JPS62291653A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having improved spectral absorbing characteristics and the light fastness of a color image by incorporating a specific coupler and/or a polymer coupler derivated from said coupler, and one kind of specific compds. to one layer of silver halide emulsion layers. CONSTITUTION:The titled material contains one kind of the coupler selected from the couplers shown by formulas I-III, and/or the polymer coupler derivated from said couplers and one kind of the compds. shown by formula IV. In formulas I-III, Za-Zc are each a non-metallic atom group necessary to forming a nitrogen contg. heterocyclic ring, Xa-Xc are each hydrogen atom or a group capable of releasing by reacting with the oxidant of a color developing agent, Ra-Rg are each hydrogen atom, etc., Y1 and Y2 are each carbon atom, etc. In formula IV, R21 and R22 are each hydrogen atom, etc., R23 is a substituent, R24 is alkyl group, R25 is cycloalkyl group, J is a group shown by formula V, etc., R26 and R27 are each hydrogen atom, etc., R28 is alkyl group etc., (l) is 0 or an integer of 1-4, (m) is 0 or 1, (n) is 0, 1 or 2.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material.
This invention relates to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light, and staining is prevented. [Background of the invention q] Conventionally, a coupling reaction between an oxidized product of an aromatic primary amine color developing agent and a color forming agent is caused by imagewise exposure of a silver halide color photographic light-sensitive material (1) and color development. It is well known that, for example, indophenol, indoaniline, indamine, azomedine, phenoxazine, phenazine, and pigments similar to these are produced and color images are formed. In this type of photography, a subtractive color method is usually used to reproduce colors.
A silver halide color photographic sensitizer in which blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers each contain a coloring agent having an extra color relationship, that is, a coupler that develops yellow, magenta, and cyan. is used. Examples of couplers used to form the above-mentioned yellow image include Asilua L! There are 1-anilide couplers, and as couplers for forming magenta color images, for example, pyrazolone, pyrazolobenzimidazole, pyrazolotriazole or indasilone couplers are known, and couplers for forming cyan color images. For example, phenol or naphthol couplers are commonly used. It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored at high temperature and humidity. It is also desired that the uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) do not turn yellow (hereinafter referred to as Y-stain) due to light or moist heat. However, in the case of magenta couplers, fading by light in uncolored areas, Y-stain due to moist heat, and color fading in dye image areas due to light is extremely large compared to yellow couplers and cyan couplers, and often poses a problem. Couplers commonly used to form magenta dyes are 5-pyrazolones. The dye formed from this magenta coupler of 5-pyrazolones has a wavelength of 550 nm.
In addition to the main absorption near 430 nn+, a major problem is that it has a sub-absorption near 430 nn+, and various studies have been conducted to solve this problem. Magenta couplers having an anilino group at the 3-position of 5-pyrazolones have small side absorption and are particularly useful for obtaining color images for printing. These techniques are described in, for example, US Patent No. 2,343,703, British Patent No. 1.
059.994 etc. However, the above-mentioned magenta coupler has the disadvantage that the image storage property, particularly the fastness of the dye image to light, is extremely poor, and the Y-stain in the uncolored area is large. Other couplers that have reduced side absorption near 430 nm include the pyrazolobenzimidazoles described in British Patent No. 1,047,612 and U.S. Pat. No. 3,770.4.
Indacilones described in No. 41, and No. 3.725.0
No. 67, British Patent No. 1,252,418, British Patent No. 1,334
, 515 and razo o[5,1-c ]-
1,2゜4-triazole type coupler, JP-A-59-1
No. 71956, Research Disclosure 1 No No.
1-pyrazolo[1,5-b] described in , 24531
-1,2゜4-triazole type coupler, 11- described in Linati Disclosure No. 24626
1-pyrazolo[1,5-C]-]1.2.3-triazole type coupler JP-A-59-162548, Lily
1 described in Disclosure N 0.24531
11-Imidazo[1,2-b]pyrazole type coupler, JP-A-60-43659, Research Disclosure No. 1(-pyrazolo[1,5-b] described in 24230)
Pyrazole type couplers, magenta couplers such as the 1-to-1-pyrazolo[1,5-d]tetrazole type couplers described in JP-A-60-33552, Research Disclosure No. 24220 have been proposed. Among these, 1 day-pyrazolo[5,1-c]-1,2゜4
-triazole coupler, 1-1-pyrazolo[1,5
-b]-]1.2.4-triazole coupler 1H
-pyrazolo[1,5-c]-1,2゜3-triazole type coupler, 11''-imidazo[1,2-b]pyrazole type coupler, 11-1-pyrazolo[1,5-b]
Pyrazole-type couplers and 1]-1-pyrazolo[1,
5-d] A dye formed from a tetrazole type coupler has significantly smaller sub-absorption near 430 nm than a dye formed from a 5-pyrazolone having an anilino group at the 3-position, and is preferable in terms of color reproduction, and further, It has the advantage that the occurrence of Y-stain in uncolored areas is extremely small when exposed to light, heat, and humidity. However, the fastness of azomethine dyes formed from these couplers to light is extremely low, and in addition, the dyes are easily discolored by light, which significantly impairs the performance of color photographic materials, especially printed color photographic materials. , it has not been put to practical use in printed color photographic materials. Similarly, the imidazo[1,2-b]-pyrazole coupler described in International Publication W08G7024G7 has good spectral absorption characteristics, good solubility and dispersibility, and high coloring property, but it has poor light resistance. It has the drawback of having low properties and being easily discolored and faded by light, so it has not been put into practical use as a print-type color photographic material. In addition, JP-A-59-125732 discloses that 11''-pyrazolo[5,1-C]-]1.2.4-h riazole type genta coupler is used in combination with a phenol compound or a phenyl ether compound. By doing so, 11-1-
Techniques have been proposed to improve the light fastness of magenta dye images obtained from pyrazolo[5,1-C]-1,2°4-triazole type magenta couplers. However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light. [Object of the Invention] The present invention has been made in view of the above-mentioned problems, and the first object of the present invention is to provide a color image that is layered in a layered manner and that has significantly improved light fastness of color images. An object of the present invention is to provide a silver halide photographic light-sensitive material. A second object of the present invention is to provide a silver halide photographic material having a dye image that is less discolored by light. A third object of the present invention is to provide a silver halide photographic material which is prevented from generating Y-stain in uncolored areas due to light, heat, and humidity. [Configuration 1 of the invention j of the invention: F, i! For a 1m target, place a small

[Halogen with one layer of halogen root emulsion layer]
Silver compound photographic light-sensitive material contains 13 [, the above-mentioned C] cognate, silver.
At least one of the emulsion layers has the general formula (a), (+1
) and (C), respectively') redundant.
at least one coupler disclosed in 13 and/or the
Polymer couplers derived from couplers as well as
At least one type b of the compound represented by the general formula [X I[]
Achieved by the silver gunkide photographic material r1 containing
Ru. General formula (a) (Rd)n. General formula (1)) General formula (C) [7a in general formulas (a), (b) Jt and (C). 7bd3 and ZC each form a nitrogen-containing heterocycle
Necessary nonmetal atoms! Represents T. Xa, XI] Jj
and XC are hydrogen atoms J: or oxidation of color developing agent, respectively.
Ill 7+52t, 1q group upon reaction with
Table 11゜Ra, R1+, RC, Rd, Re
, Rf and RgILL each hydrogen atom or substituent
represents the general formula (C)F.
released during the reaction between the puller and the oxidized form of the coloring agent.
This is a substituent that never occurs. , YIl, as a carbon atom or
t represents a nitrogen atom. Y2 is a carbon atom or a hede
” represents an atom. = means the bond between Yl and Y2 is an il bond
In a double bond, d is a double bond. (Rishi, Yl is a carbon atom and the bond between Yl and Y2 is double
The combination is 113 is 1, 114 is O'c, or
Rc is the coupler represented by the general formula 1) and the coloring phenomenon.
Unt does not come off when reacting with the oxidized form of the main drug.
is a substituent, Yl is a carbon atom, and the bond between Yl and Y2
When is a li bond, both 113 and nl are 1. Also, if Y1 is a nitrogen atom and the bond between Yl and Y2 is a double bond
i;i n and +14 are both O, and Y2 is
Hete [1 atom, Yl is a nitrogen atom and Y+ and Y2 are
If the bond between is a single bond, +13 is 1 and +5, 111
is O. In addition, the capacitors represented by general formulas (a), (L+) and (C)
The puller is located at the position where xa is bonded, and where X I+ is
Only at the bonded position and the position where Xc is bonded,
Coupling reaction with oxidized color developing agent. ] ・General formula [X It ] [In the formula, n2+ and R22 are each a hydrogen atom, an alkyl
group, cycloalkyl group, alkenyl group, aryl group or
or a heterocyclic group, and R23 represents a substituent. R
24 is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkyl group,
represents a kenyl group, an aryl group or a heterocyclic group, and R2
5 is an alkyl group, cycloalkyl group, alkenyl group, alkyl group,
R26 and R27 are each a hydrogen atom in a lyl group or
or represents an alkyl group, and R28 is an alkyl group or
Represents an aryl group. l represents O or an integer from 1 to 4
, m represents O or 1, and n represents Oll or 2.
Was. R21 and R22 may be the same or different, and may be different from each other.
It is also possible to combine with J to form a 5- or 6-membered ring. Also
When l is 2 or more, multiple R23s may be the same or different.
Often, n2+ or/and R22 and n2+ or
or a nitrogen atom bonded to R22, with a 5- to 6-membered
Forming a ring and bonding to R24, J: and R2'l
may form a 5- or 6-membered ring together with the nitrogen atom. ] [Specific structure of the invention] General formulas (a), (b) and (
C) at least one selected from the couplers shown respectively in
is also a type of coupler and/or derived from the coupler.
Polymer coupler (hereinafter referred to as ±4 couplers according to the present invention)
Hereinafter, the general formula (+1
), (b), (c) General formula (,) (Rd)n. In the magenta coupler represented by general formula (b) and general formula (c), Za. Zb and Zc are nonmetals necessary to form a nitrogen-containing heterocycle
Represents an atomic group, and Xa, Xb and Xe each represent a hydrogen atom or a color developer.
Represents a substituent that can be eliminated by reaction with the oxidized form of the image agent.
vinegar. Also, Rat Rb, Ret Rd, Re, Rr
and R each represent a hydrogen atom or a substituent. However, Rg is the coupler represented by the general formula (C) and the coloring
It will not be released when it reacts with the oxidized form of the developing agent.
It is a substituent. Yl represents a carbon atom or a nitrogen atom, Y2 is a carbon atom
or represents a heteroatom. Koni says that even if the bond between Yl and Y is a single bond,
Indicates that it may be a double bond. Ys, Y- and Y each represent a carbon atom or a nitrogen atom
represent. n++ ni+ n*+ n4+ 1191 ni and
R7 is each O or 1. However, Y is a carbon atom and the open bond between Y and Y2 is a double bond.
In the case, n, is 1, n, is 0, and
e is a coupler represented by general formula (a) and a color developing agent
A substituent that does not undergo separation upon reaction with an oxidant of
, Y is a carbon atom and the open bond between Yl and Y2 is a single
In the case of a bond, n and n are both 1. Also, Yl
If is a nitrogen atom and the bond between Y and Y2 is a double bond, then
n and n4 are both 0, and Y is a heteroatom
Yes, Yl is a nitrogen atom and the open bond between Y and Y is a single bond.
In the case, n, is 1 and n, is 0. In addition, the numbers represented by the general formulas (&), (b) and (e)
The puller is located at the position where Xa is bonded and where xb is bonded, respectively.
Emissions occur only at the positions where they are aligned and where Xe is bonded.
Coupling reaction with oxidized color developing agent. The above Ra, Rh, Rc, Rd, Re or Rr
Examples of substituents include halogen atoms, alkyl
group, cycloalkyl group, alkenyl group, cycloalkeni
group, alkynyl group, aryl group, heterocyclic group, acyl group
group, sulfonyl group, sulfinyl group, phosphonyl group, carbon
Rubamoyl group, sulfamoyl group, sia/group, spirolation
compound residues, bridged hydrocarbon compound residues, alkoxy groups,
lyloxy group, heterocyclic oxy group, siloxy group, acyloxy group,
carbamoyloxy group, carbamoyloxy group, ami7 group, acyl
Ami7 group, sulfonamide group, imide group, ureido group
, sul77moylamino group, alkoxycarbonylamine
7 groups, aryloxycarbonylamide 7 groups, alkoxy
Carbonyl group, aryloxycarbonyl group, alkyl group
Examples include thio group, arylthio group, and heterocyclic thio group.
. Examples of halogen atoms include chlorine atoms and bromine atoms.
Among them, a chlorine atom is particularly preferred. Ra, Rh, Re, Rd, Re or Rfi? weakening
Examples of alkyl groups include those with 1 to 32 carbon atoms, and alkenyl groups with 1 to 32 carbon atoms.
The alkynyl group has 2 to 32 carbon atoms, and the alkynyl group has 2 to 32 carbon atoms.
Chloalkyl group, cycloalkenyl group has 3 carbon atoms
to 12, especially those of 5 to 7 are preferred, and those containing an alkyl group, a
The lekenyl group and the alkynyl group may be linear 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, Alfkidicarbonyl, Ryoichiruoxyl
Those substituted via a carbonyl group such as carbonyl,
substitutes through a heteroatom (specifically, a hydro
xy, alkoxy, aryloxy, heterocyclic oxy,
Oxygen such as siloxy, acyloxy, carbamoyloxy
Substitution through atoms, nitro, ami/(dialky)
(including Ruami 7 etc.), Suru 77 Moyami/, Alfuki
Dicarbonylamino, aryloxycarbonylamino/
, acylamino, sulfonamide, imide, ureido, etc.
substituted through the nitrogen atom, alkylthio, ali
ruthio, heterocyclic thio, sulfonyl, sulfinyl,
Those that substitute through the sulfur atom such as sulfamoyl,
Substituted through a phosphorus atom such as sulfonyl)
You can leave it there. Specifically, for example, methyl group, ethyl group, isopropyl group
, di-decyl group, pentadecyl group, heptadecyl group, 1
-hexyl/nyl group, 1.1'-dibentynonyl group,
2-chloro-t-fluor group, trifluoromethyl group,
1-ethoxytridecyl group/1-nodoxyisoprobi
group, methanesulfonylethylmethyl group, anilino group, 1-phenylisopropyl group,
3m-butanesulfonaminophenoxypropyl group, 3
-4' - [α-[4″(p-hydroxybenzene
Sulfonyl) 7E/Xy
phenylpropyl group, 3-i4'-[α-(2″14″-
di-1-amylphenoxy)butanamide]7enyl)
-propyllk, 4-(σ(0-chlor7ヱ/xy)te
tradecanamidophenoxifpropyl group, allyl group,
Examples include cyclopentyl group and cyclohexyl group. A represented by Ra, Rb, Rc, Rd, Re or Rf
As the aryl group, a phenyl group is preferable, and a substituent (e.g.
(e.g., alkyl group, alkoxy group, acylami 7 group, etc.)
may have. Specifically, phenyl group, 4-t-butyl heptanyl group,
2.4-di-t-amylphenyltetradecanamide
Phenyl group, hexadecyloxyphenyl group, 4'-(
U-(4”-L-7゛tylphenoxy)tetrade
Examples include canamidophenyl group. Ra, R1), Re, Rd. Re or R”
The heterocyclic group preferably has 5 to 7 shells, and is unsubstituted.
They may be separated or condensed. Specifically, 2-furyl group, 2-chenyl group, 2-pyrimi group
Examples include a diinyl group and a 2-benzothiazolyl group. Rat Rb, Rc. expressed as Rd, Re or Rf
Examples of the acyl group include acetyl group, phenylacetyl group,
group, dodec/yl group, Q-2,4-di (-amyl
Furkylcarbonyl groups such as phenoxybuta/yl groups,
nzoyl group, 3-pentadecyloxybenzoyl group, p
-Arylcarbonyl groups such as chlorobenzoyl group, etc.
can be lost. Rat Rb. , Re, Rd. Re or Rf''C
Examples of sulfonyl groups include methylsulfonyl group, dode
Alkylsulfonyl groups such as silsulfonyl groups, benzene
Ants such as sulfonyl f, p-) luene and sulfonyl groups
Examples include lsulfonyl group. Represented by Ra, Rh, Rat Rd, Re or R
Examples of sulfinyl groups include ethylsulfinyl group and octyl group.
Tylsulfinyl group, 3-phenoxybutylsulfini
Alkylsulfinyl group such as ru group, phenylsulfinyl group
Nyl group, m-pentadecylphenylsulfinyl group, etc.
Examples include arylsulfinyl groups and the like. Ra, Rh, Rc, Rd. Re or Rf
Examples of the phosphonyl group include butyloctylphosphonyl group.
alkylphosphonyl group, octyloxyphosphonyl group
Alkoxyphosphonyl groups such as 7-enoxyphosphonyl
As a group, monoloxyphosphonyl group, phenylphosphonyl group
Arylphosphonyl group such as nyl group, etc. hl $ l-J
'Rahr. The number expressed by Ra, Rh, Re, Rd, Re or R[
Rubamoyl group is a furkyl group, an aryl group (preferably a fluoride group)
phenyl group), etc., for example, N-methyl
Carbamoyl group, N,N-dibutylcarbamoyl group,
N-(2-pentadecyloctylethyl)carbamoyl
group, N-ethyl-N-dodecylcarbamoyl group, N-
13-(2.4-amylphenoxy)propylene
) carbamoyl group, etc. Steps expressed as Ra, Rb, Rc, Rd, Re or Rf
Rufamoyl group is an alkyl group, an aryl group (preferably
71 nyl group) etc. are substituted (1 may be <, for example, N-propylene group).
Lopylsulfamoyl group, N. N-diethylsulfamoyl group, N-(2-be/tade
sulfamoyl group, N-ethyl-N
-dodecylsulfamoyl group, N-phenylsulfamoyl group
Examples include yl group. Rat R1), Re, Rd, Re or R
Examples of spiro compound residues include spiro 3. 3] Hebutan-1-yl and the like. Ra, Rb. Rat Rd, Re or R”
Examples of the carbonized compound residue include bicyclo ``Riri1''.
1+ze〃・7-1-ノI1. LI+:/'7rff[3
, 3.1.11″] decane-1-yl, 7,7-cymethy
rubicyclo[2.2.1]heptane-1-yl etc.
can be lost. Ra, Rb. Rc. Rd. A represented by Re or R[
The alkoxy group is further mentioned as a substituent to the alkyl group.
For example, nodoxy group,
Ropoxy group, 2-ethoxy″-r-Foxy group, pentade
Syloxy group, 2-dodecyloxyethoxy group, 7ene
Examples include thyloxyethoxy group. Rat Rh. Rat Rd. Re or R” weakens zh
As the aryloxy group, phenyloxy is preferable.
In addition, the fi substituent on the aryl group of the 7-aryl nucleus is
The atoms listed may be substituted, e.g.
phenoxy group, p-L-butylphenoxy group, m-pen
Examples include tadecylphenoxy group. Ra. Rh, Re, Rd, Re or R [mugiwa 3 r. The heterocyclic oxy group has 5 to 7 heterocyclic buttons.
Preferably, the heterocycle further has a substituent.
For example, 3. '4. -5゜6-tetrahydride
robilanyl-2-oxy group, 1-phenyltetrazole
-5-oxy group is mentioned. Ra+ R111RC+ Rdi Re or Rf″C
The represented siloxy group is further substituted with an alkyl group, etc.
(e.g.) linotylsiloxy group, triethylsiloxy group, etc.
Examples include luciloxy group, dimethylbutylsiloxy group, etc.
Ru. Represented by Ra+ Rb, Rc+ Rcl, Re or Rf
Examples of the acyloxy group include alkyl carbo
Nyloxy group, 7-arylcarponyloxy group, etc.
and may further have a substituent, specifically acetyl
chlorooxy group, α-chloroacetyloxy group, benzoyl
Examples include oxy group. A group represented by Ra, Rh, Re, Rd, Re or R[
The rubamoyloxy group has an alkyl group, an aryl group, etc.
For example, N-ethylcarbamoyloxy
cy group, N, N-noethyl group, rubamoyloxy group, N-phthalate group,
Examples include phenylcarbamoyloxy group. A that is weakened by Ra, Rh, Rc, Rd, Re or Rf.
The mino group is an alkyl group, an aryl group (-preferably a phenyl group)
For example, ethylamino
group, anilino group, pupil-chloroanilino group, 3-pentade
syloxycarbonylanilino group, 2-chloro-5-he
Examples include seven groups of xadecanamide aniline. Ra, Rh, Re, Rd, Re or Rf['represented
As the 7 acyl amide groups, there are 7 alkyl carbonyl amide groups.
, 7 arylcarbonyl amine groups (preferably 7 enyl groups)
luponylamino group), and further has a substituent.
Specifically, acetamido group, a-ethylpropane
Amide group, N-7enylace)amide group, dodecanamide
do group, 2,4-no-7-7-myl-7e/xyacetamide
group, α-3-t-butyl-4-hydroxy 7ヱ/xib
Examples include tanamide group. Strain represented by Ra, Rb, Re, Rd, Re or Rf
As the sulfonamide group, there are 7 alkylsulfonylamide groups.
, arylsulfonylamide 7 groups, etc., and further substituted
may have a group, specifically methylsulfonylamine/
i, 7 pentadecylsulfonylamine groups, benzenesulfonyl
amide group, p-toluenesulfonamide group, 2-no)
4-5-amylbenzenesulfonamide group etc.
can be lost. Ra, Rh, Rc+ Rd, Re or Rf″c expressed
The imide group may be open-chain or cyclic.
may have a substituent, for example, succinimide
group, 3-heptadecylsuccinimide group, 7-talimide
group, glutarimide group, etc. Represented by Ra, Rb, Re, Rd, Re or Rr″C
The ureido group is an alkyl group, an aryl group (preferably 7
Enyl group) v? For example, N
-ethylureido group, N-methyl-N-decylureido
group, N-phenylureido group, N-p-)lylureido
Examples include groups. The sulfamoylamino group is an alkyl group, an aryl group,
(preferably a phenyl group), etc.,
For example, N, N-dibutyl sulfate moyl amine 7 groups, N-
Methylsulfamoylamine 7M, N-phenylsul7a
Moirami/iF is mentioned. A represented by Ra, Rh, Re, Rd, Re or Rr
As the rufukidicarbonylamide 7 group, further ra substituent
For example, methoxycarbonylamide 7 groups
, me) + 7 groups of jetoxycarbonylamine, octate
and hydroxycarbonylamino group. Ra, RJ, Re,' Rd, Re or Rf't' decline
The 7 aryloxycarbonylamide groups mentioned above are substituents
For example, phenoxycarbonyl amine
and 7 groups of 4-methylphenoxycarbonylamide.
I feel angry. Represented by Ra, RIB, Re, 'Rd, Re or R[I
The alfkidicarbonyl group further has an iW substituent.
Idit) / I1g+I u IJ' J L
4 ;+! 11. , ar −11-t −/chill
Oxycarbonyl group, tosyloxycarbonyl group,
Octadecyloxycarbonyl group, ethoxymethoxycarbonyl group
Rubonyloxy group, -kunzyloxycarbonyl group, etc.
Can be mentioned. Ra, Rb, Re, Rd, Re 7 is represented by R[
The aryloxycarbonyl group further has a substituent.
For example, phenoxycarbonyl group, p-chloro
7E/oxycarbonyl group% I-hentatecyloxy
Examples include a 7e7oxycarbonyl group. Eight aa represented by Ra, Rb, Re, Rd, Re or Rf
The alkylthio group may further have a substituent, such as ν.
For example, ethylthio group, dodecylthio group, octadecylthio group
group, 7enethylthio group, 3-phenoxypropylthio group
can be mentioned. A represented by Ra, Rb, Re, Rd, Re or Rf
The lylthio group is preferably a phenylthio group, and further substituents
For example, phenylthio group, p-meth
xyphenylthio group, 2-1-octadecylphenylthio group
O group, 3-octadecylphenylthio group, 2-carboxy group
Cyphenylthio group, p-7 cetami/7enylthio group, etc.
is listed at 10° Ra, Rh, Re, Rd, R= and Rf
The heterocyclic thio group expressed is 5 to 7 shellfish heterocyclic thio groups.
A cyclic thio group is preferable, and a fused ring may also be added.
6 which may have a substituent, e.g. 2-bilinorthio group,
2-benzothiazolylthio group, 2,4-diphenoxy-
i, 3,5-triazole-6-thio group. R[l and Y are carbon atoms, and the bond between Yl and Y2
is represented by Re when is a double bond.
It will not be released upon reaction with the oxidized form of the color developing agent.
Examples of suitable substituents include alkyl groups, alkyl groups, and silyl groups.
Chloalkyl group, alkenyl group, cycloalkenyl group,
Alkynyl group, heterocyclic group, acyl group, sulfonyl group,
Sulfinyl group, phosphonyl group, carbamoyl group, sulfinyl group
Famoyl group, cyano group, spiro compound residue, bridged structure
Hydrogen compound residue, siloxy group, carbamoyloxy group,
Alfkidicarbonyl group, aryloxycarbonyl group
can be mentioned. As mentioned above, as specific examples of each group, for example, the prefectural body of Ra mentioned above
The following are examples. Reaction with oxidized products of color developing agents represented by Xa, Xb, and Xc
Examples of substituents that can be removed by reaction include halogen atoms.
In addition to carbon atoms (chlorine atoms, bromine atoms, seven atoms, etc.)
substitution through a child, oxygen atom, sulfur atom, or nitrogen atom
The following groups are listed below. As a group substituting via a carbon atom, a carboxyl group
, hydroxymethyl group, triphenylmethyl group, etc.
Xa, Xb, Xe l: Correspondingly, Formula (&') ■ (Rd)n,' Formula (b') , Rh' is Rb, Re' is Re
, Rcl' is Rd, Re' is Re, Rf'
is Rf, Rg' is R, and nl' is 111.
,n21 is n, ,l is n, and n,′ is
Mouth, 11. ' is 115, 116' is n, and 1
? ' is n, Y, ) is Y, Y2' is Y,
, Y,′ is Y, and Y,′ is Y, and Y,′ is Y.
Za' is synonymous with Za, Zb' is synonymous with zb, and Zc' is synonymous with Zc.
and R1 to R are hydrogen, an alkyl group, an alkyl group, or
is a heterocyclic group '9: reward, ) is exemplified.
Ru. Examples of groups substituted via an oxygen atom include alkoxy
cy group, aryloxy group, heterocyclic oxy group, acyloxy group,
Oxy group, sulfonyloxy group, alkoxycarbonyl group
xy group, aryloxycarbonyloxy group, alkyl group
Oxalyloxy group, alkoxyoxalyloxy group
Can be mentioned. The alkoxy group may further have a substituent, for example,
(toxy group, 2-phenoxyethoxy group, 2-cyanoe)
xy group, 7enethyloxy group, p-thalolbennoroxy group
Examples thereof include cy group. The aryloxy group is preferably a phenoxy group,
The aryl group may further have a substituent, specifically
contains phenoxy group, 3-methylphenoxy group, 3-dode
Sil7eth/oxy group, 4-methanesulfonamidophenoxy
cy group, 4-(α-(3'-pentadecyl727xy) but
Tanamide] phenoxy group, hexadecylcarbamoyl
Methoxy group 4-cyano7eth/oxy group, 4-methanesulfonate
Nyl72/oxy group, 1-naphthyloxy group, p-methoxy group
Examples include 7e/oxy groups. The heterocyclic oxy group includes 5 to 7 heterocyclic oxy groups.
A cy group is preferable, and it may be a condensed ring or have a substituent.
Specifically, 1-phenyltetrazoly
2-benzothiazolyloxy group, etc.
It will be done. Examples of the acyloxy group include acetoxy group, buto
Furkylcarbonyloxy groups such as sulfoxy groups, thinner
alkenylcarbonyloxy groups such as moyloxy groups,
Arylcarbonyloxy groups such as benzoyloxy groups
can be mentioned. The sulfonyloxy group is, for example, butanesulfonyloxy group.
Examples include fluoroxy group and methanesulfonyloxy group. As the alkoxycarbonyloxy group, for example, ethyloxy
xycarbonyloxy group, benzyloxycarbonyloxy group
The xy group is removed. As the nucleonyloxycarbonyloxy group, phenoxy
Examples include cycarbonyloxy group. As the alkyloxalyloxy group, for example, methyl
An example is an oxalyloxy group. As the alkoxyoxalyloxy group, ethoxy
Examples include xalyloxy group. As a group substituted via a sulfur atom, for example, furkyl
Thio group, arylthio group, heterocyclic group, alkyl group
Examples include xythiocarbonylthio group. As the alkylthio group, butylthio group, 2-cyano
Ethylthio group, 7enethylthio group, benzylthio group, etc.
It hurts. As the arylthio group, phenylthio group, 4-methane
Sulfonamidophenylthio! , 4-1'decile 7e winter
methylthio group, 4-7sufluoropentanamide 7enethi
ruthio group, 4-carboxyphenylthio group, 2-ethoxy group
Examples include ci-5-t-butylphenylthio group. Examples of the heterocyclic thio group include 1-phenyl-1,
2,3,4-tetrazolyl-5-thio group, 2-benzothi
Examples include azolylthio group. As the alkyloxythiocarbonylthio group, dode
Examples include syloxythiocarbonylthio group. The group substituting via the nitrogen atom is tilted. child
Here, R7 and R are hydrogen atoms, furkyl groups, and aryl groups.
, heterocyclic group, sulfamoyl group, carbamoyl group, a
Syl group, sulfonyl group, aryloxycarbonyl group,
represents an alphkidicarbonyl group, and R2 and R are bonded together.
may form a heterocycle, provided that R7 and R8 are both water.
It cannot be an elementary atom. The alkyl group may be straight chain or branched, preferably carbon
This is after number 1-22. In addition, an alkyl group has a substituent.
Examples of the substituent include an aryl group,
Alkoxy group, aryloxy group, alkylthio group,
lylthio group, 7 alkylamino groups, arylamino group,
Acylamino group, sulfonamide group, imino group, acyl
group, alkylsulfonyl group, arylsulfonyl group, carbon
Rubamoyl group, sulfamoyl group, alkyl group
group, aryloxycarbonyl group, alkyloxycarbonyl group,
7 rubonyl amide groups, 7 7lyloxycarponyl amine groups
, hydroxyl group, carboxyl group, cyano group, halogen
Examples include ion atoms. Specific examples of the alkyl group
For example, ethyl group, octyl group, 2-ethylhexy
and 2-chloroethyl group. As the aryl group represented by R1 or R1, the number of carbon atoms
6 to 32, particularly phenyl group and naphthyl group are preferable, and
The aryl group may have a substituent, and examples of the substituent include those listed above.
As a substituent to the alkyl group represented by R or R-
and alkyl groups. the aryl
Specific examples of the group include phenyl group, 1
-su7tyl group, 4-methylsulfonylphenyl group are mentioned.
It will be done. The heterocyclic group represented by R7 or R1 is 5 to 6
Shellfish are preferred, and may be fused rings, with substituents
Specific examples include 2-furyl group, 2-kyl group, and
Noryl group, 2- and rimidyl group, 2-benzothiazolyl group
, 2-pyridyl group and the like. As the sul77moyl group represented by Rt or R1,
N-furkylsul77 moyl group, N,N-dialkyl group
rufamoyl group, N-7 lylsul7 ammoyl i, N,
N-diarylsulfamoyl group, etc., and these
The furkyl group and aryl group of
sulfur group which may have the substituents listed for the sulfur group.
Specific examples of famoyl groups include, for example, N,N-diethyl
Rusul 77 moyl group, N-methylsulfamoyl N
-dodecylsulfamoyl group, N-p-)lylsul7a
A moyl group is mentioned. The carbamoyl group represented by R1 or R1 is N
-furkylcarbamoyl group, N,N-dialkylcarba
Moyl group, N-7 arylcarbamoyl group, N,N-dia
Examples include arylcarbamoyl groups, and these alkyl
group and aryl group refer to the alkyl group and aryl group mentioned above.
Carbamoyl group optionally having the substituents listed above
As a specific example, for example, N,N-noethyl group
group, N-methylcarbamoyl group, N-dodecylcarba
Moyl group, N-p-cyanophenylcarbamoyl group, N
-Gl-)lylcarpamoyl group. R? Or, as the acyl group represented by R8, for example,
alkylcarbonyl group, arylcarbonyl group, heterocycle
carbonyl group, the alkyl group, the 7-aryl group;
, the heterocyclic group may have a substituent, an acyl group
For example, hexafluorob
Tanoyl group, 2,3,4,5,6-pentafluoroben
Zoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-7lylcarbonyl group. As the sulfonyl group represented by R1 or R1,
Kylsulfonyl group, 7-arylsulfonyl group, heterocycle group
Examples include sulfonyl group, which may have a substituent, and specifically
For example, ethanesulfonyl group, benzene
sulfonyl group, octane sulfonyl group
Nyl, 0-chlorobenzenesulfonyl group, etc.
Ru. Aryloxycarbonyl group represented by R1 or R1
is the substituent listed for the aryl group above.
It may have a phenoxycarbonyl group, specifically, a phenoxycarbonyl group, etc.
Can be mentioned. The phenoxycarbonyl group represented by R1 or R1 is
It may have the substituents listed for the alkyl group,
Specifically, methoxycarbonyl group, dodecyl group
Oxycarbonyl group, benzyloxycarbonyl group, etc.
Can be mentioned. The heterocycle formed by combining R7 and R1 is 5-
A 6-membered one is preferable, and it can be saturated or unsaturated, or
It may or may not have aromaticity, and it may be a condensed ring.
The heterocycle may include, for example, an N-7 talimide group.
, N-phelic acid imide group, 4-N-urazolyl group, 1-
N-hyguntoynyl group, +3-N-2,4-dioquine group
xazolidinyl group, 2-N-1,1-nooxo-3-(
2H)-oxo-1,2-benzthiazolyl group, 1-pi
Lolyl group, 1-pyrrolidinyl group, 1-virazolyl group, 1
-pyrazolidinyl group, 1-piperidinyl group, 1-pyrroli
Nyl group, 1-imidazolyl group, 1-indolyl group, 1-
Indolyl group, 1-isoindolinyl group, 2-ynyne
Dryl group, 2-isoindolinyl group, 1-benzotria
Zolyl group, 1-pencyimigzolyl group, 1- (1,
2,4-triazolyl) group, 1- (1,,2,3-
) riazolyl) group, 1-(1,2,3,4-teFrazolyl)
) group, N-morpholinyl group, 1,2,3,4-tetra
Hydroquinolyl group, 2-oxo-1-pyrrolidinyl group,
2-IH-pyridone group, 7thalathion group, 2-oxo-
These heterocyclic groups include 1-piperidinyl group, etc.
Alkyl group, aryl group, alkyloxy group, aryl
Oxy group, acyl group, sulfonyl group, 7 alkylamino groups
, arylamino group, acylamino group, sulfonamide 7
group, carbamoyl group, sulfamoyl group, alkylthio
group, arylthio group, ureido group, alkoxycarbonyl group
group, aryloxycarbonyl group, imido group, nitro
group, cyano group, carboxyl group, halogen atom, etc.
May be replaced. Also, Za, Zb, Zc, Za', Z
a nitrogen-containing biplane ring formed by b' or Zc', and
These include virol ring, pyrazole ring, imidazole ring,
Riazole ring, thiazoline ring, oxazoline ring or tetra
Examples include torazol ring. An example of the heteroatom represented by Y2 is nitrogen. Za, Zb, Zc, Za', Zb'
or the nitrogen-containing heterocycle formed by Zc' may have
Examples of substituents include the substituents exemplified as Ra.
For example, the formula (a-1) (a
11) l(b 1)-(b-8), (e-1)-
R s z + R541Rs in (c-14)
s + Ra. 1ss-Rts +RttrRts
+ R* s t Rs s + Rs * ~R, o
When the substituent is not present, such as at the bonding position of
There is a coupler and a color developer at the position that has coupling ability.
A group that does not leave by reaction with the oxidized form of the image agent
Replace. (Ra" is Ra, Rh" is Rh, Rc- is Rc
, Rd” is Rd, Re” is Re, Rf” is R
f, Rg" is R, nl" is nl, nt'"
is n2, n, "is n, and n4'' is n, and ns" is
nS and n6''' are n@ and n7'' are n7 and Yl'''
Y, and Y2'' are Y2 and Y,'' are Y, and Y,''
is Y4, Y," is Y, Za" is Za, zb"
is synonymous with zb, and Zc'' is synonymous with Zc.
Of course, so-called screw-type couplers are also included in the present invention.
reactor. Coupler represented by general formula (a), (b) or (c)
Examples of polymer couplers derived from the formula (
having a coupler part represented by a), (b) or (c)
a monomer having an ethylenically unsaturated double bond, preferably an ethylenically unsaturated double bond.
homopolymerized monomer or copolymerized with other monomers
can be mentioned. Ingredients represented by the general formula (aL(tj) or (c))
Examples include the following: In addition, in the general formulas (,) to (c), oxidized products of color developing agents and
Substituents that do not leave during the reaction (e.g. Ra
-R1+ R++~Re5t Rs+-Ram is combined
(Rd'')n4"(Rg")nt" ■ -44("-9) General. (
alo) General formula (a-11) General formula (b-1) General formula (b-
2) General formula (b-3) General formula
(b-4) General formula (a-1) -
General formula (a-2) General formula (a3) -
General formula (a-4) General formula (a-5)
General formula (a-6) General formula (a-7)
General formula (a8) General formula (e-5)
General formula (c-6) General formula (c-7)
General formula (c-8) General formula (c-9)
General formula (clo) General formula (all)
General formula (c12) General formula (b-s)
General formula (b-6) General formula (b-7)
General formula (b-8) General formula (c-1)
General formula (c-2) General formula (c-3)
General formula (c-4) Formula (a-1)-(c”
14) In, Xal-Xaz is Xa, Xb, ~Xb
, is xb, XC1-XC14 is Xc, R+ +
-R2G is Ra, R51-R is R, and R21
~R2! is Re and R! 4- R75 is Rg and R
3g -R42 is Rf, R76~R9° is RE
They have the same meaning and are examples of the same kind. In addition, the compounds represented by each formula and the exemplified compounds shown below are
Each also includes tautomers. Expressed by formulas (,) to (c)
Among those, preferred are those represented by the formula (%) (c-10), (c-12),
Especially (a-3), (b-1), (c-3), (c-9)
, (c=10). Substituents on the heterocycle (e.g.
Ra - Rg + R11-R421R51-RIO)
The preferred ones are described below. When the coupler according to the present invention is used for positive image formation,
Xa=Xc, Xa, -Xaz Xb+-Xb*lXc. ~ Carbon 5 atoms adjacent to the carbon atom to which Xcz is bonded in general
Formula (c-13) General formula (c-14)
Sulfonyl group, sulfinyl group, phosphonyl group, carba
Moyl group, sulfamoyl group, cyano group, spiro compound
residue, bridged hydrocarbon compound residue, alkoxy group, aryl
oxy group, heterocyclic oxy group, siloxy group, acyloxy group,
xy group, carbamoyloxy group, ami7 group, 7silami
group, sulfonamide group, imide group, ureido group, sulfonamide group,
7 7 amoylamides, 7 alkoxycarbonyl amide groups,
Aryloxycarbonylamino group, alfukidicarbo
Nyl group, aryloxycarbonyl group, alkylthio group
, represents an arylthio group, a heterocyclic thio group, and R101
tRl. At least two of 2 and R1° are hydrogen atoms
isn't it. Also, two of the above R1゜11R102 and R6゜,
For example, R4゜1 and R102 are combined to be saturated or unsaturated.
rings (e.g. cycloalkanes, cycloalkenes, hetero
A ring) may also be formed, and the ring may further include R1°. may be combined to form a bridged hydrocarbon compound residue. R,,,-R,,,e k II 'Ah 3
M-71, certain 1± FNl! As a certain + substituent,
It is preferable that condition 1 below is satisfied, and it is more preferable that condition 1 is satisfied.
This is true when conditions 1 and 2 below are satisfied, especially when conditions 1 and 2 are satisfied.
It is preferable that conditions 1.2 and 3 below are satisfied.
Ru. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 Only one hydrogen atom is bonded to the carbon atom
, or not bonded at all. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.
This is the case. The most preferred substituents on the heterocycle are the following:
It is expressed by the general formula. General formula % formula % In the formula R,,,,R,. 2 and R1a3 are each hydrogen atoms
child, halogen atom, furkyl group, cycloalkyl group,
alkenyl group, cycloalkenyl group, alkynyl group, ali
two of the alkyl groups, heterocyclic groups, and acyl groups
group, where the other one is a hydrogen atom or an alkyl group
This is the case. Here, the alkyl and cycloalkyl further have a substituent.
The alkyl, the dichlorofurkyl and their substitutions may be
As a specific example of the group, Ra in the above general formula (,) is
Specifics of alkyl, cycloalkyl and their substituents
An example is given. In addition, substituents on the heterocycle (e.g. Ra-Rgw Rz~R
42+R51~R1°) is the following general formula
Those represented by are preferred. General formula % formula % In the formula, R1 is fullkylene, R2 is alkyl, cycloa
Represents Lukiru or 7 reels. The alkylene represented by R' is preferably a straight chain portion.
The number of carbon atoms is 2 or more, more preferably 3 to 6, and directly
Regardless of chain or branch, this fullkylene has no substituents.
May have. Examples of the substituent include R in the general formula (a) above.
When a is an alkyl group, the alkyl group may have
, R+o+ to R,, co
Examples and substituents that the group may have include the general
In the formula (,), Ra is a table, specific examples of groups and v substituents
can be mentioned. Also, for example, a ring formed by combining R1゜1 and R2゜2, and a bridged hydrocarbon formed by R1゜1 to R1゜3.
Specific examples of elementary compound residues and their optional substituents:
In the above general formula (a), Ra represents cyclo
Alkyl, cycloalkenyl, heterocyclic group, bridged hydrocarbon
Specific examples of elementary compound residues and their substituents are listed. Among the above general formulas, (i) R, is preferable. , where two of ~R+as are alkyl groups
(ii) one of R+o+ -R+os, e.g. R
,,. is a hydrogen atom, and the other two R1゜ and R3゜2 are connected.
together with the root carbon atom to form monocycloalkyl
If , then . Furthermore, among (i), preferred is R8°1 to R1°. The cycloalkyl group represented by R2 is 5 to 6 true ones.
is preferred, such as cyclohexyl. Alkyl and cycloalkyl represented by R2 have a substituent.
For example, the substituent to R' mentioned above and
The following are examples. Specifically, the aryl represented by R2 is phenyl.
, naphthyl. The 7-aryl group has a substituent
The substituent may be, for example, a linear or branched substituent.
In addition to alkyl, the above-mentioned substituents for R1
The following 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. Furthermore, when the coupler according to the present invention is used for negative image formation
, Xa-Xc, Xa, -Xaz, Xb, ~Xbs. The carbon atom adjacent to the carbon atom to which Xc, ~XC1, is bonded
As a child substituent, it is preferable that the following condition 1 is satisfied.
more preferable, if conditions 1 and 2 below are satisfied.
This is the case. Condition 1F] The root atom directly connected to the elementary ring may be a carbon atom.
Examples of substituents include those shown below. Preferred substituents include phenyl.
Ru. Preferred specific examples of alkylene represented by R1 are shown below.
show. The alkyl group represented by R2 may be linear or branched. Specifically, methyl, ethyl, propyl, iso-pro
Piruru, dodecyl, tetradecyl, hexadecyl, offtag
Examples include sil, 2-hexyldecyl, and the like. dicarbonyl group, furkylthio group, arylthio group,
Represents a terocyclic thio group. The group represented by R104 may have a substituent,
Specific examples of the group represented by R+114 and
As optional substituents, in the above general formula (,),
Specific examples of the group represented by Ra and substituents are listed. Preferred as R104 is a hydrogen atom or an alkyl group
It is. Specific examples of compounds used in the present invention are shown below. It is. Condition 2 At least two hydrogen atoms are bonded to the carbon atom.
ing. The most preferred substituents on the heterocycle are the following:
It is expressed by the general formula. General formula % formula % In the formula, R1゜i is a hydrogen atom, a halogen atom, an alkyl group
, cycloalkyl group, alkenyl group, cycloalkenyl
group, alkynyl group, aryl group, heterocyclic group, 7-ring group
, sulfonyl group, sulfinyl group, phosphonyl group, carbon
Bamoyl group, sulfamoyl group, sia7 group, spiro compound
residues, a-hydrocarbon compound residues, alkoxy groups, ants
ruoxy group, heterocyclic oxy group, siloxy group, 7-sil
Oxy group, carbamoyloxy group, ami7 group, acyl group
mino group, sulfonamide group, imide group, thuleido group,
7 amoylamino groups, 7 alkoxycarbonylamino groups
, 7 groups of 2aryloxycarbonylamide, alkoxycarbonate
The numbers in the rubonyl group and arylox table are as follows.
represents a group. CH= C2Hs
-(i) C-HtC4H* (t
) C4H* (i) C< Hs
- Cs H, Ca H+ --C, H2slo
11
12-C,,H2,-C,,H), -
C,, H3゜13 l4-
CH,N(C,H,)2-CH-2CH2N
H9O2C,, H23-(CHi)39Ozc+2Hz
s(t) −(CH2))S○2C12H2S
ico-CN-COCH,-COC,H. Cθ -COOC2H,' -COOC,H,, -CO
OC, 21 (2COOC1sH31F
CI BrNHCOC,jH2,-NHC
OC,,H,. -〇CH, -OC,H, -QC,,H,. -OCOC2H, -0COC(CH,). -3C,,,H,,-9C82COOH coupler of the present invention
The color tone of the colored dye depends on the arrangement of the ring atoms of the coupler.
Conditions such as location, type of substituent, and type of color developing agent, etc.
Although it can vary depending on the color, it is mainly magenta, a multicolor color
It can be used for photography, but it can be used for photographs with red tones.
, its light absorption properties are good, so it can be used for monochromatic color photography, etc.
It can be used for. The couplers of the present invention typically contain 1x per mole of halogenated system.
101 mol to 1 mol, preferably 1 x 10-2 mol-8
It can be used in the range of X 10-' moles. The coupler of the present invention may also be used with other types of magenta, such as those mentioned above.
The general formula [
XI] (hereinafter referred to as the dye image stabilizing compound of the present invention)
(referred to as a curing agent) will be explained below. General formula [XII] In general formula [XII], R2+, R22, R2 or
The alkyl group represented by R25 has 1 to 3 carbon atoms.
2, alkenyl group having 2 to 32 carbon atoms
, the cycloalkyl group has 3 to 12 carbon atoms, especially 5 to 12 carbon atoms.
7 is preferable, and the alkyl group and alkenyl group are straight chain
But it can also be a branch. A phenyl group is preferred as an aryl group.
However, J: is true even if it has a substituent. hetero lit
'A is preferably a 5- to 7-membered one, and is not substituted.
or may be condensed. J is an alkyl group represented by R2B, R27 and R28
The same applies to the aryl group represented by R26 and R26.
R 23 S1 benzene ring is in-substituted with I11 substituent, especially
Although not restricted, specifically halogen atoms, alkyl groups,
Alkenyl group, aryl group, aralkyl group, alkoxy
group, alkenoxy group, aryloxy group, alkylthio
group, aryldio group, acyl group, acyloxy group, acyl group
lylamino group, diacylamino group, alkylamino group, sulphate
Examples include sulfonamide group, alkoxycarbonyl group, etc.
be able to. Moreover, each group of R2+, R22, R24, and R25 mentioned above is
Including those with redeemable groups. As a substituent, for example, hydrogen
droxy l, alkoxy group, aryl l, acylamino
group, sulfonamide group, aryloxy group, carbamoy
Rulfonyl group, vinylsulfonyl group, nitro group, cyan group
, halogen atom, carboxyl group, amine group, alkyl
Amino group, alkoxycarbonyl group, acyl group, aryl group
to aminocarbonyloxy group, acyloxy group or
Specific examples include telocyclic groups and the like. Next, the dye image stabilization of the present invention represented by the general formula [XII]
Although typical examples of the curing agent are shown below, the present invention is not limited thereto.
It is not determined. The symbols in the exemplified compounds represent the following atoms or groups. (1) -H, (2) -CH, (3) -CF, (4
) -〇2H5, (5) -C5HI, (6) -0
CHs, (7) -0C,H1, (8) -0C,H,
,(9)-NH,,(10)-NHCH,,(b)
NHCuHzs, (12) -NHC+, Hzs
, (13) N(CH3h(27)-NHCOCH. HI-30 HI-31 Ut-1) The present invention represented by the general formula [XII] used in the present invention
A typical synthesis example of a bright dye image stabilizer is shown below. Synthesis Example 1 (Synthesis of Exemplified Compound 1-41-5) N-(4-
Phenyloxycarbonylamino-2,5-dibutoxy
phenyl)morpholine 10, N-(4-amino-2,5
-dibutoxyphenyl) morboline hydrochloride J! IQ, 81
0 and imidazole 0.17 (] to I. Ruene 501
and reacted under heating and reflux for 3 hours. After reaction, 1
Add water to 00112, extract with ethyl acetate, and wash twice with water.
After that, dry with anhydrous magnesium sulfate. Solvent under reduced pressure
The purple-white solid obtained was immediately treated with activated carbon, and then treated with methanol.
The crystals were recrystallized from a bottle to obtain 0.7 g of white crystals. Melting point 1
75-176'CFD mass spectrum (670),
NMR for both N,N'-bis(4-morpholino-2,5
-dibutoxyphenyl)urea. Elemental analysis value (C3□l-1,, N409>Theoretical value (%
) C: [16,2711~l: 8.71 N
: 8.3! i Experimental value (%) C: 66.18
1-1: 8.73 N: 8.40 Synthesis example 2
(Synthesis of Exemplified Compound H1-50) N,N-dimethyl-p
- 25 g of phenylene diamine dihydrochloride and 18 g of pyridine.
42 was stirred and mixed with 1001 fl of ethyl acetate. at room temperature
26.5Q p-dodecyloxybenzene with stirring
Add sulbonyl chloride and continue the reaction for 30 minutes. reaction solution
Pour into 5001g of water, and add 100% of ethyl acetate.
and extract it. After washing the ethyl acetate layer twice with water, it was washed with anhydrous sulfur.
Dry with sodium chloride. Ethyl acetate was distilled off under reduced pressure.
, n-hexane-ethyl acetate (10:
1) Add mixed solvent 3001Q. The obtained solid is meta
Recrystallized twice with alcohol to obtain white flocculent crystals of 25Q.
. Melting point 100-102℃ FD mass spectrum (456
), NMR revealed that N,N-dimethyl-4-(4-dode
siloxybenzenesulfonamide) aniline
I confirmed that. Original 1 analysis value (C261-14, N2 03 S)
1! J! Theory (Direct (%) C: 67.7
8 +-1: 8.75 N: 6.
08 Experimental value (%) C: 67.54 H: 8.
73 N: 6.06 Synthesis Example 3 (Exemplary Compound H1-
Synthesis of 7'8) N,N'-diphenyl-p-phenylene
Diamine 3g, dimethyl Ia Ff! ! 2.2iR,
Sodium hydrogen carbonate 1.95 (] to dimethylborumamide
Mix with 30112 and stir while keeping the internal temperature at 100℃.
React for 14 hours under stirring. Reaction attack, ethanolamine
The mixture was neutralized, poured into water, and extracted with 60 d of ethyl acetate. 2
Waterless after washing twice! ii Dry with IM magnesium. Under reduced pressure) solvent a was distilled off, and the resulting viscous solid was filtered into a column column.
After purification by Roma 1-graphy, ethyl acetate-n
- Recrystallized from hexane (1:20) mixed solvent to give 0,
White crystals of 35() were obtained. Melting point: 154°C FD mass
spectrum (288>, NMR shows that the above compound is N.N'-diphenyl-N, N'-dimethyl-p-phenylene
It was confirmed that it was a diamine. Elemental analysis value (02゜l-1: LoN) Theoretical value (%)
C: 83.291-1: 6.99 N2 97
1 Experimental value (%) C: 83.28 +1: 6.9
8 N: 9.73 The dye image stabilizer of the present invention is:
Preferably 5X per mole of the coupler of the present invention
10-2 to 5 mol, more preferably I X 10' to
It is used in the proportion of 3'Fnyl. In addition, the dye painting of the present invention
The image stabilizer is the same silver halide as the coupler of the invention.
It may be contained in the emulsion layer, but it is preferable that the capacitor of the present invention be contained in the emulsion layer.
The dye image stabilizer of the present invention and the dye image stabilizer of the present invention are contained in the same oil/water droplets.
contains. In the present invention, the capacitor of the present invention is dissolved in a high-boiling organic solvent.
The dye image stabilizer of the present invention is dissolved in a hydrophilic binder.
Added to silver halide emulsion layer after emulsifying and dispersing in a
can do. Low boiling point and/or water soluble in high boiling point organic solvents as required
It is dissolved using a neutral organic solvent, and a parent gelatin solution such as an aqueous gelatin solution is dissolved.
Stirrer, homogenizer using surfactant in aqueous binder
Nizer, Colloid Mill, Flojit Miki 1ner, Super
After emulsifying and dispersing using a dispersion means such as a sonic device,
It may be added to the hydrophilic colloid layer. dispersion liquid
or a process to remove low-boiling organic solvents at the same time as dispersion.
It's okay. 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 having a temperature of 150°C or higher is used. In the present invention, the coupler of the present invention and the dye image of the present invention
Can be preferably used when dispersing image stabilizers
High boiling point organic solvents include compounds with a dielectric constant of 6.0 or less.
For example, a phthalate ester with a dielectric constant of 6.0 or less
, phosphoric acid esters and other esters, yes! fil amides
, carbons, hydrocarbon compounds, etc. Preferably
The vapor pressure at 100℃ is 0 when the electrical constant is 60 or less and 1.9 or more.
．． It is a high boiling point organic solvent of 5 mm 1-10 or less. See you again
More preferably, the phthalate ester in the high-boiling organic solvent
or phosphoric acid esters. Furthermore, the high boiling point is charged
) The n-medium may be a mixture of two or more types. Note that the dielectric constant in the present invention is the dielectric constant at 30°0.
It shows the electric rate. Phthalate esters advantageously used in the present invention
Examples include b represented by the following general formula [IIIJ]
Ru. General formula [11] In the formula, R+s and R17 are an alkyl group and an alkyl group, respectively.
Represents a lekenyl group or an aryl group. However, R+s
The total number of carbon atoms in the groups represented by and R17 is 8 to
It is 32. More preferably, the total number of carbon atoms is
16 to 24. In the present invention, R+s and R of the general formula [11]
The alkyl group represented by I7 can be linear or branched.
For example, butyl group, pentyl group, hexyl group, 2
-ethylhexyl group, 3.5.5-trimethylhexyl
group, octyl group, decyl group, dodecyl group, tetradecyl group
group, hexadecyl group, octadecyl group, etc. RI6
Aryl 4 represented by and R17 is, for example, phenyl
alkenyl group, naphthyl group, etc., and alkenyl group is, for example,
xenyl group, heptenyl group, octaprenyl group, etc.
. These alkyl, alkenyl and aryl groups are
, containing single or multiple substituents, a
As ffi 1M group of alkyl group and alkenyl group,
, for example, halogen atoms, alkoxy groups, aryl groups,
lyloxy group, alkenyl group, alkoxycarbonyl
Examples of the substituents of the aryl group include
Halogen atom, alkyl group, alkoxy group, aryl group
, aryloxy group, alkenyl group, alkoxycarbo
Nyl group, etc. can be mentioned. In the above, preferably R+s and RI7 are
Kill group, for example 2-ethylhexyl group, 3.5.
5-trimethylhexyl group, n-octyl W, n-noni
and the like. Phosphate esters advantageously used in the present invention
Examples include those represented by the following general formula [IV]
. General formula [IV] In the formula, R+a, R+s and R20 are each an alkylene
represents an alkenyl group, an alkenyl group or an aryl group. However, carbon atoms represented by R+a, RI9 and R20
The total number of children is 24 to 54. Represented by R+a, Rls and R20 of general formula [1v]
Examples of alkyl groups include butyl, pentyl, and hexyl groups.
Syl group, 2-ethylhexyl group, heptyl group, nonyl group
, decyl group, dodecyl group, tetradecyl group, hexadecyl group
group, octadecyl group, nonadecyl group, etc.
Examples of the group include phenyl group, naphthyl group, etc.
, and alkenyl groups include, for example, hexenyl group, hexenyl group,
These include a putenyl group and an octadecenyl group. These alkyl, alkenyl and aryl groups are
, those having single or multiple substituents are also included. Like
Or R+a, R+9 and R20 are alkyl groups
, for example, 2-ethylhexyl group, n-octyl! j,
3,5.5-1~limethylhexyl L (, lononyl group
, n-decyl group, 58C-decyl group, 5ec-dodecyl
group, and octyl group. Typical high boiling point organic solvents used in the present invention are listed below.
Although examples are shown, the present invention is not limited to these.
stomach. Exemplary Takasu Point Aribetsu) 8 medium S-2CaHs C, I-1. S-12C, Hs ■ 0C*H+s(+) 0"P 0-CsH+*(ri0-CsH+5(i) 0-CsH+5(n) ■ 0=P-0-C,H,1(n) 0- C,)(,,(n) O-C,.H,,(i) 0=p-o-c,.H,,(i) 〇-C1゜14□,(i) 0C1゜1(21 (n) 0=P−○−C+ol−IH(n) 0−C,,H2,(n) 0C11Hzs(i) oc+!H!5(i) Similar to the dye image stabilizer of the present invention Amine compounds are
Japanese Patent Publication No. 47-47245, Japanese Patent Publication No. 158-1051
No. 47, No. 50-229557@. In the above-mentioned Japanese Patent Publication No. 47-47245, an amine compound is
For preventing photobleaching of zometine dyes and indoaniline dyes
It is stated that it is effective. However, 5-
Those for azomethine dyes derived from vilazolone
The anti-fading effect of the amine compound is superior to that of other anti-fading agents.
It was significantly inferior in comparison. Also, the above-mentioned Unexamined Publication 1t! l 5g-105147 and
In the same No. 59-229557, two amine compounds were produced.
When used with the pyrazolone magenta coupler, processing
To prevent magentastin in unexposed areas that occurs when
It is said that it is effective. However, certainly
Although it has the effect of preventing magentastin, it is affected by light.
The amine compound itself changes color to yellow, causing Y-stain.
It has the disadvantage that it increases. 11++ Record h'f public'Ml 47-47245@ni
Lj, amine compounds are colored and discolored like ultraviolet absorbers.
Although it is stated that it will not cause problems, image quality is very important.
In recent photosensitive materials, the coloring of amine compounds is
It cannot be ignored. In addition, amine compounds are
For use with Lazolon magenta coupler. and decrease sensitivity
It has the serious drawback of causing
It was not used in color paper sensitive materials. Also, British Patent No. 803.783, British Patent No. 106.90
No. 6, West German Patent No. M 1,159,758, 1.2
No. 00.679, U.S. Patent No. 2,695,234,
No. 3,342,597, No. 4.060,418,
Rinarch Disclosure V-N 0.12146, same
N O, 13924, Special Publication No. 58-14671, 5
No. 8-14672, JP-A-57-76543, JP-A No. 57
-179842, 58-1139, 58-11
40@, 59-81643@, etc., aromatic first
It is incorporated into light-sensitive materials as a precursor of grade amine developing agents.
There is a known technology. However, these
Using the compound with a 5-pyrazolone type magenta coupler
However, compared to conventionally known compounds, the produced pigment has better photobleaching resistance.
The stopping effect is poor. Thus, based on the knowledge of these technologies, the coupler of the present invention
Only when used together with the present invention, significant fading prevention
It has a protective effect and eliminates the traditional drawbacks of yellowing and texture.
It is completely impossible to predict that there will be no decline in the level of
I couldn't come. Generally, the dye image obtained from the couplers of this invention is
Not only does it show significant discoloration, but it also shows significant discoloration due to light.
and the color tone of the dye image changes. Dye image stabilization represented by the general formula [XI] of the present invention
The agent prevents photobleaching and photobleaching of the dye image obtained from the coupler.
Conventional phenolic and phenol-based
Effects that cannot be achieved with nyl ether dye image stabilizers
have. The coupler of the present invention and the general formula [XII] of the present invention
compounds are used in the same layer, but if the coupler is present
The compound may also be used in a layer adjacent to the existing layer. The silver halide photographic sensitivity +A advantage of the present invention is, for example, color
negative and positive film, color photographic paper, etc.
However, Toriwa GJ is provided for direct viewing.
The effect of the method of the present invention is effective when color photographic paper is used.
Demonstrated. Silver halide of the present invention including this color photographic paper
Photographic materials can be single-color or multi-color.
stomach. In the case of multicolor silver halide photographic materials, color reduction
In order to reproduce legal colors, usually - is used as a photographic color.
Contains magenta, yellow, and cyan couplers.
A silver halide emulsion layer and a non-photosensitive layer are formed on the support.
Although it has a laminated structure with an appropriate number of layers and layer order,
The number and order of layers may be changed as appropriate depending on the important performance and purpose of use.
It's okay. Halogen used in the silver halide photographic material of the present invention
The silver bromide emulsion contains silver bromide and iodobromide as silver halides.
Common halides such as silver, silver iodochloride, silver chlorobromide, and silver chloride
Any material used in silver emulsions can be used.
. The silver halide grains used in silver halide emulsions are
1 for either sex method, neutral method, or ammonia method! ? was given
The particles may be grown all at once, or they may be seeded.
After creating particles, growth may be avoided. create seed particles
The method and growing method may be the same or different.
stomach. Silver halide emulsions simultaneously contain halide ions and silver ions.
Even if mixed, if one exists, the other is mixed.
Even if I do, J: No. Also, the critical growth rate of silver halide crystals
While considering the above, the halide ions and silver ions are
1) l-1, 1) Sequentially and simultaneously while controlling ACI
It may also be generated by adding it to. Con after growth
Using the version method, the halogen composition of the particles is changed.
It's okay. 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. The silver halide grains used in silver halide emulsions are
During the process of forming and/or growing offspring, the cadaver
Mium salt, zinc 1n,! ()j! , thallium'n, iri
Dium salt or complex salt, rhodium salt or complex salt, iron salt or 8H
Add metal ions to the inside of the particles and/or
can be encapsulated on the particle surface, and in an appropriate reducing atmosphere.
By keeping it in an atmosphere, it is possible to reduce the amount of return inside the particles and/or on the particle surface.
Original sensitizing nuclei can be added. The silver halide emulsion is produced after the growth of silver halide grains.
You can remove unnecessary soluble salts or
You can leave it as is. When removing the salts, use a reservoir.
Based on the method described in H. Disclosure No. 17643.
It can be done by The silver halide grains used in silver halide emulsions are
The part and surface may consist of uniform layers, or may consist of different layers.
It may consist of Silver halide grains used in silver halide emulsions are
Particles may be such that the image is mainly formed on the surface.
In addition, even particles that are formed mainly inside the particles
good. The silver halide grains used in silver halide emulsions are
It may have a regular crystal shape, or it may have a spherical or plate shape.
It may also have an irregular crystal shape. These particles
and the ratio of the (100) plane to the (b1) plane is arbitrary.
can be used. Also, it has a composite form of these crystal forms.
Particles of various crystal shapes may be mixed. A silver halide emulsion consists of two or more halide emulsions formed separately.
A mixture of silver germide emulsions may also be used. The silver halide emulsion is chemically sensitized by conventional methods. That is,
, compounds containing sulfur that can react with silver ions, and activated gelatin.
Sulfur sensitization method using Chin, Hiren using selenium compound
sensitization method, reduction 11 sensitization method using reducing substances, gold and other
Noble metal sensitization method using noble metal compounds can be used alone or in combination.
Can be used together. Silver halide emulsions are used as sensitizing dyes in the photographic industry.
Optically enhances the desired wavelength range using known dyes.
I can feel it. Sensitizing dyes may be used alone, but two or more types may be used.
It is better to use them in combination. itself with sensitizing dye
Spectral 11 Irregular dyes that have a sensitizing effect or visible light
A compound that does not absorb substantially and is used to sensitize sensitizing dyes.
A supersensitizer may be included in the emulsion to enhance the effect. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
or prevention of fog during photographic processing and/or photographic performance.
During chemical ripening and/or
At the end of chemical ripening and/or after the end of chemical ripening, halo
By the time a silver gen- ide emulsion was applied, the photographic industry had
Adding compounds known as anti-reactive agents or stabilizers
I can do things. Silver halide emulsion binder (or protective colloid)
In this case, it is advantageous to use gelatin, but other
Graphs of gelatin derivatives, gelatin and other polymers (−
Polymers, proteins, sugar derivatives, gelatin derivatives, single
Hydrophilicity of synthetic hydrophilic polymer substances such as polymers or copolymers
You can also use colloids. The photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention;
The other hydrophilic colloid layer is a binder (or protective colloid).
D) A hardening agent that crosslinks molecules and increases film strength alone or
When used together, it hardens. The hardening agent is added to the processing solution.
The photosensitive material can be hardened to such an extent that it is not necessary to add a hardening agent.
It is preferable to add a hardening agent to the processing solution.
It is also possible to Silver halide emulsion of the silver halide photographic light-sensitive material of the present invention
to increase the flexibility of the layer and/or other hydrophilic colloid layers.
A plasticizer can be added to the material. Photographic emulsion layer and others of the silver halide photographic light-sensitive material of the present invention
For the purpose of improving dimensional stability etc. in the hydrophilic colloid layer of
A dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer is prepared by
can contain The emulsion layer of the silver halide photographic light-sensitive material of the present invention contains color-forming
In the development process, an aromatic primary amine developer (e.g.
p-phenylenediamine derivatives and aminophenol derivatives
Coupling reaction with oxidized material (conductor, etc.) to form dye
A dye-forming coupler is used. As yellow dye-forming couplers, acylace 1 to acylace
Midocouplers (e.g. benzoylacetanilides,
Viva Oylacetanilides), magenta pigment-forming caps
In addition to the coupler of the present invention, 5-pyrazolone can be used as the coupler.
coupler, pyrazolobenzimidazole coupler, pira
Zolotriazole, open chain acylacetonitrile coupler
etc., and as a cyan dye-forming coupler, Naphthol
There are couplers, phenol couplers, etc. These dye-forming couplers have a so-called Balas 1-group in their molecules.
has a group having 8 or more carbon atoms that makes the coupler non-diffusive.
It is desirable to Also, these dye-forming couplers
Four silver ions are reduced to form the child pigment.
4 Even if it is true that two silver ions are reduced
It doesn't matter if it's a 1-no or a 2-win. Between the emulsion layers of the color photographic material of the present invention (between the same color-sensitive layers)
and/or between different color-sensitive layers), the oxidized form of the developing agent or
may cause the electron transfer agent to migrate, causing color turbidity or poor sharpness.
Color anti-fogging agent to prevent visible graininess and graininess.
is used. The 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 layer.
. Parents of the protective layer, intermediate layer, etc. of the silver halide photosensitive material of the present invention
This is caused by the photosensitive material becoming electrically charged on the aqueous colloid layer due to friction, etc.
Prevents fogging due to electric discharge, and prevents the image from becoming exposed to LJ and V light.
May contain ultraviolet absorber to prevent deterioration
. The silver halide photographic material of the present invention may optionally contain
filter layer, antihalation layer, and/or irradiation layer
An auxiliary layer such as an oxidation prevention layer can be provided. this
In the layers and/or emulsion layers, color is added during development.
Contains dyes that are leached from the photosensitive material or bleached.
It's good to have it. Silver halide emulsion of the silver halide photographic light-sensitive material of the present invention
layer and/or the hydrophilic colloid layer of the photosensitive material.
The goal is to reduce gloss, improve retouchability, and prevent mutual nailing of sensitive materials.
A matting agent can be added as a matting agent. Invention J) Reducing sliding friction of silver halide photographic materials
To avoid this, lubricants can be added. The silver halide photosensitive material of the present invention has antistatic properties [L].
Antistatic agents can be added. The antistatic agent is the milk of the support.
It is sometimes used as an antistatic layer on the side where no agent is laminated.
The emulsion layer is laminated to the emulsion layer and/or the support.
Even if it is used in a protective colloid layer other than the emulsion layer on the
good. The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Or, the hydrophilic colloid layer has improved coating properties and antistatic properties.
, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (promotion of development)
, high contrast, sensitization, etc.) for the purpose of improving photographic characteristics, etc.
Various surfactants are used. The silver halide photographic light-sensitive material of the present invention includes a photographic emulsion layer,
Other layers are made of baryta paper or α-olefin polymerer, etc.
Flexible reflective support such as laminated paper, synthetic paper, vinegar
Acid cellulose, nitrate cellulose, polystyrene, polysalt
vinyl chloride, polyethylene terephthalate 1~, polycarbonate
Made of semi-synthetic or synthetic polymers such as nates, polyamides, etc.
Apply to Phil 18, rigid bodies such as glass, metal, ceramics, etc.
I can do it. The silver halide photosensitive material of the present invention can be used as a support if necessary.
After the surface has been subjected to corona discharge, ultraviolet irradiation, flame treatment, etc.
, directly or (adhesiveness, antistatic property, dimensional stability of the support surface)
properties, wear resistance, hardness, antihalation properties, friction properties
, and/or other properties to 1 or
may be applied via two or more subbing layers). When coating the silver halide photographic light-sensitive material of the present invention,
A thickener may be used to improve fabric properties. Application method and
It is an extruder that allows you to apply two or more layers at the same time.
1-1 Lusion coating and curtain coating
is particularly useful. The silver halide photographic light-sensitive material of the present invention is a silver halide photographic material of the present invention.
The emulsion layer constituting the silveride photographic light-sensitive material has a degree of
Exposure can be performed using electromagnetic waves in the spectral range. light source and
Natural light (sunlight), tungsten electric light, fluorescent light,
Mercury lamp, xenon arc lamp, carbon arc lamp, xenon lamp
Rush lamps, cathode ray tube flying sub 1-1 various lights
laser light, light emitting diode light, electron beam, XtlA, 7-ray,
Light emitted from a phosphor excited by alpha rays, etc.
Any known light source can be used. The exposure time is usually between 1 millisecond and 1 second, which is used in cameras.
Of course, the exposure time is 1 microsecond or less, for example
100 microseconds using a cathode ray tube or xenon flash lamp
Exposures of ~1 microsecond can be used;
Longer exposures are also possible. The exposure is carried out continuously.
It may be carried out at regular intervals or intermittently. The silver halide photographic light-sensitive material of the present invention is a photosensitive material known in the art.
Images can be formed by color development processing.
Ru. The color developing agent used in the color developer in the present invention is
, widely used in various color photographic processes.
This includes those known in the art. These developers are amine phenolic and p-phenylene
Contains diamine derivatives. These compounds are free
generally in salt form, e.g. hydrochloride or
1ial'l! Used in salt form. Also, these changes
The compound generally has an amount of about 0.1a to about 3
0o ma, preferably about 1 g per 1 color developer
Use at a concentration of ~15o. As the aminophenol developer, for example, 0-amine
Phenol, p-aminephenol, 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.
Even if it is, J: No. Among them, what are some examples of particularly useful compounds?
is N,N'-diethyl-〇-phI nylenediamine salt
M 3g, N-methyl-p-phenylenediamine hydrochloride
, N,N'-dimethyl-p-phenylenediamine salt M
salt, 2-amino-5-(N-ethyl-N-dodecyl
(min)-1~luene, N-ethyl-N-β-methanesulfate
Honamidoethyl-3-methyl-4-aminoaniline sulfur
m salt, N-ethyl-N-β-human 0xethyl-amino
Aniline, 4-amino-3-methyl-N. N'-diethylaniline, 4-amino-N-(2-meth
xyethyl)-N-ethyl-3-methylaniline-o-
Examples include toluene sulfonate. Applied to the processing of the silver halide photographic material of the present invention
The color developer includes the above-mentioned primary aromatic amine color developer.
In addition to the developer, well-known developer component compounds can be added.
can. For example, mono-lithium hydroxide, sodium carbonate,
Alkaline agents such as potassium carbonate, alkali metal sulfite MF
, alkali metal bisulfites, alkali metal thiocyanates
salts, alkali metal halides, benzyl alcohol,
It is also possible to optionally contain water softeners, thickeners, etc.
can. The pt- value of the color developer is usually 7 or more, most
Generally from about 10 to about 13. The silver halide photographic light-sensitive material according to the present invention has a hydrophilic colorant.
These color developing agents are contained in the id layer.
Contains it as a precursor or its precursor, and
Treated with a potash activation bath bT-giru 11 shots
The developing agent breaker is produced under alkaline production F1.
A compound that produces color developing agents and is an aromatic aldehyde.
Schiff-based precursors and polyvalent metal derivatives
on-complex brecary, phthalic acid imide derivative precary
-→ner, phosphoric acid amide derivative precursor, sugar
Amine reactant precursor, urethane type breaker
can be mentioned. These aromatic primary amine color developing agents
For example, the precursor of U.S. Pat.
No. 9, No. 2,507,114, No. 2,695゜2
No. 34, No. 3,719,492, UK] 1 Patent No. 80
Specifications of No. 3.783, JP-A-53-185628@
, Publications No. 54-79035, Lizard Disk
Logi T Sea Magazine No. 15159, No. 12146, No. 13
No. 924. These aromatic primary amine coloring agents or their blends
For the car folding machine, if it is activated, its M is enough.
It is necessary to add as much as possible to obtain the desired color development. This out
Although it depends on the type of photosensitive material, it is generally a halo.
01 to 5 moles of darkness per mole of tJi, preferably
Preferably, it is used in a range of 0.5 mol to 3 mol. this
These color developing crude drugs or their precursors can be used alone or
can also be used in combination. built into photosensitive material
Use a suitable solution such as water, methanol, ethanol, acetone, etc.
It can also be added dissolved in a solvent, and dibutyl phthalate can also be added.
ate, dioctyl phthalate, tricresyl phosphate
Added as an emulsified dispersion using a boiling point organic solvent such as
Reach Disclosure Magazine 14
to latex polymers as described in No. 850.
It can also be added by impregnation. The silver halide photographic light-sensitive material of the present invention is free from bleaching after color development.
Whitening processing and fixing processing are applied. The bleaching process is the same as the fixing process.
You can go at any time. Many compounds are used as bleaching agents.
Among them, iron (DI>), cobalt (■), copper (I)
polyvalent metal compounds such as, especially these polyvalent metal cations.
complex salts of organic acids such as ethylenediaminetetraacetic acid,
Trilotriacetate '111N-Hydroxyethylethylenedia
Aminopolycarboxylic acids such as minnielacetic acid, malonic acid,
Tartaric acid, malic acid, diglycolic acid, dithioglycol
Gold such as acid l1iK! iI salt or ferricyanate
U are used alone or in appropriate combinations such as dichromates, dichromates, etc.
I can stay. As a fixing agent, silver halide is solubilized as Ilm.
A soluble complexing agent is used. As this soluble complexing agent
For example, sodium thiosulfate, ammonium thia 1sulfate
um, potassium thiocyanate, chia 1F;! Moto, Thioe
-Tel etc. After the fixing process, a washing process is usually performed. In addition, stabilization treatment may be performed as substitute fermentation for water washing treatment.
However, both may be used together. Safety used in stabilization treatment
The stabilizer contains pl-1wA stabilizer, chelating agent, and anti-piping agent.
, etc. can be included. These specific articles PI
JP-A-58-134636, etc.
Effects] The silver halide photographic light-sensitive material of the present invention has /ff history all
'Excellent Ig4 polarity and remarkable light fastness of dye images
Specifically, discoloration and fading due to light are significantly suppressed.
control and effectively prevents Y-stain from occurring in uncolored areas.
It will be stopped. [Specific Examples of the Invention] The present invention will be specifically explained below with reference to Examples.
The embodiments described herein are not limited to this. Example 1 Gelatin on a paper support laminated on both sides with polyethylene
Chin (15, Omo/100 clt), Table-1
Couplers of the invention shown below or comparative couplers shown below
(6, (1ma/100 C1') and Table-1
The dye image stabilizer of the present invention or the comparative dye image stabilizer shown in
Add the fixing agent to the coupler in equal molar amounts to a high-boiling organic solvent.
(Example S-2) (5,0 mL' 100 c
v) After dissolving and emulsifying and dispersing, silver chlorobromide emulsion (silver bromide
Samples 1 to 25 were mixed with 80 mol%), coated and dried.
I got it. Comparison 11 Blur (b Comparison coupler (2) Comparison coupler (3) Ls11++l'll Comparison coupler (4) l Comparison color 7fi KN (#Mistable ratio agent PH-1 comparison color
Basic LTN image stabilizer PH-2 The sample obtained above was exposed to light using an optical microscope according to a conventional method.
The treatment was carried out in the following steps. [Processing process] Processing temperature Processing time Color development
Bleach fixing at 33℃ for 3 minutes and 30 seconds
Wash with water at 33℃ for 3 minutes and 30 seconds
Dry at 33℃ for 3 minutes 5
0 to 80℃ for 2 minutes The components of each treatment solution are as follows.
It is. [Color development stock solution] Benzyl alcohol 121Q diethyl
Ren glycol 1011 tansankali
Um 25 Q Sodium Bromide
0.6g anhydrous sodium sulfite
2.0g hydroxylamine Ii acid m
2,5 gN-ethyl-N-β-methane
Sulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.50 Add water
and adjust the pH to 10.2 with sodium hydroxide.
. [Bleach-fix solution] Ammonium thiosulfate 120g Metabiite
Sodium sulfate 15 tel anhydrous sulfite
Sodium 3g EDTA ferric ammonium
Ni salt 65Q Add water to make it 11, and make DH 6
．． Adjust to 1-6.8. Samples 1 to 14 processed above were sampled in a degree system (Roku Konishi Photography).
The concentration was adjusted under the following conditions using
It was measured with Each of the above treated samples was placed on an underglass outdoor sunlight exposure table.
After 12 days of exposure, the light fastness of the dye image and the Y-
I looked into Stin (YS). The results obtained are shown in Table 1.
vinegar. However, the evaluation of each item of light fastness of dye images is as follows.
be. [Residual rate] Percentage of dye remaining after light release test for initial density 1.0
. [YS] From the concentration of Y-stin after the light fastness test, the Y before the light fastness test
- minus the concentration of Stain. [Degree of discoloration] Lightfastness test at initial density 1.0 (yellow density)/
(magenta density) to yellow density before sidelight test)/
(magenta density) is subtracted, and the larger this value is, the more
, the color tone tends to change from magenta to yellowish.
means. [Spectral absorption characteristics] The spectral reflection spectrum of the obtained colored sample is converted into a color analyzer.
Measurement was performed using Iser 607 model (manufactured by Hitachi Seisakusho). child
In this case, the maximum concentration of the absorption spectrum in the visible region of each sample is set to 1.
The measurement was normalized to 0. At 430 nm for each sample
The reflection density was used as a secondary absorption index for each purity. [Sensitivity] Perform sensitometry using a conventional method to determine the sensitivity of each sample.
Expressed as relative sensitivity. Table-1 As is clear from Table 1, the present invention has low secondary absorption.
Sample 13.16.19 made using coupler is
, the conventional 4-concave 3-anilino-5-pyrazolone type car
Trial 111.4 made using puller and inductor
Compared to sample 7 made using a Chiron type coupler,
It was found that Y-stin is extremely unlikely to occur in the side light test.
However, the residual rate and degree of discoloration of the dye image area in the side light test
It can be seen that the color easily changes and fades when exposed to light. Also, from sample 2.5.8.11, it is expressed by the general formula [X■]
The dye image stabilizer of the present invention is a conventional 5-pyrazolo
Combination with in-type couplers and indashilon-type couplers
Y-Steel does not have much anti-fading effect;
It can be seen that this results in a decrease in sensitivity and a decrease in sensitivity. On the other hand, the coupler of the present invention and the general formula [XII]
Sample 14 prepared using the dye image stabilizer of the present invention
．． On 17.20.22.23.24.25, in the secondary light test
There is little discoloration or fading of the dye image, and the Y-scale of uncolored areas is small.
There is almost no tinting, and there is no decrease in sensitivity.
It turns out that there isn't. Example 2 Combinations of couplers and dye image stabilizers are shown in Table 2.
The sample was applied and tested in exactly the same manner as in Example 1, except for the following changes.
created a fee. Each sample was treated as described in Example 1.
and measured the sensitivity. Furthermore, the treated sample was treated in the same manner as in Example 1.
A light resistance test was conducted in the same manner, and the results shown in Table 2 were obtained. As is clear from Table 2, the coupler of the present invention has the general formula
Using the dye image stabilizer of the present invention represented by [XII]
Samples 27 to 32 prepared using conventional dye image stabilization
Compared to sample 26 prepared using
There is little discoloration or fading of the dye image, and the Y-scale of uncolored areas is small.
Almost no tinting occurs and no decrease in sensitivity occurs.
I understand that. <Example 3> Coating liquids for each layer were prepared so as to have the composition shown in Tables 3 and 4.
Multi-layer silver halide color is coated sequentially from the support side.
- Created a photosensitive material. Each sample was prepared in the same manner as in Example 1.
After exposure and processing, both light test (andoglass outdoor sunlight
Exposure rA) was performed for 35 days on an exposure table. Table 4 shows the results.
Shown below. Table-3 Layer 7 layers for composition Gelatin (1, Oo /f> (protective layer) 6th layer Gelatin (1,0 (1/f) (3rd intermediate layer)
Layer) Ultraviolet absorber UV-1 (0,2 (1/v2) LJV-2 (0,1 (] /1') HQ-1 (0,020/w') High boiling point solvent (Example S-6) (0,2 (1/ml') 5th layer Gelatin (1,2a/v') (red sensitive layer
) Silver chlorobromide emulsion [containing 70 mol% A (+8r) (silver mine 0.25 g/1') Cyan coupler [C-1/C-2] (0.4 mol per mol of silver halide) IQ
1 (0,01(1/i') high boiling point solvent (example)
S-2) (0,20/1') 4th layer Gelatin (1,5 (1/v2) (3rd intermediate
Layer) Ultraviolet absorber UV-1 (0,50/v') UV-2 (0,2 (1/TI') HQ-1 (0,03 (+/v'') m1 point solvent (Example S-6 ) (0,3ri/v') 3rd layer Gelatin (1,50/12) (green-sensing layer)
Silver chlorobromide emulsion [containing 70 mol% AoBr] Content 0.2 (1/f) Magenta Cabra [Table 41 (0,4Q/f) General formula [XII] Compound c Table 4] ( Additions shown in Table-4) High boiling point solvent (Example S-2) (0,25 (1/1') 2nd layer Gelatin (1,0 (1/12) (1st intermediate)
layer) HQ-1 (0.07 (1/l') high boiling point solvent
(Example S-7) (0,04!l/i') 1st layer Gelatin (2,0g/*') (blue sensitive layer)
Silver chlorobromide emulsion (!! fit 0.3/ri') yellow coupler
-Y-1 (0.8g/f) HQ -1(0.02(1/i') High boiling point solvent (e.g.
Figure S-6) (0°3a/f) Support Polyethylene coated paper () The numbers in parentheses represent coating ω or addition m. 9 /)) fr,'j&n* tl;t 1il(
UV-1) (UV-2) (IGL-1) (C-2) From these results, the dye image stabilizer of the present invention was prepared in Example-1.
Similar to the single-layer sample in 2, this phenomenon also occurred in the multi-layer sample.
Bright couplers are effective in dye image stabilization, resulting in
becomes larger as the amount added increases. Example 4 5th layer, 3rd layer and 11t! Silver halide emulsion of J
A silver halide emulsion with a silver chloride content of 100% was used.
Coated in exactly the same manner as Samples 33 to 42 of Example 3 except that
Samples 33' to 42' were prepared. Each sample is shown below
After rapid processing using various methods, a double-light test similar to Example 3 was carried out.
The result is 19, which is not shown in Table-5. [! i! 1 Process] Temperature Time For color development 9 34.7±0.3℃ 50 seconds bleach fixing
34.7±0.5℃ Stabilized for 50 seconds 30~34
℃ 90 seconds drying 60-80℃ 60 seconds [
Color developer] Pure water
800d ethylene glycol
10dN, N-diethylhydroxylamine
10 (1 chloride 2
9N-edyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 5g tetrapo
Sodium lyphosphate 2g potassium carbonate
309 optical brightener (4,4'
-diaminostilbendisulfone M derivative) 1g pure water
Add to make the total number 11, and adjust to I) Hlo, 08.
. (Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate 2 parts water 1? Aso g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) ioo,,
g Ammonium sulfite (40% solution) 27.5.
g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water.
In addition, all ■ are set to 12. (Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1Q1-hydro
Add 2g of xyethylidene-1゜1-diphosphonic acid and water.
to 12, g (pI- with FIJ or potassium hydroxide)
Adjust 1 to 7.0. From Table 5, silver chloride is added to the silver halide photographic light-sensitive material of the present invention.
Quickly using a silver halide emulsion with a content of 100T nil%
The effect of the present invention on the couplers of the present invention even when treated.
The effect of the dye image stabilizer was the same as in Example-3.
I understand that. Patent applicant Konishiroku Photo Industry Co., Ltd. Procedure 1. ? III iF Shini (1 year old) 1986 09
June 018 Commissioner of the Patent Office Kuro ITI Akio-dono 2, Name of the invention Silver halide photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo N1 Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Hitter Keio 4, Agent 102 Address 4-1 Kudankita, Chiyoda-ku, Tokyo January Kudan-Ro
Saka Building Telephone 263-9524 Specification 4 “2. Claims” and [3. Details of the invention
Column 6 of ``Explanation'', content of amendment <I> ``2. Scope of Claims'' of M.A. is supplemented as shown in the attached sheet.
Correct. (If) The column “3. Detailed description of the invention” in Book 10 of Meiji is as follows.
Correct as shown below. 1. The structural formula of general formula (C) on page 13 of the specification is as follows:
to correct. 2. The structural formula of general formula (C) on page 13 of the specification is as follows:
to correct. 3. The structural formula of general formula (C') on page 34 of Mei M is as follows.
Correct it accordingly. (Rg'nn, J to 14, the structural formula at the bottom of page 46 of Specification 1 has been corrected as follows.
do. (Rg")rtt" 5, Mei II page 49 The structural formula of general formula (C-9) is as follows.
I will correct it accordingly. 6, the structural formula of the general formula in the margin of the table on page 61 of MeiSaS is as follows.
Correct as shown below. Claims: A support having at least 11 silver halide emulsion layers.
In the silver halide photographic light-sensitive material, the halogen
At least one of the silveride emulsion layers has the following general formula (a),
Select from the couplers shown in (b) and (C), respectively.
at least one coupler and/or said coupler
Polymer couplers derived from
Contains at least one compound represented by [X J[]
A silver halide photographic light-sensitive material characterized by: General formula Ca) General formula (1)) General formula (C) [In general formulas (a), (I]) and (C), Za. zb and zC are each necessary for forming a nitrogen-containing heterocycle.
It does not represent any essential non-metallic atomic groups. Xa, xb and Xc are
Reactions with hydrogen atoms or oxidized products of color developing agents, respectively.
It then leaves and represents the group 1q. Ra, Rb, Rc, Rd, Re, Rr and Ru are
Each represents a hydrogen atom or a substituent. However, R (l is one
Oxidized product of coupler represented by general formula (C) and color developing agent
It is a substituent that does not separate during the reaction with
Ru. Yl represents a carbon atom or a nitrogen atom. Y2 is
rA represents a hydrogen atom or a heteroatom. = is Yl and Y2
The bond between may be a single bond or a double bond.
represents something. However, Yl is a carbon atom and the bond between Yl and Y2 is double
In the case of a bond, n3 is 1, n4 is O, and Rc
is a coupler represented by general formula (a) and a color developing agent
A substituent that does not leave when reacting with the oxidant of
Yes, Yl is a carbon atom and the bond between Yl and Y2 is a single bond
In the case of , both mouth 3 and n are 1. Also, Y1 is nitrogen
If the bond between Yl and Y2 is a double bond in the atom, n3 and
n, are both 0, and Y2 is a heteroatom,
If Yl is a nitrogen atom and the bond between Yl and Y2 is a single bond,
In this case, n3 is 1 and n is O. Note that caps represented by general formulas (a), (b) and (C)
ra is the position where Xa is bonded and xb is bonded, respectively.
Color development occurs only at the positions where
Coupling reaction with oxidized image agent. ] The following margin/blank -fir: 211 General formula [Xn] [In the formula, R2+ and R22 are each a hydrogen atom, an alkyl atom,
group, cycloalkyl group, alkenyl group, aryl group or
or a heterocyclic group, and R23 represents a substituent. R
24 is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkyl group,
represents a kenyl group, an aryl group or a heterocyclic group, and R2
5 is an alkyl group, cycloalkyl group, alkenyl group, alkyl group,
Does not represent a aryl group or a heterocyclic group. J is R26 and R27 are each a hydrogen atom or an alkyl group
and R28 represents an alkyl group or an aryl group.
vinegar. l represents O or an integer from 1 to 4, m represents 0 or
1, and n represents Oll or 2. R21 and R
22 may be the same or different, and can be combined with each other to form a 5-membered
A six-membered ring may also be formed. Also, when l is 2 or more,
Several R23s may be the same or different, R21 or
/ and R22, and a bond to R21 or R22
may form a 5- or 6-membered ring with the nitrogen atom,
There are no 5 shells along with the nitrogen atoms bonded to R24 and R2+
Alternatively, a 6-membered ring may be formed. ]

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula (a), (
At least one coupler selected from the couplers shown in b) and (c) and/or a polymer coupler derived from the coupler, and the following general formula [
A silver halide photographic material containing at least one compound represented by [XII]. General formula (a) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (b) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (c) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [General formula (a) ), (b) and (c), Za, Zb and Zc each represent a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle. Xa, Xb and Xc each represent a hydrogen atom or a group that can be separated upon reaction with an oxidized form of a developing agent. Ra, Rb, Rc, Rd, Re, Rf and Rg each represent a hydrogen atom or a substituent. However, Rg is a substituent that does not leave during the reaction between the coupler represented by the general formula (c) and the oxidized product of the color developing agent. Y_
1 represents a carbon atom or a nitrogen atom. Y_2 represents a carbon atom or a heteroatom. ■ indicates that the bond between Y_1 and Y_2 may be a single bond or a double bond. However, if Y_1 is a carbon atom and the bond between Y_1 and Y_2 is a double bond, n_3 is 1, n_4 is 0, and Rc is the oxidation of the coupler represented by general formula (a) and the color developing agent. It is a substituent that does not leave when reacting with the body, and when Y_1 is a carbon atom and the bond between Y_1 and Y_2 is a single bond, both n_3 and n_4 are 1. Also, if Y_1 is a nitrogen atom and the bond between Y_1 and Y_2 is a double bond, n_3 and n_4 are both 0, and Y_2 is a heteroatom, and Y_1 is a nitrogen atom and Y_
If the bond between 1 and Y_2 is a single bond, n_3 is 1 and n_4 is 0. In addition, the couplers represented by general formulas (a), (b), and (c) are capable of binding to the color developing agent only at the positions where Xa is bound, Xb is bound, and Xc is bound, respectively. Coupling reaction with oxidant. ] General formula [XII] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a substituent. R_2_4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R_2_5 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group. J has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_2_6 and R_2_7 each represent a hydrogen atom or an alkyl group, and R_2_8 represents an alkyl group or Represents an aryl group. l represents 0 or an integer from 1 to 4,
m represents 0 or 1, and n_ represents 0, 1 or 2. R_2_1 and R_2_2 may be the same or different, and may be combined with each other to form a 5- or 6-membered ring. Further, when l is 2 or more, the plurality of R_2_3 may be the same or different, and R_2_1 or/and R_2_2,
And, a 5- or 6-membered ring may be formed together with the nitrogen atom bonded to R_2_1 or R_2_2, and R_2_
4 and the nitrogen atom bonded to R_2_4 may form a 5- or 6-membered ring. ]