JP2003228156A - Silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magenta coupler capable of forming a stable image even when the composition of a processing solution varies and to provide a magenta coupler having an excellent color forming property even when a high boiling point organic solvent is diminished to make a so-called oilless state. <P>SOLUTION: A silver halide color photographic sensitive material containing at least one coupler represented by formula (1) is provided. In the formula, R<SB>1</SB>is H or a substituent; R<SB>2</SB>is a group represented by formula (2), (3) or (4) or a substituent substituted by at least one group represented by the formula (2), (3) or (4); and X is H or a group releasable on reaction with the oxidized body of a color developing agent. In the formulae (2)-(4), (EWG1) is a group having a Hammett's substituent constant σp of ≥0.4; R<SB>3</SB>is alkyl, aryl or a heterocyclic group; R<SB>4</SB>is a substituent; m is an integer of 0-3; (EWG2) is a group having a Hammett's substituent constant σp of ≥0.4 and a group capable of acting as a divalent linking group; and n is an integer of 0-4. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a novel color cup.
A silver halide color copy using the same
The present invention relates to a true photosensitive material. For more details
Silver halide color river using La coupler compound
The present invention relates to a monkey photographic light-sensitive material. [0002] 2. Description of the Related Art In recent years, silver halide color photographic light-sensitive materials
For high sensitivity, excellent sharpness and graininess
In addition, there is a strong demand for faithful color reproducibility. In recent years, as a magenta dye-forming coupler,
Pyrazolotriazole couplers with low absorption are put into practical use
Has been done. Pyrazolotriazole magenta
A puller is a compound that has excellent properties in hue.
Although it is a product, on the other hand, it has low color developability and is resistant to processing fluctuations.
Various problems such as low colorability and poor color image preservation
It is clear to have. For example, an oxidized form of an aromatic primary amine developer
So-called 4 in which the coupling position is a hydrogen atom substitution product
Equivalent couplers have excellent graininess but low color development,
Disadvantages of yellowing over time after development
Had. On the other hand, other than hydrogen atoms in the coupling position
So-called 2-equivalent carbon substituted with a leaving group (for example, a halogen atom)
Puller develops with less silver than 4 equivalent couplers
However, it has a feature that yellow coloring is difficult to occur.
However, there is a problem that the image quality deteriorates due to a decrease in graininess.
Have. In addition, many of these couplers are phosphoric acid.
For high-boiling organic solvents such as esters and phthalates
Used by dissolving and dispersing, but recently high sharpness
The amount of these high-boiling organic solvents used has been reduced
Therefore, what is called oil-less is required. However,
Many of the pyrazolotriazole magenta couplers are
There was a significant decrease in color development when used in an irres
Therefore, these improvements have been demanded. In order to solve these problems, pyrazolo
Various modifications to the substituents on the triazole ring
A puller has been proposed. For example, color image robustness
US Patent No. 4,882,266, European published patent No.
No. 183,445 to a coupler with a bulky 6-position substituent
An improvement is disclosed. Also, when using without oil
For improving the color developability of JP-A-1-102557
In the coupler molecule, a carboxyl group is introduced as a dissociation group.
A coupler is disclosed. However, this
These technologies have the problem of yellowing over time after processing.
In addition, it was insufficient for the problem of color preservation.
Improvement of color development is observed by introducing a dissociative group
Couplers are expensive and have poor crystallinity for industrial applications
Had a problem. In addition, the uncolored area is exposed to light irradiation or humid heat atmosphere.
Yellow stain or color sensitization
It is stagnant until mixed with the silver halide emulsion and coated.
New problems such as lowering the sensitivity
became. In addition, resistance to fluctuations in processing solution composition is insufficient
There was a need for improvement. In addition, pyrazoloazo currently in practical use
Most of the couplers are 2-equivalent couplers. Kara
-Reversal photographic light-sensitive materials are reversed after the first development.
Color development processing is performed from this time, but at this time with a 2 equivalent coupler
Is a 4-equivalent coupler due to its high color development per mole of silver
Has an essential problem that the sensitivity is lower than
ing. Therefore, the color reversal photographic light sensitive material is
When applying Lazolotriazole Magenta Coupler
Is preferably a 4-equivalent coupler from the viewpoint of sensitivity. Kara
-4-equivalent pyrazolotriazo to reversal photographic materials
For example, Japanese Patent Application Laid-Open No. Hei 5-
No. 10032, JP-A 63-153548, JP
6-208209, 6-214360, 7-2
61348, 2001-33921, etc.
ing. However, with these technologies, the process
To the problem of yellow coloring over time and the variation of the processing solution composition
Resistance to do was not solved. In particular, the pH of the treatment liquid
The problem that color development fluctuates in response to fluctuations
I did not come. [0008] The object of the present invention is to first
In addition, a stable image can be formed even when the composition of the processing solution is changed.
Provides a magenta coupler that can
Excellent in reducing boiling organic solvents, so-called oil-less
To provide a magenta coupler with excellent color development.
The The second object of the present invention is to prevent variations in the composition of the treatment liquid.
Stable image can be formed even with excellent color reproduction
Halogenation that is both resistant and robust and produces less stain
The object is to provide a silver color photographic light-sensitive material. [0009] Means for Solving the Problems The present inventors have made an oil level
It has sufficient color development even in the process of processing, and a set of processing solutions
Stable images can be formed even with variations in composition, graininess,
Conducting intensive research aimed at couplers with excellent image preservation
As a result, the present invention was completed. That is, the object of the present invention is as follows.
Achieved. (1) Cap represented by the following general formula (1)
A halogen containing at least one kind of
Silver halide color photographic light-sensitive material. [0012] [Chemical 3] Where R₁Represents a hydrogen atom or a substituent,
R₂Is the following general formula (2), general formula (3) or general formula
Or a group represented by (4) or at least one of the following
Represented by general formula (2), general formula (3) or general formula (4)
The substituent substituted by group is represented. X is a hydrogen atom or carbon
Can be removed in the reaction of oxidized color developing agent
Represents a group. [0014] [Formula 4] Wherein (EWG1) is a Hammett substituent constant.
Represents a group having a sigma para value of 0.4 or more, and R₃Is Archi
Represents an alkyl group, an aryl group, or a heterocyclic group. R₄Is a substituent
M represents an integer of 0-3. (EWG2) is sad
Group with a sigma para value of 0.4 or more
And represents a group that can be a divalent linking group. n is 0-4
* Represents a pyrazolot represented by the general formula (1)
A position bonded directly to the riazole skeleton or via a linking group
Represents the position. (2) In general formula (1), pyrazolo
Triazole skeleton and general formula (2), general formula (3) or
The linking group that binds the general formula (4) is represented by the following general formula (5).
The silver halide capacitor according to (1), wherein
Photographic photosensitive material. [0017] [Chemical formula 5] In the formula, L is an alkylene group or arylene.
Represents the group A₁Is -O-, -S-, -SO₂-, -N
(R₅) CO-, -N (R₅) COO-, -N (R₅)
CON (R₆)-, -N (R₅) SO₂-, -COO
-, -CON (R₅)-Or -SO₂N (R₅-
Represent. R₅And R₆Are independently hydrogen atoms, alkyl
Represents an aryl group or an aryl group. Y represents a divalent linking group
And r represents 0 or 1. ** indicates general formula (2), general formula
(3) or the position represented by the group represented by the general formula (4) and *
*** represents the position to be combined with
Represents the position of bonding with the pyrazolotriazole skeleton. (3) General formula (2) or general formula (4)
(EWG1) in general formula (3) and (E
(WG2) is a sulfonyl group (1)
And a silver halide color according to any one of (2)
Photosensitive material. (4) R in the general formula (1)₂But below
It is represented by the general formula (6) or the general formula (7).
The silver halide color photographic light-sensitive material as described in (1)
Fee. [0021] [Chemical 6] Where R₇, R₈, R₉And R₁₀Is it
Each independently represents a hydrogen atom, an alkyl group, or an aryl group.
S represents an integer of 0 to 3, and A₂Are -O-, -S-,
-SO₂-, -N (R₅) CO-, -N (R₅COO
-, -N (R₅) CON (R ₆)-, -N (R₅) SO
₂-, -COO-, -CON (R₅)-Or -SO ₂
N (R₅)-. R₁₁And R₁₂Respectively
R₃And R₄Represents a group having the same meaning as t, and t is the same as m
Represents meaning. R₁₃Represents a substituent, and w is an integer of 0 to 4.
Represents. R₁₄Is R₃Represents a group having the same meaning as **
* Indicates a pyrazolotriazole skeleton represented by the general formula (1)
Represents the position to be bound to. (5) R in the general formula (1)₂But below
It is represented by the general formula (8) or the general formula (9).
The silver halide color photographic light-sensitive material as described in (1)
Fee. [0024] [Chemical 7] Where R₇, R₈, R₉And R₁₀Is it
Each independently represents a hydrogen atom, an alkyl group, or an aryl group.
S represents an integer of 0 to 3, and A₂Are -O-, -S-,
-SO₂-, -N (R₅) CO-, -N (R₅COO
-, -N (R₅) CON (R ₆)-, -N (R₅) SO
₂-, -COO-, -CON (R₅)-Or -SO ₂
N (R₅)-. R₁₁And R₁₂Respectively
R₃And R₄Represents a group having the same meaning as t, and t is the same as m
Represents meaning. R₁₃Represents a substituent, and w is an integer of 0 to 4.
Represents. R₁₄Is R₃Represents a group having the same meaning as **
* Indicates a pyrazolotriazole skeleton represented by the general formula (1)
Represents the position to be bound to. (6) X in the general formula (1) is a hydrogen atom
Any one of (1) to (5) characterized by being a child
A silver halide color photographic light-sensitive material as described in the item. (7) R in the general formula (1)₁Is the third grade
It is represented by an alkyl group (1) to (6)
The silver halide color photographic light-sensitive material according to any one of the above
Fee. (8) In general formula (2) and general formula (3),
R₃And general formula (6), general formula (7), general formula
(8) and R in the general formula (9)₁₁Is the following general formula
(10) characterized in that (1) to (7)
The silver halide color photographic light-sensitive material according to any one of the above
Fee. [0029] [Chemical 8] Where R₁₅Is an alkyl group, alkenyl
A group or an aryl group, R₁₆Represents a substituent and x
Represents an integer of 0 to 3. Z is a halogen atom having 1 to 1 carbon atoms.
4 or 12 or more alkyl groups, aryl groups, heterocycles
Group, alkoxy group, aryloxy group, alkylthio
Group, arylthio group, alkylsulfonyl group, aryl
Sulfonyl group, amino group, anilino group, acylamino
Group, alkoxycarbonylamino group, ureido group, al
Coxycarbonyl group, carbamoyl group, cyano group, imi
Group, sulfonamido group, or sulfamoyl group
The (9) Compound SR-1 represented by the following formula
Any one of (1) to (8), characterized in that
The silver halide color photographic light-sensitive material according to one item. [0032] [Chemical 9] [0033] The present invention will be described in detail below.
The silver halide color photographic light-sensitive material of the present invention has the general formula
A novel coupler represented by (1) (hereinafter referred to as “the present invention
Also known as “plur”. ). General formula (1), general formula (2), general formula
(3) and general formula (4) will be described in detail. R in the general formula (1)₁Is a hydrogen atom or
Represents a substituent, R₁The substituent of is a halogen atom (for example,
Fluorine, chlorine, bromine), alkyl group (preferably carbon number)
1-48 linear, branched, or cyclic alkyl groups,
For example, methyl, ethyl, propyl, isopropyl,
Til, t-butyl, pentyl, hexyl, heptyl, o
Cutyl, 2-ethylhexyl, dodecyl, hexadec
, Cyclopropyl, cyclopentyl, cyclohexyl
, 1-norbornyl, 1-adamantyl), alkeni
Group (preferably an alkenyl group having 2 to 48 carbon atoms, eg
For example, vinyl, allyl, 3-buten-1-yl), ants
Group (preferably an aryl group having 6 to 48 carbon atoms,
For example, phenyl, naphthyl), a heterocyclic group (preferably
A heterocyclic group having 1 to 32 carbon atoms, such as 2-thieni
Ru, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1
-Pyridyl, 2-benzothiazolyl, 1-imidazoli
1-pyrazolyl, benzotriazol-1-y
), A silyl group (preferably a silyl group having 3 to 38 carbon atoms)
For example, trimethylsilyl, triethylsilyl,
Ributylsilyl, t-butyldimethylsilyl, t-hex
Sildimethylsilyl), hydroxyl group, cyano group, di
A tro group, an alkoxy group (preferably
Lucoxy group, for example, methoxy, ethoxy, 1-but
Xy, 2-butoxy, isopropoxy, t-butoxy,
A dodecyloxy, cycloalkyloxy group, for example,
Cyclopentyloxy, cyclohexyloxy), ants
An aryloxy group (preferably an aryl group having 6 to 48 carbon atoms)
A xy group such as, for example, phenoxy, 1-naphthoxy), f
Telocyclic oxy group (preferably a heterocycle having 1 to 32 carbon atoms)
An oxy group such as 1-phenyltetrazol-5-
Oxy, 2-tetrahydropyranyloxy), silylo
Xyl group (preferably silyloxy group having 1 to 32 carbon atoms)
For example, trimethylsilyloxy, t-butyldimethyl
Tilsilyloxy, diphenylmethylsilyloxy),
An acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms)
A xy group such as acetoxy, pivaloyloxy,
Nzoyloxy, dodecanoyloxy), alkoxyca
Rubonyloxy group (preferably an alkoxy having 2 to 48 carbon atoms)
A xoxycarbonyloxy group, for example, ethoxycarbonyl
Ruoxy, t-butoxycarbonyloxy, cycloal
Killoxycarbonyloxy group, for example, cyclohexyl
Siloxycarbonyloxy), aryloxycarbo
Nyloxy group (preferably having 7 to 32 carbon atoms)
A xoxycarbonyloxy group, for example, phenoxycarbo
Nyloxy), carbamoyloxy group (preferably carbon
A carbamoyloxy group of 1 to 48, for example, N,
N-dimethylcarbamoyloxy, N-butylcarbamo
Iroxy, N-phenylcarbamoyloxy, N-e
Til-N-phenylcarbamoyloxy), sulfamo
Yloxy group (preferably sulfamo having 1 to 32 carbon atoms)
An yloxy group, for example, N, N-diethylsulfamo
Yloxy, N-propylsulfamoyloxy), a
Alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms)
An alkylsulfonyloxy group of, for example, methylsulfur
Honyloxy, hexadecylsulfonyloxy, cyclo
(Hexylsulfonyloxy), arylsulfonyloxy
Si group (preferably arylsulfonyl having 6 to 32 carbon atoms)
An oxy group, for example phenylsulfonyloxy), a
Sil groups (preferably acyl groups having 1 to 48 carbon atoms, eg
For example, formyl, acetyl, pivaloyl, benzoyl,
Tetradecanoyl, cyclohexanoyl), alkoxy
Carbonyl group (preferably alkoxy having 2 to 48 carbon atoms)
A carbonyl group such as methoxycarbonyl,
Cycarbonyl, octadecyloxycarbonyl, cyclo
(Hexyloxycarbonyl), aryloxycarboni
Ru group (preferably aryloxycar having 7 to 32 carbon atoms)
Bonyl groups such as phenoxycarbonyl), carb
Moyl group (preferably a carbamoyl group having 1 to 48 carbon atoms)
For example, carbamoyl, N, N-diethylcarbamo
Yl, N-ethyl-N-octylcarbamoyl, N, N
-Dibutylcarbamoyl, N-propylcarbamoyl,
N-phenylcarbamoyl, N-methyl N-phenyl carbonate
Rubamoyl, N, N-dicyclohexylcarbamoy
), An amino group (preferably an amino group having 32 or less carbon atoms)
For example, amino, methylamino, N, N-dibutyl
Amino, tetradecylamino, 2-ethylhexylami
Cyclohexylamino), anilino group (preferably
An anilino group having 6 to 32 carbon atoms, for example, anilino, N
-Methylanilino), a heterocyclic amino group (preferably charcoal)
A heterocyclic amino group having a prime number of 1 to 32, such as 4-pyri
Dilamino), carbonamido group (preferably having 2 carbon atoms)
-48 carbonamido groups such as acetamide,
Benzamide, Tetradecanamide, Pivaloylamino
, Cyclohexaneamide), ureido group (preferably
A ureido group having 1 to 32 carbon atoms such as ureido,
N, N-dimethylureido, N-phenylureido),
Imido group (preferably an imide group having 10 or less carbon atoms, eg
For example, N-succinimide, N-phthalimide), Al
Coxycarbonylamino group (preferably having 2 to 48 carbon atoms)
An alkoxycarbonylamino group such as methoxy
Carbonylamino, ethoxycarbonylamino, t-butyl
Toxicarbonylamino, octadecyloxycarboni
Ruamino, cyclohexyloxycarbonylamino),
Aryloxycarbonylamino group (preferably carbon number
7 to 32 aryloxycarbonylamino groups, for example
Phenoxycarbonylamino), sulfonamide group
(Preferably a sulfonamide group having 1 to 48 carbon atoms, eg
For example, methanesulfonamide, butanesulfonamide,
Benzenesulfonamide, hexadecane sulfonamido
, Cyclohexanesulfonamide), sulfamoyl
Amino group (preferably sulfamoyl having 1 to 48 carbon atoms)
An amino group, for example, N, N-dipropylsulfamoy
Ruamino, N-ethyl-N-dodecylsulfamoylua
Mino), an azo group (preferably an azo group having 1 to 32 carbon atoms)
For example, phenylazo, 3-pyrazolylazo), a
Alkylthio group (preferably an alkylthio having 1 to 48 carbon atoms)
O groups such as methylthio, ethylthio, octylthio
E, cyclohexylthio), arylthio group (preferably
Is an arylthio group having 6 to 48 carbon atoms.
Luthio), a heterocyclic thio group (preferably having 1 to 32 carbon atoms)
A heterocyclic thio group such as 2-benzothiazolylthio
E, 2-pyridylthio, 1-phenyltetrazolylthio
E) an alkylsulfinyl group (preferably having a carbon number of 1
32 alkylsulfinyl groups, for example, dodecane
Rufinyl), arylsulfinyl group (preferably charcoal)
An arylsulfinyl group having a prime number of 6 to 32;
Sulfonylsulfinyl), alkylsulfonyl group (preferred
Or an alkylsulfonyl group having 1 to 48 carbon atoms, for example
Methylsulfonyl, ethylsulfonyl, propyls
Sulfonyl, butylsulfonyl, isopropylsulfoni
, 2-ethylhexylsulfonyl, hexadecylsulfur
Honyl, octylsulfonyl, cyclohexylsulfoni
), An arylsulfonyl group (preferably having 6 to 4 carbon atoms)
8 arylsulfonyl groups such as phenylsulfo
Nyl, 1-naphthylsulfonyl), sulfamoyl group
(Preferably a sulfamoyl group having 32 or less carbon atoms, eg
For example, sulfamoyl, N, N-dipropylsulfamo
, N-ethyl-N-dodecylsulfamoyl, N-
Ethyl-N-phenylsulfamoyl, N-cyclohex
Silsulfamoyl), sulfo group, phosphonyl group (preferred
Or a phosphonyl group having 1 to 32 carbon atoms.
Noxyphosphonyl, octyloxyphosphonyl, pheny
Luphosphonyl), phosphinoylamino group (preferably
A phosphinoylamino group having 1 to 32 carbon atoms, for example,
Diethoxyphosphinoylamino, dioctyloxyphor
Sufinoylamino). R in the general formula (1)₁Is a further substitutable group
In this case, the above substituent may be substituted.
And if substituted with two or more substituents,
These substituents may be the same or different. X in the general formula (1) is a hydrogen atom or a color.
Can be removed by coupling reaction with oxidized color developing agent
A specific example of X includes a hydrogen atom, a halogen atom
Child, alkoxy group, aryloxy group, heterocyclic oxy
Group, acyloxy group, alkoxycarbonyloxy group,
Carbamoyloxy group, alkylthio group, arylthio
Group, heterocyclic thio group, imide group, azo group, or nitrogen atom
The aromatic heterocyclic group attached to the active position of the coupler
Represent. X of these hydrogen atoms, halogen atoms, alkoxy
Si group, aryloxy group, heterocyclic oxy group, acylo group
Xyl group, alkoxycarbonyloxy group, carbamoyl
Oxy group, alkylthio group, arylthio group, heterocycle
Preferred of thio group, imide group, azo group, and azole group
For the range, see above R₁The hydrogen atom described in halo
Gen atom, alkoxy group, aryloxy group, heterocycle
Oxy group, acyloxy group, alkoxycarbonyloxy
Si group, carbamoyloxy group, alkylthio group, aryl
Ruthio group, heterocyclic thio group, imide group, azo group, hetero
Synonymous with cyclic group. These leaving groups of X can be further substituted
R₁In the group described in the substituent of
Optionally substituted with two or more substituents
The substituents may be the same or different
May be. R in the general formula (1)₂Is the general formula (2),
A group represented by general formula (3) or general formula (4), or
Expressed by general formula (2), general formula (3), or general formula (4)
Represents a substituent having at least one group. Suitable tools
As an example, the divalent chain represented by the general formula (5) is used.
A group containing a linking group, at one of the positions indicated by ***
Combined with the pyrrolotriazole skeleton and the other **
General formula (2), general formula (3) or
Bonded with the group represented by the general formula (4) at the position indicated by *
Group. The general formula (5) will be described in more detail.
The In the general formula (5), L represents an alkylene group or an
Represents a rylene group. The alkylene group of L is preferably charcoal
Prime number 1 to 36, more preferably 1 to 8 substituted or unsubstituted
Represents a linear, branched or cyclic alkylene group of
Examples of the alkylene group include methylene and ethylene.
, Trimethylene, cyclohexylene and the like.
The substituent of the substituted alkylene group is the above R₁With the substituent of
Represents a group having the same meaning as the defined group and is substituted with two or more substituents.
If substituted, these substituents may be the same or different.
It may be. The arylene group of L in the general formula (5) is preferably
Preferably it has 6 to 38 carbon atoms, more preferably 6 to 18 carbon atoms.
Represents a substituted or unsubstituted aryl group, and an unsubstituted aryl group and
For example, o-phenylene, m-phenylene, p
-Phenylene, 1,2-naphthalene, 1,4-naphthalene
Or the like. The substituent of the substituted arylene group is as described above.
R₁Represents a group having the same meaning as the group described for the substituent. A in the general formula (5)₁Are -O-, -S-,
-SO₂-, -N (R₅) CO-, -N (R₅COO
-, -N (R₅) CON (R₆)-, -N (R₅) SO
₂-, -COO-, -CON (R₅)-Or SO₂N
(R₅)-, R₅And R₆Are independently hydrogen
An atom, an alkyl group or an aryl group is represented. R₅And R
₆The alkyl group and aryl group of the above R₁Substituent of
A group having the same meaning as the alkyl group and aryl group described in
Represents. These alkyl groups and aryl groups are further substituted.
R can be changed₁Substituted with the group described in Substituent of
May be substituted with two or more substituents
In some cases, the substituents are the same or different.
May be. In general formula (5), Y represents a divalent linking group.
Specific examples thereof include an alkylene group, an arylene group,
Or an aralkylene group and an alkylene group thereof,
-Lene group, aralkylene group and A₁Group explained in
And each other form a new composite divalent linking group
You may do it. R represents 0 or 1, and ** represents a general formula
(2) a group represented by general formula (3) or general formula (4)
Indicates the position to be joined at the position indicated by *, *** is general
Binds to the pyrazolotriazole ring represented by formula (1)
Represents the position. Next, general formula (2), general formula (3) and
The general formula (4) will be described in detail. R in general formula (2) and general formula (3)
₃Represents an alkyl group, an aryl group or a heterocyclic group;
Those alkyl groups, aryl groups and heterocyclic groups are
R₁Alkyl group, aryl group and heterocycle described in 1.
Represents a group having the same meaning as the group. General formula (2), general formula (3) and general formula
(4) R in₄Represents a substituent and R₄The substituent of
R₁Represents a group having the same meaning as the group described for the substituent. R₄
The substituent of is further R₁Substituted with the substituents described in
If it is substituted with two or more substituents,
These substituents may be the same or different.
m represents an integer of 0 to 3, and n represents an integer of 0 to 4. m
Or when n is 2 or more, a plurality of substituents R₄Are the same
Or different. In the general formulas (2) and (4), (EW
G1) is a Hammett substituent constant having a sigma para value of 0.4 or more
The upper electron-withdrawing group is represented. About Hammett substituent constants
The Chemical Review (Chemical Review)
ews) Vol. 91, No. 1991. 2,165-
Page 195. Preferred group of (EWG1)
As an alkylsulfonyl group (preferably having 1 carbon atom).
-48, more preferably 1-36 alkylsulfonyl
Groups such as methylsulfonyl, ethylsulfonyl,
Isopropylsulfonyl, butylsulfonyl, hexyl
Sulfonyl, heptylsulfonyl, octylsulfoni
, 2-ethylhexylsulfonyl, cyclohexyls
Ruphonyl, dodecylsulfonyl, tetradecylsulfonyl
, Hexadecylsulfonyl, octadecylsulfonyl
, 2-hexyldecylsulfonyl, benzylsulfoni
), An arylsulfonyl group (preferably having 6 to 4 carbon atoms)
8, more preferably 6 to 36 arylsulfonyl groups
For example, benzenesulfonyl, p-toluenesulfo
Nyl, p-dodecylbenzenesulfonyl, p-hexade
Silbenzenesulfonyl, 2-octyloxy-5-t
ert-octylbenzenesulfonyl), perfluoroa
Alkyl group (preferably having 1 to 36 carbon atoms, more preferably
1 to 24 perfluoroalkyl groups, for example, trifluoro
(Romethyl), cyano group, nitro group, sulfamoyl group
(Preferably 0 to 48 carbon atoms, more preferably 0 to 24 carbon atoms.
A sulfamoyl group such as sulfamoyl, N-
Methylsulfamoyl, N-octadecylsulfamoy
N, N-dioctylsulfamoyl, N-phenyl
Sulfamoyl, N-cyclohexylsulfamoyl,
N, N-dicyclohexylsulfamoyl, N, N-di
Phenylsulfamoyl), alkylsulfinyl group
(Preferably 1 to 48 carbon atoms, more preferably 1 to 36 carbon atoms.
An alkylsulfinyl group such as methylsulfinyl
Nyl, ethylsulfinyl, butylsulfinyl, octyl
Tylsulfinyl, dodecylsulfinyl, hexadecyl
Rusulfinyl, octadecylsulfinyl, 2-ethi
Ruhexylsulfinyl, cyclohexylsulfini
And arylsulfinyl group (preferably having 6 to 6 carbon atoms)
48, more preferably 6-36 arylsulfinyl
Radicals such as benzenesulfinyl, p-toluene
Rufinil, p-dodecyloxybenzenesulfini
), An alkoxycarbonyl group (preferably having a carbon number of 2
48, more preferably 2-36 alkylcarbonyl groups
For example, methylcarbonyl, ethylcarbonyl,
Tylcarbonyl, octylcarbonyl, dodecylcarbo
Nyl, hexadecylcarbonyl, octadecylcarbonyl
, 2-ethylhexylcarbonyl, cyclohexylca
Rubonyl) and the like. These alkylsulfonyl groups and aryl
Sulfonyl group, sulfamoyl group, alkylsulfini
Group, arylsulfinyl group, alkoxycarbonyl
If the group can be further substituted, the R₁Substituent of
May be substituted with the substituents described in 2 above.
When substituted with a substituent, the substituents are the same.
It may be one or different. (EWG2) in the general formula (3) is Hammett.
An electron-withdrawing group having a substituent constant sigma para value of 0.4 or more
And represents a group that can be a divalent linking group. (EW
As a preferable example of G2), it is explained in the above (EWG1).
Lighted alkylsulfonyl group, arylsulfonyl group,
Sulfamoyl group, alkylsulfinyl group, aryl
Alkyl such as sulfinyl group and alkoxycarbonyl group
A divalent group in which one hydrogen atom of an aryl group or aryl group is removed
Groups. General formula (2), general formula (3) and general formula
* In (4) is R in the general formula (1).₂Combined
Position that directly binds to the pyrazolotriazole skeleton
Or a pyrazolotriazole skeleton via a linking group
Represents the position to be combined. R in the general formula (1)₂Is
Preferably, it is represented by general formula (6) or general formula (7).
More preferably, it is represented by the general formula (8) or the general formula (9).
The General formula (6), general formula (7), general formula
(8) and the substituent R in the general formula (9)₇~ R₁₀, R
₁₁, R₁₂, R₁₃, R₁₄, S, t, w, and A₂
Will be described in detail. R₇~ R₁₀Each independently
Child, an alkyl group or an aryl group, R₇~ R₁₀of
The alkyl group and the aryl group are the same as the above R₁With the substituent of
A group having the same meaning as the alkyl group and aryl group
The Their alkyl and aryl groups can be further substituted
In the case of R₁May have the substituent described in
If substituted with two or more substituents,
The substituents may be the same or different. s is 0-3
Represents an integer. If s is an integer greater than or equal to 2, there are multiple
R₉May be the same or different, as well as multiple
R₁₀May be the same or different. R₁₁Is R in the general formula (2).₃Same as
It is righteousness. R₁₂Is R in the general formula (2).₄Synonymous with
And t is synonymous with m. If t is 2 or more, multiple
R₁₂May be the same or different. R₁₃Represents a substituent and R₁Explained in
Represents a group having the same meaning as the substituent. R₁₄Is an alkyl group, aryl group or
R represents a ring group and R₁₄Alkyl group, aryl group and
The tero ring group is R₁The alkyl group described for the substituent of
A group having the same meaning as a reel group or a heterocyclic group is represented. R₁₄
When the alkyl group and aryl group of
R₁May be substituted with the substituents described in
And if substituted with two or more substituents,
These substituents may be the same or different. w is
Represents an integer of 0 to 4; If w is 2 or more, there are multiple R
₁₃May be the same or different. A₂Is A described in the general formula (5).₁
Is synonymous with *** is a pyrazo represented by the general formula (1)
R on the rotriazole skeleton₂Join with the position where
Position. Next, the general formula (10) will be described in detail.
To do. R in the general formula (10)₁₅Is an alkyl group, alk
Represents a nyl group or an aryl group, R₁₅An alkyl group of
The alkenyl group and aryl group are the same as the above R₁The Archi
A group having the same meaning as the above group, alkenyl group, and aryl group.
R₁₅Alkyl group, alkenyl group, and aryl
When the ru group is further substitutable, R₁Substituents described in
May be substituted with two or more substituents
The substituents may be the same or different.
May be. R in the general formula (10)₁₆Indicates a substituent
And R₁₆The substituent of is the above R₁Same as the substituents explained in
Represents the same meaning group. R₁₆The substituent of can be further substituted
In some cases, it may further have a substituent.
When substituted with a substituent, the substituents are the same.
Or different. x represents an integer of 0 to 3
The When x is 2 or more, there are a plurality of R₁₆Are the same
May be different. Z is a halogen atom having 1 to 4 or 12 carbon atoms.
The above alkyl group, aryl group, heterocyclic group, alkoxy
Si group, aryloxy group, alkylthio group, arylthio group
O group, alkylsulfonyl group, arylsulfonyl group,
Amino group, anilino group, acylamino group, alkoxy group
Rubonylamino group, ureido group, alkoxycarbonyl
Group, carbamoyl group, cyano group, imide group, sulfone
Represents a amide group or a sulfamoyl group, and is a halogen atom of Z
Child, aryl group, heterocyclic group, alkoxy group, aryl
Oxy group, alkylthio group, arylthio group, alkyl
Sulfonyl group, arylsulfonyl group, amino group,
Lino group, acylamino group, alkoxycarbonylamino
Group, ureido group, alkoxycarbonyl group, carbamoy
Group, cyano group, imide group, sulfonamide group, or
Rufamoyl group is defined as R₁Halogen source explained in
Child, aryl group, heterocyclic group, alkoxy group, aryl
Oxy group, alkylthio group, arylthio group, alkyl
Sulfonyl group, arylsulfonyl group, amino group,
Lino group, acylamino group, alkoxycarbonylamino
Group, ureido group, alkoxycarbonyl group, carbamoy
Group, cyano group, imide group, sulfonamide group, or
Synonymous with rufamoyl group. These groups can be further substituted
R₁Substituted with the substituents described in
If it is substituted with two or more substituents,
These substituents may be the same or different.
The alkyl group having 1 to 4 carbon atoms or 12 or more carbon atoms of Z is substituted or
Represents an unsubstituted linear, branched, or cyclic alkyl group.
For example, methyl, ethyl, propyl, butyl, iso
Propyl, t-butyl, dodecyl, pentadecyl, etc.
I can get lost. Next, the coupler represented by the general formula (1)
A preferred range will be described. R in general formula (1)₁
Is an alkyl group, aryl group, alkoxy group, aryl
Oxy group, anilino group, carbonamido group, alkoxy
Carbonylamino group or sulfonamide group, X is water
Elementary atom, chlorine atom, aryloxy group, alkylthio
Group, arylthio group, heterocyclic thio group, imide group, or
Bonded at the active position of the pyrazolotriazole ring with a nitrogen atom
An aromatic heterocyclic group, R₂Is represented by the general formula (5)
A divalent linking group represented by general formula (2), general formula (3), or
A group to which a group represented by the general formula (4) is bonded,
(EWG1) in formula (2) or general formula (4) is alkyl
Sulfonyl group, arylsulfonyl group, cyano group, nito
B group, alkoxycarbonyl group or perfluoroalkyl
(EWG2) in the general formula (3) is alkyls
Sulfonyl, arylsulfonyl, alkoxycarbo
A divalent group of the nyl group, R₃Is an alkyl group or aryl
R group, R₄Is a halogen atom, alkyl group, aryl
Group, heterocyclic group, hydroxyl group, cyano group, nitro
Group, alkoxy group, aryloxy group, acyl group, al
Coxycarbonyl group, carbamoyl group, carbonamide
Group, ureido group, alkoxycarbonylamino group, sulfo group
Honamide group, alkylthio group, arylthio group, al
Killsulfonyl group, arylsulfonyl group, or sulf
An amoyl group, m is 0 or 1, and n is 0 or 1.
A coupler represented by the general formula (1) is preferred. Further preferred couplers of the present invention have the general formula
R in (1)₁Is an alkyl group, aryl group, alkoxy
Ci group or aryloxy group, X is a hydrogen atom, salt
Elementary atom or aryloxy group, alkylthio group, aryl
Nitrate the thio group, imide group, or pyrazolotriazole ring
An aromatic heterocyclic group bonded with a primary atom, R₂Is general
A group represented by formula (6) or general formula (7),
R in general formula (6) and general formula (7)₇, R₈, R₉as well as
R₁₀Each independently represents a hydrogen atom, an alkyl group, or an
In the reel group, s is an integer of 0 to 2, and R₁₁Is Archi
R group or aryl group, R₁₂Is a halogen atom, an alkyl
Group, alkoxy group, aryloxy group, alkoxy group
Rubonyl group, carbamoyl group, carbonamido group, urea
Id group, alkoxycarbonylamino group, alkyl
A sulfonyl group or an arylsulfonyl group, and t is 0 or
Is 1 and A₂Is -O-, -S-, -SO₂-, -N
(R₅) CO-, -N (R₅) COO-, -N (R₅)
CON (R₆)-, -N (R₅) SO₂-, -COO
-, -CON (R₅)-Or SO₂N (R₅)-
R₅, R₆Each independently represents a hydrogen atom, an alkyl group, or
Is an aryl group and R₁₃Is a halogen atom, alkyl
Group, aryl group, alkoxy group, aryloxy group,
Silamino group, sulfonamide group, alkoxycarbonyl
Group, amino group, or imide group, and w is an integer of 0 to 3.
There are couplers that are numbers. Further preferred couplers of the present invention have the general formula
R in (1)₁Is an alkyl group, aryl group, alkoxy
Or an aryloxy group, and X is a hydrogen atom or
A chlorine atom, R₂Is general formula (6) or general formula
A group represented by (7), which is represented by the general formula (6) and the general formula
(7) R in₇, R₈, R₉And R₁₀Are independent of each other
And a hydrogen atom, an alkyl group, or an aryl group, and s is 0
Is an integer of ~ 2, R₁₁Is an alkyl group or an aryl group
And R₁₂Is a halogen atom, alkyl group, alkoxy
Group, aryloxy group, alkoxycarbonyl group, cal
Vamoyl group, carbonamide group, ureido group, alkoxy
Sicarbonylamino group, alkylsulfonyl group, or a
A reelsulfonyl group, t is 0 or 1, and A₂
Is -O-, -S-, -SO₂-, -N (R₅) CO-,
-N (R₅) COO-, -N (R₅) CON (R₆)
-, -N (R₅) SO₂-, -COO-, -CON (R
₅)-Or SO₂N (R₅)-, R₅, R₆Is it
Each independently a hydrogen atom, an alkyl group, or an aryl group.
R₁₃Is a halogen atom, an alkyl group, an aryl group,
Alkoxy group, aryloxy group, acylamino group,
Ruhonamide group, alkoxycarbonyl group, amino group,
Or a coupler which is an imide group and w is an integer of 0 to 3
Is mentioned. Further preferred couplers of the present invention have the general formula
R in (1)₁Is an alkyl group and X is a hydrogen atom or
A chlorine atom, R₂Is general formula (8) or general formula (9)
A group represented by the formula:₇, R₈, R₉And R
₁₀Are each independently a hydrogen atom or an alkyl group, and s is 0 or
Is 1 and A₂-NHCO- or -NHSO₂-, R
₁₁Is an alkyl group or an aryl group, and R₁₂Is halogen
Atoms, alkyl groups, alkoxy groups, aryloxy groups,
Alkoxycarbonyl group, carbamoyl group, carboxyla
Mid group, ureido group, alkoxycarbonylamino group,
An alkylsulfonyl group or an arylsulfonyl group
T is 0 or 1 and R₁₄Is an alkyl group or ant
R group₁₃Is a chlorine atom, an alkyl group, an alcohol
A coupler having xoxy group and w is an integer of 0 to 3.
The Further preferred couplers of the present invention have the general formula
R in (1)₁Is an alkyl group and X is a hydrogen atom
R₂Is a group represented by general formula (8) or general formula (9)
Furthermore, R₇, R₈, R₉And R₁₀Each
A hydrogen atom or an alkyl group, s is 0 or 1, and A₂
-NHCO- or -NHSO₂-, R₁₁Is Archi
R group or aryl group, R₁₂Is a halogen atom, an alkyl
Group, alkoxy group, aryloxy group, alkoxy group
Rubonyl group, carbamoyl group, carbonamido group, urea
Id group, alkoxycarbonylamino group, alkyl
A sulfonyl group or an arylsulfonyl group, and t is 0 or
Is 1 and R₁₄Is an alkyl group or an aryl group
R₁₃Is a chlorine atom, an alkyl group, an alkoxy group, w
Are couplers in which is an integer from 0 to 3. More preferred couplers of the present invention have the general formula
R in (1)₁Is an alkyl group and X is a hydrogen atom
R₂Is a group represented by general formula (8) or general formula (9)
And R₇, R₈, R₉, R₁₀Are each independently hydrogen
An atom or a methyl group, s is 0 or 1, and A₂-NH
CO- or -NHSO₂-, T is 0, R₁₁Is al
A kill or aryl group, R₁₄Is an alkyl group or ant
R group₁₃Is an alkyl group and w is an integer of 0 to 3
Couplers. More preferred couplers of the present invention have the general formula
R in (1)₁Is an alkyl group and X is a hydrogen atom
R₂Is the general formula (8) and R₇, R₈, R₉as well as
R_{1 0}Each independently represents a hydrogen atom or a methyl group, and s is 0
Or 1₂-NHCO- or -NHSO₂-
t is 0, R₁₁Is an alkyl group or an aryl group, and R
₁₄A coupler in which is an alkyl group or an aryl group
It is done. The most preferred couplers of the present invention have the general formula
R in (1)₁Is a tertiary alkyl group and X is a hydrogen atom
And R₂Is a group represented by the general formula (8),
And R₇, R₈, R₉And R₁₀Are independently hydrogen
An atom or an alkyl group, s is 0 or 1, and A₂-NH
CO- or -NHSO₂-, T is 0 and R₁₁But
An alkyl group or an aryl group, R₁₄Is an alkyl group or
Examples include couplers that are aryl groups. Further, in the general formula (2) and the general formula (3),
R₃And R in the general formula (6) to the general formula (9)₁₁Is one
In the case of a group represented by the general formula (10), a coupler is used.
Do not use environmental hormones of concern as starting materials during synthesis.
This is preferable. Moreover, the formula of the group represented by the general formula (10)
The amount is 200 or more, preferably 250 or more, more preferably
More than 300 groups are useful as anti-diffusion groups,
In addition to the coupler of the present invention, it is also resistant to various known couplers.
It can be suitably used as a dispersible group. Next, the coupler represented by the general formula (1)
Specific examples are shown, but the present invention is not limited by these.
Yes. [0071] Embedded image[0072] Embedded image[0073] Embedded image[0074] Embedded image[0075] Embedded image[0076] Embedded image[0077] Embedded image[0078] Embedded image[0079] Embedded image[0080] Embedded image[0081] Embedded image[0082] Embedded image[0083] Embedded image[0084] Embedded image[0085] Embedded image[0086] Embedded image Next, a method for synthesizing the coupler of the present invention.
State. (Synthesis Example 1) Synthesis of exemplary coupler C-2 Synthesized according to Reaction Scheme A. [0089] Embedded imageCompound A (5-nitro-2-octadecyl
Synthesis of thiobenzoic acid) 151 g of 2-chloro-5-nitrobenzoic acid (0.75
mol), 215 g of octadecyl mercaptan (0.
75 mol), 233 g of potassium carbonate (1.69 mo)
l) Add 800 ml of dimethylacetamide and add 80
The mixture was heated to 100 ° C. to 100 ° C. and stirred. React for about 4 hours
After cooling the reaction solution to room temperature, 290 ml of concentrated hydrochloric acid
And water poured into 3000 ml of liquid while stirring.
The crystals were filtered, washed with water and dried. 5-nitro
-2-octadecylthiobenzoic acid (Compound A) 335
g (yield 99.1%) was obtained. Compound B (5-nitro-2-octadecyl
Synthesis of sulfonylbenzoic acid) 5-Nitro-2-octadecylthioacetate obtained by the above method
100 g (0.221 mol) of benzoic acid, tungsten
500g ethanol to 5g sodium dihydrate
In addition, the mixture was stirred with heating. In this solution, 31% hydrogen peroxide solution 5
8.3 g (0.531 mol) was added dropwise. End of dripping
After that, the reaction was completed by stirring for 3 hours. After the reaction is complete
The mixture was poured into 2000 ml of water with stirring. This aqueous solution
To the flask was added 20 ml of concentrated hydrochloric acid. The precipitated crystals are filtered
Washed with water and dried. 5-Nitro-2-octadecyls
105 g (yield 9) of sulfonylbenzoic acid (compound B)
8.0%). Compound C (5-nitro-2-octadecyl
Synthesis of sulfonylbenzoic acid chloride) 5-Nitro-2-octadecylsulfo obtained by the above method
Tolue to 105 g (0.217 mol) of nylbenzoic acid
300 ml was added and heated to 70 ° C. and stirred. This
23.8 ml of thionyl chloride was added dropwise to the solution. Dripping
After completion, the mixture was stirred at 70 to 80 ° C. for 2 hours. After the reaction is complete
Cooled to room temperature. This toluene solution of Compound C
Used in the next step. Synthesis of Compound E Obtained according to the method described in JP-A-2001-33921
Compound D 85.2 g, sodium bicarbonate 2
Add 250 ml of isopropyl alcohol to 1.2 g
The mixture was heated and stirred for 30 minutes. To this solution, hydrazine 1 water
15.8 g of a Japanese product (80% aqueous solution) was added dropwise. End of dripping
Thereafter, the mixture was heated and stirred for 2 hours to complete the reaction. this
After cooling the reaction solution to room temperature, 500 ml of water and concentrated hydrochloric acid 2
7.0 ml was added and stirred at 20 ° C. or lower for 1 hour. This
Filter the solution to remove by-product phthalhydrazide.
It was. An aqueous hydrochloride salt solution of Intermediate E was obtained. Obtained in this way
Synthesis of Compound F in the next step
Used as is. Synthesis of Compound F Ethyl acetate was added to the hydrochloride aqueous solution of compound E obtained by the above method.
500 ml was added and stirred at room temperature. Carbonic acid in this solution
Add 176 g of sodium hydride to free compound E
Turned into. To this solution, the intermediate C obtained by the above method was added.
The ene solution was added dropwise at room temperature over 1 hour. End of dripping
Then, reaction was performed at room temperature for 1 hour. After completion of the reaction, acetate
The chill layer was separated and washed with water. This ethyl acetate solution is anhydrous
After drying over magnesium sulfate, the mixture was concentrated under reduced pressure. This
Add 1000 ml of acetonitrile to the residue and crystallize
Was precipitated. The crystals were filtered and dried. Compound F
120 g was obtained. Synthesis of Compound G Reduced iron 120g, ammonium chloride 10g and water 50m
l, add 600 ml isopropanol and 2 ml acetic acid
And stirred with heating. Compound obtained by the above method in this solution
120 g of F was added in several portions. 2 after completion of addition
The reaction was completed by stirring with heating for an hour. Vinegar in this reaction solution
Add 600 ml of ethyl acid, then filter under reduced pressure to insoluble
The debris was removed. Add water to the filtrate and extract with ethyl acetate.
I put it out. After washing the ethyl acetate solution with water, sulfuric anhydride
Dry over magnesium and concentrate ethyl acetate under reduced pressure.
It was. 112 g of compound G was obtained. Synthesis of Compound H Acetonitrile 35 was added to 80 g of the compound G obtained by the above method.
0 ml was added and stirred at room temperature. To this solution p-tolue
52.2 g of sulfonic acid chloride was added. End of addition
After completion, the solution is heated to 70 ° C. to 75 ° C. and agitated.
25 ml of lysine was added dropwise over 30 minutes. This reaction solution
Was reacted at 70 to 80 ° C. for 6 hours. End of reaction
Thereafter, the solution was cooled to room temperature and then ethyl acetate 600 m.
l, 600 ml of water and concentrated hydrochloric acid 5 were added for extraction. This vinegar
The ethyl acid solution is washed with water and then dried over anhydrous magnesium sulfate.
The dried ethyl acetate was distilled off under reduced pressure. Silica residue
Gel column chromatography (eluent: chloroform)
/ Ethyl acetate = 10/1) and purified. Compound H
91.0g was obtained. Synthesis of exemplary coupler C-2 90 g of compound H (0.095 mo) obtained by the above method.
l) Add 450 ml of isopropyl alcohol to room temperature
Stir with. To this solution, an aqueous sodium hydroxide solution (water
Add 18.9 g of sodium oxide in 200 ml of water)
Added. After the addition is complete, stir at room temperature for 1 hour to complete the reaction
Let To this reaction solution, 40.6 ml of concentrated hydrochloric acid was added dropwise to add acid.
Then, the mixture was extracted with 500 ml of ethyl acetate. This vinegar
The ethyl acid solution is washed with saturated brine, and then vinegar is used under reduced pressure.
Ethyl acid was distilled off. 300m acetonitrile in the residue
l was added to precipitate crystals. The crystals are filtered and dried
After drying, it was recrystallized with 250 ml of acetonitrile. Example
61.5 g (yield: 81.2%) of the indicated coupler C-2
Obtained. [0098]¹HNMR (CDCl₃) 60 to 10.40 (br, S, 1H), 8.70 to 8.40 (br, S, 1
H), 7.80-7.57 (m, 4H), 7.36-7.25 (d, 1
H), 7.28-7.10 (m, 3H), 5.97-5.80 (m, 1
H), 5.53 (s, 1H), 3.43 (t, 2H), 2.38
(S, 3H), 1.80-1.50 (m, 5H), 1.38 (s, 9
H), 1.35 to 1.10 (m, 30H), 0.88 (t, 3H). (Synthesis Example 2) Synthesis of exemplary coupler C-10 Synthesized according to Scheme B below. [0100] Embedded imageSynthesis of Compound J To 96.7 g (0.214 mol) of compound A with toluene 3
00 ml was added and heated to 90 ° C. with stirring. Salt in this solution
24 ml of thionyl chloride was added dropwise and the mixture was further stirred with heating for 3 hours.
It was. After completion of the reaction, it is cooled to room temperature and dissolved in toluene of Compound J
A liquid was obtained. Synthesis of Compound K A toluene solution of Compound J obtained by the above method was added to methanol.
In 220 ml of water at room temperature. After completion of dripping, at room temperature
After stirring for 1 hour, the precipitated crystals were filtered and methanol
Washed with 200 ml of water. The crystals are dried and compound K
90 g (yield: 90.3%) was obtained. Synthesis of Compound L 65 g of reduced iron, 2 g of ammonium chloride and isopropyl alcohol
Add 200 ml of Lecol, 20 ml of water and 1 ml of acetic acid
And stirred with heating. Compound obtained by the above method in this solution
K 67 g of crystals were added in several portions. Addition finished
Thereafter, the mixture was heated and stirred for 90 minutes to complete the reaction. This solution
Add 200 ml of ethyl acetate to the solution and filter while hot to insoluble
The organism was removed by filtration. Extract the filtrate by adding water to the water
After washing, this ethyl acetate solution was dried over anhydrous magnesium sulfate.
And dried. Ethyl acetate is distilled off under reduced pressure and n
-Hexane was added to precipitate crystals. Filter this crystal
And dried, 53.0 g of compound L (yield: 84.5
%)Obtained. Synthesis of Compound M 3-chlorosulfonylbenzoic acid chloride 25.0 g
(125 ml) with 125 ml of ethyl acetate
Cool to -15 ° C and stir. To this solution dicyclohexyl
19.0 g (0.105 mol) of ruamine is added dropwise, then
Triethylamine 10.6g (0.105mo
l) was added dropwise. The temperature was kept at -15 to -10 ° C. drop
After completion, the mixture was stirred for 2 hours. After completion of the reaction,
Water was added and extracted with ethyl acetate. This ethyl acetate solution
After washing with water and drying over anhydrous magnesium sulfate,
Ethyl acetate was distilled off to obtain compound M. Synthesis of Compound N To 41.6 g (0.096 mol) of the above compound L
Tonitrile 80 ml was added and stirred at room temperature. This solution
In addition, 44.1 g (0.115 of compound M) obtained by the above method was used.
mol) and then 11.0 m (0.1
35 mol) was added dropwise. After dripping is complete, stir for 4 hours at room temperature
Stir to complete the reaction. Extract the reaction with ethyl acetate
did. The ethyl acetate solution is washed with water and anhydrous magnesium sulfate.
Dried with um. The ethyl acetate was concentrated under reduced pressure.
The residue was subjected to silica gel column chromatography (elution
Liquid: n-hexane / ethyl acetate = 3/1)
did. 63.7 g (yield: 85.2%) of compound N was obtained.
It was. Synthesis of Compound O 63.7 g (0.081 m) of compound N obtained by the above method
ol) is added with 400 ml of methanol and stirred at room temperature.
It was. To this solution was added 16.3 g (0.41) of sodium hydroxide.
mol) was dissolved in 50 ml of water. Attendant
After completion of the addition, the mixture was heated and stirred at 50 to 55 ° C. for 2 hours. End of reaction
After completion, the reaction solution was poured into 3000 ml of water. This solution
While stirring the solution, 43 ml of concentrated hydrochloric acid was added to make it acidic.
As a result, crystals were precipitated. The crystals are filtered and washed with water,
Dried. 60.0 g of compound O (yield: 95.8%)
Obtained. Synthesis of Compound P 58.0 g (0.754 m) of compound O obtained by the above method
ol), sodium tungstate dihydrate 3 g
300 ml of diol was added and stirred with heating. 3 in this solution
19.8 g of 1% hydrogen peroxide was added dropwise over 1 hour.
After completion of the dropwise addition, the reaction was completed by stirring for 2 hours. This reaction
The solution was poured into 2000 ml of water with stirring. This water soluble
Add 20 g of sodium sulfite to the solution and stir at room temperature for 1 hour
After that, 20 ml of hydrochloric acid was added. Harz-like material is deposited
And extracted with ethyl acetate. This ethyl acetate solution
Separation by Kagel chromatography (eluent: ethyl acetate)
And purified. After concentrating the obtained compound P, the volume
Diluted with toluene to 350 ml. Synthesis of compound Q 350 ml of the toluene solution of Compound P obtained by the above method
Heated to 75 ° C. and stirred. To this solution thionyl chloride 9.
0 ml (0.125 mol) was added dropwise. After completion of dripping
Stirring was performed at 75 ° C. to 80 ° C. for 2 hours. Compound Q
A ruene solution was obtained. Synthesis of Exemplary Coupler C-10 Using 30.4 g (0.075 mol) of compound D,
A hydrochloride aqueous solution of Compound E was prepared in the same manner as in Synthesis Example 1.
Obtained. In this solution, 200 ml of ethyl acetate and sodium bicarbonate
65 g of lithium was added. This solution was obtained by the above method
350 ml of intermediate Q in toluene is added dropwise over 1 hour
did. After completion of the dripping, the reaction is completed by stirring for 1 hour at room temperature.
Let The aqueous layer was removed from the reaction solution, and the ethyl acetate solution was added.
Washed with water. This ethyl acetate solution was added to anhydrous magnesium sulfate.
After drying, ethyl acetate was distilled off under reduced pressure. Residue
Of silica gel column chromatography (eluent: n-
Separation and purification with hexane / ethyl acetate = 3/1). Example
55.0 g (Yield: 74.0) of the indicated coupler C-10
%)Obtained. [0110]¹HNMR (CDCl3) 48 to 11.25 (brs, 1H), 9.33 to 9.08 (brs, 1
H), 7.95-7.57 (m, 4H), 7.46-7.14 (m, 4
H), 5.95-5.76 (m, 1H), 5.43 (s, 1H), 3.
47 (t, 2H), 3.30 to 2.98 (m, 2H), 2.65 to 0.95
(M, 64H), 0.89 (t, 3H). (Synthesis Example 3) Synthesis of exemplary coupler C-50 Synthesized according to Reaction Scheme C. [0112] Embedded imageSynthesis of Compound R 2-Chloro-5-nitrobenzoic acid ethyl ester 9
1.8 g (0.4 mol), sodium p-toluenesulfinate
Thorium tetrahydrate to 130.1 g (0.52 mol)
Add 300 ml of N, N-dimethylacetamide to add 40
Heated to ~ 60 ° C and stirred. Stir for 3 hours
Then, this reaction solution was dropped into 600 ml of water while stirring.
did. The aqueous solution was cooled to 20 ° C. or lower and stirred for 1 hour.
It was. After the precipitated crystals are filtered and washed with methanol
Dried. 118 g (yield: 84.5%) of compound R was obtained.
It was. Synthesis of Compound S Reduced iron 120g, ammonium chloride 30g, and water 2
Add 00ml and 600ml isopropanol for 30 minutes
The mixture was heated and stirred for a while. Compound R obtained by the above method was added to this solution.
120 g (0.343 mol) was added in several portions.
After completion of the addition, the reaction was completed by heating and stirring for 1 hour. this
The reaction solution was filtered while hot to remove insolubles. Stir the filtrate
While stirring, 1000 ml of water was added dropwise. Precipitated crystals
Was filtered, washed with water and dried. 100 g of compound S
(Yield: 91.2%). Synthesis of compound T 100 g of compound S (0.313 mol) obtained by the above method
And 400 ml of pyridine was added to the mixture and stirred at 20 ° C.
4-hexadecyloxybenzenesulfonic acid was added to this solution.
143.6 g (0.344 mol) of chloride in several times
Added in portions. After the addition, stir at room temperature for 2 hours
To complete the reaction. To this reaction solution, ethyl acetate 600
ml, water 600ml, then concentrated hydrochloric acid 430ml
Was dripped. Let this solution stand to remove the lower aqueous layer.
It was. This ethyl acetate solution is washed with saturated brine and anhydrous
After drying with magnesium acid, reduce the ethyl acetate solution.
Concentrated under pressure. Silica gel column chromatogram
Fee (eluent: n-hexane / ethyl acetate = 2/1)
Separated and purified. 175 g of oily compound T (yield
Rate: 80.0%). Synthesis of Compound U Stir 38 g of potassium hydroxide in 250 ml of methanol.
Add and dissolve. This solution was obtained by the above method
100 g (0.143 mol) of Compound T at 20 ° C. or lower
Added. This solution was heated and stirred for 1 hour. End of reaction
After cooling to room temperature, water 600ml and ethyl acetate 600m
l was added. Next, 60 ml of concentrated hydrochloric acid was added dropwise. this
Remove the lower aqueous layer of the solution and wash the ethyl acetate solution with water.
It was. This ethyl acetate solution is dried over anhydrous magnesium sulfate
And concentrated under reduced pressure. 80 oily compound U
g (yield: 83.0%) was obtained. Synthesis of Compound V To 80 g (0.12 mol) of Compound U obtained by the above method
Acetonitrile 400ml was added and it heat-stirred. this
26 ml of thionyl chloride was added dropwise to the solution. After completion of dripping
The reaction was completed by heating and stirring for 2 hours. 2
Crystals deposited upon cooling to 0 ° C. or lower were filtered. This crystal
Was washed with acetonitrile to obtain Compound V. This
Compound V was used in the next step. Synthesis of exemplary coupler C-50 Containing 0.12 mol of Compound E according to the method of Synthesis Example 1
Prepare ethyl acetate / sodium bicarbonate aqueous solution at room temperature
And stirred. In this solution, the compound V obtained by the above-described method was condensed.
Crystals were added in several portions. Stir for 1 hour after the addition
To complete the reaction. After completion of the reaction, leave this reaction solution
Then, the lower aqueous layer was removed. Wash the ethyl acetate solution with water.
And dried over anhydrous magnesium sulfate, followed by acetic acid under reduced pressure.
Ethyl was distilled off. Silica gel column chromatography
Raffy (eluent: n-hexane / ethyl acetate = 2 /
It was separated and purified in 1). Example coupler C separated and purified
Add 200 ml of acetonitrile to -50 oil.
Crystals were precipitated. The crystals are filtered to produce acetonitrile.
And then dried. Exemplified coupler C-50 6
6 g (yield: 64.3%) was obtained. (Synthesis Example 4) Synthesis of exemplary coupler C-1 Synthesis was performed in the same manner as in Synthesis Example 1 above. 1HNMR (CDCl3) 11.10 to 10.80 (br, s, 1H), 8.50 to 8.30 (br,
s, 1H), 8.27 to 8.06 (br, s, 1H), 7.85
(D, 1H), 7.44 (d, 1H), 7.27 (s, 1H),
6.15 to 5.92 (br, s, 1H), 5.55 (s, 1H), 3.
43 (t, 2H), 3.0 (s, 3H), 1.83 to 1.53 (m,
5H), 1.50 to 1.10 (m, 39H), 0.89 (t, 3
H). (Synthesis Example 5) Synthesis of exemplary coupler C-11 Synthesis was performed according to the same method as in Synthesis Example 2 above. 1HNMR (DMSO d6) 45 (s, 1H), 11.20 (s, 1H), 9.20 (d, 1
H), 8.48 (d, 1H), 8.3 (s, 1H), 8.10
(D, 1H), 7.98 (d, 1H), 7.79 (d, 1H),
7.64 (dd, 1H), 7.39 (d, 1H), 7.30 (s, 1
H), 5.63 (s, 1H), 5.49-5.32 (m, 1H), 3.
84-3.64 (br, s, 1H), 3.48-3.35 (br, s,
2H), 1.90 to 1.66 (m, 2H), 1.59 (d, 3H),
1.40 to 1.05 (m, 49H), 0.87 (t, 3H). (Synthesis Example 6) Synthesis of exemplary coupler C-23 Synthesis was performed according to the same method as in Synthesis Example 1 above. 1HNMR (CDCl3) 64-10.40 (br, s, 1H), 8.69-8.40 (br,
s, 1H), 7.78 (d, 1H), 7.67 (d, 1H), 7.
33 (s, 1H), 7.15 (s, 2H), 6.90 (d, 1
H), 5.97-5.78 (m, 1H), 5.45 (s, 1H), 4.
17 to 3.96 (m, 2H), 3.50 to 3.30 (m, 2H), 3.0
~ 2.80 (m, 1H), 1.80-1.58 (m, 5H), 1.35
(S, 9H), 1.32-1.05 (m, 48H), 0.86 (t,
3H). The coupler of the present invention can be used in various known dispersion methods.
Higher boiling point organic solvent (if necessary
And a low boiling point organic solvent)
Oil-in-water fraction added to silver halide emulsion after being emulsified and dispersed in
The powder method is preferred. The coupler of the present invention contained in the light-sensitive material.
Amount is 1m in total²Preferably, 0.01 g to 1
0g, more preferably 1m²Per 0.1g to 2g
The 1 × 1 per mole of silver halide in the same emulsion layer
0^-3Mol to 1 mol is suitable, preferably 2 × 10
^-3Mol ~ 3 × 10^-1Is a mole. In the light-sensitive material of the present invention, the cartridge of the present invention is used.
It is preferred to use compound SR-1 in the same layer as the puller
The substituent of the compound represented by SR-1 is changed
Compound, for example, the t-octyl group of SR-1 is n-octyl
Changed to a group such as ruthel group, n-hexadecyl, or t-butyl group.
The isopropyl group of SR-1, a methyl group, or
A compound changed to an ethyl group or the like can be used in the same manner.
SR-1 is most preferred. The amount of compound SR-1 used is determined according to the cap of the present invention.
The range of 0.1 mol% to 200 mol% per mol of
Preferably 5 mol% to 100 mol%.
%, More preferably in the range of 5 mol% to 20 mol%
Preferably it is. Regarding the synthesis of compound SR-1,
No. 45-14034. The halo of the present invention
Various types of silver halide color photographic light-sensitive materials are used depending on the purpose.
Additives can be used. These additives are more specifically researched.
Disclosure (RD) Item 17643 (19
December 1978), Item 18716 (1979 1)
January), Item 308119 (December 1989)
And the corresponding locations are summarized below.
It was. [0131]     Additive type RD17643 RD18716 RD308119 1. Chemical sensitizer page 23 page 648 right column page 996 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, 23-24 pages 648 right column-996 right-998 right     Supersensitizer 649 pages, right column 4). Brightener 24 pages 998 right 5). Antifoggant 24-25 pages 649 right column 998 right-1000 right     And stabilizer 6). Light absorber, 25-26 pages, 649 pages, right column-1003 left-1003 right     Filter dye, page 650, left column     UV absorber 7). Stain inhibitor page 25 right column 650 left to right column 1002 right 8). Dye image stabilizer 25 pages 1002 right 9. Hardener page 26 page 651 left column 1004 right to 1005 left Ten. Binder page 26 Same as above 1003 right to 1004 right 11． Plasticizer, Lubricant 27 pages 650 pages right column 1006 left to 1006 right 12． Application aid, pages 26-27 Same as above 1005 left-1006 left     Surfactant 13. Static page 27 Same as above 1006 right to 1007 left     Inhibitor 14. Matting agent 1008 left to 1009 left To a silver halide color photographic light-sensitive material that can adopt the present invention
Techniques such as layer arrangement that can be used, silver halide milk
Agents, dye-forming couplers, DIR couplers, etc.
Europe, various additives, and development processing
Patent No. 0565096A1 (October 13, 1993)
Published) and the patents cited therein. Less than
Below is a list of each item and the corresponding description. 1. Layer structure: 61 pages 23-35 lines, 61 pages
41 lines-62 pages, 14 lines 2. Middle layer: 61 pages 36-40 lines, 3. Multilayer effect imparting layer: 62 pages 15-18 lines, 4). Silver halide halogen composition: 62 pages 21-25, 5). Silver halide grain habit: page 62 lines 26-30, 6). Silver halide grain size: 62 pages 31-34, 7). Emulsion production method: 62 pages 35-40 lines, 8). Silver halide grain size distribution: page 62, 41-42
line, 9. Tabular grains: 62 pages 43-46, Ten. Internal structure of particles: 62 pages 47 lines to 53 lines, 11． Emulsion latent image formation type: 62 pages 54 lines-63 pages 5
line, 12． Emulsion physical ripening / chemical ripening: p. 63, lines 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Kabaze emulsion: p. 63, lines 14-31, 15． Non-photosensitive emulsion: p. 63, lines 32-43, 16． Amount of coated silver: 63 pages 49-50 lines, 17． Photo additives: Research Disclosure (R
D) Item 17643 (December, 1978), It
em18716 (November 1979) and Item3
07105 (November 1989), below
Each item and its related description are shown in the table below. [0133]     Type of additive RD17643 RD18716 RD307105 (1) Chemical sensitizer page 23 page 648, right column page 866 (2) Sensitivity increasing agent, right column on page 648 (3) Spectral sensitizer, pages 23 to 24, page 648, right column to pages 866 to 868     Supersensitizer 649 pages, right column (4) Brightener 24 pages 647 right column 868 pages (5) Antifogging agent, pages 24 to 25, page 649, right column, pages 868 to 870     Stabilizer (6) Light absorber, page 25-26, page 649, right column, page 873     Filter dye, page 650, left column     UV absorber (7) Stain inhibitor page 25 right column 650 left column to right column 872 (8) Dye image stabilizer page 25 page 650 left column page 872 (9) Hardener page 26 page 651 left column pages 874-875 (10) Binder page 26 page 651 left column pages 873-874 (11) Plasticizer, lubricant page 27 page 650 right column page 876 (12) Coating aid, pages 26-27, page 650, right column, pages 875-876     Surfactant (13) Static 27 pages 650 right column 876-877 pages     Inhibitor (14) Matting agent 878-879 pages 18． Formaldehyde scavenger: page 64 54-5
7 lines, 19. Mercapto-type antifoggant: page 65, line 1-2, 20． Release agent such as fogging agent: page 65, lines 3-7, twenty one. Dye: 65 pages 7-10 lines, twenty two. Color coupler in general: page 65, lines 11-13, twenty three. Yellow, magenta and cyan couplers: page 65 1
Lines 4-25, twenty four. Polymer coupler: page 65, lines 26-28, twenty five. Diffusible dye-forming coupler: page 65, lines 29-31, 26. Colored coupler: 65 pages 32-38 lines, 27. Functional couplers in general: 65 pages 39-44, 28. Bleach accelerator releasing coupler: 65 pages 45-48, 29. Development accelerator releasing coupler: page 65, lines 49-53, 30. Other DIR couplers: page 65 line 54-page 4
line, 31. Coupler dispersion method: page 66, line 5-28, 32. Preservatives and fungicides: 66 pages 29-33, 33. Type of sensitive material: 66 page 34-36, 34. Photosensitive layer thickness and swelling rate: 66 pages 40 lines-67 pages 1
line, 35. Back layer: 67 pages 3-8 lines, 36. Development processing in general: page 67, lines 9-11, 37. Developer and developer: p. 67, lines 12-30, 38. Developer additive: p. 67, lines 31-44, 39. Inversion processing: 67 pages 45-56 lines, 40. Treatment liquid opening ratio: 67 pages 57 lines-68 pages 12 lines, 41. Development time: 68 pages, lines 13-15, 42. Bleach fixing, bleaching, fixing: 68 pages 16 lines-69 pages 31
line, 43. Automatic processor: Page 69, lines 32-40, 44. Washing, rinsing, stabilization: 69 pages 41 lines-70 pages 18
line, 45. Treatment liquid replenishment, reuse: page 70, lines 19-23, 46. Built-in developer sensitive material: page 70, lines 24-33, 47. Development temperature: page 70, lines 34-38, 48. Use for lens-attached film: 70 pages 39-41, [0134] EXAMPLES The present invention will be specifically described below with reference to examples.
However, the present invention is not limited by these.
Absent. Example 1 Preparation of sample 101 On an undercoated cellulose triacetate film support,
Create a color photosensitive material consisting of two layers with the following composition.
Was designated as Sample 101. The number is m²Table of the amount added per unit
The Silver halide is shown in terms of silver amount. [0136]   First layer: Silver halide emulsion layer     Silver iodobromide monodisperse tabular grain Silver amount 1.00g         Sphere equivalent average particle size 0.3 μm         Coefficient of variation 18%         AgI content 4.0 mol%     Gelatin 3.00g     Comparative coupler A 0.28g     High boiling point organic solvent Oil-1 0.08g     Surfactant W-5 25mg   Second layer: protective layer     2.00 g of gelatin     0.10 g of polymethyl methacrylate (average particle size 2.0 μm)     Surfactant W-1 0.15g     Gelatin hardener H-1 0.15g Embedded imagePreparation of samples 102 to 119 Table 1 shows the magenta coupler of the first layer of sample 101.
Same as sample 101, except replaced with zeta coupler
Samples 102 to 119 were prepared with the contents of [0138] Embedded image(Evaluation of color development / sensitivity) Continuously darkening the sample
The color temperature of 4800 degrees through the wedge with varying degrees
Expose with white light and apply the development process described below to darken the magenta image
The maximum color density (Dmax) was measured. This value is high
The higher the color developability. Sensitivity gives a color density of 0.5
The sensitivity of the sample 101 based on the sensitivity obtained from the reciprocal of the exposure amount
The value is shown as a relative value with respect to 100. The higher the value, the higher
Indicates sensitivity. (Evaluation of pH dependency of color developer) Example 1
Each sample obtained in step 1 has a continuous concentration change.
And exposed to white light with a color temperature of 4800 degrees through
Development processing was performed and the magenta density was measured. Coloring at this time
The pH of the developer is determined by taking p
Adjust to 2 points of H = 11.6 and 12.1 for processing
It was. The evaluation of pH dependence is based on the treatment at pH = 11.6.
PH = 1 when the exposure dose gives a magenta density of 1.0.
Measure the magenta density in the process of 2.1 and find it using the following formula:
I tried. (Concentration in treatment at pH 12.1—1.
0) × 100 = Change rate (%) The smaller the change rate value, the more the color developer pH
It shows that the color density change is small. (Evaluation of dependency on addition amount of color developing agent)
Each of the above samples was treated with a color developing agent [N-
Ethyl-N (2-methanesulfonamidoethyl) -3-
Methyl-4-aminoaniline, 3/2 sulfate, monohydrate
Adjusted at 2 points of 13.0g and 5.0g per liter
Except that the development processing solution is the same as the development processing solution described later.
After being used and developed, the magenta density was measured. Above
Of color developing agent can process 13.0 g per liter
Color development at an exposure amount giving a magenta density of 1.0
The magenta density in the processing where the amount of the developing agent is 5.0 g
It measured and calculated | required with the following formula. (Processing of 1.0-color developing agent 5.0 / L)
Density) × 100 = change rate (%) The smaller the rate of change, the more
It shows that the change in color density is small. (Evaluation of Yellow Stain) Each of the above samples
Give a white light of 500 lux for 1 second to the following development processing
gave. The obtained sample was placed in an atmosphere of 70 ° C./70% RH.
After 4 weeks of storage, the yellow
The concentration of in was measured. Evaluation is increased yellow density
The value obtained by subtracting the density of the blank from is shown. This value is small
The more yellow stain is generated, the better the image preservation
Are better. The above results are shown in Table 1. [0145] [Table 1] In the following, development processing will be described. [0147] (Processing process)   Processing time Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C 37 liters 2200 milliliters / m² 1st wash 2 minutes 38 ° C 16 liters 4000 ml / m² Inversion 2 minutes 38 ° C 17 liters 1100 ml / m² Color development 6 minutes 38 ° C 30 liters 2200 ml / m² Pre-bleaching 2 minutes 38 ° C 19 liters 1100 ml / m² Bleaching 6 minutes 38 ° C 30 liters 2200 ml / m² Fixing 4 minutes 38 ° C 29 liters 1100 ml / m² 2nd washing 4 minutes 38 ° C 35 liters 4000 ml / m² The composition of each treatment solution was as follows. [0148]   (First developer) (Tank solution) (Replenisher) Nitrilo-N, N, N-trimethylenephospho   Acid ・ 5 sodium salt 1.5g 1.5g Diethylenetriaminepentaacetic acid ・ 5sodium 2.0g 2.0g   salt Sodium sulfite 30g 30g Hydroquinone potassium monosulfonate 20g 20g Potassium carbonate 15g 20g Potassium bicarbonate 12g 15g 1-phenyl-4-methyl-4-hydroxy Methyl-3-pyrazolidone 1.5g 2.0g Potassium bromide 2.5g 1.4g Potassium thiocyanate 1.2g 1.2g Potassium iodide 2.0mg ― Diethylene glycol 13g 15g Add water 1000ml 1000ml pH 9.60 9.60     The pH was adjusted with sulfuric acid or potassium hydroxide. [0149]   (Reversing liquid) (Tank liquid) (Replenisher liquid) Nitrilo-N, N, N-trimethylene Phosphonic acid pentasodium salt 3.0g 3.0g Stannous chloride dihydrate 1.0g 1.0g p-aminophenol 0.1g 0.1g Sodium hydroxide 8g 8g Glacial acetic acid 15ml 15ml Add water 1000ml 1000ml pH 6.00 6.0     The pH was adjusted with acetic acid or sodium hydroxide. [0150]   (Color developer) (Tank solution) (Replenisher) Nitrilo-N, N, N-trimethylene Phosphonic acid pentasodium salt 2.0g 2.0g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate 12-hydrate 36g 36g Potassium bromide 1.0 g ― Potassium iodide 90mg ― Sodium hydroxide 3.0g 3.0g Citrazic acid 1.5g 1.5g N-ethyl-N- (2-methanesulfonic acid Amidoethyl) -3-methyl-4-amino Aniline 3/2 sulfate monohydrate 11g 11g 6-dithiaoctane-1,8-diol 1.0 g 1.0 g Add water 1000ml 1000ml pH 11.80 12.00     pH adjusted with sulfuric acid or potassium hydroxide   (Bleaching solution) (Tank solution) (Replenisher solution) Ethylenediaminetetraacetic acid, disodium salt Dihydrate 2.0g 4.0g Ethylenediaminetetraacetic acid / Fe (III) / Ann Monium dihydrate 120g 240g Potassium bromide 100g 200g Ammonium nitrate 10g 20g Add water 1000ml 1000ml pH 5.70 5.50     The pH was adjusted with nitric acid or sodium hydroxide. [0151]   (Fixing solution) (tank solution) (replenisher solution) Ammonium thiosulfate 80g 80g Sodium sulfite 5.0 g 5.0 g Sodium bisulfite 5.0g 5.0g Add water 1000ml 1000ml pH 6.60 6.60     The pH was adjusted with acetic acid or aqueous ammonia. [0152]   (Stabilizer) (Tank fluid) (Replenisher) 2-Benzoisothiazoline-3- ON 0.02g 0.03g Polyoxyethylene-p-monononyl Phenyl ether (average degree of polymerization 10) 0.3 g 0.3 g Polymaleic acid (average molecular weight 2,000) 0.1 g 0.15 g Add water 1000ml 1000ml pH 7.0 7.0. In the above development process, each bath is continuous.
The liquid is circulated and stirred, and on the bottom of each tank,
A foamed tube with a small hole with a diameter of 0.3 mm is provided at 1 cm intervals.
And nitrogen gas was continuously bubbled and stirred. From the results of Table 1, Sample 1 of Comparative Coupler A
01 and 102 are satisfactory in color development and other performances
However, there is a problem of yellow stain generation in wet heat storage.
The Comparative coupler B, comparative coupler C, and comparative coupler
-D sample 103-107 has yellow stain problem
Satisfactory results have been obtained, but oilless
Low color developability and pH fluctuation of color developer
In addition, color development changes greatly due to variations in the amount of color developing agent.
Ki In contrast, the sample of the present invention satisfies all items.
To achieve the object of the present invention.
It is clear. The coupler of the present invention is 2 equivalents
Samples 116, 117, 118 and 119 are sensitive only
Low sensitivity but other performance is satisfactory
It was. (Example 2) Preparation of sample 201 (i) Preparation of triacetyl cellulose film Triacetylcellulose is dissolved in a conventional solution casting method.
Chloromethane / methanol = 92/8 (mass ratio) and tri
Dissolve acetylcellulose (13% by mass), plasticizer
Riphenyl phosphate and biphenyl diphenyl phosphate
The sulfate is a mass ratio of 2: 1 and the total is triacetyl cell
Vans converted to 14% of roast
It was created by the de method. The thickness of the support after drying is 97 μm
there were. (Ii) Contents of the undercoat layer For both sides of the triacetylcellulose film
Undercoat was applied. The numbers are 1.0 liter of undercoat liquid
Represents the mass contained in a file. In addition, both sides before undercoating
Was subjected to corona discharge treatment. [0157] Gelatin 10.0g Salicylic acid 0.5g Glycerin 4.0g 700 ml of acetone 200 ml of methanol Dichloromethane 80ml Formaldehyde 0.1mg Add water to 1.0 liter. (Iii) Application of back layer Apply the back layer shown below on one side of the subbed support.
Clothed. [0159]   1st layer binder: acid-treated gelatin (isoelectric point 9.0) 1.00 g         Polymer latex: P-2 (average particle size 0.1 μm) 0.13 g         Polymer latex: P-3 (average particle size 0.2 μm) 0.23 g         UV absorber U-1 0.030g         UV absorber U-3 0.010g         UV absorber U-4 0.020g         High boiling point organic solvent Oil-2 0.030g         Surfactant W-1 0.010g         Surfactant W-6 3.0 mg. [0160]   Second layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.10 g         Polymer latex: P-3 (average particle size 0.2 μm) 0.11 g         UV absorber U-1 0.030g         UV absorber U-3 0.010g         UV absorber U-4 0.020g         High boiling point organic solvent Oil-2 0.030g         Surfactant W-1 0.010g         Surfactant W-6 3.0mg         Dye D-2 0.10 g         Dye D-10 0.12 g         Potassium sulfate 0.25g         Calcium chloride 0.5mg         Sodium hydroxide 0.03g. [0161]   Third layer binder: acid-treated gelatin (isoelectric point 9.0) 3.30 g         Surfactant W-1 0.020g         Potassium sulfate 0.30g         Sodium hydroxide 0.03g   Fourth layer Binder: Lime-treated gelatin (isoelectric point 5.4) 1.15 g         1: 9 copolymer of methacrylic acid and methyl methacrylate             (Average particle size 2.0 μm) 0.040 g         6: 4 copolymer of methacrylic acid and methyl methacrylate             (Average particle size 2.0 μm) 0.030 g         Surfactant W-1 0.060g         Surfactant W-2 7.0mg         Curing agent H-1 0.23 g. (Iv) Coating of photosensitive emulsion layer On the side opposite to the side where the back layer is applied, the photosensitive milk shown below
An agent layer was applied to obtain a sample 201. The number is m²near
Represents the amount added. The effect of the added compound is
There is no limit. [0163]   First layer: Antihalation layer         0.25 g of black colloidal silver         Gelatin 2.40g         UV absorber U-1 0.15g         UV absorber U-3 0.15g         UV absorber U-4 0.10g         UV absorber U-5 0.10g         High-boiling organic solvent Oil-1 0.10g         High-boiling organic solvent Oil-2 0.10g         High boiling point organic solvent Oil-5 0.010g         Dye D-4 1.0mg         Dye D-8 2.5mg         0.05 g microcrystalline solid dispersion of dye E-1. [0164]   Second layer: Intermediate layer         Gelatin 0.50g         Compound Cpd-A 0.2 mg         Compound Cpd-K 3.0mg         Compound Cpd-M 0.03 g         UV absorber U-6 6.0mg         High boiling point organic solvent Oil-3 0.010g         High boiling point organic solvent Oil-4 0.010g         High boiling point organic solvent Oil-7 2.0mg         Dye D-7 4.0 mg. [0165]   Third layer: Middle layer         0.02g yellow colloidal silver           Silver iodobromide emulsion whose surface and interior are covered in advance   (Cubic grains, average silver iodide content 1 mol%, sphere equivalent average grain size 0.06 μm)                                                   0.01g of silver         Gelatin 0.6g         Compound Cpd-D 0.02 g         High boiling point organic solvent Oil-3 0.01 g. [0166]   Fourth layer: low-sensitivity red-sensitive emulsion layer         Emulsion A Silver amount 0.10g         Emulsion B Silver amount 0.15g         Emulsion C Silver amount 0.15g         Gelatin 0.80g         Coupler Cp-1 0.15g         Coupler Cp-2 7.0mg         Coupler Cp-6 3.0mg         Coupler Cp-7 2.0mg         UV absorber U-3 0.010g         Compound Cpd-I 0.020 g         Compound Cpd-D 3.0mg         Compound Cpd-J 2.0mg         High boiling point organic solvent Oil-10 0.030g         Additive P-1 5.0 mg. [0167]   Layer 5: Medium sensitivity red-sensitive emulsion layer         Emulsion C Silver amount 0.15g         Emulsion D Silver amount 0.15g         Gelatin 0.70g         Coupler Cp-1 0.15g         Coupler Cp-2 7.0mg         Coupler Cp-6 3.0mg         Compound Cpd-D 3.0mg         UV absorber U-3 0.010g         High boiling point organic solvent Oil-10 0.030g         Additive P-1 7.0 mg. [0168]   Layer 6: High sensitivity red sensitive emulsion layer         Emulsion E Silver amount 0.15g         Emulsion F Silver amount 0.20g         Gelatin 1.50g         Coupler Cp-1 0.60g         Coupler Cp-2 0.015g         Coupler Cp-3 0.030g         Coupler Cp-6 5.0mg         UV absorber U-1 0.010g         UV absorber U-2 0.010g         High boiling point organic solvent Oil-6 0.030g         High-boiling organic solvent Oil-9 0.020g         High boiling point organic solvent Oil-10 0.050 g         Compound Cpd-D 5.0 mg         Compound Cpd-K 1.0 mg         Compound Cpd-F 0.030 g         Additive P-1 0.010 g         Additive P-4 0.030 g. [0169]   Layer 7: Intermediate layer         Gelatin 0.70g         Additive P-2 0.10 g         Dye D-5 0.020g         Dye D-9 6.0 mg         Compound Cpd-I 0.010 g         Compound Cpd-M 0.040 g         Compound Cpd-O 3.0mg         Compound Cpd-P 5.0 mg         Compound Cpd-S 0.1 g         0.050 g of high boiling point organic solvent Oil-6. [0170]   8th layer: Middle layer         Yellow colloidal silver Silver amount 0.020g         1.00g gelatin         Additive P-2 0.05g         UV absorber U-1 0.010g         UV absorber U-3 0.010g         Compound Cpd-A 0.050 g         Compound Cpd-D 0.030 g         Compound Cpd-M 0.050 g         Compound Cpd-S 0.1 g         High boiling point organic solvent Oil-3 0.010g         0.050 g of high boiling point organic solvent Oil-6. [0171]   Ninth layer: Low-sensitivity green-sensitive emulsion layer         Emulsion G Silver amount 0.25g         Emulsion H Silver amount 0.30g         Emulsion I Silver amount 0.25g         Gelatin 1.30g         Comparative coupler A 0.13g         Coupler Cp-8 0.01g         Compound Cpd-A 5.0 mg         Compound Cpd-B 0.030 g         Compound Cpd-D 5.0 mg         Compound Cpd-G 2.5mg         Compound Cpd-F 0.010 g         Compound Cpd-K 2.0 mg         Compound Cpd-R 0.02 g         UV absorber U-6 5.0mg         High boiling point organic solvent Oil-2 0.04g         Additive P-1 5.0 mg. [0172]   10th layer: Medium sensitivity green sensitive emulsion layer         Emulsion I Silver amount 0.30g         Emulsion J Silver amount 0.30g         Internally coated silver bromide emulsion         (Cubic particles, sphere equivalent average particle size 0.11 μm)                                                 Silver amount 3.0mg         Gelatin 0.70g         Comparative coupler A 0.20g         Coupler Cp-8 0.02g         Compound Cpd-A 5.0 mg         Compound Cpd-B 0.030 g         Compound Cpd-F 0.010 g         Compound Cpd-G 2.0 mg         Compound Cpd-R 0.04 g         High boiling point organic solvent Oil-2 0.04g         0.02 g of high boiling point organic solvent Oil-9. [0173]   Layer 11: High-sensitivity green-sensitive emulsion layer         Emulsion K Silver amount 0.40g         Gelatin 0.80g         Comparative coupler A 0.65g         Coupler Cp-8 0.06g         Compound Cpd-A 5.0 mg         Compound Cpd-B 0.030 g         Compound Cpd-F 0.010 g         Compound Cpd-R 0.065 g         High-boiling organic solvent Oil-2 0.15g         0.050 g of high boiling point organic solvent Oil-9. [0174]   12th layer: Yellow filter layer         Yellow colloidal silver Silver amount 0.010g         Gelatin 1.0g         Compound Cpd-C 0.010 g         Compound Cpd-M 0.10 g         Compound Cpd-S 0.15 g         High-boiling organic solvent Oil-1 0.020g         High boiling point organic solvent Oil-6 0.10g         0.20 g of a microcrystalline solid dispersion of dye E-2. [0175]   13th layer: Intermediate layer         Gelatin 0.40g         Compound Cpd-Q 0.20 g. [0176]   14th layer: Low sensitivity blue-sensitive emulsion layer         Emulsion L Silver amount 0.15g         Emulsion M Silver amount 0.20g         Emulsion N Silver amount 0.10g         Gelatin 0.80g         Coupler Cp-4 0.020g         Coupler Cp-5 0.30g         Coupler Cp-6 5.0mg         Compound Cpd-B 0.10 g         Compound Cpd-I 8.0mg         Compound Cpd-K 1.0 mg         Compound Cpd-M 0.010 g         UV absorber U-6 0.010g         0.010 g of high boiling point organic solvent Oil-2. [0177]   15th layer: Medium sensitivity blue-sensitive emulsion layer         Emulsion N Silver amount 0.20g         Emulsion O Silver amount 0.20g         Internally coated silver bromide emulsion         (Cubic particles, sphere equivalent average particle size 0.11 μm)                                                 Silver amount 3.0mg         Gelatin 0.80g         Coupler Cp-4 0.020g         Coupler Cp-5 0.25g         Coupler Cp-6 0.010g         Compound Cpd-B 0.10 g         Compound Cpd-N 2.0 mg         0.010 g of high boiling point organic solvent Oil-2. [0178]   16th layer: High sensitivity blue-sensitive emulsion layer         Emulsion P Silver amount 0.20g         Emulsion Q Silver amount 0.25g         2.00 g of gelatin         Coupler Cp-3 5.0mg         Coupler Cp-4 0.10g         Coupler Cp-5 1.00g         Coupler Cp-6 0.020g         High-boiling organic solvent Oil-2 0.10g         High boiling point organic solvent Oil-3 0.020g         UV absorber U-6 0.10g         Compound Cpd-B 0.20 g         Compound Cpd-N 5.0 mg. [0179]   17th layer: 1st protective layer         1.00g gelatin         UV absorber U-1 0.15g         UV absorber U-2 0.050 g         UV absorber U-5 0.20g         Compound Cpd-O 5.0 mg         Compound Cpd-A 0.030 g         Compound Cpd-H 0.20 g         Dye D-1 8.0mg         Dye D-2 0.010g         Dye D-3 0.010 g         0.10 g of high boiling point organic solvent Oil-3. [0180]   18th layer: 2nd protective layer         Colloidal silver Silver amount 2.5mg         Fine grain silver iodobromide emulsion       (Silver iodide content 1 mol%, sphere equivalent average particle size 0.06 μm)                                                 Silver amount 0.10g         Gelatin 0.80g         UV absorber U-1 0.030g         UV absorber U-6 0.030g         High boiling point organic solvent Oil-3 0.010 g. [0181]   19th layer: 3rd protective layer         1.00g gelatin         0.10 g of polymethyl methacrylate (average particle size 1.5 μm)         6: 4 copolymer of methyl methacrylate and methacrylic acid                               (Average particle size 1.5 μm) 0.15 g         Silicone oil SO-1 0.20g         Surfactant W-3 3.0mg         Surfactant W-2 8.0mg         Surfactant W-1 0.040g         Surfactant W-7 0.015 g. In addition to the above composition, all emulsion layers have
Additives F-1 to F-9 were added. Furthermore, each layer has the above
In addition to the composition, gelatin hardener H-1 and for coating and emulsification
Surfactants W-1, W-4, W-5, and W-6
It was. Furthermore, phenol, 1,2-
Benzisothiazoline-3-one, 2-phenoxyeta
Nord, phenethyl alcohol, p-butyl benzoate
Stealth was added. [0183] [Table 2] [0184] [Table 3][0185] [Table 4] [0186] [Table 5][0187] Embedded image[0188] Embedded image [0189] Embedded image[0190] Embedded image[0191] Embedded image[0192] Embedded image[0193] Embedded image [0194] Embedded image[0195] Embedded image[0196] Embedded image[0197] Embedded image[0198] Embedded image[0199] Embedded image[0200] Embedded imagePreparation of microcrystalline solid dispersion of organic solid disperse dye
Made (Preparation of microcrystalline solid dispersion of dye E-1)
Wet cake (contains 270g as the net amount of E-1)
In addition, BASF Pluronic F88 (ethylene oxide)
Sid-propylene oxide block copolymer) 100
g and water were added and stirred to 4000 g. Next, eye
Ultra Viscomill (UVM-2) manufactured by Mex Corporation
1700m of zirconia beads with an average particle size of 0.5mm
l and discharged through the slurry at a peripheral speed of 10 m / sec.
Milled for 2 hours at an amount of 0.5 l / min. Filter the beads
After adding water and diluting to a dye concentration of 3%, stable
Heated at 90 ° C. for 10 hours for conversion. Obtained fine dye
The average particle size of the particles is 0.30 μm, and the particle size distribution is wide.
(Particle size standard deviation × 100 / average particle size) was 20%.
It was. (Preparation of microcrystalline solid dispersion of dye E-2)
1400g of E-2 wet cake containing 30% water
270 g of water and W-4 were added to the mixture and stirred to obtain an E-2 concentration of 4
The slurry was 0% by mass. Next, crusher, Imex
Average grain in Ultraviscomil (UVM-2)
Filled with 1700 ml of 0.5 mm zirconia beads
The peripheral speed is 10 m / sec through the slurry, and the discharge amount is 0.5.
E-2 grind for 8 hours and disperse E-2 solid fine particles
I got a thing. Diluted to 20% by mass with ion-exchanged water
Thus, a microcrystalline solid dispersion was obtained. Average particle size is 0.15 μm
Met. Preparation of samples 202 to 216 The 9th to 11th layers of green sensitive milk in the sample 201
The test was carried out by changing the coupler of the agent layer in equimolar amounts as shown in Table 4.
Fees 202-210 were created. Samples 201 and 20
2, 204, 205, 208 and the ninth layer of the sample 209
Except for removing Cpd-R (SR-1) in the 11th layer
Materials 201, 202, 204, 205, 208 and Sample 2
Samples 211 to 216 were prepared in the same manner as 09
It was. [0204] [Table 6] Samples 202 to 21 obtained in this way
Example 1 Evaluation of Color Development / Sensitivity of No. 6 and Yellow Stain
The same method was used. In Example 2, the cyan density,
Maximum color density for magenta and yellow color image densities
Concentration and sensitivity were determined. The results are shown in Table 5. [0206] [Table 7] From the results shown in Table 5, Comparative Coupler A
Sample 201 had a high color density as in Example 1,
Many yellow stains occur in a humid heat atmosphere.
Similarly, samples 202 to 203 of comparative coupler C are
The highest color density in Illes is low, cyan and yellow
The color density is not well balanced, causing color changes.
I understand that In contrast, samples 205 to 21 of the present invention.
0 has no such problem and has achieved the object of the present invention.
The In the sample 208 of the present invention, the sensitivity of the magenta image is slightly higher.
Sample 2 has a low color shift from other color images.
Use of 10 can suppress the color shift
understood. In addition to this, as in Example 1, the color developer was changed.
Evaluate pH dependency and color developer addition amount dependency.
As in Example 1, the samples 205 to 21 of the present invention were used.
0 was an excellent effect. In addition, Cpd-R (S
In samples 211 to 216 from which R-1) has been removed, corresponding
In all cases, yellow stain increased.
Cpd-R (SR-1) suppresses yellow stain
I found out that

Continued front page    (72) Inventor Hiroshi Fukuzawa             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd. F-term (reference) 2H016 AA00 BE03 BF06 BG02

Claims (1)

What is claimed is: 1. A silver halide color photographic material comprising at least one coupler represented by the following general formula (1): [Chemical 1] In the formula, R ₁ represents a hydrogen atom or a substituent, and R ₂ represents a group represented by the following general formula (2), general formula (3) or general formula (4), or at least one of the following general formula (2 ), A substituent substituted with the group represented by the general formula (3) or the general formula (4). X represents a group capable of leaving in the reaction with a hydrogen atom or an oxidized form of a color color developing agent. [Chemical 2] In the formula, (EWG1) represents a group having a Hammett substituent constant having a sigma para value of 0.4 or more, and R ₃ represents an alkyl group, an aryl group, or a heterocyclic group. R ₄ represents a substituent, and m represents an integer of 0 to 3. (EWG2) represents a group having a Hammett substituent constant having a sigma para value of 0.4 or more and can be a divalent linking group. n represents an integer of 0 to 4,
* Represents a position bonded to the pyrazolotriazole skeleton represented by the general formula (1) directly or via a linking group.