JP3431359B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a silver halide color.
For photographic light-sensitive materials, more specifically, 1H-pyrazolo
[5,1-c] -1,2,4-triazole magenta
Contains couplers for color reproducibility, color development and magenta color
Silver halide color photographic materials with improved light fastness
About charges. [0002] 2. Description of the Related Art Silver halide color photographic materials are generally used.
To be sensitive to blue, green and red light.
Sensitization consisting of three selectively sensitized silver halide emulsion layers
The optical layer is coated on a support in a multilayer structure,
The photosensitive layer develops three colors, yellow, magenta and cyan.
Photographic couplers. This color image is
After the photosensitive material is exposed, it is subjected to color development with a color developer.
Can be obtained. Color development enables color development
Aromatic primary amine of developing agent and photographic coupler are acid
Reaction, resulting in azomethine or
An indophenol-based coloring pigment is produced. The coloring pigment
Vivid yellow, magenta and cyan with little side absorption
Color photographic image showing good color reproducibility to be a dye
It is important to get. [0003] Conventionally, pyrazolone compounds have been used in magenta.
Used as a puller, pyrazolone coupler
The dyes formed from these have undesirable side absorption,
Improvement was desired. To solve this problem, a U.S.
No. 3,725,065, No. 3,810,761, No. 3,758,309, No.
 3,725,067, etc.
Is being planned. However, pyrazolot with little side absorption
Riazol couplers are not enough in terms of color development
In addition, research on the improvement of color development has been continued.
No. 43, No. 60-98434, No. 61-120152, JP-A-4-260033
Nos., 4-289852 and 5-204106. I
However, the compounds described in the above patents are still unsatisfactory.
Not just a level, but further improvement was desired. on the other hand,
The pyrazolotriazole coupler described in the US patent
Low light fastness of azomethine dyes formed from
Color photographic material, especially print color photographic material
The performance of the optical material was significantly impaired. for that reason,
Research has been conducted to improve the light fastness,
No. 5-88457, No. 6-1358, No. 6-8950, JP
63-24256, JP-A-5-323530, JP-A-5-313326, etc.
Have been. However, the compounds described in the above patents
Light fastness of magenta dyes formed from them is insufficient
Therefore, the improvement has been strongly desired. [0004] SUMMARY OF THE INVENTION The present invention has the above-mentioned problems.
With the aim of providing color photographic light-sensitive materials
I do. More specifically, the first object of the present invention is the chromogenic property.
Is high enough not to deteriorate graininess (size of pigment cloud)
1H-pi which gives a dye having a preferable absorption maximum wavelength
Lazolo [5,1-c] -1,2,4-triazole type
The purpose is to provide a zeta coupler. Of the object of the present invention
Second, the light of the azomethine dye formed from the coupler
By providing color photographic light-sensitive materials with improved robustness
is there. The third object of the present invention is to reproduce color of azomethine dye.
An object of the present invention is to provide a color photographic light-sensitive material having excellent properties. [0005] The above object is achieved by the following general formula:
1H-pyrazolo [5,1-c] -1, represented by (I),
Developed 2,4-triazole magenta coupler
At least one of them being a silver halide color photographic material;
This was achieved by inclusion in the ingredients. General formula (I) [0006] Embedded image(Where R₁And R_FourIs a substituent
And R_TwoAnd R_ThreeAre hydrogen and alkyl
Group, aryl group, hydroxyl group or hydroxyl group
Represents a substituted alkyl group. R₉Is hydrogen atom, alkyl
Represents a group, an aryl group, an acyl group or a sulfonyl group. L
Is -SO_Two-, -CO-, -SO_TwoNR_Ten-, -CON
R_Ten-Or -COO-;_TenIs a hydrogen atom,
Represents an aryl group or an aryl group. A₁, A_TwoAnd A_ThreeHaso
-O-, -NR, respectively_Five-, -NR_FiveCO-, -CON
R_Five-, -NR_FiveSO_Two-, -SO_TwoNR_Five-, -CO
O-, -OCO-, -NR_FiveCONR_Five-, -OCON
R_Five-Or -NHCOO-,_FiveIs a hydrogen atom,
Alkyl, aryl or at least one hydroxy
A substituted alkyl group. B₁, B_TwoAnd B
_ThreeRepresents an alkyl group, an alkylene group, and an aryl, respectively.
Group, arylene group or at least one hydroxyl group
Represents a substituted alkyl group or an alkylene group. s is
Represents an integer of 0 to 3. X is a hydrogen atom or an aromatic first
Elimination by coupling reaction with oxidized form of secondary amine developing agent
Represents a possible group. k represents an integer of 0 to 3, u,
m, n, t and p represent 0 or 1, and q represents 1.
You. However, it is assumed that mn + tp = 0. r is 1 or 2
Represents an integer. R₁, R_Two, R_Three, R_Four, R_Five, B₁,
B_TwoAnd B_ThreeAt least one of the has a hydroxyl group
Shall be. However, the hydroxyl group referred to here is
It is not directly connected to the reel group. The compound of the present invention represented by the general formula (I)
Substituent R of the product₁, R_Two, R_Three, R_Four, R_Five, R₆,
R₇, R₈, R₉, R_Ten, L, X, A₁~ A_Three, B₁~
B_ThreeWill be described in detail. [0009] R₁As the substituent represented by
Groups (for example, straight-chain or branched-chain al
In the kill group, for example, methyl, ethyl, propyl, isop
Ropyl, butyl, t-butyl, octyl, t-octy
Le, decyl, dodecyl, tridecyl, tetradecyl, f
Xadecyl, octadecyl, triphenylmethyl),
Chloroalkyl group (preferably cycloalkyl having 3 to 8 carbon atoms)
In the kill group, for example, cyclopropyl, cyclopentyl,
Cyclohexyl, 1-norbonyl, 1-adamanche
), An alkenyl group (preferably an alkyl having 2 to 32 carbon atoms)
In the phenyl group, for example, vinyl, allyl, 3-butene-1
-Yl), an aryl group (preferably an alkyl group having 6 to 32 carbon atoms)
In the reel group, for example, phenyl, 1-naphthyl, 2-na
Fthyl), a heterocyclic group (preferably having 1 to 32 carbon atoms, 5
And an 8-membered heterocyclic group such as 2-thienyl, 4
-Pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyri
Jill, 2-benzothiazolyl, 1-imidazolyl, 1-
Pyrazolyl, benzotriazol-2-yl), cyano
Group, halogen atom (for example, fluorine atom, chlorine atom, bromine
Atom), hydroxyl group, nitro group, alkoxy group (preferably
Preferably, it is an alkoxy group having 1 to 32 carbon atoms.
Toxic, ethoxy, 1-butoxy, 2-butoxy, iso
Propoxy, t-butoxy, dodecyloxy), cyclo
An alkyloxy group (preferably having 3 to 8 carbon atoms)
A cycloalkyloxy group, for example, cyclopentyloxy
, Cyclohexyloxy), aryloxy group (preferred)
Or an aryloxy group having 6 to 32 carbon atoms, for example,
Phenoxy, 2-methoxyphenoxy, 4-methoxyp
Enoxy, 2,6-dimethoxyphenoxy, 2-naphtho
Xy), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms)
A heterocyclic oxy group such as 1-phenyltetrazole
-5-oxy, 2-tetrahydropyranyloxy, 2-
Furyloxy), silyloxy group (preferably having 1 carbon atom)
~ 32 silyloxy groups such as trimethylsilyl
Oxy, t-butyl dimethylsilyloxy, diphenyl
Methylsilyloxy), acyloxy group (preferably charcoal
An acyloxy group having a prime number of 2 to 32;
Si, pivaloyloxy, benzoyloxy, dodecanoi
Loxy), an alkoxycarbonyloxy group (preferably
Is an alkoxycarbonyloxy group having 2 to 32 carbon atoms,
For example, ethoxycarbonyloxy, t-butoxycal
Bonyloxy), cycloalkyloxycarbonyloxy
A cyclo group (preferably a cycloalkyl group having 4 to 9 carbon atoms)
A xycarbonyloxy group, for example, cyclohexylo
Xycarbonyloxy), aryloxycarbonyl
Xy group (preferably aryloxyca having 7 to 32 carbon atoms)
With a rubonyloxy group, for example, phenoxycarbonyl
Xy), carbamoyloxy group (preferably having 1 to
32 carbamoyloxy groups such as N, N-dim
Tylcarbamoyloxy, N-butylcarbamoyloxy
B) a sulfamoyloxy group (preferably having 1 to
32 sulfamoyloxy groups, for example, N, N-di
Ethyl sulfamoyloxy, N-propyl sulfamo
Yloxy), alkanesulfonyloxy group (preferably
Is an alkanesulfonyloxy group having 1 to 32 carbon atoms, for example
For example, methanesulfonyloxy, hexadecanesulfoni
Oxy), arenesulfonyloxy group (preferably
An arenesulfonyloxy group having 6 to 32 carbon atoms, for example,
Benzenesulfonyloxy), an acyl group (preferably
Is an acyl group having 1 to 32 carbon atoms, for example, formyl,
Cetyl, pivaloyl, benzoyl, tetradecanoy
), An alkoxycarbonyl group (preferably having 2 to 2 carbon atoms)
32 alkoxycarbonyl groups, for example, methoxy
Carbonyl, ethoxycarbonyloctadecyloxyca
Rubonyl), cycloalkyloxycarbonyl group (preferably
Or cycloalkyloxycarbonyl having 2 to 32 carbon atoms
Groups such as cyclohexyloxycarbonyl), a
Reeloxycarbonyl group (preferably having 7 to 32 carbon atoms)
Aryloxycarbonyl group, for example, phenoxy
Carbonyl), carbamoyl group (preferably having 1 to
32 carbamoyl groups such as carbamoyl, N,
N-dibutylcarbamoyl, N-ethyl-N-octyl
Carbamoyl, N-propylcarbamoyl), amino group
(Preferably, an amino group having 32 or less carbon atoms, for example,
Mino, methylamino, N, N-dioctylamino, tet
Radecylamino, octadecylamino), anilino group
(Preferably an anilino group having 6 to 32 carbon atoms, for example,
Anilino, N-methylanilino), a heterocyclic amino group (preferably
Preferably a heterocyclic amino group having 1 to 32 carbon atoms, for example,
4-pyridylamino), carbonamido group (preferably
C2 to C32 carbonamido group, for example, aceto
Amide, tetradecane amide), ureido group (preferably
Is a ureido group having 1 to 32 carbon atoms, for example, ureido,
N, N-dimethylureido, N-phenylureido),
An imide group (preferably an imide group having 10 or less carbon atoms;
For example, N-succinimide, N-phthalimide),
A oxycarbonylamide group (preferably having 2 to 32 carbon atoms)
An alkoxycarbonylamide group of, for example, methoxy
Carbonylamino, ethoxycarbonylamino, t-butyl
Toxylcarbonylamino, octadecyloxycarboni
Amino), an aryloxycarbonylamino group (preferably
Or aryloxycarbonylamido having 7 to 32 carbon atoms
Groups, for example, phenoxycarbonylamino), sulf
Honamide group (preferably a sulfonate having 1 to 32 carbon atoms)
In the mid group, for example, methanesulfonamide, butanesulfur
Honamide, benzenesulfonamide, hexadecane
Sulfonamide), a sulfamoylamino group (preferably
In a sulfamoylamino group having 1 to 32 carbon atoms, for example,
N, N-dipropylsulfamoylamino, N-ethyl
-N-dodecylsulfamoylamino), an azo group (preferably
Or an azo group having 1 to 32 carbon atoms, such as phenyla
Zo), an alkylthio group (preferably an alkylthio group having 1 to 32 carbon atoms)
Alkylthio group, for example, ethylthio, octylchi
E), an arylthio group (preferably an alkyl group having 6 to 32 carbon atoms)
A reelthio group such as phenylthio), a heterocyclic thio
Group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, for example,
For example, 2-benzothiazolylthio, 2-pyridylthio, 1
-Phenyltetrazolylthio), alkylsulfinyl
Group (preferably alkylsulfinyl having 1 to 32 carbon atoms)
Groups, for example, dodecanesulfinyl), arenesulfan
Finyl (preferably arene sulfone having 6 to 32 carbon atoms)
Ynyl group such as benzenesulfinyl), alka
Sulfonyl group (preferably an alkane having 1 to 32 carbon atoms)
A sulfonyl group such as methanesulfonyl, octane
Sulfonyl), arene sulfonyl group (preferably carbon
An arenesulfonyl group of the number 6 to 32;
Sulfonyl, 1-naphthalenesulfonyl), sulfa
Moyl group (preferably sulfamoyl having 32 or less carbon atoms)
Groups, for example, sulfamoyl, N, N-dipropyls
Rufamoyl, N-ethyl N-dodecyl sulfamoy
), A sulfo group, a phosphonyl group (preferably having 1 to
32 phosphonyl groups such as, for example, phenoxyphosphoni
Phenylphosphonyl). In the general formula (I), R₁The group represented by
May have a substituent, and preferred substituents are
Halogen atom, alkyl group, cycloalkyl group, alk
Nyl group, aryl group, heterocyclic group, cyano group, hydroxy
Group, carboxyl group, nitro group, alkoxy group, ant
Oxy, heterocyclic oxy, silyloxy, acyl
Ruoxy group, alkoxycarbonyloxy group, aryl
Oxycarbonyloxy group, carbamoyloxy group,
Rufamoyloxy group, alkanesulfonyloxy group,
Arenesulfonyloxy group, acyl group, alkoxyca
Rubonyl group, cycloalkyloxycarbonyl group, ant
Oxycarbonyl group, carbamoyl group, amino group,
Anilino group, heterocyclic amino group, carbonamide group, al
Coxycarbonylamino group, aryloxycarbonyl
Amino group, ureido group, sulfonamide group, sulfamo
Yl group, imide group, alkylthio group, arylthio group,
Heterocyclic thio group, sulfinyl group, sulfo group, alkanth
Ruphonyl group, arenesulfonyl group, sulfamoyl
And sulfonyl groups. Next, the substituent R of the general formula (I)_TwoAnd R_Three
Will be described in detail. R_TwoAnd R_ThreeRespectively
Hydrogen atom, alkyl group (R₁Same as the alkyl group defined in
Group), an aryl group (R₁Aryl as defined in
A group having the same meaning as the group), a hydroxyl group or at least
An alkyl group substituted by one hydroxyl group (preferably
Represents at least one of a linear or branched chain having 1 to 32 carbon atoms
Alkyl group having two hydroxyl groups, for example,
Droxymethyl, dihydroxymethyl, 1-hydroxy
Ethyl, 2-hydroxyethyl, 1,2-dihydroxy
Ethyl, 2-hydroxypropyl, 3-hydroxypro
Pill, 2,3-dihydroxypropyl, 4-hydroxy
Butyl, 3,4-dihydroxybutyl, 1,1-dimethyl
2-hydroxyethyl, 1,1-dihydroxymethyl
Ethyl, 2-trihydroxymethylethyl, 5-hydr
Roxyamyl). Also, R_TwoAnd R_ThreeAre each other
They may combine to form a ring. R_FourAs the substituent represented by
Group, cycloalkyl group, alkenyl group, aryl group,
Ring group, cyano group, halogen atom, hydroxyl group,
Toro, alkoxy, cycloalkyloxy, ant
Oxy, heterocyclic oxy, silyloxy, acyl
Ruoxy group, alkoxycarbonyloxy group, cycloa
Alkyloxycarbonyloxy group, aryloxycal
Bonyloxy group, carbamoyloxy group, sulfamoi
Ruoxy group, alkanesulfonyloxy group, arene
Ruphonyloxy group, acyl group, alkoxycarbonyl
Group, cycloalkyloxycarbonyl group, aryloxy
Cicarbonyl group, carbamoyl group, amino group, anilino
Group, heterocyclic amino group, carbonamido group, ureido group,
Imido group, alkoxycarbonylamino group, arylo
Xycarbonylamino group, sulfonamide group, sulfa
Moylamino group, azo group, alkylthio group, arylthio
O group, heterocyclic thio group, alkylsulfinyl group, array
Sulfinyl group, alkane sulfonyl group, arene
Ruphonyl group, sulfamoyl group, sulfo group, sulfonyl
And specific examples of these groups are represented by the general formula (I):₁
Is the same as that described in the description of the group represented by. R_Two, R
_ThreeAnd R_FourThe group represented by further has a substituent
And a preferred substituent is R₁Same as mentioned in the description
Righteous. In the general formula (I), R₉The group represented by is hydrogen
Atom, alkyl group (R₁Has the same meaning as the alkyl group defined in
Group), an aryl group (R₁The aryl group defined in
A synonymous group), an acyl group (R₁Acyl group defined in
And a sulfonyl group (R₁Defined by
Represents a group having the same meaning as the above-mentioned sulfonyl group). R₉Represented by
Group may further have a substituent, is preferred.
The substituent is R₁Is synonymous with the description given above. L is -S
O_Two-, -CO-, -SO_TwoNR_Ten-, -CONR_Ten−
Or -COO-. R_TenIs a hydrogen atom, an alkyl group
(R₁A group having the same meaning as the alkyl group defined in
Reel group (R₁The groups having the same meanings as the aryl groups defined in
Represents). R_TenThe group represented by further has a substituent
And a preferred substituent is R₁I gave it in the description
It is synonymous. A₁, A_TwoAnd A_ThreeIs -O-,
-NR_Five-, -NR_FiveCO-, -CONR_Five-, -NR
_FiveSO_Two-, -SO_TwoNR_Five-, -COO-, -OCO
-, -NR_FiveCONR_Five-, -OCONR_FiveOr -NH
Represents COO-. R_FiveIs hydrogen atom, alkyl group, aryl
Or a group substituted by at least one hydroxyl group.
Represents an alkyl group, more specifically an alkyl group and an aryl group.
Is R₁Has the same meaning as the group defined in
The alkyl group substituted by the hydroxyl group of R is_TwoAnd R_Three
Has the same meaning as the group defined in B₁, B_TwoAnd B_ThreeAre archi
Group, alkylene group, aryl group, arylene group or
An alkyl group substituted by at least one hydroxyl group and
And an alkylene group. Alkyl and aryl groups
Is R₁Has the same meaning as the group defined in The arylene group is
Ants having 6 to 32 carbon atoms represented by the following general formula (II)
Represents an allene group. General formula (II) [0016] Embedded image Where R₆Represents a substituent and has the general formula (I)
R₁Has the same meaning as the substituent defined in a is 0 to 4
Represents an integer. At least one hydroxyl group is substituted
The substituted alkyl group is represented by the general formula (I):_TwoAnd R_ThreeFixed in
Synonymous with the defined group. Alkylene group and at least
The alkylene group substituted by one hydroxyl group is as follows:
C1-C32 alkylene represented by the general formula (III)
Represents a group. General formula (III) [0018] Embedded image Where R₇And R₈Are hydrogen sources
Group, alkyl group, aryl group, hydroxyl group or
An alkyl group substituted by at least one hydroxyl group
And R of the general formula (I)_TwoAnd R_ThreeWith the substituent defined in
It is synonymous. b represents an integer of 0 to 4. In the general formula (I), X represents a hydrogen atom or a developing agent
It represents a group that can be removed by reaction with an oxidant. For more information,
The removable group is a halogen atom, an alkoxy group, an aryl
Oxy, acyloxy, carbamoyloxy,
Rufonyloxy group, carbonamide group, sulfonamide
Group, carbamoylamino group, heterocyclic group, arylazo
Group, alkylthio group, arylthio group, heterocyclic thio group
Which. Preferred ranges and specific examples of these groups are R₁
Are the same as those described in the description of the group represented by. X is ha
When X represents a removable group other than a logogen atom, X
The substituent which may have a substituent is preferably R₁Represented by
It is the same as the group described as the substituent of the group. X is these
Besides, via an aldehyde or ketone, four equivalents of two molecules
In some cases, it is a bis-type coupler to which a puller is connected.
Is a development accelerator, development inhibitor, desilvering accelerator or leuco dye
Or other photographically useful groups such as
It may be a group in a form blocked in terms of the nature. The compounds represented by formula (I) are described below.
A preferred range will be described. R₁Is an alkyl group,
Reel group, alkoxy group, aryloxy group, alkyl
Thio group, arylthio group, ureido group, oxycarboni
A ruamino group or an amide group is preferred. Among these,
Primary or secondary alkyl group, al
Coxy groups and aryloxy groups are preferred, and
Tertiary alkyl group or ant in terms of light and heat fastness
An oxy group is particularly preferred. R₁A group represented by
Specific examples include the following. [0022] Embedded image [0023] Embedded imageR_TwoAnd R_ThreeIs a hydrogen atom, alkyl
Group, aryl group or at least one hydroxyl group
A substituted alkyl group is preferable, and specific examples of a preferable substituent are
Examples are methyl, ethyl, propyl, isopropyl
Group, butyl group, t-butyl group, octyl group, dodecyl
Group, benzyl group, cyclohexyl group, phenyl group, hydride
A roxymethyl group or a 2-hydroxyethyl group;
I can do it. s is preferably 0 or 1. R_FourIs a haloge
Atom, alkyl group, aryl group, alkoxy group, ant
Oxy group, alkoxycarbonyl group, aryloxy
Cicarbonyl group, carbamoyl group, amino group, carboxyl
Amido group, sulfonamide group, alkylthio group or ant
Thiol groups are preferred. k is preferably from 0 to 2, most preferably
Is also preferably 1. X is a halogen atom, an aryloxy group,
Carbamoyloxy group, acylamino group, heterocyclic group,
Reel azo group, alkylthio group, arylthio group or multiple
A prime ring thio group is preferable, and a halogen atom, an aryloxy
Group, heterocyclic group, alkylthio group, arylthio group or
More preferably, the ring thio group is a halogen atom or an aryl.
A ruoxy group is most preferred. Preferred groups represented by X
Specific examples include the following. [0026] Embedded image[0027] Embedded imageNext, A₁~ A_Three, B₁~ B_ThreeAnd F
The preferred range of the substituent to be used will be described. A₁,
A_TwoAnd A_ThreeIs -O-, -NR_Five-, -NR_FiveCO
-, -CONR_Five-, -NR_FiveSO_Two-, -SO_TwoNR
_Five-, -COO-, -NR_FiveCONR_Five-Or-NHC
OO- is preferred, and R_FiveIs a hydrogen atom, an alkyl group and
Alkyl groups substituted by hydroxy groups are preferred. Preferred
I R_FiveIs a specific example of R_TwoAnd R_ThreePreferred specific examples of
It is the same as shown. B₁, B_TwoAnd B_ThreeOf the substituents of
Alkyl, aryl and at least one hydroxy
Preferred specific examples of the alkyl group substituted with a sil group include methyl
Group, ethyl group, propyl group, isopropyl group, butyl
Group, t-butyl group, octyl group, dodecyl group,
Xyl group, phenyl group, hydroxymethyl group, 2-hydrido
Roxyethyl group, 3-hydroxypropyl group, 2,3-
Dihydroxypropyl group, 4-hydroxybutyl group,
3,4-dihydroxybutyl group and 1,1-dihydro
A xymethylethyl group and the like can be mentioned. Arylene-based
Preferred specific examples include the following. [0030] Embedded imageIn the formula, * represents the pyrazolotriazole nucleus side.
Indicates a near substitution position. Alkylene group or at least one
Preferred alkylene group substituted with a hydroxyl group
Examples of the body include the following. [0032] Embedded image In the formula, * represents the pyrazolotriazole nucleus side.
Indicates a near substitution position. For compounds represented by the general formula (I)
A₁~ A_Three, B₁~ B_ThreeOf the substituent represented by
A preferred combination of numbers is that u, m, n and q are each
If t and p are 0 and u and q are 1
It is preferred that m, n, t and p are each 0.
No. In the compound represented by the general formula (I),
The substitution position of the silalkyl group is B₁, B_TwoAnd B_ThreeIncluded in
Is preferred, B_ThreeIs most preferably included
No. When the compound represented by the general formula (I) is a diffusion-resistant compound,
And particularly preferably the non-diffusible group is R₁, R_Two,
R_Three, R_Four, B₁, B_TwoOr B_ThreeIs included in
You. Next, substitution of the compound represented by the general formula (I)
Preferred combinations of groups will be described. R₁Is al
When a kill group, an alkoxy group or an aryloxy group,
R_TwoAnd R_ThreeAre a hydrogen atom, an alkyl group,
Or at least one hydroxyl group is substituted
Alkyl group, R₉Is a hydrogen atom or an alkyl group, L
Is a sulfonyl group or a carbonyl group, and X is a halogen atom
Preferably an aryl, an aryloxy group or a heterocyclic group.
New Most preferred substituents of the compounds represented by formula (I)
A good combination is R₁Is an alkyl group (preferred specific
Examples are methyl, ethyl, isopropyl and t-butyl)
And R_TwoAnd R_ThreeIs a hydrogen atom or
Alkyl groups (preferred examples are methyl, ethyl and isoprene)
Ropir) and R₉Is a hydrogen atom or an alkyl group (preferably
Preferred examples are methyl and ethyl), wherein L is sulfo.
X is a chlorine atom or an aryloxy group
(A preferred embodiment is p-methoxycarbonylphenylo
Xy, p-methylphenyloxy), wherein s is 0 or
Is 1, and u, m, n and q are each 1 and t and
And p is 0, or u and q are 1 and m, n, t and
p is 0, r is 1 and hydroxy is
The substitution position of the silalkyl group is B₁, B_TwoAnd B_ThreeIncluded in
Is the case. The following is a general formula which can be used in the present invention.
Pyrazolotriazole magenta coupler represented by (I)
Specific examples are given below, but the present invention is not limited thereby.
Not something. [0036] Embedded image [0037] Embedded image[0038] Embedded image[0039] Embedded image[0040] Embedded image[0041] Embedded image[0042] Embedded image[0043] Embedded image[0044] Embedded image[0045] Embedded image[0046] Embedded image[0047] Embedded imageThe pyrazolotriazole coupler of the present invention
5-amino-1H-pyrazole compound as starting material
Are described in JP-A-4-66573 and JP-A-4-66574.
It can be synthesized by the method described above, and the intermediate 3
(5) -Hydrazinopyrazole compounds are disclosed in JP-A-4-3.
It can be synthesized by the method described in JP-A-64170. Book
The skeleton of the pyrazolotriazole coupler of the invention is
It is described in Kaihei 3-220191 and 5-204106.
Can be synthesized by the method described above. Hereinafter, the compound represented by the general formula (I) of the present invention will be described.
A specific synthesis example of the compound is shown. Synthesis Example 1 (Synthesis of Exemplified Compound M-1) Exemplified compound M-1 is synthesized according to the following scheme.
Was completed. [0050] Embedded imageSynthesis of Intermediate (2) 98.1 g (0.365 mol) of intermediate (1) was
The solution was added to 1 liter of nitrile, cooled with water, and stirred. This
204 ml of triethylamine (1.46 mol)
The mixture was further stirred for 10 minutes. Further, intermediate (2) 86.7
g (0.365 ml) was added and stirred for 3 hours. Reaction mixture
Mix 1.5 liters of water and 1 liter of ethyl acetate
It was added to the solvent and extracted. The organic layer was diluted with 800 ml of diluted hydrochloric acid.
After washing sequentially with 800 ml of a saline solution, anhydrous sodium sulfate was used.
Dried with um. Ethyl acetate was distilled off under reduced pressure,
Used for the next step without purification. Synthesis of intermediate (4) 99 g (0.228 mol) of the intermediate (2) previously synthesized
Was dissolved in 600 ml of acetonitrile, and carbon tetrachloride 14 was dissolved.
0 g (0.912 ml) was added and the mixture was stirred at room temperature. this
89.9 g of triphenylphosphine (0.342 mol)
l) was added and stirred for 1 hour. 2 hours under reflux
After stirring, the mixture was cooled with water to room temperature. The reaction mixture is
It was added to 600 ml of chill and 800 ml of water. Saturate organic layer
After washing with 500 ml of saline, 70 ml of triethylamine
(0.5 mol) and left at room temperature for 10 minutes.
Wash with 500 ml of dilute hydrochloric acid and then with 500 ml of saturated saline
And dried over anhydrous sodium sulfate. Organic layer under reduced pressure
Distill off and purify by silica gel column chromatography.
After that, 250 ml of acetonitrile were added. Precipitated
The crystals were collected by filtration and 48.8 g of intermediate compound (4) (yield 51.
5%). The structure of the product is¹HNMR and mass
Fixed by spectrum. The melting point is 186-187 ° C
there were. Synthesis of Intermediate (5) 37 g (0.089 mol) of intermediate (4) was
Dissolved in alcohol. Hydrazi hydrate under stirring at room temperature
5.3 g (0.106 mol) was added and stirred for 30 minutes.
did. Further, after heating and refluxing for 2 hours, the mixture was cooled with water and cooled to room temperature.
And The insolubles are removed by filtration, and the organic solvent in the filtrate is reduced under reduced pressure.
The residue was distilled under reduced pressure to obtain 25 g of a glassy intermediate (5) (yield: 9).
8.5%). Synthesis of intermediate (7) 10.5 g (0.037 mol) of the intermediate (5) previously synthesized
l) in a mixed solvent of dimethylacetamide and ethyl acetate
Dissolved. While stirring at room temperature, 18.9 g of intermediate (6)
(0.0368 mol) was added dropwise, followed by triethyl alcohol.
5.6 ml (0.04 mol) of min was added dropwise. At room temperature
After stirring for 2 hours, the reaction mixture was added to 100 ml of ethyl acetate.
And 100 ml of water. The organic layer was diluted with 100 ml of dilute hydrochloric acid,
After washing sequentially with 100 ml of saturated saline, anhydrous sodium sulfate was added.
Dried with lium. After evaporating the solvent under reduced pressure, the silica
Purified by gel column chromatography
17.7 g (yield: 65.0%) of the intermediate (7) was obtained. Generate
The structure of an object is¹Solid by HNMR and mass spectrum
Specified. Synthesis of Intermediate (8) 14 g (0.25 mol) of reduced iron and ammonium chloride
1 g (0.019 mol) of isopropyl alcohol
It was added to a mixed solvent of 200 ml and 20 ml of water. Heat reflux
For 20 minutes, and then 23 g of the intermediate (7) previously synthesized
(0.031 mol) was added in portions. Further heating
After flowing for 1 hour, the reduced iron was removed by hot filtration.
Was. The solvent is distilled off under reduced pressure to give a glassy intermediate (8)
22.1 g (100% yield) was obtained. Synthesis of intermediate (9) 6.3 g of the previously synthesized intermediate (8) (0.009 mol)
l) was dissolved in 80 ml of ethyl acetate. Under stirring at room temperature,
Diacetoxypivalic acid chloride 2.1 g (0.00
9 mol), and then 1.3 ml of triethylamine was added.
(0.0093 mol) was added dropwise. The reaction mixture is
Added to 00 ml. 100 ml of diluted hydrochloric acid, saturated food
After sequentially washing with 100 ml of brine, anhydrous sodium sulfate
And dried. After distilling off the solvent, the silica gel
7. Intermediate (9) purified by chromatography and as an oil
5 g (90.4% yield) was obtained. Synthesis of Exemplified Compound (M-1) 8.5 g of the previously synthesized intermediate (9) (0.0094 mo)
l) was dissolved in 30 ml of ethanol. Under stirring at room temperature,
1.9 g (0.048 mol) of sodium hydroxide was added to water 2
A solution dissolved in 0 ml was added dropwise. Stir for 1 hour at room temperature
After that, the reaction mixture was mixed with 100 ml of ethyl acetate and 100 ml of water.
l. The organic layer was diluted with 100 ml of diluted hydrochloric acid and saturated saline 1
After washing successively with 00 ml, drying over sodium sulfate
Was. After distilling off the solvent, silica gel column chromatography
Purified by fee. The solvent is distilled off to give a powdered compound.
5.8 g (yield 75.0%) of product (M-1) was obtained. Generate
The structure of an object is¹Solid by HNMR and mass spectrum
Specified.¹ HNMR (CDCl_Three) Σ (ppm) (multiplicity, product
Minutes) 10.96 (s, 1H), 9.12 (s, 1H), 7.70 (d.d, 1H), 7.57 (d, 1
H), 7.04 (d, 2H), 6.72 (d, 2H), 6.60 (d, 1H), 6.20 (d, 1H), 4.9
9 to 4.78 (m, 1H), 4.38 to 3.90 (br, 2H), 3.91 to 3.54 (m, 6
H), 2.66-2.45 (m, 2H), 2.27 (s, 3H), 1.91-1.65 (m, 2H),
1.71 (d, 3H), 1.52-1.10 (m, 30H), 1.19 (t, 3H), 1.08 (s, 3
H), 0.87 (t, 3H) Synthesis Example 2 (Synthesis of Exemplified Compound M-3) Exemplified compound M-3 is synthesized according to the following scheme.
Was completed. [0055] Embedded imageSynthesis of Intermediate (11) Intermediate (10) 20.6 g (0.1 mol), α-bro
40.3 g (0.12 mol) of ethyl mommyristate
And 27.6 g (0.2 mol) of potassium carbonate
It was added to 200 ml of ruformamide. 5 at 80-90 ° C
After stirring for an hour, the mixture was cooled with water to room temperature. Excess potassium carbonate
After removing the aluminum, the reaction mixture was diluted with 300 ml of ethyl acetate.
1, 300 ml of water. With 300 ml of saturated saline
After washing three times, it was dried over anhydrous sodium sulfate. solvent
Was distilled off under reduced pressure to obtain an oily intermediate (11) 50.4
g (100% yield). Synthesis of intermediate (12) 50.4 g of the intermediate (11) previously synthesized (0.1 mol
l) was dissolved in 200 ml of methylene chloride. Disturb under ice cooling
While stirring, 10 ml of chlorosulfonic acid (0.14 mo
l) was added dropwise while maintaining the temperature at 10 ° C or lower. 10 ℃
For 1 hour and then at room temperature for 1 hour. Then, under water cooling,
90 ml of dimethylacetamide, 45 m of acetonitrile
l of the mixed solvent was added dropwise. Phosphorus oxychloride under reflux
18.4 ml (0.2 ml) was added dropwise. Further heating reflux
Was carried out for 1 hour, and then cooled with water to room temperature. The reaction mixture
The mixture was added to ice water and extracted with 300 ml of ethyl acetate. Saturation
After washing three times with 300 ml of saline, anhydrous sodium sulfate
Dried. The solvent is distilled off under reduced pressure to give an oily intermediate
55.9 g of the compound (12) were obtained (yield: 100%). Synthesis of Intermediate (13) 20 g (0.5 mol) of sodium hydroxide in 40 ml of water
And ethanol in a mixed solvent of 110 ml. 5
Heated to a temperature of 0 ° C and stirred with the intermediate synthesized earlier
Apply 55.9 g (0.1 mol) of body (12) for 20 minutes
And dropped. After heating under reflux for 30 minutes, concentrated hydrochloric acid
52 ml was added to make it acidic. The reaction mixture is
To 300 ml of water and 300 ml of water. With hydrochloric acid aqueous solution
After washing, it was dried over magnesium sulfate. Decompress the solvent
The residue was distilled under reduced pressure to obtain 46 g of an oily intermediate (13) (yield: 8).
9.9%). Synthesis of intermediate (14) 46 g of the previously synthesized intermediate (13) (0.072 mol
l) 130 ml of acetonitrile and dimethylacetoa
The amide was dissolved in 65 ml of the mixed solvent. Under stirring at room temperature,
26.7 ml (0.29 mol) of phosphorus oxychloride was added to 30
It was added dropwise over a period of minutes. 30 minutes at room temperature, followed by 50-6
After stirring for 30 minutes at a temperature of 0 ° C., allow to cool to room temperature.
Was. The mixture was extracted twice with 200 ml of n-hexane. n-hex
The sun is distilled off under reduced pressure to obtain an oily intermediate (14).
4.6 g (80.5% yield) was obtained. Synthesis of Intermediate (15) 1.5 g of 2-hydroxyethylamine (0.024 mo
l) and 6.1 g of sodium bicarbonate (0.072 m
ol) to 70 ml of ethyl acetate and 150 ml of water.
Was. 13.2 g of intermediate (14) previously synthesized under water cooling
(0.024 mol) over 15 minutes.
Stir for 30 minutes. After washing the organic layer with saturated saline,
Dried over magnesium sulfate. The solvent was distilled off under reduced pressure
Thereafter, the product was purified by column chromatography. Decompress the solvent
The residue was distilled under reduced pressure to obtain 12.3 g of an oily intermediate (15) (yield
Rate of 88.6%). Synthesis of Exemplified Compound (M-3) 3.6 g (0.011 mol) of intermediate (16)
-Dissolved in 22 ml (0.189 mol) of lutidine.
5. Intermediate (15) previously synthesized while stirring under water cooling
3 g (0.011 mol) was added dropwise over 20 minutes.
Thereafter, the mixture was further stirred for 1 hour. The reaction mixture was diluted with ethyl acetate 1
00 ml and 150 ml of water. 20 ml concentrated hydrochloric acid
To make it weakly acidic. After washing with saturated saline, sulfuric acid
Dried over magnesium. After distilling off the solvent under reduced pressure,
Purified by column chromatography. Solvent under reduced pressure
After distillation, 7.6 g of the exemplary compound (M-3) (yield 79.4)
%). The structure of the product is¹NMR and mass spec
It was fixed by a vector.¹ HNMR (CDCl_Three) Σ (ppm) (multiplicity, integration
Value) 10.73 (s, 0.5H), 9.86 (s, 0.5H), 8.15 (t, 0.5H), 8.00 ~
7.80 (m, 3H), 7.73 (t, 0.5H), 7.55 to 7.38 (m, 1H), 6.97 to 6.
73 (m, 3.5H), 6.20 (d, 0.5H), 5.19 ~ 5.00 (m, 0.5H), 4.91 ~
4.79 (m, 0.5H), 4.82 (t, 0.5H), 4.70 (t, 0.5H), 4.63 to 4.25
(br, 1H), 3.89 (s, 3H), 3.97 to 2.95 (m, 3H), 3.70 (t, 1H), 2.
65 to 2.50 (m, 2H), 2.13 to 1.93 (m, 2H), 1.85 to 1.40 (m, 7
H), 1.40-1.10 (m, 27H), 0.88 (t, 3H), 0.70 (s, 4.5H), 0.60
(s, 4.5H) The coupler of the present invention represented by formula (I)
Is added to a silver halide color photographic light-sensitive material.
Any sensitivity layer may be used as long as it is a green-sensitive emulsion layer of the material. So
3 × 10^-Five~ 3 × 10^-3mol / m^TwoAnd good
Preferably 3 × 10^-Four~ 2 × 10^-3mol / m^TwoAnd 1 ×
10^-Four~ 1.5 × 10^-3mol / m^TwoIs more preferred. Attachment
If the added amount is less than the above lower limit, the maximum color density becomes insufficient.
If it is more than the above upper limit, couplers are used unnecessarily
This is wasteful in terms of cost. The silver halide photographic emulsion of the present invention and the silver halide photographic emulsion
Because it is used for silver halide photographic materials using
About various technologies and inorganic and organic materials
Research Disclosure No. 308119 (19
89) can be used. In addition, more specifically, for example,
Color photography to which the silver halide photographic emulsion of the present invention can be applied
Technologies and inorganic / organic elements that can be used for photosensitive materials
For the materials, see the following in EP 436,938 A2
And in the patents cited below. [0062]       Item Applicable section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Silver halide emulsion, page 147, line 26 to page 148, line 12 3) Yellow Coupler, page 137, line 35 to page 146, line 33,                           Page 9, lines 21-23 4) Magenta coupler, page 149, lines 24 to 28; EP 42                           No. 1,453A1, page 3, line 5 to page 25, line 55                           Eye 5) Cyan coupler, page 149, lines 29-33; EP 432                           , 804A2, page 3, line 28 to page 40, line 2 6) Polymer coupler, page 149, lines 34-38; EP 435                           334A2, page 113, line 39 to page 123.                           Line 37 7) Colored Coupler, page 53, line 42 to page 137, line 34, 149                           Lines 39-45 of the page 8) Other functionalities, page 7, line 1 to page 53, line 41, page 149, 46     Line from coupler to page 150, line 3; EP 435,33                           4A2, page 3, line 1 to page 29, line 50 9) Preservatives and fungicides, page 150, lines 25-28 10) Formalin, page 149, lines 15-17     Scavenger 11) Other additives, page 153, lines 38-47; EP 421                           453A1, page 75, line 21 to page 84, 56                           Line, page 27, line 40 to page 37, line 40 12) Dispersion method Page 150, 4th to 24th lines 13) Support, page 150, lines 32 to 34 14) Film thickness / film properties Page 150, lines 35-49 15) Color development / black-and-white development, page 150, line 50 to page 151, line 47;     -Fogging step: No. 442, 323A2, page 34, lines 11 to 5                           Line 4, page 35, lines 14-22 16) Desilvering process, page 151, line 48 to page 152, line 53 17) Automatic developing machine, page 152, line 54 to page 153, line 2 18) Washing and stabilization process Page 153, lines 3 to 37 [0063] 【Example】 (Examples) Hereinafter, the present invention will be described specifically with reference to examples.
However, the present invention is not limited to this. Preparation of sample 101 127μ thick cellulose triacetate film with undercoat
Multi-layer color photosensitive composed of the following layers on a support
A material was prepared, and a sample 101 was obtained. The number is m^TwoAddition per hit
Express the amount. The effect of the added compound is the application described.
Not limited to First layer: antihalation layer Black colloidal silver 0.20g Gelatin 1.90g UV absorber U-1 0.10g UV absorber U-3 0.040g UV absorber U-4 0.10g High boiling organic solvent Oil-1 0.10g Microcrystalline solid dispersion of dye E-1 0.10 g Second layer: Intermediate layer 0.40g gelatin Compound Cpd-C 5.0mg Compound Cpd-J 5.0mg Compound Cpd-K 3.0mg High boiling organic solvent Oil-3 0.10g Dye D-4 0.80mg Third layer: Intermediate layer Fine grain silver iodobromide emulsion with fogged surface and inside (average grain
Diameter 0.06μm, coefficient of variation 18%, AgI content 1mol%) silver content
   0.050g Yellow colloidal silver Silver amount 0.030g 0.40g gelatin Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.30g Emulsion B silver amount 0.20g 0.80g gelatin Coupler CC-1 0.15g Coupler CC-2 0.050g Coupler CC-3 0.050g Coupler CC-4 0.050g Compound Cpd-C 5.0mg Compound Cpd-J 5.0mg High boiling organic solvent Oil-2 0.10g Additive P-1 0.10g Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B silver amount 0.20g Emulsion C silver amount 0.30g 0.80g gelatin Coupler CC-1 0.20g Coupler CC-2 0.050g Coupler CC-3 0.20g High boiling organic solvent Oil-2 0.10g Additive P-1 0.10g Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion D silver amount 0.40g Gelatin 1.10g Coupler CC-1 0.30g Coupler CC-2 0.10g Coupler CC-3 0.70g Additive P-1 0.10g Seventh layer: intermediate layer 0.60g gelatin Additive P-2 0.30g 2.6mg of color mixing inhibitor Cpd-I Dye D-5 0.020g Dye D-6 0.010g Compound Cpd-J 5.0mg High boiling organic solvent Oil-1 0.020g Eighth layer: Intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06
μm, Coefficient of variation 16%, AgI content 0.3 mol%) Silver content
0.020g Yellow colloidal silver Silver amount 0.020g Gelatin 1.00g Additive P-1 0.20g 0.10 g Cpd-A Compound Cpd-C 0.10 g Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E silver amount 0.10g Emulsion F silver amount 0.20g Emulsion G silver amount 0.20g Gelatin 0.50g Coupler MC-1 0.25g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg Compound Cpd-L 0.020 g High boiling organic solvent Oil-2 0.20g Tenth layer: medium-speed green-sensitive emulsion layer Emulsion G silver amount 0.20g Emulsion H silver amount 0.10g 0.60g gelatin Coupler MC-1 0.20g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.050 g Compound Cpd-L 0.050 g High boiling organic solvent Oil-2 0.010g Eleventh layer: Highly sensitive green-sensitive emulsion layer Emulsion I silver amount 0.30g Gelatin 1.00g Coupler MC-1 0.30g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0mg Compound Cpd-L 0.020 g High boiling organic solvent Oil-1 0.020g High boiling organic solvent Oil-2 0.020 g Twelfth layer: Intermediate layer 0.60g gelatin Compound Cpd-L 0.050 g High boiling organic solvent Oil-1 0.050g Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.070g Gelatin 1.10g Color mixing inhibitor Cpd-A 0.010 g Compound Cpd-L 0.010 g High boiling organic solvent Oil-1 0.010g Dye E-2 microcrystalline solid dispersion 0.050 g Fourteenth layer: Intermediate layer 0.60g gelatin Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J silver amount 0.20g Emulsion K silver amount 0.30g 0.80g gelatin Coupler YC-1 0.20g Coupler YC-2 0.10g Coupler YC-3 0.40g Sixteenth layer: medium-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.30g Emulsion M silver amount 0.30g 0.90g gelatin Coupler YC-1 0.10g Coupler YC-2 0.10g Coupler YC-3 0.60g 17th layer: Highly sensitive blue-sensitive emulsion layer Emulsion N silver amount 0.20g Emulsion O silver amount 0.20g Gelatin 1.20g Coupler YC-1 0.10g Coupler YC-2 0.10g Coupler YC-3 0.60g High boiling organic solvent Oil-2 0.10g Eighteenth layer: first protective layer Gelatin 0.70g UV absorber U-1 0.20g UV absorber U-2 0.050g UV absorber U-5 0.30g Formalin scavenger Cpd-H 0.40g Dye D-1 0.15g Dye D-2 0.050 g Dye D-3 0.10g Nineteenth layer: Second protective layer Colloidal silver Silver amount 0.10mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1
Mol%) silver amount 0.10g 0.40g gelatin Twentieth layer: Third protective layer 0.40g gelatin Polymethyl methacrylate (average particle size 1.5 μ) 0.10g 4: 6 copolymer of methyl methacrylate and acrylic acid (Average particle size 1.5μ) 0.10g Silicone oil 0.030g Surfactant W-1 3.0mg Surfactant W-2 0.030g In all emulsion layers, the above composition
Was added with additives F-1 to F-8. In addition, each layer
In addition to the above composition, gelatin hardener H-1 and coating, emulsification
Surfactants W-3, W-4, W-5, W-6
Was. Phenol and 1,2-benz are further used as antiseptic and antifungal agents.
Zuisothiazolin-3-one, 2-phenoxyethanol
, Phenethyl alcohol, butyl p-benzoate
Was added. [0085] [Table 1] [0086] [Table 2][0087] [Table 3][0088] Embedded image[0089] Embedded image[0090] Embedded image[0091] Embedded image[0092] Embedded image[0093] Embedded image[0094] Embedded image[0095] Embedded image[0096] Embedded image[0097] Embedded image[0098] Embedded image[0099] Embedded image[0100] Embedded image[0101] Embedded imageThe couplers of the ninth, tenth and eleventh layers were
Sample 10 was prepared in the same manner except that it was changed as shown in Table-4.
2 to 115 were created. The coupler is MC-1 of 101
And was applied in an equimolar amount. [0103] [Table 4]Samples 101 to 115 were converted to white at 4800K.
After exposure to wedges with light,
The magenta density of the large density part was measured. The results are shown in Table-5.
You. Table 5 shows that the coupler of the present invention has a high coloring property.
It is obvious. [0105] [Table 5] Further, the samples 101 to 115 after the development processing
Xenon light irradiation (8
5,000 lux, temperature 30 ° C, humidity 60%)
Magenta density (D_Two) Is measured and the magenta density before light irradiation
(D₁). The measurement point is the maximum concentration of the sample before light irradiation
Parts were used. The results are shown in Table-6. Table 6 shows that the present invention
Magenta dyes composed of couplers have excellent light fastness
You can see that. This is an unexpected and surprising effect. [0107] [Table 6] [0108]     Processing time Time Temperature Tank capacity Refill     First development 6 minutes 38 ° C 12 liters 2200 ml / m^Two      First wash 2 minutes 38 ℃ 4 liters 7500ml / m^Two      Inversion 2 minutes 38 ° C 4 liters 1100 ml / m^Two     Color development 6 minutes 38 ° C 12 liters 2200 ml / m^Two      Pre-bleaching 2 minutes 38 ° C 4 liters 1100 ml / m^Two      Bleaching 6 minutes 38 ° C 12 liters 220 ml / m^Two      4 minutes 38 ℃ 8 liters 1100ml / m^Two      Second water washing 4 minutes 38 ° C 8 liters 7500 ml / m^Two      Final rinse 1 minute 25 ° C 2 liters 1100 ml / m^Two The composition of each processing solution was as follows. [First developer] [Tank liquid] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5g sodium salt 1.5g 1.5g   Diethylenetriaminepentaacetic acid / pentasodium salt 2.0g 2.0g   Sodium sulfite 30g 30g   Hydroquinone monomonosulfonate 20g 20g   Potassium carbonate 15g 20g   Sodium bicarbonate 12g 15g   1-phenyl-4-methyl-4-hydroxymethyl     -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 1000 ml 1000 ml     pH 9.60 9.60   pH was adjusted with sulfuric acid or potassium hydroxide. [0110] [Reversing liquid] [Tank liquid] [Refill liquid]   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ Same as 3.0g of 5 sodium salt   Stannous chloride dihydrate 1.0g   0.1 g of p-aminophenol   Sodium hydroxide 8g   Glacial acetic acid 15ml   1000 ml with water     pH 6.00   pH was adjusted with acetic acid or sodium hydroxide. [0111] [Color developing solution] [Tank solution] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt 2.0g 2.0g   Sodium sulfite 7.0g 7.0g   Trisodium phosphate dodecahydrate 36g 36g   Potassium bromide 1.0g −   Potassium iodide 90mg −   Sodium hydroxide 3.0g 3.0g   Citrazinic acid 1.5g 1.5g   N-ethyl-N- (β-methanesulsunamide     Ethyl) -3-methyl-4-aminoaniline     ・ 3/2 sulfuric acid ・ monohydrate 11g 11g   3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g   Add water 1000 ml 1000 ml     pH 11.80 12.00   pH was adjusted with sulfuric acid or potassium hydroxide. [0112] [Pre-bleaching] [Tank liquid] [Replenisher]   Ethylenediaminetetraacetic acid disodium salt     Dihydrate 8.0g 8.0g   Sodium sulfite 6.0g 8.0g   1-thioglycerol 0.4g 0.4g   Formaldehyde sodium bisulfite adduct 30g 35g   Add water 1000 ml 1000 ml     pH 6.30 6.10   pH was adjusted with acetic acid or sodium hydroxide. [0113] [Bleaching solution] [Tank solution] [Replenisher]   Ethylenediaminetetraacetic acid disodium salt     Dihydrate 2.0g 4.0g   Ethylenediaminetetraacetic acid ・ Fe (III) ・ ammonium     ・ Dihydrate 120g 240g   Potassium bromide 100g 200g   Ammonium nitrate 10g 20g   Add water 1000 ml 1000 ml     pH 5.70 5.50   pH was adjusted with nitric acid or sodium hydroxide. [0114] [Fixing solution] [Tank solution] [Replenisher]   Ammonium thiosulfate 80g Same as tank liquid   Sodium sulfite 5.0g 〃   Sodium bisulfite 5.0g 〃   1000 ml with water     pH 6.60   The pH was adjusted with acetic acid or aqueous ammonia. [0115] [Stable liquid] [Tank liquid] [Replenisher]   1,2-benzisothiazolin-3-one 0.02 g 0.03 g   Polyoxyethylene-p-monononylphenyl ether     (Average degree of polymerization 10) 0.3g 0.3g   Polymaleic acid (average molecular weight 2,000) 0.1g 0.15g   Add water 1000 ml 1000 ml     pH 7.0 7.0

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-142727 (JP, A) JP-A-5-323533 (JP, A) JP-A-5-323534 (JP, A) JP-A-5-323534 214360 (JP, A) JP-A-7-209831 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 7/38

Claims (1)

(57) [Claim 1] It comprises a 1H-pyrazolo [5,1-c] -1,2,4-triazole coupler represented by the following general formula (I). Silver halide color photographic light-sensitive material. General formula (I) (Wherein represents R ₁ and R ₄ is a substituted group, R ₂
And R ₃ each represent a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group or an alkyl group substituted by a hydroxyl group. R ₉ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group or a sulfonyl group. L is -S
O _2- , -CO-, -SO ₂ NR _10- , -CONR _10-
Or represents -COO-, R ₁₀ represents a hydrogen atom, an alkyl group or an aryl group. A ₁ , A ₂ and A ₃ are each —O—, —NR ₅ —, —NR ₅ CO—, —CONR
_5- , -NR ₅ SO _2- , -SO ₂ NR _5- , -COO
-, - OCO -, - NR 5 CONR 5 -, - OCONR
₅ - or an -NHCOO-, R ₅ represents a hydrogen atom, an alkyl group, an aryl group or at least one alkyl group substituted by a hydroxyl group. B ₁ , B ₂ and B ₃
Is an alkyl group, an alkylene group, an aryl group,
Represents an alkylene group or an alkylene group substituted by an arylene group or at least one hydroxyl group. s represents an integer of 0 to 3. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of an aromatic primary amine developing agent. k represents an integer of 0 to 3, and u, m,
n, t and p represent 0 or 1, and q represents 1. However, it is assumed that mn + tp = 0. r represents an integer of 1 or 2. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , B ₁ , B ₂
And at least one of the substituents of B ₃ has a hydroxyl group. However, the hydroxyl group here is not directly bonded to the aryl group.