JPH04121736A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To apply high activity and high color developing densities and to obtain excellent image quality by incorporating at least one kind of acyl acetoamide type yellow dye forming couplers of a specific acyl group into at least one layer blue sensitive silver halide emulsion layers. CONSTITUTION:At least one kind of the acyl acetomamide type yellow dye forming couplers are incorporated into at least one layer of the blue sensitive silver halide emulsion layers and the total of the dry film thicknesses of the entire layer of the blue sensitive silver halide emulsion layers is confined to <=5.0mu. In the formula, R1 denotes a univalent substituent excluding hydrogen and Q denotes the nonmetal atom group necessary for forming 3- to 5-membered hydrocarbon rings or 3- or 5-membered heterocycles having at least one hetero atoms selected from N, O, S, P together with C, where R1 does not form the ring by coupling with Q.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photograph using a novel acylacetamide type yellow dye-forming coupler. It relates to photosensitive materials.

(Prior Art) A silver halide color photographic light-sensitive material (hereinafter simply referred to as a color light-sensitive material) is made of an oxidized aromatic primary amine developer by exposing the material to light and then performing color development. A color image is formed by reaction with a dye-forming coupler (hereinafter referred to as coupler).

Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively. Among these, acylacetamide couplers and malondianilide couplers are generally used as yellow dye-forming couplers (hereinafter referred to as yellow couplers) to form yellow images.

The yellow dyes obtained from these couplers are generally formed in a silver halide emulsion layer or an adjacent layer sensitive to radiation that is complementary to the radiation absorbed by the dye. It is true.

Incidentally, yellow couplers, particularly acylacetamide couplers typified by benzoylacetanilide couplers and pivaloylacetanilide couplers, are commonly used for image formation. The former generally has a high coupling activity with the oxidized aromatic primary amine developer during development, and the produced yellow dye has a large molecular extinction coefficient, so it is used in color photographic materials that require high sensitivity, especially color. It is mainly used for negative films, and the latter is mainly used for color papers and color reversal films because of its excellent yellow dye spectral absorption characteristics and fastness.

However, benzoylacetanilide type couplers have high coupling reactivity with the oxidized product of aromatic primary amine developer during color development, and the molecular extinction coefficient of the yellow azomethine dye produced is large. Pivaloylacetanilide couplers have the disadvantage of poor spectral absorption properties, but although they have excellent spectral absorption properties for yellow images, they have poor coupling reactivity with oxidized aromatic primary amine developers during color development. However, there were disadvantages in that the yellow azomethine dye produced had a low molecular extinction coefficient.

Here, the high coupling reactivity of the coupler and the large molecular extinction coefficient of the resulting dye enable high sensitivity, high gamma value, and high color density, resulting in so-called high color development, and also excellent in yellow color images. Spectral absorption characteristics are, for example, good sharpness on the long wavelength side of spectral absorption.
This means an absorption characteristic with less unnecessary absorption in the edge region.

Therefore, it has been desired to develop a yellow coupler that has the advantages of both, namely, high color development (high coupling reactivity of the coupler and large molecular extinction coefficient of the dye) and excellent spectral absorption characteristics of color images.

As the acyl group of the acylacetanilide type coupler, U.S. Pat.
No. 848) includes pivaloyl group, 7,7-dimethylnorbornane-1-carbonyl group, 1-methylcyclohexane-1-carbonyl group, etc., and JP-A-47-26133 includes cyclopropane-1-carbonyl group, A cyclohexane-1-carbonyl group and the like are disclosed. but,
These couplers were inferior in some respect, such as poor coupling reactivity, low molecular extinction coefficient of the dye, or poor spectral absorption characteristics of color images.

Furthermore, representative of acylacetanilide type couplers,
For benzoylacetanilide type and pivaloylacetanilide type couplers, a coupler having an oil-soluble diffusion-resistant group in the molecule is mixed and dissolved in a high boiling point organic solvent, and the finely dispersed dispersion is mixed with silver halide to produce a color photosensitive material. When preparing a coupler, if the amount of the high-boiling organic solvent added is low relative to the unit weight of the coupler, there is also the drawback that sensitivity and color density decrease.

Also, U.S. Pat.
-26133, and JP-A No. 62-54257,
Specifications describing acylacetanilide couplers in which the acyl group contains alkylcarbonyl or cycloalkylcarbonyl, as described in German Patent No. 56-87041, German Patent No. 54-99433, West German Patent No. 2,757,380, etc. There is no explanation or specific example regarding the color development and color image fastness related to the regulation of the film thickness of the layer containing these yellow couplers and the color light-sensitive material containing these yellow couplers.

When we actually investigated the photosensitive materials using these conventional couplers, we found that the color development and color image fastness deteriorated due to the reduction in film thickness, and that the amount of high-boiling organic solvents added to the couplers deteriorated. It has become clear that the above-mentioned problems become more serious as the .

(Problems to be solved by the invention) Therefore, the first problem to be solved by the present invention is:
To provide a color photosensitive material which exhibits high activity and high color density, shows little change in these excellent properties due to changes in the amount of high-boiling organic solvent added per unit weight of coupler, and provides a robust color image. It is in. The second is a color light-sensitive material that achieves the first object described above by reducing the dry film thickness of the color light-sensitive material, especially the dry film thickness of the blue-sensitive emulsion layer, and also improves image quality, especially sharpness. Our goal is to provide the following.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the present inventors have made various studies and found that a yellow dye-forming coupler represented by the following general formula (1) is used in a blue-sensitive emulsion layer. , the thickness of the nuclear layer is 5
．． It was discovered that the objective could be satisfied by regulating the thickness to 0 μm or less, and based on this knowledge, the present invention was accomplished.

That is, in the present invention, each small amount (at least 1
In a silver halide color photographic light-sensitive material comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and a non-light-sensitive layer, the blue-sensitive silver halide emulsion layer is At least one layer contains at least one acylacetamide type yellow dye-forming coupler whose acyl group is represented by the following general formula (1),
The total dry film thickness of all the blue-sensitive silver halide emulsion layers is 5
．． The object of the present invention is to provide a silver halide color photographic light-sensitive material characterized by having a particle size of 0 μ or less.

General formula (I) (wherein R1 represents a monovalent group, Q together with C, 3-
Represents a group of nonmetallic atoms necessary to form a 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle having at least one heteroatom selected from N, O, S, and P in the ring. However, R is not a hydrogen atom and does not combine with Q to form a ring.) The present invention will be explained in more detail below.

The acylacetamide type yellow coupler of the present invention is preferably represented by the following general formula (Y).

Formula (Y) R1 In formula (Y), R1 represents a monovalent substituent other than hydrogen, and Q
is a nonmetal necessary to form, together with C, a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle containing at least one heteroatom selected from N, S, O, and P in the ring. The atomic group, R1 is a hydrogen atom, a halogen atom (F, C12,
Br, I. The following formula (the same applies in the explanation of Yl), an alkoxy group, an alkoxy group, an alkyl group, or an amino group, R1 is a group that can be substituted on the top of benzene, and X is a hydrogen atom or a biprimary amine development A group that can be separated by a coupling reaction with the oxidized product of straw (hereinafter referred to as a leaving group) is
represent integers from θ to 4, respectively. However, when l is plural, the plural R3s may be the same or different.

Here, examples of R3 include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group,
There are alkylsulfonyloxy groups and arylsulfonyloxy groups, and examples of leaving groups include heterocyclic groups bonded to the coupling active position with a nitrogen atom, aryoloxy groups, arylthio groups, acyloxy groups, alkylsulfonyloxy groups, -aryl Sulfonyloxy group, heterocyclic oxy group,
There is a halogen atom.

When the substituent in formula [Y] is an alkyl group or contains an alkyl group, unless otherwise specified, the alkyl group is a linear, branched, or cyclic unsaturated bond even if substituted. Alkyl groups that may contain (e.g., methyl, isopropyl, t-butyl, cyclopentyl, t-
-pentyl, cyclohexyl, 2-ethylhexyl, l
, l, 3゜3-tetramethylbutyl, dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl).

When the substituent in formula [Y] is an aryl group or contains an aryl group, unless otherwise specified, the aryl group is an optionally substituted monocyclic or condensed aryl group (e.g. phenyl, 1 -naphthyl, p-tolyl, 0
-Tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyfninyl, bentafluorofninyl, p-hydroxyphenyl, p-
cyanophenyl, 3-pentadecyl fninyl, 2,4 di-t-pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl).

When the substituent in formula (Y) is a heterocyclic group or contains a heterocyclic group, unless otherwise specified, the heterocyclic group is O, N, S
, a 3- to 8-membered optionally substituted monocyclic or fused-ring heterocyclic group containing at least one heteroatom selected from P, Se, and Te (e.g., 2-furyl, 2- Pyridyl, 4-pyridyl, l-pyrazolyl, l-imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimide, phthalimide, l-benzyl-2,
4-imidazolidinedione-3-yl).

Hereinafter, substituents preferably used in formula (Yl) will be explained.

In formula (Y), R2 is a halogen atom, a cyano group, or a total number of carbon atoms (all of which may be substituted).
A monovalent group with 1 to 30 carbon atoms (e.g. alkyl group, alkoxy group) or a monovalent group with 6 to 30 carbon atoms (hereinafter abbreviated as C number)
Examples of substituents include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, a carbonamide group, a sulfonamide group, and an acyl group.

In formula CY), Q is preferably a 3- to 5-membered hydrocarbon ring having 3 to 30 carbon atoms which may be substituted together with C, or at least one of N, S.

0, C number 2 to 2 containing a hetero atom selected from P in the ring
Represents a group of nonmetallic atoms necessary to form 30 heterocycles. Further, the ring formed by Q together with C may contain an unsaturated bond within the ring. Examples of rings formed by Q together with C include cyclopropane ring, cyclobutane ring, cyclopentane ring, dichloropropene ring, cyclobutene ring, cyclopentene ring,
There are oxetane ring, oxolane ring, 1,3-dioxolane ring, thiecune ring, thiolane ring, and pyrrolidine ring. Examples of substituents include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group, and an alkylthio group.

In formula [Y], R1 is preferably a halogen atom, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or a C 1 to 30 alkoxy group, all of which may be substituted. It represents an amino group having a number of θ to 30, and its substituents include, for example, a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In formula (Y), R3 is preferably a halogen atom, any of which may be substituted, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, C2-30 alkoxycarbonyl group, C7
-30 aryloxycarbonyl group, C1-30 carbonamide group, C1-30 sulfonamide group,
Carbamoyl group having 1 to 30 carbon atoms, sulfamoyl group having ○ to 30 carbon atoms, alkylsulfonyl group having 1 to 30 carbon atoms, C
Arylsulfonyl group having 6 to 30 carbon atoms, Waleido group having 1 to 30 carbon atoms, sulf7moylamino group having 0 to 30 carbon atoms, C
Alkoxycarbonylamino group having 2 to 30 carbon atoms, 1 to 30 carbon atoms
30 heterocyclic groups, C number 1 to 30 acyl group, C number 1 to 3
0 alkylsulfonyloxy group, C6-C30 arylsulfonyloxy group, and its substituents include, for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group. group, alkylthio group, arylthio group, heterocyclic thio group,
Alkylsulfonyl group, irisulfonyl group, acyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino group, ureido group, cyano group,
Nitro group, acyloxy group, alkoxycarbonyl group,
There are aryloxycarbonyl groups, alkylsulfonyloxy groups, and arylsulfonyloxy groups.

In formula (Y), l preferably represents an integer of 1 or 2, and the substitution position of R3 is preferably the para position.

In formula (Y), X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position through a nitrogen atom.

When X represents a heterocyclic group, X is preferably a 5- to 7-membered monocyclic or condensed heterocyclic group which may be substituted, examples of which include succinimide, maleimide, phthalimide. , diglycolimide, pyrrole, pyrazole, imidazole, 1.2.4-) lyazole,
Tetrazole, indole, indazole, benzimidazole, benzotriacyl, imidazolidine-2
, 4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiazolidin-2-one, benzimidacillin-2-one, benzo Oxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidacillin-5-one, indoline-2,3-dione, 2,6-cyoxypurine, parabanic acid, 1°2. 4-triacylidine-3,5-dione,
2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone-2-gurazone, 2-amino-1,3°4-thiazolidine, 2-imino-1,3,4-thiazolidine-
4-one, etc., and these heterocycles may be substituted. Examples of these heterocyclic substituents include halogen atoms, hydroxyl groups, nitro groups, cyano groups, carboxyl groups, sulfo groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, and alkyl groups. Sulfonyl group, arylsulfonyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group,
When cX containing a sulfamoylamino group represents an aryloxy group, X preferably represents an aryloxy group having 6 to 30 carbon atoms, and is selected from the substituent groups listed above when X is a heterocycle. It may be substituted with a group.

Substituents for the aryloxy group include a halogen atom, cyano group, nitro group, carboxyl group, trifluoromethyl group, alkoxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group,
An alkylsulfonyl group or an arylsulfonyl group is preferred.

Next, particularly preferably used substituents in formula (Y) will be explained.

R1 is particularly preferably a halogen atom or an alkyl group, most preferably a methyl group.

Q is particularly preferably a group of nonmetallic atoms in which the ring formed with C forms a 3- to 5-membered hydrocarbon ring, for example, where R represents a hydrogen atom, a halogen atom, or an alkyl group, provided that , a plurality of R's may be the same or different.

Q most preferably forms a 3-membered ring together with C to which it is bonded; R2 particularly preferably represents a chlorine atom, a fluorine atom, a C number of 1
~6 alkyl groups (e.g. methyl, trifluoromethyl, ethyl, impropyl, t-butyl), C1-8
an alkoxy group (e.g. methoxy, ethoxy, methoxyethoxy, butoxy), or an aryloxy group having 6 to 24 carbon atoms (e.g. phenoxy group, p-tolyloxy, p-tolyloxy, p-
-methoxyphenoxy), and most preferably a chlorine atom, a methoxy group or a trifluoromethyl group.

R1 is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonylamide group, a carbamoyl Kg or a sulfamoyl group, and most preferably an alkoxy group, an alkoxycarbonyl group, a carbonamide group or a sulfonamide group. .

Particularly preferably, X is a group represented by the following formula [Y-1], [Y-2] or [Y-3].

Formula (Y-1) ~・-z =”' In the formula [Y-1], Z is omitted. Here, R., R,, Rs-, and R+ are hydrogen atoms, alkyl groups, aryl groups, and alkoxy groups. , represents an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, R. and R are water'y: atoms, alkyl groups,
It represents an aryl group, an alkylsulfonyl group, an arylsulfonyl group, or an alkoxycarbonyl group, and R+6 and R11 represent a hydrogen atom, an alkyl group, or an aryl group.

R. and R I 1 may be bonded to each other to form a benzene ring. R4 and Rs, Rs and R. , R. and R.

or R, and R. may be bonded to each other to form a ring (eg, cyclobutane, cyclohexane, cyclohebutane, cyclohexene, pyrrolidine, piperidine).

Especially preferred among the heterocyclic groups represented by formula (Y-1)
In the formula (Y-1), Z is a heterocyclic group.

The heterocyclic group represented by formula (Y-1) has 2 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 5 to 16 carbon atoms.

Formula (Y-2) (Kth) In formula (Y-2), at least one of R1 and R1 is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, The group is selected from a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, and the other group may be a hydrogen atom, an alkyl group, or an alkoxy group. RI4 represents a group having the same meaning as R', g or R+3, and m represents an integer of 0 to 2. Formula (Y-
The number of carbon atoms in the aryloxy group represented by 2,1 is 6 to 30
Preferably it is 6-24, more preferably 6-15.

Formula [Y-3] -N, In formula [Y-3], W may represent a nonmetallic atomic group necessary to form a pyrrole ring, pyrazole ring, imidazole ring or triazole ring together with N. (, Examples of preferred substituents include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, or a carbamoyl group. The heterocyclic group represented has 2 to 30 carbon atoms, preferably 2 to 24 carbon atoms, and more preferably 2 to 16 carbon atoms.

Most preferably, X is a group represented by formula [Y-1].

The coupler represented by formula (Y) has substituents R+, Q.

K! Dimers or more multimers may be formed which are bonded to each other via groups. In this case, the number of carbon atoms in each substituent group may be outside the range specified above.

Specific examples of each substituent in formula (Y) are shown below.

An example is shown below.

CH.

■ Examples of R2 CH, -, (, R3-, 1-CIH+ -, t-CtH
m-n-C+HsO+.

n-C++Hi+0-+ C,,H,,0 ■R3 example F.

C1゜ Br.

■.

CH,0 C,8,0 n-CI2H! 30 CHs, t-C* Hs- -COOCH.

C00C,H,.

sF1+Electric SOh NHCOCI Ht, Sow NHCl
-R33-'NHCOC1sH*-"NHCOCII831-"NHCOCItH3s-'-NHCOCH-C,H,,-"C@HI3-" CH.

-NHCOCH-CH,CH,CHCH,C,H,-ゞCHCH,C,H,-' Hs CH.

! -NHCOCHCH, So! C,,H,,-”Cs
Ht − -NHCOCHSO2C,,H,,-”-NH3Ot
C, tH□-' NHCOOC2, Hzs-'' (1) Example of X Specific examples of the yellow coupler represented by the formula [Y] are shown below.

CH.

COOC. H,- C. H,-” CH.

Y-14 Y-15 ¥-22 Y C00CR.

Y-31 Y-32 O2 S.O.

Y-40 Y-41 COOC,,H,.

N n-CBHtsS CCHtCH)3 H! x:y=80:20Ctl)t) Number average molecular weight 70° X:Y:Z:=50 Canada: 20 (tt old Number average molecular weight 70° Y-60 Y-61 formula The cyan coupler of the present invention represented by can be synthesized by the following synthetic route.

Here, the compound is J, Chem, Soc,
(C), 196g, 254'8, J, Am,
Chem, Soc,, l 934°56.271
0.5ynthesis, 1971. 258,
J, Org, Chem, 1978, 43, 1729,
CA, 1960, 66.18533y, etc.

Compounds are synthesized using thionyl chloride, oxalyl chloride, etc. without solvent or with methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N, N-
Dimethylformamide, N.

The reaction is carried out in a solvent such as N-dimethylacetamide, and the reaction temperature is usually -20°C to 150°C.
, preferably -10°C to 80°C.

The compound ni is synthesized by converting ethyl acetoacetate into an anion using magnesium methoxide, etc., and then removing evil spirits into the anion. The reaction is carried out without solvent or using tetrahydrofuran, ethyl ether, etc., and the reaction temperature is usually -2
The temperature is 0°C to 60°C, preferably -10°C to 30°C. Compound Wataru contains compound Ni and aqueous ammonia, Na as a base.
It is synthesized by reaction using an aqueous HCO3 solution, an aqueous sodium hydroxide solution, etc. without a solvent or in a solvent such as methanol, ethanol, or acetonitrile. The reaction temperature is usually -20°C to 50°C, preferably -10°C to 3°C.
It is 0°C.

Compounds are synthesized by reacting chemical compounds without solvent. The reaction temperature is usually 100-150°C, preferably 100-12D'C. When X is not H, a leaving group X is introduced after chlorination or bromination to synthesize the compound.

The compound is converted into a chloro-substituted form with sulfuryl chloride, N-chlorosuccinimide, etc., or a bromo-substituted form with bromine, N-bromosuccinimide, etc. in a solvent such as dichloroethane, carbon tetrachloride, chloroform, methylene chloride, or tetrahydrofuran.

At this time, the reaction temperature is -20°C to 70°C, preferably 10°C.
℃~50℃.

Next, the chloro-substituted product or bromo-substituted product and the protonated product H-X of the leaving group are combined with methylene chloride, chloroform, tetrahydrofuran, acetone, acetonitrile, dioxane, N-methylpyrrolidone, N, N'-dimethylimidazolidine-2- in a solvent such as on, N, N-dimethylformamide, N, N-dimethylacetamide, etc., at a reaction temperature of -20°C to 150°C, preferably -10°C to 100°C.
By reacting at °C, the cabrae of the present invention can be obtained. At this time, triethylamine, N-ethylmorpholine, tetramethylguanidine, potassium carbonate,
Bases such as sodium hydroxide and sodium hydrogen carbonate may also be used.

Examples of synthesis of couplers of the present invention are shown below.

Synthesis Example 1 Synthesis of Exemplified Compound Y-30 Gotkis, D., etal., J., Am.
Cham, Soc., 1934, Σ6, 2710, synthesized by the method described in 25 g of n-l-methylcyclopropanecarboxylic acid, 100 g of physico-methylene! N, N-
38.1 in a mixture of 1 ml dimethylformamide
g of oxalyl chloride was added dropwise over 30 minutes at room temperature. After the addition, the mixture was reacted at room temperature for 2 hours, and methylene chloride and excess oxalyl chloride were removed under reduced pressure using an aspirator to obtain an oily substance of 1-methylcyclopropanecarbonyl chloride.

100 mj of methanol in a mixture of 6 g of magnesium and 2 ml of carbon tetrachloride! was added dropwise over a period of 30 minutes at room temperature, and after heating under reflux for 2 hours, 32.6 g of ethyl 3-oxobutanoate was added dropwise over a period of 30 minutes under heating under reflux. After dropping, heat under reflux for another 2 hours and aspirate methanol.
Completely distill off under reduced pressure. Tetrahydrofuran 100mf
is added to the reactant and dispersed, and the previously obtained 1-methylcyclopropanecarbonyl chloride is added dropwise at room temperature.

After reacting for 30 minutes, the reaction solution was extracted with ethyl acetate 300ml and 7° dilute sulfuric acid water, washed with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to give 2-(1-methylcyclopropanecarbonyl)-3-oxobutane. Nityl acid oil 55
．． 3g was obtained.

A solution of 55 g of ethyl 2-(l-methylcyclopropanecarbonyl)-3-oxitubutanoate and 160 ml of ethanol was stirred at room temperature, and 60 ml of 30% aqueous ammonia was added thereto.
Add dropwise over 10 minutes.

Thereafter, the mixture was stirred for 1 hour, extracted with 300 ml of ethyl acetate and diluted hydrochloric acid, neutralized, washed with water, and the organic layer was dried over anhydrous sodium sulfate. 43g was obtained.

(1-methylcyclopropanecarbonyl)ethyl acetate 3
4g and N-(3-amino-4-chlorophenyl)-2-
44.5 g of (2,4-di-t-pentylphenoxy)butanamide was aspirated at an internal temperature of 100 to 120°C.
Heat to reflux under reduced pressure.

After 4 hours of reaction, the reaction solution was purified by column chromatography using a mixed solvent of n-hexane and ethyl acetate to obtain Exemplified Compound Y-3049.
g was obtained as a viscous oil. The structure of the compound was confirmed by MS spectrum, NMR spectrum and elemental analysis.

Synthesis Example 2 Synthesis of Exemplified Compound Y-1 8 g of Exemplified Compound Y-302 was added to 300 m of methylene chloride.
j! After cooling with water, 5.4 g of sulfuryl chloride was added dropwise over 10 minutes. After reacting for 30 minutes, the reaction solution was thoroughly washed with water, dried over anhydrous sodium sulfate, and concentrated to obtain Exemplified Compound Y-30.
chloride was obtained. 1-benzyl-5-ethoxyhydantoin 18.7g 5j-ethylamine 1.2mf,
In a solution of 50ml of N,N-dimethylformamide, the chloride of the previously synthesized exemplary compound Y-30 was dissolved in 50ml of N,N-dimethylformaldehyde.
Add dropwise over minutes at room temperature.

Then, after reacting at 40°C for 4 hours, the reaction solution was diluted with ethyl acetate.
00m1. After extracting and washing with water, wash with 2% aqueous triethylamine solution (30 t) mf, and then neutralize with diluted hydrochloric acid water. After drying the organic layer over anhydrous sodium sulfate, the solvent was distilled off, and the resulting oil was crystallized from a mixed solvent of n-hexane and ethyl acetate.

The precipitated crystals were filtered, washed with a mixed solvent of n-hexane and ethyl acetate, and then dried to obtain 22.8 g of crystals of Exemplary Compound Y-1.

The structure of the compound was confirmed by MS spectrum, NMR spectrum, and elemental analysis. Moreover, the melting point was 132-3°C.

The yellow coupler represented by the general formula (1) of the present invention has a content of 1.0 to 1.0X10-'' per mole of silver halide.
It can be used in a molar range. Preferably 5.0
The range is from X10-' to 5.0XIO-" moles, more preferably from 4.0XIO-' to 2.0X10-" moles.

Two or more kinds of the yellow couplers represented by the general formula (I) of the present invention can be used in combination, or they can be used in combination with other known couplers.

The coupler represented by the general formula (1) of the present invention can be introduced into the color photosensitive material by various known dispersion methods.

The oil-in-ice dispersion method uses low-boiling organic solvents (e.g., ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol, etc.) to apply a fine dispersion, and essentially contains low-boiling organic solvents in the buffy film. A method in which no solvent remains may be used. When using a high boiling point organic solvent, any one having a boiling point of 175°C or higher at normal pressure (specific examples will be described later) may be used, and one type or two or more types can be arbitrarily mixed and used. The ratio of the couplers of the present invention to these high boiling organic solvents can vary over a wide range, but is in the range of weight ratios of up to 5.0 per gram of coupler. Preferably O~
2.0, more preferably in the range of 0.01 to 1.0.

Moreover, the latex dispersion method described later can also be applied.

Furthermore, it can be used in combination with or in combination with various couplers and compounds described later.

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 limitations on the number of layers and the layer order of the non-photosensitive layers.The blue-sensitive layer of the present invention is sensitive to substantially the same wavelength range of 400 to 500 nm. A typical example is a silver halide photograph having a small number of light-sensitive layers on a support, each consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities. It is a photosensitive material, and the photosensitive layer is blue light,
It is a unit photosensitive layer that is sensitive to green light, red light, or infrared light, and in multilayer silver halide color photographic light-sensitive materials, the unit photosensitive layers are generally arranged in order from the support side to red light. A color-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order. However, depending on the purpose, the 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 West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A No. 571
No. 12751, No. 62-200350, 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 (RL), or BH/BL/GL/GH/RH/RL, or BH/BL/GH/GL/RL/RH They can be installed in the following order.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the side furthest from the support. .

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 N/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

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

To improve color reproduction, U.S. Patent No. 4,663.2
No. 71, No. 4,705,744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

Silver halide preferably contained in the blue-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material used in the present invention is silver iodobromide or iodochloride having an average silver iodide content of 2.0 mol% or more. It is silver oxide or silver iodochloride. Silver iodobromide or silver iodochlorobromide having an average silver iodide content of 2.0 to 25.0 mol% is preferred, and particularly preferred is silver iodobromide having an average silver iodide content of 3.0 mol%. It is silver iodobromide or silver iodochlorobromide consisting of ~20.0 mol%.

The blue-sensitive silver halide emulsion layer in the present invention is a silver halide emulsion layer having a maximum spectral absorption wavelength preferably in the range of 410 to 480 nm, and the silver halide emulsion layer contains at least one yellow dye-forming coupler. However, the yellow dye-forming coupler does not consist solely of functional couplers. Functional couplers are couplers that release photographically useful residues upon coupling, such as development inhibitor releasing (DI
R) coupler, nucleating agent or development accelerator release (DA
R) couplers, bleach accelerator releasing (BAR) couplers, dye (leuco dyes, fluorescent dyes, etc.) releasing couplers, and the like.

In the present invention, the dry film thickness of all the blue-sensitive silver halide emulsion layers is 5.0 μm or less regardless of the above-mentioned calendar number and layer structure. By setting the dry film thickness to this value, it is possible to provide high activity and high color density, maintain the property that the resulting color image is robust, and improve image quality, especially sharpness.

The dry film thickness of the entire blue-sensitive silver halide emulsion layer is preferably 4.0 μm or less. More preferable is 3.0μ
It is as follows. The lower limit of this dry film thickness can be reduced within a range that satisfies the function of the blue-sensitive silver halide emulsion layer of the color light-sensitive material, and the value is approximately 1.0 .mu.m.

On the other hand, in the light-sensitive material of the present invention, regardless of the dry film thickness of the all-blue-sensitive silver halide emulsion layer described above, the dry film thickness of all layers excluding the support and the undercoat layer of the support is 25.0 μm.
It has been found that the object of the present invention can also be achieved in the following cases. The dry film thickness of this entire layer is preferably 21.0μ
It is not more than 18.0μ, more preferably not more than 18.0μ.

As for the lower limit, the layer can be made thin within a range that satisfies the intended performance of the photosensitive material, and the value is approximately 8°0μ.

The film thickness of the photosensitive material of the present invention can be measured by the following method. The photosensitive material to be measured is stored at 25° C. and 55% relative humidity (for 2 days). After that, the total thickness of this photosensitive material was measured, and then the coating layer on the support was removed, and then,
The thickness is measured again, and the difference can be used as the total coating thickness of the photosensitive material excluding the support. To measure this thickness, for example, a film thickness measuring device (Anritsu Electric) equipped with a contact type piezoelectric transducer is used.
Co, Led, K-402B 5tand,
) can be used to measure. Note that the thickness of the coating film on the support can be removed using, for example, an aqueous solution of sodium hypochlorite.

Next, using a scanning electron microscope, take a cross-sectional photograph of the photosensitive material (magnification is preferably 3,000 times or more),
The thickness of each layer can be calculated by actually measuring the total thickness on the support and the thickness of each layer, and comparing it with the total thickness measurement value (absolute value of thickness) using the film thickness measuring device.

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. It may also be a type that exhibits 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 of up to about 10 microns in projected area diameter, 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 (RD) Nα17643
(December 1978), pp. 22-23.

“1. Emulsion preparation
ion and types)', and 41871
6 (November 1979), p. 648, by Grafkide, “
"Physics and Chemistry of Photography", published by Ballmontel (P, Gl.
afkides.

Chemie et Ph1sique Photo
graphique, Paul Montel, 1
967. ), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press, CG, F. Duffin.

Photographic Emulsion Che
Mistry (Focal Press.

1966) “Manufacture and Coating of Photographic Emulsions” by L. Zelikman et al.
, Published by Focal Press (V, L, 2e Iikm
anet al,, Making and Co
ating Photographic Emulsi
on, Focal Press, l'964)
It can be prepared using the method described in et al.

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
No. 4 and British Patent No. 1. 413. Monodispersed emulsions such as those described in No. 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 in Gutoff, Photographic Science and Engineering.
engineering), 1st
4, pp. 248-257 (1970); U.S. 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, the inside may have a multiple layered structure, and silver halides with different compositions may be bonded together by epitaxial bonding. may have been done,
Further, it may 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 Nα1
7643 and Nα18716, 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.

Additive types 1 Chemical sensitizers 2 Sensitivity enhancers 3 Spectral sensitizers, pages 23-24 Super sensitizers 4 Brighteners 5 Anti-fogging agents and stabilizers 6 Light absorbers, filter dyes, ultraviolet absorbers Anti-stin agent Dye image stabilizer Hardener Binder Plasticizer, lubricant Coating aid, Surface active agent 13 Static inhibitor RD17643 Page 27 Page 24 Page 24-25 Page 25-26 Page 23 Page 25 Right column Page 25 Page 26 Page 26 Page 27 Pages 26-27 RD 18716 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Page 649 Right column - Page 649 Right column - Page 650 Left column Page 650 Left - Right column Page 651 Left column Same as above 650 Page right column Page 650 Right column Same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is possible to react with formaldehyde as described in U.S. Pat. It is preferable to add a compound that can be immobilized to the photosensitive material.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) No. 17643. (2) It is described in the patents listed in C to G.

Examples of yellow couplers that can be used in combination with the yellow coupler represented by general formula (I) of the present invention include U.S. Pat. , No. 4,401,752,
Patent No. 4,248.961, Japanese Patent Publication No. 10739/1983, British Patent No. 1.425,020, British Patent No. 1,476.
Preferred are those described in US Pat. No. 760, US Pat. No. 3,973,968, US Pat. No. 4,314,023, US Pat.

As magenta couplers, 5-pyrazolones and other pyrazoloazole compounds are preferred, and are disclosed in U.S. Pat. No. 4,310,619, U.S. Pat. 3,061,43
2, No. 3.725.067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60
-43659, 61-72238, 60-35
No. 730, No. 55-118034, No. 60-1859
No. 51, U.S. Patent No. 4,500゜630, U.S. Patent No. 4.5
Particularly preferred are those described in No. 40.654, No. 4556.630, International Publication No. W088104795, etc.

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. 2,369.9
No. 29, 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
No. A, No. 249.453A, U.S. Patent No. 3.446
, No. 622, No. 4,333.999, No. 4,77
5.616, 4.451,559, 4.4
No. 27,767, No. 4.690.889, No. 4,
Preferred are those described in No. 254.212, No. 4,296.199, JP-A-61-42658, and the like. Also,
Imidazole couplers, such as JP-A-1-25095
No. 3, No. 1-250945, No. 2-141744,
The coupler described in EP 354,549A can also be used.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No. 17643.
-G section, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004.929, No. 4,138゜258, British Patent No. 1,146,
No. 368 and Japanese Patent Application No. 2-75916 are preferred.

Additionally, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774,181, and U.S. Pat. No. 4,777.120
It is also preferable to use a coupler having a dye precursor group as a leaving group which reacts with a developing agent to form a dye as described in the above-mentioned No.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.231 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 disclosed in U.S. Pat. No. 3,451,820, 4. o80.211, 4,367.282, 4.409,320
No. 4.576.910, British Patent No. 2,102,
It is described in No. 137, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferably, those described in U.S. Pat. No. 57-154234, U.S. Pat.

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 photosensitive material of the present invention include U.S. Patent No. 4. 130. Competitive couplers described in U.S. Pat. No. 427, etc., U.S. Pat.
Long equivalent coupler described in JP-A-60-18595
DIR redox compound releasing coupler, DIR coupler releasing coupler DIR coupler releasing redox compound or DIR described in No. 0, JP-A No. 62-24252, etc.
Redox-releasing redox compounds, European Patent No. 173.
No. 302A, No. 313,308A, couplers R, D, NcLl 1 which release dyes that after separation are described in Nos. 302A and 313,308A.
449, 2424L Bleach accelerator releasing coupler described in JP-A No. 61-201'247, etc., U.S. Patent No. 4,55
Couplers that release ligands as described in No. 5.477, couplers that release leuco dyes as described in JP-A-63-75747, couplers that release fluorescent dyes as described in U.S. Pat. No. 4,774,181, etc. Can be mentioned.

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 US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-tert-amyl phenyl) phthalate, bis(2,4-di-tert-amyl phenyl) isophthalate, bis(1,l-diethylbutylphenyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (Trifel phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphate, etc.), Benzoic acid esters (2-ethylhexylbenzoate,
dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyl laurylamide,
N-tetradeneruvirolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-
di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N- (dibutyl-2-butoxy-5-tertoctylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisobylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, a solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, nclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1 described in No. 0941. 2-penzisothiazolin-3-one, n-butyl p-hydroxybenzoate,
Phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2-(4-thiazolyl)
It is preferable to add various preservatives or fungicides such as penzimidazole.

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 barber. Preferred are color negative films for general use or movies, and color reversal films for slides or television.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. It is described on page 28 of Toru 17643 and from the right column of page 647 to the left column of page 648 of Nα18716.

The photosensitive material of the present invention has a film swelling rate T! /! is preferably 30 seconds or less, more preferably 20 seconds or less. Membrane swelling rate T
'A can be measured according to techniques known in the art. For example, 21 Green (A.fl
Photographic Science and Engineering (Photogr. S
ci. It can be measured by using a swell meter (swell meter) of the type described in Eng., ), Vol. 19, No. 2, pp. 124-129, and TV2 was treated with a color developer at 30°C for 3 minutes and 15 seconds. The saturated film thickness is defined as 90% of the maximum swollen film thickness reached at a certain time, and is defined as the time required to reach this TA film thickness.

The membrane swelling rate T% can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating.

Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned earlier, using the formula =
It can be calculated according to (maximum swelling film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD, N
Development processing can be carried out by the usual method described in pages 28 to 29 of α17643 and 615 left column to right column of Sou 18716.

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-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. Also, if necessary, hydroxylamine, diethylhydroxylamine, bis(β-carboxyethyl)hydroxylamine, sulfite, etc. l, hydrazines such as N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, various preservatives such as catechol sulfonic acid serum, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, and quaternary ammonium. salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as l-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids,
Various chelating agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1, Representative examples include l-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylene glycol (O-hydroxyphenylacetic acid) and their salts. This can be cited as an example.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they 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 being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than m1. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The ratio of the contact area with air to the volume of photographic processing solution in the processing tank (unit: am −', aperture ratio) is 0. It is preferably 1 or less, more preferably 0.001 to 0.
It is 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 solution in the processing tank, methods using a movable lid described in JP-A No. 1-82033, The slit development processing method described in No. 63-216050 can be mentioned. It is preferable to reduce the aperture ratio not only in both the color development and black-and-white development steps, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing 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 layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As a bleaching agent, known compounds can be used, and among these, iron aminopolycarboxylate including ethylenediaminetetraacetic acid iron (I[[) complex salt and 1,3-diaminopropanetetraacetic acid iron (II[) complex salt] (I[l) complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution.

Furthermore, the aminopolycarboxylic acid iron(I[[) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron(II[) complex salts is usually 4.0 to 8, but the pH can be lowered to speed up the processing. .

Known bleach accelerators may be used in the bleaching solution, bleach-fixing solution, and their pre-baths, if necessary.

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,
Hydroxyacetic acid and the like 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. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering process 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.

Furthermore, the treatment temperature is 25°C to 50°C, preferably 35°C to
The temperature is 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 stirring be as strong as possible. Specific methods for strengthening the agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460, and the method described in JP-A-62-183.
No. 461 uses a rotating means to increase the stirring effect, and furthermore, by moving the photosensitive material while connecting the wiper blade provided in the liquid and the emulsion surface, and creating turbulence on the emulsion surface, the stirring effect is further improved. Examples include a method of increasing the circulation flow rate of the entire treatment liquid.

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 the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in the above-mentioned Japanese Patent Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

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 washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
on Engineers Volume 64, P, 248-25
3 (May 1955 issue).

In the processing of the color photosensitive material of the present invention, JP-A-62-
288,838 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8,542, and other benzotriazoles, as well as other antibacterial and fungicides by Hiroshi Horiguchi, Chemistry J
(1986) Sankyo Publishing, Hygiene Technology Complete Edition, “Microbial Sterilization, Disinfection, and Anti-Mildew Technology J (1982) Kogyo Gijutsudai, Japan Antibacterial and Antifungal Society Report,” Encyclopedia of Antibacterial and Antifungal Agents J (1986) Fungicides can also be used.

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 20 minutes.
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 Nos. 57-8543 and 58-14834
All known methods described in No. 60-220345 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. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

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

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, 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 the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719.492, JP-A-53-1
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
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547,
and 5g-115438, etc.

Various processing solutions in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

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 European Patent No. 9-218443, European Patent No. 61-238056, European Patent No. 210,660A2, and the like.

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

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/rrf units, and for silver halide, it indicates the coating amount in terms of silver.However, for sensitizing dyes, the halogen in the same layer The coating amount per mole of silveride is shown in moles.

(Sample 101) 1st layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.75 2nd layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.18EX-1
0,070 EX-30,020 EX-12 [1-3 B5-1 B5-2 Third layer of gelatin (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ EX -2 EX-14 EX-10 EX-15 [1-2 2,0X10-3 0.080 0.10 0.10 0.020 1.58 Silver 0.25 Silver 0.25 6.9X10-' 1. 8X10-' 3, lX10-' 0.170 0.170 0,020 0.035 0.070 0.070 B5-1 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye I Sensitizing dye ■ Sensitizing dye m EX-2 EX-14 EX-3 EX-10 EX-15 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion sensitizing dye I Sensitizing dye ■ 0.060 1.40 Silver 1 .00 5, I 60 5.1X10-'1.4X10-' Sensitizing dye■ EX-2 EX-3 EX-4 EX-15 B5-1 B5-2 Gelatin 6th layer (intermediate layer) EX-5 B5-1 Gelatin 7th Layer (first green-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ EX-1 EX-6 2,4X 10-' 0.097 0.010 0.080 0.010 0 .22 0.10 2.25 0,040 0.020 1.13 Silver 0.15 Silver 0,15 3.0X10-' 1,OX 10-' 3.8X 10-' 0,021 0.16 EX- 7 EX-8 EX-9 HBS-1 ) (BS-3 8th gelatin layer (second green-sensitive emulsion layer) Emulsion C Sensitizing dye■ Sensitizing dye V Sensitizing dye■ EX-6 EX=7 EX-8 EX-9 B5-1 B5-3 Gelatin 9th layer (third green-sensitive emulsion layer) Emulsion E Q, 030 0.025 0.14 0.30 [+, 005 1.22 Silver 0.45 2, lX10- '?, OX to bow 2.6XlO-' 0.064 0.026 0.018 Q, 042 0,225 5.0XlO-" 0.90 Silver 1.20 Sensitizing dye■ Sensitizing dye V Sensitizing dye■ EX-1 EX-11 EX-13 B5-1 B5-2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver EX-5 B5-1 Gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Sensitizing dye■ EX-8 3,5X10-'8.0X10-' 3,OX 10-' 0,025 0.10 Q,0L5 0.25 0.10 2.25 Silver 0.050 o, og.

O,03G 1.14 Silver o, og.

Silver 0.070 Silver 0.070 3.5X 10-' 0,042 B5-1 Gelatin 12th layer (second noble emulsion layer) Emulsion G Sensitizing dye 3rd blue-sensitive emulsion layer) Emulsion H Sensitizing dye ■ B5-1 Gelatin 14th layer (first protective layer) Emulsion I 0.70 0.28 2.15 Silver 0.45 2, IX 10-' 0.15 F, OX 10-" 0,050 1.33 Silver 0,77 2.2X 10-' 0.20 0.070 1.20 0.20 0.11 0.17 HBS-15,0XIO-" Gelatin 1. 47th 15th
Layer (second protective layer) ) (-1 silver 0.61 B-1 (diameter 1.7μa+) 5.0X10
-”B-2 (diameter 1.7μ+o) o,
t.

B-30,1O 3-10,20 Gelatin 1.90 Furthermore, W-1 is added to the entire layer to improve preservability, processability, pressure resistance, anti-mold/bacterial properties, antistatic properties and coatability. , W-2
, W-3, W-4, B-4, B-5, F-1, F-2,
F-3, F-4, F-5, F-6, F-7, F-8, F
-9, F-10, F-11, F-12, F-13, F-
14 and iron salts, lead salts, gold salts, platinum salts, iridium salts,
Contains rhodium salts.

EX-1 EX EX-3 H Shi1 EX-4 H EX-5 CJ+2(n) EX-6 EX-7 EX-8 EX-9 EX-10 Shi1 EX Js JIs C2H5O5O3fEl EX-13 Shi■ EX-14 H tH- EX-15 [1-2 11) aF+q x : y=70:30 (wL%) B5-1 Tricresyl phosphate B5-2 Jean-n-butyl phthalate sensitizing dye I Exacerbating dye■ Exacerbating dye■ Sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ 2:1 (molar ratio mixture) W-2 n=2-4 Thickness and support of blue-sensitive emulsion layer of sample 101 prepared as above The total dry film thickness excluding the subbing layer of the body and support is:
They were 5.2μ and 25.4μ, respectively (see Table 1).

・Next to Samples 102 to 110, change only the amount of gelatin and change everything else so that the dry film thickness of the blue-sensitive emulsion layer and other layers becomes the value shown in Table 1A, based on sample 101. Samples were prepared using chicken and pear. However, only the hardening agent H-1 was prepared based on the amount of H-1 relative to the amount of gelatin in Sample 101, and the amount added per unit weight of gelatin was adjusted to be constant.

-Yellow coupler Y-4 represented by general formula (1) of the present invention used in the 11th to 13th layers of samples io1 to 110 of samples 111 to 120
Samples were prepared by replacing No. 8 with the comparative yellow coupler shown below in an equal molar amount and using the same methods as Nos. 101 to 110 in all other respects.

These prepared samples were cut and processed and used in the following experiments.

Samples Nos. 111 to 120 are samples in which the yellow coupler Y-4 of the present invention used in the 11th to 13th layers of Nos. 101 to 110 was replaced in equimolar amounts with the following comparative coupler.

Comparative couplers Compound examples described in U.S. Pat. No. 3,265,506 (3
A coupler (1-1) into which the following leaving group was introduced according to the synthesis method described in JP-A No. 47-26133 was subjected to wedge exposure to white light (color temperature of the light source 4800°K), and an automatic developing machine was used. The sample was processed after a separate imagewise exposure was processed using the method described below until the cumulative replenishment amount of the color developing solution was three times the volume of the mother liquor tank.

The density of the processed sample was measured, and from the characteristic curve measured with blue light, one of the photographic characteristic values was the logarithm of the reciprocal of the exposure that gave the minimum density (Ds + in) + 0.2. I asked for it. This is taken as the sensitivity (SS).The other is the exposure amount from the exposure amount that gives a density of 0.2 in the minimum density to the high exposure amount side.The density at the exposure amount of ogE = 1.0 ( D,) was read.

The obtained S and D8 are based on the value of sample 110, and the difference (ΔS,) is calculated for S, and Dl
The ratio (percentage) was calculated. For ΔS, the larger the value of +, the higher the sensation, and for D, a value exceeding 100 represents a higher density.

(1-2) The density of the sample treated with white light wedge exposure was measured, and then the sample was stored for 7 days at 80° C. and 70% RH, and the density was measured again.

From these characteristic curves, read the density after storage at the exposure amount that gives the minimum density + 1.5 on the characteristic curve measured with blue light before storage under high temperature conditions, and The ratio (D%) was calculated based on the minimum concentration +1.5 concentration.

As for the numerical value, the larger the value, the more robust the color image.

These results are summarized in Table 1B.

Processing process Processing time Processing temperature Replenishment amount 1 Tank capacity Color development 3 minutes 05 seconds 38.0℃ 600 yen
51 bleaching 50 seconds 38.0℃
140 proof 31 bleach fixing 5
0 seconds 38.0℃ □ 31 fixation
50 seconds 38.0℃ 420m1!
3 I! Wash with water 30 seconds 38.0℃
980m1! 2A stable (1)
20 seconds 38,0℃ 21 stable (2
) 20 seconds 38,0℃ 560m1 2
1 Drying 1 minute 60℃ The main replenishment amount is the amount per 1 m' of photosensitive material.The water sinking is from (2) to (1
), all the overflow of the washing water was introduced into the fixing bath. The bleach-fixing bath can be refilled by connecting the top of the automatic processor's bleach tank and the bottom of the bleach-fixing tank, and the top of the fixing tank and the bottom of the bleach-fixing tank with pipes, and supplying replenisher to the bleach tank and fixing tank. All of the overflow liquid generated was allowed to flow into the bleach-fix bath. The amount of developer brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the washing process are calculated per 1 ms of photosensitive material. It was 65mf, 501d, 50m1', 50-. Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

(Color developer) Diethylenetriaminepentaacetic acid 2.0 1-hydroxyethylidene-3,3 1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 2-Methyl-4-[N-ethyl 2 .2 Replenisher (gi 3.3 39.0 5.2 Mother liquor (g) 3.3 6.0 0.4 3.9 37, -5 1.4 1.3 mg 2.4 4.5 Roux N- (β-thyl)amino] Add water to pH Hydroxylaniline sulfate], 0IV 10,05 1.0! 10,15 (Bleach solution) 1.3-Propylenediaminetetraacetic acid Ferric ammonium hydrate Ammonium bromide Ammonium nitrate Add hydroxyacetic acid and aqueous acetic acid to pH [adjust with 7 ammonia water] Mother liquor (g) 144, 0 84.0 17.5 54.2 1.01 Replenisher (g) 206, 0 120.0 25.0 90. 0 80.0 1.01 3.60 (Bleach-fixing solution mother solution) A 15:85 mixture of the above self-bleaching solution mother solution and the following fixing solution mother solution (fixer solution) Mother solution (g) Replenisher solution (g) Ammonium sulfite 19 .0 57.0 Ammonium thiosulfate aqueous solution 280n!! 40ml (700g#') Add imidazole ethylenediaminetetraacetic acid water to pH [adjust ammonia water, acetic acid 7m] 28.5 85,5 12.5 37.5 1, Of 1 , 01! ?, 40 7.45 (Washing water) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin. (The same Amberlight I RA-
Water was passed through a mixed bed column packed with 400) to reduce the concentration of calcium and magnesium ions to 3 mg/j! Treated as follows, followed by 20 mg of sodium incyanurate dichloride
/l and 150 mg/f of sodium sulfate were added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common formalin for mother solution and replenisher solution (37%) Sodium toluenesulfinate polyoxyethylene-p 1,000 tunonylphenyl ether (average degree of polymerization 10) Add monosodium ethylenediaminetetraacetic acid salt solution to pH (unit: g) 1. 2d 013g 0.2 0.05 1,0! 7.2 From Table 1B, samples in which the yellow coupler represented by the general formula (1) was used to reduce the dry film thickness of the blue-sensitive emulsion layer and the total dry film thickness excluding the support and the undercoat layer of the support 10
2 to 110 are the corresponding samples 112 to 120 of the comparison sample
It can be seen that, compared to Sample 101.111, it provides clearly higher sensitivity and higher color density, and is superior in color image fastness under conditions of high temperature and high humidity. In particular, it can be seen that the coupler of the general formula (I) increases (and thus improves) the above-mentioned property improvement effect by reducing the dry film thickness.

Example 2 The color photosensitive material of Example 1, sample No. 107 was used as the basic composition, and the yellow coupler Y-4 in the 11th to 13th layers was variously changed as shown in Table 2, and the yellow coupler Y-4 was equimolarly loaded with Y-4. A sample was prepared by replacing it.

These prepared samples were exposed and developed according to the method described in Example 1, and the photographic characteristic values, ΔSl, and
I asked for These results are also shown in Table 2. At this time, each comparison sample was used as the reference sample, as shown in Table 2.

From Table 2, it can be seen that when the dry film thickness is within the range that satisfies the constituent requirements of the present invention, the result of replacing one type of coupler with an equimolar amount provides higher sensitivity and higher color density compared to conventional couplers. I understand that.

In addition, couplers whose active positions are substituted with leaving groups represented by formula [Y-1] exhibit higher sensitivity and color density compared to leaving groups represented by formulas [Y-23 and [Y-3]. It is also possible to show.

Since the above-described coupler of the present invention provides high color density, it can be seen that the amount of coated coupler [mol/I] can be clearly reduced compared to conventional couplers.

/ Example 3 On a subbed cellulose triacetate film support,
Sample 301, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is g/g for silver halide and colloidal silver.
The amount of silver expressed in %, and the amount expressed in g/n for coupler additives and gelatin, and the amount expressed in moles per mole of silver halide in the same layer for sensitizing dyes. Ta.

1st layer: antihalation layer black colloidal silver silver coating amount 0.20 gelatin 2.02 UV-10,
11 UV-20,20 Cp d -14,0X10-" Cp d -21,9X10-" S o I v -10,30 S o I v -21,2X10-2 2nd layer: Intermediate layer fine particle iodobromide Silver (Ag11.0 mol%, equivalent sphere diameter 0.0
7μm) Silver coating amount 0.15 1.00 6.0X10-"2.0X10-" Gelatin ExC-4 pd-3 3rd N = 1st red-sensitive emulsion layer Silver iodobromide emulsion (Ag15.0 mol%, surface High Agl type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grain, diameter/thickness ratio 7.5) Silver coating amount Silver iodobromide emulsion (AgI 4.0 mol%, internal high Agl) Type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 18%, dodecahedral particles) 0.42 Gelatin x S-1 EχS m Coating amount 0.40 1.77 4.5X10-'mol 1.5X10 -'Mole 4.0X10-'Mole 0.65 1.0X10-"2.3X10-" 0.32 xS-3 ExC-1 ExC-3 ExC-4 olv-1 4th layer: 2nd red light Emulsion layer Silver iodobromide emulsion (Ag 18.5 mol%, internal high Agl type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3.0) Silver coating amount 0.85 0.86 3.0X10-'mol 1.0X10-'mol 3.0X10-'mol 0.13 6.2X10-"4.0X10-" 0.10 Gelatin xS-1 xS-2 xS-3 ExC-1 ExC-2 ExC-4 olv-1 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion (Ag1 11.3 mol%, internal high Agl
Mold, equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1.50 Gelatin 1. o2E x
S -12,0xlO-'Mole Ex S -26,0
X10-'Mole Ex S-32,0
d -48,0xlO-" S o l v -1s, oxlo-" Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (Ag 15.0 mol%, surface height Agl type, equivalent sphere diameter 0.9 μm , coefficient of variation of equivalent sphere diameter 21%, tabular grain, diameter/thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl type, equivalent sphere diameter 0. 4 μm, coefficient of variation of equivalent sphere diameter 18%, dodecahedral particles) Silver coating amount 0.16 1.10 5.0X10-' mol 2.0X10-' mol 1, OX 10-' mol 0.50 0. 10 3.5X10-" 0.20 3.0X10-" Gelatin xS-4 xS-5 xS-6 xM-1 xM-2 xM-5 olv-1 olv-3 8th layer: 2nd green-sensitive emulsion layer Silver bromide emulsion (Ag 18° 5 mol%, internal high Agl type, equivalent sphere diameter 1.OlIm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3.0) Silver coating amount o, 57 0.40 3.5X10-' mol 1.4 X 10-' morph, QXlo-' mol 0.12 7.1 xS-6 xM-1 xM-2 EχM-3 olv-1 olv-3 9th layer: Intermediate layer gelatin olv-1 107i: 3rd green-sensitive emulsion layer Silver iodobromide emulsion (Agl 11.3 mol%, Internal height Ag
T type, equivalent sphere diameter 1.4μm, coefficient of variation of equivalent sphere diameter 28%
, plate-shaped particles, diameter/thickness ratio 6.0) 2.0X10-" 0.50 Silver coating 1 1.30 Gelatin 1.03Eχs
-42,0xlO-'mol Ex S -58,0xlO-'mol Ex S-
68,0xlO-s mol Ex M -44,5X10
-' E x M -61,0xlO-2 E x C-24,5X10 bow Cp d -51,0X10-" S o I v -10,25 11th layer: Yellow filter layer gelatin D, 45Cp
d -55,2X10-2 Solv-1, 0,12 12th layer: Intermediate layer gelatin 0.40Cpd
-30,10 13th layer: First blue emulsion layer silver iodobromide emulsion (Ag 12 mol%, average -Agl type, equivalent sphere diameter 0.55 pm, coefficient of variation of equivalent sphere diameter 25%, tabular) Particles, diameter/thickness ratio 7.0) Silver coating amount 0.20 Gelatin 1.13E x
S -73,0xlO-'Mole Ex Y -10,6
0 Y -602,OX 10-" 5olv-10,48 14th N: Second blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 19.0 mol%, internal high Ag
T type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 16%
, octahedral particles) Gelatin xS-7 EχY-1 olv-1 15th layer: Intermediate layer fine grain silver iodobromide (Agl i! Coating amount 0.19 0.39 2.0X10-' mol 0.22 0.22 2 mol%, uniform Agl type, equivalent sphere diameter 0.13 μm) silver coating ii
O,20 Gelatin 0.35 16th layer: 3rd blue-sensitive milk flIN Silver iodobromide emulsion (Ag1 14.0 mol%, internal high AgI
Type, equivalent sphere diameter 1.7 ym, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 5.0] iJ! Coating amount 1.55 Gelatin 0.97E x
S-81,5X10-'mol ExY-10,21 Solv-10,22 171i: 1st Gi layer gelatin 1.65UV-1
0,13 UV-20,21 S o l v -11,0xlO-” S o I v
-21,0X10-" 18N: 2nd protective layer fine grain silver chloride (equivalent sphere diameter 0.07 μm) silver coating 1
0.36 Gelatin 0.70B-1
(Diameter 1.5μm) 2.0X10-”B-
2 (diameter 1.5um) 0.15B, -
33,0X10-2 W-12,0xlO-2 H-10,35 CPd-71,00 This sample contains 1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl- p-hydroxybenzoate (approximately 1.000 p
pm), and 2-phenoxyethanol (about 1
0.000 ppm) was added. Furthermore, B-4, B
-5, W-2, W-3, F-1, F-2, F3, F-4
, F-5, F-6, F-7, F-8, F-9, F-10
, F-11, F-12, F-13 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

v U■ xC-1 H xC-2 H (n)C+□H2゜ xC xC (])l xC xM ExM-2 ExM-3 ExM-4 I Shil ExM ExM xY I l pd pd Pd-3 pd Pd pd CJ+s pd CH.

olv o lv olv (t) 511 xS-1 ExS xS-3 xS xS-5 ExS xS xS W n=2~4 C)1. =c) l-50□-CH, -CONH-CH2
C)1. =cH3o, -C)l.

C0II) I-CH.

Samples 302 and 303 were prepared by changing the 5olv-1 used in the blue-sensitive emulsion layers of the 13th, 14th, and 16th layers as shown in Table 3A.

Subsequently, the yellow coupler ExY-1 in the blue-sensitive emulsion layer of Samples 301 to 303 was replaced with the coupler Y48 of the present invention in an equimolar amount, and Samples 304 to 306 were prepared without changing anything else. The dry film thickness at this time is also shown in Table 3A.

Samples 301 to 306 prepared as described above in Table 3A were cut and
Processed to produce (1-1) to (1-2) described in Example 1
Its performance was evaluated using a method similar to that used in the previous experiment.

The processing steps and processing solution composition at this time are shown below, but the sample used in the experiment was a sample that was separately subjected to imagewise exposure until the cumulative replenishment amount of color developer was three times the mother solution tank capacity. After the treatment, the treated sample was used.

Note that the photographic performance ΔS and ΔD were calculated based on sample 301.

Subsequently, samples were prepared by adjusting the coating amount of the blue-sensitive emulsion layer of Sample 302 and Samples 304 to 306 so as to match the gradation of the characteristic curve of Sample 301 measured with blue light. Using this sample, the MTF pattern was exposed to sunlight, the above-described processing was performed, and the MTF value of the magenta color image was measured to evaluate the sharpness. The measurement of MTF is described in T. H. James, ed., “T.
the theory of the photograp
hic Process” (4th Ed, , M
It was carried out according to the method described in (cMillan).

The above results are summarized in Table 3B.

Processing method Color development 3 minutes 15 seconds 38℃ Bleaching 6 minutes 30 seconds 38℃ water washing
2 minutes lO seconds 24℃ constant @ 4 minutes 20 seconds 38
℃ Water washing (1) 1 minute 05 seconds 24℃ 33 sets 25171i (200d 5m1 Countercurrent piping system from (2) to (1) % formula % The replenishment amount is per 35 mm width 1 m length Next, the composition of the processing liquid is write down

(Color developer) 10β 20β lOρ 20β lOρ 10β Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 10 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Bromide Potassium 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4-(N-ethyl-N-β hydroxyethylamino)-2-methylaniline sulfate 4.5 Add water 1.0i pH 10, 05 (Bleach solution) 2.8 5.5 1.0 β 10.10 Mother liquor (g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 Replenishment amount (g) 120.0 Ethylenediaminetetraacetic acid disodium salt odor Ammonium chloride Ammonium nitrate Ammonia water (27%) Add water and H (Fixer) 10.0 11.0 140.0 +60.0 30.0 35.0 6.5ml 4.0 1.09 1.0 ℃ 6.0 5.7 Mother liquor (g3 Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (700g/ρ) 170.01 Add Th2 water 1 .0ρ pH6,7 (Stable liquid) 0.7 8.0 200,0m2 1.0ρ Mother liquor (g) Replenisher (g) Formalin (37%) 2.0m1 3.07d Polyoxyethylene-p-monononyl Phenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid 0.05 - Add sodium brine, p at 1.0, 8 5.0-8.00.45 0.08 1.0 β 5.0- 8.0 As is clear from Sample Nos. 304 to 306 in Table 3B, the yellow coupler of general formula (I) has a dry film of all layers, excluding the blue-sensitive emulsion layer, the support, and the subbing layer of the support. When the thickness of the sample falls within the specifications of the present invention, it provides higher sensitivity and higher density than comparative samples, has excellent color image fastness, and provides good results in terms of image quality and sharpness.

Furthermore, in samples using the coupler of general formula (1), the amount of high-boiling organic solvent added per unit weight of the coupler is small (even if the amount of high-boiling organic solvent added is small, the change in sensitivity and color density is small, so-called excellent It is also clear that the amount of coupler applied can be reduced since high color density can be obtained using a coupler.

In addition, in sample 301, so-called oil seepage and sweating phenomena were observed on the coating film surface of the sample in which the color image fastness experiment was conducted, but no abnormalities were observed in the other samples. . This shows that the coupler of general formula (I) has excellent compatibility with high-boiling point organic solvents, and that samples using this coupler have excellent stability of the dispersion in the coating film.

(Effect of the invention) By using the acetamide type yellow coupler represented by the general formula (I), the dry film thickness of the blue-sensitive emulsion layer is 5.0 μm or less, and furthermore, the entire layer excluding the support and the undercoat layer is A color photosensitive material having a dry film thickness of 25.0 μm or less provides high sensitivity and color density, and the resulting yellow image is robust and has excellent image quality. In particular, it is possible to provide a color photosensitive material that can reduce the amount of yellow coupler applied since it provides high color density. Furthermore, even if the amount of high-boiling point organic solvent added to the coupler is reduced, it still shows the above-mentioned excellent performance, especially with small fluctuations in photographic performance. It is possible to provide a color photosensitive material that satisfies the above requirements and can further reduce the dry film thickness.

Procedural amendment (spontaneous) August 16, 1991

Claims (2)

[Claims] (1) A silver halide color photographic light-sensitive material consisting of at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a non-light-sensitive layer, respectively, on a support. In at least one of the blue-sensitive silver halide emulsion layers, an acyl group has the following general formula (I
), and the total dry film thickness of all the blue-sensitive silver halide emulsion layers is 5.0 μm or less. Silver chemical color photographic material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a monovalent group.Q, along with C,
-Represents a group of nonmetallic atoms necessary to form a 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle having at least one heteroatom selected from N, O, S, and P in the ring. However, R_1 is not a hydrogen atom and does not combine with Q to form a ring. ) (2) The silver halide color photographic light-sensitive material according to claim 1, characterized in that the dry film thickness of the support and all layers of the support excluding the undercoat layer is 25.0 μm or less. Silver chemical color photographic material.