exposed to sunlight for 30 days using an underglass outdoor exposure stand. (D = Density after fading) <Heat/Moisture Yellow/Stain Test> Perform the above treatment without exposure to light, and place the resulting white sample in a constant temperature and humidity chamber at 85°C and 60% RH for two weeks. The blue density is expressed as increasing blue density ΔDB. Color development test> The maximum reflection density (Dmax) of each treated sample was measured, and was taken as the characteristic of "color development". <Sub-absorption density> The spectral reflection spectrum of the obtained magenta colored sample was measured using Color Analyzer Model 607 (manufactured by Hitachi). At this time, the maximum concentration of the absorption spectrum in the visible region of each sample was normalized to 1.0 and measured. 430nm of each sample
The reflection density at was used as the sub-absorption density as an index of color purity. Comparative anti-fading agent 1 Comparative anti-fading agent 2 Comparative coupler l Comparative coupler 2 Based on the results in Table 1, Samples 1 to 4 using comparative couplers will be described first. Samples 1 and 2 using 5-pyrazolone type couplers had good light fastness and color development, but D
Not only is the I absorption concentration high, but yellow stain is also high, which is not preferable. On the other hand, in Samples 3 and 4 using known pyrazolotriazole couplers, the yellow stain and side absorption density are low and good, but the effect of the antifading agent is small, the light fastness is completely inadequate, and the color development is low, which is completely undesirable. . Furthermore, for Samples 5/'5 to 8 and 15 to 17 using the couplers according to the present invention, the light fastness is certainly improved compared to Sample 6 using the antifading agent according to the present invention, but the level of light fastness is not at all improved. This was not only unsatisfactory, but also accompanied by a decrease in color development. Oxidation potential EOX is 095≦E0x≦
Sample 7.8 using an anti-fading agent that does not fall under 150
, ]5 and ]6 had almost no effect or, on the contrary, accelerated discoloration. or,! Sample 1 using the high boiling point organic solvent according to the present invention without using a single color inhibitor
In No. 7, there was almost no effect of improving light fastness, and the coloring property was decreased. Samples 9 to 14 and 18 to 29 according to the present invention exhibited high performance in both light fastness, color development, and R1 absorption density, which was completely unexpected from the previously known facts. . <Example 2> A multicolor silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on a support made of a polyethylene coating set from the support side. 1st layer: blue-sensitive silver halide emulsion layer containing yellow coupler (example NO, Y-2) at 8 mq/d1
2. Blue-sensitive silver chlorobromide emulsion converted to silver: 3 mg/dI
J, 3 mg/d of high boiling point state solution 1 (Example No. 5-6)
m' and gelatin were coated in an amount of 161 [/di']. 2nd layer: Intermediate layer hydroquinone derivative (HQ-1) at 0.45 [1/
d12 and gelatin applied to bone S with 4111Q/di+
It was painted so that 3rd layer: Green-sensitive silver chlorobromide emulsion layer Comparative coupler 3 was added at 4 mo/dr, antifading agent (example: AO
-23) to the coupler, green-sensitive silver chlorobromide emulsion to 4 ml/di2 in terms of silver, tricresyl phosphate to 4II1 g/df as a high-boiling organic solvent, and gelatin to 16111 (+/df) 4th layer: Intermediate layer UV absorber (UV-1) at 3 mq/df. (UV-2) at 3 IQ/dv', high boiling point organic solvent (Example No. , 5-2) was applied at a coating amount of 4m(]/di2, high)ron derivative (HQ-1) at 0.45mg/df and yohyseratin at a coating amount of 14mg/df. Layer: Red-sensitive silver chlorobromide emulsion layer Cyan coupler (No, C-
8) to img/dlp, exemplary cyan coupler (No, C
-5) at 3 mg/df, high boiling point organic M'S (example No.
S-2> was 2 mg/di2, the red-sensitive silver chlorobromide emulsion was 3 ffl(]/df converted to silver, and the gelatin was 1
The coating was applied so that the coating amount was 4 mM d12. 6th layer: Intermediate layer 20 Mdt' of (UV-1) as ultraviolet absorber. (UV-2) at 2 mg/df, high boiling point organic solvent (example N
o, 5-2) to 2mQ/df o and tF Seratin 61
The coating was applied so that the coating amount was 11 g/df. No. 7 Ti: Protective layer Gelatin was coated at a coating weight of 9 ma/df. The sample thus prepared will be referred to as sample 1. Next, Samples 2 to 7 were prepared which were the same as Sample 1 except that the combinations of the coupler, antifading agent, high boiling point organic solvent, and coating silver in the third layer of Sample 1 were changed as shown in Table 2. However, the coating m of the coupler and the anti-fading agent was set to be equal in mole to Sample 1, respectively. A photosensitive needle (KS-7, manufactured by Konishiroku Photo Industry ■) was attached to these samples.
After performing light pattern exposure with green light using a mold), the same treatment as in Example 1 was performed. The same test as in Example 1 was performed on the sample thus obtained. The results are shown in Table 2. (UV-11 CsLt(t) (UV-2) Comparative coupler 3 Comparative coupler 4 ρl In the table, TCP represents tricresyl phosphate. From the results in Table 2, it can be seen that in multicolor silver halide color photographic light-sensitive materials, It is clear that the same results as in Example 1 were obtained.Furthermore, according to the visual evaluation of color reproducibility using live-action prints,
Samples 3 to 7 gave a vivid impression and had particularly excellent reproducibility of purple. That is, in Samples 4 to 7 according to the present invention, good color reproduction, high color development, and light fastness were simultaneously achieved. <Example 3> Table 3 shows the silver chlorobromide emulsions used in No. 1.3 and 5B in Sample 1 of Example 2. Sample 8 was prepared in the same manner as Sample 1 of Example 2 except that silver halide emulsions were used in each case. -i42: Samples 9 to 14 were prepared by changing the composition of the third layer of Sample 8 as shown in Table 4. For each sample prepared as described above, the photosensitive needle KS-7
After light wedge exposure using green light using a mold (manufactured by Konishiroku Photo Industry Co., Ltd.), the following treatments and the same tests as in Example 2 were performed. The results obtained are also shown in Table 4. [! 28 Process] Temperature Time color development phenomenon 34.7±03℃ 50 seconds bleach fixing
34.7±0.5℃ Stabilized for 50 seconds 30~3
Dry at 4°C for 90 seconds Dry for 60 seconds [Color developer] Pure water
89h12 ethylene glycol
101gN,N-diethylhydroxylamine 109 Potassium chloride
29N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami 5g Noaniline sulfate Tetraboline Sodium phosphate 29 Potassium carbonate 3013 Add pure water to make total 12, I) Hlo, 08 adjust. (Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100d Ammonium sulfite (40% solution) 27.'5d Potassium carbonate or glacial acetic acid p) Adjust to -17,1 and add water to make the total amount 12. (Stabilizing liquid) 5-chloro-2methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1゜1-diphosphone M 2g Add water to make 1 tl, and adjust the pH to 7 with sulfuric acid or potassium hydroxide.
．． Adjust to 0. In the table, DBP represents dibutyl phthalate. From the results in Table 4, it can be seen that Sample 9 using the comparative coupler + transfer and Sample 10 using the comparative antifading agent had lower maximum densities when subjected to the rapid processing used in this example. Furthermore, the light fastness was low and not at a satisfactory level. - It can be seen that in Samples 11 to 14 according to the Riki invention, not only sufficient color density was obtained, but also the light fastness of the magenta dye and the yellow stain caused by heat and humidity were improved. When the same photo-printing printer as in Example 2 was used and visually evaluated, Samples 11 to 14 according to the present invention gave bright prints with high color purity. On the other hand, Sample 8 was inferior in color reproduction of red to purple. In Samples 9 and 10, the maximum density was insufficient, so the patterns were not solid. As described above, it is clear that the samples according to the present invention provide sufficient color development, light fastness, and color reproduction even when subjected to rapid processing. Procedural proceedings official document (spontaneous) August 17, 1985 Director General of the Japan Patent Office Mr. Michibu Ajiga Part 1, Indication of the case 1986 Patent Order No. 134287 2, Name of the invention Pigment with excellent light fastness Silver halide photographic light-sensitive material 3 from which images can be obtained, relationship with the case for correction Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1)
27) Konishi Roku Photo Industry Co., Ltd. Representative Director Keio Ide 4, Agent 102 Address 4-1-1 Kudankita, Chiyoda-ku, Tokyo, Kyushu-Rosaka Building Telephone: 263-9524 Name (7614) Patent Attorney Ichinose Miya Blindness Column 6 of ``Detailed Description of ``, Contents of Amendment (1) Item r2 of the specification and Claims J are amended as shown in the attached sheet. (II) Section 1.3, “Detailed Description of the Invention” of the specification shall be amended as follows. 1. The structural formula of general formula (c) on page 31 of the specification is amended as follows. (RF Rin) 2. Specification 11: MS page 14 The structural formula of general formula (e) is corrected as follows. ([14) When n is 3, the structural formula of general formula (C') on page 31 of the specification is corrected as follows. (RI?')it・4, regarding pages 36 and 37 of the specification, page 36 is replaced with page 37, and page 37 is replaced with page 36. 5. Modify the structural formula at the bottom of page 42 of the specification ttIS as follows. 6. The structural formula of general formula (c-9) in Specification 1 No. 47 is corrected as follows. 7. The structural formula of the general formula outside the table on page 58 of the specification is amended as follows. 80. The description "color reproducibility" on page 166, line 3 of Mei NIt is corrected to read "spectral absorption characteristics." 1/S 1st (gIJ system) 2. Claims A small amount of 4k<doshi-figure silver halide on the support! Ft 7
In addition, at least one layer of the silver halide emulsion 1γ1 has the following -
・#! Formula'(a), (11) d3J:bi(C
) at least one coupler selected from the couplers shown in I 11 and/or polymeric couplers derived from said couplers s1e and oxidized 1 position OX (
) is 0.95≦EO×≦1.50. Silver halide photographic material Fl. General formula (1)) General formula (C) (1 sentence 8 IT↑, (General formula (CI), (11) J3J: Bi(
c) Middle, 7OL. Number 7 and Zc each form a nitrogen-containing M ring! ! 1 non-gold Ii 1 atom nT. X(L
, X number (1) and Xc each represent ifF 6 M which is released from Ul'lft upon reaction with water MrM molecules or an oxidized product of a color developing agent. F<a,... + Re-, Re, RcL,
Ik, Ry-, and 1 (1 is a hydrogen atom or a substituent, respectively. There is no substituent rtI5., Yll, carbon UIi, and 1 represent a nitrogen atom. Yl represents a carbon atom or a heteroatom. Indicates that it may be a double bond. However, if Yl is a carbon atom and the bond between Yl and Yl is a double bond, n3 is 1, nl is O, and R
C is an @ substituent that does not undergo l1lII elimination during the reaction between the coupler represented by formula (a) and the oxidized color developing agent, and Yl is a carbon atom and the bond between Yl and Yl is 111F? In the case of 3 cases, n3 and nl are both 1. Also, if Y1 is a nitrogen atom and the bond between Yl and Yl is a double bond, n3 and nl are both O, and Yl is a heteroatom, Yl is a nitrogen atom, and the bond between Yl and Yl is a double bond. In the case of a single bond, n3 is 1 and nl is O. The couplers represented by general formulas ('a), (b), and (c) exhibit color development only at the positions where XL, X, and XC are bonded, respectively. 7J Tsudaring reaction with the oxidized form of the main drug. )

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one layer of the silver halide emulsion has the following general formulas (a), (b) and (c). ) and/or a polymer coupler derived from the coupler, and an oxidation potential Eox (V
) is 0.95≦E0x≦1.50,
A silver halide photographic light-sensitive material, characterized in that the silver halide is contained dispersed in a high boiling point organic solvent having a dielectric constant of 6.0 or less. General formula (a) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (b) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (c) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (General formula (a) ), (b) and (c), 7a, 7b,
and Zc each represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle. Xa, Xb and Xc each represent a hydrogen atom or a group that can be separated upon reaction with an oxidized product of a color developing agent. Ra, Rb, Rc, Rd, Re, Rf and Rg each represent a hydrogen atom or a substituent. However, Rg is a substituent that does not leave when the coupler represented by the general formula (c) reacts with the oxidized product of the color developing agent. Y_
1 represents a carbon atom or a nitrogen atom. Y_2 represents a carbon atom or a heteroatom. ■ indicates that the bond between Y_1 and Y_2 may be a single bond or a double bond. However, if Y_1 is a carbon atom and the bond between Y_1 and Y_2 is a double bond, n_3 is 1 and n_4 is 0,
and Rc is a substituent that does not leave when the coupler represented by general formula (a) reacts with the oxidized color developing agent, and when Y_1 is a carbon atom and the bond between Y_1 and Y_2 is a single bond; , n_3 and n_4 are both 1. If Y_1 is a nitrogen atom and the bond between Y_1 and Y_2 is a double bond, both n_3 and n_4 are 0, and
Y_2 is a heteroatom, Y_1 is a nitrogen atom, and Y_1
When the bond between and Y_2 is a single bond, n_3 is 1 and n_4 is 0. In addition, the couplers represented by general formulas (a), (b), and (c) are capable of binding to the color developing agent only at the positions where Xa is bound, Xb is bound, and Xc is bound, respectively. Coupling reaction with oxidant. )