JPH031136A - Silver halide color photographic sensitive material and production thereof - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material which is excellent in sharpness, causes less coating troubles at the time of production and has excellent latent image preservable stability by providing at least one layer of specific silver halide emulsion layers on a base. CONSTITUTION:At least one layer of the silver halide emulsion layers are pro vided on the base. The layers are obtd. by mixing a dispersion contg. the cyan coupler expressed by formula I and contg. the high boiling org. solvent coexisiting therewith at <=0.3 by the weight of the cyan coupler and a color sensitized silver halide emulsion, then applying the mixture on the base for over 20 minutes without stagnating the liquid. In the formula, R1 denotes a halogen atom, aliphat. group, etc.; l ' denotes 0 to 3 integer; R3 denotes a hydro gen atom or R6U; T denotes a hydrogen atom or the group which can be elimi nated by the coupling reaction with the oxidant of an arom. primary amine developing agent. The photosensitive material which is excellent in the sharp ness, causes the less coating troubles at the time of production and has the excellent latent image preservable stability is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic material and a method for producing the same.

(Prior art) Using exposed silver halide as an oxidizing agent, the oxidized aromatic primary amine color developing agent and coupler react to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is well known that pigments are often produced in this way, and color images are formed.

Among these, phenolic couplers and naphthol couplers, which are known as cyan image-forming couplers, have low fastness to heat or light of color images formed by color development, and bleach solutions (bleach-fix solutions) with weak oxidizing power. ) or a worn-out bleaching solution (bleach-fixing solution) is used for development, it has been pointed out that there is a drawback that the color density decreases. As a coupler that improves these drawbacks, a 5-position substituted naphthol cyan coupler was proposed in European Patent Publication No. 161626A. The cyan dyes obtained from these cyan couplers were excellent in light and heat fastness and in that the spectral absorption of the developed color image was almost independent of the color density.

These couplers have a problem of poor sharpness when a high boiling point organic solvent is used as a coupler for sunset scenes, so a method of using only a high boiling point organic solvent as an intermediate coating was proposed in JP-A-62-26.
It was proposed in No. 9958.

(Problems to be Solved by the Invention) However, reducing the amount of high boiling point solvent for these couplers improves sharpness, but a new problem arises: coating failures increase. Furthermore, as a result of studies, it has become clear that when the above amount is reduced, the storage stability of the latent image after exposure is also deteriorated. Therefore, in order to prevent these coating failures and to stabilize the latent image, the weight ratio of the high boiling point organic solvent to the coupler had to be approximately 1.4, and it was necessary to balance this with the improvement of sharpness. . on the other hand,
The manufacturing method of mixing a coupler emulsion dispersion and a silver halide emulsion immediately before coating is described in JP-A No. 61-90154 for polymer couplers, and in JP-A-Sho 61-90154 for ureidophenol-based cyan couplers. 63-296038
No., JP-A-63 for pyrazoloazole couplers.
-296046, a 2-equivalent yellow coupler is described in JP-A-63-296046.

However, these couplers have drawbacks such as insufficient color density being obtained when a small amount of high-boiling organic solvent is used, and spectral absorption of a color image changing depending on the color density.

Therefore, the first object of the present invention is to provide a silver halide color photographic material that has excellent sharpness, fewer coating failures during production, and improved storage stability of latent images, and a method for producing the same. The second object is to provide a silver halide color photographic light-sensitive material and a method for producing the same, in which a high color density can be obtained and a color image in which the spectral absorption of the color image hardly changes with the color density is obtained. be.

(Means for Solving the Problems) The above objects of the present invention are as follows: (1) A cyan coupler represented by the following formula (1) is included, and the weight ratio of the organic solvent to the cyan coupler is 0. .3 or less and a color-sensitized silver halide emulsion are mixed and then coated for 20 minutes without stagnation, having at least one silver halide emulsion layer on the support. and (2) a silver halide color photographic light-sensitive material comprising a cyan coupler represented by the following formula (1), wherein the weight ratio of a high boiling point organic solvent coexisting therewith to the cyan coupler is 0.3 or less. A dispersion liquid and a color-sensitized silver halide emulsion are mixed in a static mixer,
It has been found that this can be achieved by a method for producing a silver halide color photographic light-sensitive material, which is characterized in that at least one silver halide emulsion layer is coated on a support without stagnation for more than 20 minutes. Ta.

General formula (1) In general formula (1), R+ is a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amidino group, a guanidino group, or -COR4, -3O*Ra, -3OI+, a gen atom, Hydroxyl group, carboxyl group, sulfo group, amino group, cyano group, nitro group, aliphatic group, aromatic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic group group oxy group, aromatic oxy group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, aliphatic oxycarbonylamino group, aromatic represents an oxycarbonylamino group, a sulfamoylamino group, a heterocyclic group, or an imide group, l' represents an integer of O to 3, and R3 is a hydrogen atom or I? 6U
, T represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer, provided that R4 and R2 each independently represent an aliphatic group, an aromatic group, or a heterocyclic group. group, amino group, aliphatic oxy group,
or represents an aromatic oxy group, R4 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -〇R7,4Rv, -CO
Re, -5OIR? , -5ozoR〒 or imide group, U is \N-R9, -CO-5-5Oz--5o
- or a single bond 2/', where R1 represents an aliphatic group, aromatic group or heterocyclic group, R represents a hydrogen atom, aliphatic group, aromatic group or heterocyclic group, R9 and R5° each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group.

When there is a plurality of l', Rt may be the same or different, or may be bonded to each other to form a ring. Rt and R1 or R3 and T may be bonded to each other to form a ring, or R,, RI Ih or T
In any of these, dimers or multimers (oligomers or polymers) bonded to each other via divalent or divalent or more-valent groups may be formed.

The compounds used in the present invention will be explained below.

Here, the aliphatic group refers to a linear, branched, or cyclic alkyl group, alkenyl group, or alkynyl group, which may be substituted or unsubstituted, and the aromatic group refers to a substituted or unsubstituted group. The term "heterocycle" refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group, which may be a fused ring. Specific examples of aliphatic groups include methyl group, ethyl L n -propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, cyclopentyl 5, t-pentyl group, cyclohexyl group, n
-octyl group, 2-ethylhexyl group, n-decyl group,
n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, 2-hexyldecyl group,
Adamantyl group, trifluoromethyl group, carboxymethyl group, methoxyethyl group, vinyl group, allyl group, hydroxyethyl group, heptafluoropropyl group, benzyl group, phenethyl group, phenoxyethyl group, methylsulfonylethyl group, methylsulfonamidoethyl group Group, 3-(
2-ethylhexyloxy)propyl group, 3-n-decyloxypropyl group, 3-n-dodecyloxypropyl group, 3-n-tetradecyloxypropyl group, oleyl group, propargyl group, ethynyl group, 3- (2,4-di-t-pentylphenoxy)propyl group, 4-(2,4
-di-t-pentylphenoxy)butyl group, 1-(2,
4-di-t-pentylphenoxy)propyl group, 1-(
2゜4-di-t-pentylphenoxy)pentyl group, 1
-(3-tetradecylphenoxy)propyl group, 2-n
-dodecylthioethyl group, etc.

Specific examples of aromatic groups include phenyl group, p-)lyl group,
m-)lyl group, o-)lyl group, 4-chlorophenyl f,
, 4-nitrophenyl! L4-cyanophenyl group, 4-
Hydroxyphenyl L3-Hydroxyphenyl group, l-
naphthyl group, 2-naphthyl group, 0-biphenylyl group, P
-biphenylyl group, pentafluorophenyl group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 4-methoxyphenyl group, 4-1-butylphenyl group, 4t-octylphenyl group, 4-carboxyphenyl group, 4-methyl Sulfonamidophenyl group, 4-(4-hydroxyphenylsulfonyl)pheny)Lt&, 2-n-tetradecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 2-chloro-5-n-dodecyloxyphenyl group , 3-n""C-ntadecylphenyl group, 2-chloro7xyl group, 4-methoxycarbonylphenyl group,
4-methylsulfonylphenyl i, 2,4-di also includes one pentylphenyl group, etc.

Specific examples of the heterocyclic group include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-furyl group, 2-thienyl group, 3-thienyl i, 4-+noryl group, 2-imidazolyl group, -Pene imidazolyl group, 4-pyrazolyl group, 2
-Benzoxacylyl group, 2-benzothiazolyl group, ■
-imidazolyl group, 1-pyrazolyl group, 5-tetrazolyl group, 1.3.4-thiadiazol-2-yl group, 2-
Prolyl group, 3-triazolyl group, 4-oxasilyl group, 4-thiazolyl group, 2-pyrimidyl group, 2-pyrimidyl group, 1,3.5-triazin-2-yl group, 1.3.
4-oxadiazol-2-yl group, 5-pyrazolyl group, 4-pyrimidyl group, 2-biradyl group, succinimide group, phthalimide group, morpholino group, pyrrolidino group, piperidino group, imidazolidine-2,4-diocy3 -yl group, imidazolidine-2,4-dione-1-yl group,
Examples include oxazolidine-2,4-di-one-3-yl group.

Next, individual substituents in general formula (1) will be described in detail.

In general formula (1), R1 is a halogen atom, an aliphatic group,
represents an aromatic group, a heterocyclic group, an amidino group, a group represented by guani, where R4 and Rs each independently represent an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a carbon Heterocyclic group having 1 to 30 atoms, O to 3 carbon atoms
0 amino group [e.g. amino group, methylamino group, dimethylamino group, n-butylamino group, anilino group, N-
(2-n-tetradecyloxyphenyl)amino group, pyrrolidino group, morpholino group, piperidino group, 2-ethylhexylamino group, n-dodecylamino group, N-methyl-N-dodecylamino group, 3-dodecyloxypropyl amino group, 3-(2,4-di-t-pentylphenoxy)pro-ruamino group, 4-(2,4-di-t-pentylphenoxy)butylamino group, etc.], carbon atoms 1 to 30
aliphatic oxy group [e.g., methoxy group, ethoxy group, butoxy group, methoxyethoxy group, n-dodecyloxy group, 3-(2゜4-di-t-pentylphenoxy)propoxy group, etc.] or a carbon atom number of 6 to 30 aromatic oxy groups [e.g. phenoxy group, 4-n-dodecyloxyphenoxy group, 4-methoxycarbonylphenoxy group, etc.]. In the case of a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When L is an amidino group or a guanidino group, the total number of carbon atoms is 1 to 30, an aliphatic group, an aromatic group, a hydroxy group, an aliphatic oxy group, an acyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, It may be substituted with an acyloxy group, an aliphatic sulfonyloxy group, or an aromatic sulfonyloxy group, or two nitrogen atoms may be bonded to each other to form a heterocycle such as imidazole or benzimidazole.

- In formula (1), Rt is a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), hydroxy group, carboxy group, sulfo group, cyano group, nitro group, amino group having 0 to 30 carbon atoms (e.g. (amino group, methylamino group, dimethylamino group, pyrrolidino group, anilino group, etc.), aliphatic group having 1 to 30 carbon atoms, 6 to 30 carbon atoms
30 aromatic groups, carbonamide groups having 1 to 30 carbon atoms (e.g. formamide group, acetamide group, trifluoroacetamide group, benzamide group, etc.), sulfonamide groups having 1 to 30 carbon atoms (e.g. methylsulfonamide group) , trifluoromethylsulfonamide group, n-butylsulfonamide group, p-tolylsulfonamide group, etc.), carbamoyl group having 1 to 30 carbon atoms (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, N-methylcarbamoyl group), group, pyrrolidinocarbonyl group, N-n
-hexadecylcarbamoyl group, etc.), number of carbon atoms: O to 3
0 sulfamoyl group (e.g. sulfamoyl group, N-
methylsulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, N-n-dodecylsulfamoyl group, etc.), ureido group having 1 to 30 carbon atoms (for example, ureido group, 3-methylureido group, 3-phenylureido group, 3,3-dimethylureido group, etc.), acyl group having 1 to 30 carbon atoms (e.g. acetyl group, pivaloyl group, benzoyl group, dodecanoyl group, etc.), acyl group having 1 to 30 carbon atoms Acyloxy group (e.g. acetoxy group,
benzoyloxy group, etc.), aliphatic oxy group having 1 to 30 carbon atoms, aromatic oxy group having 6 to 30 carbon atoms, aliphatic thio group having 1 to 30 carbon atoms, aromatic group having 6 to 30 carbon atoms thio group, aliphatic sulfonyl group having 1 to 30 carbon atoms, aromatic sulfonyl group having 6 to 30 carbon atoms, aliphatic sulfinyl group having 1 to 30 carbon atoms, 6 to 30 carbon atoms
30 aromatic sulfinyl group, aliphatic oxycarbonyl group having 2 to 30 carbon atoms, aliphatic oxycarbonyl group having 7 to 30 carbon atoms, aliphatic oxycarbonylamino group having 2 to 30 carbon atoms, number of carbon atoms Aromatic oxycarbonylamino group having 7 to 30 carbon atoms, sulfamoylamino group having 0 to 30 carbon atoms (e.g. sulfamoylamino group, 3
．． 3-dimethylsulfamoylamino group, piperidinosulfonylamino group, etc.), a heterocyclic group having 1 to 30 carbon atoms, or an imide group having 4 to 30 carbon atoms (for example, succinimide group, maleimide group, phthalimide group, diglycolimide group, 4-nitrophthalimide group, etc.).

-a In formula (I), R1 represents a hydrogen atom or 1140, where R is a hydrogen atom and has a carbon number of 1 to 30
an aliphatic group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms, -OR7, SR? -1SO□R
1, -5OzORt or an imide group having 4 to 30 carbon atoms (e.g. succinimide group, maleimide group,
phthalimide group, diacetylamino group, etc.), and t
J represents >N-Rq, -CO-1-3Ot-5-SO-, or a single bond, R1 is an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a carbon atom represents a heterocyclic group having 1 to 30 carbon atoms, R1 represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 1 to 30 carbon atoms; , R9
and R3° are each independently a hydrogen atom, a carbon atom number of 1 to
30 aliphatic groups, aromatic groups having 6 to 30 carbon atoms, heterocyclic groups having 1 to 30 carbon atoms, acyl groups having 1 to 30 carbon atoms (e.g. acetyl group, trifluoroacetyl group, benzoyl group, p-chlorobenzoyl group, etc.) or a sulfonyl group having 1 to 30 carbon atoms (e.g., methylsulfonyl group, n-butylsulfonyl group, phenylsulfonyl group,
p-nitrophenylsulfonyl group, etc.), Rq
Ton,.

may be bonded to each other to form a ring.

- In formula (1), T represents a hydrogen atom or a group capable of being separated by a coupling reaction with the oxidizing property of the aromatic primary amine developer. Here, examples of the latter include halogen atoms (fluorine atom, chlorine atom, bromine atom, and iodine atom), sulfo group, thiocyanato group, isothiocyanato group,
Selenocyanato group, aliphatic oxy group having 1 to 30 carbon atoms, aromatic oxy group having 6 to 30 carbon atoms, aliphatic thio group having 1 to 30 carbon atoms, aromatic thio group having 6 to 30 carbon atoms , a heterocyclic thio group having 1 to 30 carbon atoms, a heterocyclic oxy group having 1 to 30 carbon atoms, an aromatic azo group having 6 to 30 carbon atoms, a heterocarbon group having 1 to 30 carbon atoms, a carbon atom Acyloxy group having 1 to 30 carbon atoms (e.g. acetoxy group, benzoyloxy group, etc.), sulfonyloxy group having 1 to 30 carbon atoms (for example, methylsulfonyloxy group, p-)
lylsulfonyloxy group, etc.), a carbamoyloxy group having 1 to 30 carbon atoms (e.g., N,N-dimethylcarbamoyloxy group, pyrrolidinocarbonyloxy group, N-ethylcarbamoyloxy group, etc.), and a carbamoyloxy group having 2 to 30 carbon atoms. There are thiocarbonyloxy groups (eg, methylthiocarbonyloxy group, phenylthiocarbonyloxy group, etc.) and carbonyldioxy groups having 2 to 30 carbon atoms (eg, methoxycarbonyloxy group, phenoxycarbonyloxy group, etc.).

- In formula [I], R2 and R1, R1 and T, or a plurality of Rt may be bonded to each other to form a ring. An example of a bond between R2 and R1 is -GHz(:0--
OCO-1-NHCO-1-C(CHs)xCO--C
There are H=CHC0-, etc. Examples of R1 and T bonding include -CH, C-5-C00, etc. As an example of multiple h combining = (CHz)x-1(CHz)n-1-OCO
-1-0CONH--NIICONI! -1-(CH-
CH) t.

-OCH! 0-5-0CHzCHgO0-5-0CHz
CH! There are O-, etc.

Next, preferred 1 in the compound represented by the general formula (N)
Examples of substituents are described below.

-a formula (in N, R3 is a halogen atom, -COR.

or -SO□R4 is preferred, and R1 is more preferably an amino group. Examples of -COR4 include carbamoyl 5, N-ethylcarbamoyl group, N-n-butylcarbamoyl group, N-cyclohexylcarbamoyl group,
N-(2-ethylhexyl)carbamoyl group, N-dodecylcarbamoyl L N-hexadecylcarbamoyl group, N-(3-decyloxypropyl)carbamoyl group,
N-(3-dodecyloxypropyl)carbamoyl group,
N ~ [3-(2,4-di-pentylphenoxy)propyl]carbamoyl group, N-(4-(2,4-di-pentylphenoxy)butylcarbamoyl group, N, N
-dimethylcarbamoyl group, N,N-dibutylcarbamoyl L N-methyl-N-dodecylcarbamoyl group, morpholinocarbabonyl group, N-methyl-N-phenylcarbamoyl, l,N-(2-tetradecyloxyphenyl)carbamoyl L N-phenylcarbamoyl i,N
-(4-tetradecyloxyphenyl)carbamoyl group, N-(2-propoxyphenyl)carbamoyl group, N
-(2-chloro-5-dodecyloxyphenyl)carbamoyl 7J, N-(2-chlorophenyl)carbamoyl group, etc. Examples of -3O□R4 include sulfamoyl group, N-methylsulfamoyl group, N.

N-diethylsulfamoyl group, N,N-diisopropylsulfamoyl group, N-(3-dodecyloxypropyl)carbamoyl group, N-(3(2,4-di-L-pentylphenoxy)propyl)carbamoyl group , N-(4
-(2,4-di-L-pentylphenoxy)butyl]carbamoyl group, pyrrolidinosulfonyl group, N-phenylsulfonyl group, N-(2-butoxyphenyl)carbamoyl group, N-(2-tetradecyloxyphenyl)carbamoyl group There are bases etc. -COR4 (R4
is preferably an amino group).

In the one-claw formula (1), (Rt)i' is preferably l'
=0, then 2'-1. When l'-1, R
t is a halogen atom, an aliphatic group, an aliphatic oxy group,
A carbonamide group, a sulfonamide group, a cyano group, etc. are preferable, and among them, a fluorine atom, a chlorine atom, a trifluoromethyl group, a methoxy group, or a cyano group are particularly preferable. R
The substitution position of 2 is preferably the 2nd or 4th position with respect to R and N H-.

- In R1 of formula (T), R6 is preferably an aliphatic group, an aromatic group, -0R1 or -5R, and U is preferably -CO- or -3(h-. Examples include methyl group, trifluoromethyl group, trichloromethyl group, ethyl group, heptafluoropropyl group, t-
Butyl group, l-ethylpentyl group, cyclohexyl group,
benzyl group, undecyl group, tridecyl group, 1-(2,
Examples of aromatic groups include phenyl group, 1-naphthyl group, 2-di-t-pentylphenoxy)propyl group, etc.
- Naphthyl group, 2-chlorophenyl group, 4-methoxyphenyl group, 4-nitrophenyl group, pentafluorophenyl group, etc. Examples of -OR7 are methoxy group, ethoxy group, isopropoxy group, n-butoxy group, isobutoxy group. group, L-butoxy group, n-pentyloxy group, n-
hexyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-decyloxy group, n-dodecyloxy group, 2-methoxyethoxy group, benzyloxy group, trichloroethoxy group, trifluoroethoxy group, phenoxy group, P-methylphenoxy group etc., -5R
Examples of , methylthio group, ethylthio group, allylthio group, n-butylthio group, benzylthio group, n-dodecylthio group, phenylthio group, pt-octylphenylthio group, p-dodecylphenylthio group, P-octyloxy There are phenylthio groups, etc. R1 is more preferably an aliphatic oxycarbonyl group (R4 is RtO- and U is -C
0-) and an aliphatic or aromatic sulfonyl group (R& is an aliphatic or aromatic group and U is -3O2-), and particularly preferably an aliphatic oxycarbonyl group.

-1%i In formula (13), T is preferably a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, or a heterocyclic thio group. Examples of aliphatic oxyne groups include methoxy group, ethoxy group, 2-hydroxyethoxy group, 2-chloroethoxy group, carboxymethoxy group, 1-carboxyethoxy group, methoxyethoxy group,
2-(2-hydroxyethoxy)ethoxy group, 2-methylsulfonylethoxy group, 2-methylsulfonyloxyethoxy group, 2-methylsulfonamidoethyl group, 2-
Carboxyethoxy group, 3-carboxypropoxy group,
2-(carboxymethylthio)ethoxy group, 2-(1
-carboxytridecylthio)ethoxy group, ■-carboxytridecyl group, N-(2-methoxyethyl)carbamoylmethoxy group, 1-imidazolylmethoxy group, 5-
Examples of aromatic oxy groups include phenoxycarbonylbenzotriazol-1-ylmethoxy group, 4-nitrophenoxy group, 4-acetamidophenoxy group, 2-acetamidophenoxy group, etc.
-acetamidophenoxy group, 4-methylsulfonylphenoquine group, 4-(3-carboxypropanamido)phenoxy group, etc. Examples of aliphatic thio groups include methylthio group, 2-hydroxyethylthio group, carboxymethylthio group , 2-carboxyethylthio group, l-carboxyethylthio group, 3-carboxypropylthio group, 2
-dimethylaminoethylthio group, benzylthio group, n-dodecylthio group, l-carboxytridecylthio group, etc. Examples of heterocyclic thio groups include 1-phenyl-1,2,
3,4-tetrazol-5-ylthio group, 1-ethyl-
1,2,3,4-tetrazol-5-ylthio group, I-
(4-hydroxyphenyl) -1,2゜3.4-tetrazol-5-ylthio group, 4-phenyl-1,2,4
-1-lyazol-3-ylthio group, 5-methyl-1,
3,4-oxadiazol-2-ylthio group, 1-(2
-carboxyethyl) -1,2゜3.4-tetrazol-5-ylthio group, 5-methylthio-1,3,4-thiadiazol-2-ylthio group, 5-methyl-1,3,
4-thiadiazol-2-ylthio group, 5-phenyl-
1,3,4-oxadiazol-2-ylthio group, 5-
Amino-1,3,4-thiadiazol-2-ylthio group, benzoxazol-2-ylthio group, 1-methylbenzimidazol-2-ylthio group, 1-(2-dimethylaminophenyl) -1,2,3, 4-tetrazol-5-ylthio group, benzothiazol-2-ylthio group, 5-(ethoxycarbonylmethylthio)-1°3.4
-thiadiazol-2-ylthio group, 1,2.4-triazol-3-ylthio group, 4-pyridylthio group, 2-
There are pyrimidylthio groups, etc. T is more preferably a hydrogen atom, a chlorine atom, an aliphatic oxy group or an aliphatic thio group, particularly preferably a hydrogen atom or an aliphatic oxy group.

Further, the latent image storage stability improvement effect of the present invention is greatly preferred when T is a group other than a hydrogen atom.

The effect is particularly great when T is a chlorine atom or an aliphatic oxy group.

The coupler represented by general formula (1) has substituents R+, R1
, R1 or T may form a dimer or a multimer of more than two molecules bonded to each other via a divalent or divalent or higher valent group, respectively. In this case, the carbon number range shown in each substituent above may be outside the regulations.

When the coupler represented by the general formula (13) forms a multimer, a typical example is a single or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue. In the case, the multimer contains repeating units of the following general formula (If) and has the general formula (I
The cyan coloring repeating unit denoted by t) is 1 in the multimer.
The copolymer may contain one or more types of non-color-forming ethylene birch monomers as a copolymerization component.

General formula [1] In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, G represents -CONH-1-C00- or a substituted or unsubstituted phenylene group, and J represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, L is -CONH-1-NHCONH
-1-NflCOO-1-NHCO-1-0COIIH
-, -N)l-1-COO-5-OCO-1-CO-1
-〇-1-5Ot-5-8830! -or-5ozs
*a, b', representing o-. ' indicates O or 1, Q is a general formula [! ] represents a cyan coupler residue obtained by removing hydrogen atoms other than the hydrogen atom of the 1-position hydroxyl group.

As the multimer, a copolymer of a cyan color-forming monomer that provides a coupler unit of general formula (If) and a non-color-forming ethylene-like monomer described below is preferred.

Examples of non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-
Butylacrylamide, diacetone acrylamide, N
-methylolacrylamide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide, N-(3
-sulfonate propyl) acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, acetoacetoxyethyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate , n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β
-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, potassium styrene sulfinate) , vinylacetophenone and sulphostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and -4-vinylpyridine and the like.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more of the non-color-forming ethylene-like monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene. , butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide and acrylic acid, potassium styrenesulfinate and N-vinylpyrrolidone, etc. can be used.

As is well known in the field of polymer couplers, the binding margin (If)
The ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to It can be selected so that its compatibility with gelatin, its flexibility, thermal stability, etc. are favorably influenced.

In order to obtain a lipophilic polymer coupler soluble in organic solvents, a lipophilic non-chromogenic ethylene-like monomer (for example, acrylic acid ester, methacrylic acid ester, maleic ester novinylbenzene, etc.) should be selected as the copolymerization component. is preferred.

A lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the above-mentioned formula (n) is dissolved in an organic solvent and then emulsified and dispersed in the form of latex in an aqueous gelatin solution. Alternatively, it may be produced by direct emulsion polymerization.

A method of emulsifying and dispersing an oil-based polymer coupler in an aqueous gelatin solution in the form of latex is described in U.S. Patent Nos. 3 and 4.
No. 51,820, and U.S. Pat.
The methods described in No. 080,211 and No. 3,370.952 can be used.

In addition, in order to obtain a hydrophilic polymer coupler soluble in neutral or alkaline water, N-(1,1-dimethyl-
Hydrophilic compounds such as 2-sulfonate ethyl)acrylamide, 3-sulfonate propyl acrylate, sodium styrene sulfonate, potassium 2-styrene sulfinate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylpyridine, etc. It is preferred to use a non-color-forming ethylene-like monomer as a copolymerization component.

The wood-philic polymer coupler can be added to the coating solution as an aqueous solution, and can also be added to water-miscible organic solvents such as lower alcohols, tetrahydrofuran, acetone, ethyl acetate, leclohexane, ethyl lactate, dimethylformamide, and dimethylacetamide. It can also be added by dissolving it in a mixed solvent with. Furthermore, an aqueous alkali solution or an alkali solution dissolved in an organic solvent may be added, or a small amount of a surfactant may be added.

Specific examples of the coupler represented by the general formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

C1 C,)l, t)CON H (A-4) (＾-9) (A-11) (8-5) CF sS O□Ni1 CH, OCo NH 0 (CHz) ss (ill C+ zHzso O
H (A Cz tls QCON H CM 3S (h NH CIl 3s Ox NH QCL CM to H (A-20) (A-21) (A-22) (A-23) (A-24) (A-29) (A-27) (^-28) (A-32) (A-33) (A-34) acos (A-37) (A-38) (A-43) (A-45) (A-46 ) (A-39) (A-40) (A-41) (A-42) H (A-50) (^-51) (A-57) (A-59) (^-53) (A- 54) CI, coc ON H (A-Li4) (A-65) (A-73) (A-75) Cb II+ a(n) (A~69) (A-70) H (A~71 ) Examples of the coupler represented by the general formula (1) other than the above used in the present invention are disclosed in JP-A-60-237448 and JP-A-60-237448;
-153640, 61-145557, patent application No. 6
It is described in the specification of No. 242090. In addition to the above patent specifications, the synthesis of these couplers is also described in the patent application filed in 1986-
No. 259752, No. 60-259753 and No. 61-
This can be carried out by the method described in No. 205344.

The amount of the high boiling point organic solvent used in the present invention is at most 0.3 g per 1 g of the coupler represented by the general formula CI) of the present invention, and if the amount of the high boiling point organic solvent used is more than this, the sharpness will deteriorate. becomes a problem.

The amount used is preferably 0.15g per gram of coupler.
.

More preferably 0605g, still more preferably 0.0
It is 1 g or less, and may be Og. Within the applicable range of the present invention (high-boiling organic solvent/coupler ratio at most 0.3), the amount of cyan coupler represented by general formula (1) added is usually 1.
OXl0-'mol/rrf to 3. The range is from OXl0-3 mol/M to 1.5 Xl0-' mol/M.

In the present invention, the stagnation time from mixing the cyan coupler-containing dispersion and the color-sensitized silver halide emulsion until coating is 20 minutes or less, preferably 10 minutes or less, more preferably 3 minutes or less.

The temperature at which the liquid stagnates before mixing is 30 to 70°C, more preferably 35 to 65°C. The temperature after mixing and before coating is preferably 35 to 50°C. Furthermore, it is preferable that the two liquids to be mixed have a volume ratio of 10 to 200 centivoise (cp) and a mixing ratio of 0.1 to 10 by volume.

As a device for mixing immediately before coating, there are known stirring devices, such as impeller-type devices with stirring blades attached to a small-capacity tank, and stirring devices for high viscosity liquids such as kneaders and dispersers. Although a static mixer can also be used, an in-line mixing device is preferred, and a static mixer is particularly preferred among in-line mixers. Published by General Chemical Research Institute (published in 1973), rTu by J. B. GRAY
rbulentRadial Mixir+g in
Published by PipesJAcademic Press'MI
Those described in XING vol. 3J (published in 1986) can be preferably used. A multi-stage mixing element inserted into a transfer pipe can be preferably used, and the shape of the element is not limited.

In addition to the cyan coupler described above, various color couplers can be used in combination with the photosensitive material of the present invention, and specific examples thereof include Research Disclosure (R1)) k17643.
, ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4.3
No. 26,024, No. 4,401,752, Special Publication No. 5
B-10739, British Patent No. 1.425.020,
1.476.760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, European Patent No. 4.351,897, European Patent No. 73.636, U.S. Patent No. 3,061,432, European Patent No. 3.725.067, Research Disclosure No. 24220 (June 1984) month), JP-A-60-33
No. 552, Research Disclosure Sou 24230
(June 1984), JP 60-43659, U.S. Patent No. 4.500.630, U.S. Patent No. 4.540.654
Particularly preferred are those described in No.

As the cyan coupler, the cyan coupler shown in the above-mentioned binding margin [1] of the present invention can be used in combination with other cyan couplers. In that case, U.S. Patent No. 4.05
2.212, 4,146.396, 4,228
．． No. 233, No. 4,296,200, No. 2,369,
No. 929, No. 2,801.171, No. 2.772.1
No. 62, No. 2,895.826, No. 3,772,00
No. 2, No. 3,758.308, No. 4,334.011
No. 4,327.173, West German Patent Publication No. 3.32
9.729, European Patent No. 121,365A, U.S. Patent No. 3,446,622, European Patent No. 4,333,999,
Cyan couplers described in 4,451,559 and 4,427,767 are preferred.

Colored couplers to correct unnecessary absorption of coloring dyes are subject to Research Disclosure Disclosure No. 17643.
- Section G, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.248, British Patent No. 1.146,3
The one described in No. 68 is preferred.

Couplers having a diffusion tank with an appropriate coloring dye include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, European Patent No. 96,570 and German Patent Publication No. 3.234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
4.367.282, British Patent No. 2.102.17
It is stated in No. 3, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
4, No. 57-154234, No. 60484248, and U.S. Pat. No. 4.248.962 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097,140;
Those described in JP-A No. 2,131.188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, etc.;
, 338,393, 4,310,618, etc., DIR redox compound releasing couplers described in JP-A-60485950, etc., European Patent No. 17
Examples include couplers that release a dye that recovers color after separation, as described in No. 3.3024.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high-boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. I can do it.

- Phosphate ester 1 as an example of a high boiling point organic solvent used in conjunction with the coupler represented by Tsuzuriyo (1)! (triphenyl phosphate, tricresyl phosphate, octyldiphenyl phosphate, tri-2-ethylhexyl phosphate, tri-n-hexyl phosphate, tri-1so-nonyl phosphate, tricyclohexyl phosphate, tributoxyethyl phosphate, tri-2-chloroethyl phosphate, etc.), benzoic acid esters (2-ethylhexyl benzoate, 2-ethylhexyl 2,4-dichlorobenzoate, etc.), fatty acid esters (di-2-ethylhexyl succinate, 2-tetradecanoate, etc.)
-hexyldecyl, tributyl citrate, etc.), amides [
(N,N-diethyldodecanamide, N-tetradecylpyrrolidone, etc.), dialkylaniline I! (2-butoxy-5tart-octyl-N, N-dibutylaniline, etc.), chlorinated paraffins (chlorine content 10% to 80%
% barafurans), phenol! ! (2,5-Gt
ert-aminophenol, 2,5-tert-
hexyl-4-methoxyphenol, 2-ethylhexyl P-hydroxybenzoate, etc.) phthalate ester IN (
(dibutyl phthalate, dicyclohexyl phthalate, didodecyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), but phosphoric acid esters and phthalic acid esters are particularly preferred.

The dispersion containing the cyan coupler has the formula (1) as the coupler.
) may contain only the cyan coupler represented by cyan dye, or may contain other cyan couplers or couplers that develop a hue other than cyan in this dispersion. It includes all couplers that form, including not only 4-equivalent cyan couplers, but also 2-equivalent couplers with normal leaving groups, DIR couplers, bleach accelerator-releasing couplers, and other couplers that release photographically useful fragments. .

The dispersion may also contain additives other than couplers, such as ultraviolet absorbers, hydroquinones, antifading agents, antifoggants, and the like.

A dispersion containing the cyan coupler of the present invention can be prepared by a known dispersion method.

Although various hydrophilic polymers can be used as the dispersion medium used for preparing the coupler emulsion dispersion used for mixing immediately before coating in the present invention, it is preferable to use gelatin. Further, the calcium content in the gelatin used for preparing the coupler emulsion dispersion of the present invention is preferably 3000 pp- or less, particularly preferably 1000 pp- or less.

In the present invention, an oil-in-water dispersion method is preferred, and in the case of oil-in-water dispersion, the cyan coupler of formula (C-1) is used at a boiling point of about 170.
A high boiling point solvent of ℃ or higher, and if necessary a boiling point of 30℃ or higher,
Preferably, it is dissolved using a low boiling point solvent of 50°C or more and about 140°C or less and/or a water-miscible organic solvent, and a surfactant is used in a hydrophilic colloid such as an aqueous gelatin solution using a stirrer, a colloid mill, or a high pressure. It can be obtained by emulsifying and dispersing it using a homogenizer, a flow jet mixer, an ultrasonic emulsifier, or the like.

In addition, in the above-mentioned oil-in-water droplet dispersion, it can also be obtained by a method that does not use a high boiling point solvent, that is, a solid dispersion method.

In the above-mentioned oil-in-water type dispersion, water in an amount not more than 10 times the amount (weight) of the cyan coupler is added to the oil phase in which the cyan coupler is dissolved to form a water-in-oil type dispersion in advance. A method is also used in which a dispersion is dispersed in a hydrophilic colloid such as an aqueous gelatin solution to finally obtain an oil-in-water type dispersion.

Organic solvents with low boiling points that are virtually unnecessary for water include ethyl acetate, propyl acetate, butyl acetate, butanol, carbon tetrachloride, diethyl ketone, methyl ethyl ketone, n-butyl carpitol acetate, methylene chloride, methyl propionate, and propionic acid. Examples include ethyl, cyclohexanone, tetrachloroethane, trichloroethane, cyclohexane, benzene, toluene, nitromethane, and chloroform. Furthermore, water-miscible organic solvents include methanol, ethanol, isopropyl alcohol, dimethyl sulfoxide, tetrahydrofuran, N-methyl-2
-pyrrolidone, dioxane, dimethylformamide, dimethoxyethane, formamide, ethylene glycol,
Acetonitrile, acetone, butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diacetone alcohol and tetrahydrothiophene-1,
There is 1-dioxide.

The low boiling point organic solvent and water-miscible organic solvent used here can be removed by a known method after emulsification.

Furthermore, the following dispersion method can be used as a known dispersion method other than the oil-in-water type dispersion described above.

(2) A method of incorporating the cyan coupler of the present invention and other couplers and additives as a hydrophilic colloid layer-filled polymer latex composition.

Examples of the polymer latex include polyurethane polymers, polymers polymerized from vinyl monomers [suitable vinyl monomers include acrylic esters (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate,
dodecyl acrylate, glycidyl acrylate, etc.),
α-substituted acrylic ester (methyl methacrylate,
butyl methacrylate, octyl methacrylate, glycidyl methacrylate, etc.), acrylamide (butylacrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl ester (vinyl acetate, vinyl butyrate, etc.), vinyl halides , (vinyl chloride, etc.),
Vinylidene halides (vinylidene chloride, etc.), vinyl ethers (vinyl methyl ether, vinyl octyl ether, etc.), styrene, X-substituted styrene (α-methylstyrene, etc.), nuclear-substituted styrene (hydroxystyrene, chlorostyrene, methylstyrene, etc.), Ethylene, propylene, butylene, butadiene, acrylonitrile, etc. can be mentioned. These may be used alone or in combination of two or more, or may be mixed with other vinyl monomers as a negative component. Examples of other vinyl monomers include itaconic acid, acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyl Examples include alkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfonic acid and the like. ] etc. can be used.

These filled polymer latexes are
No. 53, JP-A No. 51-59943, JP-A No. 53-1371
No. 31, No. 54-32552, No. 54-107941
No. 55-133465, No. 56-19043,
No. 56-19047, No. 56-126830, No. 5
It can be produced according to the method described in No. B-149038.

Here, the ratio of coupler to polymer latex used is preferably 40 to 1/10 (weight ratio).

■ A method of dissolving cyan coupler using a surfactant.

Useful surfactants may be oligomers or polymers.

■ A method of using a wood-philic polymer instead of or in combination with a high-boiling point solvent for dispersing oil droplets in water.

This method is described, for example, in U.S. Pat. No. 3,619.19.
No. 5, West German Patent No. 1,957.467.

In the oil-in-water type and other dispersion methods described above,
As the surfactant as a dispersion aid, it is preferable to use various anionic, nonionic, cationic, or amphoteric surfactants. It is also a preferable method to use a polymer or oligomer type surfactant.

In the present invention, a dispersion containing a cyan coupler (liquid A) and a color-sensitized silver halide emulsion (liquid B) are prepared separately,
Other couplers and other photographic additives can be included in the Bi as well as in the A'fL mentioned above.

Moreover, a part of the cyan coupler of the present invention can also be contained in the above B liquid. In this case, cyan coupler A liquid is included! /B liquid content preferably ranges from 1010 to 3/7, particularly preferably from 1010 to 515.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular restrictions on the number or order of the layers and non-photosensitive layers.A typical example is to deposit multiple silver halide emulsions with substantially the same color sensitivity but different photosensitivity on a support. A silver halide photographic light-sensitive material having a small number of light-sensitive layers (one light-sensitive layer, the light-sensitive layer being a unit light-sensitive layer sensitive to any one of blue light, green light, and red light). In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. Depending on the purpose, the above-mentioned order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1.121,470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the halogen emulsion in a keyaki pattern in which the photosensitivity gradually decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer N (RL),
Or DH/BL/GL/GH/RH/RL, or BH/BL/Gll/GL/l? They can be installed in the order of L/R)I, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-ray photosensitive layer/GH/R
H/GL/l? They can also be arranged in the order of L. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, blue sensitivity 1? They can also be arranged in the order of i/GL/RL/G)I/R11.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion 1,
Alternatively, they may be arranged in the following order: low-speed emulsion layer/medium-speed emulsion N/high-speed emulsion layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (IID) NIX1764
3 (December 1978), pp. 22-23, “1. Emulsion production.
and typeaa)'', and the same FJIX1871
6 (November 1979), 648 pages, graphic "Physics and Chemistry of Photography", published by Paul Montell (P.

Glafkides, Che＋＊ic et Ph1
siqus Photographique+Paul
Montel+ 1967), "Photographic Emulsion Chemistry" by Duffin.

Published by Focal Press, CG, F, Duffin,
Photograp-hic Emulsion Ch
emistry (Focal Press+ 196
6)), Zelikman et al., “Production and Coating of Photographic Emulsions J,” published by Focal Press (V., L., Zelilvan).
et al, + MakjBand Coating
Photographic emulsion,
Focal Press, 1964).

U.S. Patent No. 3,574.628, U.S. Patent No. 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413.748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and [! ngineering), 1st
4 @ pages 248-257 (1970); US Patent No. 4
．． 434.226, 4,414.310, 4,
433.048, 4,439.520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are Research Disclosure N11
It is described in I7643 and NcL18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Chemical sensitizer page 23 Page 648 right column 2 Sensitivity increasing agent
Same as above 4 Brightener Pigment Image stabilizer Hardener Binder Plasticizer, lubricant Page 24 Page 25 Page 26 Page 26 Page 27 Page 651 Left column Same as above Page 650 Right column Also prevents deterioration of photographic performance due to formaldehyde gas. Therefore, U.S. Patent No. 4,411,987 and U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

The color photosensitive material of the present invention includes Japanese Patent Application Laid-Open No. 6325774
No. 7, No. 62-272248, and JP-A-1-80
1,2-benzisothiazoline-3- described in No. 941
on, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2
- It is preferable to add various preservatives or antifungal agents such as phenoxyethanol and 2-(4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of NQ17643 and N11187
16, from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 20 μm or less, and the film swelling The speed T,/2 is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate TI/□ can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr, Sci, Eng,) + 19 by A. Green et al.
It can be measured by using a swellometer (swelling membrane) of the type described in 'L2 No.
8, the saturated film thickness is 90% of the maximum swelling film thickness reached when treated with a color developer at 30°C for 3 minutes and 15 seconds, and this Tr/
It is defined as the time required to reach the film thickness of s.

The film*m speed T1/M can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling l!lS thickness - film thickness)/film thickness. .

The color photographic material according to the present invention is described in the above-mentioned RD, Ishi 17643, pages 28-29, and Ishi t4a 18716.
615, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and sulfates thereof, Examples include hydrochloride and p-)luenesulfonate. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred.

Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pi buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or anticapri agents such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazide triethanolamine, and catechol sulfonic acids, ethylene glycol, and diethylene glycol may be used. breeding solvents such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as l-7enyl-3-pyrazolidone, viscosity-imparting agents, Various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid,
Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N.

N,N-)rimethylenephosphonic acid, ethylenediamine-
Representative examples include N,N,N,N-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. In this black and white developer, known black and white developing crude drugs such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as -phenyl-3-pyrazolidone, or aminophenols such as N-methyl-P-aminophenol may be used alone or Can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 31 per square meter of the light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0°001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.Also, the amount of replenishment can be reduced by using means to suppress the accumulation of bromide ions in the developer. .

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion bath is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (II), acid salts, quinones, and nitro compounds. Typical bleaching agents include organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (ffl) II salts, including ethylenediaminetetraacetic acid iron (厘) l salt and 1,3-diaminopropane tetraacetic acid iron (III) complex salt, are used from the viewpoint of rapid processing and environmental pollution prevention. These iron(III) aminopolycarboxylate complexes are particularly useful both in bleaching solutions and in bleach-fixing solutions.
The pli of bleach or bleach-fix solutions using complex salts is usually between 4°O and 8, but lower pH values may be used to speed up processing.
It can also be processed with

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290.812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53441623,
Compounds having a mercapto group or disulfide group described in JP-A No. 53-28426 and Research Disclosure Nil 17129 (July 1978); Thiazolidine derivatives described in JP-A-50-140129; Japanese Patent Publication No. 45-8506 , JP 52-20832, JP 53-32735, U.S. Patent No. 3,706,56
1,000 urea derivatives described in No. 1; West German Patent No. 1.127,
No. 71.5, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748.4
Polyoxyethylene compounds described in No. 30;
Polyamine compound described in No. 5-8836; other JP-A No. 49-42.434, No. 49-59,644, No. 5
No. 3-94.927, No. 4 No. 54-35.727, No. 5
Compounds described in No. 5-26.506 and No. 58-163,940; bromides, ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat. No. 3,893.
, 858, West German Patent No. 1,290,812, and JP-A-53-95,630 are preferred, and the compounds described in U.S. Pat. No. 4,552,834 are also preferred. Accelerators may be added to the photosensitive material.
(2) These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for shadows.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pka) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering step is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring be as strong as possible.A specific method for strengthening the stirring is the treatment on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461. A method of colliding liquid jets, a method of increasing the stirring effect using a rotating means as disclosed in JP-A-62483461, and a method of moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to increase the emulsion Examples include a method of improving the stirring effect by making the surface turbulent, and a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

The silver halide color photographic light-sensitive material of the present invention includes a desilvering treatment,
After treatment, -In typically undergoes a water washing and/or stabilization process. The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set to . this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
OurnaI of the 5ociety of
Motion Picture and Te1evi
sion F! ngineers Volume 64, P, 24
8-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288, 838 can be used very effectively. Also, JP-A-57-8, 54
Chlorinated disinfectants such as isothiazolone compounds and cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in No. 2, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technology Society, ``Sterilization, sterilization, and anti-mold technology of microorganisms,'' (1982) Japan Society of Industrial Technology, ed. ``Encyclopedia of anti-bacterial and anti-mold agents'' (1)
It is also possible to use the fungicides described in 1986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, Nos. 58 to 14834, and No. 6G-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Examples of the dye stabilizer that can be used include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

In a process using an automatic processor or the like, when each of the above-mentioned processing liquids undergoes i) condensation due to evaporation, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14.850
Ship base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, and U.S. Patent No. 3
．． Metal salt complex described in No. 719.492, JP-A-53-i
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1=phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64339, JP-A-57-144547,
and 5B-115438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Usually, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

In addition, West German Patent No. 2,226,7 was developed to save silver on photosensitive materials.
70 or U.S. Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 Material 101, which is a multilayer color light-sensitive material, was prepared by forming layers having the compositions shown below on a cellulose triacetate film support provided with an undercoat layer.

(Composition of the photosensitive layer) The coating amount is expressed in grams of silver/billion units for silver halides and colloidal silver, and g/-snow units for couplers, additives, and gelatin, and the amount expressed in grams of silver/units for couplers, additives, and gelatin, and the amount of sensitizing dyes expressed in g/-snow units. The number of moles is expressed per mole of silver halide in the same layer. The symbols shown below have the following meanings.

5olH high boiling point organic solvent CpM i magenta coupler UV, ultraviolet absorber CpC, cyan coupler.

CI) Y; Yellow coupler No. 17m (Haley silane prevention layer) Black colloidal silver gelatin t+v-t 1V-2 Additive-1 ol-2 2nd layer (intermediate layer) Gelatin additive-2 3rd layer (first red feeling Emulsion layer) Gelatin sensitizing dye-1 Sensitizing dye-2°0.2 1.5 0.05 0.2 2.5 0.07 0.12 4.5X10-'Mole 1.5X10-' Sensitizing dye -3 Sensitizing dye-4 CpC-1 CpC-2 CpC-5 ol-1 ol-2 4th layer (second red-sensitive emulsion layer) 0.4X10-'0.3X10-' 0.35 0.01 0 .05 0.2 0.1 Gelatin sensitizing dye-1 Sensitizing dye-2 Sensitizing dye-3 Sensitizing dye-4 CpC-3 CpC-4 ol-1 ol-2 XIO-'XIO"'Xl0-' Xl01 0.08 0.35 0.3 0.21 5th layer (third red-sensitive emulsion layer) Gelatin sensitizing dye-1 Sensitizing dye-2 Sensitizing dye-3 CpC-1 CpC-6 ol-1 ol- 2 6th layer (intermediate layer) Gelatin additive-3 7th layer (first green-sensitive emulsion layer) 0.6 0.2 Gelatin sensitizing dye-5 1,6 XIO-' Xl01 xto-' 0.06 0 .09 0.15 0.08 0.15 0.78 xto''' Sensitizing dye-6 Sensitizing dye-7 pM-1 PM-2 pY-2 ol-1 No. 811! (Second green emulsion eyebrow) 2 Xl0-' I Xl0-' 0.23 0.09 0.03 0.26 Gelatin sensitizing dye ~5 Sensitizing dye-6 Sensitizing dye-7 pM-1 pM-3 pY-2 ol-1 9th layer (intermediate layer) 10th gelatin layer (3rd green-sensitive emulsion layer) 0.53 3.5 Xl0-' 1.4 Xl0-' 0.7 Xl0-' 0.12 0 .04 0,01 o,it 0.4 pY-2 0,04 ol-1 0,25 Gelatin 0.85 Sensitizing dye-
82X10-' CpY-10,2 Sol-10,1 14th layer (3rd blue-sensitive emulsion layer) Gelatin sensitizing dye-8 pY-1 So+-1 15th layer (1st protective layer) Gelatin V-1 V-2 0゜85 1.5XIO-' 0.25 0, 13 1.8 0.1 0.2 Gelatin sensitizing dye-5 Sensitizing dye-6 Sensitizing dye-7 pM-L pM-4 ol- 1 11th layer (yellow filter layer) Yellow colloidal silver gelatin additive-3 ol-1 12th layer (1st blue-sensitive emulsion layer) 1.47 2 X 10-'0.8X10-' o, 5xio-' 0 .02 0.1 0.3 0.05 0.5 0.15 0.06 Gelatin sensitizing dye-8 pY-1 1,2 3Xl0-' 0.7 ol-1 ol-2 16th layer (2nd Protective layer) 0.01 Gelatin polymethyl methacrylate particles 1 Additive-1 C-HsO5Ose Additive-2 CpC,,2 ph-2 Cp gate, :3 I 0■ Shi! ρC-3 QCII□CIl zs ox C1l.

pc-s CpC-6 0 ■ pM-4 pY-2 1 liter Sensitizing dye-4 C1h: CtlSOzCIIzCONH-CHxCH,
・CHSOzCflzCONH-CI□Increasing dye-1 Sensitizing dye-5 Sensitizing dye-2 Sensitizing dye-6 Sensitizing dye-3 Sensitizing dye-7 (Cth)s 30 sN II (Ct Is)s
Sensitizing dye-8 ol-2 at-3 (C6H130 Y-P・0 By changing the coupler and organic solvent binder in the 3rd to 5th layers of sample 101, we prepared a sample lot as shown in Table 1. 1
11 was produced. The coating solution for the fourth layer is prepared by preparing an emulsified dispersion of the coupler by an oil-in-ice dispersion method, and then mixing it with a rogenated emulsion (used for the fourth layer). The retention times listed in Table 1 indicate the elapsed time from mixing the emulsified dispersion of the coupler and the silver halide emulsion to coating.

Further, the temperature of the coating liquid during stagnation was maintained at 40°C.

These samples were subjected to imagewise exposure for sensitometry using white light and subjected to the following color development process (38°C). This process was referred to as development process A, and the density of the processed sample was measured using a red filter.

Further, the film was exposed through a pattern similar to MTF measurement, and the same color development process was performed to calculate the MTF value at 1 s@25 cycles.

Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing
2 minutes 10 fixed arrival '4 minutes 2
Wash with water for 0 seconds Stable for 3 minutes and 15 seconds
1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer 1.0g1.1-
Diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Monomethylaniline sulfate 2.0g 4.0g 30, og 1.4g 1.3mg 4.5g Add water and bleach solution Thorium salt Ammonium bromide Ammonium nitrate Add water Fixer 1.0! pH10.0 150.0g 10.0g 1, Oj! PH6,0 Sodium sulfite 4.0g Sodium bisulfite water added 4.6g 1.08 pH6,6 Stabilizing liquid formalin (40χ) 2.0 d Added water 1.02 Furthermore, these samples are being developed Development processing (B) was carried out in the same manner as normal development processing except that the bleaching solution was changed to the following processing solution formulation.

This bleaching solution is a schematic reproduction of the state in which a large amount of photosensitive material has been processed and has become fatigued.

At the exposure amount that resulted in a cyan density of 1.5 in the development process (A), the cyan density was measured in the development process (B), and the ratio was expressed as Dc (B)%.

Bleach solution composition (Development processing B) (D-1) Ammonium bromide ammonia water (28χ) Add glacial acetic acid water (D-2) 160.0 g 7.1-00 m Add water 11 (D-2) ), put steel wool in it, seal it tightly, and leave it for Fe (I
After converting [)-EDTA into Fe(I-EDTA), this 100 at was added to (D-1), and the coating failure frequency was evaluated based on the number of comments caused by microscopic insoluble matter in the coupler. For comments, please refer to B and M.

B. M. Deryagin et al., “
Theory of film coating (Filis Coating T
theory) J, p. 183 (The Focal Press, 1964).The number of comments refers to the number of comments per 1000 tt m" when the surface of the photosensitive material is observed under a microscope. The number of comments mentioned above is practical when the number of comments is about 10 comments/dm or less.Also, latent image storage stability can be evaluated by color development after imagewise exposure for sensitometry. Treatment A was performed immediately after exposure (within 30') and the sensitivity was compared with that performed after storage at 45°C and 80% RH for 3 days after the original exposure. After exposure with the same amount of light, development processing A was performed, and the processed sample was darkened with a red filter and the difference in color density was measured.For samples 104 to 111, the dependence of the spectral absorption of the color dye on the color density was investigated. Table 2 shows the results of 0 or more, comparing the maximum absorption wavelength at each color density.

The following can be seen from these results.

In a normal coating time (1 hour), as the weight ratio of the high-boiling organic solvent to the coupler is reduced, sharpness improves, but coating failures increase, and latent image stability significantly decreases (102. 104°106). On the other hand, when the application time is shortened (10 minutes) and the above weight ratio is 6.4, there is almost no change in each value (102.103), but surprisingly, the weight ratio is 0
In the case of 626 (106, 107), it can be seen that coating failures are further reduced and the latent image stability is also improved. Furthermore, a cyan image can be obtained in which sufficient color density is maintained, the spectral absorption of the color image does not depend on the color density, and it is stable even when developed using a tired bleach or bleach-fix solution. I found out that it can be done.

Example 2 Samples 202 and 203 were made in exactly the same manner as Sample 107 in Example 1, except that the calcium content of gelatin, which was the binder in the fourth layer, was changed. The same exposure and development treatment (A) as in Example 1 was performed, and the frequency of coating failures was evaluated by the number of comets as in Example 1. The results are shown in Table 3.

From the above results, it was found that coating failures can be further improved by reducing the calcium content of gelatin, which is a binder.

(Effects of the Invention) According to the present invention, it is possible to obtain a silver halide color photographic light-sensitive material that has excellent sharpness, fewer coating failures during production, and further improved latent image storage stability. Furthermore, it is possible to obtain a silver halide color photographic light-sensitive material that provides a high color density and a color image in which the spectral absorption of the color image hardly changes with the color density.

Procedural amendment July 1999

Claims (2)

[Claims] (1) A dispersion containing a cyan coupler represented by the following formula [I], in which the weight ratio of a high-boiling organic solvent coexisting with the cyan coupler to the cyan coupler is 0.3 or less, and a color-sensitized silver halide emulsion. 1. A silver halide color photographic light-sensitive material, characterized in that it has at least one silver halide emulsion layer on a support, which is obtained by mixing the above ingredients and then coating the mixture without stagnation for more than 20 minutes. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], R_1 is a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amidino group, a guanidino group, or -COR_4, -SO_2R_4 , -SOR_4
, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, -NHCOR_
4, -NHSO_2R_4, -NHSOR_4, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Represents the group represented by,
R_2 is a halogen atom, hydroxyl group, carboxyl group, sulfo group, amino group, cyano group, nitro group, aliphatic group, aromatic group, carbonamide group, sulfonamide group,
Carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic oxycarbonyl group , represents an aromatic oxycarbonyl group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a sulfamoylamino group, a heterocyclic group, or an imide group, l' represents an integer from 0 to 3, and R_3 is hydrogen. atom or R_6U, and T represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. However, R_4 and R
_5 each independently represents an aliphatic group, an aromatic group, a heterocyclic group,
Represents an amino group, an aliphatic oxy group, or an aromatic oxy group, R_6 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -OR_7, -SR_7, -COR_5, ▲Math.
There are chemical formulas, tables, etc. ▼, -PO(R_7)_2, -
PO(-OR_7)_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CO_
2R_7, -SO_2R_7, -SO_2OR_7, SO_2OR
_7 or imide group, U represents ▲numerical formula, chemical formula, table, etc.▼, -CO-, -SO_2-, -SO- or a single bond. Here, R_7 represents an aliphatic group, aromatic group or heterocyclic group, R_8 represents a hydrogen atom, aliphatic group, aromatic group or heterocyclic group, R_9 and R_
1_0 each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group, or an aromatic sulfonyl group. When l' is plural, R_2 may be the same or different, or may be combined with each other to form a ring, R_
2 and R_3 or R_3 and T may be combined with each other to form a ring, or R_1, R_2, R
Either _3 or T may form a dimer or multimer (oligomer or polymer) that is bonded to each other via a divalent or more than divalent group. (2) A dispersion containing a cyan coupler represented by formula [I] according to claim (1) and having a weight ratio of a high boiling point organic solvent coexisting with the cyan coupler to the cyan coupler of 0.3 or less; The solution mixed with the sensitive silver halide emulsion in a static mixer is not allowed to stagnate for more than 20 minutes.
A method for producing a silver halide color photographic light-sensitive material, which comprises coating at least one silver halide emulsion layer on a support.