JPH03241338A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain superior surface quality by incorporating a specified compd. into at least one of emulsion layers and simultaneously forming at least ten of the layers by coating at a time. CONSTITUTION:When layers are formed on a base by repeated single coating or simultaneous multiple coating, at least ten of the layers are simultaneously formed by multiple coating and a compd. represented by formula I is incorporated into a red-sensitive silver halide emulsion layer. In the formula I, X is H or a group releasable by coupling with the oxidized body of an arom. prim. amine color developing agent, R1 is naphthyl or furyl and R2 is alkyl or aryl required to render diffusion resistance to a cyan coupler represented by the formula I or a cyan dye formed by the cyan coupler. A color photographic sensitive material having superior uniformity of surface quality is obtd.

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 particularly to a silver halide color photographic light-sensitive material with improved surface quality during simultaneous multilayer coating.

(Prior Art) In recent years, as the image quality of color photographic light-sensitive materials has improved, there has been a tendency to enjoy color photographs with larger prints than before. For example, in addition to 83 mm x 117 mm size prints, 89III x 127-+1 size prints have become common, and six-cut, four-cut, and large-sized prints on full paper sheets are also increasing. Along with this, the requirements for uniformity of the surface condition of color photographic materials have become increasingly strict, and even the slightest unevenness or generation of minute foreign matter is no longer acceptable.

As a means of increasing the uniformity of the coated surface of photographic light-sensitive materials,
For example, as described in JP-A-52-115214, the bottom layer is made of a thin coating composition with a low viscosity in the range of about 1 to 8 cm, and the layer immediately above the bottom layer is made of a coating composition of about 1 to 8 cm.
A method using a relatively high viscosity coating composition in the range of 0 to 100 centivoise, or a method using a hydrophilic colloid layer in the bottom layer and a sulfonic acid group or sulfuric acid group in the side chain as described in JP-A-63-11934. 80 m/min to 300 m by containing a polymer compound having an ester group or a carboxylic acid group and having an intrinsic viscosity of 0.4 to 1.8 a/g.
A method of coating within the range of /minute is known. However, 1
When multiple layers of 0Fi or more are simultaneously coated, a sufficiently uniform surface quality cannot be obtained using the above method alone. In particular, when a naphthol-based cyan coupler, which is often used in the red-sensitive emulsion layer of high-sensitivity color negative light-sensitive materials, is used, or when phenol, which is most commonly used as a preservative in general color light-sensitive materials, is used, As the coating liquid stagnates over time, the physical properties of the coating liquid deteriorate, and if the filter becomes clogged during the coating process, the uniformity of the surface quality deteriorates, and furthermore, foreign matter is generated on the coated surface.

When coating 10 or more layers at the same time, it is necessary to prepare coating solutions for 10 or more layers at the same time, which often results in a long stagnation period for each coating solution. Here, the stagnation time of the coating liquid means the time from preparation of the coating liquid to application.

Furthermore, dividing and coating the IO layer and above in two or more times not only leads to a decrease in manufacturing capacity, but also
As described in No. 847, it is necessary to contain alkali-soluble polymer particles and a surfactant in the uppermost layer upon each application, which is unfavorable in terms of performance.

(Problems to be Solved by the Invention) An object of the present invention is to provide a color photographic material with excellent uniformity in surface quality.

(Means for Solving the Problems) An object of the present invention is to provide at least each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. In a silver halide color photographic light-sensitive material having one layer, the light-sensitive material has a layer coated on a support by one or more single layer coatings and/or simultaneous multilayer coating, and at least one of the layers is The coated layer is a layer coated by simultaneous multilayer coating of at least 10 layers, and the red-sensitive silver halide emulsion layer contains at least one compound represented by the following general formula (1). A silver halide color photographic material characterized by:

General formula (1) [wherein, X represents a hydrogen atom or a group that can be separated by coupling with an oxidized product of an aromatic primary amine color developing agent, and R represents a naphthyl group, a furyl group, a thienyl group, A heterocyclic group selected from a pyridyl group, a quinolyl group, an oxacylyl group, a tetrazolyl group, a benzothiazolyl group, and a tetrahydrofuranyl group (however, the carbon atom of the heterocyclic group is bonded to the nitrogen atom of the ureido group) or Fluoromethyl, nitro, cyano, -COR, -C
OOR.

R' represents a hydrogen atom, an alkyl group or an aryl group. Further, R and R' may be combined to form a ring. ) A phenyl group having at least one substituent selected from ), and R2 is an alkyl group or a group necessary to impart diffusion resistance to the cyan coupler represented by the general formula CI) and the cyan dye formed from the cyan coupler. represents a group. (2) A silver halide color photographic light-sensitive material having at least one layer each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. The photosensitive material has a layer coated on the support by one or more single layer coatings and/or simultaneous multilayer coating, and the number of coated layers by at least one coating is at least 10 layers. 1. A silver halide color photographic material characterized in that the layers are coated by simultaneous multilayer coating, and at least one layer contains at least one compound represented by the following general formula [■].

General formula (II) (wherein, Ro represents an alkyl group having 1 to 5 carbon atoms)
.

It was discovered that they are distant relatives.

Preferred cyan couplers according to the general formula [■] of the present invention are specifically the following general formula (I a) or the general formula (I
b).

General formula (Ia) General formula (Ib) In the formula, vl is a group represented by trifluoromethyl, nitro, or sia. R represents an alkyl group [preferably an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, butyl, benzyl)] or an aryl group (preferably a phenyl group)], and R' is a hydrogen atom or represents a group. Further, R and R' may be combined to form a ring.

Y2 represents a monovalent group, preferably an alkyl group [preferably an alkyl group having 1 to 10 carbon atoms (e.g. methyl, t-butyl, ethoxyethyl, cyanomethyl)], an aryl group [preferably a phenyl group (e.g. phenyl , tolyl), naphthyl group], halogen atoms (fluorine, chlorine,
bromine, etc.), an amino group (eg, ethylamino, diethylamino), hydroxy, or Y.

m represents an integer from 1 to 3, and n represents an integer from 0 to 3. However, m + n≦5, and when cyano is bonded to the p-position of the ureido group, 2≦m+n≦5.

Z represents a group of nonmetallic atoms necessary to form a heterocyclic group or a naphthyl group, and the heterocyclic group is a 5- or 6-membered group containing 1 to 4 nitrogen atoms or sulfur atoms
A membered heterocycle is preferred.

Examples include furyl group, thienyl group, pyridyl group, quinolyl group, oxacylyl group, tetrazolyl group, hendithiazolyl group, and tetrahydrofuranyl group. Note that any substituent can be introduced into these rings, such as an alkyl group having 1 to 10 carbon atoms (for example, ethyl, i-
propyl, i-butyl, t-butyl, t-octyl, etc.), aryl groups (e.g. phenyl, naphthyl), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, P-)luenesulfonamide, etc.), sulfamoyl group (e.g. methylsulfamoyl,
phenylsulfamoyl), sulfonyl groups (e.g. methanesulfonyl, P-)luenesulfonyl, etc.), fluorosulfonyl groups, carbamoyl groups (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl groups (e.g. ethoxycarbonyl, phenoxycarbonyl) ), acyl groups (eg, acetyl, benzoyl, etc.), heterocyclic groups (eg, pyridyl, pyrazolyl, etc.), alkoxy groups, aryloxy groups, and the like.

R2 represents an alkyl group or an aryl group necessary to impart diffusion resistance to the cyan coupler represented by the general formula (1) and the cyan dye formed from the cyan coupler, and preferably has 4 to 30 carbon atoms. Examples include an alkyl group, a phenyl group, and a group represented by general formula (Ic).

General formula (I c) In the formula, J represents an oxygen atom or a sulfur atom, k is an integer from 0 to 4, l represents 0 or 1, and when k is 2 or more, two or more R4s may be the same. May be different, R1
represents a linear or branched alkylene group having 1 to 20 carbon atoms; R4 represents a monovalent group; for example, a halogen atom (preferably chloro or bromine); an alkyl group (preferably a linear or branched alkylene group having a carbon number of 1 to 20); 1 to 20 alkyl groups (e.g. methyl, tert-butyl, tert-pentyl, t
ert-octyl, dodecyl, pentadecyl, hensyl, phenethyl)), aryl groups (e.g. phenyl), heterocyclic groups (preferably nitrogen-containing heterocyclic groups), alkoxy groups (preferably linear or branched carbon atoms) From 20
alkyloxy groups (e.g., methoxy, ethoxy, t
ert-butyloxy, octyloxy, decyloxy, dodecyloxy)), aryloxy group (e.g. phenoxy), hydroxy, acyloxy group (preferably alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy, benzoyloxy)), carboxy , an alkoxycarbonyl group (preferably a linear or branched alkyloxycarbonyl group having 1 to 20 carbon atoms), an alkyloxycarbonyl group (preferably phenoxycarbonyl), an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms) ), acyl group (preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms), acylamino group (preferably 1 to 20 carbon atoms)
straight chain or branched alkylcarboxamide, benzenecarboxamide), sulfonamide group (preferably straight or branched alkylsulfonamide group having 1 to 20 carbon atoms, benzenesulfonado group), carbamoyl group (preferably is a linear or branched alkylaminocarbonyl group having 1 to 20 carbon atoms, a phenylaminocarbonyl group),
A sulfamoyl group (preferably a linear or branched alkylaminosulfonyl group having 1 to 20 carbon atoms, a phenylaminosulfonyl group), etc.

X represents hydrogen or a group that can be eliminated during the coupling reaction with the oxidation product of the color developing agent. Examples include an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, a succinimide group, etc. bonded to the coupling position, and further specific examples include US Pat. No. 3,741,563. , Japanese Patent Publication No. 47-3742
No. 5, Special Publication No. 1973-36894, Japanese Patent Application Publication No. 1972-101
No. 35, No. 50-117422, No. 50-13044
No. 1, No. 51-108841, No. 50-120334
Examples include those described in various publications such as No. 1, No. 52-18315, and No. 53-105226.

The cyan coupler according to the present invention is disclosed in, for example, US Pat.
The bottom can be formed by the methods described in Japanese Patent Application Laid-open No. 58308 and Japanese Patent Application Laid-Open No. 56-65134.

Typical examples of cyan couplers are shown below.

zHs HI Two or more of the above couplers can be contained in the same layer.

The same compound may be contained in two or more different layers. The coating amount of these couplers is preferably 0.02 g or more and 2 g or less per rrl of the photosensitive material of the present invention.
．． It is more preferably 0.05 g or more and 1.5 g or less.

In order to introduce the above-mentioned couplers into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), Benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), etc., or boiling points of about 30°C to 15°C.
Organic solvents at 0°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, 2
After dissolving in butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The polymer dispersion method described in No. 3 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

Next, the details of the general formula [■] will be explained.

The compound of general formula (n) deteriorates the physical properties of the coating liquid over time during emulsion preparation and during stagnation for liquid feeding, and if the filter clogs during the coating process, the coating surface quality deteriorates (foreign matter generation). is added to the emulsion to prevent this from occurring. The compound also has antiseptic and antifungal effects and is therefore extremely useful.

General formula [■] In the formula, Ro represents a methyl, ethyl, propyl, butyl or amyl group, and particularly preferably an n-propyl group or an n-butyl group.

The method for adding the compound of general formula CII) into a photosensitive material is as follows:
It may be dispersed in gelatin or may be dispersed in various solvents. It may also be emulsified and dispersed with a high boiling point solvent. The additive layer may be added to any layer. It is also preferable to add phenol to the layer containing the coupler, especially the layer containing the cyan coupler, and add phenol as a preservative to other layers.
! It is one of the best. Most preferably, at least one of the compounds is added to all layers. If necessary, two or more of these compounds may be mixed and added without any problem.

The amount of compound added is 0.1 mg to 1 per 1 g of dry gelatin.
0aig is preferred, and 0.5 mg to 5-g is more preferred.

The most preferred coating method as an embodiment of the present invention is to complete the product by one simultaneous multi-layer coating, whereby a product with the best surface quality can be obtained.

However, even if the separation coating method is applied two or more times, one of the
When the coating is completed by simultaneous multilayer coating of 10 or more layers including the main emulsion layer, a product with the best target surface quality can be obtained. For example, the two layers of the bottom layer, the anti-haling layer and the intermediate layer, the two upper layers, that is, the first and second protective layers and part of the emulsion layer, are coated separately, and one or more other layers are multilayered simultaneously. It is also possible to complete a product with surface quality by coating.

In the present invention, it is preferable to complete the product by applying all layers including the necessary silver halide emulsion layer etc. by one simultaneous multilayer coating. In such cases, or in cases where the first 10 or more layers are coated in multiple layers simultaneously, the bottom layer adjacent to the support should be coated with 15 cp.
It is preferable to use a coating liquid having a concentration of ~100 cp. The reason for this is that if it is less than 15 cp, color unevenness tends to occur when 10 or more layers are applied simultaneously, and if it is more than 100 cp, the coating is poor and liquid runs out at both ends. Preferably the viscosity is 20 to 70 cρ, more preferably 20 to 70 cρ.
It is 60 cp.

In another embodiment of the present invention, when coating two layers, such as a bottom layer and an intermediate layer, for example, a coating solution for the bottom layer, the bottom layer adjacent to the support is coated for 15 minutes.
It is necessary to use a coating liquid with a cp to 100 cp in order to prevent the occurrence of color unevenness, as in the above case, but this precaution is not necessary for the first layer in the case of simultaneous coating of 10 or more layers. .

In the present invention, when a product is completed by one multilayer simultaneous multilayer coating, or when the first 10 or more layers are multilayer simultaneous N coating, 9 or more layers are applied successively adjacent to the bottom layer. The viscosity of the coating liquid should be 3 ocp or more,
and the calculated average viscosity of the coating liquid of 9 or more layers is 60 to 300.
Coating is adjusted to be cρ, which means that if the viscosity of the coating liquid of nine or more layers applied successively adjacent to the bottom layer is less than 30 cp, color unevenness tends to occur < 300 cp.
Above this, it is difficult to defoam and it is difficult to transfer the liquid. Preferably 70
~250cp, more preferably 80-200cp
It is. In addition, it is particularly preferable that the viscosity of the coating liquid for the second layer adjacent to the bottom layer is greater than the viscosity of the coating liquid for the bottom layer. It is more preferably 1.5 times or more than the bottom layer, and still more preferably 1.8 to 5 times the bottom layer. From the above, the arithmetic mean of the viscosity of the coating liquid for M7 layer or more is 60 to 300.
Adjust and apply so that cρ.

When the bottom layer, for example, the anti-grain layer and the intermediate layer, are coated separately, the viscosity of the bottom layer coating liquid and the viscosity of the second layer coating liquid adjacent to the bottom layer are different from those of the higher coating liquid. There is no need to treat it with viscosity.

The viscosity of each coating liquid can be adjusted to a predetermined value by adding an aqueous solution of a known thickener. Typical thickeners include poly(sodium p-styrene sulfonate), and others with sulfonic acid groups, sulfuric esters, or carboxyl groups in the side chain, or salts thereof, as described in JP-A-63-11934. Vinyl polymers with .

The viscosity was measured using a B-type viscosity needle (manufactured by Tokyo Keiki Co., Ltd., model BL) at a sliding speed of 29.8 mm/5 ec (rotor N11).
l, 30 rpm - temperature 40°C).

In a preferred embodiment of the present invention, in this manufacturing method, the coating amount of each layer is preferably 3 cc/n or more. If the coating amount is less than that, wavy unevenness will already occur on the slide surface of the slide hopper. This is because it occurs and makes it impossible to uniformly apply multiple layers on the support.More preferably,
The coating amount of each layer is 4 to 30 cc/%. If any coating amount is 30 cc/rd or more and 10 or more layers are simultaneously coated, the coated photographic constituent layers tend to become uneven in color.

When completing a product with one simultaneous multi-layer coating,
Alternatively, if the first 10 or more layers are applied simultaneously in multiple layers, the total coating amount of the bottom layer and all 9 or more layers applied adjacent thereto is 250 cc/bo or less, and the bottom layer, for example, the anti-halation layer. When coating 2N and the intermediate layer separately, the total coating amount of all 10 or more layers including this bottom layer is preferably 250 cc/rrl or less. If this upper limit is exceeded, the photographic constituent layers to be coated This is because color unevenness tends to occur. Considering further reduction of drying conditions, a more preferable total coating amount is 200cc/
n(is.

The multi-layer simultaneous coating device used in the present invention is as described in Japanese Patent Publication No. 33-8977, etc., for example, a slide hopper type for coating between n layers as shown in Fig. 1. Using a slide hopper type coating device that is similar in type and capable of simultaneously coating 111i or more, the specified coating liquid is sent through 10 or more slits and coated so that they overlap each other as they flow down the slide surface. .

The slide hopper type coating device will be explained with reference to FIG.

The distal end 4 of the par-type liquid injection H3 is brought close to the support at a distance, a coating liquid bridge (referred to as a bead portion) 5 is formed in that portion, and coating is performed on the support 2.

The distance between the support 2 and the tip 4 is referred to as the "bead distance." At this time, in order to stabilize the bead portion 5, a vacuum chamber 6 is provided to reduce the pressure at the back of the bead, and the pressure is reduced by a pressure reduction pump 7. The degree of pressure reduction at this time is referred to as "bead back pressure."

To explain the slide hopper type liquid injector in the multilayer simultaneous coating device, each coating liquid of n layers (multilayer is referred to as n layer) is pumped through a liquid feed pump 8°7. The liquid is sent into the injector 3 by the respective slits 9.1 to 9.1. Apply a thin film of coating liquid over the width of the support 2 on each slide surface 10LI.
~, l, flows out.

The thin films of the coating liquid that flowed out are stacked one on top of the other in order from the top, and at the bead portion, n layers of the coating liquid are formed and coated on the support.

The slide homper type is named because the slide surfaces are overlapped.

The present invention can be applied to a multilayer simultaneous coating method of 10 or more layers.

Generally, n=10 to 20 layers can be simultaneously coated, but a multilayer simultaneous coating method with n=12 to 18 layers can be preferably applied.

The coating speed in the method for producing a color photosensitive material of the present invention is applicable to a support moving at a speed of 30 to 500 m/win. Preferably, a coating speed of 60 to 300 s/win, more preferably 80 to 250 m/win is employed.

The applied photographic constituent layer is dried by a conventional method. That is, the applied photographic constituent layer is immediately cooled and solidified after being applied.

For this purpose, it is brought into contact with low temperature air, usually with a dry bulb temperature of 110'C to 20C. After the coating film was cooled and solidified in this manner, it was dried by blowing a gas as is conventionally used. Drying by this wind usually has a dry bulb temperature of 15 to 4
5°C1 relative humidity 10-50% RH air 10-40
This is done by blowing at an air volume of rd/rd/sin. This method is preferable because it can prevent an increase in fog due to drying.

The required drying time varies depending on the wet coverage and drying conditions, but a drying time of 0.5 to 5 ml is typical.

The coating film dried in this way has a dry bulb temperature of 20 to 40"C.
2 It is preferable to moisten with air at a relative humidity of 50 to 70% RH.

The production method of the present invention can be applied to transparent or reflective supports. Typical transparent supports include cellulose triacetate and polyethylene terephthalate. or,
Examples of reflective supports include paper supports laminated with polyethylene, which are usually used in photosensitive materials for color printing.

When the manufacturing method of the present invention is used, it is less affected by the unevenness of the support compared to conventional manufacturing methods. Therefore, even if there is an unevenness of up to 5 μm, a color photosensitive material with a good surface condition can be coated at high speed by the manufacturing method of the present invention. In a support having unevenness, it is preferable that the interval between the peaks and the peaks of the unevenness is not 5 to 8I. Short or long intervals are acceptable. If the distance between the peaks of the unevenness is less than 41, or 8IIll1
When the value exceeds 1, the presence of unevenness is unlikely to have an adverse effect on the uniformity of coating.

The light-sensitive material of the present invention has at least 10 layers coated simultaneously on a support, including silver halide emulsion layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer.

In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. but,
Depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

JP-A-61-34541 and JP-A-61-34541 disclose a layer structure in which a fourth or more color-sensitive photosensitive layer is used in addition to the conventional three types of blue, green, and red sensitivity for the purpose of improving color reproduction. 20124
No. 5, No. 61-198236, and No. 62460448. In this case, the fourth or more color-sensitive layer may be placed at any position. Further, the fourth or higher color-sensitive photosensitive layer may be a single layer or may be composed of a plurality of layers.

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 unit photosensitive layer are a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers in a pattern in which the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be disposed on the side far from the support, and a high-sensitivity emulsion layer may be disposed on the side close to the support.

As a specific example, from the side farthest from the support: low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer (II
L) or BH/BL/GL/G) I/R1(/
RL order or BH/BL/GO/GL/RL/RH
Can be installed in this order.

Furthermore, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/1
1) They can also be arranged in the order of 1/GL/RL. Furthermore, as described in JP-A Nos. 56-25738 and 62-63936, the blue-sensitive layer/GL/IIL/G)I/RH may be arranged in this order from the farthest side from the support. You can also do it.

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

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Or low speed emulsion layer/medium speed emulsion 1! / high-sensitivity emulsion layer, etc.

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

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

The amount of silver halide used in the present invention is not particularly limited, but it is preferably 3 g/rd or more below Log/rrT in terms of silver amount, and more preferably 7 g/n (3 g/rd below).
It is preferable that it is d or more.

Further, the density of silver with respect to the gelatin binder is not particularly defined, but depending on the purpose of high-sensitivity emulsion layers, low-sensitivity emulsion layers, and other purposes, the density of silver with respect to the gelatin binder may be set to 0.
It is preferable to use it in the range of 01 to 5.0.

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

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

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

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) N111764.
3 (December 1978), pp. 22-23, ""1. Emulsion preparation
and types)'', and N1118716
(November 1979), 648 pages, graphic “
"Physics and Chemistry of Photography", published by Beaumontel (P, Gla
fkides, Chemic et Ph1siqu
e Photographique, Paul Mo
(1967) + "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, nu f
f inPhotographlc Ea+ulsi
on Chemistry (Focal Press
.

1966))), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zelikm
an etallMaking and Coatin
g Photographic E+mulsion.

Focal Press+ 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and E++gineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4,
No. 434,226, No. 414310, No. 4,43
No. 3,048, No. 4,439,520 and British Patent No. 2.112.157.

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

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure Volume 17.
643 and N1118716, 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.

Bassara Tonenori RD17643 ROI87161
Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 2
Pages 3-24 Page 648 Right column - Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25, right column Page 650, left to right column 8
Dye image stabilizer page 26 9 Hardener page 26 page 651 left column 10
Binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column 12 Coating aid, Pages 26-27 Page 650 Right column Surfactant 13 Static prevention Page 27 Page 650 Right column agent Photographic performance with formaldehyde gas In order to prevent deterioration of the photosensitive material, it is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde, as described in US Pat. No. 4,411.987 and US Pat. No. 4,435,503.

Various color couplers can be used in the present invention, specific examples of which are listed in Research Disclosure (R.
O) Seed 17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,051, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
248.961, Japanese Patent Publication No. 5B-10739, British Patent No. 1.425,020, British Patent No. 1.476.760, U.S. Patent No. 3.973.968, British Patent No. 4.314.
No. 023, No. 4,511,649, European Patent No. 249
．． No. 473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 10,619, No. 4,351,897, European Patent No. 73.636, US Patent No. 3,061,432, US Pat. month), Japanese Patent Application Publication No. 1983
-33552, Research Disclosure 24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60485951, U.S. Patent No. 4500,630, No. 4,540,654,
4, 556, 630, International Publication Ho8810
Particularly preferred are those described in No. 4795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052.212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4,296.200, No. 2.369.9
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. 4,690,889, No. 4,2
No. 54,212, No. 4,296,199, Japanese Unexamined Patent Publication No. 6
1-42658 and the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138,258, British Patent No. 1,146,36
No. 8 is preferred, and also US Pat. No. 4.7
No. 74,181, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling, and a coupler that reacts with a living herbal medicine 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. Nos. 3,451,820; 4,080,211; 4,367.282;
No. 4,576°910, British Patent No. 2.102
．． It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. A DIR coupler releasing a development inhibitor is Maeshiro's RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4,248,9
62 and No. 4,782,012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097,140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include the competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. 4.310,618, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR couplers described in JP-A-60-185950, JP-A-62-24252, etc.
R coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜30
11. A coupler releasing a dye which recovers its color after separation as described in No. 2A. D, N1111449, 24241, bleaching accelerator releasing couplers described in JP-A No. 61-201247, ligand-releasing couplers described in U.S. Patent No. 4,553.477, etc., described in JP-A-63-75747 Leuco dye-releasing coupler, U.S. Pat. No. 4,77
Examples include couplers that emit fluorescent dyes as described in No. 4,181.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters II (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Phosphoric acid or phosphonic acid esters such as bis(2,4-di-L-amylphenyl) phthalate, bis(24-di-L-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate) Phenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2=ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-ethylhexyl phenylphosphonate, etc.), benzoic acid esters I ((2-ethylhexylhenshade, dodecylbenzoate, 2-ethylhexyl-P-hydroxyhenzoate, etc.), amides [(NN-diethyldodecanamide, N , N-diethyl laurylamide, N-
(tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate,
Dioctyl azelate, glycerol tributyrate,
isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl 2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylhensen, diisopropylnaphthalene, etc.), etc. . Further, as the auxiliary solvent, an Il solvent having a boiling point of about 30"C or more, preferably about 50"C or more and about 160C or less, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. Are listed.

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 N111643 and N11187
16, page 647, right column to page 648, column t.

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 24μ or less, more preferably 20I1m or less, even more preferably 18μ or less, and the film swelling rate T , /2 is preferably 30 seconds or less, more preferably 20 seconds or less. Film thickness means the film thickness measured at 25°C and 55% relative humidity (2 days), and the film swelling rate T+/! can be measured according to techniques known in the art. For example, as described in Photographic Science and Engineering (Pbotogr.
, Sci, Eng, ), vol. 19.

No. 2, 124-129 A serometer of the type described in Makoto (
The TI/□ can be measured by using a color developing solution at 30"C for 13 minutes and 15 seconds. The saturated film thickness is 90% of the maximum swelling film thickness reached when treated with a color developer for 13 minutes and 15 seconds at a temperature of T17□. Defined as the time it takes to reach the destination.

The membrane swelling rate TI/2 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
1117643, pages 28-29, and gap 18716
615, left column to right column.

When the photosensitive material of the present invention is used in the form of a roll, it is preferably stored in a cartridge.The most common cartridge is the current 135 format cartridge.

Other cartridges proposed in the following patents can also be used (Utility Model Publication No. 58-67329, Japanese Patent Application Publication No. 58-18103).
No. 5, Japanese Unexamined Patent Publication No. 182634/1982, Japanese Unexamined Patent Publication No. 58-1988
5236, U.S. Patent No. 4,221.479, Japanese Patent Application No. 1983-57785, Japanese Patent Application No. 63-183344, Japanese Patent Application No. 63-325638, Japanese Patent Application No. 1-21862,
Japanese Patent Application No. 1-25362, Japanese Patent Application No. 1-30246, Japanese Patent Application No. 1-20222, Japanese Patent Application No. 1-21863, Japanese Patent Application No. 137181, Japanese Patent Application No. 1-33108, Japanese Patent Application No. 1999
-85198, Japanese Patent Application No. 1-172595, Japanese Patent Application No. 1999
-172594, Japanese Patent Application No. 1172593, U.S. Patent No. 4,846,418, U.S. Patent No. 4.848,69
No. 3, U.S. Pat. No. 4,832,275).

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

(Example 1) (Comparative example) On a subbed cellulose triacetate film support,
Sample 101 is a multilayer color photosensitive material obtained by simultaneously coating the first to fourteenth layers having the compositions shown below.
was created.

(Composition of photosensitive layer) Coating amounts are expressed in units of g/rrf of silver for silver halide and colloidal silver, and amounts expressed in units of g7% for coupler additives and gelatin. The number of moles is expressed per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.15 gelatin 1.5E x M -80,
02 Cp d -110,05 2nd layer (middle layer) Gelatin 1.5UV-10,
03 UV -20,06 UV -30,07 Ex F -10,004 Solv-20,07 Cp d -110,05 Third layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Agr 2 Mol%, internal high Agl type, equivalent sphere diameter 0.34, coefficient of variation of equivalent sphere diameter 29%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 2.5) Coated silver amount 0.5 Gelatin ・ 1. OE x S
-11,0xlO-' E x S -23, oxto-' E x F -31,0X10-' E x C-30,22 E x C-40,02 Solv-10,20 Cp d -110,03 No. 4 layers (medium-sensitivity red-sensitivity emulsion layer) Silver iodobromide emulsion (Agl 4 mol%, internal high Agl type, equivalent sphere diameter 0.55x, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin mixed grains, Diameter/thickness ratio 1) Coated silver amount 0.85 Gelatin 1.26E x S
-11,0X10-' E x S -23,0X10-' E x S -31,0XIO-' xC-3 xC-4 xY-14 xY-13 xC-2 pd-10 olv-1 Cp d -11th 5 layers (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type,
Equivalent sphere diameter 0.74, coefficient of variation of equivalent sphere diameter 30%, twinned mixed particles, diameter/thickness ratio 2) Coated silver amount 0.33 0.01 0.01 0.02 0.08 1.0X10-' 0.20 0.04 0.7 1.0 1.0X10-'3.0X10-'1.0X10-' 0.15 0.15 0.08 Gelatin xS-I xS-2 xS-3 xC-3 olv -I olv-2 Cp d -110,03 6th layer (middle layer) Gelatin 1.0P-20,1
7 Cp d -10,10 Cp d -40,17 Solv-10,05 Cp d -110,03 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 12 mol%, internal high Agl type,
Equivalent sphere diameter 0.31M, coefficient of variation of equivalent sphere diameter 28%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 2.5) Coated silver amount 0
．． 30 Gelatin 0.4E x S
-4s, oxto-' Ex S -60,3X10-'ExS~52.0X10-' ExM-90,2 Ex Y-130,03 ExM-80,03 Solv-10,2 Cp d -110,01 8th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol%, internal high agr type, equivalent sphere diameter 0.551 m, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin mixed grains , diameter/thickness ratio 4) Coated silver amount 0.7 Gelatin 1.0E x S
-4s, oxto-' Ex S -52,0Xl (l' Ex S -60,3 ,04 3olv-10,2 Cp d -110,03 9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag■10 mol%, internal high Agr type, equivalent sphere diameter 0.7-5 spheres Coefficient of variation of equivalent diameter 30%, normal crystal,
Twinned mixed grains, diameter/thickness ratio 2.0) Coated silver amount 0.5
0 Gelatin 0.80E x S
-42,0XIO-' E x S -52,0X10-' E x S -60,2X10-' E x S -73,0 ,02 Cp d -20,01 Cp d -92,oxto-' Cp d -102,0xlO-' 5olv-10,20 Solv-20,05 Cp d -110,02 1st O layer (yellow filter layer) Gelatin 0 .6 yellow colloidal silver 0.05Cp d -10,2 Solv-10,15 Cp d -110,02 11th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol%, internal high AgI type , equivalent sphere diameter 0.5-1 coefficient of variation of equivalent sphere diameter 15%, octahedral particles) Coated silver amount 0.4 gelatin
1.0E x S -82,0X10-' ExY -150,9 E x Y -130,09 Cp d -20,01 Solv-10,3 Cp d -110,03 12th layer (high sensitivity blue-sensitive emulsion layer ) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type,
Equivalent sphere diameter 1.3 m, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 4.5) Coated silver amount 0.
5 Gelatin 0.6E x S
-81,0X10-' ExY-15 Cpd-2 Cpd-5 olv-1 Cp d -11 13th layer (first protective layer) Fine grain silver iodobromide (average particle size 0.07ρ, %) Gelatin UV-3 UV-4 UV-5 olv-3 Cp d -11 14th layer (second protective layer) Gelatin polymethyl methacrylate particles (diameter 1.54) -1 Cpd-11 0,12 0,001 2,0X10-' 0 .04 0.02 Agr 1 mol 0.2 0.8 0.1 0.1 0.2 0.04 0.02 0.9 0.2 0.4 0.03 Furthermore, storage stability, processability, pressure In order to improve resistance, anti-fungal/anti-bacterial properties, anti-static properties, and applicability, the following Cpd-
3, Cpd-5, Cpd-6, Cpd-7, Cpd-8
, P-L P-2, W-1, W-2, and W-3 were added.

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

TJV-1: UV-2: UV 3 = UV 4: ExF-1: UV-5: C,H.

C, H5 CJsO5Os’ 5olv-1 ni tricresyl phosphate ExC-2: H 3olv-2: Diptyl phthalate 5olv-3ni Phosphate tri (2-ethylhexyl) ExC-3: 0 fights (i) ONH to CJ*0 ExC 4: H ExC 5: ExC-6: H ExM-10: tHs Z ExM-11: zHs Shil ExM 12: zns ExM-8: ExM 9: Hz ExM-13: C.O.

xY 14: 1 COOC, H.

CH.

Hs ExY 15: pd 1: C, l( ,(n) Uke ChH+z(n) pd 2: H ExS-5: Js ExS-6: C,H.

ExS-7: C,H.

ExS-8: ExS 1: zHs ExS 2: C,H.

ExS 3: C,H.

ExS 4: C.HS l: Hz=CH 3O□ CH.

0NH CH.

CM, =CH-5o□-C112C0NHHz pd 3 : υn pd 4 : pd Cpd-6: cpa-to: Cpd 7 : (I Cpd-11: Cpd 8 : Cpd-12: Cpd 9 : H W-1: W -2: C, HS (n)C4HqCHCHzCOOCHz(n)CJ*C
HCHzCOOCHSOJaC, HS W 3 C, F+JO□N(CzHt)CH
zCOOKP-1 Copolymer of vinyl pyrrolidone and vinyl alcohol (copolymerization ratio = 70:30 (weight ratio))
P-2 polyethyl acrylate (Example of the present invention) Compound Ex of the third, fourth and fifth layers of sample 101
Sample 10 listed in Table 1 by changing C-3 to another compound
Samples 2 to 105 were prepared in the same manner as Comparative Example 101.

Furthermore, by changing the residence time of the coating liquid such as emulsion during the preparation of samples 101 to 105, samples 111 to 115 listed in Table 1 were prepared.
It was created.

The stagnation time referred to here indicates the elapsed time from preparation of the coating solution to application. Also, the temperature of the coating liquid when it is stagnant is 40°C.
I kept it.

The surface quality of coated samples 101-105 and 111 to 115 was evaluated using the number of comments attributed to microscopic undissolved matter of the coupler. The comments here in terms of number of comments are B, M, Deryagin (B, M, Derya
gin) et al., “Theory of Film Coating (Film Coa
ting Theory) J page 183 (The Focal Press)
There is a description in 1964. The number of comments is 1000 per 1 dm when the photosensitive surface is observed under a microscope.
- Refers to the number of comments above.

The results are shown in Table 1. As is clear from Table 1, sample 104゜105.114 using the cyan coupler of the present invention
and No. 115 have fewer surface failures due to foreign matter generation, and less deterioration in surface quality due to stagnation over time.

Samples 101 to 105. After uniformly exposing samples 111 to 115 at 200 lux for 17,100 seconds, they were developed by processing method (A). After the treatment, the surface condition was inspected in the same manner as above, and it was found that Example samples 104, 105, and 11 of the present invention
It was reconfirmed that samples 4 and 115 had fewer surface failures. Further, similar results can be obtained by developing using processing method (B).

<Processing process Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 2 minutes 10 seconds Fixation 4 minutes 20 seconds Processing method A> Processing temperature Replenishment amount 38℃ 33M1 38℃25m 24℃ 1200+d 38℃25Jd Tank Capacity 01 0f 0ffi 01 Stable 1 minute 05 seconds 38'C25m drying 4
Minutes 20 seconds 55°C Replenishment amount is 35-01 per width 1 m length Next, the composition of the processing liquid is described.

(Fixer) Mother solution (g) Replenisher (g) Ethylenecyaminetetraacetic acid 0.5 0.7 Disodium salt Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution 170. (ld 200.0m
(70%) Add water 1.0ffi 1.
Oj! pH 6,76,6 (stable solution) Formalin (37%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt mother solution (g) Replenisher solution (g) 2, (ld 3.0m 0.3 0.45 0.05 0.08 Add water and H (color developer) Diethylenetriaminepentaacetic acid -Hydroxyethylidene 1.1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine Sulfate 4-[N-ethyl-N-β-hydroxyethylamino] = 2-methylaniline sulfate Add H 1,0ffi 1.0ffi 5.0-8.0 5.0-8.0 Mother liquor (g) Replenishment solution (g) 1.0 1.1 3.0 3.2 4.0 30.0 1.4 1.5mg 2.4 4.5 4.4 37.0 0.7 1.0ffi 1. Oji! 10.05 10.10 (Bleach solution) Ethylenecyaminetetraacetic acid ferric sodium trihydrate Ethylenediaminetetraacetic acid sodium chloride Ammonium bromide Ammonium nitrate Aqueous ammonia (27%) Add water to mother liquor (g) Replenisher (g) pH Process color development bleaching bleaching fixing stability 100.0 IO60 140.0 30.0 6.5d 1.02 6.0 120.0 11.0 160.0 35.0 4,〇- 1, 0N 5.7 <Processing method Processing time Processing temperature 3 minutes 15 seconds 38°C 1 minute 00 seconds 38°C 3 minutes 15 seconds 38°C 40 seconds 38゛C B > Replenishment amount Tank capacity 45d 1offi 20d 4f 30ad l! 20-1 Drying 1 minute 15 seconds 55°C Replenishment amount per 35 m width and 1 m length Next, write down the composition of the treatment liquid.

(Color developer) Mother solution (g) 1 full solution (g) 1.0 1.1 3.0 3.2 Diethylenetriaminepentaacetic acid 1-hydroxyethylidene 1.1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Iodide Potassium hydroxylamine sulfate 4-[N-ethyl-N-β-hydroxyethylamino] 2-methylaniline sulfate was added to pH 4,0 30,0 1,4 t, 5 mg 2.4 4.5 4. 4 37.0 O17 1,0ffi 1.0N 10.05 10.10 (Bleach solution) Common to mother liquor and replenisher (unit: g) Ethylenecyaminetetraacetic acid ferric ammonium dihydrate Ethylenecyaminetetraacetic acid disodium Ammonium chlorobromide Ammonium nitrate Bleach accelerator 120.0 10.0 100.0 10.0 0.005 mol Aqueous ammonia (27%) Add water to pH 15, (ld 1, Of 6.3 (bleach-fix solution) Common to mother liquor and replenisher solution (unit: g) Ferric ammonium ethylenediaminetetraacetate 50.0 Niumium dihydrate Disodium ethylenediaminetetraacetate 5.0th generation sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0i
d Ammonia water (27%) 6.
Add 0d water 1.01
p8 7.2 (Water wash solution) Mother liquor and replenisher common tap water were mixed with H-type acidic cation exchange resin (Amberlite TR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water is passed through a hotbed column filled with calcium and magnesium ions to a concentration of 3wg//! The following treatment was followed by the addition of 20w1g/It of sodium isocyanurate dichloride and 0.15g/l sodium sulfate. p of this liquid
H was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (unit: g) Formalin (
37%) 2. Od polyoxyethylene-p-monononyl 0.3 Phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0/pH5,
0 to 8.0 pH 6.3 Example 2 First layer to first layer of sample 101 prepared in the comparative example of Example 1
The cpa-u used in the 4th layer was added to the amount of Cp listed in Table 2.
Sample 201 was created in place of d-12. Further, Sample 211 was prepared by changing the stagnation time of the emulsion coating solution when coating the third, fourth, and fifth layers of Sample 201 as shown in Table 3. Cp d-11 to Cpd-
By changing to 12, sample 201 and sample 21! No deterioration in surface quality was observed.

Samples 201 and 21 were prepared by the method described in Example 1.
The surface quality of No. 1 was evaluated. The results are shown in Table 3.

As is clear from Table 3, the compound Cpd-1 of the present invention
The sample containing No. 2 has no surface defects due to stagnation over time and has a stable and high surface quality.

After uniformly exposing samples 101, 111, 201 and 211 at 200 lux for 1/100 second, processing method (A
). When surface condition was inspected after treatment,
It was reconfirmed that Samples 201 and 211 using the compound of the present invention had fewer surface failures. A similar result can be obtained even if development is performed using processing method (B).

Table 2 [Effects of the Invention] As explained above, in the multilayer color photographic material of the present invention having 10 or more photographic layers, at least one emulsion layer contains the compound represented by the general formula [I]. Moreover, since at least 10 layers, preferably all the layers, are applied simultaneously by one coating, it has extremely excellent surface quality.

[Brief explanation of drawings]

FIG. 1 is a schematic side view of a slide hopper type coating device used in the present invention. In the figure, 1: Vanoquanoprora 2: Support 3 Nislide hopper type liquid injector 4: Tip of same liquid injector 5: Coating liquid bridge (bead part) 6: Vacuum chamber 7: Vacuum pump 8, ~8
．． ．． : Liquid feeding pump 9I~9, : Liquid feeding slit 7 to 10 Ni Ride surface

Claims (1)

[Claims] (1) In a silver halide color photographic light-sensitive material having at least one layer each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. , the light-sensitive material comprises at least one of these silver halide emulsion layers on a support,
It is characterized by having at least 10 layers coated simultaneously in one coating, and containing at least one compound represented by the following general formula [I] in the red-sensitive silver halide emulsion layer. Silver halide color photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A heterocyclic group selected from a naphthyl group, a furyl group, a thienyl group, a pyridyl group, a quinolyl group, an oxazolyl group, a tetrazolyl group, a benzothiazolyl group, and a tetrahydrofuranyl group (however, the nitrogen atom of the ureido group has a carbon atom of the heterocyclic group). ) or trifluoromethyl, nitro, cyano, -COR, -
COOR, -SO_2R, -SO_2OR, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -OR-, OCOR, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲Mathematical formulas, There are chemical formulas, tables, etc.▼(
R represents an alkyl group or an aryl group, and R' represents a hydrogen atom, an alkyl group or an aryl group. Further, R and R' may be combined to form a ring. ) A phenyl group having at least one substituent selected from ), and R_2 represents an alkyl group or an aryl group necessary to impart diffusion resistance to the cyan coupler represented by the above general formula [I] and the cyan dye formed from the cyan coupler. represent. ]
(2) In a silver halide color photographic light-sensitive material having at least one layer each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. , the light-sensitive material comprises at least one of these silver halide emulsion layers on a support,
A silver halide color having at least 10 layers coated simultaneously in one coating, and containing at least one compound represented by the following general formula [II] in at least one layer. Photographic material. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_0 represents an alkyl group having 1 to 5 carbon atoms.)