JPH02273746A - Silver halide color photographic sensitive material and production thereof - Google Patents

Abstract

PURPOSE:To lessen the degradation in sensitivity and the deterioration in color reproducibility and further the deterioration in film strength even if colored cyan couplers are used in a large amt. by providing silver halide emulsion layers obtd. by applying a liquid mixed with a specific liquid dispersion and a color sensitized silver halide emulsion just before the application on a base. CONSTITUTION:At least one layer of the silver halide emulsion layers are provided on the base. The silver halide emulsion layers are obtd. by applying the liquid mixed with the liquid dispersion contg. the colored cyan couplers and contg. a high boiling org. solvent coexisting therewith at <=10 (including 0) by the weight of the colored cyan couplers and the color sensitized silver halide emulsions just prior to the application on the base. The degradation in sensitivity and the deterioration in color reproducibility and further the deterioration in film strength are lessened even if the colored cyan couplers are used in the large amt.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic material having high sensitivity, excellent color reproduction and sharpness, and a method for producing the same.

[Prior art]

Conventionally, in color photographic materials, especially color negative materials, cyan dye is added before color development in order to correct unnecessary absorption on the short wavelength side of the cyan dye generated by the coupling reaction between the cyan coupler and the oxidized product of the developing agent. It is a well-known technique to use a colored cyan coupler that has maximum absorption on the shorter wavelength side and develops a cyan color after development.

In particular, as disclosed in U.S. Pat. It is known that if an attempt is made to shorten the spectral sensitivity distribution of the human eye to bring it closer to the spectral sensitivity distribution of the eye, the saturation of red will drop significantly. As one of the most effective means for solving this problem, strengthening of masking using colored couplers is pointed out in Japanese Patent Application No. 62-285586.

[Problem to be solved by the invention]

However, it has been found that increasing the amount of colored cyan coupler in order to eliminate the above-mentioned decrease in saturation causes a significant decrease in sensitivity and deterioration in color reproducibility due to distortion of the spectral sensitivity distribution.

It was also found that the adverse effects of the colored cyan coupler can be alleviated by using a large amount of a high boiling point solvent when dispersing the colored cyan coupler, but with this method, a significant deterioration in coating film strength was observed.

SUMMARY OF THE INVENTION Therefore, the main object of the present invention is to provide a silver halide color photographic material that exhibits less deterioration in sensitivity, color reproducibility, and film strength even when a large amount of colored cyan coupler is used. .

[Means to solve the problem]

The above objects of the present invention are as follows: (1) A dispersion containing a colored cyan coupler and having a weight ratio of a high boiling point organic solvent coexisting with the colored cyan coupler to the colored cyan coupler of 10 or less (including 0), and a color sensitized dispersion. A silver halide color photographic light-sensitive material comprising, on a support, at least one silver halide emulsion layer obtained by coating a liquid mixed with a silver halide emulsion immediately before coating, (2) Colored Cyan A dispersion containing a coupler and having a weight ratio of a high boiling point organic solvent coexisting with the colored cyan coupler to the colored cyan coupler is 10 or less (including 0) and a color-sensitized silver halide emulsion are mixed in a static mixer. A method for producing a silver halide color photographic light-sensitive material, characterized in that the silver halide emulsion layer is coated on at least the L layer support, preferably in multiple layers, without being allowed to stagnate for 20 minutes or more. Ta.

In the present invention, applying the mixed solution immediately before application means that the stagnation time after mixing until application is performed is 20 minutes or less, preferably 10 minutes or less, and more preferably 1 minute or less.

The temperature at which the liquid stagnates before mixing is 28 to 70°C, more preferably 32 to 60°C, and the temperature after mixing until coating is preferably 35 to 50°C. Further, the two liquids to be mixed are both 10 to 200 centipoise (cp), and the mixing ratio is 0. 1-1. Preferably, the capacitance ratio is 0.

As a device for mixing immediately before coating, there are known stirring devices, such as impeller-type devices with stirring blades attached to a small capacity tank, and stirring devices for high viscosity liquids such as kneaders and dispers. Although a mixer can also be used, preferably an in-line mixing device, especially a static mixer among in-line mixers. As a static mixer, the book by S. J. Cheno et al.
"Static Mixing Handbook" published by Sogo Kagaku Kenkyusho (1973), written by J. B. GRAY rTu
rbulent Radial Mixing in
Published by Pipes J Academic Press rMIX
Those described in ING vol. 3 J (published in 1986) can be preferably used. A multi-stage mixing element inserted into the transfer piping can be preferably used, and the shape of the element is not limited.

The colored cyan coupler used in the present invention is as follows:
Those represented by 1) are preferred.

- Monna (I) In the formula, R represents an aliphatic group, an alicyclic group, an aromatic group or a heterocyclic group, and R2 represents a group capable of substituting on the naphthol ring. A-B-N=N-D represents a coupling-off group, and A is a reaction between the oxidized color developing agent and the coupler of general formula (I), whereby the carbon atom at the coupling active position of the coupler and A B represents a divalent aromatic group or a heterocyclic group, and D represents an aromatic group or a heterocyclic group. n represents an integer from 0 to 4.

In addition, at least one of the groups represented by A, B and D in the - pattern hole (1) has a sulfo group, a carboxyl group, or an alkali metal salt thereof, an ammonia salt, an alkylamine salt or a pyridinium salt as a substituent. . By having such a water-soluble group, A-B-N
The coupling-off group represented by =ND flows out into the developer after being separated from the coupler residue.

Examples of the aromatic group represented by R1 include substituted or unsubstituted aromatic groups having 6 to 30 carbon atoms.

Examples of the heterocyclic group include substituted or unsubstituted heterocyclic groups in which the heterocyclic residue has 2 to 30 carbon atoms, and examples of the heteroatom in the heterocycle include N, 0.5SSe, etc. ,
Preferably it is a nitrogen-containing unsaturated heterocycle. The aliphatic group refers to an aliphatic hydrocarbon group, including substituted or unsubstituted, linear or branched alkyl groups, alkenyl groups, and alkynyl groups, preferably having 1 to 20 carbon atoms, substituted or unsubstituted It is an alkyl group. Examples of the alicyclic group include substituted or unsubstituted 3- to 8-membered, preferably 5- or 6-membered cycloalkyl or cycloalkynyl groups.

Rz represents a group (including an atom, the same applies hereinafter) that can be substituted on the naphthol ring, and typical examples include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group,
Examples include aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, etc.
The number of carbon atoms contained in this Rt is 0 to 30. 2 R
Examples of cyclic R2 when 2 is present include a dioxymethylene group. The aliphatic group herein refers to an aliphatic hydrocarbon group including alkyl, alkenyl, and alkynyl groups, and may have conventional substituents.

The colored cyan coupler represented by formula (1) is preferably one in which R is an aromatic group or a heterocyclic group, and particularly preferably the colored cyan coupler represented by general formula (n).

-Represents an alkyl group or an alkoxy group of Monna (II). R8 represents an alkyl group having 1 to 3 carbon atoms. M represents a hydrogen atom or 1/m number of m-valent cations.

Here, preferably n=o.

Specific examples of the colored cyan coupler represented by the general formula (n) are illustrated below.

(II-1) In the formula, R2, A, B and n have the same meanings as in formula (1),
R3 and R1 are each a hydrogen atom, -R7, OR9, S
R9, 0CRq, NH3OzRw, has 3 to 2 carbon atoms
4) represents a straight-chain or branched alkyl group, but R
1 and R9 do not represent a hydrogen atom at the same time. R4,
R and R6 are each a hydrogen atom, a halogen atom, or a carbon number of 1 and 3 (■-2) (n-3) (n-5) (It-6) (n-4) (■ (■ (■ (n -12) (■ (■ (II-17) (n-18) (n-21) (It-22) (■-19) (II-20) Shuut'1 (II-23) S) LJ lNa (n-25) (n-27) (n-26) (If-28) (n-29) (II-1) Furthermore, in -Momonena (1), R+ is an aliphatic group or an alicyclic group. Specific examples of colored cyan couplers representing groups are shown below.

(III-2) (III-3) (CHz)z (CHz)z (I[l-4) (I[[-6) (III-7) (III-5) (I[I-8) ( I[[-9) (I[[-12) (III-13) (III-10) (III-11) The above colored cyan coupler in which R1 represents an aliphatic group or an alicyclic group is, for example, US patent cylinder 4,0
No. 04,929, No. 4,138°258 and British Patent No. 1,146,368.

In addition to the above-mentioned couplers, compounds included in general formula (1), such as eg.

Colored cyan couplers are generally used together with cyan couplers in red-sensitive emulsion layers to correct unnecessary absorption of coloring dyes. Further, when there are two or more red-sensitive emulsion layers, the colored cyan coupler may be contained in at least one of them, but it is preferably contained in two or more layers.

In the present invention, the weight ratio of the high boiling point organic solvent to the colored cyan coupler in the dispersion containing the colored cyan coupler is expressed by the following formula.

The above ratio is 10 or less, but from the viewpoint of improving sharpness, it is preferably 5 or less, and most preferably O.

Even when two or more photosensitive layers containing colored cyan couplers are provided, the effects of the present invention can be achieved if at least one of the layers complies with the present invention, but it is preferable that the two or more layers comply with the present invention.

In addition, according to the present invention, colored cyan coupler, which has conventionally been used in an amount of 0.1 g/rW or less, can be reduced to 0.1 g/rW.
/rrf or more can be applied.

As the high boiling point organic solvent, any organic solvent with a boiling point of 150°C or higher can be used, but preferably phosphoric acid esters, phthalic acid esters, citric acid esters, benzoic acid esters, phenol derivatives, alkylamides, fatty acid esters , trimesic acid ester, etc.

A dispersion containing a colored cyan coupler may contain only the colored cyan coupler as a coupler, or may contain other cyan couplers or couplers that develop a hue other than cyan. Other cyan couplers include all couplers that form cyan dyes, including not only 4-equivalent cyan couplers but also 2-equivalent couplers with normal leaving groups, DIR couplers, bleach accelerator-releasing couplers, and other photographically useful couplers. There are couplers that release fragments.

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

A dispersion containing a colored cyan coupler can be prepared by a known dispersion method.

First, in the case of dispersing oil droplets in water, the colored cyan coupler is dissolved using a high boiling point solvent with a boiling point of about 150°C or higher, and if necessary, a low boiling point solvent with a boiling point of 100°C or lower and/or a water-miscible organic solvent. It can be obtained by emulsifying and dispersing a surfactant in a hydrophilic colloid such as an aqueous gelatin solution using a stirrer, a colloid mill, a high-pressure homogenizer, a flow jet mixer, an ultrasonic emulsifier, etc.

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

In addition, in the above-mentioned oil-in-water type dispersion, 10 times the amount (weight) of the colored coupler is added to the oil phase in which the colored coupler is dissolved.
The following method can also be used: add water to form a water-in-oil dispersion in advance, and then disperse this in a hydrophilic colloid such as an aqueous gelatin solution to finally obtain an oil-in-water dispersion. .

Organic solvents with low boiling points and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, carbon tetrachloride, diethyl ketone, methyl ethyl ketone, n-butyl carpitol acetate, methylene chloride, methyl propionate, and propionic acid. Examples include ethyl, cyclohexanone, tetrachloroethane, trichloroethane, cyclohexane, benzene, toluene, nitromethane, and chloroform.

Furthermore, water-miscible organic solvents include methanol, ethanol, isopropyl alcohol, dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, dioxane, dimethylformamide, dimethoxyethane, formamide, ethylene glycol, acetonitrile, acetone, and butyrolactone. , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol 7-methyl ether, diacetone alcohol and tetrahydrothiophene-1,1-dioxide.

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

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

[A method of incorporating the colored coupler of the present invention and other couplers and additives as a hydrophilic colloid layer-filled polymer latex composition. ] Examples of the polymer latex include polyurethane polymers, polymers polymerized from vinyl monomers [suitable vinyl monomers include acrylic esters (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, glycidyl acrylate, etc.] ), α-substituted acrylic esters (methyl methacrylate, butyl methacrylate, octyl methacrylate, glycidyl methacrylate, etc.),
Acrylamide (butylacrylamide, hexylacrylamide, etc.), α-substituted acrylamide (butylmethacrylamide, dibutylmethacrylamide, etc.), vinyl esters (vinyl acetate, vinyl butyrate, etc.), vinyl halides, (vinyl chloride, etc.), vinylidene halides ( (vinylidene chloride, etc.), vinyl ethers (vinyl methyl ether, vinyl octyl ether, etc.), styrene, X-substituted styrene (α-methylstyrene, etc.), nuclear-substituted styrene (
hydroxystyrene, chlorostyrene, methylstyrene, etc.), ethylene, propylene, butylene, butadiene,
Acrylonitrile and the like can be mentioned. These may be used alone or in combination of two or more, or may be mixed with other monomers as minor components. Other vinyl monomers include itaconic acid, acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate,
Examples include sulfoalkyl methacrylate and styrene sulfonic acid. ] etc. can be used.

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

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

[A method of dissolving colored couplers using a surfactant. ]

Useful surfactants may be oligomers or polymers.

A method of using a hydrophilic polymer in place of or in combination with a high-boiling point solvent for oil-in-water type dispersion. This method is described, for example, in US Pat. No. 3,619,195 and German Patent No. 1,957,467.

The dispersion method preferably used in the present invention is a method in which a high boiling point organic solvent is not used (in other words, solid fine powder dispersion). precipitation method) and/or in the presence of a dispersant (e.g. anionic, nonionic or cationic surfactant) by known comminution means, e.g. ball milling (ball mill, vibratory ball mill, planetary ball mill, etc.), sand milling, colloid milling. , jet milling, roller milling, etc. (mechanical method), in which case a solvent (e.g., water, alcohol, etc.) that does not dissolve the coupler of the present invention may coexist. However, they do not need to coexist.

For the reprecipitation method, for example, the coupler is mixed with a suitable solvent (e.g. ethanol, methyl ethyl ketone, acetone, DMF
), a non-solvent (for example, toluene) that is miscible with these may be added to precipitate a fine powder of the coupler, in which case a dispersing surfactant (nonionic, anionic or cationic agent) may be used.

Alternatively, the coupler may be first dissolved in a suitable solvent by controlling the pH and then crystallized by changing the pH (neutralization method).

The coupler particles in the dispersion have an average particle size of 10 μm or less,
More preferably 2 μm or less, particularly preferably 0.
It is more preferable that the powder be a fine powder of 5 μm or less, and in some cases, 0.1 μm or less.

In the oil-in-water type and other dispersion methods described above, it is preferable to use various anionic, nonionic, cationic or amphoteric surfactants as the surfactant as the dispersion aid. It is also a preferable method to use polymer or oligomer type surfactants disclosed in JP-A-53-138726, JP-A-55-113031, and the like.

In the present invention, a dispersion containing a colored coupler (liquid A) and a color-sensitized silver halide emulsion (liquid B) are prepared separately and mixed immediately before coating.
The liquid may also contain other couplers and other photographic additives.

Moreover, a part of the colored coupler can also be contained in the above B liquid. In this case, the ratio of A liquid content/B liquid content of the colored coupler is preferably in the range of 1070 to 3/7, particularly preferably in the range of 1010 to 515.

In the color-sensitized silver halide emulsion according to the present invention, those sensitized to red are particularly effective, and it is particularly useful to use the dyes represented by the following pattern (a).

General formula [A] -21-・-1 (Xl)1 In the general formula [A], Zl and Zt each represent a group of nonmetallic atoms necessary to form a basic heterocycle (however, from the viewpoint of color sensitization) represents that when used alone, it is not preferable for Zl and Zz to form an oxazole ring or an imidazole ring at the same time. Ro and RIz represent an alkyl group,
At least one of them represents an alkyl group substituted with a hydroxyl group, a carboxyl group, or a sulfo group.

LI, Lx, L, s and L4 each represent a methine group (however, L and L3 may be bonded together to form a carbocyclic ring).

Xl represents an acid anion, 2.1. , m mz , m
3 and n- each represent 0 or 1 (O when forming an inner salt) (however, m.

+mt +m==1.2 or 3).

The basic heterocycle is a monocyclic or bonded 5- or 6-membered nitrogen-containing heterocyclic group known as a nucleus forming a cyanine dye, such as thiazole, thiazoline, imidazole, imidacilline, imidazolidine, Thiazolidine, oxazole, oxazoline, oxazolidine,
Selenazole, selenazoline, selenazolidine, pyrrole, viroline, pyrrolidine, pyridine, benzothiazole, benzoxazole, benzoselenazole, benzimidazole, indole, indolenine, naphtho [1
,2・d]thiazole, naphtho[1,2・d]oxazole, naphtho[2,3・d]oxazole, naphtho[2
, 1・d]selenazole, naphtho(1,2・d)selenazole, etc. These heterocyclic groups may further include alkyl groups (for example, methyl group, ethyl group, etc.), alkoxy groups (
For example, methoxy group, ethoxy group, etc.), halogen atom (for example, chloro atom, bromine atom, fluorine atom, etc.), carbamoyl group, sulfamoyl group, alkoxycarbonyl group (
For example, methoxycarbonyl, ethoxycarbonyl), phenyl group, cyano group, etc. may be substituted.

Further, the compound of the above-mentioned -Momona [A] is preferably a compound represented by the following -Momona [mouth].

- Monana [mouth] (Xz), l□ In the above - Monna [mouth], Y represents S or Se, Y2 represents S, Se, O or NR, RI3 and R14 represent R, , , R, □. W1 to W& each represent a lower alkyl group, an alkoxy group, a halogen atom, an aryl group, an alkoxy group, a carbonyl group, a cyano group, a carbamoyl group, or a sulfamoyl group; , and Wb
Xt is synonymous with viscous.

n! is synonymous with nl.

Ro represents an alkyl group, an aryl group, an aralkyl group or an alkenyl group.

RIS represents an alkyl group, an aryl group, or a heterocyclic group, and the alkyl group is preferably a lower alkyl group, such as methyl, ethyl, propyl, etc., with an ethyl group being particularly preferred.

Examples of the heterocyclic group include aromatic heterocyclic groups such as thienyl and furyl, and acidic heterocyclic groups represented by the following symbol (C), and examples of the aryl group include a phenyl group.

General formula [C] In general formula [C], Q is, for example, a pyrazolone derivative, an isoxacilone derivative, an oxacilone derivative, 2, 4.
6-drichetohexahydropyrimidine derivative, 2-thio-2,4,6-drichetohexahydropyrimidine derivative, rhodanine derivative, 2,4-thiazolidinedione derivative, 2-thio-2,4-oxazolidinedione derivative,
5 selected from thianaftynone derivatives, hydantoin derivatives, indation derivatives, oxindole derivatives, etc.
Represents a group of nonmetallic atoms necessary to form a 6-membered or 6-membered heterocyclic nucleus. Specific examples of dyes useful in the present invention are shown below, but the present invention is not limited thereto.

(E1) (E4) (E2) (E5) (E3) (E6) (E7) (E8) (E9) (E13) (E14) (stomach (stomach (E11) (E12) (stomach (E17) (stomach (stomach (E20) (stomach (stomach (stomach (E27) (E22) (E23) (E24) (stomach (E30) (E31) (E33) (E32) (E34) C,H.

C, H3 (E35) The amount of the sensitizing dye added in the present invention is preferably 10 to 1000 mg, more preferably 20 to 400 mg per mole of silver halide.

It is preferable to use the above-mentioned sensitizing dyes alone or in an amount that produces a supersensitizing effect, or in combination of two or more to achieve the desired spectral wavelength range. When used in combination, the usage ratio is the optimum amount mentioned above. can be selected arbitrarily.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The support surface is coated before or after priming.
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

(For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used. U.S. Patent No. 268129
4, No. 2761791, No. 3526528, and No. 3508947, etc., multiple layers may be applied simultaneously.

The silver halide color photographic light-sensitive material of the present invention is provided with at least IN of each of the silver halide emulsion layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. Generally, there are no particular restrictions on the number and order of the silver halide emulsion layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive unit consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive unit is a photosensitive layer unit that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the photosensitive layer unit is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the above-mentioned arrangement order may be reversed, or a layer arrangement may be adopted in which different photosensitive layers are sandwiched between the same color-sensitive layer.

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

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

The plurality of silver halide emulsion layers constituting each photosensitive layer unit are a high-speed emulsion layer, a low-speed emulsion layer, as described in West German Patent No. 1.121.470 or British Patent No. 923,045. A two-layer structure can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-112751, JP-A No. 62-200350, JP-A No. 6
As described in Nos. 2-206541 and 62-206543, a low-sensitivity emulsion layer is provided on the side remote from the support.
A highly sensitive emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, low-sensitivity blue-sensitive N (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitive layer (GH) / low-sensitivity green-sensitive layer (GL) /high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive NCRL),
Alternatively, they can be installed in the order of B H/B L/G L/G H/RH/RL, or in the order of B H/B L/GH/GL/RL/RH.

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

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

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

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

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

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

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Nα17643
(December 197B), pp. 22-23.

'6■, Emulsion preparation
tion and types)”, and the same Na18
716 (November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", Published by Paul Montell (P, Gl.
afkides.

Chemic et Ph1sique Photog
Raphique, Paul Montel.

1967 “Photographic Emulsion Chemistry” by L Duffin, published by Focal Press (G, F, Duffin+ Photog
rapicEmulsion Che+++1str
y (Focal Press, 1966), Zelikman et al. [Manufacture and coating of photographic emulsions], published by Focal Press (V, L, Zelikn+an at al
,.

Making and Coating Photo
rapic En+ulsion+Focal Pr
ess, 1964).

U.S. Patent Nos. 3,574,628 and 3,655.39
No. 4 and British Patent No. 1. 413. Monodispersed emulsions such as those described in No. 748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4.
434゜226, 4,414,310, 4,
433.048, 4,439.520, and British Patent No. 2,112,157.

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

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are subject to Research Disclosure NC
It is described in L17643 and Na18716, and the relevant parts are summarized in the table below.

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

Additive seeds RD17643 RD187
161, chemical sensitizers page 23 64
Page 8, right column 2, Sensitivity enhancer
Same as above 3, spectral sensitizer, pages 23-24
Page 648 right column ~ Super sensitizer
Page 649 right column 4, brightener page 24 5, antifoggant page 24-25 page 649 right column ~ and stabilizer 6, light absorber, page 25-26 page 649 right column ~ filter dye, 650
Page left column UV absorber 7, anti-stain agent Page 25 right column 650 left to right column 8, dye image stabilizer page 25 9, hardener 10, binder 11, plasticizer, lubricant 12, coating aid, Surfactant 13, static inhibitor 26 pages 26 pages 27 pages 26-27 pages 651 pages left column Same as above 650 pages right column 650 pages right column 27 pages Same as above In addition, to prevent deterioration of photographic performance due to formaldehyde gas , U.S. Patent No. 4,411°987 and U.S. Pat.
, 435.jt in issue 503! It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with the formaldehyde loaded thereon.

In the present invention, color couplers that give yellow, magenta, and cyan dyes, which are the three primary colors of the subtractive color method, can be used, and specific examples thereof are described in the aforementioned Research Disclosure (RD) Nα17643, ■-C-G. Described in the patent.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,326
, No. 024, No. 4,401.752, No. 4,248,
No. 961, Special Publication No. 58-10739, British Patent No. 1,
No. 425.020, No. 1.476.760, U.S. Patent No. 3. No. 973°968, No. 4,314,023,
4.511.649, European Patent No. 249,473A
Preferably, those described in No.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, 4.351. No. 897, European Patent No. 73,636, U.S. Patent No. 3,061,432, U.S. Patent No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-335
No. 52, Research Disclosure 24230
(June 1984), JP-A No. 60-43659, No. 6
No. 1-72238, No. 60-35730, No. 55-1
No. 18034, No. 60-185951, U.S. Patent No. 4
．． No. 500.630, 4. 540゜654, same 4
, No. 556,630, International Publication No. WO3B104795, etc. are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,233
No. 4,296,200, No. 2,369,929, No. 2. 801. No. 171, 2,772,162
No. 2. No. 895゜826, 3,772,002
No. 3,758.308, No. 4,334.011, No. 4゜327.173, West German Patent Publication No. 3. 32
9°729, European Patent No. 121.365A, European Patent No. 24
No. 9.453A, U.S. Pat. No. 3,446,622, U.S. Pat. No. 4,333,999, U.S. Pat.
, No. 451,559, No. 4,427.767, No. 4,
No. 690,889, No. 4゜254.212, No. 4,2
Those described in No. 96,199, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of color-developing dyes are described in Research Disclosure Nα17643 Section ■-G, U.S. Patent No. 4,163°670, and Japanese Patent Publication No. 5
No. 7-39413, U.S. Patent No. 4,004,929,
No. 4,138,258, British Patent No. 1,146,36
The one described in No. 8 is preferred. Also, U.S. Patent Nos. 4 and 7
No. 74,181, a coupler that corrects unnecessary absorption of a color-forming dye by a fluorescent dye released upon coupling, or a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777,120. It is also preferred to use couplers having a dye precursor group as a leaving group.

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

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; 080°211, 4,367.282, 4.409.320,
No. 4,576.910, British patent tube 2.102.17
It is stated in No. 3, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-154234, No. 60-184248, No. 61-37346, U.S. Patent No. 4.248,96
No. 2, No. 4,782,012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
Those described in JP-A No. 2,131,188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. DIR redox compound emitting couplers, DIR couplers emitting couplers, DIR described in JP-A-60-185950, JP-A-62-24252, etc.
Coupler-releasing redox compound or DIR redox-releasing redox compound, European Patent No. 173.302A
R
,D, Nα11449, 242411 JP-A-61-
No. 201,247, and the bleach accelerator releasing couplers described in U.S. Patent No. 4. Ligand-releasing couplers described in US Pat.
Couplers that emit fluorescent dyes as described in No. 1 can be mentioned.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the emulsification dispersion method are described in US Pat. No. 2,322.027 and the like.

Various couplers, ultraviolet absorbers, stabilizers,
Some hydrophobic photographic additives such as anti-stinting agents, similar to the colored cyan couplers mentioned in this invention, include hydrophilic colloid solutions (sometimes containing silver halide emulsions).
If stagnation aging is performed after mixing with the ester, the formation of undissolved aggregates may occur. Therefore, in addition to the present invention, it is an object of the present invention to suppress the stagnation time of other hydrophobic additives after mixing with the hydrophilic colloid solution to 20 minutes or less, preferably 10 minutes or less, and more preferably 1 minute or less. This is also desirable in order to further increase the effect of

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and Patent Application No. 1983-
Benziisothiazolone, n-butyl p-hydroxybenzoate, phenol, 2-(
It is preferable to add various preservatives or antifungal agents such as 4-thiazolyl)benzimidazole.

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

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643 and Nα18716
It is described from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling rate TI/□ is preferably 30 seconds or less. The film thickness means the film thickness measured at 25 degrees and 55% relative humidity (2 days), and the film swelling rate TI/□ can be measured according to a method known in the art. For example, Nee Green (A.

Photographic Science and Engineering (Photogr, Sc) by Green) et al.
i, [ing,).

It can be measured by using a swellometer (swelling membrane) of the type described in Vol.
1/2 is defined as the time required to reach a film thickness of TI/l, where 90% of the maximum swelling film thickness reached when treated with a color developing solution at 30° C. for 13 minutes and 15 seconds is the saturated film thickness.

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

The color photographic material according to the present invention includes the above-mentioned RD, N
α17643, pages 28-29, and the same no.

Development processing can be carried out by the usual method described in 615 left column to right column of No. 18716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, and 3-methyl. -4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, and P-)luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than mf. 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.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■), cobalt (I[
I), compounds of polyvalent metals such as chromium (■), copper (n), peracids, quinones, nitro compounds, etc. are used.

It is preferable to use aminopolycarboxylic acid iron (I[I) complex salts and persulfates, including iron (III) ethylenediaminetetraacetic acid complex salts, as bleaching agents from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron aminopolycarboxylate (II
I) Complex salts are particularly useful in both bleach and bleach-fix solutions. These iron aminopolycarboxylic acids (DI
) The pH of the bleach or bleach-fix solution using complex salts is usually 5.
5-8, but for faster processing, lower p
It can also be treated with H.

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

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Te1evi-s
ion Engineers Volume 64, P, 248
253 (May 1955 issue).

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the photosensitive layer) The coating amount is expressed in g/rrr of silver for silver halide and colloidal silver, and in g/rd for couplers, additives and gelatin. The number of moles of sensitive dyes is expressed per mole of silver halide in the same layer.

For chemical structural formulas that take the form of salts, the notation method used in chemical abstracts is followed.

1st layer (antihalation layer) Black colloidal silver...0.15 Gelatin...2.9UV-1
(Ultraviolet absorber) ・0.03UV-2 (Ultraviolet absorber) ・0.06UV-3 (Ultraviolet absorber) Solv-2 (solvent) ExF-1 (cyan dye) ExF-2 (cyan dye) 2nd layer (Low-sensitivity red-sensitive emulsion N) Ag1 4 mol% Uniform Equivalent sphere diameter 0.4 μm Number of fluctuations in equivalent sphere diameter 37%, plate-like grains Diameter/thickness ratio 3.0 Coated silver amount Gelatin ExS-1 (enhancing dye) ...0.4 ...0.8 ...Ol ...0゜ ...0゜ ...0゜ (E5) ...4.0XIO-' ExS-2 (sensitizing dye) (E6) ...0. lXl0-' ExS-5 (enhancing dye) (E34) ...6.5X10-' ExS-7 (enhancing dye) (E35) ...6.5X10-' ExC-1 (cyan coupler) ・ 0 .17E
xC, -2 (cyan coupler) ・0.03E
xC-3 (Magenta Colored Cyan Coupler) (I[-
3)...0.045 3rd layer (mid-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2:1 internal height Agl, equivalent sphere diameter 0.65 μm, variation in equivalent sphere diameter Coefficient 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount...0.65 iodobromide emulsion (Ag 14 mol%, uniform-Agl type, equivalent sphere diameter 0)
．． 4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter/thickness ratio 3.0) Coated silver amount
...0.1 gelatin ...
1.0ExS-1 (enhancing dye) (E5)...5.0XIO-' ExS-2 (sensitizing dye) (E6)...0.2X10-' ExS-5 (sensitizing dye) ( E34)...8.2X10-' ExS-7 (enhancing dye) (E35)...8.2X10-' ExC-1 (cyan coupler)...0.31E
xC-2 (cyan coupler)...0.01Ex
C-3 (Magenta colored cyan coupler) (III-
3)...0.09 4th layer (high sensitivity red-sensitive emulsion N) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μm, equivalent sphere diameter Coefficient of variation 25%, plate-like particles, diameter/thickness ratio 2.5) Coated silver amount...0.9 Gelatin...0.8ExS-1 (sensitizing dye) (E5)...6. 4X10-' ExS-2 (enhancing dye) (E6) ...0.9X10-' ExS-5 (sensitizing dye) (E34) ...10.4X10-' ExS-7 (sensitizing dye) (E35) ...10.4xlO-' ExC-1 (cyan coupler) ...0.07E
xC-4 (cyan coupler)...0.05ExC
-3 (Magenta colored cyan coupler) ([[-3)
...0.05 Solv-1 (solvent) -0,07Sol
v-2 (solvent) -0,20Cpd-7(
Antifoggant)...4.6X10-' 5th layer (middle layer) Gelatin...0.6UV-4
(Ultraviolet absorber) ...0.03UV-5 (ultraviolet absorber) ...0.04Cpd-1 (color mixture prevention agent) ...0.1 Polyethyl acrylate latex ...0.08Solv-1 (solvent)
・0.05 No. 61g (Low sensitivity green emulsion N) Silver iodobromide emulsion Ag1 4 mol% uniform type. Equivalent ball diameter 0.
4μ, equivalent sphere diameter 0.7μm, coefficient of variation of equivalent sphere diameter 37%
, plate-shaped particles, diameter/thickness ratio 2゜ coated silver amount
...0.18 gelatin
...0.4ExS-3 (sensitizing dye) ...
・2 X 10-'ExS-4 (enhancing pigment)
・ 7X10-'ExS-5 (sensitizing dye) ・
lXl0-'ExM-5 (magenta coupler)...
・0.11ExM-7 (yellow colored magenta coupler) ...0.0
3ExY-8 (DIR coupler) -0,01So
lv-1 (?Container J) ・0.
09S, 1v-4 (solvent) ・0.01
7th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, core-shell ratio 1:1
surface height AgI type, equivalent sphere diameter, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 4.
0) Coated silver amount Gelatin ExS-3 (sensitizing dye) ExS-4 (sensitizing dye) ExS-5 (sensitizing dye) ...0.27 ...0.6 ...2X10-' ...・7 X 10-'...lXl0-' ExM-5 (magenta coupler) ...0.17Ex
M-7 (yellow colored magenta coupler)
...0.04ExY-8(
DIR coupler) ...0.02 Solv-1 (solvent) ・0.14 S, Iv-4 (solvent) ・0.02 No. 87
W (high sensitivity green emulsion N) Silver iodobromide emulsion (Ag 18.7 mol%, silver amount ratio 3:4:2
Multilayer structure particles, Agl content of 24 mol, 0 mol%, 3 mol% from the inside, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 1.6) Coating Silver amount...0.7 Gelatin...0.8ExS-4 (
Exacerbating dye)...5.2X10-'ExS-5 (sensitizing dye) lXl0-'Eχ5-8 (enhancing dye)...0.3X10-'ExM-5 (magenta coupler)...0. IExM-6 (yellow colored magenta coupler)
...0.03ExY-8 (DIR coupler) ExC-1 (cyan coupler) ExC-4 (cyan coupler) Solv-1 (solvent) Solv-2 (?8 simultaneous D Solv-4 (? uniform) Cpd -7 (Antifoggant) 9th layer (middle layer) Gelatin...0.6Cpd
-1 (color mixing prevention agent) ... 0.04 Polyethyl acrylate latex ... 0.12 Solv-1 (
Solvent) -i・0.02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI6
Mol%, internal high AgI type with core-shell ratio of 2:1, equivalent sphere diameter of 0. 7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount...0.68 silver iodobromide emulsion (AgI 4 mol%, coefficient of variation of uniform equivalent sphere diameter) 37%, plate-like particles, diameter/thickness...0.02...0.02...0.01...0.25...0.06...0.01...lXl0 -' Ratio 3.0) Coated silver amount...0.19 Gelatin...1,0ExS-3
(Sensitizing dye) 6X10-'ExM-10
(DIR coupler) ・0. 19Solv-1 (solvent) -0,20 11th layer (yellow filter layer) Yellow colloidal silver...0.06 Gelatin...0.8Cpd-
2 (yellow dye)...0,13Solv-
1 (solvent) ・0.13Cpd-1 (color mixing prevention agent) ...0.07Cpd-6 (antifogging agent) ...0.002H-1 (hardening agent)
...0.13 12th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol%, uniform-Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 15%, Plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount
...0.3 silver iodobromide emulsion (Ag1 3 mol%,
Uniform Agl type, equivalent sphere diameter 3.0 μ, coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount
...0.15 gelatin
...1.8ExS-6 (sensitizing dye)
・ 9X10-'ExC-1 (cyan coupler) ...0.06ExC-4 (cyan coupler)
...0.03ExY-9 (DIR coupler)
...0.14ExY-11 (yellow coupler)
・・0.89Solv-1 (solvent) ・0
．． 42 13th layer (middle N) Gelatin...0.7ExY
-12 (DIR coupler) ・0. 20Solv-
1 (solvent) - 0.34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, internal cylinder Agl type,
Equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount...0.5 Gelatin...0.5ExS-6 (
Sensitizing dye)...lXl0-'ExY-9(D
IR coupler)・0.01ExY-11 (yellow coupler)...0.20 ExC-1 (cyan coupler)・0.02Solv
-1 (I agent) -0, IQ 15th layer (first protection N) Fine grain silver bromide emulsion (Ag 12 mol%, uniform -Agl type, equivalent sphere diameter 0.07 μm) Coated silver amount...0.12 Gelatin...0.9UV-4 (
UV absorber) ...0.11UV-5 (UV absorber) ...0.16Solv-5 (solvent) ・0.02H-1 (hardener)
...0.13Cpd-5 (scavenger)
...0.10 Polyethyl acrylate latex...0.09 16th layer (second protective layer) Fine grain silver bromide emulsion (Ag1 2 mol%, homogeneous Agl type,
Equivalent sphere diameter: 0.07 μm) Amount of coated silver: 0.36 Gelatin: 0.55 Polymethyl methacrylate particle diameter: 1. 5μ...0.2 H-1 (hardener)...0.17 In addition to the above components, each layer contains emulsion stabilizer Cpd-3 (0,
07g/r), surfactant Cpd-4 (0.03g/r
rf) was added as a coating aid.

V-1 V-2 UV-3 UV-4 ShiN UV-5 olv-1 olv-2 olv-4 CsH+ 1(t) olv-5 0-P+OCJ+5(n))s xF-1 N(CsHs)z xS-6 ExC-1 ExC-3 xM-7 xM xY-8 CI! .

ExC-4 Song xM-5 H2 xM-6 xY-9 xY-11 CPd-7 Cpd-6 (antifogging agent) Cpd-1 (color mixing prevention agent) H-1 (hardening agent) CHxl=CH3OzCH□C0NIC) ItCH yo N
HCOC1'hSOzCH=CHtCpd-5 (scavenger) Hs Cpd-2 (yellow dye) Cpd-3 (stabilizer) Cpd-4 (surfactant) (Preparation of comparative sample 101) Second layer, third layer and third layer A four-layer magenta colored cyan coupler (ExC-3: m-3) and other cyan couplers ExC-1 and ExC-2 or ExC-4 were both mixed in a 2:1 mixed solvent of ethyl acetate and water. 70″C
A water-in-oil emulsion is formed by heating and melting the water and stirring in the presence of Aerosol OT (manufactured by American Cyanamid).Then, the emulsion is added to an aqueous gelatin solution, and a high-speed stirrer is used to form an oil-in-oil emulsion. A dispersion of the mold was prepared. Sample 101 was prepared by stirring and mixing this dispersion with a color-sensitized silver halide emulsion liquid, and then coating the dispersion at the same time as other layers with gentle stirring after 2 hours of stagnation.

(Preparation of Comparative Sample 102) The exemplary coupler (I[[
-1) was produced in the same manner as Sample 101 except that Sample 101 was used.

(Preparation of Comparative Sample 103) The example coupler (I[
-3) was produced in the same manner as Sample 101 except that Sample 101 was used.

(Production of Comparative Sample 104) It was produced in the same manner as Sample 103 except that the stagnation time of the 2N, 3rd, and 4th layers was set to 30 minutes.

(Preparation of sample 105 of the present invention) A sample was prepared in the same manner as sample 103 except that the stagnation time of the second, third, and fourth layers was set to 20 minutes.

(Preparation of sample 106 of the present invention) A sample was prepared in the same manner as sample 103 except that the stagnation time of the second, third, and fourth layers was set to 10 minutes.

(Preparation of sample 107 of the present invention) A sample was prepared in the same manner as sample 101 except that the stagnation time of the second, third, and fourth layers was set to 1 minute.

At that time, the coupler dispersion and the color-sensitized silver halide emulsion were mixed in a Koch type SMV static mixer (Koch Engineerin) installed immediately before coating.
Static mixing was carried out by G. Co., Ltd.).

(Preparation of sample of the present invention in 10 days) Example coupler (II
It was produced in the same manner as Sample 107 except that I-1) was used.

(Preparation of Sample 109 of the Present Invention) Exemplary coupler (II
-3) was produced in the same manner as Sample 107 except that Sample 107 was used.

(Preparation of sample 110 of the present invention) The second layer, the third layer, and the fourth layer were prepared in the same manner as sample 101, except that they were prepared as shown below.

A single dispersion of magenta colored cyan coupler (II-3) was prepared in the same manner as the dispersion preparation method for sample 101 (liquid A). Other cyan couplers (ExC-1, Ex
C-2, ExC-4) were separately added in the form of a water-in-oil type dispersion to a silver halide emulsion that had been color sensitized in advance, and the solution was stagnated and aged in this state for 2 hours to create a solution ( B
Liquid), A liquid, and B liquid were mixed immediately beforehand in the same manner as sample 109 (retention time: 1 minute), and the mixture was coated simultaneously with other layers.

(Preparation of Sample 111 of the Present Invention) Magenta colored cyan coupler (II-3) in the second, third and fourth layers and other cyan coupler Ex
Both C-1 and ExC-2 or ExC-4 are heated and dissolved at 70°C in a 2:1 mixed solvent of ethyl acetate and water. At this time, tricresyl phosphate, which is a high boiling point organic solvent, was added and mixed in a weight ratio of four times the weight of the colored cyan coupler.

Thereafter, a water-in-oil emulsion was formed by stirring in the presence of Aerosol OT, and the emulsion was added to an aqueous gelatin solution to prepare an oil-in-water dispersion using a high-speed stirrer. This dispersion was mixed with a color-sensitized silver halide emulsion liquid one minute before coating, and coated simultaneously with the other layers.

(Preparation of Comparative Sample 112) In preparing the coupler dispersions for the second, third, and fourth layers of Sample 111 of the present invention, the weight ratio of tricresyl phosphate to colored cyan coupler was 12.
It was produced in the same manner as Sample 111 except that it was doubled.

Samples 101 to 112 prepared in this manner were wedge-exposed using an interference filter using red-resolution exposure at 600 nm and 640 nm, and then developed at 38°C according to the following processing steps, and then subjected to sensitometry. I took measurements.

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

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β-hydroxyethylamino) = 2 - Add methylaniline sulfate solution and bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate solution Add water 2.0g 4.0g 30.0g 1.4g 1.3mg 2.4g 4.5g 1.02 pH10.0 100゜0g ■0゜150゜10゜1゜pH6゜Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium sulfite 4.6g Add water 1.01 pH 6.6 Stabilizing liquid formalin (40%) 2. Omj
! Add 0.3 g of polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) to water i, ox From the results of this sensitometry, determine the sensitivity of the red-sensitive layer and use Table 1.
(expressed as a relative value when the sensitivity of sample 101 at 640 nm is set as 100).

As is clear from the results shown in the table, the sensitivity on the short wavelength side, which decreases over time due to stagnation, was further recovered by the present invention, and at the same time, a color photographic material with high sensitivity and excellent sharpness in the entire red-sensitive layer was obtained. .

Further, although Sample 112 had high sensitivity and good photographic properties, a new problem occurred in that film peeling occurred due to buffing film at the cut edge portion of the developed sample.

(Effects of the Invention) According to the present invention, it is possible to obtain a silver halide color photographic light-sensitive material that exhibits little reduction in sensitivity, deterioration in color reproducibility, and further deterioration in film strength even when a large amount of colored cyan coupler is used.

Agent Patent attorney (8107) Kiyotaka Sasaki (and 3 others) Procedural amendment March 1990 βρ date

Claims (2)

[Claims] (1) Coating a dispersion containing a colored cyan coupler in which the weight ratio of a high boiling point organic solvent coexisting with the colored cyan coupler to the colored cyan coupler is 10 or less (including 0) and a color-sensitized silver halide emulsion. 1. A silver halide color photographic light-sensitive material comprising, on a support, at least one silver halide emulsion layer obtained by coating a solution mixed immediately before. (2) A dispersion containing a colored cyan coupler in which the weight ratio of a high-boiling organic solvent coexisting with the colored cyan coupler to the colored cyan coupler is 10 or less (including 0) and a color-sensitized silver halide emulsion are statically combined. After mixing with a standard mixer,
A method for producing a silver halide color photographic light-sensitive material, which comprises coating at least one silver halide emulsion layer on a support without stagnation for 20 minutes or more.