JPS63296046A - Silver halide photographic sensitive material with suppressed hold-up deterioration in coupler dispersion - Google Patents

Abstract

PURPOSE:To reduce the trouble about applying the titled material by mixing a specified coupler dispersing solution and a silver halide emulsion just before applying a dispersing solution. CONSTITUTION:The titled material provides with a layer composed of the mixed solution obtd. by mixing the oil-in-water type coupler dispersing solution contg. a coupler shown by formula I and the photosensitive silver halide emulsion just before applying the dispersing solution. In the formula, Z is a nonmetal atomic group necessary for forming a heterocyclic ring contg. a nitrogen atom., X is H atom. or a group capable of releasing by reacting with the oxidant of a color developing main agent, R is H atom. or a substituent group. The concrete example of the magenta coupler shown by the formula is exemplified by the compd. shown by formula II, and said compd. may be used with another kind of the magenta coupler. Thus, the number of generation of the application trouble due to the dispersibility of the pyrazoloazole type coupler is lessened by using the titled material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material with improved coating failure.

[Prior art]

In silver halide color photographic light-sensitive materials, a combination of a highly sensitive silver halide emulsion and a yellow coupler, cyan coupler and magenta coupler is usually used. Among these, the pyrazoloazole type coupler described in British Patent No. 1,252,418 etc. has low side absorption of the coloring dye and is preferable for color reproduction, but after mixing the oil-in-water type coupler dispersion and the silver halide emulsion, There was a problem of stagnation and deterioration of dispersibility, which could lead to coating failure if there was a delay before coating.

[Purpose of the invention]

An object of the present invention is to improve the stagnation stability of a mixture of an oil-in-water dispersion of a pyrazoloazole coupler and a silver halide emulsion, and a further object is to reduce coating failures by using the coupler. An object of the present invention is to provide a silver halide color photographic light-sensitive material.

[Structure of the invention]

As a result of various studies, the object of the present invention was to unexpectedly discover that immediately before coating an oil-in-water coupler dispersion containing a coupler represented by the following general formula [M-I] and a photosensitive silver halide emulsion. It has been found that the present invention can be achieved using a silver halide photographic light-sensitive material characterized in that the mixed solution is coated on at least one layer of a support.

In the formula, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

In this case, the term "immediately before coating" refers to a stagnation time of 30 minutes or less, preferably 10 minutes or less, after mixing the oil-in-water coupler dispersion and the silver halide emulsion until coating.
Particularly preferably, the time is 1 minute or less. Also, the stagnation temperature is 28 ~
The temperature is 70°C, preferably 32-60°C.

In the magenta coupler represented by the general formula [M-1] according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by Z has a substituent. May have.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl, but in addition to these, halogen Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyan, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfonyl Examples include famoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio groups, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl group ring; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group ring; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.; As an ureido group, an alkylureido group, an arylureido group, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; As the heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-chenyl group , 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferred, for example, 3
．． 4. 5. 6-tetrahydrobilanyl-2-oxy group, 1-phenyltetrazole-ra-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzo Thiazolylthio group, 2,4-diphenoxy-1,3,5-)riazole-6-thousand group, etc.; As siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; as imide group, succinate Acid imide group, 3-he1tadecylsuccinimide group, phthalimide group, glutarimide group, etc.; spiro compound residues include spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
] heptan-1-yl, tricyclo[3°3.1.1co-7]decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, etc. .

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxy carbonylamino, aryloxycarbonylamino,
each group such as carboxyl, (R1' is the same as the above R, Z' is the same as the above Z, R2' and R1' represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group); Preferably, it is a halogen atom, especially a chlorine atom.

Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

More specifically, what is represented by the general formula [M-1] is represented by, for example, the following general formulas [M-n] to [M-■].

General formula [M-II] General formula [M-1[[] General formula [M-fV] General formula [M-V] General formula [M-VI] General formula [M-[1 to [M-■] ] (Koi IINte R2
~R and X have the same meanings as R and X above.

Moreover, the general formula [preferred among M-II] is represented by the following general formula [M-■].

It has the same meaning as R, X and Z.

Among the magenta couplers represented by the general formulas [M-11 to ''[M-■], particularly preferred are 1) those of the general formula [M-
[This is a magenta coupler represented by 1.

The most preferred substituents R and R1 on the heterocycle are those represented by the following general formula [M-IXI.

General formula [M-[I R1-CH, in which R1 has the same meaning as R above.

Preferred as R9 is a hydrogen atom or an alkyl group.

In addition, substituents that the ring formed by Z in general formula [M-II] and the ring formed by Zl in general formula [M-■] may have, and general formulas [M-II] to [M
-Vl], R2-R6 is represented by the following general formula [M-
X] is preferable.

General formula [M-X] -R'-3Q2-R' R1 in the formula
represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R- preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the straight chain has one branch.

The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one.

Typical specific examples of the compounds according to the present invention are shown below.
:r::! : In addition to the above typical examples of compounds according to the present invention, specific examples of compounds according to the present invention include Japanese Patent Application No. 61-9791.
Among the compounds described on pages 66 to 122 of the specification, No. 1 to 4, 6, 8 to 17.

19~43.45~59.61~104.106~12
Compounds represented by 1°123-162.164-223 can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society (Journal of the Che)
mical Society), Perkin (Perkin)
kin) I (197)), 2047-2052,
U.S. Patent No. 3,725,067, JP 59-9943
No. 7, No. 58-42045, No. 59-162548, No. 59-171956, No. 60-33552, No. 80-43659, No. 60-172982 and No. 6
It can be synthesized by referring to No. 0-190779 and the like.

The couplers of the invention typically have IX per mole of silver halide.
10-' mole-1 mole, preferably I x 10-''
It can be used in the range of mol to 8 x 10-' mol.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

An oil-in-water coupler dispersion is one in which a solution of a high-boiling organic solvent containing a coupler as a solute is emulsified and dispersed as oil droplets in a hydrophilic binder.
A high boiling point organic solvent of 50°C or higher, a low boiling point if necessary,
and/or dissolved using a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, A step of removing the low-boiling organic solvent may be included after or simultaneously with zero dispersion, which can be obtained by emulsification and dispersion.

Examples of high boiling point solvents include phenol derivatives that do not react with the oxidized form of the developing agent, phthalates, phosphates, citric esters, benzoates, alkylamides,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150
An organic solvent having a temperature of ℃ or higher is used.

Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane,
Examples include nitroethane and benzene.

Anionic surfactants, nonionic surfactants, cationic surfactants can be used as dispersion aids when the coupler is dissolved in a high boiling point solvent alone or in combination with a low boiling point solvent and dispersed using mechanical or ultrasonic waves. It is preferable to use a surfactant, an amphoteric surfactant, or the like.

The silver halide emulsions used in the present invention include conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any silver bromide can be used, especially silver bromide,
Silver iodobromide and silver chloroiodobromide are preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The grains may be grown all at once or after forming seed grains. , the method of making and growing the zero-type particles that may be grown may be the same or different.

Silver halide emulsions may be prepared by mixing halide ions and silver ions at the same time, or by mixing one of them in a solution in which the other is present. , it may be produced by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and/or pAg in a mixing pot. By this method, halogen ions with a regular crystal shape and a nearly uniform particle size can be produced. Silver oxide particles are obtained. Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( At least 11 selected from (including complex salts)! By adding metal ions using II, these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere.
Reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

Silver halide grains may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical or plate shapes. In the particles, any ratio of 1loo1 face to (1111 face) can be used. Also, particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The size of the silver halide grains used is 0.05 to 30 .mu.I, preferably 0.1 to 20 .mu.I.

Silver halide emulsions may have any grain size distribution. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. Monodisperse emulsion as used herein refers to one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less. In the case of silver oxide, the diameter is shown, and in the case of particles with a shape other than spherical, the diameter when the projected image is converted to a circular image of the same area.) may be used alone or in combination of several types. A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of separately formed silver halide emulsions of 2 FI or more.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, hemioxanol dyes, and the like are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

The light-sensitive silver halide emulsion of the present invention is green-sensitive, but depending on the purpose, it may be used that has color sensitivities other than linear, such as blue sensitivity or red sensitivity. can.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

' To mix the oil-in-water coupler dispersion and the photosensitive silver halide emulsion, a homomixer or a commonly known static mixer using flow can be used.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The light-sensitive material contains a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogging agent, a chemical sensitizer, Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or emulsion layers may contain dyes that are washed out of the light-sensitive material during development or are bleached.

Photosensitive materials include formalin scavengers, optical brighteners,
A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retardant, and a bleach accelerator can be added.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example-1 A core/shell type monodispersed silver iodobromide emulsion with an average grain size of 0.5 μm containing 10 mol % of the core and 2 mol % of the shell, containing an average of 5 mol % of silver iodide (0 silver halide per 1 kg of emulsion) Emulsion 1 was chemically sensitized with gold and sulfur sensitizers and further treated with -Anhydro 5.5'- as a green-sensitive sensitizing dye. Add diphenyl-9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide, then add 4
-Hydroxy-6-methyl-1,3,3a, 0.25 g of 7-chitrazaindene and 20 mg of 1-phenyl-5-mercaptotetrazole were added.

Next, a dispersion for mixing and coating with this sensitized emulsion (
[M-1)) and ([M-2)) were adjusted as follows.

Dispersion ([M-1)] 20 g of magenta coupler (H-1) and 5 g of colored magenta coupler (CM-1) were mixed with 25 g of tricresyl phosphate (hereinafter abbreviated as TCP) and ethyl acetate (hereinafter referred to as E8). Abbreviation.) Sodium triisopropylnaphthalene sulfonate dissolved in a mixture of 100i1 and 4. Added to 300 al of 7.5% aqueous gelatin solution containing
It was emulsified and dispersed in a colloid mill and adjusted to 500M1.

Dispersion ((T2)) 20g of magenta coupler (example coupler 4), 5g of colored magenta coupler (CM-1), 30g of TCP,
7,5 containing 4 g of sodium triisopropylnaphthalene sulfonate dissolved in a mixture of E^100 zil
% gelatin aqueous solution, and emulsified and dispersed using a colloid mill to adjust the volume to 500 liters.

Sample T-1 The dispersion ([M-1
)] was prepared by adding 500 i+1 of the resulting coating solution and coated on a cellulose triacetate film support within 1 minute after mixing to give a silver content of 186/da''.

Samples T-2 to T-5 Coating liquids prepared and mixed in the same manner as sample T-1 were
Silver content after 10 minutes, 30 minutes, 1 hour, and 2 hours at ℃
It was applied so that the amount was 100 mg/da.

Sample T-6 The dispersion ((14-
2)] by adding 500I11 of the coating solution, after mixing 1
Within minutes, 18i+j of silver! /da”.

Samples T-7 to TIO A coating solution prepared and mixed in the same manner as Sample T-6 was
Silver content after 10 minutes, 30 minutes, 1 hour, and 2 hours at ℃
xII/da".

Then, a portion of these samples was given a magenta color density of 0.
．． A portion of the sample was exposed to green light through a sensitometric wedge, and then processed through the following processing steps to obtain a sample with a dye image.

Processing process (38℃) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash 3 minutes 15 seconds Fix
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds stabilization 1 minute 30
The composition of the treatment liquid used in each treatment step is as follows.

Color developer composition: Add water to make 11 Bleach solution composition:

Adjust the pH to e, o.

Fixing solution composition: Stabilizing solution composition: For each color image obtained, the number of points showing poor color development was measured by observation with a magnifying glass.

The results obtained are shown in Table-1.

From the results in Table 1, it can be seen that according to the present invention, a good photographic material can be obtained which has high sensitivity and is free from coating failures due to poor color development.

Example 2 In the following examples, the amount added in the silver halide photographic material is per IN2 unless otherwise specified.

In addition, silver halide and colloidal silver are shown in terms of silver.

Multilayer color photographic material sample 1 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample-1 (standard) First layer; antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer; Intermediate layer (1,L,) Gelatin layer containing an emulsified dispersion of 2.5-di[-octylhydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion M (RL-1)
Monodisperse emulsion (emulsion 1) consisting of 8 g Br I with an average grain size (r) of 0.40 μm and Δg of 16 mol %...silver coating amount 1.8 g/z2 sensitizing dye 1... per 1 mol of silver 5.0x 10-' molar sensitizing dye ■・
... o, sx to-' Morcian coupler (C-1) per 1 mole of silver... 0.085 mol colored cyan coupler (CC-1>... to 1 mole of silver) o, oos mol DIR compound (D-1)... 0.0015 mol per mol of silver DIR compound (D-2)... 0,002 mol per mol of silver High boiling point organic solvent (IIBS)...Coupler and DIR
The same weight as the total weight of the compounds No. 41; High-sensitivity red-sensitive silver halide emulsion layer (R11-1
) Monodisperse emulsion (emulsion ■) consisting of 8 g Brl containing 8 g 16.0 mol % of average grain size (r) 0.8 μg... Trowel application 111.3 H/m"
Sensitizing dye 1... 2.5X 10-' mol sensitizing dye for 1 mol of silver...
... 0.8X 10-' mol cyan coupler (C-2) per mol of silver 0.007 mol cyan coupler (C-3) per mol of silver 0.8x 10-' mol cyan coupler (C-3) per mol of silver 027 mol Colored cyan coupler (CC-t)...0.0015 mol per mol of silver DIR compound (D-2)... o, oot mol per mol of silver■S...Coupler and 5th layer with the same weight as the total weight of DIR compounds; middle layer (1, L,) Same as the 2nd layer, gelatin layer.

6th layer; low sensitivity green-sensitive silver halide emulsion layer (GL-1)
Emulsion ■... Amount of coated silver 1.5 g/brass 2 Sensitizing dye ■... 2.0 g per mole of silver. OX to-' molar sensitizing dye ■・
... t, ox to -' mole magenta coupler [M-1] for 1 mole of silver... 0.090 mole colored magenta coupler for 1 mole of silver (CM-1>... for 1 mole of silver 0.004 mol DIR compound (D-1)... o, ooto mol DIR compound (D-3)... 0.0030 mol HBS... per 1 mol silver Seventh layer with the same weight as the total weight of the coupler and DIR compound; high-sensitivity green-sensitive silver halide emulsion layer (G11-1
) Emulsion ■... Coated silver mass 1.4 g/m2 Sensitizing dye ■... 1.2x 10-' mol sensitizing dye ■ per 1 mole of silver
... 0.8X 10-' mole magenta coupler [M-1>... per 1 mole of silver 0.015 mole colored magenta coupler (CM-1) per mole of silver... 0.002 mol DIR compound (D-3)... 0.0010 mol based on 1 mol of silver BS... Same weight as the total weight of coupler and DIR compound 8th layer; Yellow filter single layer (YC -1) Gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2,5-di-t-octylhydroquinone.

9th layer; low sensitivity blue-sensitive silver halide emulsion layer (BL-1>
Average particle size 0.48μ plow, 8g Br containing 16 mol%
Monodisperse emulsion (emulsion ■) consisting of 1 silver coated amount: 0.9 g/m" Sensitizing dye V... 1.3X to 'mol yellow coupler (Y-1) per 1 mole of silver ... 0.29 mol 11Bs per 1 mol of silver... 10th layer with the same weight as the total weight of the coupler and DIR compound; Highly sensitive blue-sensitive emulsion layer (BH-1) Average grain size 0.8μ so, 8 Monodispersed emulsion (emulsion ■) consisting of 8 girls containing 17 mol% of silver...Silver coverage: 0.5 g/m2 Sensitizing dye V...1.OX 10-' mole yellow coupler (per mole of silver) Y-1>... 0.08 mol per mol of silver DIR compound (D-2)... 0.0030 mol per mol of silver HBS... Same as the total weight of coupler and DIR compound Weight 11th layer; 1st protection M (Pro-1) Silver iodobromide (8 gl 1 mol%, average grain size 0.07 μm)
... Silver coating amount: 0.5 H/m2 Gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

12th layer: Gelatin layer containing second protection 1@(Pro-2) polymethyl methacrylate particles (1.5 μm diameter) and formalin scavenger (H3-1).

In addition to the above composition, each layer contains a gelatin hardener (H-
1) and (H-2) and a surfactant were added.

The magenta coupler dispersions and silver halide emulsion preparations for the sixth and seventh layers were prepared as follows.

[Magenta coupler dispersion]

To make a coupler dispersion, first add a high boiling point organic solvent (2,4-dinonylphenol) to 1° of the coupler, then add 3g of a low boiling point organic solvent to 1g of the coupler and dissolve at 50°C to 60°C. (liquid 1) 6 then gelatin 0
．． 83. Solution 2): Add 1411 parts of pure water to the following 5% solution of 5urf-1 and dissolve it.

Mix (Liquid 1) and <Liquid 2), disperse with an ultrasonic homogenizer, add gelatin and water to make the total gelatin concentration 20%, and finish it to 1000zt' to obtain an oil-in-water coupler dispersion. Obtained.

The silver halide emulsion was prepared by chemically ripening the silver halide emulsion with a total gelatin content of 40FI and a finish of 100011.
Gelatin and pure water were added so that the

The sixth layer of sample 1 was prepared by mixing a 1:1 silver halide emulsion and a coupler dispersion prepared to 1,000 zl, and coating the mixture 2 hours later.

Next, the magenta coupler of the 6th NI, the high boiling point solvent (IIB
s) Samples 2 to 17 were prepared by changing the dispersing surfactant and coating method as shown in Table 2.

The method for evaluating the frequency of margin coating failures is described below in Japanese Patent Application Laid-Open No. 62-85.
242, by observing a certain area of a colored sample with an optical m1fi mirror.

5urf-I 5urf-
2 The compounds contained in each layer of sample 1 are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; anhydro-9-ethyl-3,3'- G
(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye ■; anhydro-5,5'-diphenyl-9-
Ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye ■; anhydro-9-ethyl-3,3'-di(3-sulfopropyl)-5,6,5', 6 "-dibenzoxacarbocyanine hydroxide sensitizing dye V; anhydro-3,3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine hydroxide-tll L: 4HI l C -1 H h -I M-I UV-1 UV-2 HS -1 ;1 C(CH2=CH5O□C1l□)zccH2s, 0□
(CH2)2)N(C!1□)2S03 Each sample prepared in this way was exposed to green light so that the magenta color density was 1.0, and then exposed as shown in Example 1. A similar development process was performed.

Margin Table 3: As is clear from the results in Table 3, the coating method of the present invention makes the electric layer thinner! In the I coating, the number of occurrences of 114 due to coating was reduced by 1 fr, a more significant improvement effect was obtained, and the improvement was improved to a level where there were no major problems.

Claims (1)

[Claims] A mixture of an oil-in-water coupler dispersion containing a coupler represented by the following general formula [M-I] and a light-sensitive silver halide emulsion immediately before coating is coated on a support in at least one layer. A silver halide photographic material characterized by being constructed by coating. General formula [M-I] ▲ Numerical formulas, chemical formulas, tables, etc. May have. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ]