JPS61269153A - Formation of dye image - Google Patents

Abstract

PURPOSE:To enhance rapid processing aptitude and development processing stability by processing an imagewise exposed specified silver halide color photographic sensitive material with a color developing solution. CONSTITUTION:The silver halide color photographic sensitive material having a silver halide emulsion layer contg. a magenta coupler represented by the formula shown on the right (Z is a nonmetallic atomic group necessary to form an N-contg. optionally substd. hetero ring, X is H or a group to be release by the coupling reaction with the oxidation product of a color developing agent, and R is H or a substituent) is formed on a reflective support. The sensitive material is imagewise exposed and processed with a color developing solution contg. at least bromine ions in a concn. of >=7X10<-3>mol/l, and having, prefer ably, a pH of about 9- about 13, at a treting temp. of 20-70 deg.C, preferably, for 1-10min.

Description

[Detailed description of the invention]

E. Industrial Application Field] The present invention relates to a method for forming a dye image, and more specifically to a method for forming a dye image.
Safe against fluctuations in composition of image solution, especially fluctuations in bromide ion concentration.
Excellent color with consistent sensitivity and gradation and minimal fog
The present invention relates to a method of forming an elementary image. [Invention 11 In recent years, silver halide color photographic light-sensitive materials (hereinafter simply referred to as color photographic materials)
The development process for photosensitive materials (referred to as photosensitive materials) has been accelerated,
Furthermore, to improve work efficiency and reduce costs, W of developer replenisher
The so-called low replenishment type, which reduces the amount of replenisher due to shrinkage.
The number of developing solutions has been increasing. These industry trends
Correspondingly, rapid processing of silver halide photographic materials
Highly desirable for gender and low replenishment type aptitude.
Ru. However, with low replenishment type developer,
Halogen ions accumulate in higher concentrations than conventional types. In general, halogen ions have the effect of inhibiting development;
Iodine ions are particularly strong, followed by bromide ions and chlorine ions.
In order of
very weak. Therefore, in order to meet the above needs,
There have been no studies using silver chlorobromide emulsions with relatively high chlorine content.
However, if the silver chloride content is high, the sensitivity will decrease.
Therefore, it is difficult to significantly increase the chlorine content.
That is the current situation. Bromine ions are also effective ions as fog suppressants.
Photographic performance changes due to variations in density, especially silver chlorobromide.
In the case of color photosensitive materials using
The disadvantage is that the sensitivity and gradation vary greatly, which is very important.
There is. Normally, in the general market, color photosensitive materials are
Continuously processed using an automatic processing machine
, control the bromide ion concentration in those developers at a constant level.
Although efforts have been made to
Fluctuations in the bromide ion concentration occurred, which may be due to the influence of
cormorant. The color when the bromide ion concentration fluctuates like this
Changes in sensitivity and 1@lll given to photosensitive materials are particularly important when directly
It seriously impairs the quality of ornamental color prints.
. For the above reasons, it prevents fluctuations in the bromide ion concentration in the developer.
Because of the difficult situation, the bromide ion concentration has changed.
There is a strong desire for a method to prevent gradation fluctuations even when moving.
There is. On the other hand, to form a dye image using color photosensitive materials,
, usually an aromatic primary amine color-forming ring imaging agent is exposed to light.
When reducing silver halide grains in color photosensitive materials
itself is oxidized, and this oxidized product is pre-precipitated into the color photosensitive material.
It reacts with the coupler contained in it to form a dye.
Therefore, it is done. And normally, as a coupler,
Yellow, magenta,
Three types of couplers are used to form three cyan pigments.
It is. Among these, in order to form a magenta dye image,
Generally 5-pyrazolone, cyanoacetophenone, indica
Chiron couplers etc. are used. Previously, it was put into practical use as a magenta dye image-forming coupler.
Most of them were 5-pyrazolone couplers.
there were. formed from this 5-pyrazolone coupler
Although dye images have some advantages, they also lack sufficient color tones.
, but a sub-absorption with a yellow component near 430n■
exists, and the tail on the long wavelength side is sharply cut, and there is no
, there are drawbacks in spectral absorption characteristics such as color turbidity,
The colored pigment image lacked vividness. Especially color plates for direct viewing that carry an image on a reflective support.
This was an important issue in lint. As a coupler without side absorption, US Pat. No. 3,125.
No. 067, JP-A-59-99437, JP-A No. 59-16
No. 25413, No. 59-171956, Research De
Disclosure magazine No. 24220, No. 24230 and
Pyrazolotriazole described in No. 24531, etc.
Coupler couplers are particularly excellent. In addition, the photographic properties are improved due to the fluctuation of the bromide ion concentration in the developer mentioned above.
The change in performance varies depending on the type of coupler.
Selecting a small coupler is desirable. The present inventors have discovered the maze described in Japanese Patent Application No. 59-276725.
Coupler is preferable for color reproduction, and also
The performance change with respect to bromide ion concentration fluctuation of 1 is
It is a relatively small coupler (hereinafter referred to as Br fluctuation resistance).
However, the 3r fluctuation resistance is still not sufficient.
, these couplers were also found to be prone to fogging,
Further improvements are required for practical use. [Object of the invention] $J [17) 117) [9+”1”114・ □
:, □Development processing stability, especially the bromide ion concentration of the developer
:.・Stable sensitivity and gradation against fluctuations
(Providing a method for forming an FfI image)
It is to provide. The second object of the present invention is to provide excellent color reproducibility and to prevent fogging.
It is an object of the present invention to provide a low dye image forming method. [Configuration of the Invention] As a result of intensive research, the inventors have found that the above-mentioned purpose of the present invention has been achieved.
is magenta represented by the following general formula [I] on a reflective support.
Silver halide emulsion layer containing coupler and silver chlorobromide emulsion
Imagewise exposure of a silver halide color photographic light-sensitive material having
After that, the bromide ion concentration is at least 7 x 10-3 mol.
/l or more and hydroxylamines 0.02 mol/l
J! Processed with a color developer containing ~0.15 mol/I2
We have discovered that what can be achieved by a dye image forming method
. General formula [I] [In the formula, 2 is a nonmetallic atom necessary to form a nitrogen-containing heterocycle
represents a group, and the ring formed by 2 may have a substituent.
good. X is formed by a reaction with a hydrogen atom or an oxidized product of a color developing agent.
Represents a substituent that leaves off. Further, R represents a hydrogen atom or a substituent. ] [Tools of invention
Physical Configuration] The present invention will be specifically explained in the following margin. In the magenta coupler represented by general formula (I) and general formula CI) according to the present invention, Z is a nitrogen-containing hetero
Represents a group of nonmetallic atoms necessary to form a ring, and by Z
The ring formed may have a substituent. X is formed by a reaction with a hydrogen atom or an oxidized product of a color developing agent.
represents a substituent that can be removed. Moreover, R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include a halogen atom, a
Alkyl group, cycloalkyl group, alkenyl group, cycloa
alkenyl group, alkynyl group, aryl group, heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group
group, carbamoyl group, sulfamoyl group, noano group,
Pyro compound residue, bridged hydrocarbon compound residue, alkoxy
group, aryloxy group, heterocyclic oxy group, siloxy group
, acyloxy group, carbamoyloxy group, amino group,
Acylamino group, sulfonamide group, imide group, urei
do group, sulfamoylamino group, alkoxycarbonyl
Amino group, aryloxycarbonylamino group, alco
xycarbonyl group, aryloxycarbonyl group, alkyloxycarbonyl group,
Examples include kylthio group, arylthio group, and heterocyclic thio group.
It will be done. Examples of halogen atoms include chlorine atoms and bromine atoms.
Among them, a chlorine atom is particularly preferred. The alkyl group represented by R includes those having 1 to 32 carbon atoms.
The alkenyl group and alkynyl group have 2 to 3 carbon atoms.
2, cycloalkyl group, cyclo□ alkenyl group has 3 to 12 carbon atoms, especially 5 to 7 carbon atoms.
is preferable, and an alkyl group, an alkenyl group, an alkynyl group
The 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, cyano, halogen atom, heterocycle, cyclo
loalkyl, cycloalkenyl, spiro compound residues,
In addition to bridge hydrocarbon compound residues, acyl, carboxy, and carboxyl
Bamoyl, alkoxycarbonyl, aryloxycal
Those substituted via a carbonyl group such as carbonyl, and
substitutes through a heteroatom (specifically, a hydro
xy, alkoxy, aryloxy, heterocyclic okyne,
Oxygen such as siloxy, acyloxy, carbamoyl oxine, etc.
Substitution via atoms, nitro, amino (dialky)
), sulfamoylamino, alkoxy
carbonylamino, aryloxycarbonylamino
, asolamino, sulfonamide, imide, ureido, etc.
substituted through the nitrogen atom, alkylthio, ali
ruthio, heterocyclic thio, sulfonyl, sulfinyl,
Those that substitute through the sulfur atom such as sulfamoyl,
(e.g. those substituted via a phosphorus atom such as sulfonyl)
You may do so. Specifically, for example, methyl group, ethyl group, isop'
aepvya, 1-rough 2511. ．． ．． Tsu, auf, ya
1, ivy group, l-hexylnonyl group, 1.1・-
dipentylnonyl group, 2-chloro-t-butyl group, tri-
Fluoromethyl group! -ethoxytridecyl group, 1-methane
Toxyisopropyl group, methanesulfonylethyl group, 2
．． 4-di-monoamylphenoxymethyl group, anilino group
, l-phenylisopropyl group, 3-m-butanesulfonate
aminophenoxyprobyl group, 3-4・-(α-[4
...(p-hydroxybenzenesulfonyl)phenoxy
]dodecanoylamino)phenylpropyl group, 3-(4
・-[α-(2..., 4...-di-t-amylphenoki
c) Butanamide] phenyl)-propyl group, 4-[α
-(0-chlorophenoxy)tetradecanamidopheno
[xy]propyl group, allyl group, cyclopentyl group,
Examples include lohexyl group. The aryl group represented by R is preferably a phenyl group.
, substituents (e.g., alkyl groups, alkoxy groups, acyl groups)
amino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecane
amidophenyl group, hexadecyloxyphenyl group, 4.
-[α-(4...-t-butylphenoxy)tetradeca
and amidophenyl groups. The heterocyclic group represented by R is preferably 5- to 7-membered.
may be substituted, may be fused, or may be substituted or fused.
. Specifically, 2-furyl group, 2-chenyl group, 2-pyryl group,
Examples include midinyl group and 2-benzothiazolyl group. Examples of the acyl group represented by R include an acetyl group and a fluoride group.
Phenylacetyl group, dodecanoyl group, α-2,4-di-
Alkyl carbo such as t-amylphenoquine butanoyl group
Nyl group, benzoyl group, 3-pentadecyloxybenzo
Aryl carbonyl group, p-chlorobenzoyl group, etc.
and the like. The sulfonyl group represented by R is a methylsulfonyl group
, an alkylsulfonyl group such as a dodecylsulfonyl group,
Such as benzenesulfonyl group, p-toluenesulfonyl group
Examples include arylsulfonyl groups and the like. As the sulfinyl group represented by R, ethylsulfinyl
Nyl group, octylsulfinyl group, 3-phenoxybutyl group
Alkylsulfinyl group such as rusulfinyl group,
Nylsulfinyl group, m-pentadecylphenylsulf
Examples include arylsulfinyl groups such as vinyl groups, etc.
. The phosphonyl group represented by R is butyl octyl phosphor.
Alkylphosphonyl group such as honyl group, octyloxy
Alkoxyphosphonyl group such as phosphonyl group, phenoxy
Aryloxyphosphonyl group such as cyphosphonyl group,
Examples include arylphosphonyl groups such as phenylacetyl groups, etc.
It will be done. The carbamoyl group represented by R is an alkyl group, an aryl group,
It may be substituted with a group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group,
Rubamoyl group, N-(2-pentadecyl octylethyl
) Carbamoyl group, N-ethyl-N-dodecylcarbamo
yl group, N-(3-(2,4-di-t-amylphenokyl group)
ci)propyl)carbamoyl group, and the like.
・The sulfamoyl group represented by the blank space R below is an alkyl group, an aryl group.
It may be substituted with a group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-diethyl group
Rusulfamoyl group, N-(2-pentadecyloxye
thyl) sulfamoyl group, N-ethyl-N-dodecyl group
Examples include rufamoyl group, N-phenylsulf 7-moyl group, etc.
can be lost. Examples of spiro compound residues represented by R include spiro[
3,3]hebutan-■-yl and the like. Examples of the Ikuhashi carbonized compound residue represented by R include Bisik
ro[2,2,1]heptan-1-yl, trinculo[3
,3,1,M"]]decan-1-yl7,7-tmethyl
-bicyclo[2,2,1]hebutan-1-yl etc.
It will be done. The alkoxy group represented by R further has a linkage to the alkyl group.
Those listed as substituents may be substituted, for example,
Methoxy group, propoxy group, 2-ethyne ethoxy group,
Pentadecyloxy group, 2-dodenyloxyethoxy group
, phenethyloxyethoxy group, and the like. The aryloxy group represented by R is phenyloxy
is preferable, and the aryl nucleus is further substituted with the aryl group.
Optionally substituted with those listed as groups or atoms,
For example, phenoxy group, p- is -butylphenoxy group, m
-pentadecylphenoxy group and the like. The peterocyclic oxy group represented by R is a 5- to 7-membered heterocyclic group.
Preferably, the heterocycle has a substituent.
For example, 3°4.5.6-tetrahydrogen
Dropyranyl-2-oxy group, l-phenyltetrazo
-5-oxy group is mentioned. The siloxy group represented by R is further substituted with an alkyl group, etc.
For example, trimethylsiloxy group, trimethylsiloxy group,
Examples include ethylsiloxy group, dimethylbutylsiloxy group, etc.
It will be done. As the acyloxy group represented by R, for example, alkyl
Carbonyloxy group, arylcarbonyloxy group, etc.
and may further have a substituent, specifically
Acetyloxy group, α-chloroacetyloxy group, ben
Examples include zoyloxy group. The carbamoyloxy group represented by R is an alkyl group, an alkyl group,
It may be substituted with a lyl group, for example, N-ethyl group.
Rubamoyloxy group, N,N-diethylcarbamoyl group
Examples include xyl group, N-phenylcarbamoyl oxine group, etc.
It will be done. The amino group represented by R is an alkyl group or an aryl group (preferably
or phenyl group), etc., for example,
ethylamino group, anilino group, m-chloroanilino group,
3-pentadecyloxycarbonylanilino group, 2-k
Examples include lor-5-hexadecaneamide anilino group, etc.
Ru. The acylamino group represented by R is an alkyl carboxyl group.
nylamino group, arylcarbonylamino group (preferably
is a phenylcarbonylamino group), and furthermore,
It may have a substituent, specifically an acetamide group, an α-ethyl group, etc.
Tylpropanamide group, N-phenylacetamide group,
Dodecanamide group, 2,4-di-monoamylphenoxy
Acetamide group, α-3-t-butyl 4-hydroxyph
Examples include phenoxybutanamide group. The sulfonamide group represented by R is an alkyl sulfonamide group.
Honylamino group, arylsulfonylamino group, etc.
and may further have a substituent. Specifically, methylsulfonylamino group, pentadecyl group
sulfonylamino group, benzenesulfonamide group, p-)
Luenesulfonamide group, 2-methoxy-5-t-amido
Examples include rubenzenesulfonamide group. The imide group represented by R may be open-chain or cyclic.
It may also have a substituent, for example, amber.
Acid imide group, 3-heptadecyl succinimide group, lid
Examples thereof include a limide group and a glutarimide group. The ureido group represented by R is an alkyl group, an aryl group (
(preferably phenyl group) etc.
, for example, N-ethylureido group, N-methyl-N-decyl
Luureido group, N-phenylureido group, N-p-tri
Examples include a leureido group. The sulfamoylamino group represented by R is an alkyl group,
Substituted with an aryl group (preferably a phenyl group), etc.
For example, N,N-dibutylsulfamoylamide
group, N-methylsulfamoylamino group, N-phenylamino group
Examples include rusulfamoylamino group. As the alkoxycarbonylamino group represented by R,
It may further have a substituent, for example, metquin carbo
nylamino group, methoxyethoxycarbonylamino group,
Examples include octadecyloxycarbonylamino group, etc.
. The aryloxycarbonylamino group represented by R is
It may have a substituent, for example phenoxycarbonyl
Amino group, 4-methylphenoxycarbonylamino group
Can be mentioned. ) The alkoxycarbonyl group represented by R is
It may further have a 1' substituent, for example a methoxycarbonyl group.
, butyloxycarbonyl group, dodecyloxycarbonyl group
group, octadecyloxycarbonyl group, ethoxymetho group
oxycarbonyloquine group, benzyloxycarbonyl group
etc. The aryloxycarbonyl group represented by R further has a substituent
For example, a fenoquine carbonyl group,
p-chlorophenoxycarbonyl group, m-pentadecyl
Examples include oxyphenoxycarbonyl group. The alkylthio group represented by R further has a substituent.
For example, ethylthio group, dodecylthio group,
tadecylthio group, phenethylthio group, 3-phenoxy
Propylthio group is mentioned. The arylthio group represented by R is preferably a phenylthio group.
Furthermore, it may have a substituent, for example, a phenylthio group,
p-methoxyphenylthio group, 2-t-octylphenyl
ruthio group, 3-octadecylphenylthio group, 2-cal
Boxyphenylthio group, p-acetaminophenylthio
Examples include groups. The heterocyclic thio group represented by R includes 5 to 7 shellfish heterocyclic thio groups.
A locyclic thio group is preferred, and may further have a fused ring, or
It may have a substituent. For example, 2-pyrinorthio group
, 2-benzothiazolylthio group, 2,4-diphenoxy
-1,3,5-) lyazole-6-thio group.
. It is released by reaction with the oxidized product of the color developing agent represented by X.
Examples of substituents include halogen atoms (chlorine atoms, odor
low carbon atoms, oxygen atoms, sulfur
Examples include groups substituted via an atom or a nitrogen atom. As a group substituting via a carbon atom, a carboxyl group
Other examples include the general formula % (R1. has the same meaning as the above R, and Z. has the same meaning as the above Z).
Yes, R1 and R1 are hydrogen atoms, aryl groups, and alkyl groups.
Represents a kill group or a heterocyclic group. ), hydro
Examples include quinmethyl group and triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy
group, aryloxy group, heterocyclic oxy group, acyloxy group
cy group, sulfonyloxy group, alkoxycarbonyloxy group
cy group, aryloxycarbonyloxy group, alkyl group
Examples include xalyloxy group and alkoxyoxalyloxy group.
can be lost. The alkoxy group may further have a substituent, for example,
Ethoxy group, 2-phenoxyethoxy group, 2-cyanoe group
Toxy group, phenethyloxy group, p-chlorobenzyl group
Examples include xy group. The aryloxy group is preferably a phenoxy group.
, the aryl group may further have a substituent. Ingredients
Physically, phenoxy group, 3-methylphenoxy group, 3-
Dodecylphenoquine group, 4-methanesulfonamidophene
Noxy group, 4-(α-(3・-pentadecylphenoxy
) butanamide] phenoxy group, hexidecylcarbamo
ylmethoxy group, 4-cyanophenoxy group, 4-methane
Sulfonylphenoxy group, l-naphthyloxy group, p-
Examples include methoxyphenoxy group. The heterocyclic oxyne group is a 5- to 7-membered heterocyclic oxyne group.
A ring group is preferable, and a fused ring group may be used.
You may do so. Specifically, I-phenyltetrazoly
Luoquine group, 2-benzothiazolyloxy group, etc.
It will be done. Examples of the acyloxy group include acetoxy group, butane
Alkylcarbonyloxy groups such as trunoxy groups, thinner
alkenylcarbonyloquine groups such as moyloxy groups,
Arylcarbonyloxy group such as penzoyluoquine group
can be mentioned. As the sulfonyloquine group, for example, butanesulfonyl
Examples include a fluoroxy group and a methanesulfonyloquine group. As the alkoxycarbonyloxy group, for example, ethyloxy
oxycarbonyloxy group, benzyloxocarbonyloxy group
Examples include xy group. The aryloxycarbonyl group is phenoquinocal
Bonyloxy group etc. are mentioned. As the alkyloxalyloxy group, for example, methyl
An example is an oxalyloxy group. As the alkoxy oxalyloxy group, ethoxy
Examples include xalyloxy group. Examples of groups substituted via a sulfur atom include alkyl
Thio group, arylthio group, heterocyclic thio group, alkylthio group
Examples include xythiocarbonylthio group. As the alkylthio group, butylthio group, 2-cyano
Ethylthio group, phenethylthio group, benzylthio group, etc.
Can be mentioned. As the arylthio group, phenylthio group, 4-methane
Sulfonamidophenylthio group, 4-dodecylphenethyl group
Ruthio group, 4-nonafluoropencunamidophenethyl
Thio group, 4-carboxyphenylthio group, 2-ethoxy
-5-t-butylphenylthio group and the like. Examples of the heterocyclic thio group include! - phenyl 1,
2,3.4-tetrazolyl-5-thio group, 2-benzothi
Examples include azolylthio group. As the alkyloxythiocarbonylthio group, dode
Examples include syloxythiocarbonylthio group. Examples include those represented by the general formula -N.
group, heterocyclic group, sulfamoyl group, carbamoyl group
, acyl group, sulfonyl group, aryloxycarbonyl
group, represents an alkoxycarbonyl group, and R4 and R5 are
They may be combined to form a heterocycle. However, R4 and R2
・ cannot both be hydrogen atoms. The alkyl group may be straight chain or branched, preferably carbon
It is a prime number of 1 to 22. In addition, an alkyl group is a substituent
The substituent may include, for example, an aryl group.
, alkoxy group, aryloxy group, alkylthio group,
Arylthio group, alkylamino group, arylamino group
, acylamino group, sulfonamide group, imino group, acylamino group,
group, alkylsulfonyl group, arylsulfonyl group,
Carbamoyl group, sulfamoyl group, alkoxycarbo
Nyl group, aryloxycarbonyl group, alkyloxy
carbonylamino group, aryloxycarbonylamino
group, hydroxyl group, carboxyl group, cyano group, halo
Examples include gen atoms. Specific examples of the alkyl group include, for example, ethyl group.
, oxytyl group, 2-ethylhexyl group, 2-chloroethyl group
Examples include ru groups. The aryl group represented by R4 or R5 is carbon
Number 6 to 32, particularly phenyl group and naphthyl group are preferable,
The aryl group may have a substituent, and examples of the substituent include
Alkyl represented by R4' or R5・ above
Those listed as substituents to the group and alkyl groups are listed.
It will be done. Specific examples of the aryl group include, for example:
phenyl group, l-naphthyl group, 4-methylsulfonyl group
Examples include phenyl group. The heterocyclic group represented by R4 or R6 is 5 to 6
A membered ring is preferable, and it may be a fused ring, and the substituent is
May have. Specific examples include 2-furyl group, 2-kyl group,
Noryl group, 2-pyriminol group, 2-benzothiazolyl group
, 2-pyridyl group and the like. As the sulfamoyl group represented by R4 or R6,
N-alkylsulfamoyl group, N,N-dialkyl group
rufamoyl group, N-arylsulfamoyl group, N,
N-diarylsulfamoyl 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 metal group. Sur
Specific examples of famoyl groups include N,N-diethyl
Sulfamoyl group, N-methylsulfamoyl group, N-
dodecylsulfamoyl group, N-p-)lylsulfamo
An example is an yl group. The carbamoyl group represented by R4 or R6 is,
N-alkylcarbamoyl group, N,N-dialkylcar
Bamoyl group, N-arylcarbamoyl group, N,N-di
(Arylcarbamoyl group, etc.)
The alkyl group and aryl group of these are the alkyl group and aryl group of
It may have the substituents listed for the lyl group. mosquito
Specific examples of rubamoyl groups include N,N-diethyl
Carbamoyl group, N-methylcarbamoyl group, N-dode
Rubamoyl group, N-p-cyanophenylcarbamo
yl group, N-p-)lylcarbamoyl group. Examples of the acyl group represented by R4 or R6 include
Alkylcarbonyl group, arylcarbonyl group, hetero
Examples include ring carbonyl groups, such alkyl groups, and aryl groups.
The heterocyclic group may have a substituent. Asil
Specific examples of the group include hexafluoro.
Butanoyl group, 2゜3.4.5.6-pentafluorobe
nzoyl group, acetyl group, benzoyl group, naphthonyl group
, 2-furylcarbonyl group, and the like. The sulfonyl group represented by R4. or R6.
Rukylsulfonyl group, arylsulfonyl group, heterocycle
Examples include sulfonyl groups, which may have substituents, and specifically
For example, ethanesulfonyl group, benzene
Sulfonyl group, octanesulfonyl group, naphthalene sulfonyl group
Honyl group, p-chlorobenzenesulfonyl group, etc.
It will be done. Aryloxycarbonyl represented by R4 or R6
The group has the substituents listed for the aryl group above.
may have a phenoxycarbonyl group, specifically a phenoxycarbonyl group, etc.
can be mentioned. The alkoxycarbonyl group represented by R4 or R5I is
, may have the substituents listed for the alkyl group above.
, specific examples include methoxycarbonyl group and dodecyl group.
oxycarbonyl group, benzyloxycarbonyl group, etc.
can be mentioned. The heterocycle formed by combining R4 and R1 is
A 5- to 6-membered one is preferable, and it may be saturated or unsaturated.
, and may or may not have aromaticity;
It can also be a synthetic ring. Examples of the heterocycle include N-phthal
imido group, N-succinimide group, 4-N-urazolyl
group, 1-N-hydantoynyl group, 3-N-2,4-dio
xoxazolidinyl group, 2-N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, ■-pyrrolidinyl group, 1-pyrazolyl
group, ■-pyrazolidinyl group, ■-piperidinyl group, 1-
pyrrolinyl group, l-imidazolyl group, 1-imidazolinyl group
1-indolyl group, 1-isoindolinyl group, 2
-isoindolyl group, 2-isoindolinyl group, l-beta
ndzotriazolyl group, 1-benzimidazolyl group, 1-
(1,2,4-triazolyl) group, 1-(1,2,3-
) riazolyl) group, 1-(1,2,3,4-tetrazolyl)
) group, N-morpholinyl group, 1.2.3.4-tetra
Hydroquinolyl group, 2-oxo-1-pyrrolidinyl group,
2-IH-pyridone group, phthaladione group, 2-IH-pyridone group,
Tosoh 1-piperidinyl group etc. are mentioned, and these
Heterocyclic groups include alkyl groups, aryl groups, and alkyloxy groups.
group, aryloxy group, acyl group, sulfonyl group,
Kylamino group, arylamino group, acylamino group, sulphate
sulfonamino group, carbamoyl group, sulfamoyl group,
Alkylthio group, arylthio group, ureido group, alco
xycarbonyl group, aryloxycarbonyl group, imide
do group, nitro group, cyano group, carboxyl group, halogen
It may be substituted by an atom or the like. In addition, as a nitrogen-containing heterocycle formed by Z or Z.
, pyrazole ring, imidazole ring, triazole ring or
Examples include a tetrazole ring, and the ring may have
Examples of the substituent include those described for R above.
. In addition, general formula (1) and general formula (If) to [■] described below
The substituents (for example, R1R1 to R,) on the heterocycle in the
It has the same meaning as R, X, and Z. ), the so-called bi
Forming a solid coupler is, of course, included in the present invention. Also, formed by Z, Z・, Z... and Zl described below
The ring may further include another ring (for example, a 5- to 7-membered cycloalkene)
may be condensed. For example, in general formula (V)
R6 and R6 are R7 and R8 in general formula (VI)
are bonded to each other to form a ring (for example, a 5- to 7-membered cycloalke).
benzene). What is represented by the following margin general formula (1) is more specifically, for example,
It is represented by the following general formulas (If) to [■]. General formula (n) General formula (I [[) % formula % General formula [■] N N -Nil General formula (V) General formula (VI) H-N -81 General formula [■] -N-N The above general In formula (II) ~ [■], Rl''-R@ and
X has the same meaning as R and X above. Moreover, among the general formula (I), the following general formula [
■]. General formula [■] N −N , −, / In the formula, R, , X and 2. is RlX and RlX in general formula (r)
It is synonymous with Z. Magenta coupler represented by the general formula (n) to [■]
Among these, particularly preferable ones are represented by general formula (II)
It is a magenta coupler. In addition, the substituents on the heterocycle in general formulas (1) to [■]
For that matter, in the general formula [■], R is also the general
In formulas (I[) to [■], R1 satisfies the following condition l
The following conditions and conditions and 2 are more preferable.
The following condition 1. is particularly preferable.
This is a case where conditions 2 and 3 are satisfied. Condition 1: The root atom directly connected to the heterocycle is a carbon atom. Condition 2 Only one hydrogen atom 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 R and R5 on the heterocycle are
is represented by the following general formula (IX). General formula [■] HFLe oC- In the formula, Re, R+. and Rz are hydrogen atoms and ha, respectively.
rogen atom, alkyl group, cycloalkyl group, alkenyl group
group, cycloalkenyl group, alkynyl group, aryl group
, heterocyclic group, acyl group, sulfonyl group, sulfinyl
group, phosphonyl group, carbamoyl group, sulfamoyl group
, cyano group, spiro compound residue, bridged hydrocarbon compound residue
group, alkoxy group, aryloxy group, heterocyclic oxy
group, siloxy group, acyloxy group, carbamoyloxy
group, amino group, °acylamino group, sulfonamide group,
imide group, ureido group, sulfamoylamino group, alkaline
Koxycarbonylamino group, aryloxycarbonyl
Amino group, alkoxycarbonyl group, aryloxycarbonyl group
Rubonyl group, alkylthio group, arylthio group, hetero
Represents a ring thio group, Rs. At least two of RIo and R1 are not hydrogen atoms. Also, two of the above Rs, Rho and RIl, for example R9
and R7° are combined to form a saturated or unsaturated ring (e.g. cyclo
alkanes, cycloalkenes, heterocycles).
Furthermore, R11 is bonded to the chain ring to form a bridged hydrocarbon compound residue.
It may also form a group. The group represented by R5-R18 may have a substituent
, R, ~RI+ and examples of groups represented by
Examples of substituents that may be substituted include the above-mentioned general formula (1).
Specific examples of the group represented by R and substituents are listed. Also, for example, a ring formed by combining R8 and R10 and R3
-Specifics of the bridged hydrocarbon compound residue formed by R1
Examples and their optional substituents include the general formula
Cycloalkyl, cycloalke represented by R in CI)
Specific examples of bridged hydrocarbon compound residues with a heterocyclic group and
The substituents include. Among the general formulas (TX), (i) Re-R
1, when two of them are alkyl groups, (ii) Rs to R
1, for example, Rl 1 is a hydrogen atom, and the others
2 R11 and Rho combine to form a cylinder with the root carbon atom.
When forming chloroalkyl, Furthermore, among), 2 among R9 to RIl is preferable.
one is an alkyl group and the other is a hydrogen atom or an alkyl group, and the other one is a hydrogen atom or an alkyl group.
This is the case for the alkyl group. Here, the alkyl and cycloalkyl further have a substituent.
The alkyl, the cycloalkyl and their substitutions may be
As a specific example of the group, R in the above general formula CI) represents
Specific examples of alkyl, cycloalkyl and their substituents are listed.
can be lost. The following margins also indicate the ring and ring formed by Z in general formula (I).
Even if there is a ring formed by Zl in the general formula [■]
Good substituents and general formulas [II) to CVI)
R1-R8 is represented by the following general formula (X):
preferable. General formula (X) -R'-9ot-R'' In the formula, R1 is alkylene, R'' is alkyl, cycloalkyl
Represents kill or aryl. The alkylene represented by R1 is preferably a straight chain carbon
The number is 2 or more, more preferably 3 to 6, and the linear
Regardless of branching. Also, this alkylene has a substituent
Good too. Examples of the substituent include R in the above-mentioned general formula (1)
is an alkyl group, a substituent that the alkyl group may have
The following can be mentioned. Preferred substituents include phenyl.
Ru. Preferred specific examples of alkylene represented by R1 are shown below.
show. The alkyl group represented by R2 may be a linear, monobranched group. Specifically, methyl, ethyl, propyl, 1so-propyl
lumibutyl, 2-ethylhexyl, octyl, dodecyl
, tetradecyl, hexadecyl, octadacil, to 2-
Examples of the cycloalkyl group represented by R8 include xyldecyl and the like.
is preferred, such as cyclohexyl. Alkyl and cycloalkyl represented by R1 have a substituent.
For example, the substituent to R1 described above and
The following are examples. Specifically, the aryl represented by R2 is phenyl.
, naphthyl. The aryl group has a substituent
It's okay. Examples of the substituent include linear or branched atom groups.
In addition to Rkyl, those exemplified as substituents for R1 mentioned above
can be mentioned. In addition, if there are two or more substituents, those substituents must be the same.
They may be the same or different. Among the compounds represented by general formula (1), which one is special? This is preferable
is represented by the following general formula (X[). General formula (X[) In the formula, R and X are synonymous with R and X in general formula [I].
RI, R1 is R1°R1 in general formula (X)
is synonymous with 2h margin below C, H. C,,11,UC2h C,H. Margin below: C, 115 C, H. CHi CHi CH. C, IIl. c+alltt CH112! C, lI. C Superintendent 21h Below margin C, It. C2N. catt(1 C)H,% C1H++(11 C,H. C,H5 C,H,s C,H. Below margin ^ C, H,. c, n. C,III 0C11,C0NHCH2Cl,OCI+1ocn,c
n, so, cut C, lI. C, lI. xHI C2U. C,H. C2B. C211°C11! Margins C, I+ below. C12H2ul2H25 0g Below margin CIl! CH. QC,! +5 NHSO2C+5Hia CI. CJly(t) C1l. C, l+, a(1) 12 et al. CH2 CI+. CH! CI, C.H. (1) C1, Cuhll (1) C1l. H and H mouth C, 11°c7i,. 3g 1i! e C1l. Margin below C2H N -N -N 5O N N N C
, xHxsN N N (, H. C,, H,, N -, N -NH-N N N CJs NN 8116O N N Nll N N N11 Between 88□C, H. C, H. N N 811 Between NN□ n n nn (,
,H,. Between 88□+91 N -N -N N -N -N C1, IIl. CJs Cjb ” “Also,
Synthesis of puller is published in Journal of the Chemical Society
Iati (Journal or theChem)
ical Society), Parkin (P e
rkin) 1 (1977), 2047-205
2. U.S. Patent No. 3,725,067, JP-A-59-99
No. 437, JP-A-58-42045, JP-A-59-1
No. 62548, JP-A-59-171956, JP-A-60
-33552 and JP-A No. 60-43659 etc.
Synthesis was performed using The couplers of the invention typically contain 1Xl per mole of silver halide.
0-3 mole to 1 mole, preferably I
A range of 1 to 5xio-' moles can be used. Moreover, the coupler of the present invention is different from other types of magenta couplers.
They can also be used together. The color developing solution used in the dye image forming method of the present invention
The bromide ion concentration in the color developer is 7 x 10 mol/
J! There is no particular upper limit as long as it is above, but preferably
5 X 10-' mol/l or less, more preferably 2.5
X 10 mol/i or less. As mentioned above, color development is carried out using bromine ions as a fog suppressant.
Although it has been done in the past to exist in liquid, this
Variations in bromide ion concentration cause variations in photographic performance, especially
This is a major cause of variations in sensitivity and gradation. deer
However, in the development process of the color photosensitive material of the present invention, bromine ions are
If it is 7 x 10'mol/l or more, the bromide ion concentration is
Even when there is variation, the variation in sensitivity and N-tone is extremely small.
You can obtain color prints of high and stable quality.
It is. In addition, color development used in the dye image forming method of the present invention
Hydroxylamines are contained in the liquid along with the above bromine ions.
Contains 0.02 mol/l to 0.15 mol/l, (under JX
, preferably a 0.03 mole color developing solution according to the present invention.
The content is in the range of mol/) to 0o12 mol/l.
Ru. The hydroxylamines used in the present invention are preferably
It is represented by the following general formula [Xn]. General formula [XTi] In the general formula [Xn], RlolRl may be the same or different.
hydrogen atoms, alkyl groups, and alkyl groups, respectively.
Kenyl group, alkynyl group, aryl group and heterocyclic residue
represents a group, and 816% R11 are combined with each other to form a ring
RIQ' RI+ may further contain hydroxyl
The mino group may be substituted to form a bis body or a tris body.
. Y represents a hydrogen atom or a hydrolyzable group. here
A group that can be hydrolyzed is a group that can be hydrolyzed during development.
refers to a group that forms a hydroxylamino group;
It is a blocking group for xylamino group. R+os RI+ is more preferably each hydrogen
atoms, alkyl groups having 1 to 16 carbon atoms, and 6 to 2 carbon atoms
6, and the alkyl group and aryl group are other
It may have a substituent, and RIo and R1° are 5- to 6-membered
It may have a ring. Hydroxylamines represented by the general formula [XI[]
When used by adding a treatment liquid, Y is a hydrogen atom,
In terms of solubility, RlO and R1+ are hydrogen atoms and carbon atoms, respectively.
Number 1 to 5 alkyl groups and RIOlRll are pyrrolidium
Preferably, it forms a ring, piperidine, or morpholine ring.
Preferably, and even more preferably, F! toSR11 respectively
hydrogen atom, methyl group, ethyl group, 2-ethoxyethyl
group, tetrahydro-2-furfuryl group. In addition, hydroxylamine represented by the general formula [XIr]
may form salts with acids. Next, hydroxylamine represented by the general formula [XIr]
Specific compounds of the class are listed, but are not limited to these.
isn't it. Exemplary hydroxylamines NPh 0H-HCtNH20H""2Hs S 04
(CHA OCHzCH2)+N-OH(HOCH2C
&)2 N-OHα])
(6) CHmiC-OH5-N-OHn C4He NH
OHC1 (3 or α′I)
Ring (°0″H...]・
N-0H'H0t0...■ (n C1s Hsy)z N OH""72Hs
S 04 φ nC15 & yNHOH-He4 U0H A number of hydroxylamines represented by the general formula [XI[]
Tsuka is easily available as a reagent, and then
It can be easily synthesized according to the general synthesis method described in the literature.
Can also be done. For example, oxidation of amines [PCC
Chal and Ni R Patra (B, C, Chal
lls and A, Rl Butler)],
The Chemistry of the Amino Group (Th
e Chemistry of theAslno
Qroup) pages 320-335, Interscientific
Interscience Publishers, New York (Interscience Pub!1shers
, New York) 1968, Oxime Return
Former [H Feuer and PφF Pinsent,
Journal of American Chemical Society
-(H. Feuer and B. F. Vlincent,
Journal of American Cheg
+1cal 5ociety)] 84. 3
77L1962, Amine Oxide Houpe (COE)
18>Reaction [Nie C Sea Pe and E R Tora
Sample (A, C, Qopa and 5. R, Tru
mbull )) Oh fj nitz'y-reaction (O
rganlc Reac-Tons) '1L31
7-493.1960), hydroxylamine ole
Addition reactions to fins [M. Niss Gibson, The K.
Mistry of the Amino Group (K, S,
Gibson, The Chemistry o
r tha Am1no Group)]
pp. 61-85, Interscience Publishers
New York (Interscience P
publishers, New York) 1
968, substitution of active halides and hydroxylamines
reaction (U.S. Pat. No. 3,491,151) etc.
well known. Also, U.S. Patent Nos. 3,864,131 and 3,287
, No. 124, No. 3,287.125, No. 3,293,
No. 034, 1ift No. 3,405.034, 1ift No. 3,4
Specifications of hydroxylamines are listed in the specification of No. 55,916.
Compounds are described. Traditionally, hydroxylamines were used as preservatives in developing solutions.
Although it is known that the present invention uses
13r fluctuation resistance in the development process of color-sensitive materials
Roxyl 7min WIfI! Dependency, i.e. hydroxyl
Improved resistance to Sr fluctuations achieved in the optimum I range of amines
There is no literature describing or suggesting that
It was something that I could not have predicted. Aromatic primary amino acid used in the color developer according to the present invention
Color-based color developing agents are used in various color photographic processes.
This includes well-known methods that are widely used. child
These developers are aminophenol-based and p-7-nylene-based.
Contains diamine derivatives. These compounds are in free form
Salt forms, such as hydrochloride or sulfur salts, are generally used because they are more stable than their salt forms.
Used in acid salt form. Additionally, these compounds are generally
About 0.1 (1 to about 30 (l) of color developer 11)
degree, preferably about 1 g to about 15 g per color developer 11
(Used at a concentration of
Phenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1゜4-dimethylbenzene, etc.
is included. Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-〇-phenylenediamine compound
, alkyl groups and phenyl groups are substituted with any substituents.
You can leave it there. Among them, examples of particularly useful compounds include
, N,N'-diethyl-p-phenylenediamine hydrochloride
salt, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamide
Ethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N. N'-diethylaniline, 4-amino-N-(2-meth
xyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate. The color developing solution according to the present invention includes the above-mentioned primary aromatic amine.
In addition to the color developer, it is usually added to the color developer.
various components such as sodium hydroxide
alkaline agents such as aluminum, sodium carbonate, potassium carbonate,
Alkali metal sulfites, alkali metal bisulfites, alkaline
Potash metal thiocyanates, alkali metal halides,
Benzyl alcohol, water softener and thickener are optional.
It can also be included. pH value of this color developer
is usually 7 or more, preferably about 9 to about 13
, more preferably 9.5 to 11. In the dye image forming method of the present invention, using a color developer
The treatment temperature is selected between 20°C and 70°C, preferably
is 30'C to 50C. In addition, the color development processing time is usually 1 minute to 20 minutes.
, more preferably 1 minute to 10 minutes. The color photosensitive material used in the present invention has the general formula [I
] containing a magenta coupler and a silver chlorobromide emulsion.
If it has a silver halide emulsion layer, it can be used as a single color.
Or it could be one for multiple colors. Multicolor color photosensitive material
In some cases, photographic colors are usually used to perform subtractive color reproduction.
As a puller, use magenta, yellow, and cyan colors.
Silver halide emulsion layer containing puller and non-photosensitive
It has a structure in which layers are laminated on a support in an appropriate number and order of layers.
However, the number of calendars and layer order depend on the priority performance and purpose of use.
You may change it as appropriate. Magenta coupler represented by the general formula [I] of the present invention
A silver chlorobromide emulsion is used for the silver halide emulsion layer containing
However, if the emulsion used is essentially a silver chlorobromide emulsion,
good. Here, the silver chlorobromide emulsion essentially refers to the effect of the present invention.
Halogen in silver halide emulsions as long as it does not damage the
The composition may contain some iodine, and the amount is approximately 1
less than mol% and the remainder consists of chlorine and bromine.
, preferably 5 mol% or more of chlorine, more preferably 15
It is mol% or more. When the color photosensitive material used in the present invention is for multiple colors
contains the halogenated compounds used in other silver halide emulsion layers.
There are no particular restrictions on the halogen composition of silver particles, but
From the viewpoint of quick processing suitability and low replenishment type suitability, chlorine is
A silver halide consisting essentially of silver chlorobromide in a mole percent or more
It is preferable that there be. Silver halide emulsion of color photosensitive material used in the present invention
(hereinafter referred to as the silver halide emulsion of the present invention)
Silver halide grains can be produced using the acid method, neutral method, or ammonia method.
It may be obtained from either method. The particles grow all at once
You can let it grow, or you can grow it after creating seed particles.
good. The method of collecting and growing seed particles is the same.
However, it may be different. Silver halide emulsions simultaneously contain halide ions and silver ions.
Even if they are mixed, if one of them is present, the other is mixed.
You may. In addition, the critical growth rate of silver halide crystals is
While taking into consideration the I of the halide ion and silver ion in the
IH, l) Sequential and simultaneous addition while controlling A++
It may be generated by doing this. Converge after growth
The halogen composition of the particles may be changed using the
stomach. When producing the silver halide emulsion of the present invention, if necessary,
By using a silver halide solvent, silver halide grains can be
Particle size, particle shape, particle size distribution, particle growth
You can control the speed. □Yo□71. ．． Ka, one 1o2. Kera □□(
Halogen contained in the silver chlorobromide emulsion used in the silver chloride emulsion layer
The average particle diameter of the silver oxide particles is preferably 0°2μ11 to 2μ.
A diameter of about 0.4 μm is used, but a diameter of about 0.4 μm is particularly preferable.
The layer is ~1.5μ. The average particle size is defined by the following formula. Here, rl indicates the particle diameter of each particle, and nl indicates the number thereof. The grain size here refers to spherical silver halide grains.
, its diameter, and, in the case of particles other than cubic or spherical, its diameter.
represents the diameter of a circular image with the same area as the projected image of The color light-sensitive material used in the present invention has a blue-sensitive emulsion layer,
It is for multicolor use, having a green-sensitive emulsion layer and a red-sensitive emulsion layer.
In this case, the grain size of the silver halide grains used in the blue-sensitive emulsion layer is
The average grain size is smaller than that of silver halide grains used in other emulsion layers.
Large silver halide grains are preferred. Generally, silver halide emulsions are optically green-sensitized or
Even if the spectral sensitivity is sensitized to red or red, the blue
It has photosensitivity. For this reason, even when exposed to blue light,
Not only blue-sensitive emulsions, but also green-sensitive emulsions that should not be exposed.
Even red-sensitive emulsions and red-sensitive emulsions are exposed to light to some extent.
is unavoidable. For this reason, the blue sensitivity of a blue-sensitive emulsion and the red sensitivity of a green-sensitive emulsion are different from each other.
If the blue sensitivities of sensitive emulsions are close, after blue exposure,
When processed in color development, combined with a blue-sensitive emulsion
In addition to the dyes produced by the reaction of couplers, red-sensitive emulsions
and from couplers combined with green-sensitive emulsions.
Partial pigments are formed, causing color turbidity and poor color reproducibility.
It turns into Various efforts have been made to prevent such deterioration of color reproducibility.
An example of what has been done but no effective method has been found
For example, using a yellow filter dye, green-sensitive emulsions and
Attempts have been made to reduce the blue sensitivity of red-sensitive emulsions.
Ru. However, in the case of multicolor color photographic paper, it is usually
The blue-sensitive emulsion layer is unsuitable, and if the blue-sensitive emulsion layer is
A yellow filter dye layer is provided above the dye layer, and a yellow filter dye layer is provided below.
Even if the
In this case, the blue sensitivity of the blue-sensitive emulsion is
is greatly reduced, making it difficult to put it into practical use.
. Therefore, the magenta according to the present invention having the above-mentioned good characteristics
Color reproducibility is improved by using a coupler.
Due to the factors mentioned above, color reproducibility may be greatly affected.
Deterioration must be avoided at all costs. child
Therefore, the blue sensitivity of blue-sensitive emulsions is lower than that of green-sensitive emulsions and red-sensitive emulsions.
Designed so that the blue sensitivity is significantly higher than that of the emulsion.
Silver halide grains needed and used in blue-sensitive emulsions
The grain size of the halo used in green-sensitive emulsions and red-sensitive emulsions is
It is preferable that the grain size is larger than the grain size of silver germide grains. More ingredients
Physically, it can be used as a color photographic paper.
In order to obtain the necessary sensitivity as a blue-sensitive emulsion,
The average silver halide grain used in the emulsion is 0.6μ■ or smaller.
The above is preferable. The silver halide photographic light-sensitive material used in the present invention has a multicolor color.
In the case of a color-sensitive material, the specific layer structure is
On the body, sequentially from the support side, a yellow dye image forming layer, an intermediate
layer, a magenta dye imaging layer of the present invention, and a UV absorber.
Contains intermediate layer, cyan dye image forming layer, ultraviolet absorber
Particularly preferred are intermediate layers and protective layers containing
stomach. Silver halide grains used in the silver halide emulsion of the present invention
In the process of particle formation and/or growth,
, cadmium salt, zinc salt, lead salt, thallium salt, iridium
Mu salt or complex salt, rhodium salt or complex salt, iron salt or complex salt, etc.
Add metal ions using
It can be incorporated into the surface and in a suitable reducing atmosphere.
By leaving the particles in place, a reduction bottle feeling can be created inside the particles and/or on the particle surface.
Can give a nucleus. The silver halide emulsion of the present invention is characterized by the growth of silver halide grains.
After the completion of the process, unnecessary soluble salts may be removed or
Otherwise, it may be left as is. When removing cough salts
, the method described in Research Disclosure No. 17643
It can be done based on. Silver halide grains using the silver halide emulsion of the present invention
The child may consist of a uniform layer inside and on the surface,
It may consist of different layers. Silver halide grains used in the silver halide emulsion of the present invention
A particle is a particle whose latent image is mainly formed on the surface.
It is also possible to use grains that are formed inside the grains as a writer.
Even a child is fine. Silver halide grains used in the silver halide emulsion of the present invention
The crystals may have regular crystal shapes, spherical or plate shapes.
It may also have an irregular crystal shape such as a shape. these
The ratio of (100) and (111) planes in particles is arbitrary.
can be used. Also, it has a composite form of these crystal forms.
Particles of various crystal shapes may be mixed.
. The halogen compound emulsion of the present invention consists of separately formed halogen compound emulsions.
Even if two or more types of silver halide emulsions are mixed and used
good. The silver halide emulsion of the present invention is chemically sensitized by a conventional method.
Ru. That is, compounds containing sulfur that can react with silver ions,
Sulfur sensitization method using activated gelatin, using selenium compound
selenium sensitization method using reducing substances, reduction sensitization method using reducing substances,
Noble metal sensitization method using other noble metal compounds can be used alone or
can be used in combination. The silver halide emulsion of the present invention is widely used in the photographic industry for sensitization.
Using pigments known as dyes, the desired wavelength range is
Can be optically sensitized. Sensitizing dyes may be used alone, but
, two or more types may be used in combination. sensitizing dye and
dyes that do not themselves have spectral sensitizing properties or
A compound that does not substantially absorb visible light and is a sensitizing dye.
Even if the emulsion contains a supersensitizer that strengthens the sensitizing effect of
good. The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
Preventing fogging during storage, photo processing, and/or
is chemically aged, and is used to maintain stable photographic performance.
and/or at the end of chemical ripening and/or at the end of chemical ripening.
After that, by the time silver halide emulsion was applied, the photographic industry
Compounds known as antifoggants or stabilizers
can be added. Mercapto complex in the color photosensitive material used in this invention
By containing a ring compound, the effects of the present invention can be further enhanced.
can be improved. Preferred mercapto heterocyclic compounds have the following general formula [XI
II]. General formula [XIII] In the formula, ZO is an imidacillin ring, an imidazole ring, an imidazole ring,
Silone ring, pyrazoline ring, pyrazole ring, pyrazolone ring
, oxazoline ring, oxazole ring, oxacylone ring,
Thiazoline ring, thiazole ring, thiazolone ring, selenazo
Phosphorus ring, selenazole ring, selenazolone ring, oxadia
Zole ring, thiadiazole ring, triazole ring, tetra
Zole ring, benzimidazole ring, benztriazole
ring, indazole ring, benzoxazole ring, benzucci
Azole ring, benzselenazole ring, pyrazine ring, pyryl ring
midine ring, pyridazine ring, triazine ring,
;xazine ring, thiazine ring, tetrazine ring, quinazine ring
ring, phthalazine ring and polyazaindene ring
j (e.g. doriazaindene ring, tetrazaindene ring
ring, pentazaindene ring, etc.).
represents the atomic group necessary to The ring residue may have substituents, and these substitutions
. Examples of the group include an alkyl group, an aryl group, and an alkenyl group.
group, sulfamoyl group, carbamoyl group, doacyl group
, etc. Mercapto heterocyclic compound represented by general formula [XIII]
, most preferably consists of a triazole ring
It is a mercaptotriazole compound. Compound represented by the above general formula (xm) used in the present invention
Specific examples of things are listed below, but they are not limited to these.
Many. Exemplary mercapto heterocyclic compound 〇1 (to 3 □N
AN□c General formula [XI [[] used in the present invention
For example, the mercapto heterocyclic compound disclosed in Japanese Patent Publication No. 4g-4
No. 2974, No. 57-51666, Special Publication No. 1974-10
No. 2621, French Patent No. 701,053, French Patent No. 70
No. 1,301, No. 1, 563.019, U.S. Patent No.
No. 3,457,078 and The Journal of ΦF
Photographic Science (The Journ)
al of Photoaraphlc 5cienc
e) 19, 083-87, etc. The addition l of the mercapto heterocyclic compound used in the present invention is
, depending on the conditions of use, 1 mol of silver halide
1 x 10 to 1 x 10 mol, more preferably 1 x 10 to 1 x 10 mol per unit.
Show the results. In addition, the addition method is the usual photo addition method.
The method of adding the agent, e.g. with water or with an appropriate EIH value.
acid or alkaline aqueous solution, or methanol,
The halogenated compound of the present invention is dissolved in an organic solvent such as tanol.
Added to silver emulsion. The mercapto heterocyclic compound used in the present invention can be used alone or
, two or more types may be used together, and furthermore, in the photographic industry.
Other compounds known as antifoggants or stabilizers
It is also permissible to add additional information. Addition position of mercapto heterocyclic compound used in the present invention
As for the chlorobromide containing the magenta coupler of the present invention,
Either in the silver emulsion layer and/or in other photographic constituent layers.
Although the effects of the present invention are also achieved, especially the magenta of the present invention
Preferably used in silver chlorobromide emulsion layers containing couplers.
Ru. Added to silver chlorobromide emulsion layer containing magenta coupler
There is no particular restriction on the timing, but it is preferable to
Silver chlorobromide milk containing magenta coupler after the completion of coloring.
It is preferable to add it all at once just before the application of the agent.
It may also be added in portions. In the present invention, a dye image, especially a magenta dye image.
For the purpose of preventing deterioration, the following general formula [A] ~ CHI and
Image stability indicated by [J], [K])
It is preferable to use General formula [AI In the formula, R5 is a hydrogen atom, an alkyl group, an alkenyl group, an atom
Represents a lyl group or a heterocyclic group, R2, Rs, Ri, R
s is a hydrogen atom, a halogen atom, a hydroxy group,
Alkyl group, alkenyl group, aryl group, alkoxy group
or 7 acylamide groups, R4 is an alkyl group,
Represents a hydroxy group, an aryl group, or an alkoxy group. In addition, R3 and R2 are ring-closed with each other to form a 5-membered or 6-membered ring.
In this case, R4 may be a hydroxy group or an alkali group.
In addition, R, and R4 are ring-closed, and a five-membered carbon is formed.
A hydrogenated ring may be formed, in which R, is furkyl
group, aryl group, or heterocyclic group, provided that R
Except when 1 is a hydrogen atom and R4 is a hydroxy group
Ku. In the general formula [AI, R1 is a hydrogen atom,
:. Alkyl group, alkenyl group, aryl group or heterocyclic group
Of these, as an alkyl group, for example,
thyl group, ethyl group, propyl group, n-octyl group, te
Straight chain or branched with rt-octyl group, hexadecyl group, etc.
Examples include branched alkyl groups. Also, if it is R1
Examples of the alkenyl group that can be used include 7lyl, 7lyl,
Examples include nyl and octenyl groups. Furthermore, the %RI
Examples of the 7-yl group include 7-el and naphthyl groups.
It will be done. Further, as the heterocyclic group represented by R, tetra
Specific examples include fluoropyranyl group and pyrimidyl group.
It will be done. Each of these groups can have substituents, such as
Examples of the furkyl group having a substituent include a benzyl group and a nidooxy group.
Shimethyl group, 7-aryl group with substituents
methoxy7enyl group, chlorphenyl group, 4-hydro
Examples include xy-3,5-dibutylphenyl group. In the general formula [AI, R2, R5, R5 and R1 are
Hydrogen atom, halogen atom, hydroxy group, alkyl group,
alkenyl, aryl, alkoxy or acyl
There are 7 ami groups, among which, furkyl group, alkyl group
Regarding the nyl group and aryl group, as described above for RI.
Same as alkyl group, alkenyl group, aryl group
Can be mentioned. Further, as the halogen atom, for example,
Examples include fluorine, chlorine, and bromine. further back
Examples of the alkoxy group include nodoxy group, ethoxy group, etc.
can be specifically mentioned. Furthermore, the acyl amine
The group is represented by R'CONH-, and in Uni, R'
is an alkyl group (e.g. methyl, ethyl, n-propyl,
n-butyl, n-octyl, tert-octyl, ben
(allyl, octyl, etc.), alkenyl groups (allyl, octyl, etc.)
groups such as tenyl and oleyl), aryl groups (e.g.
groups such as phenyl, diphenyl, naphthyl, etc.), or
or heterocyclic group, Y 9 , t, Y I7
Tsu1. □, 1,6 Yu: Can do □. , 1 In addition, in the general formula [AI, % R4 is alkyl'j
: group, hydroxy group, aryl group or alkoxy
,・groups, among which alkyl groups, aryl groups
As for the alkyl group represented by R+,
Specific examples include the same groups as the metal group. Ma
Regarding the alkenyl group of R1, the above-mentioned R2, R,, R,
and the same alkoxy group mentioned for R6.
can be mentioned. R6 and R2 close each other to form a benzene ring
As a ring, for example, chroman, coumaran, methylenezoon
Examples include xybenzene. Also, R1 and R1 are ring-closed to form a benzene ring.
Examples of the ring include kidney bean. these
The ring includes Wl, a substituent (e.g. alkyl, alkoxy, 7-ring)
It may also have a Also, R, and R2, or Ra and R1 form by ring closure
Atoms in the ring form spiro compounds as spiro atoms.
It is also possible to form a bis body by using R,, R4, etc. as a linking group.
It may be done. A 7-er/-11S compound represented by the general formula IAI or
or phenyl ether compounds, preferred are
, RO- group (R is an alkyl group, an alkenyl group, an aryl group)
or a heterocyclic group)
It is particularly preferably a compound represented by the following general formula [A-11
It can be expressed as General formula [A-1] CH9 In the formula, R is an alkyl group (e.g. methyl, ethyl, propyl
, n-octyl, tert-octyl, benzyl, hetsubo
(sudecyl), alkenyl groups (e.g. allyl, octenyl)
oleyl, oleyl), aryl groups (e.g. phenyl, naphyl),
) or hete b-ring group (e.g., tetrahydropyrani)
(R, pyrimidyl) groups represented by eRs and
R1° is a hydrogen atom, a halogen atom, (for example, 72
chlorine, bromine), alkyl groups (e.g. methyl, ethyl
, n-butyl, benzyl), alkoxy groups (e.g. ali
hexenyl, octenyl), or alkoxy groups (
For example, methoxy, ethoxy, penciloxy),
R1+ is a hydrogen atom, an alkyl group (e.g. methyl, ethyl
, n-butyl, benzyl), alkenyl groups (e.g. Eva, 2
- flobenyl, hexenyl, 9f-nyl), or ali
group (e.g. phenyl, methoxyphenyl, chlorophenyl)
phenyl, naphthyl). The compound represented by the general formula [AI] is disclosed in U.S. Patent No. 3,
No. 935,016, No. 3,982,944, No. 4
．． No. 254,216, JP-A No. 55-21004, No. 5
No. 4-145530, British Patent Publication No. 2,077.455
No. 2,062, No. 888, U.S. Patent No. 3,764
, 337, No. 3.432300, IQ No. 3,57
No. 4,627, IE [No. 3,573,050, vF Yanzhao
No. 52-152225, No. 53-20327, No. 53
-17729, 55-[1321, British Patent No. 1
, No. 347,558, Publication No. 2.086,975, Special
Publication No. 54-12337, Publication No. 48-31625, United States
Also includes compounds described in Patent No. 3,700,455 etc.
nothing. The amount of the compound represented by the general formula [AI] is mazen.
It is preferably 5 to 300 mol% based on Tacoupler, and more
Preferably it is 10 to 200 mol%. The following is a representative example of the compound represented by the general formula [AI].
Give an example. Type (1) RI Type (2) Type (3) Type (4) Type (5) Type (6) Type (7) 11'K' Type (2) Below margin type (4) Type (5) Type (6) A-7 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, human mixi group, aryl group, aryl group
xy group, acyl group, acylamino group, acyloxy group,
Sulfonamide group, dichlorofurkyl or alkoxyca
Rubonyl group % R2 is hydrogen atom, alkyl group
, alkenyl group, 71)-l group, acyl group, cycloal
A kill group or a heterocyclic group, R1 is a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, aryl group
, aryloxy group, acyl group, acyloxy group, sulfur
Hon 7 Mi Y group, cycloalkyl group or alkoxyl
Hail the Bonyl group. Each of the groups listed above may be substituted with other substituents.
For example, an alkyl group, an alkenyl group, an alkoxy group,
Aryl group, aryloxy group, hydroxy group, alco
oxycarbonyl group, aryloxycarbonyl group, acyloxycarbonyl group,
7 groups, acyloxy group, carbamoyl group, sulfo group
Examples thereof include a amide group, a sulf77 moyl group, and the like. In addition, R2 and R1 close each other to form a 5- or 6-membered ring.
R2 and R2 may form a closed ring together with a benzene ring.
Examples of rings include chroman ring, methylenedioxy
Examples include benzene rings. Y is necessary to form a chroman or coumaran ring
Hail atomic groups. Chroman or coumaran ring is a halogen atom, furkyl
group, dichlorofurkyl group, alkoxy group, fulkenyl group,
alkenyloxy group, hydroquine 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 [Bl, those particularly suitable for the present invention
Compounds with general formulas [B-1], [B-2], [[3]
-3], [B -4], [B-5]
Included. General formula [B-13 to 1 General formula [B-2] to 1 General formula [B-3] General formula [B-4] General formula [B-5] General formula [B-1], [B-2] ], [B-3], [B
-4] Ascent [R, , R, , R2 in B-51
and R4 have the same meaning as in the general formula [Bl].
Rs%Rs, Rt, R1, R9 and Ro. is hydrogen atom, halogen atom, alkyl group, alkoxy group
, hydroxy group, fulkenyl group, alkenyloxy group,
7 aryl group, aryloxy group or heterocyclic group
It will be. Furthermore, R1 and R1, R, and R7, R2 and R, R8 and R
1, Re and Rho cyclize with each other to form a carbocycle
Furthermore, the carbocycle may be substituted with an alkyl group.
Good too. The general formula [B-1], [B-2], [B-3],
R1 up R in [B-4] and [B-5]
4 is hydrogen atom, furkyl group, alkoxy group, and droxy
group or cycloalkyl group, R5, R,, R,, R3,
R9 and Rgo are hydrogen atoms, alkyl groups, or
Compounds that are loalkyl groups are particularly useful. The compound represented by the general formula [Bl is tetrahedron (Te
trahedron), 1970. vo126,474
3” 4 Fuji 1 page, Journal of the Chemical Society of Japan, 1972. No. 10
, pp. 0987-1990, Chemical (ehem, Let
t, ), 1972 (4) pp. 315-316, Japanese Patent Publication No. 5
5 = represents the compound described in No. 139383, and contains
and synthesize according to the methods described in these
be able to. The amount of the compound represented by the general formula [Bl] is as follows.
5 to 300 for the magenta coupler according to the emulsion of the present invention.
Mol% preferably, more preferably 10 to 200 mol%
It is. Typical specific examples of these compounds are shown below. The following is a blank general formula [C] R1 to 1 General formula [D] In the formula, R1 and c/R2 are hydrogen atoms, halogen atoms, atom
Alkyl group, alkenyl group, alkoxy group, alkenyl group
xy group, hydroxy group, aryl group, aryloxy group
, 7yl group, acylamide 7 group, acyloxy group, sulfonate
amide group or alkoxycarbonyl group.
. Each of the groups listed above may be substituted with other substituents.
For example, halogen atom, alkyl group, alkenyl group,
Alkoxy group, aryloxy group, hydroxy group, alkoxy group, aryloxy group, hydroxy group,
Koxycarbonyl group, 71J-Luoping dicarbonyl group,
Acylamino group, carbamoyl group, sulfonamide group,
Examples include sulfamoyl group. Y is a benzene ring and a dichroman or zocoumaran ring
Hail the groups of atoms 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 the general formula [CI Oori [DI], this
Compounds particularly useful in the invention have general formulas [C-1] and [C-2
], [D-13 and [D-2]
Included. General formula [C-1] General formula [C-2] General formula [D-1] General formula [D-2] General formula [C-1], [0-2], [D-1] D
-2], R7 and R2 are represented by the general formula [CI or
Up [same meaning as in DI, R5, R
R1 and Re are hydrogen atoms, halogen atoms, and alkyl atoms.
Kyl group, alkoxy group, hydroxy group, alkenyl group,
Alkenyloxy groups, aryl groups, and 7-aryloxy groups are also included.
or a heterocyclic group, and further R3, R4, R4
and R1, Fts and R6, R, and R2, and R2 and R, and
may be cyclized with each other to form a carbon ring, and furthermore, the carbon
Bare rings may be substituted with alkyl groups. The above general formula [C-1], [C-2], [D-1]
[D-21, R9 and R2 are hydrogen atoms,
alkyl group, alkoxy group, hydroquine group or cycloa
alkyl group, R7, R4% R3, R6, R7 and R8 are
is a hydrogen atom, an alkyl group, or a cycloalkyl group
The compound is extremely useful. Compounds represented by the general formula [CI, [DI] are those of the Chemical Society of Japan.
Magazine (J, Chew, Soe, part C) 1
968. (14) * pp. 1937-18, Synthetic Chemistry
Association Journal 1970.28 (1), pp. 60-65, Tetra
Hedron (Tetrahedron Letters)
1973, (29), 2707-2710.
Containing compounds listed in 11 of these
It can be synthesized according to the law. The usage amount of the compound represented by the general formula [CI, [DI] is
, 5 to 30 for the magenta coupler according to the present invention.
Preferably 0 mol%, more preferably 10 to 200 mol%
%. Specific representative examples of these compounds are shown below. Below is the general formula (E) in which I<' is a hydrogen atom, a furkyl group, an alkenyl group,
Aryl group, acyl group, cycloalkyl group or hetero
represents a cyclic group, R3 is a hydrogen atom, a halogen atom, an alkyl atom,
Kyl group, alkenyl group, aryl group, aryloxy group
, acyl group, acylamino group, 7-syloxy group, sulfo
amide group, cycloalkyl group or alkoxycarboxylic group
Represents a bonyl group. R” R4 is a hydrogen atom, a halogen atom, an alkyl group
, alkenyl group, aryl group, acyl group, acylamino
group, sulfonamide group, cycloalkyl group or alkyl group.
Represents a koxycarbonyl group. 1 Each of the groups listed above is a substitute for other substituents.
0 which may be substituted with, for example, an alkyl group, an alkenyl group
group, alkoxy group, aryl group, 71-noroxy group
, hydroxyl group, alkyl dicarbonyl group, aryl group
oxycarbonyl group, acylamino group, carbamoyl group,
Examples include a sulfonamide group and a sulfamoyl group. In addition, R1 and R2 open each other to form a 5- or 6-membered 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,
7-syl group, acylamino group, 7-syloxy group, sulfone
7 represents a mido group or an alkoxycarbonyl group. Y is necessary to form a chroman or coumaran ring
Represents a group of atoms. Chroman or coumaran ring is a halogen atom, alkyl
group, cycloalkyl group, alkoxy group, alkenyl group,
Alkenyloxy group, hydroxy group, aryl group, aryl group
may be substituted with a hydroxyl group or a heterocyclic group.
Furthermore, a spiro ring may be formed. Among the compounds represented by the general formula (E),
Compound 1 has the general formula (E-1). (E-23, (E-33, (E-43 and (E-53
It is included in the alternative compounds. General formula (E-13 R1 General formula (E-2) RI General formula (E-33 General formula (E-4) General formula (E-5) R1 in general formulas (E-1) to (E-5) , R2, R
3 and (/R' have the same meaning as in the above general formula (E)
Have a taste, R', R', R? , R feeling, Rs up R” is
Hydrogen atom, halogen atom, furkyl group, alkoxy group,
Hydroxy group, alkenyl group, alkenyloxy group, a
Represents a aryl group, an aryloxy group or a heterocyclic group.
Also, R8 and R1, R6 and Rte, Rte and R-R-
R- and R- and R'' are cyclized with each other to form a carbocycle
Furthermore, the carbocycle may be substituted with an alkyl group.
Good too. In the general formulas (E-1) to (E-5), t(',
R'', R' and R4 are hydrogen atoms, alkyl groups, or
Cycloalkyl group, %R in the general formula (E-5)
3 R4 is a hydrogen atom, an alkyl group, an alkoxy group,
a hydroxy group or a cycloalkyl group, and the above-mentioned general
Formula (E-1) ~ [E ~ 5] 1: # Ite, R', R1
, R', R@, R"J: I/R1' is a hydrogen atom, an alkali
Compounds that are kill groups or cycloalkyl groups are particularly
It is for use. The compounds shown in Table I according to the general formula [E] are tetrahedron (
Tetrahedron Letters) 1965
．． (8) +457-480 pages Journal of the Chemical Society of Japan (J, C
hew, Soc, part C) 1966° (2
2), pp. 2013-2016, (Zh, Or
G, Khim) 1970. (6). 1230-1237,
and be synthesized according to the methods described therein.
I can do it. The amount of the compound represented by the general formula [E-13] is as follows.
5 to 300 moles for the magenta coupler according to the present invention.
preferably 10 to 200 mol%, more preferably 10 to 200 mol%.
be. Specific representative examples of these compounds are shown below. The following is a blank general formula CF) In the formula, R is a hydrogen atom, an alkyl group, an alkenyl group, an ali
group, acyl group, cycloalkyl group or heterocycle
represents a group, R2 is a hydrogen atom, a halogen atom, an alkyl group
, alkenyl group, aryl group, aryloxy group, 7-syl group
7 groups of acylamine groups, 7 groups of acyloxy groups, 7 groups of sulfone groups.
group, cycloalkyl group, or alkoxycarbonyl group
Hail to you. R is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group.
group, aryl group, acyl group, 7-sylamine group, sulfonate group,
amide group, cycloalkyl group or alkoxylic group
Hail the Bonyl group. R1 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 may be substituted with other substituents.
For example, an alkyl group, an alkenyl group, an alkoxy group,
Aryl group, aryloxy group, hydroxy group, alco
oxycarbonyl group, aryloxycarbonyl group, acyloxycarbonyl group,
7 groups, carbamoyl group, sulfonamide group, sulfonamide group,
Examples include famoyl group. Also, R3 and R2 close each other to form a 5-shell or 6-shell ring.
You may. 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, acylamino group, acyloxy
group, sulfonamide group, or alkoxycarbonyl
Hail to the foundation. Y Necessary to form bacroman or coumaran ring
Hail a group of atoms. Chroman or coumaran ring is a halogen atom, furkyl
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 of general formula [F-13, [F-2], [F
-3], [F -4'l and [F -5]
Enveloped in compounds. Below are the margins General formula (F-1) General formula CF-2) General formula (F-3) OR' General formula [F-43 General formula (F-5) General formula [F-1] Upstream [F-5 ] in R7, R2
, R1 and R1 are the same as in the above general formula [F]
R1, R6, Rte, R-1R1 and R2
゜ is a hydrogen atom, a halogen atom, an alkyl group, 1
Alkoxy group, hydroxy group, alkenyl group,
Kenyloxy group, aryl group, aryloxy group
or heterocyclic groups. Furthermore, R1 and R6, R1 and R1, R2 and R8, R, and R
, and IR so and R1° are cyclized with each other to form a carbon ring.
Furthermore, the carbocycle may be substituted with an alkyl group.
Good too. Also, [F-3], [F-4] and [F-5] smell.
The two R, -R, are the same or different.
Good too. The general formulas [F-1], [F-2], [F-3], [
F-4] 1< ,, R2 at upstream [F-5]
, and R5 is a hydrogen atom, an alkyl group, a cycloalkyl
group, R4 is a hydrogen atom, an alkyl group, an alkoxy group, a hydrogen atom,
Roxy group or cycloalkyl group, further R6, R
1. R, R, and R7゜ are hydrogen atoms, alkyl groups, or
Particularly useful are compounds that are cycloalkyl or cycloalkyl groups. The compound represented by the general formula [F] is tetrahedron
(Tetrahedron Lettsrs) 1
9F O, Vol 26.4743-4751, Japan
Journal of the Chemical Society 19f 2. No. 10.1987-199
Page 0, Synthesis 197L
Vol 6t392-393, (Bul So
e, Chins Be1g) 197L
Vo184()), 747-759 is truly described.
and according to the methods described therein.
This concludes the synthesis. The usage amount of the compound represented by the general formula [F] is determined according to the above book.
5 to 300 mol% based on the magenta kapfu according to the invention
is preferable, more preferably 10 to 200 mol%
. Specific representative examples of compounds represented by general formula [F] are shown below.
show. The following is a blank general formula CG) R R'' In the formula, R1 and R3 are a hydrogen atom and a halogen atom, respectively.
, furkyl group, alkenyl group, alkoxy group, hydroxy group
cy group, aryl group, aryloxy group, 7 syl group, acyl group
lamino group, acyloxy group, sulfonamide group,
Represents a loalkyl group or an alkoxycarbonyl group. 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 alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents.
I-1! as a substituent, for example, an alkyl group, alkenyl
group, alkoxy group, aryl group, aryloxy group,
droxy group, alkoxycarbonyl group, aryloxy
Carbonyl group, acylamino group, carbamoyl group, sulfur
Examples include phonamide group and sulfamoyl group. In addition, R2 and Rj are ring-closed with each other, and carbonization of 5 shells or 6R
A hydrogen ring may be formed. Carbonized water of these 5 or 6 molluscs
Bare rings include halogen atoms, alkyl groups, cycloalkyl groups,
Alkoxy group, alkenyl group, hydroxy group, aryl
substituted with a group, an aryloxy group, a heterocyclic group, etc.
Good too. Y represents the atomic group necessary to form an indane ring,
The ring is a halogen atom, an alkyl group, an alkenyl group,
Alkoxy group, cycloalkyl group, hydroxy group, ali
Substituted with aryl group, aryloxy group, or heterocyclic group, etc.
or may further form a spiro ring. Among the compounds represented by general formula (G), particularly useful for the present invention
Compounds represented by general formulas (G-1) to (G-3)
included in the compound. The following are margins General formula (G-1) General formula (G-2) General formula (G-3) General formula (G-1) to (R1.R2 in G-33 and
R3 has the same meaning as in general formula (G), R',
R', R@, R', R'' and R'1.t, each h hydrogen
atom, halogen atom, alkyl group, alkoxy group, alkyl
Kenyl group, hydroxy group, aryl group, aryloxy
represents a group or a heterocyclic group. R4 and R5, R% and R6,
R8 and R7, Rγ and R8, and R and R9 are ring-closed with each other.
may form a hydrocarbon ring, and the hydrocarbon ring;
It may be substituted with an alkyl group. In the general formulas CG-1) to (G-3), R1 and
R5 is a hydrogen atom, an alkyl group, a flukoxy group, a hydroxy group
cy group or cycloalkyl group, R'' is a hydrogen atom, alkyl
R group, hydroxy group or cycloalkyl group, R', R
', R'', Rma, R1 and R9 are hydrogen atoms, alkyl groups
or cycloalkyl groups are particularly useful.
. The amount of the compound represented by the general formula [G]
It is preferably 5 to 300 mol% based on the zenta coupler,
More preferably, it is 10 to 200 mol%. Typical specific examples of compounds represented by general formula [G] are shown below.
show. The following is a blank general formula [H) R3 where R' and R2 are each a hydrogen atom, /% rodene raw material
child, alkyl group, alkenyl group, aryl group, acyl group
, acylamino group, acyloxy group, sulfonamide group
, represents a cycloalkyl group or an alkoxycarbonyl group.
vinegar. R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group
group, alkoxy group, hydroxy group, aryl group, aryl group,
yloxy group, acyl group, acylamine 7 group, acyloxy group
cy group, sulfonamide group, cycloalkyl group or alkyl group
Represents a koxycarbonyl group. Each of the groups listed above is substituted with other substituents)
For example, an alkyl group, an alkenyl group,
Alkoxy group, aryl group, aryloxy group, hydro
Kin group, alkoxycarbonyl group, aryloxycar
Bonyl group, acylamino group, carboxylic group, sulfone
Examples include amide group and sulfamoyl group. In addition, R1 and R2 and R2 and R3 are ring-closed with each other, and five shells or
or six true hydrocarbon rings may be formed, and the hydrocarbon ring
is a halogen atom, an alkyl group, a cycloalkyl group, an alkyl group,
Koxy group, alkenyl group, hydroxy group, aryl group,
It may be substituted with an aryloxy group, a heterocyclic group, etc. Y represents an atomic group necessary to form a kidney bean ring, and
The indane 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
The compound - is a compound represented by general formulas (H-1) to (H-2).
included in the compound. General formula [:H-2] General formula (H-3) R', R2 and in general formulas (H-1) to (H-3)
R3 has the same meaning as in general formula (H), R4,
[(S, l(@, R?, R@ and R'li
, shaky hydrogen atom, halogen atom, alkyl group, alkyl
Koxy group, hydroxy group, alkenyl group, aryl group,
Represents an aryloxy group or a heterocyclic group. Also with R4
R1, R5 and R6, R@ and R], Rf and R1 and R8
R@ 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 (H-1) to (H-3:l), R' and
and R2 are each a hydrogen atom, and an alkyl group *Q is a cycloa
alkyl group, R5 is a hydrogen atom, an alkyl group, an alkoxy group
, hydroxy group or ncroa “′”&i, R'tR
'・1゛′1″・1°1v1゛t゛+h. Each hydrogen atom, alkyl group, or cycloalkyl
Particularly useful are compounds that are (.) group.
, 1 Synthesis of the compound represented by the general formula [H]
The method is known and described in U.S. Pat. No. 3.057929, C
heIll. Ber, 1972. 95(5), 18f
Pages 3-1674, Chemist-ry Let
Manufactured according to ter8+ 1980.739-742
Can be built. The compound magenta coupler represented by the general formula [H]
It is preferably 5 to 300 mol%, more preferably 1
0 to ZOO mol%. Specific representative examples represented by the general formula [H] are shown below. Below, the blank space represents the general formula (J), /-1, or an aryl group, and Y is a 5- to 7-membered ring together with a nitrogen atom.
represents a group of nonmetallic atoms necessary to form a heterocycle, provided that
and among the nonmetallic atoms containing nitrogen atoms forming the bicyclic ring,
If there are two or more heteroatoms, at least two heteroatoms
B atoms are heteroatoms that are not adjacent to each other. ] As the aliphatic group represented by R″r%, even if it has a substituent,
Good saturated alkyl groups, and unsaturated groups that may have substituents
A furkyl group is mentioned. Examples of saturated alkyl groups include
For example, methyl group, ethyl group, butyl group, octyl group,
Examples include decyl group, tetradecyl group, hexadecyl group, etc.
Examples of unsaturated alkyl groups include ethynyl group,
Examples include propenyl group. The cycloalkyl group represented by R1 has a substituent.
A 5- to 7-membered cycloalkyl group that may be
Examples include a lopentyl group and a cyclohexyl group. As the aryl group represented by R1, each W1 substituent
represents a phenyl group or a naphthyl group which may have Aliphatic group, cycloalkyl group, aryl represented by R1
Substituents for groups include alkyl groups, aryl groups, and alkyl groups.
xy group, carbonyl group, carbamoyl group, acylami 7
group, sul77 moyl group, sulfonamide group, carbonyl
Oxy group, alkylsulfonyl group, arylsulfonyl group
group, hydroxyl group, heterocyclic group, alkylthio group, aryl
These substituents can be further substituted.
It may have a group. In the general formula (J), Y together with the nitrogen atom is 5 to 7
Represents a group of nonmetallic atoms necessary to form a membered heterocycle
is a group of nonmetallic atoms containing nitrogen atoms forming the heterocycle.
At least two must be heteroatoms, and
In this case, two heteroatoms should not be adjacent to each other.
The bicyclic ring of the compound represented by the general formula (J)
If all the heteroatoms are adjacent to each other, mazen
The dye can function as an image stabilizer.
I don't like it because there isn't. of the 5- to 7-membered ring of the compound represented by the general formula (J)
The heterocycle may have a substituent, and examples of the substituent include alkaline
Kyl group, aryl group, 7-syl group, carbamoyl group, alkyl group,
Coquin carbonyl group, sulfonyl group, sulf77 moyl group
etc., and may further have a substituent. In addition, 5 to 7
The heterocycle of the shell ring may be saturated, but if the saturated heterocycle is
Preferably, a benzene ring or the like is fused to the heterocycle.
or may form a spiro ring. The compound represented by the general formula (J) of the present invention
[The amount used is represented by the above general formula (1] of the present invention.
It is preferably 5 to 300 mol% based on the magenta coupler.
more preferably 10-200 mol%. Typical specific examples represented by general formula (J) are shown below. Margin below J-63 J-64 ■ C+2 H2E Among the compounds represented by the above general formula (J), piperazine
type compounds and homopiperazine type compounds are particularly preferred,
More preferably, the following general formula (J-1) or (
J-2']. General formula (J-1) General formula (J-2) In the formula, R2 and R'' are a hydrogen atom and an alkyl group, respectively.
Or represents an aryl group. However, R2 and R3 are water at the same time.
It never becomes basic. R4~R'' are each hydrogen atoms
represents a child, an alkyl group, or a 7-aryl group. In the general formulas (J-13 and (J-2)), R2 and
R3 is a hydrogen atom, an alkyl group, or an aryl group, respectively.
represents a group, but as an alkyl group represented by R2 or R1
For example, methyl group, ethyl group, butyl group, octyl group, etc.
group, dodecyl group, tetradecyl group, hexadecyl group,
Examples include octadecyl group. Represented by R2 or R3
Examples of the aryl group include phenyl group. The alkyl group and aryl group represented by R2 or R' are
It may have a substituent, and examples of the substituent include a halogen atom,
Alkyl group, aryl group, alkoxy group, aryl group
Examples include a cy group, a heterocyclic group, and the like. The total number of carbon atoms of R2 and R' (including substituents) is 6 to
40 is preferred. In the general formula (J-1) or (J-2), R4
~R'' is a hydrogen atom, an alkyl group or an aryl group, respectively.
represents an alkyl group represented by R4 to R'3.
Examples of such groups include methyl group and ethyl group. R
4~I? The aryl group represented by I is a phenyl group.
etc. Compound represented by the above general formula (J-1) or (J-2)
Specific examples of the compounds include the above-mentioned exemplified piperazine compounds (J-
1) to (J-30) and exemplary homopiperazine compounds (
J-51) to (J-62). Next, a representative matrix of the present invention represented by the general formula (J)
An example of synthesis of a zenta dye image stabilizer is shown. Synthesis Example-1 (Synthesis of Compound J-2) 9.0 g of piperazine and 55 g of myristyl bromide
Calix anhydrous carbonate was dissolved in 100 iQfl acetone.
15 g of aluminum was added thereto, and the mixture was boiled and refluxed for 10 hours to react. After the reaction, the reaction solution was poured into 500 m of water, and then ethyl acetate was added.
Extracted with 500 dances. Add ethyl acetate layer to magnesium sulfate
After drying with
was gotten. Recrystallize with acetone 3 ood to obtain white scales.
34 g (yield 70%) of crystals were obtained. Melting point: 55-58°C Synthesis Example-2 (Synthesis of Compound J-34) 18 g of 4-morpholinoaniline was dissolved in 100 ml of ethyl acetate.
After dissolving the mixture, while stirring and keeping the reaction solution at 20°C,
Acetic anhydride12. J! was added little by little. After adding acetic anhydride
After cooling with water and removing the precipitated crystals, diluted with ethyl acetate.
Recrystallize to obtain 18.5 g of white powder crystals (yield 75%).
Obtained. α207-210°C General formula (K) In the formula, R1 is an aliphatic group, a cycloalkyl group, or an aryl group.
Y represents a heterocyclic ring with 5 to 7 shell rings together with a nitrogen atom.
Mere bonds or divalent hydrocarbons needed to form
represents a group. R21R'lR'IRS, R@, R?
are hydrogen atoms, aliphatic groups, cycloalkyl groups, or
or represents an aryl group. However, R2 and R4 and R3 and R
6 is a nitrogen atom that combines with each other to form a simple bond,
May form an unsaturated bilobed ring with 5 to 7 shells together with Y
, and when Y is a simple bond, Rs and R7 are mutually
to form a simple bond, and together with the nitrogen atom and Y
An unsaturated pentagonal heterocycle may also be formed. Also, Y
When it is not just a bond, is it R5 and YSR? and Y or
Y forms an unsaturated bond by itself, and the nitrogen atom becomes unsaturated with Y.
A 6-shell or 7-shell heterocycle may be formed. The aliphatic group represented by R' may have a substituent.
unsaturated alkyl groups, and unsaturated alkyl groups that may have substituents.
Examples include alkyl group. For example, as a saturated furkyl group,
For example, methyl group, ethyl group, butyl group, octyl group, dode
Examples include sil group, tetradecyl group, hexadecyl group, etc.
, as unsaturated alkyl groups, for example, ethynyl group,
Examples include a lopenyl group. The cycloalkyl group represented by R1 has a substituent.
For example, Schiff
Examples include a bentyl group, a cyclohexyl group, and the like. As the aryl group represented by R1, even if it has a substituent,
Represents a good phenyl group or naphthyl group. R”? Aliphatic group, cycloalkyl group, aryol
As a substituent for the group, an alkyl group, an ali' −
/L-i, A22゜E4, CalkrK=lkM, Ka22
．． . yl group, acylami/group, sulfamoyl group, sulfone
Amide group, carbonyloxy group, alkylsulfonyl group
, arylsulfonyl group, hydroxy group, heterocyclic group,
Examples include a furkylthio group, an iri-ruthio group, etc.
The substituent may further have a substituent. In the general formula (K), Y is 5 to 7 together with the nitrogen atom.
A simple bond or a bond necessary to form a biplane ring
It represents a divalent hydrocarbon group, but when Y is just a bond,
, furthermore, R5 and R7 combine with each other to form a simple bond.
to form an unsaturated 5-membered heterocycle;
When Y is a divalent monovalent hydrogen group, i.e., a methylene group
is Rs and Yl or R? and Y form an unsaturated bond.
, may form an unsaturated (I) ring of 6Rm, and
In the case of a tyrene group, R5 and Y, R' and Y* or Y itself
forms an unsaturated bond and forms a compound ring of unsaturated heptad rings.
Furthermore, the divalent hydrocarbon group represented by Y may be substituted with
It may have a substituent, and this substituent includes an alkyl group, a carbon
Rubamoyl group, alkyl-o-dicarbonyl group, acyl-a
Mino group, sulfonamide group, sulf77 moyl group, aryl group
and a heterocyclic group. H-11 Formula (K) NiMite, R2, R3, R'l
R'tR6 and R7 are each a hydrogen atom, an aliphatic group,
Represents a cycloalkyl group or a 717-l group, but %R''~
The aliphatic group represented by R7 may have a substituent.
unsaturated alkyl groups and unsaturated alkyl groups that may have substituents.
Examples include kill groups. Examples of saturated alkyl groups include
, methyl group, ethyl group, butyl group, octyl group, dodecyl group
Examples include ru group, tetradecyl group, hexadecyl group, etc.
Examples of unsaturated alkyl groups include ethynyl group and propylene group.
Examples include penyl group. As the cycloalkyl group represented by R2-R7, substituted
A 5- to 7-membered cycloalkyl group which may have a group, e.g.
For example, cyclopentyl group, cyclohexyl group, etc.
It will be done. The aryl group represented by R2-R7 has a substituent.
Examples include a phenyl group, a naphthyl group, and the like. Aliphatic group or cycloalkyl group represented by R2 to R7 above
, as substituents for aryl groups, alkyl groups, aryl
group, alkoxy group, carbonyl group, carbamoyl group,
Silami 7 groups, sulfamoyl group, sulfonamide group,
Carbonyloxy group, alkylsulfonyl group, aryl
Sulfonyl group, hydroxy group, heterocyclic group, alkyl group
Examples include O groups. The compound represented by the general formula (K) has a 5-7 shell ring.
It is preferable that the compound has the same heterocyclic ring as the unsaturated one.
stomach. The amount of the compound represented by the general formula (K) below is as follows:
Magenta coupler represented by the general formula (1) of the present invention
It is preferably 5 to 300 mol%, more preferably
It is 10 to 200 mol%. Typical specific examples of the compound represented by the general formula (K) are shown below.
vinegar. In the margin below, -34 to -35 to -36 to -37 to -38 to -41 Next, a representative synthesis of the compound represented by the above general formula [K]
Give an example. Synthesis Example-1 (Synthesis of Compound -14) Piperazine9. Og and 1 myristyl bromide 28゜
In dissolved 601Q acetone, anhydrous potassium carbonate a
, O,, were added, and the mixture was boiled and refluxed for 20 hours to react. After the reaction, pour the reaction solution into 300.11 water and add vinegar.
Extracted with ethyl acetate. Ethyl acetate layer
After drying with magnesium sulfate, ethyl acetate is distilled off.
, the desired product was obtained as white crystals. Acetone 100TII
Recrystallization with II gives 12 g of white flaky crystals (yield: 4
3%). The binder (or protective coating) of the silver halide emulsion of the present invention has a melting point of 175 to 180°C.
It is advantageous to use gelatin as the id), but
In addition, gelatin derivatives, gelatin and other polymeric groups
Raft polymers, proteins, sugar derivatives, 11 celluloses
, synthetic hydrophilic polymer substances such as single or copolymers, etc.
Hydrophilic colloids can also be used. Photographing color photosensitive materials using the silver halide emulsion of the present invention
The true emulsion layer and other hydrophilic colloid layers are made of a binder (
or protective colloid) which cross-links molecules and increases film strength.
Hardening is achieved by using a coating agent alone or in combination. Hardener
is photosensitive to such an extent that it is not necessary to add a hardening agent to the processing solution.
It is desirable to add the material in an amount that can harden the material, but
It is also possible to add a hardening agent. Color photosensitive materials using the silver halide emulsion of the present invention
Softness of silver halide emulsion layers and/or other hydrophilic colloid layers
Plasticizers can be added to increase flexibility.
According to the present invention,
Photographic emulsion layer of color light-sensitive material using silver halide emulsion
For other hydrophilic colloid layers to improve dimensional stability, etc.
Dispersions of water-insoluble or poorly soluble synthetic polymers (late
x) can be included. The emulsion layer of the color photosensitive material used in the present invention contains color-forming
In the development process, aromatic primary amine developers such as
p-phenylenediamine derivatives and aminophenol derivatives
Coupling reaction with oxidized material (conductor, etc.) to form dye
A dye-forming coupler is used. The pigment forming property
The coupler is used for each emulsion layer to determine the sensitivity spec of the emulsion layer.
The pigments are selected to form pigments that absorb light.
is common, and the yellow dye form is common in blue light-sensitive emulsions.
The green light-sensitive emulsion layer contains magenta dye-form couplers.
cyan dye formation in the red light-sensitive emulsion layer.
A coupler is used. However, depending on the purpose, the above
Creating color photosensitive materials through combinations and different uses
It's okay. As a yellow dye-forming coupler, acylacetate 1-a
Midocouplers (e.g. benzoylacetanilides,
pivaloylacetanilides), magenta pigment-forming caps
In addition to the coupler of the present invention, 5-pyrazolone can be used as the coupler.
Couplers, open-chain acylacetonitrile couplers, etc.
, as cyan pigment forming power/blur, naphtholcap
and phenol couplers. These dye-forming couplers have a ballast group in their molecules.
has a group having 8 or more carbon atoms that makes the coupler non-diffusive
things are desirable. Moreover, these dye-forming couplers have one molecule
4 silver ions are reduced to form the pigment
Even with the required 4-equivalence, two silver ions are reduced
Either of the two is fine as long as it is done. As a yellow dye image-forming coupler, acylaceto
Amide-type benzoylmethane-type 4-equivalent or 2-equivalent capacitor
Pullers are typical, for example, U.S. Patent No. 2,186,
No. 849, No. 2,322,027, No. 2.728
, No. 658, No. 2,875,057, No. 3,
No. 265,506, No. 3,277.155, No. 3
, No. 408,194, No. 3,415,652, No. 408,194, No. 3,415,652, No.
No. 3,447,928, No. 3,664.841, No. 3,664.841, No. 3,664.841, No.
No. 3,770,446, No. 3,778,277,
Same No. 3,849,140, Same No. 3,894,875
, British Patent No. 778,089, British Patent No. 808,276
, No. 875,476, No. 1i 1,402,511
No. 1,421,126 and No. 1.513,
Specifications of No. 832 and Japanese Patent Publication No. 49-13576,
JP-A No. 48-29432, JP-A No. 48-66834, JP-A No. 48-66834,
No. 49-10736, No. 49-122335, No. 5
No. 0-28834, No. 50-132926, No. 50
-138832, 51-3631, 51-17
No. 438, No. 51-26038, No. 51-26039
No. 51-507344, No. 51-53825-No.
No. 51-75521, No. 51-89728, No. 51-
No. 102636, No. 51-107137, No. 51-1
No. 17031, No. 51-122439, No. 51-
No. 143319, No. 53-9529, No. 53-82
No. 332, No. 53-135625, No. 53-14
No. 5619, No. 54-23528, No. 54-4854
No. 1, No. 54-65035, No. 54-133329
, No. 55-598, etc. Cyan dye image-forming couplers include phenolic,
Naphthol-based 4-equivalent or 2-equivalent cyan dye image type
Typical couplers are U.S. Pat. No. 2,306,4
No. 10, No. 2,356,475@, No. 2.362,
No. 598, No. 2,367.531, No. 2,369
, No. 929, No. 2,423,730, No. 2,47
No. 4,293, No. 2,476.008, Li 2
, No. 498,466, No. 2,545.681, No. 498,466, No. 2,545.681, No.
No. 2,728,660, No. 2,772,162, No. 2,772,162, No.
No. 2,895,826, No. 2,976.146
, No. 3,602.836, No. 3,419,390
No. 3,446,622, No. 3,476.56
No. 3, No. 3,737,318, No. 3.7513.
No. 308, No. 3,839,044, British Patent No. 47
No. 8,991, No. 945,542, fi 1,0
No. 84,480, No. 1.377.233, No. 1,
No. 388,024 and No. 1,543.040 (7)
Each light 111. Average Hini Toku R 1974-374258, 50
-10135@, No. 50-25228, No. 50-11
No. 2038, No. 50-117422, No. 50-130
No. 441, No. 51-6551, No. 51-37647
, No. 51-52828, No. 51-108841, No. 51-108841, No. 51-52828, No. 51-108841, No.
No. 53-109830, No. 54-48237, No. 5
No. 4-68129, No. 54-131931, No. 55-
It is described in various publications such as No. 32071. Pigment formation that does not require adsorption to the silver halide crystal surface
Hydrophobic compounds such as chemical couplers can be prepared using the solid dispersion method or latex method.
A variety of methods are used, including the oil-in-water emulsion dispersion method and the oil-in-water emulsion dispersion method.
This is the chemical structure of hydrophobic compounds such as couplers.
It can be selected as appropriate depending on the situation. Oil-in-water emulsification
The dispersion method is a method of dispersing hydrophobic additives such as couplers.
can be applied, and usually high-boiling organic solvents with a boiling point of about 150°C or higher
Low boiling point and/or water-soluble organic solvent as necessary
Hydrophilic binder such as gelatin aqueous solution
using a stirrer, homogenizer,
Lloyd mill, 70-jit mixer, ultrasonic device, etc.
After emulsifying and dispersing using a dispersing means, the desired hydrophilic compound is
It may be added to the lloid layer. Dispersion or simultaneous with dispersion
A step of removing the low boiling point organic solvent may be added. As a high boiling point organic solvent, it does not react with the oxidized form of the developing agent.
Phenol derivatives, phthalate esters, phosphate esters
Alkyl, citric acid ester, benzoic acid ester, alkylar
Boiling point of mido, fatty acid ester, trimesic acid ester, etc.
An organic solvent 1 having a temperature of 150° C. or higher is used. Using a hydrophobic compound alone or in combination with a low-boiling point solvent
Dissolved in a solvent and dispersed in water using mechanical or ultrasonic waves.
Anionic surfactants, nonionic surfactants are used as dispersion aids when
Ionic surfactants and cationic surfactants can be used.
I can do it. Between the emulsion layers of the color photosensitive material used in the present invention (same-
between color-sensitive layers and/or between different color-sensitive layers), developing agent
The oxidant or electron transfer agent may migrate and cause color turbidity,
To prevent deterioration of sharpness and noticeable graininess, color
Pre-inhibitors are used. The color antifoggant may be used in the emulsion layer itself or in the middle.
An interlayer may be provided between adjacent emulsion layers and used as the intermediate 1.
. Color photosensitive materials using the silver halide emulsion of the present invention include
It is possible to use image stabilizers to prevent the deterioration of dye images.
come. Protective layer, intermediate layer, etc. of color photosensitive material used in the present invention
There are 11 photosensitive materials in the hydrophilic colloid layer! Charges up due to rubbing etc.
Prevents fogging due to discharge caused by
May contain ultraviolet absorbers to prevent deterioration.
stomach. Color photographic material using the silver halide emulsion of the present invention
includes a filter layer, an antihalation layer and/or an ink layer.
Auxiliary layers such as anti-radiation layers can be provided. In these layers and/or in the emulsion layer, the
Dye that flows out or bleaches from color photographic paper
It may be included. Color photosensitive materials using the silver halide emulsion of the present invention
Silver halide emulsion layer and/or other hydrophilic colloid layer
In order to reduce the gloss of photosensitive materials, increase the ease of writing, and
A matting agent can be added to prevent mutual pecking.
. Additionally, lubricants can be added to reduce sliding friction. In the color photosensitive material using the silver halide emulsion of the present invention,
An antistatic agent can be added for the purpose of preventing static electricity. Antistatic
The blocking agent is used in the antistatic layer on the side of the support that is not laminated with the emulsion.
The emulsion layer and/or support
Protective colloid other than the emulsion layer on the side where the emulsion layer is laminated
It may also be used as a layer. Photographing color photosensitive materials using the silver halide emulsion of the present invention
The true emulsion layer and/or other hydrophilic colloid layer may have coating properties.
improvement, anti-static, improved slipperiness, emulsification and dispersion, prevention of adhesion and
Aiming to improve photographic properties (promotion of development, increase in contrast, sensitization, etc.)
Various surfactants are used as targets. The reflective support used in the present invention is made of plastic.
film, i.e. polyester (e.g. polyethylene)
terephthalate, etc.), vinyl alcohol, vinyl chloride,
Homopolymers and copolymers such as vinyl fluoride and vinyl acetate
polymer, cellulose acetate, acrylonitrile, acrylic
Alkyl ester of methacrylate, alkyl methacrylate ester
, Meccrylonitrile, Alkyl vinyl ester, Al
Homopolymers such as kyl vinyl ether, polyamide, etc.
Copolymers and the like can be mentioned. Also, paper or
Synthetic paper and polyolefins (polyethylene, polypropylene)
Bonding of two or more types of substrates such as laminates with
A body etc. is used. The reflective support according to the present invention is white in order to have reflective properties.
containing pigments or containing white pigments on a transparent support.
A hydrophilic colloid layer may be applied. The white pigment used may be inorganic and/or organic.
a white pigment, preferably an inorganic white pigment,
Such materials include alkali metals such as barium sulfate.
Carbonates of alkaline earth metals such as sulfates of the genus, calcium carbonate, etc.
Salt, finely divided silicic acid, synthetic silicates, calcium silicate
, alumina, alumina hydrate, titanium oxide, zinc oxide,
Examples include talc and clay. The color photosensitive material used in the present invention may be supported as necessary.
The surface of the holding body is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc.
After that, directly or (adhesiveness, antistatic property, dimensional
degree stability, wear resistance, hardness, antihalation, friction
properties and/or other properties) 1 or
may be applied via two or more base coats. Coating of color photosensitive materials using the silver halide emulsion of the present invention
When using cloth, thickeners may be used to improve applicability.
good. The coating method involves applying two or more layers at the same time.
Ex-dollion coating and curtains that can be made
Coatings are particularly useful. The color photosensitive material used in the present invention is the photosensitive material of the present invention.
Spectral region to which the emulsion layer constituting the material is sensitive
Can be exposed using electromagnetic waves. As a light source, natural light (
sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon
Arc lamp, carbon arc lamp, xenon flash lamp, cathode
Wire tube flying spot, various laser lights, light emitting diodes
excited by code light, electron beams, X-rays, gamma rays, alpha rays, etc.
Any known light source, such as light emitted from a phosphor
It can be used. The exposure time is usually 1 millisecond to 1 second, which is used in cameras.
Of course, exposures shorter than 1 microsecond, such as cathode ray tubes and
100 microseconds to 1 mic using Senon arc lamp
You can also use exposures of 1 second or longer.
Exposure is also possible. Even if the exposure is carried out continuously,
It may be done in your absence. In the present invention, after color development processing,
However, the processing liquid that has the fixing ability is used for fixing.
If it is a liquid, it is bleached first. The bleaching
Metal complex salts of organic acids are used as bleaching agents in the process.
[Complex salts]
At the same time, the uncolored part of the color former is converted into silver halide.
It has the effect of producing color, and its composition is aminopolyte.
Iron and copolymerize with organic acids such as recarboxylic acid or oxalic acid and citric acid.
It is coordinated with metal ions such as balt and copper. this
The most commonly used metal complex salts of organic acids such as
Preferred lilic acids include polycarboxylic acids or
Examples include aminopolycarboxylic acids. These political
Bonic acid or aminopolycarboxylic acid is an alkali metal salt,
May be ammonium salt or water-soluble amine salt
. Specific representative examples of these include the following:
I can do it. [1] Ethylenediaminetetraacetic acid [2] Nitri-O-triacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethyl
ammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid sodium salt The bleaching agent used bleaches the metal complex salts of organic acids such as those mentioned above.
It is contained as a whitening agent and may also contain various additives.
can. As additives, especially alkali halides or
Ammonium halides, e.g. potassium bromide, sodium bromide
Re-halogenation of sodium chloride, ammonium bromide, etc.
It is desirable to contain a genifying agent, metal salt, and chelating agent.
Yes. Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
l1! i agent, alkylamines, polyethylene oxy
Items known to be added to normal bleaching solutions such as
can be added as appropriate. Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite
ammonium, sodium bisulfite, ammonium metabisulfite
, potassium metabisulfite, sodium metabisulfite
Sulfites such as 1111! , I1m sand, sodium hydroxide
potassium hydroxide, sodium carbonate, potassium charcoal
, sodium bisulfite, sodium bicarbonate, potassium bicarbonate
um, acetic acid, sodium acetate, ammonium hydroxide, etc.
I) Hit buffer consisting of various salts alone or with 2f1 or more
above can be included. While replenishing the bleach-fixing solution (bath) with bleach-fixing replenisher,
When carrying out brightening treatment, thio 1i is added to the bleach-fixing solution (bath).
ll! Contains salt, thiocyanate or sulfite, etc.
Alternatively, the bleach-fix replenisher may contain these salts.
It is also possible to cool the solution and replenish it to the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution,
as desired in the white fixing bath and in the bleach fixing replenisher storage tank.
Blow in more air or oxygen.
or a suitable oxidizing agent such as hydrogen peroxide, bromine
Acid salts, persulfates, etc. may be added as appropriate. The following margins [Examples] Specific examples are shown below to further explain the present invention.
However, the present invention is not limited thereto. Example-1 The following emulsions EM-1 to EM-4 were prepared by a conventional method.
...Containing 25 mol% chlorine, average particle size 0.30μ
Akebono's silver halide emulsion EM-2 with silver chlorobromide grains: average grain size 0 containing 25 mol% chlorine
．． Silver halide emulsion EM-3 containing 55 μm silver chlorobromide grains...average grain size 0 containing 25 mol% chlorine
Silver halide emulsion EM-4 with silver chlorobromide grains of .
Silver halide emulsion having 31 μ silver iodobromide grains Next, EM-1 to EM-4 were sensitized with sulfur, and the following sensitizing dyes [
After sensitization, add the following stabilizer [8]
EM-a-d was prepared by adding 1 g per mole of silver halide.
Manufactured. Magenta couplers shown in Table 1 for E M -a and Qd
A sample coated with polyethylene film was coated on a polyethylene coated paper support.
The cloth was dried to prepare samples No. 1 to 6. The resulting sample was wedge-exposed and then subjected to the next processing step.
Therefore, processing for sensitometric measurements and fog measurements
I did it. The results are shown in Table-1. Table 1 shows the measured values of Capri and the relative sensitivity (S
)showed that. Here, process with the following color developing solutions [A] to [D].
Sensitivity when processed with color developer [D]
is set as 100, and with the following color developing solutions [E] to [H]
When processed, the impression when processed with color developer [E]
Each degree is expressed as 1 degree relative to 100 degrees. Furthermore, TE is a value expressing NWA, and ΔTE is a value during its fluctuation.
When processed with color developer [A] to [03 with a value representing
is based on the color when processed with color developer [0].
Color development when processed with color developer [E] to [)-1]
Fluctuation value based on γ when treated with liquid [E]
The smaller the absolute value of Δ7, the better the 3r fluctuation resistance.
It is. Standard processing steps (processing temperature and processing time) [1] Color development 38°C 3 minutes 30 seconds [2] II
White fixing 33℃ 1 minute 30 seconds [3 washes N2
5-30℃ 3 minutes [4] Drying 75-80℃ approximately 2 minutes Processing solution composition (color developer) Benzyl alcohol 1511 ethylene
Glycol 1521F Potassium Sulfite
2. OQ sodium chloride
0.29 potassium carbonate
30.017 Hydroxylamine sulfate
4.1g [Example hydroxyamine* (2>)
(0.05f/L,) Polyphosphoric acid (TPPS)
2.5a3-methyl-4-amino-N-e
Chill-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescence enhancement
Whitening agent (4,4'-diaminostilbenzsulfonic acid derivative) 1.00 hydroxy acid
Potassium chloride 2. Add OQ water and
Adjust the amount to 1 and adjust the pH to 10.20Ill. Potassium bromide (expressed as Sr concentration) is added to the developer with the above composition.
) in the amounts shown in Table 1 to create color developing solutions [A] to [H].
f-adjusted. (Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 6oQ ethylene
Diaminetetra ii\il 3c + thiosulfur
Ammonium acid (10% solution) 100yj sulfite
Ammonium (40% solution) 27.51f carbonate
Adjust the pi to 17.1 with lime or glacial acetic acid and add water.
Make the total amount 1 no. The sensitizing dye [A
I, stabilizer [B], comparative coupler [CI and [DI]
The structural formula is shown below. Sensitizing dye [AI stabilizer [B] vomiting” bite alarm

[0] O α Colorful Color (D) As is clear from Table 1, when Sample No. 1.2, which is not the invention and which is a combination of the silver chlorobromide emulsion of the invention and a comparative coupler, is used. The color developing solutions [E] to [H
] Even when processed with 8" f1 degree fluctuation, the sensitivity and gradation change are large, resulting in image quality that is too soft or too high contrast, and also causes a large deviation in color balance, so it is not practical. Also, when using Sample No. 3.4.5 according to the present invention, which is a combination of the silver chlorobromide emulsion of the present invention and the coupler of the present invention, color developing solutions [A] to [D] other than the present invention were used. When sample N
O, 3, 4, 5 in the color developing solution [E] to [H
] In the method of the present invention, B "concentration V is [
Although the sensitivity and gradation fluctuate to the same extent as A] ~ [01, the fluctuations in sensitivity and gradation are small, and samples No. 1 and 2 are compared to [E] ~ r
Fluctuations in sensitivity and gradation are approximately 1/2 compared to processing with [H]
The resistance to 13r fluctuations is improved, and the fluctuations are within a practically acceptable range. Regarding fog, [A]
- It is suppressed to a lower level than in the case of processing [D] and is stable. In addition, sample No. 016 using a silver iodobromide emulsion other than the one according to the present invention cannot be evaluated in any color developer in the middle of development after 3 minutes and 30 seconds, and is significantly inferior in suitability for rapid processing. Example-2 Sample No. 013 prepared in Example-1 was subjected to wedge exposure and then processed according to the same processing steps as in Example-1. However, the color developing solution is shown in Table 2 [1-1F~[
N-4] was used. This color developer [I-1] ~rN
-4] contains the hydroxylamines and KBr shown in the table, and the other compositions are the same as the color developing solution described above. Table 2 shows the Δte of dye uniformity obtained by processing samples No. 3 with each color developer. Here, Δ7 is a variation value based on Te when each of T-N is processed with a developer of N001. Table 2 As is clear from Table 2, when the type and amount of hydroxylamine is within the scope of the present invention, the llil modulation with respect to 3r concentration fluctuations is small and does not pose a practical problem, but when the amount of hydroxylamine is outside the scope of the present invention. In this case, gradation fluctuations become large, which causes a problem such as a shift in color balance as described above. Example-3 Example-1 using EM-ac produced in Example-1
Color photosensitive material sample N00 was coated using the same method as above.
7 to 10 were produced. At this time, when preparing sample N099, exemplified mercapto heterocyclic compound 13 was added to silver halide 1
It was added at a concentration of 40 mg per mole. The obtained sample was subjected to wedge exposure and then processed according to the same processing steps as in Example-1. Table 3 shows the relative sensitivities S and Δte for each of the color photosensitive material samples Nos. 097 to 10, based on the time when they were processed with the color developer [E]. Compliment 3 As is clear from Table 3, it can be seen that it can be used in the present invention and is excellent. However, r-0,55μm and 0
．． No difference is observed in the 75μ layer. In addition, by coexisting a mercapto heterocyclic compound, even better B "fluctuation resistance" can be achieved. The image quality was stable with almost no noticeable fluctuations.Example-4 By sequentially coating the following layers on a polyethylene coated paper support, f[!II color photosensitive material sample No.
, 11 were produced. Here, the amount of each compound added is per dm of color photosensitive material. ! 111...The following yellow coupler [E] (8,
0ma) and blue-sensitive silver chlorobromide emulsion (average grain size 0.75μ-
Blue-sensitive emulsion layer 2 containing 3.5 mg (calculated as metallic silver) and 20 mc+ of gelatin...Intermediate layer 3 containing 0.31 ga of dioctylhydroquinone and 10 ml of gelatin...Example Magenta Turnip 7- [ 127] (4
, OIg) and EM-1) prepared in Example-1 (1.710> in terms of metallic silver), an exemplary mercaptoheterocyclic compound 13-h (6X10 mσ), and an edge-sensitive emulsion layer having 2o1 g of gelatin. 4... Intermediate layer containing 0.3 mg of dioctylhydroquinone, the following ultraviolet absorber [F] lo, and 15 mo of gelatin 5... The following cyan coupler [G] (3, OB)
Red-sensitive silver chlorobromide emulsion (average grain size 0.4μ - 2.51F in terms of metallic silver) and 151 g of gelatin, red-sensitive emulsion layer 6...the following ultraviolet absorber [F] 4.0 Intermediate layer 7 having ■g and gelatin 10■0...Protective layer having gelatin 101G (7) Cyan cuff "Lar C cow" The obtained multicolor color photosensitive material sample No. 11 was forged,
The magenta dye image obtained even when bleach-fixed, washed with water, and processed with a liquid according to the processing steps described above has little fog and is excellent in stable tone reproduction and color reproduction, and the dye image forming method of the present invention is excellent. B: It can be seen that it has resistance to fluctuations. Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural Publication 1 Official Book (Spontaneous) August 11, 1986

Claims (1)

[Scope of Claims] A silver halide color photographic material having a silver halide emulsion layer containing a magenta coupler represented by the following general formula [I] and a silver chlorobromide emulsion on a reflective support is imagewise exposed. After that, the dye image is processed with a color developer having a bromide ion concentration of 7×10^-^3 mol/l or more and containing hydroxylamines from 0.02 mol/l to 0.15 mol/l. Formation method. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. You can. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ]