JPS628146A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material having improved sharpness and granular characteristic by specifying the silver density of green sensitive layers constituted of 1 or >=2 layers at >=5.0X10<-1>g/cm<3> and the total of the dry film thickness of the green sensitive layers at <=4.5mum. CONSTITUTION:The green density of the green sensitive layers constituted of 1 or >=2 layers is >=5.0X10<-1>g/cm<3> and the total of the dry film thickness of the green sensitive layers is <=4.5mum. The green density provides the tendency to the deterioration of the granular characteristic and an increase of fogging if said density is made excessively high; therefore, the more preferable range is >=7.0X10<-1>g/cm<3> and <=2.0g/cm<3>. The deteriorated coatability, pressure characteristic and stability of emulsified matter and the generation of a side effect such as a decrease of the coloring density are resulted if the dry film thickness of the entire green sensitive layer is made excessively small; therefore, the more preferable range of the dry film thickness is >=1.0mum and <=4.0mum. The green sensitive layers preferably contain the magenta dye image forming coupler expressed by the formula in at least one layer of the green sensitive layers and more preferably contain the coupler in all of the green sensitive layers.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to silver halide color photographs and light-sensitive materials, and more particularly to silver halide light-sensitive materials with improved sharpness and graininess.

[Conventional technology]

BACKGROUND ART There has been a demand for silver halide color photographic materials, especially photosensitive materials for photographing, that have high sensitivity and excellent image quality. Particularly in recent years, in this industry, with the spread of compact cameras that are convenient to carry, there has been a desire for image quality on a small screen to be equivalent to that obtained by enlarging a large screen. In other words, there is a strong demand for the development of a silver halide color photographic material that maintains its resolution, power, and sharpness even when the magnification is increased. In order to improve the sharpness, light scattering of the emulsion film is improved □
Small i<t″6″′required”9″・′:0 side”677°°−“
11 As a means of improvement, there is a known technique to improve sharpness by increasing the grain size of silver lodenide emulsion grains to a small region of 1 light scattering (1 fundamentals of the photographic industry). Edited by Silver Halide Photography, Photographic Society of Japan)
However, according to □, this technique has the disadvantage of unification of visual granularity due to coarsening of grains and particles. Second, dyes are used to reduce light scattering in emulsion films,
A technology is known that improves visual sharpness through the effect of preventing halaysia.
, No. 711, 220). However, this technique has the disadvantage of reduced sensitivity. Therefore, there is a need for new technology that improves sharpness without deteriorating graininess or sensitivity.
:

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic material with improved sharpness. Another object of the present invention is to provide a silver halide color photographic material with improved sharpness without impairing graininess. Still another object of the present invention is to provide a silver halide color photographic material having high sensitivity and improved sharpness.6 Other objects of the present invention will become clear from the following description.

[Structure of the invention]

The above object of the present invention is that the silver density of the green-sensitive layer composed of one layer or two or more layers is 5. OX 10-'g/am' or more, and the total dry film thickness of the green-sensitive layer is 4°5μ
This is achieved by a silver halide color photographic light-sensitive material which is characterized in that it has a photosensitive material of less than 30%. Silver density in the present invention is expressed by the following formula. d=N/V (ir/eel') In the above formula, d is the silver density in the present invention, and N is the amount of silver contained in the green-sensitive layer (i.e., the amount of silver contained in the silver halide grains contained in the green-sensitive layer). 1 to the atom, ■ is the volume of the green-sensitive layer. The volume of the green-sensitive layer is expressed as the product of the coating area and the dry film thickness. Silver halide color photographic light-sensitive material of the present invention (hereinafter referred to as light-sensitive material) When the green-sensitive layer has two or more layers, the silver amount N and volume V in the above formula are the total amounts of all the green-sensitive layers, respectively. Atomic absorption spectrometry is used as a method for measuring the silver amount. In addition, the dry film thickness can be measured by taking an enlarged photograph of the cross section of the dry sample with a scanning electron microscope and measuring the film thickness of each layer.The above silver density is 5.OX 10-' The purpose of the present invention can be achieved with a value of 2.0 g/am' or more, but if the value is too large, graininess tends to deteriorate and fog increases.
The cI is preferably 13 or less, and the more preferable range is 7.0×
10-'g/cn+3 or more 2.0g or more 2.0g Base Cl
In light-sensitive materials with a brightness of 11' or less, the total dry film thickness of all green-sensitive layers is 4.5 μm or less, but if the dry film thickness is extremely thin, coating properties, pressure characteristics, and emulsion stability may be affected. Since side effects such as deterioration of color density and decrease in color density occur, the dry film thickness is preferably 0.8 layers or more, more preferably 1.0 layers or more and 4.0 μm or less. The light-sensitive material of the present invention preferably contains a magenta dye image-forming coupler represented by the following general formula (1) in at least one scrap of the green-sensitive layer, and preferably contains the coupler in all of the green-sensitive layers. Most preferred. According to this embodiment, the above objects of the present invention are achieved to a higher degree, and the stability of the photosensitive material over time is improved. General Formula (r) In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. In the magenta coupler represented by the general formula (1), the substituent represented by R is, for example, one in which the root atom directly connected to the ring is a carbon atom, and one hydrogen atom is bonded to the carbon atom. Examples include alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, heterocyclic groups, spiro compound residues, and bridged hydrocarbon compound residues. The alkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group have 2 to 3 carbon atoms.
As the dichlorofurkyl group and the cycloalkenyl group, those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and 1 to 7 carbon atoms are preferable. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups include substituents (for example, 7 aryl, cyano,) 10 dene atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues,
In addition to bridged hydrocarbon compound residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and 7lyloxycarbonyl, and further substituted via a heteroatom, specifically, Hydroquine, alkoxy, aryloxy, heterocyclic oquine, siloxy, acyloxy, carbamoyloxy, etc. substituted via an oxygen atom, nitro, amino (including dialkylamino, etc.), sul77moylamino, flukoxyluponyl7mino,7 lyloxycarbonylamide, sulfonamide, imide, ureido, etc. substituted via nitrogen atom, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
(such as those substituted via a sulfur atom such as sulf77moyl, and those substituted via a phosphorus atom such as phosphonyl). Specifically, for example, methyl group, ethyl group, isopropyl group, she-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1,1'-dipentylnonyl group,
2-chloro-butyl group, trifluoromethyl group, 1
-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl i, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl JJ, 3-m-butanesulfonaminophenoxypropyl group, 3-4'-5a-(4"(p-hydroxybenzenesulfonyl)phenoxy]dodecanoyl7mino)phenylpropyl group, -3-14'-(ff-(2"
, 4”-di-t-7milphenoxy)butane7mido]phenyl)-propyl group, 4-[Q-(.-chlorophenoxy)tetradecanamidophenoxy]
Examples include propyl group, allyl group, cyclopentyl group, and cyclohexyl group. The 7-aryl group represented by Rt' is a phenyl group.
□ Preferably, it may have a substituent (for example, a furkyl group, an alkoxy group, an acylamide group, etc.). Specifically, phenyl group, 4-t-butyl 7enyl group,
2.4-not-7 milphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4''-t-butylphenoxy)tetradecanamidophenyl group, etc. The heterocyclic group to be R''Chyt is preferably a 5 to 7 true heterocyclic group, which may be substituted or fused. Specifically, 2-7lyl group, 2-chenyl group, 2-
Examples include pyrimidinyl group and 2-benzothiazolyl group. As the acyl group represented by R1', for example, 7 cetyl group,
7-enyl acetyl group, dodecanoyl group, fulkylcarbonyl group such as a-2,4-di-t-7-milphenoxybutanoyl group, aryl group such as benzoyl group, 3-bentatecyloxybenzoyl group, p-chlorobenzoyl group, etc. Examples include carbonyl group. The sulfonyl group represented by R is methylsulfonyl group, dodecylsulfonyl group @1 alkyl: 8,
. , 2. 16. Ia X/l, t, : A-J
Examples include 7-arylsulfonyl groups such as J,p-)/L='Jenesulfonyl groups. Examples of the sulfinyl group represented by R include ethylsulfinyl group, octylsulfinyl group, furkyl 1sulfinyl group such as 3-□phenoxydibutylsulfinyl group, arylsulfinyl group such as phenylsulfinyl group%m-pentadecyl phenylsulfinyl group, etc. can be mentioned. The phosphonyl group represented by R''Ch includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxy group such as an octyloxyphosphonyl group,
Ants such as cisphonyl group and phenoxyphosphonyl group
”-ruoxyphosphonyl group, phenylphosphonyl group
Examples include arylphosphonyl groups such as :. The carbamoyl group represented by R is an alkyl group,
゛Substituted with a 7-aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group,
1-N, N-butylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-13-(2,4
-Shi7mil7eth/xy)propyl)carbamoyl group, and the like. The sulfamoyl group represented by R is substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.,
For example +t N-7' lobilsul7 amoyl group, N, N-
Examples include butylcarbamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group, and the like. Examples of spiro compound residues represented by R include spiro [
3,3]hebutan-1-yl and the like. Examples of the carbonized compound residue represented by R include bicyclo[2,2,1]hebutan-1-yl, tricyclo[3
, 3,1,1"']decan-1-yl, 7,7-tumethyl-bicyclo[2,2,1]heptan-1-yl, etc. The substituents listed above may be substituted, for example, methoxy group, propoxy group, 2-ethoxyethoxy group,
Examples thereof include a pentadecyloxy group, a 2-dodecyloxyethoxy group, and a fewinteryloxyethoxy group. The aryloxy group represented by R is preferably 7-enyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the atom group,
For example, phenoxy group, p--butyl 7ヱ/xy group, m
-pentadecylphenoxy group and the like. The heterocyclic oxy group represented by R preferably has 5 to 7 heterocycles, and the heterocycle may further have a substituent, for example, 3゜4.5.6-tetrahydro. Examples include biranyl-2-oxy group and 1-phenyltetrazol-5-oxy group. The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, and a trimethylbutylsiloxy group. Examples of the acyloxy group represented by R″c include an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloroacetyloxy group, etc. The carbamoyloxy group represented by Rr! may be substituted with a furkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N,N-noethylcarbamoyloxy group, Examples include N-phenylcarbamoyloxy group, etc. The ami7 group represented by R may be substituted with an alkyl group, an aryl group (preferably a 7enyl group), etc., such as an ethylamino group, a 7enyl group, 7 l-chloroanili groups,
Examples include 7 groups of 3-pentadecyloxyluponylaniline, 7 groups of 2-chloro-5-hexadecaneamide aniline, and the like. Examples of the acylamine group represented by R include alkylcarbonyl group, arylcarbonylamine group (preferably phenylcarbonylamino group), etc., and may further have a substituent, specifically, acetamide group. group, α-ethylpropanamide group, N-phenylacetamide group,
Examples include dodecanamide i, 2,4-di-t-7milphenoxyacetamide group, and α-3-t-butyl 4-hydroxyphenoxybutanamide group. As the sulfonamide group represented by R, Al □
Examples include a kylsulfonyl 7mino group and a ryosulfonyl amine 7 group, and may further have a substituent. Specifically, 7 methylsulfonylamide groups, 7 bentatecylsulfonylamide groups, benzenesulfonamide group, p-)
Examples include a luenesulfonamide group, a 2-7toxy5-t-7 milbenzenesulfonamide group, and the like. The imide group represented by R may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, a talimide group. , glutarimide group, and the like. The ureido group represented by R is an alkyl group, an aryl group (
(preferably phenyl group), etc., for example, N-ethylureido group, N-methyl-N-7'
silureido group, N-71 nylureido group, N-p-)
Examples include a lylureido group. The sul77moyl7mi7 group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), and examples thereof include N,N-butylsul7amoylamy7 groups, N-methylsul7amoylamy7 groups, N-phenylsul7amoylamy7 groups, etc. . The alkoxycarbonylamide 7 group represented by R is,
It may further have a substituent, such as a methoxycarbonylamine group, a methoxyethoxycarbonyl group, a ruamino group, an octadecyloxycarbonyl group, and the like. The aryloxycarbonyl 7 group represented by R″? is,
It may have a substituent, such as phenoxycarbonyl 7 group and 4-methyl 7-ethyl/oxycarbonyl 7-mino group. The phenoxycarbonyl group represented by R may further have a substituent, such as methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octatecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxy Examples include carbonyl group. The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group,
Examples include p-chlor 7e/xycarbonyl 6% m-pentadecyloxyphenoxycarbonyl group and the like. R'? The alkylthio group represented may further have a substituent, for example, an ethylthio group, a dodecylthio group,
Examples include octadecylthio group, 7enethylthio group, and 3-phenoxypropylthio group. The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-7cetaminophenylthio group. The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio group, which may further have a condensed ring or a substituent, for example, 2- Examples include pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-syriazole-6-thio group. Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by Examples include groups substituted via. As a group substituted via a carbon atom, carbo (R'1
is the same as the above R, Z' is the same as the above Z, R2' and R3' are a hydrogen atom, a 7-aryl group,
□Represents an alkyl group or a heterocyclic group, indicated by )
group, a hydroxymethyl group, and a tri-7enylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, 7-aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, furkyloxalyloxy groups, □alkoxy An example is an oxalyloxy group. The alkoxy group may further have a substituent, for example,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, 7enethyloxy group, and p-chlorobenzyloxy group. The aryloxy group is preferably a phenoxy group, and the 7-aryl group may further have a substituent. Specifically, 7-enoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-CCI-(3'-pentadecyl 7/xy)butanamide] phenoxy group, hexidecylphenoxy group, carbamoylmethoxy group, 4-cyanophenoxy group,
Examples include 4-methanesulfonyl 7eth/oxy group, 1-su7thyloxy group, p-methoxy 72/oxy group, and the like. The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include 1-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, and the like. Examples of the acyloxy group include a 7-cetoxy group, a fulkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include a 7-arylcarbonyloxy group such as a benzoyloxy group. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a 7-ethyloxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include a nidoxyoxalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a pencylthio group, and the like. The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecyl7enethylthio group, 4-/sufluorobencunamido7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t -butylphenylthio group and the like. Examples of the heterocyclic thio group include 1-7 enyl-1.
2.3.4-Tetrazolyl-5-thio group, 2-benzothiazolylthio group, etc. may be mentioned. Examples of the fulkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Ru. Here, R4' and R6' are hydrogen atoms, alkyl groups,
Represents an aryl group, a heterocyclic group, a 77 moyl group, a carbamoyl group, a 7 syl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R1' and R
5' may be bonded to form a heterocycle. However, R1'
and R3' are never both hydrogen atoms. The furkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, furkyl 7mi 7 group, arylami 7 group, acylami 7 group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, 7lylsulfonyl group,
Examples include a carbamoyl group, a sul77moyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkyloxycarbonylamine group, a 7lyloxycarponylamino group, a hydroxyl group, a carboxyl group, a cyano group, and a halogen atom. Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group. The aryl group represented by R4' or R5' preferably has 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The aryl group may have a substituent, and examples of the substituent include those listed above as a substituent for the alkyl group represented by R4' or R5' and an alkyl group. Specific examples of the aryl group include a phenyl group, a 1-su7tyl group, and a 4-methylsulfonylphenyl group. The heterocyclic group represented by R4' or Rs7 is 5 to 6
Shellfish are preferred, and may be fused rings or have substituents. Specific examples include 2-7lyl group, 2-quinolyl group, 2-pyrimidyl group, 2-penzothiazolyl group, -pyridyl group and the like. The sul77moyl group represented by R4' or Rs' includes N-furkylsulfamoyl it, N,N-dialkylsulfamoyl group, N-7lylsul7amoyl i,
Examples include N,N-noarylsulfamoyl group, and these alkyl groups and aryl groups may have substituents listed for the furkyl group and aryl group.
Specific examples of the sulf77moyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group,
Examples include N-dodecylsulf77moyl M and Np-tolylsulfamoyl group. The carbamoyl group represented by R4' or Rs' is
Examples include N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these furkyl groups and aryl groups are the same as those mentioned for the alkyl group and 7aryl group. may have other substituents. Specific examples of the carbamoyl group include N,N-noethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group, N-
-p-)lylcarpamoyl group. Examples of the acyl group represented by R4' or R1' include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. Specific examples of the acyl group that may be used include hexafluorobutanoyl group, 2t3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group, 2-7lyl carbonyl group, etc. can be mentioned. Examples of the sulfonyl group represented by R4' or RS' include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group, Examples include a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, and a p-chlorobenzenesulfonyl group. The 7-aryloxycarbonyl group represented by R4' or R1' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like. The alkoxycarbonyl group represented by R4' or R, 7 may have the substituents listed above for the furkyl group, and specific examples include methoxycarbonyl group, dodecyloxycarbonyl group, benoloxycarbonyl group. Examples include groups. The heterocycle formed by combining R1' and R5' is preferably a 5- to 6-true heterocycle, which may be saturated or unsaturated, and may have aromaticity or aromaticity. , or may be a condensed ring. Examples of the heterocycle include N-7 thalimide group, N-succinic acid, imido group, 4-N-urazolyl group, 1-N-hyguntoynyl!, 3-N-2,4- Dioxooxazolidinyl group, 2-N-1,1-dioxo-3-(2'H)-oxo-1,2-benzthiazolyl group, 1-'pyrrolyl group, 1-pyrrolinonyl group, 1-pyrazoli □ group, 1-pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolyl group, 1-indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-'isoindolinyl group, 1
-benzotri7zolyl group, □1-pencyimigzolyl group, 1-(1,2,4-)riazolyl) group, 1-(
1,2,3-F+77zolyl) 1 group, 1-(1
, 2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2 :'-I H, -pyridone group, 7 Examples include thalassion group, 2-oxo-1-piperidinyl group, etc., and these heterocyclic groups include alkyl groups,
Aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, 7 alkylamino groups, 7 arylamino groups, acylamino group, sulfonamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group , an aryloxycarbonyl group, an imide group, a nitro group, a sia7 group, a carboxyl group, a halogen atom, or the like. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those mentioned above for R. There are many things that can be mentioned. In addition, in general formula (1) and general formulas (If) to [■] described later, the substituents on the heterocycle (for example, R9R1 to R,) are moieties (herein, R", X, and Z" are (synonymous with R, X, and Z in formula (T)) forms a so-called screw-type coupler, which is of course included in the present invention. or,
The ring formed by z, z', z'' and 1 below-mentioned 21 can further be formed by other rings (for example, 5 to 7 shells of dichloroflukene).
may be condensed. For example, R5 and R6 in the general formula (V), and Rt and R in the general formula (Vl), may be bonded to each other to form a ring (for example, a 5- to 7-shell cycloalkene, benzene). . More specifically, what is represented by the general formula (1) is represented by, for example, the following general formulas (n) to [■]. General formula [■] General formula (I[[) General formula [■] N -N -NH General formula (V) General formula [VI) N -N -NH General formula [■] Said general formula [■] ~ [ (2)], R1-Rs and X have the same meanings as R and X, and R1 to R@ or X may form a dimer or more multimer. Also, among the general formula (1), the following general formula [
■]. General formula [■] In the formula, R+ -X and Zl are R9X in general formula (I)
and Z. Among the magenta couplers represented by the general formulas (II) to [■], particularly preferred is the magenta coupler represented by the general formula (If). Regarding the substituents on the heterocycle in general formulas (13 to [■]), R in general formula [1] and R in general formulas (n) to [■] satisfy the following condition 1. It is preferable that the
□This is true if conditions 1 and 2 below are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom. The most preferred substituents R and R on the heterocycle are those represented by the following general formula (IX). General formula CI R1 ■ R3゜-C- In the formula, R==R+. and R11 are each a hydrogen atom, 7%
Rodene atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, 'alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro Compound residue, aromatic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami7 group, acylamino group, sulfonamide group,
Represents an imide group, a ureido group, a sul77moylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino7 group, an alkoxycarbonyl group, an aryloxycarbonyl group, a furkylthio group, an arylthio group, a heterocyclic thio group, and R. At least two of R1° and RI 1 are not hydrogen atoms (1° and two of the above R,,R, and R1+, for example, R9
and RIG may be combined to form a saturated or unsaturated ring (e.g. dichloroflucan, cycloalkene, heterocycle) (and mathematically R1 may be combined to form a bridged hydrocarbon compound residue). The group represented by R9-R1 may have a substituent,
Specific examples of the groups represented by R, to R11 and substituents that some of the groups may have include examples of the group represented by R in the aforementioned general formula CI) and Va exchangers. Also, for example, a ring formed by combining R9 and R1° and R1
Specific examples of the bridged hydrocarbon compound residue formed by -R1 and its optional substituents include dichlorofurkyl, cycloalkyl, hetero m-group-carbohydrated Specific examples of hydrogen compound residues and their substituents are listed. Among the general formulas ([), (i) when two of Rt to R1 are furkyl groups, (i)
i) When one of R- to R11, for example R8, is a hydrogen atom, and the other two R1 and R6 combine to form dichlorofurkyl together with the root carbon atom, the following is true. Furthermore, among (i), it is preferable that two of %R and -R11 are alkyl groups, and one of the others is a hydrogen atom or a furkyl group. Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the furkyl, the dichlorofurkyl, and their substituents include the alkyl and cycloalkyl 11 represented by R in the general formula [1], The synthesis of the coupler is described in the Journal of the Chemical Society, Perkin I (Journal
of the Che+5ical 5ocie
tyPerkin I) (1977),
No. 2047-2052, U.S. Pat.
Synthesis was performed with reference to No. The magenta coupler represented by general formula (I) is commonly:
The magenta coupler can be used in a range of 1X10-' mol to 1 mol, preferably 1X10-' mol to 8X10-' mol, per 1 mol of helodenated fi.The magenta coupler can also be used in combination with other types of magenta couplers. That is, the green-sensitive silver halide emulsion layer containing the magenta coupler represented by the general formula (I) may contain other magenta couplers and/or colored magenta colors. (The content of magenta couplers and/or colored magenta couplers other than the coupler represented by 13 is
Preferably, it is less than 30 mol% of the total coupler amount,
Particularly preferably less than 15 mol%. Magenta couplers other than the magenta coupler of general formula (1) that can be used in the green-sensitive silver halide emulsion layer of the light-sensitive material of the present invention include: pyrazolone compounds, indashilon compounds, cya-7 acetyl compounds, the present invention It is possible to use other pyrazoloazole compounds, and pyrazolone compounds are useful. A specific example of a magenta coupler that can be used is disclosed in JP-A-49-1
No. 11631, No. 56-29236, No. 5 Fu 947
No. 52, Japanese Patent Publication No. 48-27930, U.S. Patent No. 2,6
No. 00,788, No. 3.062,653, No. 3,40
No. 8,194, No. 3,519,429 and Research
There is one described in Diskrotsuya No. 12443. Colored magenta couplers that can be used in the green-sensitive layer of the present invention include U.S. Pat. No. 2,801°171;
Examples include those described in Japanese Patent Publication No. 3,519,429 and Japanese Patent Publication No. 4B-27930. The amount of the green-sensitive magenta coupler added to the light-sensitive material of the present invention is generally from 2X 10-' to 1 mole of silver in the emulsion layer.
1 mol is preferable, more preferably 1×10-” to 5×
Use to-' moles. When adding the coupler, it can be incorporated into the green-sensitive silver halide emulsion layer by the above-mentioned oil protect dispersion or latex dispersion method, or if the coupler is alkali-soluble, it may be added as an alkaline solution. The silver halide used in the photographic material of the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, but a monodisperse emulsion is preferred. In a preferred embodiment of the invention, one side of the support contains a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a cyan dye-forming coupler. and at least one of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer contains monodisperse silver halide grains. Examples include aspects. these! ! ! In this case, two or more types of monodisperse silver halide grains may be mixed, and in this case, the average grain size thereof may be the same or different. Polydisperse 7% silver lodenide grains may also be used in combination. The photosensitive material of the present invention may have a so-called reverse layer structure as the structure of its photosensitive emulsion layer. In addition, the so-called reverse layer structure (first, Japanese Patent Application No. 193609/1983 filed by the present applicant;
202065, etc.), and a remarkable effect can be obtained particularly in an inverted layer structure. In the light-sensitive material of the present invention, the light-sensitive silver halide emulsion layer functioning as the same color-sensitive layer including the green-sensitive layer may be separated into two or more layers having different sensitivities. In order from the side farthest from the body: ■ High-sensitivity layer (BH) of the blue-sensitive silver halide emulsion layer, low-speed layer (BL) of the blue-sensitive silver halide emulsion layer, high-sensitivity layer (of the green-sensitive silver halide emulsion layer) GH), low-speed layer of green-sensitive silver halide emulsion layer (
G L ”), high-speed layer of red-sensitive silver halide emulsion layer (
RH>, low-speed layer (RL) of red-sensitive silver halide emulsion layer
or ■High-sensitivity layer (BH) of blue-sensitive silver halide emulsion layer, high-sensitivity layer (G) of green-sensitive silver halide emulsion layer.
H), high-sensitivity layer (RH) of red-sensitive silver halide emulsion layer;
A low-speed layer (BL) of a blue-sensitive silver halide emulsion layer, a low-speed layer (GL) of a green-sensitive silver halide emulsion layer, a low-speed layer (RL) of a red-sensitive silver halide emulsion layer, etc. High sensitivity of blue-sensitive silver halide emulsion layer (BH) in ■, especially ■, high-sensitivity layer of blue-sensitive silver halide emulsion layer (BH), high-sensitivity layer of green-sensitive silver halide emulsion layer (GH), high-sensitivity layer of red-sensitive silver halide emulsion layer ' The silver halide contained in □ (RH) has an average grain size (average grain size) of 0.40 to 3.00.
μ■ is preferable, more preferably 0.50 to 2.50 μ
− is. For example, in ■, ■, especially in ■, the low-sensitivity layer (BL) of the blue-sensitive silver halide emulsion layer, the green □low-sensitivity layer (GL) of the silver-sensitive silver halide emulsion layer, and the red-sensitivity layer
. The average grain size (average grain size) of the silver halide contained in the low-speed layer (RL) of the transparent silver halide emulsion layer is preferably 0° to 20 to 1.50 μm, more preferably 0.2 μm.
0-1. ) 0μ rise. In addition, the low sensitivity layer (BL) of the blue-sensitive silver halide emulsion layer, the low sensitivity layer (GL) of the green-sensitive silver halide emulsion layer, and the low sensitivity layer (RL) of the red-sensitive silver halide emulsion layer have medium sensitivity. When the layer is separated into a low-sensitivity layer and a low-sensitivity layer, it is preferable that the former has a thickness of 0.30 to 1.50 μm, and the latter has a thickness of 0°15 to 1.0θμ. In a preferred embodiment of the present invention, the monodisperse silver halide grains in the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer are determined by electron micrographs. 1! When observed, most of the silver halide grains appear to have the same shape, are uniform in grain size, and have a grain size distribution as shown below. In other words, when the standard deviation S of the particle size distribution is divided by the average particle size, the value is 0.20 or less, more preferably 0.15 or less. What does particle size mean here? , is the same as the grain size described above for the average grain size, and in the case of spherical silver halide grains, the diameter, or in the case of grains with shapes other than cubic or spherical,
This is the diameter when the projected image is converted into a circular image with the same area. Furthermore, it is also possible to use a mixture of two or more types of monodispersed emulsions in the low-speed layer. These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol-3-
Sensitizers of water-soluble salts such as methylbenzothiazolium chloride, or ruthenium, palladium, platinum, aluminum, iridium, etc., specifically ammonium chloroparadate, potassium chlorooleate, and sodium chloroparadate ( Depending on the amount of these substances, they act as sensitizers or capri suppressants.)
The sensitizer may be chemically sensitized by using a combination of a gold sensitizer and a sulfur sensitizer, a gold sensitizer and a selenium sensitizer, etc. alone or in combination as appropriate. The silver halide emulsion used in the light-sensitive material of the present invention is chemically ripened by adding a sulfur-containing compound, and at least one hydroxytetrazaindene and mercapto group is added to the silver halide emulsion before, during, or after the chemical ripening. At least one nitrogen-containing heterocyclic compound may be contained. The silver halide used in the light-sensitive material of the present invention contains an appropriate sensitizing dye at a rate of 5 x 101 to 3
Optical sensitization may be carried out by adding 0-'mol. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more types. Examples of sensitizing dyes that can be advantageously used in the present invention include the following: I can list kimono. That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat.
, 503°776, 2,519,001, 2,
No. 912,329, No. 3,656゜959, No. 3,6
No. 72,897, No. 3,694,217, No. 4,02
No. 5゜349, No. 4,046,572, British Patent No. 1,
No. 242,588, Special Publication No. 44-14030, No. 52
-24844 etc. can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in, for example, British Patent No. 505,979 and British Patent No. 505,979. Further, as a sensitizing dye used in a red-sensitive silver lodenide emulsion, for example, U.S. Pat.
No. 4, No. 2,270,378, No. 2 442.710
Representative cyanine dyes, merocyanine dyes, and composite cyanine dyes described in Japanese Patent No. 2,454,629, No. 2,776.280, etc. can be cited as representative examples. Furthermore, U.S. Patent 2゜213.99
No. 5, No. 2,493,748, No. 2,519,001
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Pat. These sensitizing dyes may be used alone or in combination. The light-sensitive material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary. A representative example of a particularly preferred spectral sensitization method is, for example, the Japanese Patent Publication No. 43-1999, which concerns the combination of benzimidazo-locarpocyanine and benzoxazolocarbocyanine.
No. 4936, No. 43-22884, No. 45-1843
No. 3, No. 47-37443, No. 48-28293,
No. 49-6209, No. 53-12375, JP-A-5
No. 2-23931, No. 52-51932, No. 54-8
No. 0118, No. 58-153926, No. 59-116
Examples include methods described in No. 646 and No. 59-116647. Further, regarding the combination of carbocyanine having a penzimigsol nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47
-11114, 47-25379, 48-38
City No. 406, No. 4B-38407, No. 54-3453
No. 5, No. 55-1569, No. 50-33220, No. 50-38526, No. 51-107127, No. 51-115820, No. 51-135528, No. 5
Examples thereof include No. 2-104916 and No. 52-104917. Further, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publications No. 32753/1983, No. 11627/1983, and Japanese Patent Publication No. 1483/1983 regarding merocyanine. For example, Tokko Sho 4B-384
08, 4B-41204, 50-40662, JP-A-56-25728, JP-A-58-10753,
No. 58-91445, No. 59-116645, No. 5
No. 0-33828 and the like. Furthermore, regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication No. 43-493
No. 2, No. 43-4933, No. 45-26470, No. 46-18107, No. 4 Fu 8741, JP-A-59
-114533, etc., and the method described in Japanese Patent Publication No. 114533, which uses zeromethine or thumethine merocyanine, monomethine or trinotine cyanine, and styryl dye, can be advantageously used. In order to add these sensitizing dyes to a silver helodenide emulsion, a hydrophilic dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethyl 7-olamide, or fluorinated alcohol described in Japanese Patent Publication No. 50-40659 is added in advance. It is used by dissolving it in a solvent. It may be added at any time at the start of chemical ripening, during ripening, or at the end of chemical ripening of the silver halide emulsion (or, in some cases, it may be added in the step immediately before coating the emulsion). The material may contain water-soluble dyes as filter dyes in the hydrophilic colloid layer or for various purposes such as preventing irradiation; such dyes include oxonol dyes, merocyanine dyes, and 7zo dyes. Among them, oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful.Specific examples of dyes that can be used include British Patent No. 584,609, British Patent No. 1,
No. 277.429, JP-A-48-85130, JP-A No. 49
-99620, 49-114420, 49-1
No. 29537, No. 52-108115, No. 59-25
No. 845, U.S. Patent No. 2,274,782, U.S. Patent No. 2,53
No. 3,472, No. 2,956,879, No. 3,125
, No. 448, No. 3,148,187, No. 3,177.
No. 078, No. 3,247,127, No. 3,540,8
No. 87, 6°°゛゛°"°"9゛6°, 653, 9G5
9.143. ″“°”″′1゛: □Same 4,071,31
No. 2, No. 4,070,352. The photosensitive material used in the present invention is the green-sensitive halo □
Along with the silver denden emulsion layer, a blue-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer can be shared as described above. Blue-sensitive silver halide hole: 114M□
7 red. 32. 2□2I, 1I□U, Yoya, 7.1 Coupler, that is, reacts with the oxidized form of the color developing agent L''
'8''*t**t, i!(4''*t-t*5-ex=°
“1-1 kill.
41゛The pigment form ah-i''- is each''. Emulsion layer′. against breast milk
[Dye that absorbs the photosensitive spectrum of the agent layer is formed]
□I is usually selected as a blue-sensitive emulsion.
IML=itv-t'>9゜*FflIth2? -h'
, #e, *pc*q'' layer uses a yellow dye-forming coupler, and the green-sensitive emulsion layer uses a cyan dye-forming coupler. 71. Kakati-s ntn<yut, e
Ayo, 3, 2, ga. A silver halide color photographic light-sensitive material may be prepared in a similar manner. As the yellow coupler used in the blue-sensitive silver halide emulsion layer, a known closed ketomethylene coupler can be used. Among these, benzoylaceto-7nilide and pivaylaceto-7nilide compounds can be advantageously used. A specific example of the yellow coupler is disclosed in Japanese Patent Application Laid-Open No. 47-28133.
No. 48-29432, No. 50-87650, No. 51-17438, No. 51-102636, Special Publication No. 45-19956, No. 46-19031, No. 51-
No. 33410, No. 51-10783, U.S. Patent No. 2,8
No. 75,057, No. 3,408,194, No. 3,51
There are those described in No. 9゜429, etc. As the cyan coupler used in the red-sensitive silver lodenide emulsion layer, phenolic compounds, nethol compounds, etc. can be used. Specific examples include U.S. Patent No. 2,423,730;
There are those described in No. 474°293, No. 2,895,826, and No. 4 No. 117422 of 1974. A common colored cyan coupler can be used in combination with the red-sensitive silver halide emulsion layer. As a colored cyan coupler, Japanese Patent Publication No. 55-32461 and British Patent No. 1
, No. 084,480, etc. can be used. In the photosensitive material of the present invention, known configurations can be applied to layers other than the photosensitive layer such as the yellow filter layer, other intermediate layers, protective layer, and anti-norresitin waste. In a preferred embodiment of the present invention, a compound (hereinafter referred to as a DIR compound) that releases a development inhibitor or its precursor by reacting with an oxidized form of a color developing agent is added to at least one of the light-sensitive silver halide emulsion layers. More preferably, when a light-sensitive silver halide emulsion layer having substantially the same color sensitivity is separated into two or more layers having different sensitivities, a blue-sensitive silver halide emulsion layer is contained. By containing it in at least one of the high-sensitivity ff1 (BH) of the silver emulsion layer, the high-sensitivity layer (GH) of the green-sensitive silver halide emulsion layer, and the high-sensitivity layer (RH) of the red-sensitive silver halide emulsion layer. be. A typical example of a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting effect when separated from the active site is introduced into the active site of the coupler.For example, British Patent No. 935.454, U.S. Patent No. 3,
No. 227,554, '4,095,984, No. 4,
149.886, JP-A-57-151944, etc. The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor. In addition, in the present invention, U.S. Pat.
, No. 928,041, No. 3,958,993, No. 3,
No. 961゜959, No. 4,052,213, Japanese Unexamined Patent Publication No. 1973
No. 3-110529, No. 54-13333, No. 55-
The above-mentioned DIR compounds also include compounds that release a development inhibitor but do not form a dye when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 161237. Furthermore, JP-A-54-145135 and JP-A-56-1
When reacted with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Or so-called timing D, which is a compound that releases a development inhibitor through an elimination reaction.
IR compounds are also included in the above DIR compounds. Also, JP-A No. 58-160954, No. 58-16294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
R compounds are also included in the above DIR compounds. More preferred DIR compounds used in the present invention can be represented by the following general formulas (X) and (XI), and among these, the most preferred DIR compound is a compound represented by the following general formula [revised]. General formula [X] Coup-inhibitor In the formula, Coup is a coupler component (compound) capable of coupling with the oxidized form of a color developing agent, such as open-chain ketomethylene compounds such as acylacetanilides and acylacetate esters, pyrazolones, Pyrazolotriazoles,
These are dye-forming couplers such as virazolinobenzimigzoles, indacilones, indasilones, phenols, and naphthols, and coupling components that do not substantially form dyes such as acetophenones, indanones, and oxacylones. In addition, the inhibitor in the above formula is a component (compound) that is released by reaction with a color developing agent and inhibits the development of silver halide.
Preferred compounds include bicyclic compounds and heterocyclic mercapto compounds such as benztriazole and 3-octylthio-1,2°4-triazole. Examples of the above-mentioned heterocyclic group include a tetrazolyl group, a thiactuzolyl group, an oxadiazolyl group, a thiazolyl group, an oxacylyl group, an imidazolyl group, and an F7zolyl group. Specifically, 1-phenyltetrazolyl group, 1-ethyltetrazolyl group, 1-(4-hydroxyphenyl)tetrazolyl group, 1,3.4-thiazolyl group,
Examples include 5-methyl-1,3,4-oxadiazolyl group, benzthiazolyl group, benzoxasilyl group, benzimidazolyl group, and 4H-1,2,4-)riazolyl group. In addition, in the above general formula (X), the inhibitor is bonded to the active site of Coup. General formula [x1] Coup-TIME-inhibitor In the formula, the inhibitor is the same as defined in the above general formula (XI). Coup also includes a coupling component that produces a diffusible dye, similar to that defined in general formula (U). 'MME is the following general formula [■], (X
I), ()l) and (XV), but are not limited to these. General formula [■] R1 In the formula, X2 represents an atomic group necessary to complete the benzene ring or the 7talene ring, Y2 represents R1 10-1-S-1-N- (here R23 represents a hydrogen atom, an alkyl group, or a 7-aryl group, and is bonded to the coupling position, and R1+ and R2□ each represent the same group as the above Rzs, but are substituted at the ■ position. and is bonded to a heteroatom contained in the inhibitor. General Formula (XII) In the formula, W is the same group as Y in the general formula (n), and R24 and R2S are also the same groups as R21 and R22 in the general formula (m), respectively. R2, is a hydrogen atom, an alkyl group, an aryl group, a 7-sil group, a sulfone group, an alkoxycarbonyl group, or a heterocyclic residue, and %R, is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, or a flukoxy group , represents an amide group, an acylamido group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, and this tanning group is bonded to the coupling position of Coup by W, and the 2S and binds to the heteroatom of the inhibitor. Next, an example of a tanning group that releases an inhibitor through an intramolecular nucleophilic substitution reaction is shown by general formula (XIV).
□ - General formula revision V] In the Nu -E set, Nu is electron-rich oxygen, sulfur, or nitrogen.
It is a nucleophilic group having an elementary atom, and is bonded to the coupling position of Coup. E is an electrophilic group having an electron-poor carbonyl, thiocarbonyl, phosphinyl, or thiophosphinyl group, and is bonded to the heteroatom of the inhibitor. A bond that is sterically related and, after N is released from the Coup, undergoes an intramolecular nucleophilic substitution reaction with the formation of a 3- or 7-shell ring, and thereby releases the inhibitor. General formula (XV) Coup 0CH2-inhibitor Coup and 1 inhibitor have the same meanings as above. The above DIR compound is preferably added to the photosensitive silver helodenide emulsion layer. The present invention In photosensitive materials, two DIR compounds are present in the same layer.
It may contain more than one species, and the same DIR compound may contain all different two
It may be included in more than one layer. These DIR compounds are generally preferably used in amounts of 2X10-' to 5XIO-' moles, more preferably 2X10-' to 5XIO-2 moles per mole of silver in the emulsion layer. The silver halide emulsion layer and other photographic constituent layers of the light-sensitive material of the present invention contain non-diffusible couplers, polymer couplers, etc. that react with the oxidized form of the developing agent to form a diffusible dye that bleeds appropriately. Couplers other than the pyrazolotriazole magenta coupler may be used in combination. Regarding non-diffusible couplers that react with the oxidized form of these developing agents to form diffusible dyes that bleed moderately, the present applicant's patent application No. 1982-
For polymer couplers, reference can be made to the description in Japanese Patent Application No. 193611. The method of adding the DIR compound and the like is substantially the same as that for the magenta coupler of the present invention. That is, the above DIR
In order to incorporate the compound, etc. into the coating solution for silver halide emulsion and other photographic constituent layers according to the present invention, if the DIR compound, etc. is alkali-soluble, it may be added as an alkaline solution; In this case, the coupler, etc. is mixed with a high boiling point solvent (HBS) according to the method described in the above-mentioned US patent specification.
It is preferable to dissolve it in combination with B S ), disperse it in the form of fine particles, and add it to the silver halide emulsion. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. I can't help it. It is also possible to use a mixture of two or more DIR compounds. Furthermore, to explain in detail the preferred method of adding DIR compounds, etc. in the present invention, one or more kinds of DIR compounds, etc. are added together with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary. Organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially the high-boiling, α-solvents (HB S ), and/or the low-boiling solvents (L B
S), mixed with an aqueous solution containing the anionic surfactant and/or nonionic surfactant and/or hydrophilic Pine Goo, and dispersed into an emulsion using a high-speed rotating mixer, etc.
Added to silver halide emulsions. In addition, the above-mentioned DIR compound etc. may be dispersed using the above-mentioned latex dispersion method. The light-sensitive material of the present invention may contain various other photographic additives, such as those described in JP-A No. 46-2128,
Color stain inhibitors described in U.S. Pat. Color image fading prevention agent, antistatic agent,
Hardeners, surfactants, plasticizers, wetting agents, etc. can be used. In the light-sensitive material of the present invention, the woody colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as fulpmin and casein, and hydroxyethyl cellulose. Examples include cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol, and polyacryl 7mide. Examples of the support for the photosensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, a glass plate, cellulose triacetate, cellulose nitrate, or polyethylene. There are transparent supports such as polyester films such as terephthalate films, poly7mid films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the photosensitive material. Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2゜761.791;
It is also possible to use a simultaneous coating method of two or more layers according to the method described in No. 941,898. There are no particular limitations on the method of processing the photosensitive material according to the present invention, and any processing method can be applied. For example, typical methods include bleaching and fixing after color development, followed by washing and/or stabilization if necessary, and methods in which bleaching and fixing are carried out separately after color development, and as necessary. A method of further washing with water and/or stabilizing treatment depending on the situation; or a method of performing pre-hardening, neutralization, color development, stop-fixing, washing with water, bleaching, fixing, washing with water, post-hardening, washing with water, color development, and washing with water. , a method in which supplementary color development is carried out, stopping, bleaching, fixing, washing with water, and stabilization in this order; a development method in which the developed silver produced by color development is bleached with halodenesin, and then color development is performed again to increase the amount of produced dye, etc. , any method may be used. The color developing solution used in processing the light-sensitive material of the present invention is, although not limited to, an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or higher, more preferably a pH of 9 to 12. This aromatic primary amine developing agent as a color developing agent is a compound having 7 primary amine groups on an aromatic ring and has the ability to develop exposed silver halide. Precursors that form such compounds may also be added. The color developing agent mentioned above is typically p7z nylennoamine type, and the following are preferred examples. 4-7 minnow N, N-noethylaniline, 3-methyl-
4-7 minnow N, N-diethyl 7-niline, 4-7 minnow N-ethyl-N-β-hydroxyethyl 7-niline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-7minor N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-7min/-N-
Ethyl-□N-β-hydroxyethyl 7-niline, 3-nodoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-7toxy 4-amino-N-ethyl-N-β-nodoxy Ethylaniline, 3-7cetamido4-7minorN, N-dinomethyl7niline, N-ethyl-N-β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-7minoaniline, N- Ethyl-N-β-(β-methoxyethoxy)ethyl-3-
Methyl-4-7mi/aniline and salts thereof such as sulfate, hydrochloride, sulfite, 9-)luenesulfonate and the like. Furthermore, for example, JP-A-48-64932, JP-A-50-1
31526, No. 51-95849, and those described by Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951) are also mentioned as representative examples. The amount of these aromatic t11-class amino compounds to be used depends on where the activity of the developer is set, but in order to increase the activity, it is preferable to increase the amount used, and the amount used is 0.002 It is used in the range of mol/11 to 60.7 mol/Q. In addition, two or more compounds may be used in appropriate combination depending on the purpose. For example, 3-
Methyl-4-7 minnow N, N-noethylaniline and 3-
Combinations of methyl-4-7 minnow N-ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-7 minnow N-ethyl-N-β-hydroxyethylaniline, etc., can be freely combined according to the purpose. Can be used. There are various other things that are usually added to the color developing solution □
Ingredients such as sodium hydroxide, sodium carbonate
Alkaline agents such as 1-mu, alkali metal sulfites, flu-
1. Potassium metal bisulfite, alkali metal thiocyanate
”. Acid salts, alkali metal halides, pencil flu
Reference 7-1, *, b2. V1, wafi 1M□71,9 engineering□
□ (Can be optionally included. As an additive other than the above added to the color developing solution)
For example, potassium bromide, heptammonium bromide, etc.
□ Bromide, alkali iodide, nitrobenzimidazo
. -mercaptobenzimidazole, 5-methylene
In addition to compounds for rapid processing solutions such as rubenztriazole and 1-phenyl-5-norcaptotetrazole, there are anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, and the like. Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above-mentioned 7-minoboricarboxylic acids include the following. Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, ethyl ether di7minetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminetetraacetic acid nonodium salt, diethylenetriaminepentaacetic acid sodium salt, nitrilotriacetic acid sodium salt, etc. Bleach The liquor may contain various additives along with the bleaching agents mentioned above. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. The bleach-fix solution may further contain a halide such as potassium bromide, and as in the case of the bleach solution described above, various other additives,
For example, pH buffering agents, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained. The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned. From the viewpoint of rapid processing, the processing temperature for various processing steps such as color development, bleach-fixing (or bleaching and fixing), and further water washing, stabilization, and drying, which are carried out as necessary, of the photosensitive material of the present invention is set at 3.
Preferably, the reaction is carried out at a temperature of 0°C or higher. The photosensitive material of the present invention is disclosed in JP-A-58-14834 and JP-A-58-14834.
E Examples Specific examples of the present invention will be described below, but the implementation of the present invention is not limited to these. In all the examples below, the amount of photosensitive material added is per 1 m2 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver. Example 1 A multilayer photosensitive material sample 1-1 consisting of each layer having the composition shown below was prepared on a triacetyl cellulose film support. 1st layer: anti-halesian layer (HC-1) gelatin layer containing black colloidal silver 2nd layer: dark layer (1, L> gelatin layer Ill; low-sensitivity red-sensitive silver halide emulsion layer (RL-1) ) Average grain size (r) 0.30 μgloss t Monodisperse emulsion consisting of AgBrI containing 6 mol% of AgI (emulsion 1)... Silver coating amount 1.89 g/m2 (RL-1) Average grain size (r) 0 , 30/jm, AIHI 6 mol%
Monodispersed emulsion (emulsion I) consisting of AgBrI containing...-
Silver coating amount 1.89g, /+s2 Sensitizing dye I...6X10-5 mol per mol of silver Sensitizing dye ■...1. OX 10-S Morcian coupler (C-1)...0.06 mol per silver 1 mole Colored cyan coupler (CG-1)...0.003 mol DIR compound per 1 mol silver (D-1)...0.0 per mole of silver
015 mol D I R (lll & l (D -2)... 0.002 mol 4th layer for 1 silver mol number 2; High sensitivity red sensitivity/% Silver lodenide emulsion layer (RH-1
) Monodisperse emulsion (emulsion ■) consisting of AgBrI containing average grain size (r) 0.5 μmyAg1 7.0 mol%... Silver coating amount 1.3.7 m2 Sensitizing dye ■... Per 1 mole of silver 3×10-'mol sensitizing dye ■...1. OX 10-' Moaresian coupler (c-i)...0.03 mol per mol of silver DIR compound (D-2)...0.03 mol per mol of silver.
001 layer 5th layer; Intermediate layer (I, L,) Same gelatin layer as the 2nd layer 6th layer;
) Sensitizing dye ■...2.5X 10" moles per mole of silver Sensitizing dye ■...1.2X per mole of silver 1G-
'Morsian coupler (M-1)...0.045 mol per mol of silver Colored magenta coupler (CM-1)...0.009 mol per mol of silver DIR compound (D-1) ...0.0 per mole of silver
010 mol DIR compound (D-3)... o, o per 1 mol of silver
ao mole 7th layer; Highly sensitive green-sensitive silver halide emulsion layer (GH-1) Emulsion n... Silver amount cloth fi 1.4 g/m2 Sensitizing dye ■.
... t, sx io-' mole per mole of silver sensitizing dye ■...1. OX 10-' mole magenta coupler (M-1)...o, o per mole of silver
ao mole DIR compound (D-3)...0.0% per mole of silver.
0010 mol 8th layer; Yellow filter single layer (YC-1) Yellow gelatin layer containing colloidal silver 9th layer; Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Average grain size 0.48 μm vA-gI 6 mol% A containing
Monodispersed emulsion (emulsion ■) consisting of gBrI... Silver coating amount 0.9 g/m2 Sensitizing dye ■... 1.3X 10-' per mole of silver
Mol yellow coupler (Y-1)...0.29 mol per mol of silver 10th layer; high sensitivity blue-sensitive emulsion layer (BH-1) average grain size 0
．． 8 μm* Monodispersed emulsion (emulsion ■) consisting of AgBrI containing 15 mol% of AgI...silver coating amount 0.5 g/m
2 Sensitizing dye V...1. OX 10-'
Mol Yellow coupler (y-i)...0.08 mol per mol of silver DIR compound (D-2)...0.08 mol per mol of silver.
0015 mol 11th layer; 1st protective layer (Pro-1) Silver iodobromide (AgI 1 mol % average grain size 0.07 μ so, silver coating to, 5 g/so 2) and ultraviolet absorber UV-1, UV
12th layer of gelatin layer containing -2; second protective layer (Pro-2) gelatin layer containing polymethyl methacrylate particles (diameter 1.5μ ring) and formalin scavenger (H3-1). In addition to the composition, a gelatin hardener (H-
1) and a surfactant were added. Sensitizing dye 1: 5.5'-dichloro9-ethyl3
゜3'-di(3-sulfopropyl)thiacarpo di-7 dihydroxide sensitizing dye■;9-ethyl-3,3'-no(3-sulfopropyl)-4,5,4',5',- Dibenzothiacarbocyanine hydroxide color enhancement zm; s, s'-diphenyl-9-ethyl-3
．． 3'-C (3-sulfopropyl) sensitizing dye ■; 9-
Ethyl-3,3'-no(3-sulfoxacarbonaniphopropyl)-5,6,5',6'-dibetonzoxacarbocyanine hydroxytoside sensitizing dye V; 3,3-di(3 - Sulkhob Peer)
゛-4,5-Benzo5'-7 toxythiacyanine C-1; C, 11. CC-1: D-1; h D-2; D-3; M-1; ll CM-1; PM-1: Y-1; G UV-1; UV-2: H8-1; H-1 ; Next, Sample 1 was prepared except that the amounts of magenta coupler and gelatin contained in the low-sensitivity green-sensitive layer/1 (GL-1) and the high-sensitivity green-sensitivity layer (GH-1) were changed as shown in Table 1. −
Samples 1-2 to 1-12 were prepared in the same manner as in Example 1. Each of the samples 1-1 to 1-12 prepared in this manner was subjected to continuous exposure using white light, and then subjected to the following development treatment.・Processing process (38℃) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water
Fixed for 3 minutes and 15 seconds 6
Washing with water for 30 minutes Stabilizing for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows. [Color developer] 4-7 minnow 3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine sulfate 2.0g anhydrous carbonate Potassium 37.5g Sodium Bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to make IQ. [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100° Ethylenenoaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150g Ice vinegar 1! l
Add to, o, and g water to make a liquid, and adjust the pH to 6.0 using aqueous ammonia. [Fixer] Ammonium thousand sulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water and IQ
and adjust the pH to 6.0 using acetic acid. [Stabilizer] Formalin (37% aqueous solution) 1, 5
, Q Konigux (Roku Konishi Photo Industry Co., Ltd. 91) 7
．． Add 5 ml of water to make 1 q. Each sample obtained was treated under conditions of 55° C. and 65% RH for 3 days. Using white light (W) and blue light (B), the relative sensitivity (S), sharpness (M T F ), and R
MS was measured. The results are shown in Table 2. Note that the relative sensitivity (S) is the relative value of the reciprocal of the exposure amount that gives a fog density of +0.1, and the sensitivity of sample 1-1 is set to 100.
The value is shown as . Sharpness is determined by the MTF of the dye image, and the MT at 1 layer/■
It is shown as a relative value of F (Sample 1-1 is LOG). The RMS value is the minimum density + 1.2 when the circular scanning aperture is 2.
It is expressed as a value 1000 times the standard deviation of the variation in density value that occurs when scanning with a 5 μm microdensitometer. Table 2 =, -, , /' As is clear from the results in Table 2, according to the present invention, a photosensitive material with little deterioration in sensitivity and graininess and improved sharpness to 1[W] can be obtained. It is also found that by using the coupler represented by the general formula (1) as the magenta coupler contained in the green-sensitive layer, image quality deterioration under high temperature and high humidity conditions can be improved. Example 2 Multilayer samples 2-1 to 2-12 were prepared in the same manner as in Example 1, except that only the layer structure was changed as described below. When the same evaluation as in Example 1 was performed, it was confirmed that this layer structure also had a significant sharpness improvement effect and storage stability improvement effect. (H1 order) Layer-1 to layer-3; Layer-4 same as scrap-1 to layer-3 of Example-1; Layer 1 same as layer-2 of Example-1. L. Layer-5: Same as layer-6 of Example-1 GL-1 Layer-6; Same r and L as layer-2 of Example-1. Layer-7: Same as layer-9 of Example-1 BL-1 Layer-8; Same as layer-2 of Example-1 1. L. Layer-9; RH-1 layer-1 same as /1l-4 of Example-1
0: Same I and L as layer-2 of Example-1. Layer-11; GH-1 layer-12 same as M-7 of Example-1
; Same as layer-8 of Example-1 YC-IN-13: Same as layer-10 of Example-1 B) (-1 layer-14; Example-1
Pro-1 layer-15 same as layer-11; N of Example-1
Pro-2 same as -12 [Effect of the invention] According to the present invention, the sharpness of the light-sensitive material is improved without impairing the graininess. Therefore, the light-sensitive material of the present invention can provide excellent sharpness and graininess. Furthermore, when applied in combination with the known technique for improving sharpness, it is possible to reduce the defects, ζ, that is, deterioration of graininess and decrease in sensitivity associated with the known technique, and to obtain excellent sharpness. . Furthermore, by using the coupler represented by the general formula (I) as the coupler contained in the green-sensitive layer of the light-sensitive material of the present invention, the above effects are enhanced and the storage stability of the light-sensitive material is improved. Ru.

Claims (1)

[Claims] The silver density of the green-sensitive layer composed of one layer or two or more layers is 5.0 x 10^-^1 g/cm^3 or more, and the total dry film thickness of the green-sensitive layer is 4.5 μm A silver halide color photographic material characterized by the following: