JPS63281157A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sharpness of the titled material by using a specified polymer coupler for the titled material, and by incorporating a nonphotosensitive silver halide emulsion or a silver halide emulsion with its inner side or the surface of a particle fogged in a protective layer. CONSTITUTION:The polymer coupler contg. at least one kind of a repeating unit shown by formula I is incorporated in at least one layer of photosensitive silver halide emulsion layers. And, at least one layer of an auxiliary layer is mounted on the place at more far distance from a supporting body than said emulsion layer which is positioned at the most far distance from the supporting body. At least one layer of the auxiliary layer contains the substantially nonphotosensitive silver halide emulsion, or the silver halide emulsion with its inner part or the surface of the particle fogged, and at least one layer of the auxiliary layer contains a colloidal silver. Thus, the sharpness of the titled material without injuring the film strength and the processing stability, is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic material with improved sharpness without compromising film strength or processing stability.

(Prior Art) Generally, the image sharpness of a photographic light-sensitive material decreases as the thickness of the silver halide emulsion layer increases, especially due to light scattering of silver halide emulsion grains. In particular, in multilayer color photographic materials having red-sensitive, green-sensitive, and front window emulsion layers, light scattering accumulates due to the multilayer structure, and the sharpness of the lower emulsion layer is significantly reduced. Become.

Therefore, in the art, image sharpness has been improved by reducing the film thickness, using silver halide grains with less light scattering, and developing effects such as edge effects.

By the way, in multilayer color fluorescent materials, it is necessary to fix each coupler in a separate layer in order to reduce color mixture and improve color reproduction.There are many ways to make couplers diffusion resistant. Are known.

One method is to introduce a long chain aliphatic group into the coupler molecule to prevent diffusion.

Since the coupler produced by this method is immiscible with an aqueous gelatin solution, it is necessary to solubilize it in an alkali and add it to the aqueous gelatin solution, or to dissolve it in a high boiling point organic solvent and emulsify and disperse it in the aqueous gelatin solution.

Such color couplers may cause crystal precipitation in emulsions or have high boiling points. ! When a solvent is used, a large amount of gelatin is required to soften the emulsion layer, which is contrary to the desire to thin the emulsion layer to improve sharpness.

Another method of making couplers diffusion resistant is the use of polymeric coupler latexes obtained by polymerizing monomeric couplers.

Conventional methods for adding polymer couplers to hydrophilic colloid compositions in the form of latex include adding latex made by emulsion polymerization directly to gelatin silver halide emulsions, and adding lipophilic couplers to hydrophilic colloid compositions by polymerizing monomeric couplers. It is known to disperse polymer couplers in latex form in aqueous gelatin solutions. An example of the former emulsion polymerization method is the emulsion polymerization method in aqueous gelatin described in U.S. Patent No. 3,370,952.
No. 4,080.21 describes the emulsion polymerization method in water.
It is stated in No. 1. An example of the method of dispersing the latter in the form of a lipophilic polymer coupler latex is given in U.S. Pat.
No. 1,820.

The method of adding polymer couplers to hydrophilic colloid compositions in latex form has many advantages over other methods.

First, because the hydrophobic material is made into latex, the strength of the formed film does not deteriorate.Also, latex can contain a high concentration of monomeric coupler, so it is easy to emulse a high concentration of coupler. can be contained, and the increase in viscosity is small.

Furthermore, it has the advantage that there is no color mixing due to its completely non-migration property, and that there is little precipitation of the coupler in the emulsion film.

When this polymer coupler is used, it does not deteriorate the strength of the membrane, so it does not require a large amount of gelatin to strengthen the membrane, unlike when a low molecular weight coupler is used.

Therefore, by using a polymer coupler, the emulsion layer's
1iJN becomes possible.

However, when a polymer coupler is added in the form of a latex to a photosensitive silver halide emulsion layer, the sharpness can be improved without impairing the film strength or the stability of the emulsified dispersion. In particular, fluctuations in photographic performance due to fluctuations in iodide ion concentration are greater than when a low molecular weight coupler is mixed with a high boiling point organic solvent.

Incidentally, silver halide color photographic light-sensitive materials are processed in automatic processing machines installed at each processing laboratory, but compositional changes in the processing solution may occur between each processing laboratory or even within the same processing laboratory. Another problem is that photographic characteristics change due to fluctuations in conditions, making it impossible to obtain stable photographic performance. These changes in the composition of the processing solution and fluctuations in conditions are caused by the elution and elution of photographically active substances from the light-sensitive material during the development process.
This is thought to be due to accumulation or other causes. Therefore,
In order to respond to variations in processing conditions, it is required to precisely control the development time, the temperature and pH 1 of the developer, and the halogen ion concentration in the developer. however,
Compared to the development time or the temperature and pH of the developer, the halogen ion concentration in the developer is difficult to quantify and therefore difficult to control. In particular, the large dependence of photographic performance on halide ion concentration is a fatal flaw for silver halide color photographic light-sensitive materials, and reducing this is an important factor in producing silver halide color photographic light-sensitive materials. This is essential, and as described above, there has been a strong desire for a technique for improving sharpness by thinning the emulsion film without impairing film strength or processing stability.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide color photographic material with improved sharpness without impairing film strength or processing stability.

(Means for Solving the Problems) An object of the present invention is to form one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support. A color photographic light-sensitive material comprising a polymer coupler containing at least one repeating unit represented by the general formula CI) in at least one light-sensitive silver halide emulsion layer, and the most distant from the support. A substantially non-photosensitive silver halide emulsion or This was achieved by a silver halide color photographic light-sensitive material containing a silver halide emulsion fogged inside or on the surface of the grains, and containing colloidal silver in at least one of the auxiliary layers.

As a result of the research conducted by the present inventors, it has been found that large fluctuations in photographic performance due to fluctuations in the iodide ion concentration in the processing solution due to the use of polymer couplers are caused by the fact that the light-sensitive silver halide emulsion layer located farthest from the support is This is significantly improved by containing a substantially non-photosensitive silver halide emulsion or a silver halide emulsion fogged inside or on the surface of the grains in at least one layer of auxiliary N (hereinafter referred to as UiN) in a distant position. Ta. However, if the protective layer contains a silver halide emulsion that is substantially non-photosensitive or a silver halide emulsion that is covered inside or on the surface of the grains, the film will be fixed when developed using a hanging automatic processor, etc. Uneven development occurred due to poor liquid drainage caused by the falling ring of developer from a clip or the like.

In order to overcome this drawback, the present inventors conducted further research and found that this development unevenness can be significantly improved by further containing colloidal silver in at least one of the at least one protective layer. I discovered that.

Even when colloidal silver was included in the protective layer, fluctuations in photographic performance due to fluctuations in iodide ion concentration in the processing solution did not worsen.

By the way, looking at the conventional technology for using fine-grain silver halide emulsions in the protective layer, it is found that the protective layer contains fine-grain silver halide emulsions to prevent the release of iodide ions and ready-to-develop preparations and to improve processing solution contamination. For example, French patent 912. '605, U.S. Patent 3,892,57
2. Disclosed in U.S. Patent 3°961.963, etc.
Also, a patent, U.S. Pat. No. 3,737.31, is characterized in that a deposited layer containing colloidal silver is provided as a separate layer to prevent the elution of the fine grain halogenated emulsion in the protective layer into the processing solution.
No. 7 has been disclosed, but there is no example in which variations in photographic properties due to variations in the concentration of halide ions, particularly iodide ions, in the processing solution are improved, and there is no example in which a polymer coupler is used in the photosensitive silver halide emulsion layer of the present invention. There is no example of improving the fluctuations in photographic performance and uneven development due to fluctuations in the iodide ion concentration in the processing solution.

Next, the polymer coupler used in the present invention will be explained.

General formula (1) In the formula, R represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and D is -COO-1-CONR'
-1 or a substituted or unsubstituted phenyl group,
E represents a substituted or unsubstituted alkylene group, phenylene group, or aralkylene group, and F is 100NR'-5
-NR'C0NR'-1-NR' COO-1-NR
'C0-1-OCONR'-2-NR'-2-COO
-1-〇C0-1-CO-1-〇-1-S-1-3O□
-1-NR' 5O2-1 or 18○, NR'- Rl represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. When there are two or more R's in the same molecule, They may be the same or different.

Substituents in D, E and R' include alkyl groups (
For example, methyl group, ethyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, etc.), aryloxy group (
For example, phenyloxy group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, etc.), acylamino group (for example, acetylamino group), carbamoyl group, alkylcarbamoyl group (for example, methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl group (
(e.g. dimethylcarbamoyl group), arylcarbamoyl group (e.g. phenylcarbamoyl group), alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), alkylsulfonamide group (e.g. methanesulfonamide group), arylsulfone Amide group (e.g. phenylsulfonamide group), sulfamoyl group, alkylsulfamoyl group (e.g. ethylsulfamoyl group), dialkylsulfamoyl group (e.g. dimethylsulfamoyl group), alkylthio group (e.g. methylthio group, arylthio group) (for example, a phenylthio group), a cyano group, a nitro group, and a halogen atom (for example, fluorine, chlorine, bromine, etc.), and when there are two or more of these substituents, they may be the same or different.

i! ,m,ni! Q, which represents O or 1, represents a cyan, magenta, yellow dye-forming coupler residue capable of coupling with the oxidized form of an aromatic-grade amine developer to form a dye.

Among the color coupler residues represented by Q, cyan-forming coupler residues include phenolic type (n) (I[
[), or a naphthol type (IV) (V) compound (in which the 1-position OH group and the hydrogen atom other than the coupling site are separated and connected to F in the general formula (1)) are preferred.

In the formula, R1+ represents a group that can be substituted on the phenol ring or naphthol ring, and examples thereof include a halogen atom, a hydroxy group, an amino group, a sulfo group, a cyano group, an aliphatic group, an aromatic group, a heterocyclic group, a carbonamide group, sulfonamide group,
Carbamoyl group, sulfamoyl group, acyloxy group,
Examples include acyl group, aliphatic oxy group, aliphatic thio group, aliphatic sulfonyl group, aromatic oxy group, aromatic thio group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, etc. The number of carbon atoms in RI + is 0 to 3
It is 0.

Rlz is -CONRI3R1', -NHCOR", -N
HCOORI5. -NH3O□RI51-NHCONR
”represents RI4 or -NH3O□RI3R14, R
13 and R14 are hydrogen atoms, aliphatic groups having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, butyl group, methoxyethyl group, n-decyl group/n-dodecyl group, n-hexadecyl group, trifluoromethyl group) group, heptafluoropropyl group, dodecyloxypropyl group, 2,4-diter
t-amylphenoxyprobyl group, 2,4-tar
t-amylphenoxybutyl group, etc.), aromatic groups having 6 to 30 carbon atoms (e.g., phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group,
RIS is Aliphatic groups having 1 to 30 carbon atoms (e.g. methyl group, ethyl group, butyl group, dodecyl group, hexadecyl group, etc.), aromatic groups having 6 to 30 carbon atoms (e.g. phenyl group, tolyl group, 4-chlorophenyl group, naphthyl group) R13 and R" represent a heterocyclic group (e.g., 4-pyridyl group, quinolyl group, 2-furyl group, etc.); ), p' is O~3, q' is O
~2, r', and S' each represent an integer from 0 to 4.

X represents an oxygen atom, a sulfur atom or RI4N,
R1'' represents a hydrogen atom or a monovalent group.

When R1- represents a monovalent group, examples of RI6 include aliphatic groups having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, butyl group, methoxyethyl group, benzyl group, etc.), and 6 carbon atoms.
~30 aromatic groups (e.g., phenyl group, tov)I/group, etc.), heterocyclic groups having 2 to 30 carbon atoms (e.g., 2-pyridyl group, 2-pyrimidyl group, etc.), 1 to 30 carbon atoms carbonamide groups (e.g. formamide group, acetamide group, N-methylacetamide group, benzamide group, etc.), sulfonamide groups having 1 to 30 carbon atoms (e.g. methanesulfonamide group, toluenesulfonamide group, 4-chlorobenzenesulfone amide group, etc.), imide group having 4 to 30 carbon atoms (e.g., succinimide group, etc.) -o RI 7, S
RI? , -COR", -CONrll"RIS, -CO
COR", -COCONR"R", -C○○R", -C
OCOOR+', So, Rlq, -5otOR",
-5O2N Rl ff Rl m and N RI 'l
Mention may be made of Rl6. Here RIS and R
11 may be the same or different, and each represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (methyl group, ethyl group, butyl group, dodecyl group, methoxyethyl group, trifluoromethyl group, heptafluoro propyl group, etc.), aromatic groups having 6 to 3 carbon atoms (e.g. phenyl group, tolyl group,
4-ri o.

phenyl group, pentafluorophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group, etc.) or a heterocyclic group having 2 to 30 carbon atoms (e.g. 4-pyridyl group, 3-pyridyl group, 2-furyl group). R1ff and R1 may be bonded to each other to form a heterocycle (eg, morpholino group, pyrrolidino group, etc.).

Examples of RI9 include the substituents shown in R17 and RIS excluding hydrogen atoms.

Zl represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Examples of groups that can be separated include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, atoms, etc.), carbon number 1~
30 aliphatic oxy groups (e.g., methoxy group, ethoxy group, 2-hydroxyethoxy group, carboxymethyloxy group, 3-carboxyprooxy group, 2-methoxyethoxycarbamoylmethyloxy group, 2-methanesulfonylethoxy group, 2-carboxymethylthioethoxy group, triazolylmethyloxy group, etc.), carbon number 6-30
aromatic oxy groups (e.g. phenoxy group, 4-hydroxyphenoxy group, 2-acetamidophenoxy i, 2
．． 4-dibenzenesulfonamide phenoxy group, 4-phenylazophenoxy group), C2-C30 heterocyclic oxy group (e.g. 4-pyridyloxy group, 1-phenyl-5-tetrazolyloxy group) etc.), aliphatic thio group having 1 to 30 carbon atoms (e.g., dodecylthio group, etc.), 6 carbon atoms
~30 aromatic thio groups (e.g., 4-dodecylphenylthio group, etc.), heterocyclic thio groups having 2 to 30 carbon atoms (e.g., 4-dodecylphenylthio group, etc.),
-pyridylthio group, l-phenyltetrazol-5-ylthio group, etc.), acyloxy group having 2 to 30 carbon atoms (e.g. acetoxy group, benzoyloxy group, lauroyloxy group, etc.), carbonamide group having 1 to 30 carbon atoms (e.g. , dichloroacetylamide group, trifluoroacetamide group, heptafluorobutanamide group, pentafluorobenzamide group, etc.), sulfonamide group having 1 to 3 carbon atoms (e.g., methanesulfonamide group, toluenesulfonamide group, etc.), carbon number 6 to 30 aromatic azo groups (e.g., phenylazo group, 4-chlorophenylazo group, 4-
methoxyphenylazo group, 4-pivaloylaminophenylazo group, etc.), carbon number 1. ~30 aliphatic oxycarbonyloxy groups (e.g., ethoxycarbonyloxy groups,
dodecyloxycarbonyloxy group), carbon number 6-3
0 aromatic oxycarbonyloxy group (e.g. phenoxycarbonyloxy group, etc.), carbamoyloxy group having 1 to 30 carbon atoms (e.g. methylcarbamoyloxy group, dodecylcarbamoyloxy group, phenylcarbamoyloxy group, etc.), carbon number 1 to 30 and which has a nitrogen atom connected to the active position of the coupler (for example, a succinimide group, a phthalimide group, a hydantoinyl group, a pyrazolyl group, a 2-benzotriazolyl group, etc.).

Y represents an atomic group necessary to form a 5-, 6-, or 7-membered ring together with the carbon atom to which it is bonded, and represents R' O R'R'R' R- alone or in combination, R'', R1 each represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkyloxy group, an alkyloxycarbonyl group, an arylcarbonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, or a cyano group.

Next, examples of substituents preferably used in the present invention are listed below.

Preferred examples of R1+ include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), aliphatic groups (e.g., methyl, ethyl, isopropyl, etc.), carbonamide groups (e.g., acetamide, benzamide, etc.),
Sulfonamide group (e.g. methanesulfonamide group,
toluenesulfonamide group, etc.).

Preferred R12 is 100NRI3R'', examples include carbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, decyloxypropyl group, dodecyloxypropyl group, 2.4 -Di-tert-amylphenoxypropyl group, 2,4-di-tert-amylphenoxybutyl group, and the like.

Preferred as X is RlbNg, and further R
Preferred examples of I4 are -COR" (for example, formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl group, p-chlorobenzoyl group, etc.), -COOR" (
For example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, dodecyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.), -5on R'! (For example, methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexadecanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, p-chlorobenzenesulfonyl group, etc.) , -〇〇NR"R" (N,N-dimethylcarbamoyl group , N,N-diethylcarbamoyl L N,N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbamoyl group, 3,4-dichlorophenylcarbamoyl group, 4-methanesulfonylphenylcarbamoyl group, etc.) , -S O
x N R"R" (e.g., N, N-dimethylsulfamoyl group, N, N-diethylsulfamoyl group, N,
Of 114, which is a group represented by N-dipropylsulfamoyl group, etc.), -COR
These are groups represented by ", -COOR" and -8O□R1".

Preferred groups as Zl are hydrogen atom, halogen atom,
They are an aliphatic oxy group, an aromatic oxy group, a heterocyclic thio group, and an aromatic azo group.

Couplers represented by general formulas [11], [nll, [IV], [V] have substituents R1, RI2, X or Zl.
It may be a multimer of 231 or more molecules bonded to each other via a divalent or more polyvalent linking group. In this case, the number of carbon atoms shown in each of the above-mentioned substituents is not limited to this.

As the magenta color forming coupler residue, the general formula % formula % [
] (Xnl and the coupler residue represented by [Xnl (A
Any part of r 1Z'' and R'''-R3'' represents the general formula [linked to F in 11].

Ar General formula [■] Otsu + H General formula [■] General formula [IX] General formula [X] General formula rxr general formula [XII] Otsu + h In the formula, Ar represents a 2-pyrazolin-5-one coupler. Substituents of known types in position 1, such as alkyl groups, substituted alkyl groups (e.g. haloalkyl such as fluoroalkyl,
cyanoalkyl, benzylalkyl, etc.), aryl group or substituted 7-aryl group C Substituents include alkyl groups (e.g. methyl group, ethyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, etc.), aryloxy groups (e.g. phenyl group, etc.). sulfur group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, etc.), acylamino group (e.g., acetylamino group), carbamoyl group, alkylcarbamoyl group (e.g., methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl group (
(e.g. dimethylcarbamoyl group), arylcarbamoyl group (e.g. phenylcarbamoyl group), alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), alkylsulfonamide group (e.g. methanesulfonamide group), arylsulfone Amide groups (e.g. ethylsulfonamide), sulfamoyl groups, alkylsulfamoyl groups (e.g. ethylsulfamoyl), butylkylsulfamoyl groups (e.g. dimethylsulfamoyl), alkylthio groups (e.g. methylthio, arylthio) (eg, phenylthio group), cyano group, nitro group, halogen atom (eg, fluorine, chlorine, bromine, etc.), and when there are two or more of these substituents, they may be the same or different.

Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group. represents a heterocyclic group (eg, triazole, thiazole, benzothiazole, furan, lysine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole, etc.).

Rte is unsubstituted or rLa anilino group, acylamino group (e.g. alkylcarbonamide group, phenylcarbonamide group, alkoxycarbonamide group, phenyloxycarbonamide group), ureido group (e.g. alkylureido group, phenylureido group), These substituents include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), linear or branched alkyl groups (e.g. methyl group, t-butyl group, octyl group, tetradecyl group, etc.), and alkoxy groups. (e.g. methoxy group, ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (e.g. acetamide group, benzamide group, butanamide group, octaneamide group, tetradecaneamide group, α-(2,- gtert
-amylphenoxy)acetamide group, α-2,4-di-tert-amylphenoxy)butyramide group, α-
(3-pentadecylphenoxy)hexaneamide group, α
-(4-hydroxy-3-tert-butylphenoxy)tetradecanamide group, 2-oxo-pyrrolidine-1
-yl group, 2-oxo-5-tetradecylpyrrolidine-
1-yl group, N-methyl-tetradecanamide group, etc.)
, sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, ethylsulfonamide group, p-toluenesulfonamide group, octane sulfonamide group, p-dodecylbenzenesulfonamide group, N-
methyl-tetradecanesulfonamide group, etc.) sulfamoyl group (e.g., sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N,N-
Dimethylsulfamoyl group, N, N-dimethylsulfamoyl group, N-hexadecylsulfamoyl group, N-[
3-(dodecyloxy)-propyl]sulfamoyl group, N-[4-(2,4-di-tart-amylphenoxy)butylcarbamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc.), carbamoyl group ( For example, N-methylcarbamoyl group, N-butylcarbamoyl group, N-octadecylcarbamoyl group, N-[4-(2,
(4-di-tert-amylphenoxy)butylcarbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc.), diacylamino group (N-succinimide group, N
-phthalimide group, 2,5-dioxo-1-oxazolidinyl group, 3-dodecyl-2,5-dioxo-1-hydantoinyl group, 3-(N-acetyl-N-dodecylamino)succinimide group, etc.) alkoxycarbamoyl group ( For example, methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxysulfonyl group (for example, methoxysulfonyl group, butoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), Oxysulfonyl group (e.g. phenoxysulfonyl group,
p-methylphenoxysulfonyl group, 2,4-dite
rt-amylphenoxysulfonyl group, etc.), alkanesulfonyl group (e.g., methanesulfonyl group, ethanesulfonyl group, octanesulfonyl group, 2-ethylhexylsulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl group (e.g., benzenesulfonyl group) ,
4-nonylbenzenesulfonyl group, etc.), alkylthio groups (e.g., methylthio group, ethylthio group, hexylthio group, benzylthio group, tetrabutylthio group, 2-(
2,4-di-tert-amylphenoxy)ethylthio group, etc.), arylthio group (e.g., phenylthio group,
p-tolylthio group, etc.), alkyloxycarbonylamino groups (e.g., methoxycarbonylamino group, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), alkylureido groups (e.g., N-methyl ureido group, N, N-dimethylureido group, N-methyl-N-dodecylureido group, N-hexadecylureido group, N,
N-diotadecylureido group, etc.), acyl group (e.g., acetyl group, benzoyl group, octadecanoyl group,
(p-dodecaneamide benzoyl group, etc.), a nitro group, a carboxyl group, a sulfo group, a hydroxy group, or a trichloromethyl group.

However, among the above substituents, those defined as alkyl groups have 1 to 36 carbon atoms, and those defined as aryl groups have 6 to 3 carbon atoms.

R1I, R12, RNko, R14, RXs,
Rth, R11, R211・R2゛・Rzo・R
3" and R"' each represent a hydrogen atom, a hydroxyl group, or an unsubstituted or substituted alkyl group (preferably one having 1 to 2 carbon atoms, for example, a methyl group, a propyl group, a t-butyl group, a tri-butyl group, fluoromethyl group, tridecyl group, etc.), aryl group (preferably one having 6 to 20 carbon atoms).

For example, phenyl group, 4-t-butylphenyl group, 2.
4-di-t-amylphenyl group, 4-methoxyphenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), alkylamino group (preferably has 1 to 20 carbon atoms. For example, methylamino group, diethylamino group, t-
butylamino group, etc.), acylamino group (preferably one with 2 to 20 carbon atoms, e.g., acetylamino group, propylamide group, benzamide group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, etc.), alkoxy Carbonyl group (preferably one with 2 to 20 carbon atoms)
For example, methoxycarbonyl group, butoxycarbonyl group, 2-ethylhexyloxycarbonyl group), alkylcarbonyl group (preferably one with 2 to 20 carbon atoms, e.g. acetyl group, butylcarbonyl group, cyclohexylcarbonyl group, etc.), arylcarbonyl group groups (e.g.
Preferably those having 7 to 20 carbon atoms, benzoyl group, 4-
t-butylbenzoyl group, etc.), alkylthio group (preferably one with 1 to 20 carbon atoms, such as methylthio group, octylthio group, 2-phenoxyethylthio group, etc.),
ruthio group (preferably one with 6 to 20 carbon atoms, for example,
phenylthio group, 2-butoxy-5-t-octylphenylthio group, etc.), carbamoyl group (preferably 1 carbon number)
~20 0 For example, N-ethylcarbamoyl L N
, N-dibutylcarbamoyl group, N-methyl-N-butylcarbamoyl group, etc.), sulfamoyl group (preferably one having up to 20 carbon atoms).

For example, N-ethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-dipropylsulfamoyl group, etc.) or sulfonamide group (preferably 1 carbon number
to 20 (e.g., methanesulfonamide group, benzenesulfonamide group, p-)luenesulfonamide group, etc.).

ZX represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Examples of groups that can be removed include a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an oxygen atom, Coupling-off groups to be linked (e.g. acetoxy, propanoyloxy, benzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxyl, 4-titanesulfone) Amidophenoxy group, α-naphthoxy group, 4-cyanoxyl group, 4-methanesulfonamide-phenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxy-ethoxy group, 5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), coupling-off groups linked via a nitrogen atom (other special Gansho 5
7-189538, specifically benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,
4,5.6-pentafluorobenzamide group, octane sulfonamide group, p-cyanophenylureido group, N
, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, 1-benzyl-5-ethoxy-3-hydantoinyl group, 2-oxo-1゜2-dihydro-1-
Pyridinyl group, imidazolyl group, pyrazolyl group, 3,5
-diethyl-1,2゜4-triazol-1-yl group,
5- or 6-bromobenzotriazol-l-yl group, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl group, etc.), coupling-off groups linked via a sulfur atom (e.g. Phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, benzylthio group, 2-cyanoethylthio group, 5-phenyl -2
, 3,4°5-tetrazolylthio group, 2-benzothiazolyl group, etc.). Preferably, the detachable group is a halogen atom, a phenoxy group, or a coupling-off group connected via a nitrogen atom, and particularly preferably a halogen atom, a phenoxy group, a pyrazolyl group, an imidazolyl group, or a triazolyl group.

Yellow color-forming coupler residues include those of the acylacetanilide type, especially of the pivaloylacetanilide type [XI
I[], benzoylacetanilide type [XIV], [X
V] is preferred.

[Xlff] 2k [XIV] In the formula, R1, Rco4, Rss and Rco are each a hydrogen atom or a well-known substituent of a yellow color-forming coupler residue, such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group , halogen, atom, alkoxycarbamoyl group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group,
Alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamido group, arylsulfamoyl group, arylsulfonamide group, arylsulfamoyl group, arylsulfamoyl group, carboxy group, sulfo group, nitro group, cyano group , thiocyano group, etc., and these substituents may be the same or different.

Z3 is a hydrogen atom or the following general formula [XVI], [X■],
Represented by [X■] or [X[X].

0R''[XVI]R3'l represents an optionally substituted aryl group or heterocyclic group.

Ro and R3″ each represent a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amine group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, or an unsubstituted or substituted phenyl group. represents a group or a heterocyclic group, and these groups may be the same or different.

■ Represents the nonmetallic atoms required to form .

-S formula [XIX] is preferably [XX
] to [XXII].

■ R'' In the formula, R4o% R'' is a hydrogen atom, an alkyl group, an alkyl group, an alkoxy group, an aryloxy group, or a hydroxy group. W2 represents an oxygen or sulfur atom;

The polymer coupler latex of the present invention may be a homopolymer of monomeric couplers of general formula (1), or may be a copolymer of monomeric couplers of general formula (1), or may be a copolymer of monomeric couplers of general formula (1). It may also be a copolymer of a monomeric coupler of formula (1) and a non-chromogenic ethylene-like monomer that does not couple with the oxidation product of an aromatic-grade amine developing agent. Two or more types of monomeric couplers included in general formula [I] may be used as the physical coupler.

Examples of non-color-forming ethylene-like monomers that do not couple with the oxidized product of aromatic-grade amine developers include acrylic esters, methacrylic esters, crotonic esters, vinylesternorimaleic acid esters, and fumaric acid esters. Examples include acid diesters, itaconic acid diesters, acrylamides, methacrylamides, vinyl ethers, and styrenes.

More specific examples of these monomers include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tart-butyl acrylate, hexyl acrylate, 2- Ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, 2-
Examples include (2-methoxyethoxy)ethyl acrylate. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate/tert-butyl methacrylate, cyclohexyl methacrylate, 2
-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, and the like. Examples of crotonate esters include butyl crotonate and hexyl crotonate. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, and the like. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like.

Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include diethyl itaconate, dimethyl itaconate, dibutyl itaconate, and the like. Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, dimethylacrylamide,
Examples include diethylacrylamide and phenylacrylamide. Methacrylamides include methylmethacrylamide, ethylmethacrylamide, n-butylmethacrylamide, tert-butylmethacrylamide, 2
-Methoxymethacrylamide, dimethylmethacrylamide, diethylmethacrylamide and the like. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene,
Examples include ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, vinylbenzoic acid methyl ester, 2-methylstyrene, and the like.

Examples of other monomers include allyl compounds (such as allyl acetate), vinyl ketones (such as methyl vinyl ketone), and vinyl heterocyclic compounds (such as vinyl pyridine).
, glycidyl esters (e.g. glycidyl acrylate, etc.), unsaturated nitriles (e.g. acrylonitrile, etc.), acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (e.g. monomethyl itaconate, etc.), monoalkyl maleate ( (e.g., monomethyl maleate, etc.), citraconic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid (e.g., acryloyloxymethylsulfonic acid, etc.), acrylamide alkylsulfonic acid (e.g., 2-acrylamide-2-
methylethanesulfonic acid, etc.). These acids may be salts of alkali metals (eg, Na, etc.) or ammonium ions.

Among these monomers, those monomers are preferably used because of their hydrophilicity, lipophilicity, copolymerizability of the monomers, color development of the produced polymer coupler, oil pKa', color tone of the produced dye, etc. Comonomers that can be used include acrylic esters, methacrylic esters, styrenes, maleic esters, acrylamides, and methacrylamides.

Two or more of these monomers may be used in combination.

Examples of combinations when using two or more types include n-
Examples include butyl acrylate and styrene, n-butyl acrylate and methyl acrylate, methacrylic acid and monobutyl acrylate, and the like.

The proportion of the color-forming portion corresponding to general formula (1) in the polymer coupler of the present invention is usually desirably 5 to 90% by weight, but from the viewpoint of color reproduction, color-forming property, and stability, it is preferably 30 to 80% by weight.
% by weight is preferred, in which case the molecule ff1 (grams of polymer containing 1 mole of monomeric coupler) is about 500
~4000, but is not limited to this.

The polymeric coupler latex of the present invention is based on coupler monomer and is applied to the silver halide emulsion layer at 0.00.
0.005 mol to 0.5 mol, preferably 0.01 mol to 0.00 mol.
It is best to add 1 mole.

The lipophilic polymer coupler used in the present invention can be polymerized by emulsion polymerization or solution polymerization. Regarding the emulsion polymerization method, see US Pat. No. 4.080.211, US Pat. No. 3.370.952, and! The method described in US Pat. No. 3,451,820 can be used to disperse the oil-based polymer coupler in the form of a latex in an aqueous gelatin solution.

These methods can also be applied to the formation of homopolymers and copolymers; in the latter case the comonomer may be a liquid comonomer, which in the case of emulsion polymerization normally also acts as a solvent for the immobilized monomer. .

Examples of emulsifiers used in the emulsion polymerization method include surfactants, polymeric protective colloids, and copolymer emulsifiers. Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants known in the art.

Examples of anionic activators include soaps, sodium dodecylbenzenesulfonate, sodium lauryl sulfate,
Examples include sodium dioctyl sulfosuccinate and sulfates of nonionic surfactants. Examples of nonionic activators include:
Examples include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxypropylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines. Examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Examples of the polymeric protective colloid include polyvinyl alcohol and hydroxyethyl cellulose. These protective colloids may be used alone as emulsifiers or in combination with other surfactants.For information on the types of these active agents and their effects, see Be1g1sche Chemis.
cheIndustrie, 28. 16-20
(1963).

In order to disperse a lipophilic polymer coupler synthesized by a solution polymerization method in an aqueous gelatin solution in the form of latex, first place the lipophilic polymer coupler in an organic solvent. After that, this is dispersed into a latex form in an aqueous gelatin solution using an ultrasonic wave, a colloid mill, etc. with the help of a dispersant. A method for dispersing lipophilic polymeric couplers in aqueous gelatin solution in the form of a latex is described in U.S. Pat.
No. 451.820. As the solvent for dissolving the lipophilic polymer coupler, esters such as methyl acetate, ethyl acetate, propyl acetate, alcohols, ketones, halogenated hydrocarbons, ethers, etc. can be used.

Moreover, these organic solvents can be used alone or in combination of two or more.

In producing the polymer coupler of the present invention, the solvent used in the polymerization is preferably one that is a good solvent for the monomer and the resulting polymer coupler, does not react with the polymerization initiator, and has a small chain transfer constant for radicals. Specifically, water, toluene, alcohol (e.g. Eva, methanol, ethanol, isopropanol, t-butanol, etc.), acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, dimethylformamide, dimethyl sulfoxide, acetonitrile,
Methylene chloride etc. can be mentioned, and these solvents are 2
You may use a mixture of more than one species.

The polymerization temperature needs to be determined taking into account the type of polymerization initiator and the type of solvent used, but it is usually 30 to 12
It is in the range of 0°C.

Examples of the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the cyan dye-forming polymer of the present invention include those shown below.

Examples of water-soluble polymerization initiators used in the emulsion polymerization method include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, sodium 4,4'-azobis-4-cyanovalerate, and 2°2'- Water-soluble ab compounds such as azobis(2-amidinopropane) hydrochloride and hydrogen peroxide can be used.

In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobutyronitrile, 2.2'-
Azobis-(2,4-dimethylvaleronitrile), 2.
2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2゜2'-azobisisobutyrate,
Lipophilic azo compounds such as 1.1'-azobis(cyclohexane-1-carbonitrile), 4.4'-azobis-4-cyanovaleric acid, benzoyl peroxide, lauryl peroxide, chlorobenzyl peroxide, diisopropyl peroxide Examples include lipophilic peroxides such as oxydicarbonate and di-t-butyl peroxide. Among these, benzoyl peroxide, chlorobenzyl peroxide, lauryl peroxide and the like are preferred.

In the emulsion polymerization method and the solution polymerization method, these polymerization initiators are used in a range of 0.01 to 10 weight percent, preferably 0.01 to 10 weight percent, based on the entire monomer. It can be contained in a range of 1 to 5% by weight.

Preferred examples of the polymer coupler used in the present invention will be shown next, but the invention is not limited thereto.

C-11 CH3 ShiE ShiE Hs CH3CHs I Ti CH3 ■ Hs ■ C-23 CH3 Hs CH.

Ma Shi CH! C, CH2CHh-! J7-Hs CH.

M-7 Shi CHICH, CH! CHhτ- CH.

1 CH2 CM.

M-15 M-16 Hs " -I H2 Y-5 Shihe I'I ko shi ni CH.

■ Y-1(1 In the above specific examples, the copolymerization ratio represents a weight ratio.

Typical synthesis examples of polymer couplers used in the present invention are shown below.

Synthesis Example 1 2-Hebutafluorobutanamide-5-methacrylamide Synthesis of copolymer coupler ('C-13) of phenol and butyl acrylate 3 2-Hebutafluorobutanamide-5-methacrylate was placed in a 300 ml three-tube flask. Amidophenol 18g 5-butyl acrylate 22g
and 160 g of dioxane were added, stirred under a nitrogen stream, and heated to 80°C. Dimethyl azobisisobutyrate 0.

A solution of 6 g dissolved in dioxane 1Qm1 was added to initiate polymerization.

After 5 hours, the polymerization solution was cooled to room temperature, added to 1.5 ml of water, and the precipitated solid was filtered off and washed thoroughly with water. By heating and drying this solid under reduced pressure, 37.9 g of polymer coupler C-13 was obtained.

Nitrogen analysis of this polymer coupler confirmed that the copolymer formed contained 45.2% of jtLfi coupler repeating units.

Synthesis Example 2 Synthesis of copolymer coupler (M-1) of l-(2,4-dichlorophenyl)-3-methacrylamide-5-pyrazolone and butyl acrylate 1-(2,4-dichlorophenyl)-3-methacrylamide A mixture of 22.5 g of -5-pyrazolone, 27.5 g of butyl acrylate, and 200 mJ of dimethylacetamide was stirred in a nitrogen stream for 8 hours.
After heating to 5°C, dimethyl azobisisobutyrate 0. 5
10 ml of dimethylacetamide containing g was added to initiate polymerization. After 4 hours, the reaction solution was cooled, poured into 1.5 ml of water, and the precipitated solid was filtered off and washed thoroughly with water. By pre-heat drying this solid under reduced pressure, the polymer coupler (M
-1) was obtained in an amount of 48.6 g.

This polymer coupler was determined by nitrogen analysis to confirm that the copolymer formed contained 46.1% monomeric coupler repeat units.

Synthesis Example 3 Synthesis of copolymer coupler (Y-1) of α-(4-methoxybenzoyl)-α-(1-pivalyl)-2-chloro-5-acryloylaminoacetanilide and 2-ethylhexyl acrylate 3i A 1.21 aqueous solution containing 1 g of eulermethyltauride in a flask was heated to 80°C while stirring and passing a nitrogen stream, and after adding 15 ml of a 2% aqueous solution of potassium persulfate to the aqueous solution, α-(4
-methoxybenzoyl)-α-(1-pivalyl)-2-
Chloro-5-acryloylaminoacetanilide 20g
A solution prepared by heating and dissolving 20 g of 2-ethylhexyl acrylate in 500 ml of ethanol was added dropwise over 20 minutes.

After reacting for 1 hour, add 5 m of 2% aqueous solution of potassium persulfate! added. After a further 1 hour, methanol and water were distilled off.

After cooling the formed latex, the latex solution was adjusted to pH 6.0 with one layer of sodium hydroxide.

The polymer concentration of the latex formed was 6.1%, and nitrogen analysis showed that the polymer contained 51.7% monomeric coupler repeat units.

The silver halide emulsion contained in the protective layer includes silver chloride,
Any of silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide may be used, but the content of silver iodide is preferably 3 mol% or less, and 2
．． Particularly preferred is 0 mol% or less.

The grain shape of the silver halide may be cubic, tetradecahedral, octahedral, spherical, or tabular, and may be monodisperse or polydisperse.
When the standard deviation S of the particle size distribution is divided by the average particle size r,
It is desirable that the value is 0.20 or less.

Non-photosensitive silver halide emulsions do not ripen after grain formation! Ii manufactured.

A silver halide emulsion whose grain surfaces or interiors are fogged refers to a silver halide emulsion that can be uniformly developed regardless of the unexposed or exposed areas of a photographic light-sensitive material.

The silver halide emulsion with a fogged grain interior used here consists of core-shell type silver halide grains consisting of a silver halide inner core with a fogged surface and a silver halide outer shell covering the surface. It is an emulsion.

A surface-fogged silver halide emulsion can be prepared by adding a reducing agent or gold salt to an emulsion capable of forming a surface latent image under appropriate pH and pAg conditions, or by heating it under low pAg conditions, or - It can be prepared by a method that provides 41-degree exposure. As the reducing agent, stannous chloride, hydrazine compounds, ethanolamine, thiourea dioxide, etc. can be used.

Internally fogged silver halide grains are prepared by depositing silver halide on the surface of the surface fogged silver halide grains to form an outer shell.

The thickness of the shell can be adjusted by adjusting the amount of silver halide in the shell portion to be deposited with respect to the grain size of the silver halide grains whose surfaces are covered.

The amount of the silver halide emulsion is preferably 0.01 g to 1 g/rd, and 0.03 g to 0.5 g/r+? is particularly preferred.

Further, the grain size of the silver halide emulsion contained in this MN is 0.03 to 0.5. μ is preferably 0.05 to 0
．． 3μ is particularly preferred.

The colloidal silver contained in the protective layer may be yellow colloidal silver generally used for yellow filter wear, or blue, cyan or black colloidal silver used for antihalation layers.

Alternatively, magenta or brown colloidal silver may be used.

Preferably, it is blue, cyan, black, magenta or brown colloidal silver.

Colloidal silver is disclosed in U.S. Pat. No. 3,459,563, 2,
It can be prepared by the method described in No. 688,601, Belgian Patent No. 622.695, etc.

Application of one of these colloids! The amount of reaction is o, oo.

1~O,Ig/rrf is desirable, especially 0.0005~
0.05g/nf is desirable.

The degree of capture of iodide ions in the developer depends on the amount of silver halide emulsion, grain size, halogen composition, luminosity,
It depends on whether the emulsion is fogged or not, or the thickness of the outer shell in the case of an internally fogged emulsion, and can be most preferably adjusted depending on the developer composition, development time, etc.

The photosensitive materials to which the present invention is applied include, for example, color negative films, color reversal films (inner and outer molds), color papers, color positive films, color reversal papers,
Any color photographic light-sensitive material such as color diffusion transfer process or Gouy transfer process may be used, but it is particularly preferably applied to color reversal film and color reversal paper.

The preferred silver halide contained in the photographic emulsion layer of the photographic window optical material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less silver iodide. preferable. Particularly preferred is about 2 mol % to about 2 mol %.
Silver iodobromide containing up to 5 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.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), 11h1764
3 (December 1978), pp. 22-23, '■, Emulsion preparation a
ndtypes)'', and N118716 (19
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafki
des.

Chemic et Ph1sique Photog
raphique paul montel.

1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F. Duffin, Photo
graphicEmulsion Chen+1s
try (Focal Press + 1966
)), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zelikman
et al.

Making and Coating Photo
rapic emulsion.

Focal Press + 1964).

Tabular grains having aspect ratios of about 5 or greater can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
ience and Engineering),
Volume 14, pages 248-257 (1970); US Pat. No. 4,434.226, US Pat. No. 4,414,310 1.
It can be easily prepared by the methods described in 4°433.048, 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, it may have 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 subject to research disclosure.
643 and No. 18716, and the relevant sections 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.

Additive 1 type RD17643 RD 113T161 Chemical sensitizer page 23 Page 648 right column 2 Anger intensity increasing agent Same as above 3 Spectral sensitizer, 2
Pages 3-24 Page 648 Right column - Super sensitizer
Page 649 right column 4 Brightener page 24 5 Anti-fogging agent pages 24-25 Page 649 right column ~
and stabilizer 6 light absorber, fu pages 25-26 page 649 right column~
Ilter dyes Page 650 Left column Ultraviolet absorber 7 Stain inhibitor Page 25 Right IV1 Page 650 Left to right columns 8 Dye image stabilizers Page 25 9 Hardeners Page 26 Page 651 Left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant Page 27 650 Right column 12 Coating aid, surface Pages 26-27 Same as above Activator 13 Static inhibitor Page 27 Same as above Various color couplers can be used in civil engineering inventions A specific example is the Research Disclosure (RD) mentioned above.
It is described in the patent described in Magnet 17643, ■-〇-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;
Same 1st. 476, 760, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0.619, No. 4,351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3. 725. No. 067, Research Disclosure & 24220 (June 1984), JP-A-1983-
No. 33552, Research Disclosure N124
230 (June 1984), JP 60-43659, U.S. Pat. No. 4,500,630, U.S. Pat. No. 4,540.
Particularly preferred are those described in No. 654 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228.23
No. 3, No. 4. 296. 200, No. 2.369,
No. 929, No. 2,801°171, No. 2,772.
No. 162, No. 2゜895.826, No. 3,772
．． No. 002, No. 3,758,308, No. 4,33
No. 4,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121゜365
A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,33
No. 3,999, No. 4.451, No. 559, No. 4.4
27.767, European Patent No. 161.626A, etc. are preferred.

Colored couplers for correcting unnecessary withdrawal of coloring dyes are available from Research Disclosure Sou 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. No. 258, British Patent No. 1,146.
The one described in No. 368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity 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. No. 3,451,820; U.S. Pat. No. 4,080,211; U.S. Pat.
It is described in No. 173, 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 RD17,643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in US Pat. No. 4,248,962.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , multi-equivalent couplers described in JP-A No. 4.31<1.618, etc., JP-A-60-18595
Examples thereof include DIR redox compound-releasing couplers such as those described in European Patent No. 173.302A, and couplers that release dyes that recover color after separation, as described in European Patent No. 173.302A.

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. No. 2,322.027 and the like.

The steps, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat. etc. are listed.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Magnet 17643, page 28, and Magnet 18716, 6
It is described from the right column on page 47 to the left column on page 648.

The color photographic light material according to the present invention can be found in the aforementioned RD, pages 28-29 of Magnet 17643, and 6 of Kaimagne 18716.
51. Development processing can be carried out by the usual methods described in the left column to right column.

The p-silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after desilvering treatment such as fixing or bleach-fixing.

The amount of water used in the washing process depends 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 over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Jo
urnal of the 5ociety o
r MotionPicture and Te1e
vision Engineers) Volume 64, P.
248-253 (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 greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively as a solution to such problems. can. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi , Sanitary Technology Gold Wire "Sterilization, Disinfection, and Antifungal Technology of Microorganisms" and Japan Antibacterial and Antifungal Science Wire "Encyclopedia of Antibacterial and Antifungal Agents" can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 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 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C is selected.

Furthermore, the photosensitive 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 Nos. 57-8543 and 58-1483
No. 4, No. 59-184343, No. 60-220345,
No. 60-238832, No. 60-239784, 60-
No. 239749, No. 61-4054, No. 61-11874
All known methods described in No. 9 etc. can be used. In particular, a stabilizing bath containing 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

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

Example 1 Preparation of emulsion Add 110 g of coupler C-1 to 0-24 cc of high-boiling organic solvent,
Add 40 cc of ethyl acetate to dissolve, and pour this solution into
l containing ee-sodium butylnaphthalene sulfonate
Emulsion A was prepared by adding to 1100 g of an aqueous O% gelatin solution and stirring and emulsifying the mixture using a homogenizer emulsifying machine.

Preparation of emulsion B Emulsion B was prepared in the same manner as emulsion A except that coupler C-3 was used in place of coupler C-1 in emulsion A and the amount of 0-2 was changed to 5 cc.

Preparation of Emulsion C Emulsion C was prepared in the same manner as Emulsion B except that coupler C-4 was used in place of coupler C-3.

Preparation of emulsion An emulsion was prepared in the same manner as emulsion A except that coupler C-5 was used in place of coupler C-1 in emulsion A and the amount of 0-2 was changed to 2CC.

Emulsion A in the third layer and fourth layer, emulsion B in the sixth layer, emulsion C in the seventh layer, emulsion layer in the 1θ layer and 11th layer, each with the following coupler coating amount and high boiling point. The organic solvent was added in a coating amount of (0-2).

A multilayer color photosensitive material consisting of each layer with the following composition was prepared on a triacetate film base, and sample 101 was prepared.
And so.

1st layer; volleyion prevention layer black colloid S 0.25g/rd ultraviolet absorber U-10,04g/m ultraviolet absorber U-20,1g/rd ultraviolet absorber U-30,1glrd compound A-22, 0■/d High boiling point organic solvent 0 1 0. 1 cc/rr
Gelatin N containing r (dry film w - 2μ) 2nd N: Intermediate layer compound H - 10,05 g/rrf High boiling point organic solvent ○ -20,05 cc/n (gelatin N containing (dry film thickness - 1 μ) 3rd Layer: First red-light emulsion layer Monodisperse silver iodobromide emulsion...Amount of silver...0
．． 5 g/rrr (Iodine content f4 mol%, average particle size 0.3 μs/r-Q, 15) Sensitizing dye S-11,4■/- Sensitizing dye S-20,06■/d Compound A-12 , Ow/rd coupler C-10, 30g1rd high boiling point 8g solvent 0 2 0. 12cc/rl
Gelatin layer containing (dry film thickness 1μ) 4th layer; 2nd red-sensitive emulsion layer sensitizing dye S-11,6*/m and sensitizing dye S2 0.0
Polydisperse silver iodobromide emulsion containing 6IIf/m...11 amount...
0.8 g/d (Iodine content 2.5 mol%, average particle size 0°55 μs/?-0,27) Coupler C-10,708/nf Gelatin containing high boiling point organic solvent ○-20,28 cc/m N (dry film thickness 2°5μ) 5th N: Intermediate layer compound H-10, 1g/n? High boiling point organic solvent 0 2 0. 1 cclrd
Gelatin layer (dry film r￥1μ) 6th layer; 1st green emulsion layer sensitizing dye S-3 (3,3 w/m) and sensitizing dye S-
Monodisperse silver iodobromide emulsion containing 4 (1,5■/m)...Amount of silver...0
．． 1 g/m (iodine content 3 mol%, average particle size 0.
3μs/F-0,15) Compound A-12,0■/d Coupler C-30,40g1cd High boiling point organic solvent 0-2 0. Gelatin layer containing 24 cc/m (dry film thickness 1μ) 7th layer: 2nd green-sensitive emulsion layer
Tabular silver iodobromide emulsion C containing 0.05 mg/rrr)
Silver content: 0.8 g/r+ .13μ
) Coupler c-40,80g/nf High boiling point solvent 0-2 0. 48'cc/rr
Gelatin layer (dry film thickness 2.5μ) containing 8th layer; Intermediate layer compound H-10.05g/nf High boiling point i solvent 0-2 0. Gelatin layer containing 1 cc/m (dry film thickness 1μ) 8th layer: yellow filter, more yellow colloid! 9 0.1 g/m Compound H-10.02 g/n (Compound H-20.03 g/n (High boiling point organic solvent 0-2 Gelatin JW (dry film thickness 1μ) containing 0.04 cc/r/) 1st O layer ;11th
11 emulsion layer Silver iodobromide emulsion containing sensitizing dye S-5 (1,0 s/d) Silver amount...0.7 g/m (Iodine content 2.5 mol%, average grain size 0°4p
s/F=0.30) Coupler C-50,5glrd High boiling point organic solvent 0 2 0. Gelatin layer containing 1 cc/m (dry film yL 1.5 μ) 11th layer; 2nd blue emulsion layer Tabular silver iodobromide emulsion C containing sensitizing dye S-5 (1.7 μ/m) 1! Amount... 1.1g/n ((Iodine content 2
．． Coupler c-s 1. 2 g/m high boiling point organic solvent 02 0.24 cc/n (containing gelatin N (dry film thickness 3 μ) 12th layer; 1st protective layer UV absorber U-10,02 g/n? UV absorber
U-20.03g/m Ultraviolet absorber U-30.03g/rr? Ultraviolet absorber U-40, 29g/n? High boiling point organic solvent 0 1
0. Gelatin N (dry membrane w-1) containing 28 cc/m
μ) 13th layer; second protective layer polymethyl methacrylate particles (average particle size l).

In addition to the above composition, a gelatin hardening agent H-3 and a surfactant were added to each gelatin layer (dry thickness 0.8μ) containing 5μ).

The compounds used to prepare the samples are shown below.

-t K-shi5t'Ill Ht CH3CCH2 CH3 H H t-U, ttq H H-3 CHz =CH3(h CHz C0NHCHzCHz ”CH30t CH2C0NHCHzC-H9
SO3" C! H2S-2 C4H9SOs' Cs H++ sample 104
Preparation Sample 104 was prepared in exactly the same manner as Sample 101, except that the amount of gelatin applied in the third and fourth layers of Sample 101 was reduced to give a dry film thickness of 0.8 μm and 2°0 μm, respectively.

Preparation of emulsion E Instead of coupler C-110g of emulsion A, C-131
Emulsion E was prepared in the same manner as Emulsion A except that the amount of O-2 was changed to 2 g and 1 cc.

Preparation of sample 107 The third layer coupler of sample 104 and the coating amount of 0-2 are as follows:
2 each. 411tlrd, 0. 03cc/r
d.

The coating amount of the 4th layer coupler and 0-2 is 0°84 each.
g/rd, emulsion E so that it becomes 0.07cc/rrr
Sample 107 was prepared in exactly the same manner as sample 104, except that the coating was performed using the same method as sample 104.

Preparation of Samples 102.105.108 The 13th layer of Samples 101.104.107 was a substantially non-photosensitive fine-grain silver iodobromide emulsion (coated silver amount: 0.1 g/m,
Sample 102.105.10B was prepared in exactly the same manner as Sample 101.104.107 except that it contained iodine content of 1 mol % and average particle size of 0.1 μm.

Preparation of Sample 109 A surface-covered fine-grain silver iodobromide emulsion (coated silver amount 0.2 g/rd, iodine content 1 mol%, average grain size, 0.1 μm) is added to the 13th layer of Sample 107. Sample 109 was produced in exactly the same manner as Sample 107 except for this.

Preparation of Sample 110 Instead of the fine-grain silver iodobromide emulsion covered with the surface of the 13th layer of sample 109, a fine-grain iodobromide emulsion was used in which the emulsion was covered with the inside of the grain with a shell of 100 silver bromides. Silver emulsion (coated silver amount 0°2 g/cd, average grain size 0.12
Sample 110 was prepared in exactly the same manner as Sample 109 except for containing μ).

Preparation of samples 103, 106, 111 to 113 Sample 102
．． Samples were prepared in exactly the same manner as Samples 102 and 105.108 to 110, except that the 13th layer of 105.108 to 110 contained the yellow colloidal silver used in the 8th layer (coated silver amount 0.1 μ/rrr). lO3,106,111-113 were produced.

Preparation of sample 114 Sample 114 was prepared in exactly the same manner as sample 10゛8 except that the black colloid used in the first layer (0.005 g/n?) used in the first layer was added to the 13th Fi on sample 10. did.

The sharpness of the cyan density of Samples 101 to 114 prepared in this manner was measured using an MTF C variable UfJ transfer function value of 20 cycles/m.

Further, assuming a developer in which the concentration of potassium iodide in the first developer was increased, a developer completely similar to the developer described below was prepared except that the potassium iodide was changed to 10 mg.

Difference in sensitivity at a cyan density of 1.0 (ΔIogE
) was sought. The larger the value of this sensitivity difference, the greater the fluctuation in photographic performance with respect to fluctuations in the potassium iodide concentration of the first developer, which is not preferable.

In addition, the degree of uneven development caused by poor developer drainage at this time was examined. Furthermore, these samples were scratched with a needle having a diameter of 1 mm while applying a load to examine the load at which the membrane would break. It can be said that the larger the load, the stronger the membrane strength.

Incidentally, the development treatment was carried out as follows.

Processing process Time Temperature First development 6 minutes 38℃ water washing
2 minutes inversion, 2 minutes color development, 6 minutes adjustment, 2 minutes bleaching, 6 minutes fixing, 4 minutes washing, 4 minutes stabilization, 1 minute drying at room temperature. The composition of the processing solution used is as follows.

700m
j! Nitrilo N,N,N-)rimethylenephosphonic acid pentasodium salt 2. g Sodium sulfite 30g Hydroquinone monosulfate (Oak I7L%)
20g potassium carbonate 4 33
g1-phenyl 4-methyl 4-hydroxymethyl-3-pyrazolidone 2g potassium bromide 2.5g potassium thiocyanate 1.2g potassium iodide
Add water to 2m 10
00mj! Anti-soft cinnabar water 700m
j+Nitro N-N-N-trimethylenephosphonic acid pentasodium salt 3g stannous chloride (dihydrate) Igp-aminophenol 0.1g sodium hydroxide
8g glacial acetic acid
Add 15ml water to 1000mj
! Matawata Star 1 Tatsumizu 700m
l Nitro・N-N-N-)rimethylenephosphonic acid pentasodium salt 2g Sodium sulfite 7g Sodium tertiary phosphate (dodecahydrate) 36g Potassium bromide
1g potassium iodide
90m sodium hydroxide 3
g Citrazic acid 1.5gN・Ethyl-N-(β-methanesulfonamidoethyl)-3・Methyl-4-aminoaniline・sulfate 11g5. &-Jijia Saikuri 7- I, l? -5゛oh1'
Add 1 g water 1
000mj+ri! water water 700
ml! Sodium sulfite 12g Ethylenediamine/sodium tetraacetate (dihydrate) 8g 1,000-glycerin 0.4 ml l! Add water to 1000mj! Hoshiwata Ascites 800r
rl Sodium ethylenediaminetetraacetate (dihydrate) 2g Iron (I) ethylenediaminetetraacetate (I) ammonium (dihydrate) 120g Example water 800ml
Sodium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water
1000n1 Regular Wednesday 800m
1! Formalin (37% by weight) 5. Q
mj! Girikikine calls -r- also l/=(shi7x=
yy--*rvc%庺%al l') 0.5
, Add y water and add 1000ml,
Similar results were obtained when washing after fixing was performed using the following washing liquid.

Add 0.4 g of thorium salt water and 1,000 ml of sodium hydroxide. It can be seen that the sharpness is excellent without worsening the amount dependence or development unevenness.

In addition, the protective layer consisting of two layers, the 12th layer and the 13th layer, is made into three layers, the 13th layer is yellow colloidal silver or black colloidal silver, and the 14th Fii is the 137H fine grain silver iodobromide of samples 108 to 110. In both cases where an emulsion is used, or where the fine-grain silver iodobromide emulsion is contained in the 13th layer and colloidal silver is contained in the 14th layer, the results of the present invention are similar to the results in Table 1, compared to the comparative example. As a result, excellent results were obtained in sharpness without deteriorating film strength, dependence on Kl amount in the first developer, and uneven development.

Also, when preparing emulsion A, the amount of high boiling point organic solvent 0-2 was
When made cc, coupler C-1 was not dissolved.

Example 2 Preparation of emulsions F, G, H Instead of coupler C-110g of emulsion A, M
-12, M-1, 12 g of Y-1, amount of 0-2 l c
Emulsions F, G,
H was prepared.

Preparation of samples 201-203 37th of samples 101-103! , 4th layer, 6th layer, 7th layer
Sample 10 was used for each layer except that the amount of gelatin applied in the 10th layer and 11th layer was reduced and the dry film thickness was adjusted as shown in Table 2.
Samples 201 to 203 were prepared in exactly the same manner as Samples 1 to 103.

Preparation of samples 204 to 206 Emulsion E was used instead of emulsion A in the third and fourth layers of samples 201 to 203, emulsion F was used instead of emulsion B in the sixth layer, and emulsion F was used instead of emulsion B in the sixth layer.
Samples 204 to 206 were prepared in exactly the same manner as Samples 201 to 203, except that Emulsion G was used instead of Emulsion C in the layer, and Emulsion H was used instead of Emulsion in the 1st O layer and the 11th layer.
was created.

Regarding these samples 201 to 206, in the same manner as in Example 1, the MTF of cyan, magenta, and yellow, the dependence on K11l in the first developer, development unevenness, and film strength were examined.

The results are shown in Table 2.

As shown in Table 2, it can be seen that the present invention is superior to the comparative example in sharpness without worsening film strength, Kll dependence during first development, or development unevenness.

In addition, when preparing emulsions B, C, and D, a high boiling point organic solvent 0-
The amount of 2 is 4cc, 4Ce%2CC, lcc
, lcc, 0. At 5cc, the coupler did not melt.

Example 3 Preparation of emulsion F Coupler $15 10g, antifading agent *1610g1
Stin inhibitor *17 was dissolved in Ig, 118 was added to 0.1 g, high boiling point organic solvent *11 and *19 (15 g in total), and 40 cc of ethyl acetate was added to dissolve this solution.
Emulsion F was prepared by adding to 100 g of a 10% gelatin aqueous solution containing sodium butylnaphthalene sulfonate and stirring and emulsifying using a homogenizer emulsifier.

This emulsion F was added to the following 6th N and 7th layers in the following coating amounts.

Preparation of Sample 301 A color photographic material was prepared by coating the following first to twelfth layers on a paper support laminated on both sides with polyethylene. The first coated polyethylene layer contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The ingredients and coating amounts in glrd units are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin... 1.30 2nd layer
Layer (Antihalation N) Black colloidal silver...0.10 Gelatin...0.70 Third layer (
Low sensitivity red sensitivity N) Silver iodobromide spectrally sensitized with red sensitizing dyes (*1 and *2) (silver iodide 5.0 mol%, average grain size 0.4μ)
... 0.15 gelatin
... 1.00 cyan coupler (*
3) ... 0.14 cyan coupler (, *
4) ... 0.07 anti-fading agent (*5,
*6 and *7) ... 0.10 coupler solvent (*8
and *9) ... 0.06 4th layer (high sensitivity red sensitivity N) Iodobromide 1 spectrally sensitized with red sensitizing dyes (*1 and *2)
! (Iodide 116.0 mol%, average particle size 0.7μ
) ... 0.15 gelatin
... 1.00 cyan coupler (*3) ... 0.20 cyan coupler (
*4) ... 0.10 anti-fading agent ($5,
+116 and *7) ... 0.15 coupler solvent (
*8 and *9) ... 0.10 5th layer (middle layer) Magenta colloid silver ... 0.02 Gelatin ... 1.00 Color mixing prevention agent ($10) ... 0.08 Color mixing prevention Agent solvent (*11 and *12) ... 0.16 Polymer latex (*13) ... 0. lO 6th layer (low sensitivity green sensitivity N) Silver iodobromide (silver iodobromide) spectrally sensitized with green sensitizing dye (*
Silver iodide 2.5 mol%, grain size 0.4μ)...0
．． 10 Gelatin ... 0.80 magenta coupler (*15) ... 0.10 anti-fading agent ($16) ... 0.10 anti-stain agent (*17) ... 0.01 anti-stain agent ( *18) ... 0.001 coupler solvent <*11 and *19) ... 0.15 7th layer (
Highly sensitive green sensitive layer) Silver iodobromide spectrally sensitized with a green sensitizing dye ($14) (silver iodide 3.5 mol%, grain size 0.9μ)...0.
10 Gelatin...0.80 Magenta coupler (*15)...0. 1O anti-fade agent ($16) ... 0.10 anti-stain agent (*17) ... 0.01 anti-stain agent (* 18) ... 0.001 coupler solvent (*11 and *19)・・・ 0.15 8th
1i (yellow filter N) 1 yellow colloid ... 0.20
Gelatin... 1. OO color mixing inhibitor (*lO)... 0.06 color mixing inhibitor solvent (*ll and *12)... 0.15 polymer latex (*13)... 0. lO 9th layer (low sensitivity blue sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye ($20) (silver iodide 2.5 mol%, grain size 0.5 μ)...0.
15 Gelatin...0.50 Yellow coupler ($21)...0.20 Stain inhibitor (*18)...0.001 Coupler solvent (*9)...0.05 No. 101!
(High-sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye ($20) (silver iodide 2.5 mol%, grain size 1.2 μ)...0.
25 Gelatin... 1.00 Yellow coupler ($21)... 0.40 Stain inhibitor ($18)... 0.002 Kabrane medium (*9)... 0. lO 11th
Layer (UV absorbing layer) Gelatin... 1.50 Ultraviolet absorber (*22, *6 and *7)... 1.00 Color mixing inhibitor ($23>... 0.06 Color mixing inhibitor solvent ( *9)...0.15 anti-irradiation dye (*24)...0.02 anti-irradiation dye (*25)...0.02 No. 127!
(Protective layer) Gelatin... 1.50 Gelatin hardening agent (*26)... 0.17*15
,5'-dichloro-3,3°-di(3-sulfobutyl)
-9-Ethylthiacarbocyanine Na salt *2 Triethylammonium-3-(2-(2-[3
-(3-sulfopropyl)nut(1,2-d)thiazoline-2-indenmethyl]-1-butenyl)-3-nut(1°2-d)thiazolino]brobanesulfone-*
3 2-(α-(2,4-di-t-amylphenoxy)
hexaneamide)-4,6-dichloro-5-ethylphenol*4 2-[2-chlorobenzoylamide]-4-chloro-5-[α-(2-chloro-4-t-amylphenoxy)octanamide] -Phenol*5 2-(2-hydroxy-3-sec-5-t-butylphenyl)benzotriazole*6 2-(2-hydroxy-5-t-butylphenyl)benzotriazole*1 2-(2-hydroxy -3,5-t-butylphenyl)6-chlorobenztriazole *8 Di(2-ethylhexyl) phthalate *9 Trinonyl phosphate *10 2. 5-di-t-octylhydroquinone*
11 Tricresyl phosphate *12 Dibutyl phthalate *13 Polyethyl acrylate $14 5. 5'-diphenyl-9-ethyl-3
゜3'-Disulfopropyloxacarbocyanine Na
Salt *157-chloro-6-methyl-2-[1-(2-octyloxy-5-(2-octyloxy-5-t-octylbenzene-sulfonamide) 2-propyl] -
1H-pyrazolo[1,5-b] [1,2,4]
) Riazole $16 3.3.3', 3°-tetramethyl-5°6
．． 5', 6' Tetrapropoxy-1,1°-bisspiroindane $173-(2-ethylhexyloxycarbonyloxy)-1-(3-hexadecyloxyphenyl)-2-
Pyrazoline*18 Preparation of 2-methyl-5-octylhydroquinone sample 302 Sample 301 and sample 301 except that the gelatin coating amount of No. 6 and No. 7 N of sample 301 was reduced from 0.80 g/rrr to 0.50 g/n, respectively. Sample 302 was prepared in exactly the same manner.

Preparation of emulsion G Emulsion G was prepared in the same manner as emulsion F except that 2 g of coupler M-18t was used instead of 10 g of coupler 115 in emulsion F, and the combined amount of $11 and *19 was changed from 15 g to 2 g.

Preparation of Sample 303 Sample 303 was prepared in exactly the same manner as Sample 302 except that Emulsion G was used instead of Emulsion F in the sixth and seventh layers of Sample 302.

Preparation of Samples 304 to 306 The twelfth layer of Samples 301 to 303 was a substantially non-photosensitive fine-grain silver chlorobromide emulsion (silver chloride 97 mol%, average grain size 0.2μ, coated silver amount 0°07). Samples 304 to 306 were prepared in exactly the same manner as particles 301 to 303, except for adding the particles (g/n?).

Preparation of Samples 307 to 309 Samples 307 to 307 were prepared in exactly the same manner as Samples 304 to 306, except that black colloidal silver was added to the 12th layer of Samples 304 to 306 so that the coated silver MO was 91 /d.
309 was produced.

The magenta density sharpness of samples 301 to 309 prepared in this manner was measured using an MTF (modulation transfer function) value of 20 cycles/fl.

Further, assuming a developer in which the concentration of potassium iodide in the first developer was increased, a developer was prepared which was exactly the same as the developer described below, except that the potassium iodide was changed to 10 μl.

Difference in sensitivity at a magenta density of 1.0 (Δlog E) was obtained.

The larger the value of this sensitivity difference, the greater the fluctuation in photographic performance with respect to fluctuations in the potassium iodide concentration of the first developer, which is undesirable.

In addition, the degree of uneven development caused by poor developer drainage at this time was examined. Furthermore, these samples were scratched with a needle with a diameter of 1 dragon while applying a load to examine the load at which the membrane would break. It can be said that the larger the load, the stronger the membrane strength.

(Processing process) First development (black and white development) 38℃ 1°15” water
Washing 38°C 1'30' reverse exposure 100 Lux or more 12 or more color development 38°C 2°15" water washing
38℃ 45” bleach fixing 38℃ 2’00” water washing
38°C 2"15" [Treatment liquid composition] Nitrilo-N,N,,N-)rimethylenephosphonic acid, pentasodium salt 0.6g Diethylenetriaminepentaacetic acid, pentasodium salt 4.0g Potassium sulfite 30. 0g potassium thiocyanate 1.2g potassium carbonate
35.0g hydroquinone monosulfonate potassium salt 25.0g diethylene glycol 15.0ml11-phenyl-
4-Hydroxymethyl-4-methyl-3-pyrazolidone 2.0g Potassium bromide 0.5g Potassium iodide
5.0■ Add water
ll (pH 9,70) Benzyl alcohol 15.0 ml diethylene glycol 12.0 m7! 3.6
-Cythia 1.8- Octanediol 0.2g Nitrilo-
N, N, , N-1-rimethylenephosphonic acid, pentasodium salt 0.5g Diethylenetriaminepentaacetic acid, pentasodium salt 2.0g Sodium sulfite 2.0g Potassium carbonate
25.0g hydroxylamine sulfate 380g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g potassium bromide 0.5g potassium iodide
1.0■ Add water
11 (pH 10,40) 2-mercapto-1,3,4-1-lyazole 1.0g ethylenediaminetetraacetic acid disodium trihydrate 5. Og ethylenediaminetetraacetic acid/Fe(IIl)/ammonium hydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate (700g/f liquid) 160.0mA glacial acetic acid 5.0ml Add water
ll (pH 6,50) Procedural amendment 1. Display of incident Showa t2 patent application No. 1/7431
No. 1, No. 2, Title of the invention, Silver halide power, 2 - Photographic light-sensitive material, 3, Relationship with the case of the person making the amendment, Become the patent applicant, 4, Subject of the amendment, details of the "detailed description of the invention" in the specification, 5 , the statement in the "Detailed Description of the Invention" section of the Description of Contents of the Amendment is amended as follows.

1) No. 70! Page/1st line "/-phenyl" "/-phenyl" and correct it.

2) Line 3 of the iot page "P-amine phenol" "P-amine phenol" and correct it.

3) iot page/first line "Rufonamidoethyl" "Rufonamidoethyl" and correct it.

4) λth line from the bottom of the first core page "You can see that the sharpness is excellent." After the "Attachment" Insert.

Attachment The above sample /θ/~//Hiro was treated with the following processing steps and processing solution composition. Similarly, in the following case, compared to the comparative example, the film strength of the present invention was dependent on the amount of KI in the first developer. It was found that the image quality and sharpness were excellent without deteriorating development unevenness.

First development minute jr'c First washing ≠ seconds 31 1 Reversal 4411 Jl #Color development lf
i J minutes 31 1 bleaching #
377 z bleach fixing ≠#3
1z Second water washing (1) is 3rs Second washing +21/l 31N The composition of each treatment solution was as follows.

- Developer solution Nitrilo N, N, N-) Rimethi λ, Oyrun, *
Xun Hakushi, Measure 41 Mu Sodium Sulfite JOf Hydroquinone Monosulfonic Acid -〇? Potassium potassium carbonate 331! -Phenyl-μm Methyl-Hiroshi-λ, O? Hydroxymethyl-3
- Pyrazolidone potassium bromide λ・jf Potassium thiocyanate / , 2f Potassium iodide λ, O ~ Add water
/ 000rnlpH, 60 pH was adjusted with hydrochloric acid or potassium hydroxide.

First washing solution mother liquor ethylenediaminetetramethylene/2.02 Conodium phosphonate phosphate j, Of water added 1000alp) (7,0
0 pH was adjusted with hydrochloric acid or hydroxide.

Invert solution without pH adjustment: stannous chloride cohydrate/0fp-aminophenol 0. /f Sodium hydroxide re Glacial acetic acid
/jmj add water
toomlpH 4,00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer salt Sodium sulfite 7, Of trisodium phosphate hydrate salt 361 Potassium bromide
l・Of potassium iodide
Sodium hydroxide
3. Of citradinic acid /
, jfN-ethyl-N-(β-meta7 lit
Sulfonamidoethyl)-3-methyl-deraminoaniline sulfate 3.6-cythiaoctane/, /, 0ft-diol water added / 000 go pH/
/, rO pH was adjusted with hydrochloric acid or potassium hydroxide.

Bleach solution Ethylene diamine acetic acid, λ io, or thorium salt, cohydrate salt Ethylene diamine acetic acid, Fe i, 2 oy (n
[)・Ammonium chloride Ammonium bromide 1oor Ammonium nitrate 101 Bleach accelerator
Add o, oz mole water
1000rrlpHt, JO pH was adjusted with hydrochloric acid or aqueous ammonia.

Bleach-fix solution salt ethylene diamine fluoroacetic acid λs j, Of thorium cohydrate ammonium thiosulfate rot sodium sulfite lλ, oy add water
/ 000fpH6, AO pH is adjusted with hydrochloric acid or aqueous ammonia.

Second washing liquid tap water t-H type strongly acidic cation exchange resin (Amberlite IR-/JOB manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-≠oo)
2 was packed, water was passed through the hotbed 2 column, and the calcium and magnesium ion concentrations were treated as follows: sodium incyanurate dichloride-〇■/l and sodium sulfate/,! Add 1/1 and add. The pH of this solution is 4
．． j～7゜! within the range of

Polyoxyethylene-p-mono 0, jmj nylphenyl ether (average i this time 1o) without pH adjustment

Claims (1)

[Scope of Claims] A color photographic material comprising one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support,
At least one photosensitive silver halide emulsion layer contains a polymer coupler containing at least one repeating unit represented by general formula [I], and the photosensitive silver halide emulsion layer is located farthest from the support. The emulsion layer has at least one auxiliary layer located further away from the support, and at least one of the auxiliary layers contains a substantially non-photosensitive silver halide emulsion or a halogen fogged inside or on the surface of the grains. A silver halide color photographic material containing a silver halide emulsion and containing colloidal silver in at least one of the auxiliary layers. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and D represents -COO-, -CONR'
-, or a substituted or unsubstituted phenyl group,
E represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, F represents -CONR'-,
-NR'CONR'-, -NR'COO, -NR'CO
-, -OCONR'-, -NR'-, -COO-, -O
CO-, -CO-, -O-, -S-, -SO_2-, -
Represents NR'SO_2- or -SO_2NR'-. R' represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. When two or more R's exist in the same molecule, they may be the same or different. l, m
, n represents 0 or 1. Q represents a cyan, magenta, or yellow dye-forming coupler residue capable of coupling with an oxidized form of an aromatic primary amine developer to form a dye.