JP2516026C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial applications)   The present invention relates to a silver halide light-sensitive material. (Background technology)   Silver halide color light-sensitive materials (hereinafter referred to as light-sensitive materials) are made of blue light, green light and
Three silver halide emulsion layers selectively sensitized to be sensitive to red light
The photosensitive layer is coated on a support in a multilayer structure. For example, the so-called
On color photographic paper (hereinafter referred to as color paper), the side that is normally exposed
A red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are provided.
An intermediate layer, a protective layer, and the like, which prevent color mixing and absorb ultraviolet rays, are provided in the space between the layers.   Also, in the case of a so-called color positive film, generally the side far from the support,
Green-sensitive emulsion layer, red-sensitive emulsion layer, and blue-sensitive emulsion layer are sequentially applied from the side
. In color negative film, the layer arrangement is diverse, and the blue-sensitive emulsion
Layers, a green-sensitive emulsion layer and a red-sensitive emulsion layer in this order.
In the case of a light-sensitive material having two or more emulsion layers having different color sensitivity and different sensitivities, a color-sensitive material is provided between the emulsion layers.
Sensitive materials in which emulsion layers with different sexes are arranged are sometimes seen, and a bleachable yellow filter layer,
An intermediate layer, a protective layer, etc. are inserted.   To form a color photographic image, three colors of yellow, magenta and cyan are used.
A photographic coupler is included in the photosensitive layer, and the exposed photosensitive material is used as a so-called color developer.
Perform color development processing with chemicals. Oxidized aromatic primary amine forms coupler and cup
The coloring reaction is provided by the ring reaction, but the coupling speed at this time is low.
Good color developability, as large as possible, giving high color density within a limited development time
Preferred are preferred. Furthermore, the coloring pigments are all vivid cyan with little side absorption,
Providing color photographic images with good color reproduction with magenta and yellow dyes
Is required.   On the other hand, the formed color photographic image or color print is composed of sunlight, fluorescent light,
Observed under various light source conditions, such as tungsten light and their mixed light
Due to the potential, gray and other light sources can be observed under any light source such as these.
It is necessary to create an image consisting of a combination of dyes so that the color balance is not lost. (This performance is called observation light source dependence).   The human eye, for example, saw objects that were gray in sunlight under tungsten light
Sometimes, it can be recognized as gray at short intervals. This is called dark adaptation
Is a combination of the three primary colors cyan, magenta, and yellow, including all gray
In color reproduction by the so-called subtractive color reproduction method, dark adaptation becomes impossible.
It is known that there is a combination region of coloring dyes. Dyes in such areas
In the combination of, for example, the image that looks gray in sunlight is different light source
Underneath it can appear reddish or greenish gray.   This phenomenon is caused by the color that can be observed under various light sources.
It is very unfavorable as a photographic image.
Is always desired.   Also, improving color reproduction is the supreme proposition for color photography, and various efforts have been made.
Power has been attempted, but to improve color reproduction, the absorption spectra of
It is generally known that sharpening tends to decrease the dependence on the observation light source.
Therefore, development of a method capable of improving these at the same time has been strongly desired. (Object of the invention)   An object of the present invention is to provide a light source under various light sources such as sunlight, fluorescent light, and tungsten light.
Silver halide photosensitivity with improved observation light source dependence such that rays appear as gray
It is to provide materials.   Breakthrough improvement of color reproduction especially in the region from red to magenta and blue and dependence on observation light source
The object of the present invention is to provide a silver halide light-sensitive material satisfying the above requirements. (Structure of the invention)   According to the present invention, at least one kind of a resin represented by the following general formula (II) is provided on a reflective support.
A red-sensitive silver halide emulsion layer containing a puller, at least one of the following general formulas (II)
A green-sensitive silver halide emulsion layer containing a coupler represented by I), and at least
Blue-sensitive silver halide milk containing one kind of coupler represented by the following general formula (IV)
Each of these emulsion layers has a silver bromide content of 10 mol% or less.
, Or silver chloride, and these couplers are each dispersed in the emulsion layer.
A high boiling organic solvent having a boiling point of 160 ° C. or more and / or a water-insoluble
molecule In a color developer having a benzyl alcohol content of 5 cc / l or less, which is present in the compound
Formed during the coupling reaction with oxidized paraphenylenediamine
The spectral absorption peak wavelength of each of the coloring dyes falls within the range represented by the relationship of the following formula (I).
A silver halide photosensitive material.   1/2 (λy + λc) ≧ λm ≧ 1/2 (λy + λc) −10 Expression (I)   λc: Spectral absorption peak wavelength (nm) of cyan coloring dye   λm: Spectral absorption peak wavelength (nm) of magenta coloring dye   λy: Spectral absorption peak wavelength (nm) of yellow coloring dye[However, in the general formulas (II) to (IV), R_FourIs a substituted or unsubstituted fat
Represents an aromatic, aromatic or heterocyclic group;_FiveIs an alkyl group having 2 to 15 carbon atoms or carbon
A methyl group having at least one substituent,₆Is a hydrogen atom, a halogen atom,
Represents a substituted or unsubstituted aliphatic group, aromatic group or acylamine group;₇
Represents a hydrogen atom or a substituent;₈Is a substituted or unsubstituted N-phenyl Represents a carbamoyl group, and Za and Zb are methine, substituted methine, ＮN- or-
NH-, Y_Two, Y_ThreeAnd Y_FourIs the bond with the hydrogen atom or the oxidized form of the developing agent.
It represents a group that can be eliminated during the pulling reaction. ]   The spectral absorption spectrum of the coloring dye and its spectral absorption peak wavelength were used
The structure of couplers and color developing agents and the use of high-boiling solvents
It is largely determined by physical properties, especially dielectricity and refractive index (The Journal of Food
Original Chemistry 61: 562 (1957). In addition, high boiling point solvents and
It is possible to change the absorption sharpness to some extent by changing the ratio of the pullers.
is there.   In order to improve color reproducibility and enhance color vividness, the absorption spectrum of coloring dyes
It is first necessary to sharpen the file. In particular, red, purple,
For areas such as blue, especially in the cyan and yellow areas of the magenta dye
It is preferable to reduce as much as possible side absorption. Spectral absorption of coloring dye
The three factors that greatly control the yield are listed, but the most dominant factor is the coupler.
The use of the coupler represented by the general formula (III) makes it possible to obtain cyan and yellow areas.
Sub-absorption of the region is significantly reduced, and accordingly, the saturation of the region ranging from red, purple and blue is improved,
It has been found that the color reproducible area is greatly expanded. However, the general formula (III)
The improvement in color reproducibility by using the coupler indicated by
Was also found to be significantly worse. This reduces the spectral absorption characteristics of the coloring dye.
Much worse than the level generally expected to occur due to
Met. Regarding the observation light source dependence, see The Journal of Photography.
This is described in detail in Volume Science, Volume 20, (1972), page 149.
Using coloring dyes used in conventional color photography
Find the relationship between the absorption wavelength peaks of each dye so that the observation light source dependence is the best.
I'm worried. The relations shown there are shown below as formulas (II) and (III).   The present inventors have proposed a coupler represented by the general formula (II) and a coupler represented by the formula (III)
, Their structures and their dispersion media using couplers represented by (IV)
age By changing the polarity of the high boiling solvent used
, A color photographic light-sensitive material which satisfies the relations of the formulas (II) and (III)
Was. Nevertheless, the observation light source dependence was in a remarkably bad state. Book
The inventors have observed the observation light source dependence of a sample in which the peak wavelength of such a coloring dye was changed.
While further examining, the regions represented by formulas (II) and (III)
We found that there was an optimal area in a completely different place. It is represented by the formula (I)
And the spectral absorption peaks of the cyan, magenta, and yellow coloring dyes.
It has been found that it is related to the wavelength. Such a discovery was completely unexpected
However, this discovery dramatically improved the color reproducibility and simultaneously made the observation light source dependent.
It has enabled inventions beyond the conventional general concept of improvement.   In the present invention, the cyan coloring dye, the magenta coloring dye and the yellow coloring dye
Possible spectral absorption peak wavelengths are 665 ± 15 nm and 542.5 ± 1, respectively.
5 nm, 440 ± 15 nm, more preferably 665 ± 10 nm, 542.5 ± 1
0 nm and 440 ± 10 nm.   Next, the couplers used in combination in the present invention will be described in detail.
.   In the general formulas (II) to (IV), R_Four~ R₇Examples of the substituent of
Group, aromatic group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic group
Shiki, described in U.S. Pat. No. 4,540,654, column 2, line 41 to column 4, line 29
Groups. Preferred R_FourExamples of alkyl groups, alkoxy groups,
And a heterocyclic oxy group.
May be substituted with the groups described above. More specifically, R₇Archi in
Examples of phenyl groups are preferably straight-chain or branched chains having 1 to 32 carbon atoms
Alkyl group, aralkyl group, cycloalkyl group, for example, methyl, ethyl,
Propyl, isopropyl, isobutyl, t-butyl, trifluoromethyl, tri
Decyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) p
Ropyl, 3- {4-} 2- [4- (4-hydroxyphenylsulfonyl) pheno
[Xy] dodecaneamide {phenyl} propyl, 2-ethoxytridecyl, cyclo
Pentyl and a 3- (2,4-di-t-amylphenoxy) propyl group.
. In the general formula (II), (III) or (IV), Y_Two, Y_ThreeOr Y_FourBut When a leaving group (hereinafter referred to as a leaving group) is represented, the leaving group may be oxygen, nitrogen,
Or activated carbon coupled through a carbon atom to an aliphatic group, an aromatic group,
Ring group, aliphatic / aromatic or heterocyclic sulfonyl group, aliphatic / aromatic or
A group that bonds to a heterocyclic carbonyl group, a halogen atom, an aromatic azo group, etc.
And the aliphatic, aromatic or heterocyclic group contained in these leaving groups is represented by R_FourForgive
May be substituted with any of the following substituents. When two or more of these substituents
And these substituents may further be R_FourHas a substituent that is
It may be.   Specific examples of the coupling-off group include a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom, etc., an alkoxy group (for example, an ethoxy group, a dodecyloxy
Group, methoxyethylcarbamoylmethoxy group, carboxylpropyloxy group,
A methylsulfonylethoxy group, an aryloxy group (eg,
Nonoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.),
Siloxy group (eg, acetoxy group, tetradecanoyloxy group, benzoyl
Xy group), an aliphatic or aromatic sulfonyloxy group (eg, methanesulfo
Nyloxy group, toluenesulfonyloxy group, etc.), acylamino group (for example,
Chloroacetylamino), heptafluorobutyrylamino, etc.) and aliphatic
Or an aromatic sulfonamide group (for example, methanesulfonamino group, p-toluene
Sulfonylamino group, etc.), alkoxycarbonyloxy group (for example, ethoxy
Rubonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxy
Carbonyloxy group (for example, phenoxycarbonyloxy group, etc.);
Aromatic or heterocyclic thio groups (eg, ethylthio, phenylthio, tetrazolyl,
Carbamoylamino group (eg, N-methylcarbamoylamino)
Group, N-phenylcarbamoylamino group, etc.) 5- or 6-membered nitrogen-containing
Ring groups (for example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group
Group, 1,2-dihydro-2-oxo-1-pyridyl group, etc.), imide group (for example,
Succinimide group, hydantoinyl group, etc.), aromatic azo group (for example, phenyla
Azo group), and these groups further include R_FourA group permitted as a substituent of
It may be substituted. Aldehyde as a leaving group bonded via a carbon atom There are bis-type couplers obtained by condensing 4-equivalent couplers with hydrs or ketones
. The leaving group of the coupler used in the present invention is a development inhibitor, a development accelerator or the like.
It may contain a useful group. Preferred combinations of leaving groups in each formula
Will be described later.   In the cyan coupler of the general formula (II), R_FourOf an aliphatic group having 1 to 32 carbon atoms
For example, methyl, butyl, tridecyl, cyclohexyl, allyl
Examples of the aryl group include a phenyl group and a naphthyl group.
And examples of the heterocyclic group include a 2-pyridyl group, a 2-imidazolyl group,
Examples thereof include a furyl group and a 6-quinolyl group. These groups are furthermore alkyl groups
, Aryl group, heterocyclic group, alkoxy group (for example, methoxy group, 2-methoxy
A methoxy group), an aryloxy group (for example, 2,4-di-tert-amylpheno)
Xy, 2-chlorophenoxy, 4-cyanophenoxy, etc.), alkenyl
An oxy group (for example, 2-propenyloxy group and the like), an acyl group (for example, acetyl
Group, benzoyl group, etc.), ester group (for example, butoxycarbonyl group,
Nonoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl
Group, toluenesulfonyloxy group, etc.), amide group (eg, acetylamino group
, Methanesulfonamide group, dipropylsulfamoylamino group, etc.)
Moyl group (for example, dimethylcarbamoyl group, ethylcarbamoyl group, etc.),
Rufamoyl group (for example, butylsulfamoyl group and the like), imide group (for example,
Succinimide group, hydantoinyl group, etc.), ureido group (for example,
Raid group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (eg,
For example, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic
Group thio group (for example, ethylthio group, phenylthio group, etc.), hydroxy group,
Groups selected from the group consisting of amino, carboxy, nitro, sulfo, halogen, etc.
It may be substituted.   R in the general formula (II)_FiveIs an alkyl group having 2 to 15 carbon atoms or 1 or more carbon atoms
Methyl group having the above substituents, for example, ethyl group, propyl group, butyl group
, Pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl
Group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanami
Dome Examples thereof include a tyl group and a methoxymethyl group.   In general formula (II), Y_TwoIs a hydrogen atom or a coupling-off group (coupling
Includes leaving atoms. The same applies to the following, but examples thereof include halogen atoms (eg,
For example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (for example, ethoxy
Si, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxy
Propyloxy group, methylsulfonylethoxy group, etc., aryloxy group (eg
For example, 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphen
Phenoxy group, etc.), acyloxy group (eg, acetoxy group, tetradecanoyl)
Oxy group, benzoyloxy group, etc.), sulfonyloxy group (for example, methanes
Sulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (for example,
Chloroacetylamino group, heptafluorobutyrylamino group, methanesulfonyl
Amino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group
(For example, ethoxycarbonyloxy group, benzyloxycarbonyloxy group
An aryloxycarbonyloxy group (for example, phenoxycarbonyloxy)
A thio group), an aliphatic or aromatic thio group (eg, an ethylthio group, a phenylthio group).
Group, tetrazolylthio group, etc.), imide group (for example, succinimide group,
And an aromatic azo group (eg, a phenylazo group).
These leaving groups may include photographically useful groups.   Preferred examples of the cyan coupler represented by the general formula (II) are as follows.
.   Preferred R in the general formula (II)_FourIs a substituted or unsubstituted alkyl group,
And particularly preferably a substituted aryloxy-substituted alkyl group.   In general formula (II), R_FiveIs an alkyl group having 2 to 15 carbon atoms or 1 or more carbon atoms
A methyl group having a substituent of the formula:
O group, acylamino group, aryloxy group and alkyloxy group are preferred.   In general formula (II), R_FiveIs an alkyl group having 2 to 15 carbon atoms.
It is particularly preferably an alkyl group having 2 to 4 carbon atoms.   Preferred R in the general formula (II)₆Is a hydrogen atom, a halogen atom and a chlorine atom
And a fluorine atom is particularly preferred.   Preferred Y in General Formula (II)_TwoIs a hydrogen atom, a halogen atom, an alkoxy Group, aryloxy group, acyloxy group and sulfonamide group.   In general formula (II), Y_TwoIs preferably a halogen atom, a chlorine atom,
A fluorine atom is particularly preferred.   The substituent of the general formula (III) will be described. R₇Is an alkoxy group, aryloxy
R represents a hetero group or a heterocyclic oxy group;₇Can be described in detail.₇Arco
The xy group is, for example, a methoxy group, an ethoxy group, an i-propoxy group, a hexyloxy group.
Di-, t-butoxy, dodecyloxy, 2-ethylhexyloxy,
Ziroxy group, cyclohexyloxy group, 2-chloroethoxy group, 2-phenoxy
Ethoxy group, 2- (2,4-dichlorophenoxy) ethoxy group, allyloxy
A group, etc.,₇Aryloxy group is, for example, a phenoxy group, 2,4-
Dichlorophenoxy group, 4-methylphenoxy group, 4-nonylphenoxy group, 3
-Pentadecylphenoxy group, 3-butanamidophenoxy group, 2-naphthoxy
Group, 1-naphthoxy group, 4-methoxyphenoxy group, 3,5-dimethoxypheno
A xy group, a 3-cyanophenoxy group, or the like;₇Examples of the heterocyclic oxy group are
For example, 2-pyridyloxy group, 2-thienyloxy group, 2-methyltetrazole
-5-oxy group, 2-benzothiazoleoxy group, 2-pyrimidineoxy group, etc.
Represents   Y of the general formula (III)_ThreeRepresents a hydrogen atom or a coupling-off group, respectively.
Examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, etc.),
Alkoxy groups (eg, methoxy, ethoxy, dodecyloxy, methoxy
Tylcarbamoylmethoxy, methylsulfonylethoxy, etc.), arylthio
O group (for example, phenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group)
Group, 4-t-butylphenoxy group, 4-carboethoxyphenoxy group,
Anophenoxy group, 2,4-dichlorophenoxy group, etc.), acyloxy group (eg,
For example, an acetoxy group, a tetradecanoyloxy group, etc.), an amide group (for example,
Chloroacetamide group, benzenesulfonylamino group, trifluoroacetamide
Imide group (e.g., succinimide group, phthalimido group, 5,5-
Dimethyl-2,4-dioxooxazolidinyl group, 1-benzyl-5-ethoxy
Hydantoinyl group, etc.), nitrogen heterocyclic group (eg, pyrazole group, 4-chloro)
Pi Razol group, 3,5-dimethyl-1,2,4-triazol-2-yl group,
Dazole group, 3-chloro-1,2,4-triazol-2-yl group, etc.),
Kirthio group (for example, ethylthio group, dodecylthio group, 1-ethoxycarbonyl
Dodecylthio group, 3-phenoxypropylthio group, 2- (2,4-di-tert-a
Milphenoxy) ethoxy group, etc.), arylthio group (for example, phenylthio group
, 2-butoxy-5-tert-octylphenylthio group, 4-dodecyloxyphene
Nylthio group, 2- (2-ethoxyethoxy) -5-tert-octylphenylthio
Group, 3-pentadecylphenylthio group, 3-octyloxyphenylthio group, 3
-(N, N-didodecylcarbamoyl) phenylthio group, 2-octyloxo-
5-chloro-phenylthio group, etc.), heterocyclic thio group (for example, 1-phenyl
Tolazole-5-thio group, 1-ethyltetrazole-5-thio group, 1-dodecyl
-1,2,4-triazole-5-thio group, etc.). These leaving groups
More preferred are groups capable of leaving with a mercapto group, and particularly preferred are allyl groups.
Thiol group. Za and Zb in the general formula (III) are methine, substituted methine-N =
Or an -NH- group. Particularly preferred among the magenta couplers of the general formula (III)
The couplers are represented by the following general formulas (III-1) to (III-4).   Particularly preferred couplers among these are (III-2) and (III-3),
A more preferred compound is (III-2). Formulas (III-1) to (III-4)
) In R₇Is as described above, and R₉, R_TenAre the same or different
Well each hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group,
Cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy
Group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamido
, Anilino, ureido, imide, sulfamoylamino, carbamo
Ylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxy
Carbonylamino group, aryloxycarbonylamino group, sulfonamide group,
Carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group
, An alkoxycarbonyl group and an aryloxycarbonyl group. R₉, R_Ten
Or Y_ThreeMay be a divalent group to form a bis form.   See R₉And R_TenAre a hydrogen atom and a halogen atom (for example,
A chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, a propyl group, a t-butyl group).
Tyl group, trifluoromethyl group, tridecyl group, 3- (2,4-di-t-amyl)
Phenoxy) propyl group, allyl group, 2-dodecyloxyethyl group, 3-pheno
Xypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentel group, ben
A phenyl group, a 4-t-butylphenyl group,
, 4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.),
Heterocyclic group (for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2
-Benzothiazolyl group, etc.), cyano group, alkoxy group (for example, methoxy group,
An ethoxy group, a 2-methoxyethoxy group, a 2-dodecyloxyethoxy group,
Tansulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group,
2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy
Group (for example, 2-benzimidazolyloxy group, etc.), acyloxy group (for example,
, Acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (e.g.,
For example, N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.
), Silyloxy group (for example, trimethylsilyloxy group, etc.), sulfonylo
Xy group (for example, dodecylsulfonyloxy group, etc.), acylamino group (for example,
, Cetamide group, benzamide group, tetradecaneamide group, α- (2,4-di-t
-Amylphenoxy) butyramide group, γ- (3-t-butyl-4-hydroxy)
Phenoxy) butyramide group, α- {4- (4-hydroxyphenylsulfonyl)
Phenoxy didecamide group, etc.), anilino group (for example, phenylamino group,
2-chloroanilino group, 2-chloro-5-tetradecanamidanilino group, 2-chloroanilino group
Chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group,
2-chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodeca
Amide / anilino group, etc.), ureido group (eg, phenylureido group, methyl
Ureido group, N, N-dibutylureido group, etc.), imide group (for example,
Succinimide group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoy
), A sulfamoylamino group (eg, N, N
-Dipropylsulfamoylamino group, N-methyl-N-decylsulfamoyl
An amino group, an alkylthio group (eg, a methylthio group, an octylthio group,
Tradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio
Group, 3- (4-t-butylphenoxy) propylthio group, etc.), arylthio group
(For example, a phenylthio group, a 2-butoxy-5-t-octylphenylthio group,
3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetra
Decanamidophenylthio group, etc.), heterocyclic thio (eg, 2-benzothiazo
A thiol group, etc.), an alkoxycarbonylamino group (for example, methoxycarbonyl)
Amino group, tetradecyloxycarbonylamino group, etc.), aryloxyca
Rubonylamino group (for example, phenoxycarbonylamino group, 2,4-di-tert
-Butylphenoxycarbonylamino group, etc.), sulfonamide group (for example,
Tansulfonamide group, hexadecanesulfonamide group, benzenesulfonamide
Group, p-toluenesulfonamide group, octadecanesulfonamide group,
Tyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group
(For example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N-
(2-dodecyloxyethyl) carbamoyl group, N-methyl-N-dodecylcal
Bamoyl group, N- {3- (2,4-di-tert-amylphenoxy) propyl) ca
Rubamoyl group, etc.), acyl group (eg, acetyl group, (2,4-di-tert- Milphenoxy) acetyl group, benzoyl group, etc.), sulfamoyl group (for example,
, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N- (
2-dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecyl sulf
Famoyl group, N, N-diethylsulfamoyl group, etc.), sulfonyl group (for example,
For example, methanesulfonyl, octanesulfonyl, benzenesulfonyl,
Ensulfonyl group, etc.), sulfinyl group (eg, octanesulfinyl group,
Dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl
(For example, methoxycarbonyl group, butyloxycarbonyl group, dodecylca
Rubonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (
For example, a phenyloxycarbonyl group, a 3-pentadecyloxy-carbonyl group
, Etc.).   In the general formula (IV), an N-phenylcarbamoyl group R₈Substitution of phenyl group
The group is_FourCan be arbitrarily selected from the group of substituents allowed for,
When there are two or more substituents, they may be the same or different.   Preferred R₈Examples thereof include the following general formula (IVA).   General formula (IVA)   [Where G₁Represents a halogen atom or an alkoxy group;_TwoIs a hydrogen atom,
Represents a halogen atom or an alkoxy group which may have a substituent. R¹⁴Is a substituent
Represents an alkyl group which may have ]   G in the general formula (IVA)_TwoAnd R¹⁴Examples of the substituent include an alkyl group
, Alkoxy group, aryl group, aryloxy group, amino group, dialkylamino
Group, heterocyclic group (for example, N-morpholino group, N-piperidino group, 2-furyl group, etc.)
), Halogen atom, nitro group, hydroxy group, carboxyl group, sulfo group,
Typical examples include a carbonyloxy group.   Preferred leaving group Y_FourIs a group represented by the following general formula from (X) to (XVI)
including.   R₂₀Represents an aryl group or a heterocyclic group which may be substituted.  R_{twenty one}, R_{twenty two}Represents a hydrogen atom, a halogen atom, a carboxylic ester group, and an amino group, respectively.
, Alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group, alkyl
Rusulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted
Represents a nyl group or a heterocyclic ring, and these groups may be the same or different. Represents the non-metallic atoms required to form.   Of the formulas (XIII), (XIV) to (XVI) are preferred.   Where R_{twenty three}, R_{twenty four}Represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,
R represents an aryloxy group or a hydroxy group;_{twenty five}, R₂₆And R₂₇Is water
A hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group;
_TwoRepresents an oxygen or sulfur atom.   Specific examples of these couplers are shown below. (II-1) (II-2) (II-3) (II-4) (II-5) (II-6) (II-7) (II-8) (II-9) (II-10) (II-11) (II-12) (II-13) (II-14) (II-15) (II-16) (II-17) (II-18) (II-19) (II-20) (II-21) (II-22) (II-23) (III-1)(III-2) (III-3) (III-4)(III-5) (III-6) (III-7)(III-8) (III-9) (III-10) (III-11) (III-12) (III-13)(III-14) (III-15) (III-16)(III-17) (III-18) (III-19) (III-20) (III-21) (III-22) (III-23) (III-24) (III-25) (III-26) (III-27) (III-28) (III-29) (III-30)(III-31) (III-32) (III-33)(III-34) (III-35)(III-36) (III-37)(III-38) (IV-1)(IV-2) (IV-3)(IV-4) (IV-5)(IV-6) (IV-7)(IV-8) (IV-9)(IV-10) (IV-11)(IV-12) (IV-13)(IV-14) (IV-15) (IV-16) (IV-17) (IV-18) (IV-19) (IV-20) (IV-21) (IV-22) (IV-23) (IV-24) (IV-25)(IV-26) (N-27)(IV-28) (IV-29)(IV-30) (IV-31)(IV-32) (IV-33)(IV-34) (IV-35)(IV-36) (IV-37)(IV-38) (IV-39)  The coupler represented by the general formula (II) or (III) or (IV) is a photosensitive layer.
Make up 0.1 to 1.0 mol per mol of silver halide is usually used in the silver halide emulsion layer.
Or 0.1 to 0.5 mol. Also represented by the general formula (II) or (III), (IV)
The molar ratio between the couplers is usually in the range of about 1: 0.2 to 1.5: 0.5 to 1.5 in molar ratio.
However, it is possible to design a photosensitive material outside this range.   In the present invention, various known techniques may be used to add the coupler to the photosensitive layer.
Surgery can be applied. Usually, oil droplets in water known as the oil protection method
Gelatin containing surfactant can be added by a dispersion method and dissolved in a solvent.
Emulsify and disperse in aqueous solution. Alternatively, use water or water in a coupler solution containing a surfactant.
Alternatively, an aqueous gelatin solution may be added to form an oil-in-water dispersion with phase inversion. Also Al
The potassium-soluble coupler can also be dispersed by a so-called Fisher dispersion method.
From the coupler dispersion, by a method such as distillation, noodle washing or ultrafiltration,
After removing the low boiling organic solvent, it may be mixed with a photographic emulsion.   As a dispersion medium of such a coupler, a high-boiling organic compound having a boiling point of 160 ° C. or more is used.
A solvent and / or a water-insoluble polymer compound is used. The higher the dielectric constant, the better
The larger the refractive index is, the longer the wavelength of the coloring dye spectral absorption peak becomes. For example,
Alkyl talates (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl phosphate,
Ricresyl phosphate, dioctyl butyl phosphate), citrate S
Ter (eg, tributyl acetyl citrate), benzoate (eg,
Octyl breath acid), alkylamides (eg, diethyl laurinoleamide), fats
Fatty acid esters (for example, dibutoxyethyl succinate, dioctyl azela
Boiling point of phenols (eg, 2,4-di (t) amylphenol) etc.
The above high boiling organic solvents are mentioned. As the water-insoluble polymer compound, for example,
Compounds described in JP-B-60-18978, columns 18 to 21; Acrylamides and methacrylamides as one monomer component
Limers (including homopolymers and copolymers) and the like can be mentioned.   More specifically, for example, polymethyl methacrylate, polyethyl methacrylate
, Polybutyl methacrylate, polycyclohexyl methacrylate and poly-t-
Butyl acrylamide and the like can be mentioned. In addition, these high-boiling organic solvents and
And / or water-insoluble polymer compound, together with lower grades such as ethyl acetate and butyl acetate
Alkyl acetate, ethyl propionate, secondary butyl alcohol, methyl iso
Butyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate
Which boiling point organic solvent having a low boiling point of 30 ° C. to 150 ° C. is used alone or as required.
Can be used.   The molecular weight and the degree of polymerization of the polymer compound used in the present invention are substantially different from the effects of the present invention.
There is no significant effect, but as the molecular weight increases, it takes time to dissolve in the cosolvent.
It is difficult to emulsify and disperse due to problems such as darkness and high solution viscosity, resulting in coarse particles.
, That As a result, it is easy to cause problems such as a decrease in color developability and a cause of poor coating properties.
Become. To cope with this problem, using a large amount of co-solvent to lower the viscosity of the solution is a new
This will cause problems in the process. From the above viewpoint, the viscosity of the polymer compound is
The viscosity when dissolving 30 g of the polymer compound in 100 cc of the auxiliary solvent used is 500.
It is preferably 0 cps or less, more preferably 2000 cps or less. Also used in the present invention
The molecular weight of the polymer compound that can be used is preferably 150,000 or less, more preferably 80,000 or less.
Lower, more preferably 30,000 or less.   The ratio of the high molecular compound to the auxiliary solvent used in the present invention depends on the high molecular compound used.
Depending on the type of product, solubility in co-solvent, degree of polymerization, etc., or coupler
It varies over a wide range depending on the solubility of the polymer. Usually at least a coupler,
Two or three of high boiling organic solvent (coupler solvent) and high molecular compound are auxiliary solvents
Is easily dispersed in water or aqueous hydrophilic colloid solution
The amount needed to be low enough to Cosolvents are used. The higher the degree of polymerization of the polymer compound, the higher the viscosity of the solution.
Therefore, by-products of the polymer compound to the auxiliary solvent are determined uniformly regardless of the polymer compound.
Although difficult to determine, it is usually preferred to be in the range of about 1: 1 to 1:50 (weight ratio).
The ratio (weight ratio) of the polymer compound to the coupler used in the present invention is 1:20.
20: 1, more preferably 1:10 to 10: 1.   From the same hue coupler group represented by the general formulas (II) and (III);
Pullers can be selected and used together. In this case, the coupler may be co-emulsified.
It is also possible to emulsify the mixture and mix it, and further add a discoloration inhibitor described below to the coupler.
Can also be used in admixture with.   The light-sensitive material of the present invention may include, as necessary, the coupler of the present invention represented by the above general formula.
Outside special couplers can be included. For example, in the green-sensitive emulsion layer
, Containing a colored magenta coupler to provide a masking effect
it can. In each of the color-sensitive emulsion layers or in an adjacent layer thereof Include a development inhibitor releasing coupler (DIR coupler) and a development inhibitor releasing hydroquino.
Can be used in combination. Released from these compounds upon development
Development inhibitors are used to improve the sharpness of an image, to reduce the size of an image, or to improve monochromatic saturation.
Which brings the interlayer effect.   In the photographic emulsion layer of the present invention or the layer adjacent thereto, the current (elephant accelerator)
Alternatively, add a coupler that releases a nucleating agent to improve photographic sensitivity,
It is also possible to obtain effects such as improvement in graininess and hardening of gradation.   In the present invention, the ultraviolet absorber can be added to any layer. Preferably
Containing an ultraviolet absorber in the layer containing the compound represented by the general formula (II) or in the adjacent layer.
You. The ultraviolet absorber that can be used in the present invention is Research Disclosure 1764
Compounds listed in item C of item VIII of No. 3 and preferably having the following general formula
It is a benzotriazole derivative represented by (XVII).   Where R₂₈, R₂₉, R₃₀, R₃₁And R₃₂May be the same or different, and represent a hydrogen atom
Or R which is an aromatic group₁May be substituted with an acceptable substituent for_Three
1And R₃₂May be closed to form a 5- or 6-membered aromatic ring composed of carbon atoms.
Good. Among these groups, those which may have a substituent further include R₁Allowed against
May be further substituted with a substituent.   The compounds represented by the above general formula (XVII) can be used alone or in combination of two or more.
Wear.   The method for synthesizing the compound represented by the general formula (XVII) or other compound examples is as follows.
JP-B-44-29620, JP-A-50-151149, JP-A-54-95
No. 233, U.S. Pat. No. 3,766,205 No., EP0057160, Research Disclosur
e) No. 22519 (1983, No. 225). In addition,
No. 58-111942, Japanese Patent Application Nos. 57-61937 and 57-63602.
High-molecular-weight purple dyes described in Nos. 57-129780 and 57-133371.
External radiation absorbers can also be used. Use low molecular weight and high molecular weight UV absorbers together
You can also.   The above-mentioned ultraviolet absorber is used for high-boiling organic solvents and low-boiling organic solvents in the same manner as the coupler.
It is dissolved in a single or mixed solvent and dispersed in a hydrophilic colloid. High boiling organic solvent
The amount of the medium and the UV absorber is not particularly limited, but is usually based on the weight of the UV absorber.
High boiling organic solvents are used in the range of 0% to 300%. Compounds that are liquid at room temperature
Or a combination is preferable.   The ultraviolet absorber of the general formula (XVII) is used in combination with the combination of the coupler of the present invention.
Then, it is necessary to improve the storability of the color dye image, particularly the cyan image, particularly the light fastness.
Can be. This UV absorber and shear The coupler may be co-emulsified.   The amount of UV absorber applied should be sufficient to provide photostability to the cyan dye image
It is good to use, but if it is used in too much, the unexposed part (white background) of the color photographic light-sensitive material becomes yellow
Usually, it is preferably 1 × 10^-FourMol / m^Two~ 2 × 10^-
ThreeMol / m^Two, Especially 5 × 10^-FourMol / m^Two~ 1.5 × 10^-3Mol / m^TwoSet to range
Is done.   In the usual light-sensitive layer composition of color paper, the red-sensitive emulsion layer containing cyan coupler
An ultraviolet absorber is contained in any one of the adjacent layers, preferably in both layers.
Confuse. When adding an ultraviolet absorber to the intermediate layer between the green sensitive layer and the red sensitive layer, prevent color mixing.
May be co-emulsified with the agent. When an ultraviolet absorber is added to the protective layer, make it the outermost layer.
Still another protective layer may be applied. The protective layer has a particle size of any size.
Agent and the like.   To improve the storability of coloring dye images, especially yellow and magenta images
Can be used in combination with various organic and metal complex-based discoloration inhibitors. Wear. Hydroquinones, gallic acid derivatives, p-a
There are lucoxyphenols and p-oxyphenols, and dye image stabilizers,
Anti-thein or antioxidants are available from Research Disclosure 17643
Patents are cited in paragraphs VII I or J of the issue. Also, fading prevention of metal complex system
Stoppers are described in Research Disclosure No. 15162 and the like.   To improve the heat and light fastness of yellow images, phenols and high
Droquinones, hydroxy chromans, hydroxy coumarans, hindered ami
And their alkyl ethers, silyl ethers or hydrolyzable precursors
Although many compounds belonging to the derivatives can be used, the following general formulas (XVIII) and (XIX)
The compound represented by the formula (IV)
It is effective for simultaneously improving light fastness and heat fastness.   [In the above general formula (XVIII) or (XIX), R₄₀Represents a hydrogen atom, an aliphatic group, an aromatic
Group, heterocyclic group or positionR₅₀, R₅₁And R₅₂May be the same or different, and each represents an aliphatic group, an aromatic group,
Group, an aliphatic oxy group or an aromatic oxy group, and these groups are represented by R₁Allowed in
May have a substituent. R₄₁, R₄₂, R₄₃, R₄₄And R₄₅Are the same but different
May be a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, respectively.
, Hydroxyl group, mono Or a dialkylamino group, an imino group and an acylamino group. R₄₆,
R₄₇, R₄₈And R₄₉May be the same or different, and represent a hydrogen atom and an
Represents an alkyl group. X is a hydrogen atom, an aliphatic group, an acyl group, an aliphatic or aromatic
Sulfonyl group, aliphatic or aromatic sulfinyl group, oxy radical group and
Represents a hydroxyl group. A is required to form a 5-, 6- or 7-membered ring
Represents a non-metallic atomic group. ]   A method for synthesizing a compound corresponding to the general formula (XVIII) or (XIX) or a compound other than those described above
Examples of the compound are British Patents 1,326,889, 1,354,313 and 1,410,846.
Nos., U.S. Pat. Nos. 3,336,135 and 4,268,593, and JP-B No. 51-1420.
Nos. 52-6623, 58-114036 and 59-5246.
It is listed.   Compounds represented by formulas (XVIII) and (XIX) may be used in combination of two or more.
And may be used in combination with a conventionally known discoloration inhibitor.   The amounts of the compounds represented by formulas (XVIII) and (XIX) are used in combination.
0.5 to 200 for yellow coupler
%, Preferably in the range of 2 to 150% by weight to achieve the intended purpose.
. Preferably, it is co-emulsified with the yellow coupler of the general formula (IV).   The coupler of the present invention represented by formula (III) also has a
The above-mentioned various dye image stabilizers, stain inhibitors or antioxidants improve storage stability.
Although effective, the following general formulas (XX), (XXI), (XXII), (XXIII), (XXIV)
Since the compounds represented by and (XXV) greatly improve light fastness,
preferable. General formula (XX) General formula (XXI) General formula (XXII) General formula (XXIII)General formula (XXIV) General formula (XXV)   [In the above general formula from (XX) to (XXV), R₆₀Is R of the general formula (XVIII)₄₀When
Synonymous with R₆₁, R₆₂, R₆₄And R₆₅May be the same or different, each
Hydrogen, aliphatic, aromatic, acylamino, mono- or dialkyl
Amino group, aliphatic or aromatic thio group, acylamino group, aliphatic or aromatic
Group oxycarbonyl group or -OR₄₀Represents R₄₀And R₆₁Is combined with 5
It may form a six-membered or six-membered ring. Also, R₆₁And R₆₂And a 5 or 6 member ring
May be formed. X represents a divalent linking group. R₆₆And R₆₇Are the same but different
And each represents a hydrogen atom, an aliphatic group, an aromatic group, or a hydroxyl group.
R₆₈Represents a hydrogen atom, an aliphatic group or an aromatic group. R₆₆And R₆₇And five members together
Alternatively, a 6-membered ring may be formed. M represents Cu, Co, Ni, Pd or Pt. R₆₁
To R₆₈Up to an aliphatic group or an aromatic group,₁With the substituents allowed for
It may be substituted. n is an integer from 0 to 3; m is an integer from 0 to 4
Represent integers, respectively R₆₂Or R₆₁And when these are 2 or more, R₆₂Or R₆₁Is the same
May also be different. ]   In the general formula [XXIV], preferred X is And the like are typical examples, where R₇₀Represents a hydrogen atom or an alkyl group.   Preferred R in the general formula (XXV)₆₁Is a group capable of hydrogen bonding. R₆₂, R₆₃
And R₆₄At least one of the groups represented by is a hydrogen atom, a hydroxyl group, an alkyl group
Or a compound which is an alkoxy group is preferred.₆₁To R₆₈Substituents up to
Is preferably a substituent having a total of 4 or more carbon atoms.   These compounds are disclosed in U.S. Pat. Nos. 3,336,135, 3,432,300 and 357.
No. 3050, No. 3574627, No. 3700455, No. 3764337, No.
393,016, 398,2944, 4,254,216, 427,999
No. 0, British Patent Nos. 1347556, 2062888, 2066975,
No. 2,077,455, JP-A-60-97353, JP-A-52-152225
Nos. 53-17729, 53-20327, 54-145530, and 55
No.-6321, No.55-21004, No.58-24141, No.59-105
No. 39, JP-B-48-31625 and JP-B-54-12337, the synthesis method and
Also described are compounds other than those listed above.   Among the anti-fading agents which are advantageously used in the present invention, the general compounds (XX) to (XXIV)
The compound represented by the formula is used in an amount of 10 to 20 with respect to the magenta coupler used in the present invention.
0 mol%, preferably 30 to 100 mol% is added. On the other hand, in the general formula (XXV)
Show The compound is used in an amount of 1 to 100 mol% based on the magenta coupler used in the present invention.
Preferably, 5 to 40 mol% is added. These compounds are co-milk with magenta couplers
It is preferred that the   In order to prevent fading, for example, JP-A-49-11330 and JP-A-50-57223
One technique is to surround the dye image with an enzyme blocking layer made of a substance with low oxygen permeability.
Japanese Patent Application Laid-Open No. 56-85747 discloses an oxygen-permeable material on the support side of a color image forming layer of a color photographic light-sensitive material.
Excess rate is 20ml / m^Two・ It is disclosed that the layer below hr ・ atom is provided.
Applicable to   The silver halide emulsion layer according to the present invention has a chlorobromide content of 10 mol% or less.
Contains silver or silver chloride.   The crystal form, crystal structure, particle size, There is no limitation on the particle size distribution and the like. However, the coefficient of variation is less than 0.15, preferably 0.1
It is desirable that the emulsion is a monodisperse emulsion of 0 or less. Silver halide crystals can be normal crystals
It may be a twin crystal, and may be any of a hexahedron, an octahedron, and a tetrahedron. Research de
0.5 micron thickness or less as described in Disclosure No. 22534
Tabular grains having a diameter of at least 0.6 microns and an average aspect ratio of 5 or more.
You may. However, the silver halide emulsion in at least one of the silver halide emulsion layers is
An emulsion mainly containing cubic or tetradecahedral normal silver halide grains
Is preferred.   The crystal structure may be uniform, or the inside and outside may have different compositions.
Silver halide with different composition due to epitaxial junction
May be joined or may be composed of a mixture of particles of various crystal forms. Ma
The latent image may be formed mainly on the surface of the child or may be formed inside.   The grain size of silver halide is as small as 0.1 micron or less. Particles or large size particles with projected area diameters of up to 3 microns can be used, with a narrow distribution
Or a polydisperse emulsion having a wide distribution.   These silver halide grains are It can be produced by a commonly known method.   The silver halide emulsion is prepared by a conventional chemical sensitization, that is, a sulfur sensitization method, a precious metal.
Sensitization can be performed by a sensitization method or a combination thereof.   As the support used in the present invention, polyethylene terephthalate or triacetate cell
Any of a transparent support such as loin and a reflective support described below may be used. Anti
Radiation supports are more preferred, for example, baryta paper, polyethylene coated paper, poly
Propylene-based synthetic paper, transparent support provided with a reflective layer or combined with a reflector, eg
For example, a glass plate, polyethylene terephthalate, cellulose triacetate,
Polyester film such as Lurose, polyamit film, polycarbonate
Film, polystyrene film, etc.
It can be selected as appropriate.   The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are each sensitive to methine dyes and the like.
It has been spectrally sensitized to have color properties. For the dye used Means cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine color
Element, holobora cyanine dye, hemicyanine dye, styryl dye, and hemi
Oxonol dyes are included. Particularly useful dyes are cyanine dyes, merocyanine
It is a pigment belonging to pigments and complex merocyanine pigments. These dyes have a base
As the sex heterocyclic nucleus, any nucleus commonly used for cyanine dyes can be applied.
That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazoline nucleus
Nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
A lysine nucleus or the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these nuclei
Nuclei in which an aromatic hydrocarbon ring is fused to the
Nin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzo
Thiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazo
Nucleus, quinoline nucleus and the like can be applied. These nuclei are substituted on carbon atoms
Is also good.   Merocyanine dyes or complex merocyanine dyes have a ketomethylene structure
As the nucleus, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolyl nucleus
Gin-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus,
A 5- to 6-membered heterocyclic nucleus such as an obarbituric acid nucleus can be applied.   These sensitizing dyes may be used alone, or a combination thereof may be used,
Combinations of sensitizing dyes are often used, especially for supersensitization. A typical example is rice
Japanese Patent Nos. 2688545, 2977229, 3397060, 3520252,
No. 3527641, No. 3617293, No. 3628964, No. 36664
No. 80, No. 3672898, No. 3679428, No. 3703377, No. 3
No. 769301, No. 3814609, No. 3837862, No. 4026707
No., British Patent Nos. 1344281 and 1507803, Japanese Patent Publication No. 43-4936
53-12375, JP-A-52-110618, No. 52-109925.   Along with sensitizing dyes, dyes having no spectral sensitizing effect or visible light
A substance which does not qualitatively absorb and which exhibits supersensitization may be contained in the emulsion.   The color photographic light-sensitive material of the present invention includes an undercoat layer, an intermediate layer, and a protective layer in addition to the above-described constituent layers.
And other auxiliary layers. If necessary, red-sensitive silver halide emulsion
A second ultraviolet absorbing layer may be provided between the layer and the green-sensitive silver halide emulsion layer. this
It is preferable to use the above-mentioned ultraviolet absorbent for the ultraviolet absorbent layer, but other known ultraviolet absorbents may be used.
An external ray absorbent may be used.   It is advantageous to use gelatin as a binder or protective colloid of a photographic emulsion.
However, other hydrophilic colloids can also be used.   For example, gelatin derivatives, graft polymers of gelatin with other polymers,
Proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl
Lecellulose, cellulose sulfate S Derivation of sugars such as cellulose derivatives such as ters, sodium alginate and starch derivatives
Body: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
Vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Mono- or copolymers such as polyvinylimidazole and polyvinylpyrazole
A large number of synthetic hydrophilic polymer substances can be used.   Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull.Soc, Sci.P.
Enzyme-treated gelatin as described in hot. Japan No. 16, page 30 (1966)
May be used, and hydrolysates or enzymatic degradation products of gelatin may also be used.
You.   In the light-sensitive material of the present invention, a photographic emulsion layer and other hydrophilic colloid layers may have stills.
Includes whitening agents such as ben-based, triazine-based, oxazole-based, or coumarin-based
It may be. These may be water-soluble, and a water-insoluble brightener may be used in the dispersion.
It may be used in the form. Specific examples of the optical brighteners are described in US Pat. Nos. 2,632,701 and 326.
9840, same No. 3359102, British Patent Nos. 852075 and 1319763, Research D
Isclosure Volume 176, Volume 17643 (December 1978), page 24, left column, 9-36
It is described in the description of Brighteners on the line.   In the light-sensitive material of the present invention, the hydrophilic colloid layer contains a dye or an ultraviolet absorber.
If present, they may be mordant, such as by cationic polymers
. For example, British Patent No. 684475, U.S. Pat. Nos. 2,675,316 and 28394
No. 01, No. 2882156, No. 3048487, No. 3184309, No. 3
445231, West German Patent Application (OLS) 1914362, JP-A-50-47
Nos. 624 and 50-71332 can be used.
Wear.   The light-sensitive material of the present invention comprises a hydroquinone derivative, an amino
It may contain phenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc.
Specific examples thereof are described in U.S. Pat. Nos. 2,360,290, 2,336,327 and 240,372.
No. 1, No. 2418613, No. 2675314, No. 2701197, No. 27047
No. 13, No. 2728659, No. 2732300, No. 2735765,
50-92988, 50-92989, 50-93928, 50
No. 110337, No. 52-146235, Japanese Patent Publication No. 50-23813, etc.
It is listed.   The color photographic light-sensitive material of the present invention may contain, in addition to the above, various photographic additives known in the art.
Additives such as stabilizers, antifoggants, surfactants, couplers other than the present invention, fillers
Luter dye, anti-irradiation dye, developing agent, etc. may be added as necessary.
Can be.   Further, in some cases, substantially in the silver halide emulsion layer or other hydrophilic colloid layer
Non-photosensitive fine grain silver halide emulsion (for example, having an average grain size of 0.20 μm)
The following silver chloride, silver bromide, and silver chlorobromide emulsions) may be added.   The color developing solution that can be used in the present invention is This is an alkaline aqueous solution mainly containing a roughenylenediamine-based color developing agent.
4-amino-N, N-diethylaniline, 3-methyl-4 as color developing agents
-Amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydrido
Roxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydro
Xyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanes
Rufoamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-me
Representative examples include tokinethylaniline.   The color developer contains alkali metal sulfites, carbonates, borates and phosphates.
PH buffers, bromides, iodides, and development inhibitors such as organic antifoggants;
, An antifoggant and the like. If necessary, water softener, hydro
Preservatives such as xylamine, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, sodium boroha
Fogging agent such as idride, 1-phenyl Auxiliary developing agents such as -3-pyrazolidone, viscosity-imparting agents, US Pat. No. 4,083,723
Polycarboxylic acid-based chelating agents described in West German Patent Publication (OLS) 2622250
The antioxidant described above may be included.   Also, by promoting a coupling reaction such as benzyl alcohol,
-It is possible to include a compound that promotes development.
Compounds that promote coupling have broad spectral absorption spectra of coloring dyes.
To the color reproducibility, so that it is not very suitable for the purpose of the present invention.
Not good. Benzyl alcohol is less than 5cc per liter of color developer.
Is the content of   The photographic emulsion layer after color development is usually bleached. Bleaching is simultaneous with fixing
Or may be performed individually. Examples of the bleaching agent include iron (III
), Compounds of polyvalent metals such as cobalt (III), chromium (VI) and copper (II), peracids
Kind, quinone And nitrone compounds. For example, ferricyanide, dichromate
, Iron (III) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid
Amino, such as nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid
Complex salts of polycarboxylic acids or organic acids such as citric acid, tartaric acid and malic acid;
Sulfate, permanganate; nitrosophenol and the like can be used. this
Potassium ferricyanide, sodium iron (III) ethylenediaminetetraacetate and
And ammonium iron (III) ethylenediaminetetraacetate are particularly useful. ethylene
The iron (III) complex diaminetetraacetate can be used in an independent bleaching solution or in a one-bath bleach-fixing solution.
It is also useful.   After the color development or the bleach-fix processing, washing may be performed. Color development at 18 ° C and 5
It can be performed at any temperature between 5 ° C. Preferably 30 ° C. or higher, particularly preferably 3 ° C.
Perform color development at 5 ° C. or higher. The time required for development is preferably as short as about three and a half minutes or less.
For continuous development, replenishment of the solution is preferable. Replenish liquid of 330cc to 160cc, preferably 100cc or less per meter
You.   Bleaching and fixing can be carried out at any temperature between 18 ° C and 50 ° C, preferably at 30 ° C or higher.
New When the temperature is 35 ° C. or higher, the processing time can be reduced to 1 minute or less, and the solution is replenished.
The amount can be reduced. The time required for washing after color development or bleach-fix is usually within 3 minutes.
For one minute or less using a multi-stage countercurrent stabilization process as described in JP-A-57-8543.
The inside can be washed with water.   Colored pigments are not only degraded by light, heat or temperature, but also by mold during storage.
Deterioration and fading. Cyan images are particularly susceptible to mold deterioration and use antifungal agents
Is preferred. Specific examples of the fungicide are described in JP-A-57-157244.
There are 2-thiazolylbenzimidazoles as described. Fungicides are sensitive materials
May be incorporated in the photosensitive material, or may be added from the outside in the developing process.
If a fungicide can be present therein, it can be added in any step. (Example)   Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
There is no. (Reference example)   On a paper support laminated on both sides with polyethylene,
I made photographic paper. The coating solution was prepared as follows.   Preparation of the first layer coating solution; 10 g of ethyl acetate was added to 10 g of the yellow coupler (a) and 23 g of the color image stabilizer (b).
and 4 ml of the solvent (c) were added and dissolved, and this solution was added with 10% dodecylbenzenesulfonate.
It was emulsified and dispersed in 90 ml of a 10% aqueous gelatin solution containing 5 ml of sodium phosphate.
On the other hand, a silver chlorobromide emulsion (silver bromide ratio: 80 mol%, silver content: 70 g / kg) is shown below.
4 × 10 4 blue-sensitive dyes per mole of silver chlorobromide^-FourA blue-sensitive emulsion was prepared by adding mol. Emulsified
The powder and the emulsion are mixed and dissolved, and the concentration is adjusted with gelatin so that the composition shown in Table 1 is obtained.
A coating solution for one layer was prepared.   Silver halide emulsion used in this reference example (1) Was prepared as follows.   (1 liquid)   H_TwoO 1000ml   5.5 g of NaCl   25g gelatin   (2 liquids)   Sulfuric acid (1N) 20ml   (3 liquids)   The following compound (1%) 2ml   (4 liquids)   2.80 g of KBr   NaCl 0.34 g   H_TwoAdd O and 140ml   (5 liquids)   AgNO_Three                                    5g   H_TwoAdd O and 140ml   (6 liquids)   KBr 67.20 g   8.26 g of NaCl   K_TwoIrCl₆ (0.001%) 0.7ml   H_TwoAdd O and 320ml   (7 liquids)   AgNO_Three                                120g   NH_FourNO_Three(50%) 2ml   H_TwoAdd O and 320ml   (Liquid 1) was heated to 75 ° C., and (Liquid 2) and (Liquid 3) were added. Then, (4 liquid
) And (5 liquids) were added simultaneously for 9 minutes. After another 10 minutes, (Sixth solution) and (7
Solution) was added simultaneously for 45 minutes. Five minutes after the addition, the temperature was lowered and desalted. water
And dispersed gelatin, adjusting the pH to 6.2, changing the average particle size to 1.01 μm,
Coefficient (standard deviation divided by average grain size; S / d) 0.08, silver bromide 80
% Of a monodisperse cubic silver chlorobromide emulsion. This milk The agent was optimally chemically sensitized with sodium thiosulfate.   The same applies to the silver chlorobromide emulsions (2) and (3) in the green-sensitive and red-sensitive emulsion layers.
According to the method, the amount was changed by changing the amount of the chemical, the temperature, and the time.   Emulsion (2) was 75 mol% of silver bromide having a grain size of 0.45 μm and a coefficient of variation of 0.07.
Emulsion (3) contained 70 mol% of silver bromide having a grain size of 0.51 μm and a variation coefficient of 0.07.
Monodispersed cubic silver chlorobromide.   The structural formulas of the compounds used in this reference example, such as couplers, are as follows.   Magenta coupler (a)  Color image stabilizer   (A)   (B)  (C)   UV absorber   (A)   (B)  (C)   (D)   (E)  Color mixing inhibitor   (A)   (B)   solvent   (A)  (B)   (C)   (D)   The following dyes were used as irradiation prevention dyes for each emulsion layer.   Green-sensitive emulsion layer  Red-sensitive emulsion layer   The following sensitizing dyes were used for each emulsion layer.   Blue-sensitive emulsion layer  Green-sensitive emulsion layer   Red-sensitive emulsion layer [Table 1]   The coating liquids of the first to seventh layers are adjusted by adjusting the balance of surface tension and viscosity to form polyethylene.
A sample 101 was prepared by applying the solution on a paper support having both sides laminated.   Next, Samples 102 to 116 were prepared in exactly the same manner except for the changes shown in Table 2.
did.   These samples were provided with a Toshiba color evaluation fluorescent lamp (FL) having a color temperature of 5000 ° K (FL).
(40SW-50-EDL) Red when observed under gray so that the density becomes 1.0
, Green and blue were adjusted in exposure amount. In addition, the amount of light
Red, green, blue, single exposure, (red + green), (red + blue), (green + blue) light combination
By exposure, cyan, magenta, yellow, blue, green, and red (hereinafter C, M, Y, B, G, R
, Abbreviated as), and developed by the following processing steps.
Processing was performed.   The measurement of the concentration was performed by FSD-103 manufactured by Fuji Photo Film.   The composition of each processing solution is as follows. (Developer solution A) 2.0 g of nitrilotriacetic acid / 3Na Benzyl alcohol 15ml 10 ml of diethylene glycol Na_TwoSO_Three                          2.0g 0.5 g of KBr Hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-ethyl-N-   [Β- (methanesulfonamido) ethyl]   -P-phenylenediamine sulfate                                     5.0g Na_TwoCO_Three(Monohydrate) 30.0 g Add water and add 1000ml                              (PH 10.1) (Bleach-fix solution formulation A) Ammonium thiosulfate (54wt%) 150ml Na_TwoSO_Three                           15g NH_Four[Fe (III) (EDTA)] 55 g EDTA ・ 2Na 4g Add water and add 1000ml                              (PH 6.9)   The samples obtained in this manner, which were colored in gray, C, M, Y, B, G, and R, respectively, were
Color measurement using a color analyzer M-307 manufactured by
According to the IE1964 color difference formula, FL40SW-50-EDL of 5000 ° K and (a
) 2854 ° K tungsten light, (b) 4200 ° K fluorescent fluorescent lamp (FL40
SW-S), (c) daylight fluorescent lamp of 6500 ° K (FL40S-S), (d) three
Average color difference ΔE from the wavelength type fluorescent lamp (FL40S • EL) at the time of observation under each light source
I sought. The smaller the color difference ΔE, the lower the observation light source dependence.   R, G, B, C, M, Y, each color sample Is plotted against the CIE 1964 uniform color space based on the colorimetric results.
The evaluation of good color reproducibility was performed.   Regarding the evaluation of color reproducibility, how much vivid color can be reproduced (saturation)
It is necessary to consider two points of whether the color can be faithfully reproduced (hue). color
Saturation can be represented by the width of the reproduction area in the CIE 1964 uniform color space.
However, at this time, in order to comprehensively evaluate changes in all colors, the importance of each color is taken into consideration.
Need to be inserted. This is described in the Journal of Photography book.
It is described in detail in QuScience Vol. 14, p. 87 (1966), and
Each color was weighted to define the following A value. The larger this A value is,
This indicates that the overall color reproduction range is wide. A = 32C_R ^*+ 28C_G ^*+ 24C_B ^*+ 16C_Y ^*+ 10C_M ^*+ 12C_C ^*   (I = R, G, B, C, M, Y,)   For the fidelity of the hue, the deviation from the sample 101 for the magenta color was
It is represented by a hue angle difference Δθ in the E1964 uniform color space.   The CIE1964 color difference is described in detail in JIS Z8729- 1970.
I have.   The values of ΔE, Δθ, and A obtained in this manner are represented by C, M, and Y, and the dyes at the time of single color development
Peak wavelength λ_maxAre shown in Table 3.   In the color print of the present invention, A is 109 or more, Δθ is −5 to +5, and ΔE is
It is desirable that it is 2.3 or less. [Table 2] [Table 3] (Example 1)   The emulsions used for Samples 101 to 116 prepared in Reference Examples are shown below.
Samples 201 to 216 were changed to silver chloride emulsions as described above, and sensitizing dyes and dyes were further changed.
Produced.   Next, a method for preparing a silver chloride emulsion used in Example (1) of the present invention will be described.   The pure silver chloride emulsion used for the blue-sensitive layer was prepared as follows.   (8 liquids)   H_TwoO 1000ml   5.5 g of NaCl   32g gelatin   (9 liquids)   Sulfuric acid (1N) 20ml   (10 liquids)   1.7 ml of the following compound (5%)   HOCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoOH   (11 liquids)   8.60 g of NaCl   H_Two130 ml with O   (12 liquids)   AgNO_Three                          25g   NH_FourNO_Three(50%) 0.5ml   H_Two130 ml with O   (13 liquids)   NaCl 34.4 g   K_TwoIrCl₆   (0.001%) 0.7ml   H_Two285ml with O   (14 liquids)   AgNO_Three                        100g   NH_FourNO_Three (50%) 2ml   H_Two285ml with O   (Liquid 8) was heated to 72 ° C., and (Liquid 9) and (Liquid 10) were added. Then, (1
Solution 1 and Solution 12 were simultaneously added over a period of 60 minutes. After another 10 minutes, (13
Solution) and (solution 14) were added simultaneously over 25 minutes. 5 minutes after the addition, lower the temperature,
Desalted. Add water and dispersed gelatin, adjust pH to 6.2, Mean particle size 0.8 μm, coefficient of variation (standard deviation divided by mean particle size;
S / d) A monodispersed cubic pure silver chloride emulsion of 0.1 was obtained. Gold and sulfur sensitized to this emulsion
Was given. Gold is 1.0 × 10^-Five/ Mol Ag added and optimized with sodium thiosulfate
Chemical sensitization was applied.   Next, a silver halide emulsion having a silver chloride content of 99.5 mol% for the green-sensitive layer was prepared as follows.
Prepared.   (15 liquids)   H_TwoO 1000ml   5.5 g of NaCl   32g gelatin   (16 liquids)   Sulfuric acid (1N) 24ml   (17 liquids)   (10 liquids) Compound 1% 3ml   (18 liquids)   0.11 g of KBr   NaCl 10.95g   H_TwoAdd O and 220ml   (19 liquids)   AgNO_Three                          32g   H_Two200 ml with O   (20 liquids)   0.45 g of KBr   NaCl 43.81 g   K_TwoIrCl₆ (0.001%) 4.5ml   H_TwoAdd O and 600ml (21 liquids)   AgNO_Three                        128g   H_TwoAdd O and 600ml   (Liquid 15) was heated to 40 ° C., and (Liquid 16) and (Liquid 17) were added. afterwards,
(Liquid 18) and (Liquid 19) were added simultaneously for 10 minutes. After another 10 minutes, (
Solution 20 and Solution 21 were added simultaneously for 8 minutes. 5 minutes after addition, lower the temperature
, Desalted. Water and dispersed gelatin are added, the pH is adjusted to 6.2, and the average particle size is 0.2.
A monodispersed cubic silver chlorobromide emulsion having a size of 3 μm, a coefficient of variation of 0.1, and 99.5 mol% of silver chloride was obtained.
Was. 4.1 × 10 4 chloroauric acid was added to this emulsion.^-FiveMol / Molar addition was performed to sensitize gold.   Similarly, by changing the composition and temperature of (18 liquid) and (20 liquid), the average particle size was set to 0.1.
Monodisperse cubic silver chlorobromide milk for red-sensitive layer with 4 μm, coefficient of variation 0.1 and silver chloride 99 mol%
The resulting emulsion was subjected to gold and sulfur sensitization. Gold is 4.1 × 10^-FiveMol / mol
Ag was added, and optimal sensitization was performed with sodium thiosulfate.   Next, sensitizing dyes and irradiation preventing dyes will be described.   Sensitizing dye for blue sensitive layer   Sensitizing dye for green sensitive layer   Sensitizing dye for red sensitive layer   Irradiation dye for green sensitive layer  Anti-irradiation dye for red-sensitive layer   The obtained samples 201 to 216 were exposed to light similar to that of the reference example, and the following steps were performed.
Was performed.   The temperature, time and formulation of each step are shown below. (Color developer formulation -B) 800cc water Diethylenetriaminepentaacetic acid   1.0 g of 5Na salt 0.2 g of sodium sulfite N, N-diethylhydroxyl   Amine 4.2g Potassium bromide 0.01g 1.5 g of sodium chloride 8.0 g of triethanolamine N-ethyl-N- (β-methane   Sulfonamidoethyl) -3-   Methyl-4-aminoaniline   4.5 g of sulfate Potassium carbonate 30.0g 4,4'-diaminostilbene   Fluorescent whitening agent (Sumitomo Chemical Co., Ltd. Whitex4) 2.0g 1000cc in total with water                                    (PH 10.1) (Bleach-fix solution formulation-B) Water 700cc Ammonium thiosulfate (54-wt%) 150cc 15g sodium sulfite NH_Four[Fe (III) (EDTA)] 55 g EDTA · 2Na (dihydrate) 4g 8.61 g of glacial acetic acid 1000cc in total with water                                      (PH 5.4) (Rinse liquid formulation) 0.4 g of EDTA · 2Na (dihydrate) 1000cc in total with water                                      (PH 7.0)   Refer to the samples developed and developed in gray, C, M, Y, R, G, B, respectively.
Colorimetry was performed according to the method of the example, and the results shown in Table 4 were obtained.   From the results shown in Table 4, the combination of the present invention was obtained using 5-pyrazolone conventionally used.
It shows better color reproducibility than the combination using the magenta coupler,
Λ which was optimal in the conventional combination_maxHue and viewing light source for different areas
Λ that simultaneously satisfies dependencies_maxIt can be seen that there is a range of values.   Since benzyl alcohol was removed from the color developing solution, 5-pyrazine in Reference Example was removed.
Uninvented combinations are better than combinations using zolone type magenta couplers
Significant improvement in saturation. [Table 4] (The invention's effect)   The multilayer silver halide light-sensitive material of the present invention has improved color reproducibility over a period of time,
Even when the image is observed under the changed light source, the color balance is less likely to be lost.

Claims (1)

A red-sensitive silver halide emulsion layer containing at least one coupler represented by the following general formula (II) on a reflective support, and at least one type represented by the following general formula (III) And a blue-sensitive silver halide emulsion layer containing at least one kind of coupler represented by the following general formula (IV). Contains silver chlorobromide or silver chloride having a silver bromide content of 10 mol% or less, and these couplers are each dispersed in the emulsion layer.
Coupling with an oxidized paraphenylenediamine developer in a color developing solution having a benzyl alcohol content of 5 cc / l or less in a high boiling organic solvent having a boiling point of 60 ° C. or more and / or a water-insoluble polymer compound. A silver halide photosensitive material characterized in that the spectral absorption peak wavelength of each coloring dye formed upon reaction is in the range represented by the following formula (I). 1/2 (λy + λc) ≧ λm ≧ 1/2 (λy + λc) −10 Formula (I) λc: Spectral absorption peak wavelength of cyan coloring dye (nm) λm: Spectral absorption peak wavelength of magenta coloring dye (nm) λy: Spectral absorption peak wavelength (nm) of yellow coloring dye [However, in the general formulas (II) to (IV), R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, and R ₅ represents an alkyl group having 2 to 15 carbon atoms or 1 carbon atom. Represents a methyl group having the above substituent, R ₆ is a hydrogen atom, a halogen atom,
A substituted or unsubstituted, aliphatic group, an aromatic group or an acyl amine group represents, R ₇
Represents a hydrogen atom or a substituent, R ₈ represents a substituted or unsubstituted N-phenylcarbamoyl group, and Za and Zb represent methine, substituted methine, ＮN— or —NH—
And Y ₂ , Y ₃ and Y _{4 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. ]