JPS6167035A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a sharpness and a graininess of an image and a shelf life of the photographic material by incorporating core-shell type silver halide particles to at least one of silver halide emulsion layers and by comprising an acyclic urea derivative to the above described material. CONSTITUTION:The above-described silver halide emulsion layer contains prefer ably >=70wt% of the core-shell type silver halide particles on the basis of the total silver halide particles contd. in the silver halide emulsion layers. The acyclic urea derivative contains at least one of an urine group which does not form a part of such a ring structure as barbituric acid and urazol.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the invention (Field of application for filial duties) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, to a silver halide color photographic light-sensitive material without deteriorating image quality, storage stability, etc. of the light-sensitive material. The present invention relates to a highly sensitive multilayer color photographic material with improved sharpness.

(Prior art) In recent years, there has been a remarkable trend toward compact cameras, and the screen size of color photographic materials has become smaller and smaller (
(Small format) is desired. Therefore, it is necessary to increase the magnification during printing, and relatively poor image quality such as graininess and sharpness has become a major problem. Many studies have been made to improve the graininess and sharpness of such color photographic materials.

In order to improve graininess and sharpness, for example,
No. 15495 describes a method of providing a gelatin layer or a medium-sensitivity emulsion layer between a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. JP-A No. 58-97045 discloses that a high-speed emulsion layer and a low-speed emulsion layer are separated by an intermediate layer, and at least one of the high-speed and low-speed emulsion layers is developed by reacting with an oxidized product of a color developing agent. A method of adding a DIR compound that releases an inhibitor is described. However, although these methods provide satisfactory results in terms of sensitivity and graininess, they are still not sufficient and do not provide excellent sharpness.

It is well known that the silver halide tt of the silver halide emulsion layer is reduced in order to improve sharpness, but increasing the number of couplers to obtain the desired gradation generally reduces graininess. deteriorates. Furthermore, the method of thinning the emulsion layer by reducing the amount of gelatin (tK) has drawbacks such as deterioration of the storage stability of the light-sensitive material under high temperature and high humidity conditions.

(Object of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material that is excellent in sharpness, graininess, and storage stability of the photographic light-sensitive material.

(2) Structure of the Invention The object of the present invention is to provide a silver halide photographic light-sensitive material having a sensitizing silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. In both cases, one silver halide emulsion layer contains core/shell type halogen [silver grains], and the above-mentioned /% Cl
This is achieved by a silver halide photographic material characterized by containing an acyclic urea derivative compound in the silver non-silver photographic material.

Core/shell type silver halide grains used in the present invention contain 4 to 30 moles of silver iodide) A core having a silver halide composition consisting of silver halide and an iodide coating on the core It is preferable that the shell has a silver halogenide FM having a silver content of 0 to 6 mol %. The thickness of the shell is preferably such that it does not hide the desirable qualities of the core, but is also thick enough to hide the unfavorable qualities of the core. In terms of the wing body, it is preferable to use silver halide grains in which the thickness of the shell is in the range of 0.01 to 0.1 μm.

More preferably, the silver halide composition of the core is a silver halide containing 8 to 20 mol % of silver iodide, and the silver iodide content of the shell is 0.5 to 4 mol % of silver halide. It is silver.

The above-mentioned A/shell type silver halide grains preferably have a silver halide composition other than the above-mentioned silver iodide mainly consisting of silver bromide, but may contain silver chloride as long as it does not affect the effects of the present invention. .

The shape of the core/shell type silver halide grains may be, for example, hexahedral, octahedral, dodecahedral, plate-like, or spherical, and may be normal crystal or twin crystal, but may be hexahedral or octahedral. , dodecahedral normal crystal grains are preferred.

In addition, it is preferable that the core/shell type silver halide grains have a monodisperse diameter distribution with a variation coefficient of grain size distribution of 0.15 or less, since sharpness is less likely to deteriorate due to light scattering. where the coefficient of variation of the particle size distribution is as follows (
5) is defined by Eq.

Cause 1≦0.15 Here, 3 is the standard deviation and i is the average particle size.

Here, the grain size is, in the case of spherical silver halide grains,
Its diameter, or in the case of particles with shapes other than cubic or spherical, the diameter when its projected image is converted to a colleague of the same area, where the diameter of an individual particle is ri, and the diameter of a particle with diameter ri is When the number is ni, i is defined by the following formula.

ni Note that the above particle size can be measured by the six-step method commonly used in the technical field for the above purpose. A typical method is Ragland's [Particle Size Analysis Method JA].

S, T, M7 Embodiment on Wright, Mark Croscovey, 1955, pp. 94-122. "Photographic Process Theory" by Mies and James, 3rd ed.
It is described in Chapter 2 of MacBaran Publishing (1966). The particle size can be measured using the projected area or approximate diameter of the particle. If the particles are of substantially uniform shape, the particle size distribution can be expressed fairly accurately as diameter or projected area.

Core/shell type silver halide grains can be produced by using a core of a silver halide grain that is sensitive to metallization and coating the core with a shell.

The monodisperse silver halide grains of the core ``'f-K'' forming the backing can be obtained by the double jet method while keeping the pAg constant. The silver chloride emulsion was disclosed in Japanese Patent Application Laid-Open No. 1983-1988.
The method described in No. 521 can be applied. For example, it can be produced by adding an aqueous potassium gelatin solution and an ammoniacal silver nitrate aqueous solution to an aqueous gelatin solution containing silver halide seed particles while changing the addition rate as a function of time. In this case, highly monodisperse silver halide grains can be obtained by appropriately selecting the time function of addition rate, pl(, pILgs temperature, etc.).

The shell is made of soluble halogen compound solution and soluble silver salt solution.
- It can be formed by depositing on the core of monodisperse silver halide grains by the double jet method.

Regarding the above-mentioned core/shell type I silver vagina preparation method, for example, West German Patent No. 1,16,9.2g□, British Patent No. 1,027,146, #Kaisho 57-15423
2%, Japanese Patent Publication No. 51-1417, etc. are also described. In the M manufacturing process of the core/shell type silver halide grains used in the present invention, for example, cadmium salt, nine zinc salt, lead salt, thallium A salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, etc. may be present together.

In the light-sensitive material of the present invention, the silver halide emulsion N1 containing core/shell type silver halide grains is combined with the silver halide emulsion/fm! containing core/shell type silver halide grains. It is preferable that the content is 70% by weight or more of the total silver halide envelopes contained in I! ! Preferably, all PK particles are core/shell type particles. In the present invention, core/
Shell-type silver halide grains may be used alone,
Two or more types of core/shell type silver halide grains having different average grain diameters or two or more types of core/shell type 5N halide grains having different silver iodide contents may be used in any mixture.

The distribution state of silver iodide in the above silver halide grains is as follows:
It can be detected by various physical measurement methods, and can also be investigated by measuring luminescence at low temperatures, as described in the Abstracts of the 1986 Annual Conference of the Photographic Society of Japan. .

Examples of acyclic urea derivatives used in the present invention have at least one ureylene group and, as in the case of compounds such as barbylic acid and urazole, the ureylene group present Group (-NH-C-NH-
) refers to a compound that does not form part of a ring structure. These acyclic urea derivative compounds include compounds having divalent groups containing one or more nitrogen atoms between the carbonyl group and the imino group in the ureylene group, as explained in more detail below. do.

A more preferable acyclic urea derivative compound has the following general formula (1
).

ExplosionRs HN-C-Xn-Nl (fh CI) (
In formula H, -X- is -HN-C-.

The group t- is represented, and n represents O or l.

R and 16 represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, and an aryl group such as, for example, a phenyl group.

Further, R3 and R4 represent a group selected from a hydrogen atom, a methyl group and an ethyl group.

Next, specific representative examples of the acyclic urea derivative compounds used in the present invention are shown.

A -I H, N-C-N) 12 A-2H, N-C-NHCH3 A -3N2 N -C-NHO214sPeng A-4H2N-C-NHCH3 Mat A-s HIN-C-NHC6HtsToki A -6CH ,NH-C-NHCH3 A-7C1H5NH-C-NHCH3 - A -8H,N-C-Nf4CH,OH■ A -9HOC)1. CH,NH-C-N)(-CH,
CH,0I-1Of(OH A -12N2 N -C-N H-C-N FlzA
-15H2N-C-N1 (-CH, -NH-C-N)
f.

A-18Cl-1, -CH-NH-CO-NH.

C-ruNH-Co-NN2 Human-19CI, -Cf(-NH-Co-NH.

CH, -CH-NH-Co-NH.

CH3 The acyclic urea derivative compound used in the present invention is preferably water-soluble, but compounds added using a solvent other than water can also be used. Addition amount is 0.11/m
It is preferable that the button thickness is 2-011/m or less, but the button thickness is preferably 2-011/m or less so as not to significantly impair the brittleness of the film.

The addition position may be at least one of the hydrophilic colloid layers on the side of the emulsion layer containing core/shell type silver halide grains, and may be in this emulsion layer or other layers. This is a layer containing preferable core/shell type silver halide grains.

The acyclic urea derivative compound used in the present invention is conventionally known as a formaldehyde gas scavenger (see US Pat. No. 3,141,771). However, in the present invention, a completely different and unexpected effect was obtained by combining the core/shell type silver halogenide grains.

In the present invention, it is more effective to apply the layer containing core/shell type silver halide grains to the upper layer (as viewed from the exposure direction) of the a number of emulsion layers than to apply it to the lower layer (of course, the layer containing core/shell type silver halide grains layer, and this embodiment is most preferred). It is effective to apply this to an emulsion layer (a layer above the magenta dye-forming layer) which has a relatively large contribution to sharpness.

The effects of the present invention are speculated as follows. That is, in a normal R configuration, a halogenated steel color photographic light-sensitive material has a panchromatic layer, an ortho layer, and a regular layer from the support side. With small formats (discs), the sharpness of the image quality is significantly reduced, but the ortho layer has a large contribution to sharpness. One of the factors that reduces the sharpness of the ortho layer is the amount of silver halide in the layer above the ortho layer and copying. Therefore, in order to improve the sharpness of the ortho layer, K is a regular and lower qJIJ.

It is necessary to make the film thinner.

When core/shell type particles are used in the regular layer and an acyclic urea derivative compound is used, gamma increases. Therefore, to achieve the target gradation, the gamma must be lowered by the increased amount. That is, the amount of emulsion and fogger attached can be reduced, resulting in a lower amount of silver and a thinner film, and the sharpness of the ortho layer is improved. Of course, the sharpness of the panchromatic layer also improves.

The silver halide emulsion used in the light-sensitive material of the present invention can be spectrally sensitized using various dyes. Dyes used include polymethine dyes including cyanine, merocyanine, complex cyanine and complex merocyanine (i.e. di-, tri-, tetra- and polynuclear cyanine and merocyanine), oxonol, hemioxonol, styryl, merostyryl and strephthocyanine. .

・/Anine spectral sensitizing dye, quinolinium, pyridinium, isoquinolinium, 3H-indolium, oxacillium, oxazolinium, thiazolium, thiazolinium, selenazolium, selenacylinium, imidazolium, imidazolinium, benzoxazolinium,
Derived from benzothianzolium, benzoselenazolium, penzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, thiazolinium, dihydronaphthothiazolium, biryllium and imidazopyrazinium quaternary salts It contains two basic heterocyclic nuclei connected by a methine bond, such as:

Merocyanine spectral sensitizing dye, barbituric acid, 2-
Thiobarbic acid, rhodanine, hydantoin, 2-
Thiohydantoin, 4-thiohydantoin, 2-virasoII-5-one, 2-inxacillin-5-one, indan-1,3-dione, cyclohexane-1,3-
dione, 1,3-dioxane-4,6-dione, pyran°phosphorus-3°5-dione, pentane-2,4-dione,
Alkylsulfonylacetonitrile, malononitrile,
It includes those in which acidic cough tacyanin dye-type hedge-based heterocyclic nuclei such as those derived from isoquinolin-4-one and chroman-2,4-dione are bonded through methine bonds.

Spectral sensitizing dyes useful for sensitizing silver halide emulsions include British Patent No. 742.112 and US Pat. No. 1.846.3.
No. 00, No. 1,846.301, No. 1.846,30
No. 2, No. 1,846,303, No. 1,846,304
No. 2.078.233, No. 2.0 s 9.72
No. 9, No. 2.165,338, No. 2.213,238, No. 2.231,658, No. 2.493,747,
No. 2.493.748, No. 2,526.632, No. 2.739.964, No. 24,292), No. 2.778,823, No. 2.917.516, No. 3
．． 352.857, 3,411.916, 3,
No. 431,111, No. 2,295,276, No. 2,4
81. fi No. 98, No. 2,503,776, No. 2.
688,545, 2.704.714, 2.9
No. 21,067', No. 2.945,763, No. 3
．． No. 282.933, No. 3,397,060, No. 3.
No. 660,102, No. 3,660,103, No. 3,3
No. 35.010, No. 3,352,680, No. 3,38
No. 4,486, No. 3,397,981, No. 3,482
．． No. 978, No. 3,623.881, No. 3,718,
No. 470 and No. 4,025,349. Examples of useful dye combinations, including supersensitizing dye combinations, include U.S. Pat. Nos. 3,506,443 and 3,672.
．． No. 898. An example of a supersensitizing combination consisting of a spectral sensitizing dye and a non-light absorbing additive is the use of thiocyanate in the spectral sensitization process as disclosed in U.S. Pat. No. 2,221,805. US Patent 2.
U.S. Pat.
No. 7,089, using sulfonated aromatic compounds; Using iodide as disclosed in No. 826, Gilman et al.
Other compounds can be used, including compounds such as those described in [Review - Off the Mechanism of Supersensitivity/4.

The above-mentioned sensitizing dye may be added at any time in step D, such as at the beginning of chemical ripening (also called second ripening) of the silver halide emulsion, during the course of ripening, after the end of ripening, or at an appropriate time prior to emulsion coating. do not have.

Add a small amount of sensitizing dye to the milk of the Joki. As for the method, five types, I, and D methods can be applied. U.S. Patent No. 3.464), 987
As described in No. KgC, the coloring matter was dissolved in a scratch-generating organic solvent, the solution was dispersed in a hydrophilic colloid, and this dispersion was added to 1v1 of whole milk. good. Furthermore, the sensitized colors J of the present invention may be individually the same.
fr, can be dissolved in different solvents and these fg solutions can be mixed or added separately before being added to the emulsion.

In the present invention: C, when adding a sensitizing dye to a silver halide photographic material, water-miscible dyes such as menal alcohol, ethyl alcohol, acetone, etc. Because the solvent is used wisely.

In the invention, when a sensitizing dye is added to a silver halide emulsion, addition 1j [, halogenation @91 per mole]
X 10-' Mornai L2.5 X 10-2%, preferably 1. Ox 10-'mol·t 1.
Ox is 10-3 mol.

Including the core/shell-type halogenated steel particles used in the present invention, various types of halogenated steel particles used in the electrical shock material of the present invention, Bachelor of Chemistry?) Can destroy sensitivity. Sunaichi active gelanan; water-soluble white j+,) Ifi, Bo J'
Ml palladium salt, water soluble rhodium salt, water I'? Precious metal sensitizers such as l-based iridium; Ikari sensitizers; selenium sensitizers: chemical sensitizers such as V-based sensitizers such as boriaban and stannous chloride; Alternatively, they can be used together for chemical sensitization.

As the above-mentioned yellow lichen enhancer, known ones can be used. Examples include thiosulfate, allylthiocarbamide thiourea, allylthiocyanate, cystine, p-)luenethiosulfonate, and rhodanine. Other U.S. Patent Nos. 1.57.1,944 and 2. ．． $1
No. 0.689, No. 2.278.947, No. 2.728
, No. 668, No. 3.501.313, No. 3.656.
No. 955, German Patent No. 1,422,869, 11'!
Sulfur sensitizers described in Publication No. 56-24937, JP-A No. 55-45016, etc. can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the resolution of the emulsion. It varies over a considerable range under various conditions such as pH sensitivity and silver halide grain thickness, but as a guide, it is approximately 10% per 81 moles of halide.
-7 moles - about IO-"8 moles are preferred.

In the present invention, selenium enhancement ii% is used instead of sulfur sensitization, but selenium sensitizers include allyl isoselenocyanate-based aliphatic isoselenocyanates,
Selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenophosphate-1
-L-diethyl selenide, diethyl diselenide, and other selenides, specific examples of which are U.S. Pat. No. 1.574,944 and U.S. Pat.
No. 2, No. 1,623.499.

The amount added may vary over a wide range as with the sulfur sensitizer, or may be used as a guideline, approximately 10-10% per mole of silver halide.
The amount is preferably about 7 mol to 10 −3 mol.

As the gold sensitizer, various gold compounds can be used, regardless of whether the gold oxidation number is +1 or +3. Typical examples include chlorauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like.

The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is approximately 10 moles per mole of silver halide.
(li, in mol l) is preferred.

The sensitization method for silver halide grains can be carried out in combination with other metals, for example, sensitization methods using metals such as platinum, palladium, iridium, rhodium, or their salts.

In the present invention, reduction sensitization can also be used in combination. Examples of the λ base agent include, but are not limited to, known stannous chloride, thiourea dioxide, hydrazine derivatives, and Nran compound.

It is preferable to carry out reduction sensitization during the growth of the s O silver sensitization grains or after completion of sulfur sensitization and gold sensitization.

The silver germide emulsion used in the light-sensitive material of the present invention is
Known at any point in its manufacturing process
It is also possible to use agent A. silver halide 14
As for Moe (Al US 51'F No. 3.271.157, US No. 3.531,289, US No. 3,574,628,
Organic thioethers described in JP-A-5.1-1.019, JP-A-54-158917, and JP-A-58-30571, (b) JP-A-53-824+18, ~I
Thiourine peptides described in No. 55-77737 and No. 455-29829, (C) JP-A-53-1443
The AgX solvent which has a rare thiocarbonyl group on the enzyme straddle sulfur, cypress and nitrogen atom distributed in No. 19,
(d) imidazoles described in JP-A-54-100717, (e) sulfates, Cf) thiocyanates, f
g) Ansonia, (h) hydroxyalkyl-substituted ethylene diamines described in JP-A-57-196228, substituted mercaptotetrazoles described in Yama JP-A-57-202531, (j) JP-A-Sho 57-202531; 58-543
Examples include the substituted pensoipodazoles listed in No. 33.

The silver halide emulsion used in the present invention (() is used to prevent the occurrence of fog during its manufacturing process, storage, or development processing).
Various compounds may be added at the end of chemical ripening for the purpose of stopping or stabilizing photographic performance.

For example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazole, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptopenzimidanols, aminotriazole/I' mercaptotriazoles, nitropenttriazoles, mercaptotetrazoles (especially 1-7enyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinthione, and also benzenethiosulfine. Acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone, S! More antifoggants such as aminophenol derivatives, aminophenol derivatives, ascorbic acid hexaconductors, and many other compounds known as stabilizers can also be added during chemical ripening. Alternatively, it is preferable to add it before coating.

As binders for silver halide emulsions, gelatin and various other polymeric compounds are used.

Gelatin includes not only seratin but also derivative gelatin, and derivatives include a reaction product of gelatin acid anhydride, a reaction product of gelatin and inocyanate, or a compound containing gelatin and an active halogen atom. The reaction products, etc. will be given as a monetary gift. Examples of acid anhydrides used with gelatin include maleic anhydride, phthalic anhydride, benzoic acid anhydride, isatoic anhydride, succinic anhydride, and the like. is, for example, phenyl isocyanate, p-bromophenyl isocyanate, p-4o
Examples include a-phenyl isocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, and naphthyl incyanate.

Furthermore, as a compound having an active halogen atom, ell
, t [Benzene sulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-7 enoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, y(do,p-)luenesulfonyl chloride, nI-nitrobenzenesulfonyl chloride , m-sulfopenzoyl diquarite, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride 5
Ido, 3-ditro-4-aminobenzenesulfonyl chloride, 2-carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2-ditro-5-methylbenzenesulfonyl a-lide, phthalyl chloride, p -Nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate, furoyl chloride, and the like.

In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, as hydrophilic colloids for preparing a silver halide emulsion, L'Ff, colloidal albumin, agar, gum arabic, texturan, etc. , alkynic acids, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26, polyacrylamide, imidized polyacrylamide, casein, urethane carboxylic acid groups such as vinyl alcohol-vinyl cyanacetate copolymers, or cyano Acetyl St-containing vinyl alcohol polymer, polyvinyl alcohol-holivinyl pyrrolidone, hydrolyzed polypimol acetate, polymer obtained by polymerization of protein tang or saturated unanylated protein and vinyl group-containing hexamer, polyvinyl pyridine , polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. can also be used.

The silver halide emulsion according to the present invention may be used as a coating aid, to prevent static electricity, to improve slipperiness, to disperse emulsions, to prevent adhesion, and to improve photographic properties (for example, to accelerate development, increase contrast, and sensitize). The surfactant may also be included.

That is, U.S. Pat. No. 2,240,472, U.S. Pat. No. 2,831,
7 G No. 6, 3.158,484, 3,210
, No. 191, No. 3,294,540, No. 3,507
．． 660, British Patent No. 1,012.495, British Patent No. 1,012.495
22゜878, 1,179.290, 1.19
8,450%, U.S. Patent No. 2,739.891, 2.
823.123, 1,179.2su0, 1,1
No. 98.450, No. 2,739.891, No. 2,82
No. 3,123, same: ',, No. 068.101, same 3,4
No. 15,649, No. 3,666,478, No. 3,75
No. 6.828, British Patent No. 1,397,218 @, 3
．． 113°816, 3,411,413, 3,
473.174, 3.345,974, 3.7
No. 26.683, No. 3,843,368, Pelky 7
Grant 731,126+5, Furukoku Tokudou No. 1,138,5
No. 14, No. 1.159.825, No. 1,374,78
No. 0, U.S. Patent No. 2.271,623, U.S. Patent No. 2.288.
No. 226, No. 2.944.900, No. 3,235.
No. 919, No. 3,671,247, No. 3,772.0
No. 21, No. 3,589.906, No. 3,666.47
No. 8, No. 3.754,924, West German patent question OL81
, No. 961,683 and Japanese Patent Publication No. 117414/1989, No. 59025/1973, Japanese Patent Publication No. 378/1978, No. 4
No. 0-379, No. 43-13F122, for example, saponins (steroids), alkylene ogicide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl or alkylaryl ether polyethylene). Glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of glycone), glycidol derivatives (e.g. alkenyl succinic polyglycerides, alkylphenol polyglycerides), polyhydric alcohol fats Anti-acid esters, alkyl esters of sugar, urethanes or ethers! ! Non-ionic surfactants, triterpenoid saponins, alkyl carbons: salt, alkylbenzenesulfoneffl)J
[, Alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-
～-Alkyltaurifs, sulfosuccinic esters,
Anionic surfactants containing chaste groups such as carboxy, melpho, phospho, sulfate, Nisder phosphate groups, such as sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. , amino acids, aminoalkyl sulfones [8, amphoteric surfactants such as aminoalkyl sulfates or phosphates, alkyl betaines, amine imides, amine oxides, alkyl amine salts, fatty acids or aromatic compounds; g Quaternary ammonium group, pyridium, imidazolium, etc. 1! D cationic surfactants such as monocyclic quaternary ammonium salts and sulfonium or sulfonium salts containing aliphatic or dicyclic rings may be used as development accelerators in the halogen (arsenic) emulsions of the present invention.
In addition to the above-mentioned surfactants, West German patents [(OLS)
2.002. No. F171, No. 2.445.611, No. 2.3 fin.

No. 878, British Patent No. 1.352.19 fi, etc. 2
It may contain imidazoles, 1,000-onythyl compounds, selenoethers, etc., which have been taught.

The sensitive material of the present invention is a color sensitive material, such as an edge-sensitive silver halide emulsion, a silver halide emulsion adjusted to red sensitivity and blue sensitivity, containing magenta, cyan, and yellow couplers in combination, respectively. The method and material used for silver ions may be used, and it is desirable that the coupler be non-diffusible and have hydrophobic properties called ballast groups in the molecule. In addition, a colored coupler having a color correction effect may be used, and the coupler may also be a coupler whose coupling reaction product is colorless.

As the yellow color-forming coupler, known open-chain ctomethylene couplers can be used; dibenzoylacetanilide and piparoylacetanilide compounds are advantageous. Specific examples of usable brightly colored couplers, U.S. Pat. No. 2.875°057 and U.S. Pat.
1) No. 6, No. 3,408.194, No. 3.55
1.155, 3,582.322, 3,725
, No. 072, No. 3,891.445, Western Patent No. 1,5
No. 47,868, West German Patent Application (OLS) 2.21: U, No. 461, No. 2.219.917, No. 2.261.
No. 361, No. 2.414,006, No. 2.26: (
, No. 875, etc.

As the magenta color-forming coupler, pyrazolone compounds, indazolono compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

Specific examples of magenta color forming couplers that can be used (US Pat. No. 2.600.788 1.py) 2. g H3,
608@, 3,062.653, 3,127,2
No. 69, No. 3.311゜476, No. 3.419.39
No. 1, No. 3,519.429, No. 3.558,319
@, 3.582.322, 3,615.506
No. 3,834,908, No. 3,891.445, West German Patent No. 1,810°464, West German Patent Application (OL
S) No. 2.408,665, No. 2.417,945
As the cyan color-forming couplers described in Japanese Patent Publication No. 2.418,959, No. 2.424,467, and Japanese Patent Publication No. 40-6031, phenolic compounds, nafthol compounds, etc. can be used. . Specific examples are U.S. Patent Nos. 2.369.929 and 2.434,2.
No. 72, No. 2,474.293, No. 2.521.90
No. 8, No. 2,895.826, No. 3,034,892
° No. 3.311,476, No. 3.458,31
No. 5, No. 3.476.563, No. 3,583.971
No. 3,591.383, No. 3.767.411
'F+, West German patent publication g (OLS) No. 2.414,830, OLS No. 2.454,329, ``Japanese Patent Application Publication No. 1973-59838
This is what is written in the issue.

As a colored coupler, for example, U.S. Patent No. 3.47
(No. 5,560, No. 2,521,908, No. 3,0
No. 34,892, Special Publication No. 44-2016, No. 38-2
No. 2385, No. 42-11304, No. 44-3246
No. 1, West German patent application (OLS) 2,418,959
You can use those listed in the issue.

Coupler/tl development inhibitor releasing compound (hereinafter referred to as DI)
(referred to as R compound).

Examples of DIR compounds include U.S. Pat. No. 3,148.062, U.S. Pat.
010゜818, JP-A-52-69624, JP-A No. 55
Compounds that react with oxidized color developing agents to form dyes and release development inhibitors, as described in No. 135835 and No. 57-44831;
．． No. 632゜345, No. 3.958.993, No. 3.938,996, No. 3.928,041, No. 3,961,959, I# Kaisho 52-67628, No. 51-6724 and Special Patent Application No. 50-125202, a compound which releases a stain inhibitor but does not form a dye upon reaction with an oxidized product of a color developing agent, A compound that releases a development inhibitor by an intramolecular nucleophilic substitution reaction as described in Japanese Patent Application No. 145135/1983 and U.S. Pat. Compounds that emit
No. 154234 and the like describes a compound which releases a development inhibitor by reaction with an oxidized product of a color developing agent, which releases a development inhibitor by electron transfer along a conjugated chain.

Two or more of the couplers indicated by - and the above-mentioned 1JiR compounds may be contained in the same layer. Furthermore, the same compound may be contained in two or more different layers.

Coupler and DIR compounds can be introduced into the silver halide emulsion layer using known methods, such as U.S. Pat.
The method described in No. 027 can be used.

For example, 7-tar acid alkyl esters (dibutyl 7-thalerate, dioctyl phthalate), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl 7-osphate), citric acid esters (e.g. acetyl citric acid). tributyl).

Benzoic esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), sweet or organic solvents with a boiling point of about 30°C to 150°C, yl, tb, rosé ethyl, phthalocyanate, etc. After elucidation into 1-class alkyl acetate, ethyl propionate, secondary butyl alcohol, methyl imbutyl ketone, β-ethogyzoethyl acetate, methyl heptaroso-A-butyl acetate, present aqueous colloid Vg Distributed? L ” x 1 slag point organic TG medium and low boiling point organic solvent are combined in total.
You can stay there.

If the couplers exhibit carbon r-waves, sulfo-off, etc., they are introduced into the hydrophilic colloid as an alkaline aqueous solution; 5xlO-3 to 5 mol per mol, preferably l
Xl0-''mol to 1.0mol can be added.

In addition, the I R compound is generally: s X 10-' mol to 5 x lQ' % per 1 mol of silver, preferably FiI X 10-
'Mo, 'L+7'J to 1 x 101 mol is added.

In the present invention, the following general formula (
The use of the coupler represented by II) improves the sharpness ratio by thinning the layer as described above.
Further, it is particularly preferable since the heat resistance of the undeveloped photosensitive material is large and the same effects as described above can also be obtained. That is, when a coupler represented by the following general formula (II) is used as a color-forming coupler, an undeveloped light-sensitive material is left at 55° C. for 2 days.
The rise of Capri in the 4th meeting will be suppressed to a large extent.

General formula ('I) In the formula, X is the following ta+, (
bl and (C1); W is a hydrogen atom; group t-
i, RyFi water atom, alkoxycarbonyl group,
It represents a phenoxy7carbonyl group, a sulfonamide group, a sulfamoyl group, an azilaξ] group, or a carbamoyl group.

Quantity (in the formula, Zl = saturated or unsaturated, L5 member size or 6
Represents a group of nonmetallic atoms necessary to form a membered ring. ) (h) Cast-1, Pa (where Z2 is saturated, unsaturated, 4 scissors, 5 iso or 6 to form a ring (receiving the necessary non-metallic atomic group) - ~ 4
3 (wherein, z represents a non-gold J11 atomic group necessary to form a saturated or unsaturated 4-, 5-, 6-ring ring.

) In the yellow coupler according to the present invention described at @, the general formula [
11) R6 of K is a tert-group f k group, 7g,
It is preferable that W is a hydrogen atom, and R11 is a chlorine atom, a fluorine atom, or a methyloxy group.

Next, typical examples of groups that can be eliminated during color development in the general formula rlHC are described below (1) Next, specific representative examples of the yellow coupler represented by the general formula (6) used in the present invention ( shows.

H3 Y-5 Y-15 0H.

/N\ n/ Y-13 Y-14 H,020 OA? 1T3 Y-21 CH.

C/ The yellow coverr represented by the general formula [■] may be used alone or in combination with 2fl1M or more.

It is also possible to use a 4-equivalent yellow coupler in combination.

Furthermore, the effects of the present invention can be obtained by containing a substance capable of promoting a development inhibiting substance in the non-photosensitive whip on the side far from the support of the emulsion layer containing core/shell type silver halide grains used in the present invention. is even more pronounced, which is preferable.

As the substance capable of accelerating the development inhibitor, fine silver halide grains having substantially no photosensitivity are preferably used. In this case, the average particle size is particularly preferably 0.02 μm to 0.00 μm.
2μ silver bromide, silver iodide or silver iodobromide grains are used,
The addition # is Q as the amount of silver, l ~ 5 Q IQ /
d@', preferably 2 to 10 M9/dm'.

In addition to the above substances, for example, JP-A-52-60622
The organic polymers described in No. 50-23228, the fine grain silver halide described in No. 49-53438, and the bismuth compounds described in No. 49-53438 can also be used.

The above-mentioned non-photosensitive layer is a layer having functions such as a protective layer, an intermediate layer, a filter layer, and an anti-scratch layer, which are well known in the art.

The photosensitive material of the present invention uses hydroquinone derivatives, aminephenol derivatives, gallic acid derivatives,
It may also contain ascorbic acid derivatives, specific examples of which are described in U.S. Pat. Nos. 2,360,290 and 2,336,3.
No. 27, No. 2,675,314, No. 2.701.19
No. 7, No. 2,704,713, No. 2,728,659
No. 2,732,300, No. 2,735,765, JP-A-50-92988, JP-A-50-92989,
It is described in Japanese Patent Publication No. 50-93928, No. 50-110337, Japanese Patent Publication No. 50-23813, etc.

Effective antistatic agents include diacetylcellulose, styrene perfluoroalkylridium maleate copolymers, and alkali salts of reaction products of styrene-maleic anhydride copolymers and p-aminebenzenesulfonic acid. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use monocolloidal silicon oxide. Also,
Examples of the latex added to improve the physical properties of the film include copolymers with other ethylene group-containing monomers, such as acrylic esters and vinyl esters. Examples of gelatin thickening agents include glycerin and glycol compounds, and examples of thickeners include styrene/sodium maleate copolymer and alkyl vinyl ether-maleic acid copolymer.

Examples of the support for the photosensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene composite paper, glass film, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, and the like. These supports are appropriately selected depending on the intended use of each photosensitive material.

These supports are subjected to undercoat processing if necessary.

After exposure, the silver halide photographic material of the present invention can be developed by a commonly used known method.

That is, color development can be carried out by a color development method commonly used for silver halide color five-dimensional optical materials. In the reversal method, the image is first developed with a black-and-white negative developer, then exposed to white light or treated with a bath containing a capri agent, and then color developed with an alkaline fJ developer containing a color developing agent. There are no particular restrictions on the processing method, and any processing method can be applied; for example, typical methods include color development followed by bleach-fixing, followed by washing with water and stabilization as necessary, or color development. After development, bleaching and fixing can be carried out separately, followed by further water washing and stabilization treatment if necessary.

It is also known to process low-silver halide light-sensitive materials using an amblifier agent such as hydrogen peroxide, cobalt@salt, and these methods can also be used for processing. In addition, some of these processes are carried out at high temperatures in order to be carried out quickly, while others are carried out at room temperature or lower in special cases. In addition to high-temperature rapid processing, pre-hardening treatment can also be performed. Further, depending on the type of processing agent used, auxiliary baths such as various types of neutralizing baths may be required, and these auxiliary baths may be used as necessary.

Particularly useful color developing agents used for color development of the light-sensitive material of the present invention include primary phenylene diamines and derivatives thereof, and representative examples include the following.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl/L/ -N-β-hydroxyethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl 7゛niline, 3-β-methanesulfonamidoethyl 4-7mi/-N, N-diethylaniline, +3
-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-
Ethyl-N-β-methoxyenalaniline, 3-acetamido-4-amino-N, N-diethylaniline, 4-
Amino-N, N-diethylaniline, N-ethyl-N-
β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-
β(β-methoxyethoxy)ethyl-3-methyl-4-
Aminoanilines and their salts, such as sulfates, danates,
In order of sulfite, P-toluenesulfone rg! Salt, etc.

(Example) First, the method for preparing the emulsions used in the examples is shown below.

[Preparation of homogeneous emulsion]

Silver nitrate aqueous solution and alkali halide aqueous solution were added in advance to gelatin aqueous solution and excess chloride, and allowed to fall naturally into a reaction vessel kept at 60°C. Next, Demol N aqueous solution manufactured by Kao Atlas Co., Ltd. and magnesium sulfate aqueous solution were added to precipitate. , desalt, add gelatin, pAg 7.
8, pu 6.0 emulsion was obtained.

Further, chemical ripening was performed using IJium (thiosulfate), chloroauric acid, and rhodan ammonium, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added, and gelatin was added to make the mixture uniform. A silver iodobromide emulsion was obtained. By changing the alkalinolide composition, silver iodide mortar was produced, and silver nitrate aqueous solution and alkali IJ/.
The average particle size and particle size distribution were varied by varying the addition time of the aqueous Ride solution.

[Core/shell emulsion manufactured by 1] Into a reaction pot, seed particles of halogenated scissors and seratin water and liquid were added in advance, and the pAg and pH in the reaction pot were adjusted.
While controlling pAg and pH, ammoniacal silver nitrate aqueous solution and potassium iodite and potassium bromide aqueous bath solutions were added in proportion to the increase in surface M during particle growth to grow core particles. What about ammoniacal nitric acid aqueous solution and potassium bromide aqueous solution?
A core/shell type silver iodobromide emulsion was obtained by adding it in proportion to the increase in surface area during grain growth.

Next, a Demol N aqueous solution manufactured by Kao Atlas Co., Ltd. and a magnesium sulfate aqueous solution were added to perform precipitation and desalting, and gelatin was added to obtain an emulsion with pAg of 7.8 and pH of 6.0.

Furthermore, sodium thiosulfate, chloroauric acid, and rhodan ammonium were added, chemical ripening was performed, and 4-hydroxy-6
-Methyl-1,3,3a.

7-chitrazaindene was added and gelatin was further added to obtain a core/shell type silver iodobromide emulsion. Here, by changing the ratio of potassium iodide and potassium bromide, by changing the ratio of silver iodide from the button, and by changing the addition rate of ammoniacal silver nitrate and potassium halide, by changing the grain size by K,
By changing the pAg value during the knitting reaction [the knots were changed respectively.

In addition, in the following examples, sharpness was determined by exposing the sample to light (2, as shown in the following examples) through a wedge whose spatial frequency was varied in the range from 3 lines/home to 100 lines/u+. MTF of the image obtained after processing
(Modulation Transfer Func
tion), and the spatial frequency is 10 lines/gate and 30 lines/gate.
The MTF values in lines/mm were compared to evaluate sharpness.

Example 1 A TrT layer was applied on a subbed triacetate film support in the following order to prepare sample No. 2-ceramic 10 as shown in Table 1 below.

1st layer Green-sensitive silver halide layer Silver iodobromide emulsion containing 6 mol of silver iodide (average grain size 0.3
μ, containing 0.25 mol of silver halide and 40.9 mol of gelatin per 1 kg of emulsion) was prepared in a conventional manner, and this emulsion 1
kg was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine was added as a green-sensitizing dye. , then 4-hydroxy7-6-methyl-
1,3,3a,7-chitrazaindene and saponin were added, followed by the following dispersion 1, which was coated to a dry film thickness of 3.0 μm.

(Dispersion-1) As a 1ze/ta coupler, 1-(2,4,6-tri21
phenyl-3-(3-(2,4-di tCrt-
Amylfenogis) amide] benzamide 5-
Pyrazolone to g '6) Dissolved in a mixture of 102 licresyl phos7ate and 30 ml of ethyl acetate, 2
200 ml of an aqueous solution of 5tisgelatin containing g K 7
711 and emulsified and dispersed using a colloid mill.

21st - Yellow filter: Saponin was added to an aqueous gelatin solution in which yellow colloidal silver was dispersed, and 1 (1) was applied to obtain a dry film BP-1, 2μ.

Third layer: JPc-sensitive silver halide layer The following dispersion-2 in '#-sensitive silver halide emulsion 1 to 9 as shown in Table-1
, and as shown in Table 1, the acyclic urea derivative compound according to the present invention was added, and saponin was further added to prepare a coating solution of 1:1.
Manufactured. These coating liquids were applied in different amounts so as to obtain approximately the same r.

4th layer...Protective layer 4 1,2-bisvinylsulfonylethane 02y as saponin and hardening agent in 100ml of Tigelatin aqueous solution
was added and coated to a dry film thickness of 1.2 μm.

(Dispersion-2) As a yellow coupler, 3-[α-(2,4-Gte
30 g of rl-amylphenoxy)butanamide]-benzoyl-2'-methoxy-acetanilide was mixed with 15.9 g of tricresyl phosphate and 50 ml of ethyl acetate.
The mixture was dissolved in a mixture of 1 ml of sodium triisoflobilnaphthalene sulfonate, added to 5 ml of Ameze and Ratin Water Soluble Numa-200rn/8 containing 39 f of sodium triisoflobilnaphthalene sulfonate, and emulsified and dispersed in a colloid mill.

``2゛N, Product 7゛Gakuwhite top + 1 large tree of j Obtained.

Processing process (38'0) Processing time Color development
3 minutes 15 seconds 4 Mortar 6 minutes 30 seconds water flow 3 minutes 15 seconds 'i1: Gradual 6 minutes 30 seconds water wash
Stabilization for 3 minutes and 15 seconds and stabilization for 1 minute and 30 seconds The composition of the processing solution used in each processing step is as follows.

Color developing solution composition: Bleaching composition: Fixing solution composition: Stabilizing solution composition ゛For the obtained color image, the gradation value (gamma) of the yellow coloring layer and the brightness H7 (MTF) of the magenta coloring layer
The results are shown in Table 2 along with the dry film thickness of the third layer.

Table-2 The following is clear from the results in Table 2.

The samples of the present invention (positive 1 to 1m6) all have the same dry film thickness of the 3rd layer (yellow coloring layer) when the gamma of the yellow coloring layer is almost the same as that of the non-invention samples (7th to positive 10). is thin, and the M TF value of the magenta coloring layer is accordingly improved. That is, the effect of the present invention was exhibited in the sample of the present invention in which core/shell type silver halide grains were used in the positive layer and the non-) type A urinary cord compound according to the present invention was used. There is.

? - Motion 4 Odor f11 - 2 Example 1 @I The same procedure as Example 1 was carried out except that the yellow coupler in Dispersion 2 of -1 was changed to the compound of 3.
1' sensitive silver halide layer and retention i+t! II- was applied to prepare samples N[111 to 13].

These samples were left at 55 DEG C. for 2 days, exposed to light using a conventional wedge '4, and then developed in the same manner as in Example 1 to obtain the results shown in Table 3. Here △Fog
The values represent the increase in capri of the heat-treated sample relative to the non-heat-treated sample.

The emulsion of t rcc silver halide and the acyclic n' compound according to the present invention were prepared as sample rt of Example 1-1.
Same as 4.

Table 3 From Table 3, compared to sample 1 () containing the coupler used in Example 1, all the samples containing the imitation ・f erotic coupler shown by the general formula mark had an increase in fog after heat treatment. It turns out that it is low. In addition, sample number 11~t! All of the samples of n13 require a smaller amount of coating liquid to obtain almost the same gamma than the samples to which the acyclic urea derivative compound according to the present invention is not added, and the MTF value of the magenta coloring layer is improved. ing.

Home use a1-3 'C where the emulsion containing silver bromide grains with an average grain size of 01μ is added to the protective layer of Example 1 and the amount of silver added is 4 mq/dq'.
r! Sample No. 14 was prepared in the same manner as Sample No. 4 in Example-1, except that the sample No. 4 was added. Also, the average particle size O1
Instead of an emulsion containing 1 micron silver bromide grains, an average grain size of 0.
Sample Na 15 was prepared by using an emulsion containing silver iodobromide grains (containing 67 μm silver iodide) with an added silver amount of 2 to /d712. These samples were exposed to light and developed in the same manner as in Example-1 along with the sample Nn4, and the table
The result of 4 was 14.

Table 4 From Table 4, it can be seen that the MTF value of the sample in which fine grain silver halide was added to the straightening layer was further improved.

Example 4 On a support made of a subbed polyethylene terephthalate film, the following layers 11 (next) were coated from the support side to prepare paper stock N116.

No. 111... Anti-halation M Black colloidal silver was dispersed in an aqueous gelatin solution and coated at a ratio of 39 g/m' of gelatin and 0.3 g/m' of silver.0 Second layer/Intermediate layer The aqueous gelatin solution was dried into a film. The coating was applied to a thickness of 1.0μ.

3rd layer...Red-sensitive low-sensitivity silver halide emulsion layer 8.5
Silver iodobromide emulsion containing 7 ruti silver iodide (average grain size 0.7 μm)
, containing 0.25 mol of silver halide and 40 g of gelatin per tcg of emulsion) was prepared by the method of preparing a homogeneous emulsion. 1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and K was used as a red-sensitive sensitizing dye, i'ITJ (9-
Ethyl-3,3'-di(3-sulfopropyl)-1
,5.・1',5'-dibenzothiacarbocyanine hydroxide, % 7E5, 5'-cyclo9-ethyl-3+37-c(3-sulfopropyl)thiacarbocyanine hydroxide, 4'e water 5.5'- Dichloro-
Add 3',9-diethyl-3-(4-sulfobutyl)oxythiacarbocyanine hydroxide, then add 025 g of 4-hydroxy-6-menalium 1°3.3a, 7-titrazaintene, I-phenyl-5-mercaptotetrazole 20 Immediately, 0.2 g of polyvinylpyrrolidone was added, and then 500 rr+l of Lower V Dispersion (0-1) was added. The red-sensitive, low-sensitivity silver halide emulsion thus obtained was coated to a depth of 3.0 μm in dry film thickness.

4 layers -- 5th layer same as the 2nd round of the intermediate layer Red-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion containing 7 mol of silver iodide (average grain size 1.0μ, emulsion i
Silver halide 0.25 mol, gelatin 30 per kQ! !
) were prepared by the method of preparing a homogeneous emulsion. This emulsion 1kQ was chemically typed with gold and Sarujubeiqi 11, and was made into a #sensitizing dye by Ning et al.
-di(3-sulfopropyl)-4,5,4',5
'-Dibenzothiacarbocyanine hydroxide, anhydrous 5
, s'-cyclo9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-3'I9-diethyl-3
-(4-sulfobutyl)oxathiacarbocyanine hydroxide is added, then 4-hydroxy-6-methyl-
1, 3, 3a.

7-chitrazaimpun 0.25g, 1-phenyl-5-
Mercaptotetrazole 8~, polyvinylpyrrolidone 0
．． 2.9 and further the following dispersion (0-2) 5110
ml was added. The infrared sensitive silver halide emulsion thus obtained was coated to a dry film thickness of 2.0 μm.

6th layer - 7th layer, same as the 2nd layer...Low sensitivity to green light! #c#No.Rogge/Silver Emulsion Layer 1 kg of the silver iodobromide emulsion shown in Table 5 (containing 0.25 mol of silver halide and 405 gelatin per emulsion) was chemically sensitized with gold and sulfur sensitizers. Anhydrous 5,5'-dichloro-9-ethyl-3,3'-
Di(3-sulfopropyl)oxacarbo/anine hydroxide, anhydrous 5,5'-diphenyl-9-ethyl-3
, :4'-di(3-sulfopropyl)oxacarbocyanine and anhydrous 9-ethyl-3+3'-di(3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroquine. Add, then 4-hydroxy-6-methyl-1,3,3a,? - Tedrazaintene 0.25g, I-phenyl-5-mercaptotetrazole 2gmQ and polyvinylpyrrolidone 0.2g
0 mouth, and further 1:' dispersion (M -13500m
1 was added. The silver Rochenide emulsion thus obtained was coated to a total dry film thickness of 3.0 .mu.m.

8th drop Intermediate layer 9th layer same as 2nd layer Highly sensitive buried silver halide emulsion layer Silver iodobromide emulsion containing 7 mol of silver iodide (average grain size 1.2μ, emulsion 1
・Silver halogenide 0.25 mol, gelatin 30.9
) was prepared by the method of preparing a homogeneous emulsion. This emulsion lkQ was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxa was used as a green-sensitive sensitizing dye. Carbocyanine hydroxide, 2F=water 5, 5'-diphenyl-9-ethyl 3°3'-di(3-sulfopropyl)oxacarbocyanine and anhydrous 9-ethyl-3,3
7-di(3-sulfoprovir)-5,6,5',
Add 6'-dibenzoxacarbocyanine hydroxide followed by 4-hydroxy-6-methyl-1,3,3
a.

7-thitradiindene 0.25,9,1-phenyl-
5 = mercaptotetrazole 5 mo and polyvinylpyrrolidone 02! Added j. Next, add the following dispersion [
M-2] 2200m was added in the morning to prepare a green-sensitive Hg#u silver halogenide emulsion, and dried 11. *Coated to a thickness of 20μ.

10th layer Same as 21st - 11th J meeting Yellow filter 2,
Dissolve 73 g of 5-di-t-octylhydroquino and 1.5 g of 2-ethylhexyl phthalate (1, toml of ethyl acid) and disperse in an aqueous solution of seratin containing sodium triisopropylnaphthalenesulfonate 03I. Add the nuta dispersion and add gelatin to the stiffness 7099/m', 2,
5-di-t-octylhydroquinone 0.10. ? The coating was applied at a ratio of 1/2 to give a dry bra thickness of 1.2 μm.

No. 121 A Blue-sensitive low-sensitivity silver halide emulsion layer table-5
The silver iodobromide emulsion shown in (emulsion 1 kfl equivalent υ), silver halogenide 0.25 mol, gelatin 80 fiftam) IA+9 was chemically sensitized with gold and sulfur sensitizers, and then blue-sensitive sensitized. Anhydrous 5,5'-dimethoxy-3,3'-di(3-sulfopropyl)thiacyanine hydroxide was added as a dye, and then 4-hydroxy-6-methyl-1,3,3
a, 7-trazaindene 0.25, 9.1-phenyl-5-mercaptotetrazole 21) mq and polyvinylpyrrolidone 0.2. ? In addition, add the following dispersion (
Y-1) 10100O' was added. The resulting blue-sensitive halide emulsion was coated with a dry film thickness of 3.
It was applied so that θμ.

13 layers Blue-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion containing 5 mol of iodide (average grain, ff” 1.
0 μ, 0.25 mol of silver halide per gram of emulsion, 40 gelatin! J) homogeneous emulsion v4111! It was prepared by the method of 1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and then anhydrous 5°5'-
dimethoxy-3,3'-di(3-sulfopropyl)thiacyanine hydrochloride was added, then 4-hydroxy-6-methyl-1,3,3a, 7-child trazaindene 0
．． 10 Jlp of 25,9,1-phenyl-5-mercaptotetrazole and 0.2 g of polyvinylpyrrolidone were added, followed by 150 ml of the following dispersion (Y-1). The blue-sensitive highly sensitive silver halide emulsion thus obtained was coated to a dry film thickness of 2.0 μm.

14th M... Intermediate layer di-2-ethyl phthalate) 2,9.2-[3-
Cyano-3-(n-dodecylaminocarbonyl)allylidene]1-ethylpyrrolidine 2I and ethyl acetate 2m
1, and dispersed in an aqueous gelatin solution containing 0.6 jp of sodium triisopropylnaphthalene sulfonate to make a dispersion, and further, the average particle size was 0.08μ.
Add fine grain silver iodobromide to gelatin 1.0 f
It was coated at a ratio of silver: j/m' and silver: 0.611/m' to a dry film thickness of 1.0 μm.

15th layer: A gelatin aqueous solution containing 4 g of gelatin and 0.2 g of 1.2-bisvinylsulfonylethane per 100 mA of protective plating layer. ? /m' to give a dry film thickness of 1.2μ.

Dispersions using the above-mentioned emulsion layer buttons were prepared as follows.

Part 1゛η (Ci -1) The following cyan coupler (0-1) 60,9. Below DI)L
Chemical compound (D-1) 2. OjJ and dodecyl gallate I), 5fl''f dibutyl phthalate, a mixture of diethyl laurylamide and ethyl acetate (weight ratio 4:1:
6) 120m7! The mixture was heated and dissolved, added to an aqueous gelatin solution containing 2 g of sodium triimpropylnaphthalene sulfonate at 7.5 pm, and emulsified and dispersed using a colloid mill to adjust the concentration to 10,100 O.

Dispersion (C-23) 5 g of the following cyan coupler (C-2), 111 of the following cyan coupler (C-3), 2.0 of the following DIR compound (D-1)
, 9, and dodecyl gallate 0.59 were dissolved in a mixture of dibutyl tucrate, diethyl laurylamide and ethyl acetate (weight ratio 4:1:fi) by heating to 60rnt, and sodium triinpropylnaphthalene sulfonate 2
．． The mixture was added to 400 mε of a 7.5% Seratin aqueous solution in Fl, and emulsified and dispersed in a colloid mill to adjust 1000rntK.

Dispersion (M-11) Magenta coupler (M-1) below 54, '7. Power 5-do magenta coupler (CM-1) 14 g, DIR compound (D-2) 0.5, q, 1) IR compound (
D-3) 0.57 to tricresyl phosphate 1,400
Mixture of Tanehira 1389.4 Non-Haethyl 280 me VC
Is understood, t11 sodium inglovirnaphthalene sulfonate 8 i 'j? Add to 7.5% gelatin 5ooix, emulsify and disperse with a colloid mill,
000 Fubutsu police.

Dispersion [81-2] The following magenta coupler (M-120g, colored magenta coupler (CM-1) 4, L and 2゜5-di-
t-Octylhydroquinone 1.9 ]) I R Compound (D-2) 0.31ft tricresyl phosphate 705.0% ethyl 280ml dissolved in a mixture containing 8gt of purified sodium triisopropylnaphthalene sulfone 7, Add to 500vrl of 5% gelatin, emulsify and disperse in a colloid mill, and adjust to 10100O! ! did.

Min WlL product (Y-t) 50g% of the following yellow coupler (Y-1) and DIR
Dissolve 0.5 g of compound (+)-2) in a mixture of 25 g of tricresyl phosphate and 150 d of 0-modified ethyl %t,
) IJ Inopropyl Naphthalene Sulfone Sodium 8
11 pieces of 7.5% gelatin containing 500ml of persimmon were added to flower buds, emulsified in a colloid mill, and adjusted to 1000ml.

Dispersion CY<3 The following yellow coupler (Y-1) 50.9 and L) I
0.5.9 of R compound (D-2) was added to 25 g of tricresyl phosphate and 150 g of ethyl 11j. Add the Q mixture to 500 mJ of 7.5 tisgelatin containing 8 g of Tomoe Zoshi white goods KIML and sodium triisoglobyl naphthalene sulfonate, emulsify and disperse with a colloid mill, and add to 1000 ml.
K adjusted.

(Compound used) Cyan coupler (0-1) 2-(4-n-butylsulfonylphenylureido)-
5-(α-(2,4-di-t-amylphenoxy)-butanamide]-phenolic cyan coupler (0-2
) 1-hydroxy-N-(δ-(2,4-d-tert-amylphenoxy)butyl]-2-naphthoamidocyan coupler (0-3) 1-hydroxy-4-[β-methoxyethylaminocarbonylmethoxy) -N-[δ-(2.4-di-t-amylphenoxy)butyl]-2-naphthamide magenta coupler (M-1) 1-(2,4.6-)lichloro)phenyl-3-(3 −
(2.4-di-tert-amylphenoquine) acetamide] benzamide 5-pyrazolone colored magenta coupler (CM-1) 1-(2,4.6-)lichloro)fue-ru 3-(3-(octatecyl succine) imido)-2-chloro]anilino-4-(α-naphthylazo)-5-pyrazolone yellow coupler (Y-1) α-piparoyl-α-(1-benzyl-2-phenyl-
3,5-dioxo-1,2,4-triacylidine-4-
yl)-2'-chloro-5'-[α-(dodecyloxycarbonyl)pentoxycarbonyl]acetanilide D I R. Compound (D-1) 4-(4-1(ethyl-5-tetrazolyl)thiomethyl-3-methyl-1-phenyl-5-pyrazolyloxyph-1-hydroxy-N-(4-(2.

4-tert-pentylphenoki/)butyl]-2
-naphthamide DIR, compound (D-2) β-(4-(1-(p-nitrophenyl)-4-(1-
phenyl-5-tetrazolyl)thiomethyl-3-undesol-5-pyrazolyloxy]-1-hydroxy-2-
Naphthamide) propionic acid D I l(, Compound (D-3) β-(4-(1-(p-nitrophenyl)-4-(1-
Ethyl-5-tetrazolyl)thiomethyl-3-wandecyl-5-pyrazolyloxy)-1-hydroxy-2-naphthamido)propionic acid.
The silver iodobromide emulsions in #1 #4 and the 12th layer were changed from uniform emulsions to core/shell emulsions, and the silver iodobromide emulsions in the 7th and 12th layers were changed from uniform emulsions to core/shell emulsions.
Sample No. 17 was prepared by adding the non-Sakai type rhinoceros derivative composition according to the present invention to the bag shown in No. 5. In addition, No. 718 and No. 121f4 each adjusted the coating liquid blue and prepared the sample Nn.
It was applied to obtain almost the same grade as 16. The dry film thickness at this time is 2.6μ for the 7th layer and 2.5μ for the 12th layer.
Met.

After performing the square expansion process, we obtained the results shown in -J''-16.

These samples were tested in the same manner as in Example 1, including Rikou and Kazan Table 6. From Table 6, it is clear that the samples of the present invention are superior in sharpness to the comparative samples.

(3) Effects of the Invention The light-sensitive material of the present invention has improved sharpness without deteriorating graininess or storage stability. Therefore, the light-sensitive material of the present invention has excellent sharpness, graininess, and storage stability, and also has excellent heat resistance. Due to the improved trench sharpness, there is no decrease in sensitivity as would be the case with a reduction in the amount of silver halide.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having 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, at least one silver halide emulsion layer has a core/silver halide emulsion layer. 1. A silver halide photographic material comprising shell-type silver halide grains and further comprising an acyclic urea derivative compound in the silver halide photographic material.