JPH043053A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve film surface characteristics and sharpness by forming on layer of nonphotosensitive hydrophilic colloidal layer on the outermost layer, providing photosensitive silver halide emulsion layers contg. yellow couplers and specifying the weight ratio of the org. solvent incorporated into the emulsion layers to the yellow couplers to <=0.4. CONSTITUTION:This photosensitive material has one layer of the nonphotosensitive hydrophilic colloidal layer on the outermost layer furthest from a base and is provided with the photosensitive silver halide emulsion layers contg. the yellow couplers adjacent thereto. The weight ratio of the high boiling org. solvent incorporated into the photosensitive silver halide emulsion layers to the yellow couplers is specified to <=0.4. Namely, the two-layered protective layers which are heretofore plural and have problems in stable production are made into the simple one-layer constitution; in addition, the ratio of the high boiling org. solvent in the photosensitive emulsion layers contg. the yellow couplers applied and provided relatively near to the front surface is decreased as a means for obviating the deterioration in the film surface characteristics. Adhesiveness and perspiration characteristic are improved in this way and the color photosensitive material having the excellent sharpness is obtd. by the stable production process.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, to improvement of film surface characteristics and sharpness of the /'% silver halide light-sensitive material. This relates to improvement in performance and stable production.

(Prior Art) Generally, in a silver halide photographic light-sensitive material, a protective layer containing a hydrophilic colloid such as seratin as a binder is coated on a silver halide emulsion layer. However, the silver halide photosensitive materials produced in this way may cause adhesion due to contact with other photosensitive materials or other substances during manufacturing, storage as a product, processing, and storage after processing. There is. To solve this problem, a protective layer containing particles of inorganic substances such as silicon dioxide, titanium dioxide, calcium carbonate, and silver halide, and organic substances such as polymethyl methacrylate and cellulose acetate propionate is used. A well-known method is to coat the surface and make the surface matte. However, this matting causes problems such as the surface slippage of the silver halide photosensitive material becoming poor and the photosensitive material being easily scratched, and film transport in cameras and projectors becoming worse. It is difficult to prevent adhesion.

Furthermore, in general, the outermost layer or the hydrophilic colloid layer or silver halide emulsion layer near the outermost layer contains an ultraviolet absorber or a color forming coupler dissolved in a high-boiling organic solvent, which further deteriorates the adhesive properties. I'm letting you do it. In particular, when stored under high temperature and high humidity, there is a phenomenon in which ultraviolet absorbers or coloring couplers dissolved in high-boiling organic solvents become oily particles and ooze out onto the film surface (sweating phenomenon). From this point of view, the situation is extremely unfavorable.

As a method for improving the surface characteristics of these films,
No. 46, a method has been proposed and implemented in which the outermost protective layer is separated into two layers and the content of a high-boiling organic solvent or oily substance in the outermost layer is minimized. However, problems such as the complexity of manufacturing due to the large number of calendars and the deterioration of uniform coating properties have arisen, and the result has not always been satisfactory.

On the other hand, in recent years, silver halide photosensitive materials, especially photographic photosensitive materials, have become satisfactory with ultra-high sensitivity photosensitive materials such as 15O1600, and prints with large magnifications suitable for small format cameras such as 110. There is a growing demand for sensitive materials with excellent sharpness and graininess.

Many methods for improving sharpness have been known in the past, one of which is disclosed in U.S. Pat. 409°433, a method for reducing the thickness of photographic emulsion layers and suppressing light scattering, and other techniques include DIR, which releases development inhibitors.
A method of adding a compound to a sensitive material, for example, as described in US Patent No. 3.
227. No. 554, No. 3,701,783, No. 3,
No. 703゜375, No. 4,052,213, No. 4,1
38.258, 4,146,396 and 4.
477.563, and U.S. Pat. No. 4,248,962, 4.421.845
It is known to add a DIR compound to a sensitive material via a timing group as described in No. Naturally, the above-mentioned dyeing method is accompanied by a significant decrease in sensitivity, making it difficult to apply it to high-sensitivity light-sensitive materials in which high sensitivity is essential.

When applied to low- or medium-sensitivity sensitive materials, for example, if the size of silver halide grains is increased to compensate for the decrease in sensitivity due to dyes, the graininess naturally deteriorates, which has both advantages and disadvantages.

Further, due to its characteristics, DIR compounds have a desensitizing effect and a softening of the tone, and there are naturally limitations on how they can be used. The most common method for improving sharpness is to reduce the thickness of the silver halide emulsion layer.

As a means to reduce the thickness of the emulsion layer, Japanese Patent Publication No. 45-4
No. 0155, No. 46-22513, JP-A-57-94
The polymer couplers disclosed in No. 752 and No. 58-28745 have made it possible to make the layer thinner, and the sharpness has been significantly improved, but a technique for making the layer even thinner is an eternal research subject.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide color photosensitive material that has improved adhesion and perspiration properties.
The second objective is to provide a color photosensitive material with excellent sharpness, and the third objective is to provide a stable product using a stable manufacturing method.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color light-sensitive material having a silver halide emulsion layer and a substantially non-light-sensitive hydrophilic colloid layer on a support. The outermost layer has one non-photosensitive hydrophilic colloid layer, adjacent to which a photosensitive silver halide emulsion layer containing a yellow coupler is provided. It has been found that the above problems can be solved by a silver halide color photographic light-sensitive material in which the weight ratio of the high boiling point organic solvent to the yellow coupler is 0.4 or less.

The present invention is a yellow coupler that is applied relatively close to the surface as a means to change the protective layer from a two-layered protective layer, which was complicated and had problems in terms of stable production, to a simple one-layered one and not to cause deterioration of the film surface characteristics. We have found a method for reducing the amount of high-boiling organic solvent in a photosensitive emulsion layer containing .

The hydrophilic colloid materials used as binders in the protective layer of the present invention are gelatin and phthalated gelatin, which is a gelatin derivative. The protective layer of the present invention may contain inorganic substances such as silica, magnesium oxide, calcium carbonate, polymethyl methacrylate cellulose acetate chlorobionate, or an alkali consisting of acrylic acid and methyl acrylate as disclosed in JP-A-51-135958. Soluble polymer particles and the like can be used as a matting agent. The average size of these particles is preferably about 0.5 to 10 μm, particularly preferably 1 to 6 μm.

The protective layer of the present invention can contain an ultraviolet absorber, a high-boiling organic solvent, a slip agent, an organic fluoro compound, a surfactant, or a hardening agent.

Although the thickness of the protective layer of the present invention is not particularly limited, it is preferably 0. The thickness is 4 to 6 μm, more preferably 0.6 to 4 μm. The yellow coupler to be contained in the silver halide emulsion layer of the present invention can be added by the method described below.
0, preferably 0. It is 2-0.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper. Among these, it can be preferably used for color photosensitive materials for photography such as color negative films and color-positive films.

When the present invention is used in color photographic materials, it can be applied to photosensitive materials with various configurations and photosensitive materials in which layer configurations and various color materials are combined.

A typical example is illustrated below. JP 47-49031, JP 49-3843, JP 50-21248, JP 59-58147, JP 59-60437,
JP 60-227256, JP 61-4043, JP 61-43743, JP 61-42657
A combination of the coupling speed and diffusivity of a color coupler and the layer structure, as shown in No. Japanese Unexamined Patent Publication No. 49-154
No. 95, U.S. Pat. No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, Japanese Patent Publication No. 53-3701
No. 7, Special Publication No. 53-37018, Japanese Patent Publication No. 51-490
No. 27, JP-A-52-143016, JP-A-53-9
No. 7424, JP-A-53-97831, JP-A-62-
200350 and JP-A No. 59-177551, which stipulate the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers with different color sensitivities.

Next, yellow couplers that can be used in the present invention will be described.

Among yellow couplers, pivaloylacedoanilide yellow couplers have better photofading resistance than benzoylacedoanilide yellow couplers, and have recently been used in color paper and other color negative photosensitive materials. However, pivaloylacedoanilide type yellow couplers generally have lower coupling activity with the oxidized form of aromatic primary amine developers than benzoylacedoanilide type yellow couplers, and moreover, they have a lower coupling activity with the oxidized product of aromatic primary amine developers. Since the molecular extinction coefficient of the azomethine dye is 20% to 30% lower, in order to match the tone with the penzoylacetanilay F type coupler on the photographic characteristic curve, the coupler coating amount and/or silver halide coating amount must be increased by 50%.
% to 100%, which inevitably leads to an increase in emulsion film thickness, resulting in deterioration of sharpness, deterioration of processability, and increase in cost. Therefore, color photography such as color negative photosensitive materials In light-sensitive materials for use in photosensitive materials, it is desirable to use benzoyl type yellow couplers, and among the benzoyl type yellow couplers, 2-equivalent couplers are preferable.

The benzoylacedoanilide type 2-equivalent yellow coupler used in the present invention will be explained in detail below.

The benzoylacedoanilide type 2-equivalent yellow coupler used in the present invention is preferably represented by the following general formula (Y).

General formula (Y) In the general formula (Y), R represents an aryl group, R2 represents a hydrogen atom, a halogen atom, an alkoxy group, or an aryloxy group, and R2 represents a halogen atom, an alkyl group, an alkoxy group, or an alkoxy group. , an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a ureido group, or an alkoxycarbonylamino group, where X is a nitrogen atom or a sulfur atom, and A heterocyclic group, an aryloxy group, an alkoxy group, an arylsulfonyloxy group, an arylsulfonyloxy group, or a heterocyclicoxy group bonded to the coupling active position of the yellow dye-forming coupler represented by formula (Y), and l is Each represents an integer from θ to 4, provided that
When i is plural, R1 may be the same or different.

In the general formula (Y), R preferably has 6 carbon atoms.
~30 optionally substituted aryl groups, and the substituents include halogen atoms (e.g. fluorine, chlorine,
bromine, iodine], alkyl groups (for example, methyl, ethyl,
j-propyl, S@C-butyl, t-butyl, cyclohexyl, allyl, t-octyl, n-dodecyl, trifluoromethyl), alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, n-tetradecyloxy, penzyloxy) , nido 0 group, amino group (eg, methylamino, diethylamino, pyrrolidyl), carbonamide group (eg, acetamide, benzamide), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, dodecanesulfonamide), and the like.

Examples of R1 include phenyl group, P-)lyl group, 〇-tolyl group, 4-chlorophenyl group, 2-chlorophenyl group, 4
-Nitrophenyl group, 3-nitrophenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl L4-methoxy-3-[2-(2,4-di-pentylphenoxy)butanamide]- Examples include phenyl group, 4-methoxy-3-methanesulfonamidophenyl group, and the like.

In the general formula (Y), R8 is a hydrogen atom, a halogen atom (
aR representing an optionally substituted alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 3 o carbon atoms; for example, fluorine, chlorine, bromine, iodine);
When l represents an alkoxy group, substituents include halogen atoms (e.g. fluorine, chlorine, bromine, iodine), alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, n-butoxy, n-hexyloxy, n- octyloxy, 2-ethylhexyloxy, n-dodecyloxy, n-tetradecyloxy, n-hebodecyloxy), and the like. When R2 represents an aryloxy group, its substituent includes a halogen atom (e.g. fluorine, chlorine,
Examples include bromine, iodine), alkyl groups (eg, methyl, ethyl, inpropyl, t-butyl), and alkoxy groups (eg, methoxy, ethoxy). Examples of R□ include hydrogen atom and halogen atom, as well as methoxy group, ethoxy group, n-
butoxy group, methoxyethoxy group, benzyloxy group,
Examples include n-tetradecyloxy group and phenoxy group.

In general formula (Y), R1 is preferably a halogen atom (
(e.g. fluorine, chlorine, bromine, iodine), 1 to 3 carbon atoms
0 alkyl group, aryl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, 2 to 30 carbon atoms
an alkoxycarbonyl group, an aryloxycarbonyl group having 7 to 30 carbon atoms, a carbonamide group having 1 to 30 carbon atoms, a sulfonamide group having 1 to 30 carbon atoms,
Carbamoyl group having 1 to 30 carbon atoms, number of carbon atoms θ to
30 sulfamoyl group, an alkylsulfonyl group having 1 to 30 carbon atoms, an arylsulfonyl group having 6 to 30 carbon atoms, a ureido group having 1 to 30 carbon atoms, or an alkoxycarbonylamino group having 2 to 30 carbon atoms. .

When the above substituent contains an alkyl group, the substituent includes a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a cyano group, a nitro group, an aryl group (e.g., phenyl, P-tolyl, 2-methoxyphenyl). , alkoxy groups [e.g. methoxy, ethoxy, butoxy, benzyloxy, n-hexyloxy, 2-ethylhexyloxy,
n-octyloxy, n-decyloxy, n-dodecyloxy, n-dodecyloxyethquine, 2-(2,4-
di-pentylphenoxy)ethoxy], alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, n-dodecyloxycarbonyl), carbonamide groups (e.g. acetamide, dodecanamide, benzamide), sulfonamide groups (e.g. methanesulfonamide, dodecanesulfonamide, toluenesulfonamide), carbamoyl groups (e.g. N,N-dimethylcarbamoyl, N-methyl-N-
octadecylcarbamoyl, N-F"decyl-N-phenylcarbamoyl), aryloxy groups (e.g. phenoxy, P-dodecyloxyphenoxy, 2,4-di-t
-pentylphenoxy, P-1-octylphenoxy)
, alkylthio groups (e.g. methylthio, benzylthio)
, arylthio groups (e.g. phenylthio, p-dodecyl phenylthio), alkyl or arylsulfonyl groups (e.g. methylsulfonyl, dodecylsulfonyl, 2
-hexyldecylsulfonyl, P-)lylsulfonyl,
p-dodecylphenylsulfonyl, p-dodecyloxyphenylsulfonyl), sulfinyl groups (e.g. methylsulfinyl, phenylsulfinyl), imide groups (e.g. succinimide, maleimide, phthalimide)
, heterocyclic groups (e.g. pyridyl, imidazolyl, furyl)
etc. Furthermore, when the above substituent (R1) contains an aryl group, the W substituent includes a halogen atom (e.g., fluorine, chlorine, bromine, iodine), an alkyl group (e.g., methyl, ethyl, i-propyl, allyl, benzyl, t-
butyl, 5ec-butyl, cyclopentyl, cyclohexyl, t-octyl, n-decyl, n-dodecyl), aryl groups (e.g. phenyl, P-)lyl), alkoxy groups (e.g. methoxy, ethoxy, n-dodecyloxy)
, alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl), and the like.

In the general 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 specifically a monocyclic or condensed 5- to 7-membered heterocyclic ring which may be substituted, examples of which include succinimide, maleimide, phthalimide, diglycolimide, Virol, pyrazole, imidazole, 12.4-) lyazole, tetrazole, indole, indazole, benzimidazole,
Benzotriazole 1, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-
2,4-dione, imidazolidin-2-one, oxazolin-2-one, thiazolin-2-one, benzimidacillin-2-one, benzoxazolin-2-one, benzothiapurin-2-one, 2- Vilorin-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-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4-thiazolidin-4-one, etc.
These heterocycles may be substituted, such as halogen atoms (e.g. fluorine, chlorine, bromine, iodine).
, hydroxyl group, nitro group, cyano group, carboxyl group, sulfo group, carboxylade group, sulfonate group,
Sulfinate groups, alkyl groups (e.g. methyl, ethyl, n-decyl, [-butyl, trifluoromethyl, carboxymethyl), alkoxy M (fM such as methoxy, ethoxy, methoxyethoxy), acyl groups (e.g. acetyl, benzoyl), alkoxy Carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, i-propoxycarbonyl, n-dodecyloxycarbonyl), carbamoyl groups (e.g. N,N-dimethylcarbamoyl, N
-methoxyethylcarbamoyl, N-tetradecylcarbamoyl), sulfonyl groups (for example methanesulfonyl, benzenesulfonyl, 4-hydroxybenzenesulfonyl), sulfamoyl groups (e.g. N-methylsulfamoyl, N-phenylsulfamoyl, -dodecylsulfamoyl), carbonamide a! (e.g. acetamide, benzamide, trifluoroacetamide, pentafluorobenzamide), sulfonamide groups (e.g. methanesulfonamide, p-toluenesulfonamide)
, amino groups (e.g. amino, N,N-dimethylamino,
N,N-diethylamino, pyrrolidino, piperidino), etc.

When X represents an aryloxy group, X is specifically an aryloxy group having 6 to 30 carbon atoms, and when X is a heterocyclic group, it is substituted with a group selected from the group of substituents listed above. Examples of substituents on the aryloxy group that may be substituted include carboxyl group, cyano group, nitro group, alkoxycarbonyl group, halogen atom, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group,
An alkyl group, an alkylsulfonyl group or an arylsulfonyl group is preferred.

Next, examples of substituents particularly preferably used in the present invention will be described for each of the above-mentioned substituents R, R, R3 and X.

R is preferably a phenyl group or a phenyl group substituted with a chlorine atom, a methyl group, a methoxy group, an ethoxy group or a butoxy group.

Ryo is preferably a chlorine atom or an alkoxy group having 1 to 8 carbon atoms, more preferably a chlorine atom or a methoxy group, and most preferably a chlorine atom.

R5 is preferably a halogen atom (e.g. fluorine, chlorine,
bromine, iodine), alkoxy groups (e.g. methoxy, ethoxy, butoxy, methoxyethoxy, benzyloxy, dodecyloxy, tetradecyloxy), alkoxycarbonyl groups [e.g. ethoxycarbonyl, dodecyloxycarbonyl, (l-dodecyloxycarbonyl)ethoxycarbonyl , (1-dodecyloxycarbonyl)pentyloxycarbonyl], aryloxycarbonyl group (e.g. phenoxycarbonyl, 2,5-di-1-pentylphenoxycarbonyl), carbonamide group [e.g. acetamide, tetradecaneamide, 2-hexyldecaneamide , 2-(2゜4-di[-pentylphenoxy)butanamide, 4-(2,4-di-L-pentylphenoxy)butanamide, 3-dodecanesulfonyl-2
-methylpropanamide, benzamide, 4-dodecyloxybenzamide], sulfonamide groups (e.g. methanesulfonamide, F'decanesulfonamide F', hexadecanesulfonamide, N-methylhexadecanesulfonamide, benzenesulfonamide, toluenesulfonamide, 4-dodecylbenzenesulfonamide, 4-
tetradecyloxybenzenesulfonamide), carbamoyl (e.g. N-methylcarbamoyl, N,N-dihexylcarbamoyl, pyrrolidinocarbonyl, N-tetradecylcarbamoyl, N-phenylcarbamoyl,
N-(4-tetradecyloxyphenyl)carbamoyl] or a sulfamoyl group (e.g. N-methylsulfamoyl, N-butylsulfamoyl, N-hexadecylsulfamoyl, piperidinosulfonyl, N,N-dioctylsulfamoyl) famoyl, N-phenylsulfamoyl)
and more preferably an alkoxycarbonyl group, a carbonamide group or a sulfonamide group.

E is preferably an integer of 0 to 2, more preferably 1.

When X represents a heterocycle, X is preferably represented by the following general formula (Y
−2).

General formula (Y-2) In general formula (Y-2), Z is Rs Rs Rh Rs R
6RvR4R@Rh ORs Rq Rl. R1 R4, RS, R, and R9 represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or an amino group, and R4 and R
? represents a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, or an alkoxycarbonyl group; R1° and R1+ represent a hydrogen atom, an alkyl group, or an aryl group; R1° and R11 are bonded to each other; R4 and R may form a benzene ring
s, Rs and Rh, R- and R1 or R4 and R.

are bonded to each other to form a ring (e.g. cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine,
piperidine).

Among the heterocyclic groups represented by general formula (Y-2), particularly preferred ones are R4Ra Rs Rh Rs R6R? is a heterocyclic group.

The total number of carbon atoms in the heterocyclic group represented by the general formula CY-2) is 2 to 30, preferably 4 to 20, more preferably 5.
~16. Examples of the heterocyclic group represented by the general formula CY-2) include succinimide group, maleimide group, phthalimide group, 1-methylimidazolidine-2,4-dione-3-yl group, 1-benzylimidazolidine-2, 4
-dione-3-yl group, 5,5-dimethyloxazolidin-24-dione-3-yl group, 5-methyl-5-propyloxazolidin-2,4-dione-3-yl group, 5
, 5-dimethylthiazolidine-2,4-dione-3-yl group, 5,5-dimethylimidazolidine-2,4-dione-3-yl group, 3-methylimidazolidinetrione-
1-yl group, 2゜4-triacylidin-3,5-dione-4-yl group, 1-methyl-2-phenyl-1,2
, 4-triacylidin-3,5-dione-4-yl group,
1-benzyl-2-phenyl-1,2,4-triacylidin-3,5-dione-4-yl group, 5-hexyloxy-1-methylimidazolidin-24-dione-3-yl group, -benzyl group 5-ethoxyimidapridine-2
, 4-dione-3-yl group, and I-benzyl-5-dodenyloxyimidapridin-2,4-dione-3-yl group.

Among the above heterocyclic groups, imidazolidine-2,4dione-
3-yl group (e.g. 1-benzyl-imidazolidine-2
, 4-dione-3-yl group) is the most preferred group.

When X represents an aryl group, the following groups are preferred examples.

In the coupler represented by the general formula (Y), the above-mentioned heterocyclic groups are more preferable as the substituents R9 and X.

Dimers or multimers of more than 11% may be formed by bonding to each other via groups with a valence of 11 or more. Good too.

When the coupler represented by the general formula (Y) forms a multimer, a typical example is a single or copolymer of an addition polymer ethylenically unsaturated compound (yellow color-forming monomer) having a yellow dye-forming coupler residue. . In this case, the multimer contains the repeating unit of the general formula (Y-3), and even if one or more types of yellow-colored ship repeating units represented by the general formula (Y-3) are contained in the multimer, Often, it may be a copolymer containing one or more non-color-forming ethylene type monomers as a copolymerization component.

General formula (Y-3) In the formula, R represents a water bladder atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and A represents -CONH-5-COO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, L is -CONII-5-NHCON
H-1-NIICOO--NIIGO-1-0CONI
'l--1111-1-COO--oco--co-1
-o--s--sosu-NH5Ch- or -5OZM
B-represents a, bSc represents 0 or 1, Q represents a yellow coupler residue represented by the general formula (Y) from which the t molecule is removed.

As the multimer, a copolymer of a yellow color-forming heptamer represented by a coupler unit of general formula (Y-3) and a non-color-forming ethylene birch monomer shown below is preferred.

Examples of non-color-forming ethylene monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic acid, α-alkylacryl M (e.g. methacrylic acid, etc.) Amides or esters derived from these acrylamides (e.g. acrylamide, methacrylamide, n-butylacrylamide, L
-butylacrylamide, diacetone acrylamide,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, -butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-
hydroxymethacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylaterile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene) ), itaconic acid,
ntraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether)
, maleic acid ester, N-vinyl-2-pyrrolidone,
Examples include N-vinylpyridine and 2- and -4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more of the non-color-forming ethylene monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene. , butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the general formula (Y-3
) The ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to The agent can be selected such that its compatibility with, for example, gelatin, its flexibility, thermal stability, etc. are favorably influenced.

The yellow polymer coupler used in the present invention is prepared by dissolving a lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the general formula (Y-3) in an organic solvent in an aqueous gelatin solution. It may be made by emulsifying and dispersing it in the form of latex, or it may be made directly by emulsion polymerization.

U.S. Patent No. 3,45 describes a method for emulsifying and dispersing lipophilic polymer couplers in an aqueous gelatin solution in the form of latex.
No. 1,820, and U.S. Pat. No. 4,08 for emulsion polymerization.
The methods described in No. 0.211 and No. 3,370.952 can be used.

Specific examples of the yellow dye-forming coupler represented by the general formula (Y) are shown below, but the present invention is not limited thereto.

(Y-4) (Y-5) (Y-6) (Y-11) l (Y (Y-8) (Y-12) (Y (Y-14) (Y-15) (Y-18) (Y-19) Hj (Y-16) 1-CHt CHh--m-HCHz CDT-111 (Y-17) (Y-20) (Weight ratio) These couplers represented by the general formula rY) Examples of compounds and/or synthetic methods other than those mentioned above are, for example, U.S. Patent No. 340
No. 9439, No. 3408194, No. 364449
No. 8, No. 3730722, No. 3770445,
Same No. 3842576, Same No. 3933501, Same No. 3
No. 941601, No. 3973968, No. 3990
No. 896, No. 3998641, No. 4008086
No. 4012259, No. 4022620, No. 4032347, No. 4046575, No. 40
No. 49458, No. 4057432, No. 41151
No. 21, No. 4133958, No. 4138263, No. 4138557, No. 4157919, No. 4201584, No. 4203768, No. 420
No. 6278, No. 4229577, No. 426601
No. 9, No. 4269936, No. 4286053,
Same No. 4289847, Same No. 4268591, Same No. 4
No. 238564, No. 4248961, No. 4289
No. 847, No. 4304845, No. 4314023
No. 4326024, No. 4327175, No. 4336327, No. 4356258, No. 44
No. 04274, No. 4401752, No. 44435
No. 36, No. 4511649, No. 4617256, No. 4711837, British Patent No. 1580999, No. 2011398, West German Patent No. 3107173, European Patent No. 1it (EP) No. 30747, No. 24
No. 9473, JP-A-48-66835, JP-A No. 48-99
No. 432, No. 50-108925, No. 50-1329
No. 26, No. 50-158329, No. 51-3631, No. 51-145319, No. 52-58922, No. 52-115219, No. 54-121126, No. 5
No. 5-538, No. 55-598, No. 55-93153
No. 55-163538, No. 56-30126,
No. 56-30127, No. 56-74250, No. 56
-92539, 56-153343, 56-1
No. 61543, No. 56-164343, No. 57-22
No. 238, No. 57-155538, No. 58-2173
No. 8, No. 58-42046, No. 59-159163, No. 59-174839, No. 59-222837,
No. 60-35730, No. 60-144740, No. 6
No. 0-166948, No. 62-200349, No. 62
-204259 and Re5earch Discl.
It is described in Osure magazine (RD) No. 18053 (1979).

In the present invention, a pivaloylacedoanilide type 2-equivalent yellow coupler may be used in combination with the above benzoylacedoanilide type 2-equivalent yellow coupler.The pivaloylacedoanilide type 2-equivalent coupler produces a solid color image. , and the tailing on the long wavelength side is small a
The pivaloylacedoanilide type 2-equivalent coupler preferably used in combination in the present invention is a coupler in which R1 is represented by a t-butyl group in the general formula (Y), and specific examples thereof are as follows: There are couplers such as, but not limited to.

(y~52) (Y-57) (Y-58) H2 (Y-55) (Y-56) (Y-59) (Y-60) CIl= CH1 (Y-61) (Y-62) ( Y (Y-66) (Y-63) H (Y-64) (Y-67) (Y-68) (Y-69) (Y-70) 1M (Y-73) C[1s (Y-71 ) p (Y-72) Cρ (Y-75) The coupler used in the present invention can be introduced into the photosensitive 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 boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high-boiling point organic solvents include phthalic acid esters (dibutyl phthalate, synchrohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl) phthalate, bis(2,4-di-t-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2
-ethylhexyl diphenyl phosphate, tricyclohexyl phthalate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl phenyl phosphate, etc.), Ethylhequinruhenzoate,
dodenruhensoate, 2-ethylhexyl-ρ-hydroquinchenshade, etc.), amides (N,N-diethyldodecanamide, N,N-stylaurylamide, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sehagate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-ter
t-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.)
Examples include.

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or more, preferably 50°C or more and about 160°C or less, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include 2-ethoxyethyl acetate and dimethylformamide.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. No. 4,199.363, West German Pat. Are listed.

The preferred silver halide contained in the photographic emulsion layer of the photographic photosensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. It is. Particularly preferred are silver iodobromide, silver bromide, and silver chlorobromide containing from about 2 mol % to about 10 mol % (hereinafter referred to as the margin) of silver iodide.

Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, they may have twin planes, such as those explained in the Photographic Society of Japan line, the Basic Silver Salt Photographic Line of Photo Industry (Corona Publishing Co., Ltd., p. 163). Select from single twins containing one crystal plane, parallel multiple twins containing two or more parallel twin planes, nonparallel multiple twins containing two or more nonparallel twin planes, etc. depending on the purpose. In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and Japanese Patent Publication No. 55-427.
37, disclosed in Japanese Patent Application Laid-Open No. 60-222842 (1
Dodecahedral particles consisting of 10) faces can be used. Furthermore, Journal of ImagingSc
(211) as reported in 1986 is representative (hl
) plane particles, (hhl) plane particles represented by (331),
(hko) plane particles representing the (210) plane and (321)
(hkl) plane particles, which are representative of (100
) plane and (111) plane coexisting in one particle, (100) plane and (110) plane coexisting, or (111) plane and (110) plane coexisting, etc.
Particles having one surface or many surfaces coexisting can also be selected and used depending on the purpose.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 80% or more of all grains fall within ±30% of the average grain size in terms of grain number or weight can be used in the present invention. Also, the p1 target for photosensitive materials! lil
In order to satisfy the above requirements, two or more types of monodispersed silver halide emulsions having substantially the same color sensitivity in emulsion layers having different grain sizes can be mixed in the same layer or coated in separate layers. Furthermore, a combination of two or more types of polydisperse silver halide emulsions or monodisperse emulsions and polydisperse pores IP+ may be mixed or layered for use.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chisic et Phys
ique PhotographiquePaul M
ontel, 1967), ``Photographic Emulsion Chemistry'' by Duffin, published by 7T-Karpres (G, F, UffinP
photographic emulsion chem
istry (Focal Press.

1966), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al.
net et aLMaking and Coati II
Ig Photographic Esulsion.

Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. It is also possible to use a method in which good 0 grains are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling PAg and PH during grain formation. For more information, please see Photographic Science.
and Engineering (Photographic
5science andεBineeriB) Volume 6, pp. 159-165 (1962) i Journal of
Photographic Science (Journal o
fPhotographic 5science) + 1
2tk, pp. 242-251 (1964), U.S. Patent No. 3,655,394 and British Patent No. 1.413,
It is described in No. 748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in Cleve's Theory and Practice of Photography J.
Theory and Practice (19
30) ).

131 pages; Gatoff, Photographic Science
& Engineering (GutoffPhotog
rapic 5science and engine
ering), Vol. 14, pp. 248-257 (1970
): U.S. Patent No. 4.434.226, U.S. Patent No. 4.414
．． No. 310, No. 4.433,048, No. 4,439.
520 and British Patent No. 2,112.157. The use of tabular grains has advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in U.S. Pat. No. 4,434,226 cited above. .

Tabular grains are preferred as emulsions of the present invention.

In particular, particles with an aspect ratio of 3 to 8 account for 50% of the total projected area.
The preferred crystal structure of the tabular grains accounting for % or more is --like, the inside and outside may have different halogen compositions, and the emulsion grains may have a layered structure. British Patent No. 1,027,1
No. 46, U.S. Patent No. 3,505.068, U.S. Patent No. 4,44
4.877 and Japanese Patent Application No. 58-248469.

Silver halides of different compositions may be bonded by epitaxial bonding, for example, Rodan silver, silver halide, etc.
It may be bonded with a bonding material other than silver halide, such as lead oxide.

The silver halide emulsion of the present invention preferably has a distribution or structure regarding the halogen composition in its grains.
Typical examples are JP-B No. 43-13162 and JP-A No. 6.
These are core-shell type or double-structured particles in which the interior and surface layers of the particles have different halogen compositions, as disclosed in JP-A No. 1-215540, JP-A-60-222845, JP-A-61-75337, and the like. In such particles, the shape of the core portion and the overall shape including the shell may be the same or different. Specifically, the core part has a cubic shape, and the shape of the shelled particle may be cubic or octahedral. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral. Furthermore, although the core portion is a clearly regular particle, the shelled particle may have a distorted or irregular shape. In addition, instead of a simple double structure, it is possible to create a triple structure as disclosed in JP-A No. 60-222844, or a multilayer structure with more than that, or a halogen with a different composition on the surface of the core-shell double structure particle. You can apply a thin layer of silver.

In order to give a structure to the inside of a particle, it is possible to create a particle having not only the above-mentioned enveloping structure but also a so-called bonding structure. These examples are disclosed in Japanese Patent Application Laid-Open No. 59-13354.
0, Japanese Patent Publication No. 58-108526 EP199290A
2. Japanese Patent Publication No. 58-24772, Japanese Patent Publication No. 59-16254
etc. are disclosed. The crystal to be bonded can have a composition different from that of the host crystal and can be formed by bonding to an edge, part of a corner, or surface of the host crystal.

Such a bonded crystal can be formed even if the host crystal is uniform in terms of halogen composition or has a core-shell structure.

Of course, a combination of silver halides is possible in the case of a bonding structure, but a bonding structure can be formed by combining silver halide with a silver salt compound that does not have a rock salt structure, such as silver rhodan or silver carbonate. Further, non-silver salt compounds such as PbO may also be used if a bonded structure is possible.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, or conversely, the core part has a low silver iodide content. Grains with a low silver iodide content and a high shell part may be used. Similarly, grains with a bonded structure may have a high silver iodide content in the host crystal and a relatively high silver iodide content in the bonded crystal. It may be a low particle or vice versa.

In addition, the boundaries where the halogen compositions of particles with these structures develop may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to compositional differences, or may be actively continuous boundaries. It may also be one with some structural changes.

The silver halide emulsion used in the present invention is EP-009672.
781, EP-0064412B1, etc., or DE-2
The surface may be modified as disclosed in JP-A-60-221320, No. 306447C2.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but an internal latent image type emulsion can also be used by selecting the developer or development conditions, as disclosed in JP-A-59-133542. can. A shallow internal latent image type emulsion covered with a thin shell can also be used depending on the purpose.

It is known that silver halide solvents are useful in promoting ripening. For example, it is known to have an excess of halide ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant a, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used.

Chemical sensitization is described by James (T. H.),
The Photographic Ink Process, 4th edition, Macmillan Publishing, 1977, (T. H. James, The
Theory of the Photography
c Process+ 4th ed.

Mac++ H1an, 1977), pp. 67-76, or as described in Research Disclosure 12 (1, 19
April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Patent Nos. 2,642.361, 3,297.446, 3
, No. 772.031, No. 3゜857.711, No. 3.
901,714, 4 266.018, and 3,904,415, and British Patent No. 1,315,
pAg 5-10, pH 5-10 as described in No. 755
Chemical sensitization can be carried out using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or multiple combinations of these exacerbants at 8 and 30-80"C. Chemical sensitization is optimally carried out using gold compounds and thiocyanates. In the presence of the compound, also U.S. Pat.
266.018 and 4,054,457, or in the presence of a sulfur-containing compound such as hypo, thiourea-based compounds, or rhodanine-based compounds, or in the presence of a chemical sensitizing aid. Chemical sensitization is also possible. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine.

Examples of chemical enhancement aid modifiers include U.S. Patent No. 2,131.0.
No. 38, No. 3,411.914, No. 3゜554.75
No. 7, JP-A-58-125526, and the aforementioned Duffin, Photographic Emulsion Chemistry J, pp. 138-143.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazole M (especially I-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, Tetraazaindene M
A number of compounds known as antifoggants or stabilizers can be added, such as (*4-hydroxyWm(1,3,3a,7)tetraazaindenes), pentaazaindenes, etc. For example, U.S. Patent 3,954
．． No. 474, No. 3,982.947, Special Publication No. 52-2
8.660 can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the basic 8111M nuclei commonly used for cyanine dyes can be applied to these dyes. Namely, viroline nucleus, oxazoline nucleus,
Thiozoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring in these nuclei A fused nucleus, that is, an indolenine nucleus, a benzindolenine nucleus, an indole Maki, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl M nucleus, etc. 5-6jl#
j[ff ring nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

A typical example is U.S. Patent No. 2,688,545, 2.9
No. 77.229, No. 3,397.060, No. 3,52
No. 2.052, No. 3.527,641, No. 3,617
, No. 293, No. 3,628.964, No. 3,666.
No. 480, No. 3.672898, No. 3,679,42
No. 8, No. 3.703.377, No. 3,769,301
No. 3゜814.609, No. 3,837.862, No. 4.026,707, British Patent No. 1,344,28
No. 1, No. 1,507.803, Special Publication No. 43-4936
No. 53-12,375, JP-A-52-110.6
No. 18, No. 52-109,925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral enhancement effect or a substance that does not absorb substantially any visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The dye may be added to the emulsion at any stage of emulsion preparation that has been known to be useful.
This is most commonly carried out after chemical sensitization is completed and before application, but chemical aggravating agents are used as described in U.S. Pat. Spectral sensitization can be performed at the same time as chemical sensitization by adding it at the same time, or it can be performed prior to chemical sensitization as described in JP-A-58-113,928.
It is also possible to start the spectral sensitization by adding it before the completion of the halogenated polymer precipitation. Furthermore, U.S. Patent No. 4.2
Adding these said compounds separately as taught in No. 25.666, i.e. some of these compounds are added before chemical sensitization and the rest after chemical sensitization. is also possible, as described in U.S. Pat. No. 4,183,75
Any time during silver halide grain formation including the method taught in No. 6 may be used.

The amount added is 4X10-” per 111 moles of halogenide.
It can be used in an amount of 8X10-' moles, but when the silver halide grain size is more preferably 0.2 to 1.2 .mu.m, about 5X10-' to 2XIQ-' moles is more effective.

The various additives mentioned above are used in the photosensitive material related to the present technology, but other various additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure+-Item 17643 (December 1978) and Item 18716 (November 1979), and the relevant sections are summarized in the table below. Ta.

Types of additives Chemical enhancers Sensitivity enhancers Brightening agents Ultraviolet absorbers Anti-stain agents Dye image stabilizers Hardeners Binder Plasticizers, lubricants Preventing agents 1? D17643 RD18716 Page 23, page 648, right column, same as above, page 24, page 25, right column, page 650, left to right column, page 25, page 26, page 26, page 27, page 650, right column, same as above, page 651, left column.Also prevents deterioration of photographic performance due to formaldehyde gas. Therefore, U.S. Patent No. 4,411,987 and U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

The photosensitive material of the present invention includes U.S. Patent No. 4.740.454, U.S. Pat.
It is preferable to contain a mercapto compound described in JP-A No. 1283551.

The light-sensitive material of the present invention may contain a fogging agent, a development accelerator, and a halogenated l! It is preferred to include compounds that release solvents or their precursors.

The dye dispersed in the photosensitive material of the present invention by the method described in International Publication No. 088104794, Japanese Patent Application Publication No. 1-502912, or EP 317,308A, U.S. Pat.
, 420,555 and JP-A-1-259358.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, ■-C-G, and Research Disclosure No. 307105, cited above.
■It is described in the patent described in -〇-G.

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
4.011, 4,327.173, West German Patent Publication No. 3329.729, European Patent No. 121.365A
No. 249°453A, U.S. Patent No. 3.446,
No. 622, No. 4.333,999, No. 4,775
, No. 616, No. 4,451.559, No. 4,42
No. 7,767, No. 4, No. 690, No. 889, No. 4
．． Preferred are those described in No. 254.212, No. 4,296.199, and Japanese Patent Application Laid-Open No. 61-42658.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4, 576910, British Patent No. 2.102.
No. 137, European Patent No. 341188A, etc.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, No. 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure Sou 17643.
-G section, ■-G section of Nct 307105, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413,
U.S. Patent No. 4,004,929, U.S. Patent No. 4,138,2
No. 58, UK Patent No. 1,146,368 is preferred, and the fluorescent dye released upon coupling as described in U.S. Pat. No. 4,774,181 compensates for unwanted absorption of the chromogenic dye. Coupler, U.S. Patent No. 4.
It is also preferred to use couplers having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 777.120.

Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention.

The DIR coupler that releases the development inhibitor is the above-mentioned 1? I
] 17643, ■-F term and same inhibition 307105, ■
-Patents described in Section F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248,
Preferred are those described in US Pat. No. 63-37346, US Pat. No. 63-37350, US Pat. No. 4,248,962, and US Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
Same No. 2.13L No. 188, JP-A-59-157638
No. 59-170840 is preferred.
Also, JP-A-60-107029, JP-A No. 60-2523
Also preferred are compounds that release fogging agents, development accelerators, halogenated W&solvents, etc. through redox reactions with oxidized forms of developing agents, as described in Japanese Patent Application Laid-open No. 144940 and Japanese Patent Publication No. 1-45687.

Other compounds 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. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing coupler, DIR coupler releasing coupler, Df described in JP-A-6224252 etc.
R coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173302A
No. 313,308A, a coupler that releases a dye that restores color after separation, R, D, disorder 11449, 24
241, bleaching accelerator releasing coupler described in JP-A No. 61-201247, etc. Gantt-releasing coupler described in U.S. Pat. No. 4,555,477, etc., JP-A-63-7574
Examples thereof include a coupler that releases a leuco dye described in No. 7, a coupler that releases a fluorescent dye described in US Pat. No. 4,774, and US Pat. No. 181.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3-one, n-butyl p-hydroquine benzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941
-dimethylphenol, 2-phenoxyethanol, 2
It is preferable to add various preservatives or fungicides such as ~(4thiazolyl)benzimidazole.

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

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of NQ17643, 64 of NQ18716
From the right column on page 7 to the left column on page 648, and Na307105
It is described on page 879 of .

In the photosensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and 16 μm or less. is particularly preferable, and the film swelling rate TI/□ is preferably 3 o seconds or less, more preferably 20 seconds or less. The film thickness means the film thickness measured at 25°C relative temperature and 55% humidity (2 days). , Wl, swelling rate TI/□ can be measured according to techniques known in the art.
) et al.
Engineering (PhoLogr, Sci, Eng,
), 19@, No. 2, pages 124-129, it can be measured by using a swellometer (swelling membrane), and T I/□ was treated with a color developer for 13 minutes and 15 seconds at 30°C. 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 1/2 of the saturated film thickness.

The membrane swelling rate T17□ 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 can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

In the photosensitive material of the present invention, it is preferable to provide a hydrophilic colloid layer (referred to as a back layer) with a total dry film thickness of 2 μm to 20 μm on the side opposite to the side where the emulsion layer is present. It is preferable to contain the aforementioned light absorbers, filter dyes, ultraviolet absorbers, static inhibitors, hardeners, binders, plasticizers, lubricants, coating aids, surface active agents, and the like. The swelling rate of this layer is 150-500%.
is preferred.

The color photographic material according to the present invention includes the above-mentioned RD,
lh 17643 pages 28-29, NQ18716 651 left column to right column, and NQ18716 880~
It can be developed by the usual method described on page 881.

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 used 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.

Examples include β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates. Among these, especially 3
-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may be a pH range developer such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It typically contains an inhibitor or antifoggant. In addition, if necessary, hydroxylamine, diethylhydroxylamine, gnitite, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers. , an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, various calcinates such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, for example, Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,! Representative examples include +,N,N-tetramethylenephosphonic acid, ethylenediaminedi(0-hydroxyphenylacetic acid), and salts thereof.

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 1-phenyl-3-pyrazolidone, or amine phenols 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 to be processed, but is generally 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

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

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
For example, the slit development method described in Japanese Patent No.-216050 can be mentioned. Reducing the aperture ratio is important not only for the color development and black-and-white development process, but also for subsequent processes,
For example, it is preferable that it can be used in all steps such as bleaching, bleach-fixing, fixing, washing with water, 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 milk layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. On the bleaching side, compounds of polyvalent metals such as iron (m), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include mt=salts of iron (II[),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-noaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, etc., or aminopolycarboxylic acids such as citric acid, tartaric acid, malic acid, etc. Complex salts etc. can be used. Among these, aminopolycarboxylic acid iron(m)tf salts, including ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt, are used from the viewpoint of rapid processing and environmental pollution prevention. Preference is given to iron aminopolycarboxylate (II[
) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (III
) The pH of the bleach or bleach-fix solution using complex salts is usually 4.
0-8, but lower pH for faster processing
It can also be processed with

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
．． No. 290.812, No. 2,059.988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Mercap! No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. 17129 (July 1978), etc. -1i or a compound having a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B No. 45-8506, l# JP-A-52-208
No. 32, No. 53-32735, U.S. Patent No. 3,706
, 561; West German Patent No. 1,1
No. 27,715, iodide salts described in JP-A-58-16-235; West German Patent No. 966.410, JP-A No. 2,748
, 430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and other JP-A Nos. 49-40,943, 49-59,644,
Compounds described in No. 53-94.927, No. 54-35,727, No. 55-26.506, and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat. No. 3,893.
, No. 858, West German Patent No. 1.290,812, and JP-A No. 53-95.630 are preferable, and the compounds described in U.S. Pat. No. 4.552.834 are also preferable. Bleaching accelerators may be added to the photosensitive material, and these bleaching accelerators are particularly effective when bleaching and fixing color photosensitive materials for photography.

In addition to the above-mentioned compounds, it is preferable that the bleaching solution and bleach-fixing solution contain an organic acid for the purpose of preventing bleach staining, and this is particularly preferred! The acid is a compound having an acid dissociation constant (pea) of 2 to 5, and specifically, acetic acid, propionic acid, etc. are preferable.

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

In the present invention, the fixing solution or bleach-fixing solution has pH!
l! In order to maintain the temperature, a compound having a pKa of 6.0 to 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole, is added at 0.1 to 10 mol/l. is preferred.

The total time for 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. In addition, the processing temperature is 25°C to 5°C.
0°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering process, it is preferable to strengthen the stirring as much as possible. Specific methods for strengthening the stirring include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62483460; , Japanese Patent Publication No. 62-1133
No. 461 is a method of increasing the stirring effect using a rotating means, in which the photosensitive material is moved while the emulsion surface is brought into contact with a wiper blade provided in the liquid, and the emulsion surface is made turbulent to improve the stirring effect. Examples include a method of improving the effect and a method of increasing the circulation flow rate of the entire processing liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, thereby increasing the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-1.91257, No. 60-191258, No. 6
It is preferable to have the photosensitive material conveying means described in No. 0-191259. The above-mentioned Japanese Patent Application Laid-Open No. 60-191257
As described in the above issue, such a conveyance means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing performance deterioration of the processing liquid. Such an effect is particularly effective in shortening the processing time in each step and reducing the amount of processing and f 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
urn-al of tbe 5ociety of
Motion Picture and Te1evi
sion 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 significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to this problem,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8.542
Chlorine-based disinfectants such as isonaazolone compounds, siacheadazoles, chlorinated sodium isonurate, and other benzotriazoles described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technology" Full volume “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Industrial Technology Center, Japanese Society of Antibacterial and Antifungal Research ``Encyclopedia of Antibacterial and Antifungal Agents'' (
It is also possible to use the fungicides described in (1986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range 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 No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, for example, it
Stabilizing baths containing a dye stabilizer and a surfactant can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine or Examples include aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added 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 a 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 compound described in No. 7, No. 3,342,
No. 599, Research Disclosure N1114,
850 and N11lI5,159, aldol compounds described in No. 13,924,
Examples include metal salt complexes described in US Pat. No. 3,719,492 and urethane compounds described in JP-A-53-135628.

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 and JP-A No. 57-
No. 144547 and No. 58-115438.

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

Further, the silver halide photoluminescent material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66042, and the like.

(Examples) The present invention will be explained in more detail below with reference to 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 light-sensitive material consisting of each layer having the composition shown below, was prepared.

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

1st layer: Antihalation layer black colloidal silver Silver coating amount 0.20 Gelatin 2°20UV-10,07 UV-30,03 UV-40°20 Cpd-114,0XIO-2 Cpd-121,9X10” 5olv-10 ,30 Solv-21,2XlO'-2 Second layer/intermediate layer fine grain silver iodobromide (Ag11.0 mol%, equivalent sphere diameter 0.0
7μm) Silver coating amount 0.15 Gelatin 1.00ExC-
26,0xlO”2 Cpd-132,0xlO-2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (Ag15.0 mol%, surface height AgI 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
0,42 silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 18%, dodecahedral grains) Silver coating amount 0.40 Gelatin 1 .90ExS-
24,5X10-'molExS-11,5xlO-'molExS-34,0XIO-5molExC-30,65ExC-81,0XIO"ExC-22,3XIO-'5olv-10,32 4th layer 2nd Red-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI
Type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%,
Plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0
．． 85 Gelatin 0.9■ExS-
23,0XIO-'mol ExS-11,0XIO-'mol ExS-33,0XIO" mole ExC-30,13 ExC-76,2X10"ExC-24,0XIO" 5olv-10,10 5th layer: 3rd red Sensitive emulsion layer Silver iodobromide emulsion (Ag1 11.3 mol%, internal high Agl
Type, 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 ■, 20ExS-
22,0xlO-'Mole ExS-16,0x1O-"Mole ExS-32,0XIO-'Mole ExC-78,5XIO"ExC-97,3Xio-" 5olv-10,12 Solv-20,12 6th layer: Intermediate Layered gelatin 1.00Cpd-
18,0xlO-2 Solv-1' 8.0x10-2 7th layer, first green emulsion layer Silver iodobromide emulsion (Ag15.0 mol%, surface height AgI 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 (AgI 4.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 18%, dodecahedral grains) Silver coating amount 0.16 Ceratin 1 ．． 2ExS-
85,0XIO-'mol ExS-52,0XIO-'mol ExS-61,oxto-'mol ExM-90,50 ExM-130,10 ExM-153,5xlO-2 Solv-10,20 Solv-33,0xlO" 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high iodine type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%,
Plate-shaped particles, diameter/thickness ratio 3゜0) Silver coating amount
0.57 gelatin
0.45ExS-83,5xlO-'molExS-51,4xlO-'molExS-67,o'xto-'molExM-90,12 ExM-137,lXl0-'ExM-103,5xlO-!5olv-10 ,15 Solv-31,0XIO-' 9th layer: Intermediate layer Seratin 0.50Solv-
12, oxlo-2 1st O layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high Ag
Type I, equivalent ball diameter 1. 4 μm, coefficient of variation of equivalent sphere diameter 28
%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1.30 Gelatin
1.20ExS-82,oxxo-'molExS-58,0XIO-'molExS-68,0xlO-smolExM-144,5X10-'ExM-81,oxio-2 ExC-74,5xlO-'Cpd-141 ,0XIO-' Sol v-10,25 11th layer, yellow filter layer gelatin 0,50Cpd-
155,2X:O-” Sol, v-10,12 12th layer: Intermediate layer gelatin 0.45Cpd-1
30,t.

13th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (Ag1 2 mol%, uniformly iodine type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 25%, tabular grains, diameter/thickness ratio 7)゜0) Silver coating amount
0.20 gelatin 1
．． 00ExS-93,0xlO" molExY-150,60 ExY-162,3X10" 5olv-10,746 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high Ag
Type I, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 16%
, octahedral particles) Silver coating amount 0.19 Gelatin 0.35ExS-9
2,0xlO-'mol ExY-150,22 Solv-10,264 15th layer: Intermediate layer fine grain silver iodobromide (AgI 2 mol%, uniform iodo type,
Equivalent sphere diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36 16th layer:
Third blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high Ag
Type I, equivalent sphere diameter 1.7 μm, coefficient of variation of equivalent sphere diameter 28%
, plate-shaped particles, diameter/thickness 5゜0) Silver coating amount
l, 55 gelatin
1.00ExS-101゜xY-15 olv-1 17th layer, protective layer fine grain silver chloride (equivalent sphere diameter 0.0 Gelatin V-1 V-4 V-3 olv-1 olv-2 B-1 (diameter 1 .5 μm) M-2 (Diameter 1.5 μm) pd-16 5×IO-” Mol 0, 21 0, 252 7 μm) 0, 36 2, 50 0, 10 0, 21 0, 03 1.0XIO-” 1 .0X10-"2.0XIO-" 0,15 3.0X10-' 2.0XIO-2 0,35 1,0 In addition to the above, the sample thus prepared also contained 1°2-benzisothiazolin-3-one. (average 2 for gelatin)
00 ppm), n-butyl p-hydroxybenzoate (about 1,000 ppm), and 2-phenoxyethanol (about 109,000 ppm) were added. In addition, B-4, B5, W-2, W-3, 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, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

5olv-1 amount of the 13th layer of sample 101: 0.746 g
/rd to 0.623g/rrr, 5o1v of the 14th layer
-1 amount 0,264g/r/ to 0.220g/d, and further 5olv-1 amount 0.220g/d in the 16th layer. 252g/proof 0.
Sample 102 was prepared in the same manner as Sample 101 except that the weight was changed to 210 g/n.

Here, the variable of 5 olv-1 was adjusted when preparing the emulsified dispersion since it was added to each layer as an emulsified dispersion.

Similarly, the amount of 5olv-1 in layers 13, 14, and 16 was adjusted to the ratio shown in Table 1, and samples 103 to 107
It was created. These samples were exposed to light through an MTF measurement pattern for sharpness measurement and subjected to color development processing as described later, and the MTF values at 30 cycles per 1M were measured and calculated, and are shown in Table 1.

Next, samples 101 to 107 were cut into 3.5 cm x 10 cm pieces, and two pieces of each were subjected to the color development process described below, and one of the developed samples was then heated at a temperature without touching each other. It was stored in an atmosphere of 65° C. and 80% relative humidity for 7 days, and the remaining one was stored at room temperature.

The turbidity of the sample thus obtained was measured using a Hitachi spectrophotometer U-3200 equipped with an integrating sphere. Table 1 shows the values obtained by subtracting the turbidity values of products stored at room temperature, which were measured in the same manner. The smaller this value is, the less oily stains appear on the surface of the photosensitive material, indicating that the transparency is better.

Next, for samples lO1 to 107, 10anXIO (to)
The pieces were cut into pieces and stored at 80°C and 70% relative humidity for one day without touching each other. The amount of oily substance on the surface was calculated by absorbing the oily substance that appeared on the surface using a filter paper that had been weighed in advance using a precision balance, and then weighing the filter paper again, which is shown in Table 1.

The smaller this value is, the better the result is.

Next, each sample of samples 101 to 107 was added to 51JX5CII+
Prepare 4 pieces each cut to size, and heat at 35℃.
After being stored for one day at a relative humidity of 80%, the back side of the sample and the protective layer of the sample were stacked so that they were in contact with each other, a load of 1000 g was applied, and the sample was stored for 10 days at 35° C. in an atmosphere of 80% humidity.

Thereafter, the samples were peeled off, and the area ratio of the bonded portion was determined, and the average value of the four samples for each sample was recorded in Table 1.

Color development processing in Examples was carried out according to the following processing method.

Processing method Color development processing was carried out at 38°C according to the following processing steps.

Color development 3 minutes 15 seconds Bleached white 6 minutes 30 seconds Water washing 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid i, 0g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g potassium iodide
1.3 ■ Hydroxylamine sulfate 264g
Add 4.5g of 4-(N-ethyl-N-β-hydroxyethylamino) 2-methylaniline sulfate water.
1. Oj! pH Bleach solution: Ferric ammonium salt, ethylenediaminetetraacetic acid, disodium salt, ethylenediaminetetraacetic acid, ammonium bromide, ammonium nitrate, and pH.Fixer solution: ethylenediaminetetraacetic acid disodium salt, sodium sulfite, ammonium periosulfate solution (70%), and sodium bisulfite solution. pH stabilized solution 10°1 00°l Oo ■ 50°10°1°6°■.

4゜0g Formalin (40%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add water to make 2. The samples of the present invention in which the amount of 5olv-1, which is the solvent for the yellow coupler added, was set to 0.4 to 0 had better film surface characteristics such as adhesion and perspiration compared to the comparative example in which the amount of 5olv-1 was 0.6 or more. It can be seen that this is an area with excellent characteristics.

It can also be seen that the MTF, which represents sharpness, is simultaneously improved as a result of the decrease in film thickness by 5 olv-1.

Example-2 On a subbed cellulose triacetate film support,
Sample 201, which is a multilayer color photosensitive material, was prepared by simultaneously coating each layer having the composition shown below.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/rrr of silver for silver halide and colloidal silver, and the amount expressed in g/n (unit of silver) for coupler additives and gelatin.
Regarding the sensitizing dye, the number of moles is expressed per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.15 Seratin 1. 5ExM-80,0
2 Second layer (middle layer) Seratin 1. 5UV-1
0,03 UV-20,06 UV-30,07 ExF-10,004 Solv-20,07 3rd layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high Agr type,
Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 2.5) Coated silver amount
0. 5 Gelatin 1.
0ExS-11,0XIO-'ExS-23,0XIO-'ExS-31,0XIO-' ExC-30,22 ExC-40,02 Solv-10,007 4th layer (mid-sensitivity red-sensitive emulsion layer) Iodobromide Silver emulsion (Ag1 4 mol%, internal high Agl type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twinned mixed grains, diameter/thickness ratio l) Coated silver amount
o, 85 Seratin 1.2
6ExS-11,0xlO-'ExS-23,0xlO-' ExS-31,Ox1. O" ExC-30,33 ExC-40,01 ExY-140,01 ExY-130,02 ExC-20,08 Cpd-101,0XIO-' 5olv-10,10 5th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%,
Twinned mixed particles, diameter/thickness ratio 2) Coated silver amount 0.7 Ceratin 1.
0ExS-11,0X10-'ExS-23,0XIO-'ExS-31,0XIO'-5 ExC-50,07 ExC-60,08 Solv-10,15 Solv-20,08 6th layer (intermediate layer) Gelatin 1.0P-20,1
7 Cpd-10,10 Cpd-40,17 Solv-10,05 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 2 mol%, internal high Agl type,
Equivalent ball diameter 0. 3 μm, coefficient of variation of equivalent sphere diameter 28%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 2.5) Coated silver amount 0130 gelatin
0. 4ExS-45,oxlo-'ExS-6o,3X10-"ExS-52,0XIO-' ExM-160,15 ExY-130,03 ExM-80,03 Solv-10,2 8th layer (medium sensitivity green Sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, mixed twin grains, diameter/thickness ratio 4) Coated silver amount
0.7 Gelatin 1.0E
xS-45,0XIO-' ExS-52,0XIO- ExS-60,3XlO"' ExM-160,20 ExM-80,03 Ex~1-10 0.015
ExY-130,04 Solv-10,2 9th layer (high sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgT 10 mol%, internal high AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 2.0) Coated silver amount 0.50 gelatin
0.80ExS-42,0XIO-'ExS-52,0XIO-'ExS-60,2X10-'ExS-73,0XIO-" ExM-110,06 ExM 12 0.02ExM
-80,02 Cpd-20,01 Cpd-92,0XI (1-'Cpd-102,0XIO-' 5olv-10,20 Solv-20,05 10th layer (yellow filter layer) Gelatin 0.6 yellow colloidal silver 0,05Cpd-10,2 Solv-10,15 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, internal high AgI type, equivalent sphere diameter 0.5 μm, equivalent sphere diameter Coefficient of variation 15%, octahedral particles) Coated silver amount 0.4 Gelatin 1.0ExS-1
12,0xlO-' ExY-150,9 ExY-130,09 Cpd-20,01 Solv-11,19 12th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI Type, equivalent sphere diameter 1.3 μm, coefficient of variation of equivalent sphere diameter 25%, normal crystal, mixed twin grains, diameter/thickness ratio 4.5) Coated silver amount 0. 5 Seratin
0.6ExS-111,0XIO-' ExY-150,15 Cpd-20,001 Cpd-52,0>g 10-5olv-10,18 13th layer (protective layer) Fine grain silver iodobromide (average grain size 0 .07 μm, Ag11 mol%) 0.2 Gelatin 1.7M-2 (average particle size 1.5 μm) 0. 2H-10,4 UV-40,2 UV-20,08 UV-30,07 Solv-30,04 Furthermore, preservability, processability, pressure resistance, anti-mold/bacterial properties, antistatic properties, and applicability In order to improve the cpa-
a, Cp d ・-5, Cpd-6, Cpd-7, Cp
d-8, B-5, B-mW-2, W-4, and W-3 were added.

5olv- of the 1112th blue-sensitive emulsion layer of sample 201
Samples 202 to 207 were prepared by simultaneously applying one amount at the values shown in Table 2 below.

These samples were subjected to measurement of MTF value, adhesion test, and perspiration property in the same manner as in Example 1. However, 1.
The frequency per rrm was calculated at 40 cycles.

The obtained results showed that even in the sample using a different photosensitive material from Example 1, the effects of the present invention were clearly exhibited as in Example 1.

Example 3 On a subbed cellulose triacetate film support,
Sample 301, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/durability unit, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, silver halide 1 in the same layer
The coating amount is expressed in moles.

(Sample 301) First layer (antihalation layer) Black colloidal silver Silver 0.09 Dispersion A of organic solid disperse dye; 10 g/rrr Dispersion B of organic solid disperse dye; 5 g/rd gelatin
1゜40 Second layer (middle layer) 2.5-di-t-pentadecylhydroquinone 0.18ExM-
80,07 ExC-20,02 ExF-10,002 UV-10,06 UV-20,08 UV-30,]0 3olv-10,10 Solv-20,02 Gelatin 1.04 Third layer (
Donor layer for multilayer effect on red-sensitive layer) Emulsion J
Silver 1,2 emulsion K
Silver 2.0ExS-124X10”” ExC-40,10 EX-140,10 Solv-10,10 Solv-20,10 4th layer (middle layer) Cpd-10,040 Solv-10,020 Gelatin 5th layer ( 1st red-sensitive emulsion layer) Emulsion A Emulsion B xS-1 xS-3 xS-2 ExC-3 EX-2' xM-10 ExC-4 EX-23 V-1 V-2 V-3 olv-1 Gelatin No. 6 layers (third red-sensitive emulsion layer) Emulsion D xS-1 0, 80 Silver 0.25 Silver 0.25 1.5X10-'1.8X10-'2.5X10-' 0, l 7 0, 17 0, 020 0, 020 0, 020 0, 07 0, 05 0, 07 0, 060 0, 87 Silver 1.60 1, 0XIO-' xS-3 xS-2 Ex, C-2 ExC-6 ExC-3 EX -2' ExC-4 olv-1 olv-2 Gelatin 7th layer (second red-sensitive emulsion layer) Emulsion G xS-1 xS-3 xS-2 ExC~3 EX-2' ExC-2 ExC~4 ExC- 5 14XlO-' 2, 0XIO-' 0, 0 1 0 0, 080 0, 05 0, 05 o, oi.

Oo　22 0, 10 1, 63 silver 1゜0 1.0X10-' ■, 4X10-5 2.0XIO-” 0,200 0,200 0,050 o, ois O,200 UV-1 EX-25 U~r2 UV-3 gelatin 8th layer (middle layer) pd-1 EX-26 oLv-1 gelatin 9th layer (first green emulsion layer) Emulsion A Emulsion B xS-6 xS-5 xS-4 xS-12 ExM~9 ExY-8 ExY-10 0,07 0,020 0,05 1, 30 0,040 0,050 0,020 0,80 silver 0.15 silver 0.15 3, 0XIO-' 1.0X10-' 3.8X10-” 5, 0XIO-' 0,200 0,021 0, O30 ExY-13 EX-27 olv-1 olv-3 seven' latin 10th layer (middle layer) EX-22 EX-25 olv-1 olv-4 gelatin 11th layer (3rd green emulsion layer) Emulsion E xS-6 xS-5 xS-4 xt-12 ExY-12 ExY-11 ExY-8 0,005 0,l　00 o, t o.

o, o t.

Ol 63 0, Ol 8 0, 040 0, l 60 o, o s O850 Silver 1.2 3, 5X10-' 8, 0XIO-'3.0X10-' 0, 5X10-' 0, 015 0, 500 0 , 025 ExY-140,020 Solv-10,25 Solv-20,10 Seratin l554 12th layer (yellow filter layer) Yellow colloidal silver Silver 0.05 Dispersion of organic solid disperse dye B 15g/rdCpd-10
,08 Solv-10,03 Gelatin 0.95 13th layer (
1st blue-sensitive emulsion layer) Emulsion A f80.08 emulsion B
Silver 0.07 emulsion F
Silver 0.07ExS-83,5xlOsuExY-150,721 ExY-130,042 EX-290,020 Solv-10,56 Gelatin 1.10 14th layer (second blue-sensitive emulsion layer) Emulsion G xS-8 ExY -15 xC-4 olv-1 Gelatin 15th layer (third blue-sensitive emulsion layer) Emulsion H xS-8 ExY-14 ExY-15 EX-29 olv-1 Gelatin 16th layer (protective layer) Emulsion I UV-5 UV~4 olv-1 Silver 0.45 2, 1XIO□1 0,154 0,007 0, Book Silver 0゜77 2, 2XlO-' 0,010 0,60 0,01 0 0,45 0,69 EX -30 EX-31 B-1 (diameter approx. 1.5 μm) B-2 (diameter approx. 1.5 μm) pd-16 Ceratin 0, 01 0, Ol o, i.

Oo　10 0,02 0, 20 1,80 / In addition to the above, the sample prepared in this way contained l.

2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl p-hydroxybenzoate (approximately 1,000 ppm), and 2-phenoxyethanol (approximately 10,000 ppm relative to gelatin) were added. B-4, B-5, F-1, F-2, F-3
,F-4,F-5゜F-6,F-7,F-8,F-9,
Contains F-10, F-11, F-12, F-13, iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

Samples 302 to 305 Samples 302 to 305 were prepared in the same manner as Sample 301 except that the amounts of 5olv-1 in the 13th to 15th layers of Sample 301 were set as shown in Table 3.

Table 3: Adhesion, perspiration, and MTF values were measured in the same manner as in Example-1. Samples 303 to 305 of the present invention, each having a 5olv-1/coupler ratio of 0.4 or less, were all Example-1.
Results similar to those of 1 and -2 were obtained.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

UV-4: ExF-1・ 2Hs C, H5 C, H, O20゜ ExC-2: UV-5 x/y 70:30 (wt%) Solv-1: of acid Li cresyl 5olv-2: dibutyl phthalate 5olv-3ni Phosphate tri (2-ethylhexyl) Solv-4 ExC-4: 5-CHCOOCR.

(18 hat”io (J C(J N t'1tJU
tiz Shith SL;Pit ShiIJ(JtiExM
-10: ExM 11: (n)C+□82s 12Hzs j7 ExM-8 ExM 9: CH.

C00C,H.

A Molecular weight = approx. 20° ExM-12+ ExM-13: l ExM-14 ExM-15: CI! ExM-14 (Example coupler (Y-74) ) ExY-15: (Example coupler (Y-2) ) ExM-16: CH.

C00C,H.

ExY-13: (Exemplary coupler (Y 19)) CH.

CH.

ExM-16 (Example coupler (Y-73) ) ExS ExS 5: ExS-10: ExS-11: ExS-12: (CH2) l Sol Na ExS ExS ExS-8: 2: Using polymerization initiator 1-1 CH3 CH.

l: CH,=CH-8o2-CH.

CH,=CH CH2 C0NH-CH2 ONH CH2 pd Co H+5(n) CH Co Hll(n) H Cpd-3 Cpd-42 cpa-s: Cpd-6: Cpd-7: Cpd-8 N□~ Cpd- 13: Cpd 14: Cpd C=F2. SO-N (C+ H2)CH2COOK
pd Cpd-10 C,H.

(n)C,H,CHCH2COOCH2(n)C,H,
CHCH2COOCHSO, NaC2H6 ■ OOH NC00HCH.

GoCH, -CHsuT 6CH.

CH]-m-hole CH2-CH57 n=2-4 C,H.

(n)C,H,,NH,7! 'Q, -NHOH:l 7N NHCa　H1+(n) C=　H=　NH'T'N'T″NHOHN(/N X-14 l X-22 X-23 CH.

C,H.

C,H,Ol -N C@HB(n) EX-29 O2 Dispersion A of organic solid disperse dye EX-30 shown below was dispersed by the following method.

That is, 21.7 ml of water and 3 mL of sodium p-octylphenoxyethyne ethoxyethanesulfonate in a 5% aqueous solution.
mf and 596 aqueous solution of p-octylphenoxyboi
0.5 g of nooxyethylene ether (degree of polymerization 10) was placed in a 700 mA pot mill, and dye EX-305.0 was added.
g and zirconium oxide piece (diameter 1mm) 500mf
f was added and the contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion.

After dispersion, the contents were taken out and added to 8 g of a 12.5% aqueous seratin solution, and the beads were removed by filtration to obtain a dye gelatin dispersion A.

Dispersion B of organic solid disperse dye EX-30 below was replaced with EX-31 in Dispersion A above.

The following was produced in the same manner as dispersion A.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 4. Subject of amendment: "Detailed description of the invention" in the specification. Title of the invention 3. Person making the amendment. Relationship with the case. 1990 Japanese Patent Application No. 104667. Silver halide color photographic light-sensitive material.

Claims (1)

[Claims] A silver halide color light-sensitive material having a silver halide emulsion layer and a substantially non-light-sensitive hydrophilic colloid layer on a support, which has one non-light-sensitive hydrophilic colloid layer as the outermost layer furthest from the support. A photosensitive silver halide emulsion layer containing a yellow coupler is provided adjacent to this, and the weight ratio of the high boiling point organic solvent to the yellow coupler contained in the photosensitive silver halide emulsion layer is 0.4 or less. A silver halide color photographic material.