JPH09304854A - Photosensitive silver halide photographic emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rapidly processable silver halide emulsion having high sensitivity and excellent in graininess by specifying the percentage of flat platy silver halide particles, average silver chloride content and the depth of a latent image. SOLUTION: This silver halide photographic emulsion contains flat platy silver halide particles each having an aspect ratio of >=2, preferably 5 to <20 by >=50%, preferably >=70%, especially preferably >=80% of the total number of all silver halide particles, has at least >=50mol%, preferably >=80mol% average silver chloride content and forms a latent image of 20 to <100nm, preferably 50 to <100nm depth. It contains silver chlorobromide, silver chloroiodobromide or silver chloroiodide as the silver halide and may have parts different from each other in halogen compsn. in each particle. The average silver iodide content is preferably <=1.0mol%. A salt of a metallic ion is preferably allowed to exist at the time of forming particles, in a desalting process or at the time of chemical sensitization.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide emulsion having high sensitivity, excellent graininess and capable of rapid processing.

[0002]

2. Description of the Related Art It is clear that the demand for rapid processing has been increasing in recent years. However, in the case of printing light-sensitive materials, the processing has been speeded up by introducing an emulsion having a high silver chloride content, whereas in color photographic light-sensitive materials for photographing, for example, color negatives, it takes about 3 minutes to develop the color, so The conversion was insufficient. This is because an emulsion having a high silver chloride content is advantageous for rapid development, but the gradation tends to be hard and the graininess is poor, and it is difficult to prepare tabular grains with a silver chloride emulsion. In recent years, (11
1) A method for preparing an emulsion consisting of tabular silver chloride grains whose main plane is the plane has been developed. For example, JP-B-64-8326 and 64-8324, JP-A-1-250943, and JP-B-3-14328 , Tokuhei 4-81782, 5-4
No. 0298, No. 5-39459, No. 5-12696
No. 63-21893, 63-21893.
No. 8, No. 63-218149, No. 62-218959.
No. is described in detail. Further, a method for preparing tabular grains of silver chloride having a (100) plane as a main plane has been developed, and for example, JP-A-5-204073 and JP-A-51-88017.
No. 63-24238, JP-A No. 7-146522, and the like. However, these emulsions still could not solve the problem of high contrast and poor graininess.

Further, regarding silver chloride tabular grains, a method for producing tabular grains of silver chlorobromide whose main plane is (100) plane, and
The method for processing it with a processing solution for a color light-sensitive material is described in JP-A-6-301129, JP-A-5-204073 and JP-A-6-301407.
A large number of documents such as No. 324446 disclose a manufacturing method and an example of treating it with a processing solution for a color photographic material, but these Examples are very satisfactory in gradation and inferior in graininess, and are very satisfactory. It was not at the level where it went slowly, but at the level where improvement in the sensitivity granularity ratio was desired. Regarding the depth of the latent image, for example, there is a description in JP-A-1-140152 that tabular grains preferably have a depth of the latent image of not less than 2 nm and less than 50 nm, but tabular grains made of silver chloride. Is not mentioned.

[0004]

The problem to be solved by the present invention is to provide a silver halide emulsion having high sensitivity, excellent graininess and capable of rapid processing.

[0005]

The above objects have been achieved by the following means. (1) The number of tabular silver halide grains having an aspect ratio of 2 or more is 50% or more, the average silver chloride content is at least 50 mol%, and the latent image depth is 2 nm or more and less than 100 nm. A light-sensitive silver halide photographic emulsion characterized by being present. (2) The photosensitive silver halide photographic emulsion as described in (1) above, wherein the latent image has a depth of 50 nm or more and less than 100 nm.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The tabular silver halide emulsion used in the present invention will be described in detail below. In the tabular silver halide emulsion used in the present invention, the average aspect ratio of the emulsion means the average value of the ratio of the diameter to the thickness of the silver halide grains. That is, it is the average value of the values obtained by dividing the diameter of each silver halide grain by the thickness. Here, the average value of the aspect ratio is the average of all tabular grains of the silver halide grains. The total number average here means that the whole state of the silver halide emulsion is reflected without any deviation. Specifically, it is possible to randomly extract 500 or more tabular grains and investigate. Is practically sufficient. Here, the diameter means the diameter of a circle having an area equal to the projected area of a grain when the silver halide emulsion is observed with a microscope or an electron microscope. Here, the grain thickness is represented by the distance between two parallel planes constituting a tabular silver halide grain. Therefore, an average aspect ratio of 2 or more means that the diameter of this circle is twice or more the thickness of the particles.

The aspect ratio of the tabular silver halide grains used in the silver halide emulsion of the present invention is preferably 5 or more and less than 20. The tabular silver halide grains account for 50% of all silver halide grains.
However, it is preferably 70% or more, more preferably 85% or more. The tabular silver halide emulsion of the present invention has a latent image depth of 2 nm or more and less than 100 nm, preferably 50 nm or more and less than 100 nm. The latent image depth is defined as follows. First, the latent image distribution function is defined as follows. The samples coated under the conditions shown in Table 1 in the examples are treated as follows. The development processing conditions are N-methyl-P-aminophenol sulfate 2.5 g L-sodium ascorbate 10 g Sodium metaborate 35 g Potassium chloride 1 g Water is added to 1 liter (adjusted to pH 9.6) of sodium thiosulfate to a processing solution. It is added at 0 to 10 g / liter and treated at 20 ° C. for 7 minutes. By varying the amount of sodium thiosulfate here the depth of the latent image in the silver halide grains developed during processing can be varied.

When the amount of sodium thiosulfate is changed, the value of X defined below is obtained. X = (S / 2) × {1- (Ag ₁ / Ag ₀ ) ^1/3 } S: average grain size (nm) of silver halide emulsion Ag ₁ : unexposed emulsion-coated sample is subjected to the above treatment Remaining amount of silver after processing Ag ₀ : amount of coated silver before processing The same sample was exposed for 1/100 second and developed under the same conditions to give a density of (fog + 0.1). Ask. Considering Y as a function of X, this relationship is called a latent image distribution function. The latent image depth is defined by the value of X when the above-mentioned function Y of X takes a maximum value with X> 0. There are the following methods for forming a photosensitive nucleus inside a tabular silver halide grain. The first method is a method in which tabular silver halide grains are Ostwald-ripened in the presence of fine silver halide grains.

Specifically, the amount of the silver halide fine grain emulsion (FG) to be used is 10 ⁻⁶ silver halide in FG with respect to 1 mol of silver halide in the tabular silver halide grain emulsion (TG). -1 mol, preferably ^10-5
It is in the range of 10 ^-1 mol, particularly preferably 10 ^-4 to 10 ^-1 mol. The halogen composition of FG is not particularly limited, but the average silver chloride content is preferably higher than TG, and the average silver iodide content is preferably lower than TG. The average particle diameter of FG may be 0.12 μm or less, preferably 0.1 μm or less, and particularly preferably 0.09 μm or less. As for the addition of FG, a fine grain emulsion prepared in advance may be added at one time, dividedly, or continuously over a period of time. It is also possible to continuously introduce fine particles prepared separately in a small-sized and well-stirred reaction container into the TG reaction container. The position where FG is added may be the chemical sensitization step of TG or the coating solution preparation step thereafter.
It is preferably in the latter stage of chemical sensitization, particularly preferably from the time when the chemical sensitization process is substantially completed to the time before preparation of the coating solution. Further, FG is, after being added to the TG emulsion, subjected to Ostwald ripening until the time of preparation of the coating solution, so that T is substantially completely removed.
It is preferably deposited on G. Specifically, it is sufficient that FG particles are dissolved and disappeared (as a result of Ostwald ripening) in an emulsion system in which TG and FG are mixed at the time of preparing a coating solution, and as a result, FG is not substantially found. FG may or may not be chemically sensitized, but is preferably not chemically sensitized.

The second method is to add shells by adding silver and halogen after the chemical sensitization. The shelling in this method can be carried out continuously after the completion of the chemical sensitization step, or can be carried out after once undergoing a settling water washing step. The addition rates of silver and halogen at the time of attaching the shell can be arbitrarily selected. The shell thickness distribution can be changed by selecting the addition rate. When the addition rate is remarkably lowered, the shell thickness distribution becomes large and the emulsion becomes soft in gradation. Regarding the halogen composition of the shell, it is preferable that the average silver chloride content is substantially equal to or higher than the value of the surface portion of the tabular grain TG before attachment to the shell. Is substantially equal to or less than. The term “substantially equal” means that the difference in value is within 8 mol%.

The halogen composition of the emulsion of the present invention has an average silver chloride content of at least 50 mol%, preferably 80 mol% or more. The method for producing the tabular silver halide grains of the present invention will be described. Among the emulsions of the present invention (11
1) Regarding nucleation of an emulsion having a plane as a main plane, JP-B-64-8326, 64-8325 and 64-83.
No. 24, Japanese Patent Laid-Open No. 1-250943, Japanese Patent Publication No. 3-143.
No. 28, Japanese Patent Publication No. 4-81782, Japanese Patent Publication No. 5-4029
No. 8, No. 5-39459, No. 5-12696, and JP-A Nos. 63-213836, 63-218938, 63-281149, and 62-218959. Further, as a prior art of tabular grains having a (100) plane as a main plane, there is disclosed in JP-A-5-20.
No. 4073, JP-A-51-88017 and JP-A-63-88017.
No. 24238, JP-A-7-146522 and the like. In the method for preparing a silver halide grain emulsion whose main plane is the (111) plane, it is preferably formed in the presence of at least one compound of the following general formula (I). General formula (I)

[0012]

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The general formula (I) will be described in detail. In the general formula (I), R ₁ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, isopropyl group, t-butyl group, n-octyl group,
n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group), carbon number 2
-20 alkenyl groups (e.g., allyl group, 2-butenyl group, 3-pentenyl group) and C7-20 aralkyl groups (e.g., benzyl group, phenethyl group) are preferable. Each group represented by R ₁ may be substituted. Examples of the substituent include the substitutable groups represented by R _{2 to} R ₆ below. R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom or a group capable of substituting it. Examples of the substitutable group include the following. A halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (For example,
Allyl group, 2-butenyl group, 3-pentenyl group, etc., alkynyl group (eg, propargyl group, 3-pentynyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), aryl group (eg, phenyl group) , Naphthyl group, 4-methylphenyl group, etc.), heterocyclic group (for example,
Pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group etc.), alkoxy group (eg methoxy group, ethoxy group, butoxy group etc.), aryloxy group (eg phenoxy group, 2-naphthyloxy group etc.),
Amino group (eg, unsubstituted amino group, dimethylamino group, ethylamino group, anilino group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), ureido group (eg, unsubstituted ureido group, N- Methylureido group, N-phenylureido group, etc.), urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), sulfonylamino group (eg, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group ( For example, unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl group, N-
Phenylsulfamoyl group etc.), carbamoyl group (eg unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group etc.), sulfonyl group (eg mesyl group, tosyl group etc.), sulfinyl group ( For example, methylsulfinyl group, phenylsulfinyl group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), acyl group (eg, acetyl group, Benzoyl group, formyl group, pivaloyl group etc.), acyloxy group (eg acetoxy group, benzoyloxy group etc.), phosphoric acid amide group (eg N, N-diethyl phosphoric acid amide group etc.), alkylthio group (eg methylthio) Group, ethylthio group, etc.), aryl Thio group (for example, phenylthio group), cyano group, sulfo group, carboxy group, hydroxy group, phosphono group, nitro group, sulfino group, ammonio group (for example, trimethylammonio group), phosphonio group, hydrazino group, etc. is there. These groups may be further substituted. When there are two or more substituents, they may be the same or different. R ₂ and R ₃ , R ₃ and R ₄ ,
R ₄ and R ₅ , R ₅ and R ₆ may be condensed to form a quinoline ring, an isoquinoline ring or an acridine ring.

[0014] X ^- represents a counter anion. Examples of the counter anion include a halogen ion (a chloride ion and a bromine ion), a nitrate ion, a sulfate ion, a p-toluenesulfonic acid ion, and a trifluoromethanesulfonic acid ion. In the general formula (I), preferably R ₁ represents an aralkyl group, and R ₂ , R ₃ , R ₄ , R ₅ and R ₆
At least one of the above represents an aryl group. More preferably, in the general formula (I), R ₁ represents an aralkyl group, and R _1
4 represents an aryl group, and X ⁻ represents a halogen ion. Specific examples of the compound represented by formula (I) are shown below, but the compound of the present invention is not limited thereto.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

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[0022]

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In the present invention, any of the nucleation methods described in these prior arts can be used.
The method of crystal growth of the present invention by physical ripening in the presence of fine silver halide grains (fine grains are dissolved and substrate grains grow) is described below. In the fine grain emulsion addition method, it is 0.
An AgX fine grain emulsion having a diameter of 15 μm or less, preferably 0.1 μm or less, more preferably 0.06 to 0.006 μm is added, and the tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added either continuously or continuously. Fine grain emulsion is AgNO in mixer provided in the vicinity of the reaction vessel ₃ solution and X ^-
The salt solution may be supplied and continuously prepared, and then immediately added continuously to the reaction vessel, or may be previously prepared in a batch manner in another vessel and then continuously or continuously added. The fine grain emulsion can be added in a liquid form or as a dry powder. The dry powder may be mixed with water immediately before addition, liquefied and added. The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes. If the disappearance time becomes long, ripening occurs between the fine particles and the particle size becomes large, which is not preferable. Therefore, it is preferable not to add the entire amount at once. It is preferable that the fine particles are substantially free of twinned grains. Here, the multiple twin particles refer to particles having two or more twin planes per particle. "Substantially not contained" means that the ratio of the number of multiple twin grains is 5% or less, preferably 1% or less, more preferably 0.1% or less. Further, it is preferable that substantially no single twin particles are contained. Further, it is preferable that the composition does not substantially include a screw dislocation. Here, "substantially not included" complies with the above-mentioned rules.

The halogen composition of the fine particles is AgCl, Ag
Br, AgBrl (I ^- content is preferably 10 mol% or less, more preferably 5 mol% or less) and a mixed crystal of two or more thereof. For other details, see JP-A-6-5936.
The description in No. 0 can be referred to. The total amount of fine grains added is required to be 20% or more of the total amount of silver halide, preferably 40% or more, and more preferably 50% or more and 98% or less. The Cl content of the fine particles is preferably 10% or more, more preferably 50% or more and 100% or less. As the dispersion medium at the time of nucleation, ripening and growth, a conventionally known dispersion medium for AgX emulsion can be used, but the methionine content is particularly preferably 0 to 50 μmol / g, more preferably 0 to 30 μmol. / G of gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are preferably formed. In addition,
No. 16365, Journal of the Photographic Society of Japan, 29 (1), 17,
22 (1966), Vol. 30 (1), 10, 19 (1
967), pp. 30 (2), 17 (1967), and 33 (3), 24 (1967) can be preferably used as a dispersion medium. The pH at the time of growth by adding fine particles needs to be 2.0 or more, but is preferably 3 or more and 10 or less. More preferably, the pH is 4 or more and 9 or less.

Although pCl needs to be 1.0 or more,
1.6 or more is preferable. More preferably, it is 2.0 or more and 3.0 or less. Under these growth conditions, a grain whose main plane is the (111) plane and a grain whose (100) plane is the main plane can be formed. It is particularly preferable for tabular grains having the (100) plane as the main plane. Here, pCl is defined as pCl = −log [Cl ⁻ ] with respect to the activity [Cl ⁻ ] of Cl ions in the solution. Written by THJames THE THEORY OF THE RHOTO
It is described in detail in Chapter 1 of the GRAPHIC PROCESS, 4th Edition.

When the pH is 2.0 or less, for example, in the case of tabular grains having the (100) plane as the main plane, lateral growth is suppressed and the aspect ratio is lowered, so that the emulsion covering power is reduced. Tends to be low, and the sensitivity becomes low. When the pH is 2.0 or higher, an emulsion having a high lateral growth rate and a high aspect ratio and a high covering power can be obtained, but the fog is high and the sensitivity is easily lowered. p
When Cl is 1.0 or less, the growth in the vertical direction is promoted, the aspect ratio is reduced, the covering power of the emulsion is low, and the sensitivity is lowered. When the pCl is 1.6 or more, the aspect ratio is increased to increase the covering power, but the fog is high and the sensitivity is easily reduced. At this time, when the substrate grains are grown with silver halide fine grains, the fog is low even at a pH of 6 or more and / or a pCl of 1.6 or more, resulting in a high sensitivity, a high aspect ratio, and a high covering power.

The monodispersity of the emulsion of the present invention is preferably 30% or less, preferably 5% or more 25, considering the monodispersity degree based on the coefficient of variation defined by the method described in JP-A-59-745481. % Or less is particularly preferable. The silver halide solvent that can be used in the present invention includes U.S. Pat. Nos. 3,271,157 and 3,531,289,
No. 3,574,628, JP-A-54-1019,
(A) Organic thioethers described in JP-A-54-158917, JP-A-53-82408 and JP-A-55-777.
(B) thiourea derivatives described in JP-A No. 37, 55-2982, etc., described in JP-A No. 53-144319.
(c) A silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, JP-A-54-
(D) imidazoles described in 100717, (e)
Examples thereof include sulfite and (f) thiocyanate. Particularly preferred solvents include thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more per 1 mol of silver halide and 1 ×.
It is 10 ^-2 mol or less.

The emulsion of the present invention is any one of silver chlorobromide, silver chloroiodobromide and silver chloroiodide. It is also possible to have a portion having a different halogen composition in the grain. The average silver iodide content is 1.
It is preferably at most 0 mol%. The particles of the present invention
It is preferable that a salt of a metal ion is present during grain formation, a desalting step, and chemical sensitization. When the particles are doped with metal ions, the particles are dissolved in a solvent at the time of particle formation and added, or separately prepared fine particles doped with metal ions are added and deposited on the target particles by Ostwald ripening. The position where the metal ions are doped can be arbitrarily selected such as the whole particle, only the core part of the particle, or only the shell part, only the epitaxial part of the particle, or only the base particle. Mg, Ca, Sr, Ba, Al, Sc,
Y, La, Cr, Mn, Fe, Co, Ni, Cu, z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, B
i, etc. can be used. These metals can be added in the form of salts that can be dissolved at the time of grain formation, such as ammonium salts, acetates, nitrates, phosphates, hydrates, or hexacoordinated complex salts and tetracoordinated complex salts. For example, CdBr ₂ , CdC
l ₂ , Cd (No ₃ ) ₂ , Pb (No ₃ ) ₂ , Pb (C
_{H 3 COO) 2, K 3} (Fe (CN) 6), (NH 4)
₄ (Fe (CN) ₆ ), K ₃ IrCl ₆ , (NH ₄ ) ₃
RhCl ₆ , K ₄ Ru (CN) _{6 and the} like can be mentioned. As a ligand of a coordination compound, halogen, H ₂ O, N
It can be selected from H ₃ , cyano group, cyanate group, thiocyanate group, nitrosyl group, thionitrosyl group, oxo group and carbonyl group. These metal compounds are
They can be used alone or in combination of two or more.

The photographic emulsion used in the present invention is spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; Nucleus fused with an aromatic hydrocarbon ring, that is, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, An imidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2 as a nucleus having a ketomethylene structure.
A 5- or 6-membered heterocyclic nucleus such as a -thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
No. 617,293, No. 3,628,964, No. 3,666,480, No. 3,672,898, No. 3,679,428, No. 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
No. 7,803, Japanese Patent Publication No. 43-4936, No. 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925.

It is preferable to add potassium iodide before and after the addition of the sensitizing dye. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but is described in U.S. Pat. Nos. 3,628,969 and 4,225,666.
As described in Japanese Patent Application Laid-Open No.
It can be carried out prior to chemical sensitization as described in JP-A-113928, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization.
Furthermore, the addition of these said compounds separately as taught in US Pat. No. 4,225,666,
That is, it is also possible to add a part of these compounds prior to chemical sensitization and add the remainder after chemical sensitization,
At any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756. The addition amount is 4 × 1 per mol of silver halide.
It can be used in an amount of 0 ^-6 to 8 x 10 ^-3 mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 µm, about 5 x 10 ^-5 to 2 x 10 ^-3 mol is more effective. Is.

The silver halide emulsion of the present invention is subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization in the chemical sensitization step of the silver halide emulsion. You can rub. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th. Edition, published by Macmillan, 1977, (TH James, The Th
eory of the PhotographicP
process, 4th ed, Macmillan, 1
977) 67-76 and using active gelatin, and Research Disclosure 120, April 1974, 12008;
Research Disclosure, Volume 34, June 1975.
Mon, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031,
No. 3,857,711, No. 3,901,714
Nos. 4,266,018, and 3,90.
4,415, and sulfur, selenium, tellurium, gold at pAg 5-10, pH 5-8 and temperature 30-80 ° C as described in GB 1,315,755.
It can be platinum, palladium, iridium or a combination of several of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. Palladium compound is palladium 2
It means a valent salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, chlorine;
Represents a bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate. As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat.
The sulfur-containing compounds described in Nos. 57,711, 4,266,018 and 4,054,457 can be used. Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, known unstable selenium compounds are used, and specifically, colloidal metal selenium and selenoureas (for example, N,
Selenium compounds such as N-dimethylselenourea, N, N-diethylselenourea), selenoketones, and selenoamides can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. No. 2,131,03
No. 8, No. 3,411,914, No. 3,554,7
57, JP-A-58-126526 and the above-mentioned Duffin, "Photographic Emulsion Chemistry", pages 138-143.

The silver halide emulsion of the present invention is preferably subjected to reduction sensitization during grain formation. Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing in a low pAg atmosphere of pAg1 to 7 called silver ripening, or a method of ripening, and a pH 8 called high pH ripening.
Any method of growing or aging in a high pH atmosphere of -11 can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. As reduction sensitizers, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Further, the alkynylamine compounds described in US Pat. No. 5,389,510 are also preferably used. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide. Reduction sensitizers include water or alcohols, glycols, ketones,
It is added after being dissolved in a solvent such as ester or amide.
The reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

Acid for silver during the process of making the emulsions of the present invention
It is preferable to use an agent. The oxidizing agent for silver is
Has the effect of converting to silver ions by acting on metallic silver
Refers to a compound. Especially the formation process of silver halide grains and
Extremely small silver particles by-produced during chemical sensitization
Is a compound that can be converted into a silver ion. here
The silver ions generated in the above are silver halide, silver sulfide, selenium
It may form a silver salt that is hardly soluble in water such as silver chloride,
And the like, a silver salt easily soluble in water may be formed. Oxidation to silver
The agent may be inorganic or organic. inorganic
Ozone, hydrogen peroxide and its addition
Object (eg, NaBO)_Two・ H_TwoO_Two・ 3H _TwoO, 2Na
CO_Three・ 3H_TwoO_Two, Na_FourP_TwoO₇・ 2H_TwoO_TwoTwo
Na_TwoSO _Four・ H_TwoO_Two・ 2H_TwoO), peroxy acid salt
(For example, K_TwoS_TwoO₈, K_TwoC_TwoO₆, K_TwoP
_TwoO₈), Peroxy complex compounds (eg, K_Two[Ti
(O_Two) C _TwoO_Four] 3H_TwoO, 4K_TwoSO_Four・ Ti
(O_Two) OH ・ SO_Four・ 2H_TwoO, Na_Three[VO
(O_Two) (C_TwoH_Four)_Two] ・ 6H_TwoO), permanganate
Salts (eg, KMnO_Four), Chromates (eg, K_Two
Cr_TwoO₇) And other halogens such as iodine and bromine
Element, perhalogenate (eg potassium periodate)
High valent metal salts (eg, hexacyanoferric acid
Lithium) and thiosulfonate. Also,
Examples of organic oxidants include quinones such as p-quinone and peroxides.
Organic peroxides such as acetic acid and perbenzoic acid, active halogen
Compounds that release (eg, N-bromosuccinimide,
Lolamine T, chloramine B) are mentioned as examples.

Preferred oxidizing agents used in the emulsion of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonate and organic oxidizing agents of quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. US Patent No. 5,36
The disulfide compounds described in 4,754 and EP 627657A2 are also preferably used. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously.

The emulsion of the present invention includes a process for producing a light-sensitive material,
Various compounds can be contained for the purpose of preventing fogging during storage or photographic processing or stabilizing photographic performance. That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example triazain Denes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindene Known as antifoggants or stabilizers, such as classes, it can be added to many compounds. For example, US Pat. No. 3,9
54,474, 3,982,947, Japanese Patent Publication Sho 52
What was described in No. 28860 can be used. One of the preferred compounds is U.S. Pat. No. 4,952,4
There are compounds described in No. 90. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, control the crystal habit of the grains, reduce the grain size, reduce the solubility of the grains, control the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The above-mentioned various additives are used in the light-sensitive material using the emulsion of the present invention, but various additives other than the above can be used according to the purpose. These additives are described in more detail in Research Disclosure Ite.
m 17643 (December 1978), Item 1
8716 (November 1979) and Item 30
8119 (December 1989), and the corresponding places are summarized in the table below. Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23 648 page right column 996 page 2 Sensitivity enhancer same as above 3 Spectral sensitizer, page 23 to page 648 right column to 996 right to 998 right supersensitizer 649 Page right column 4 whitening agent page 24 998 right 5 antifoggant and stabilizer page 24-25 page 649 right column 998 right-1000 right 6 light absorber, filter dye page 25-26 page 649 right column-1003 left- 1003 right UV absorber 650 left column 7 anti-stain agent page 25 right column 650 left to right column 1002 right 8 dye image stabilizer page 25 1002 right 9 hardening agent page 26 651 left column 1004 right to 1005 left 10 binder Page 26 same as above 1003 right to 1004 right 11 plasticizer, lubricant page 27 page 650 right column 1006 left to 1006 right 12 coating aid, surface Activator, page 26-27, ibid., 1005 left to 1006 left, 13 static inhibitor, page 27, ibid., 1006 right to 1007 left, 14 matting agent, 1008 left to 1009 left

A light-sensitive material using the emulsion of the present invention is provided that at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer is provided on a support. Well, there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, the order of arrangement may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer has a structure as described in JP-A-61-43.
748, 59-113438, 59-1134
No. 40, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, etc., and may contain a color mixing inhibitor as commonly used.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. Usually, it is preferable to arrange the layers so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the silver halide emulsion layers. JP-A-57-112751, JP-A-62-20035
No. 0, 62-206541, 62-206543
As described in Japanese Patent Application Laid-Open No. H10-284, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support. As a specific example, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL,
Alternatively, they can be installed in the order of BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-25738.
No. 63936, the blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.
It can also be arranged in the order of.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.
The arrangement may be changed as described above even in the case of four or more layers. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

For the light-sensitive material using the emulsion of the present invention, it is preferable to use non-light-sensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that the coupler is not pre-coupled. . The fine grain silver halide has a silver chloride content of 0 to 100 mol%, and may optionally contain silver bromide and / or silver iodide. Preferably, the silver bromide content is 50 mol% to 100 mol% and the silver iodide content is 1 mol% or less. The fine grain silver halide preferably has an average grain size (average value of circle-equivalent diameter of projected area) of 0.01 to 0.5 μm,
0.02-0.2 μm is more preferable. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized nor spectral sensitization.
However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

A light-sensitive material using the emulsion of the present invention has a fog agent, a development accelerator, a silver halide solvent or a solvent thereof described in JP-A No. 1-106052, irrespective of the amount of developed silver produced by the development processing. It is preferable to include a compound that releases the precursor of. The light-sensitive material using the emulsion of the present invention is described in International Publication W088 / 04794, Japanese Patent Publication No.
Dyes dispersed by the method described in 502912 or EP 317,308A, US Pat. No. 4,420,55
No. 5, and the dyes described in JP-A-1-259358 are preferably contained.

It is preferable to use a colored coupler in a light-sensitive material using the emulsion of the present invention in order to correct unnecessary absorption of a color-forming dye. Colored Coupler is research
Disclosure No. 17643 term VII-G,
No. 307105, Section VII-G, U.S. Pat.
163,670, Japanese Examined Patent Publication No. 57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258.
And those described in British Patent No. 1,146,368 are preferred. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, and US Pat.
It is preferable to use a coupler having a dye precursor group as a leaving group capable of reacting with a developing agent to form a dye as described in 7,120. A light-sensitive material using the emulsion of the present invention is disclosed in JP-A-60-185950 and JP-A-62-242.
No. 52, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, compound and the like can also be used.

Photosensitive materials using the emulsion of the present invention include phenethyl alcohol, JP-A-63-257747 and JP-A-6-257747.
2-272248 and JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-
Butyl p-hydroxybenzoate, phenol, 4
It is preferable to add various preservatives or fungicides such as -chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole. The emulsion of the present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. Suitable supports which can be used in a light-sensitive material using the emulsion of the present invention are described in, for example, RD. No. 2 of 17643
Page 8, ibid. No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

In the light-sensitive material using the emulsion of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm.
m, preferably 23 μm or less, more preferably 18 μm or less, particularly preferably 16 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129, and T1 _{/ 2} can be measured with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swelled film thickness that is reached when the swelling is performed is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. Also,
The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material using the emulsion of the present invention has a total dry film thickness of 2 μm to 20 on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of μm. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of the back layer is preferably from 150 to 500%. The color photographic light-sensitive material using the emulsion in the present invention can be prepared by the method described in RD. No. 176
43, pp. 28-29, ibid. No. 18716, 651 left column to right column; 307-8, 880-881
Development can also be carried out by the method described on the page.

Techniques such as layer arrangement which can be used for the emulsion of the present invention and photographic light-sensitive materials using the emulsion, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives and the like. , And the development processing are described in European Patent No. 0565096A1 (published on October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding places. 1. Layer structure: p. 61, lines 23-35, p. 61, lines 41-62
Page 14 line 2. 2. Intermediate layer: page 61, lines 36-40, 3. Multilayer effect imparting layer: page 62, lines 15-18, 4. Silver halide composition: page 62, lines 21-25, 5. Silver halide crystal habit: page 62, line 26-30, 6. Silver halide grain size: page 62, lines 31-34, 7. Emulsion manufacturing method: page 62, line 35-40, Silver halide grain size distribution: 62-page 41-42
Line, 9. 9. Tabular grains: page 62, lines 43-46, 10. Internal structure of particle: page 62, line 47 to line 53, Emulsion latent image forming type: page 62 line 54-page 63 5
Line, 12. 12. Physical ripening and chemical ripening of emulsion: page 63, line 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, Fogging emulsion: p. 63, lines 14-31, 15. Non-photosensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49-50, Photographic additives: Research Disclosure (R
D) Item17643 (December 1978), It
em18716 (November 1979) and Item3
07105 (November, 1989), and each item and its related description are shown below.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. Anti-staining agent Page 25 Right column 650 Left column-Right column Page 872 8. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener page 26 page 651 left column 874 to 875 page 10.Binder page 26 page 651 left column 873 to 874 page 11.plasticizer and lubricant page 27 650 page right column page 876 12. Coating aid, 26 to 27 Page 650 page right column 875 to 876 surface active agent 13. static page 27 page 650 right column 876 to 877 inhibitor 14. matting agent page 878 to 879

18. Formaldehyde scavenger: 6
P. 4, lines 54-57, 19. Mercapto-based antifoggant: page 65, lines 1-2, 20. Release agents such as fogging agents: Page 65, lines 3-7, 21. Dye: page 65, line 7-10, 22. General color couplers: p. 65, lines 11-13, 23. Yellow, magenta and cyan couplers: p. 65 1
Lines 4-25, 24. Polymer coupler: page 65, lines 26-28, 25. Diffusible dye-forming coupler: p. 65, lines 29-31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39-44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49-53, 30. Other DIR couplers: Page 65, Line 54-Page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40-page 67, 1
Row, 35. Back layer: page 67, line 3-8, 36. General processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12-30, 38. Developer additive: Page 67, lines 31-44, 39. Inversion processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57-page 68, line 12, 41. Developing time: page 68, lines 13-15, 42. Bleaching-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic processor: Page 69, lines 32-40, 44. Rinsing, rinsing, stabilization: page 69, line 41-page 70, line 18
Line, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70, lines 34-38, 48. Use for film with lens: page 70, lines 39-41,

[0052]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 Preparation of Emulsion A-1 Gelatin-1 (deionized alkali-treated bone gelatin containing 40 μmol per 1 g of gelatin) in a reaction vessel 19.5.
g, HNO ₃ (1N) 7.8 cc, 1582 cc of an aqueous solution containing 1.3 g of NaCl was added, and while maintaining the temperature at 40 ° C., Ag-1 liquid (AgNO ₃ 20 g in 100 cc)
And X-1 solution (NaCl 7.05 in 100 cc).
(including g) was simultaneously mixed and added at 62.4 cc / min in 15.6 cc increments. After stirring for 3 minutes, solution X-2 (100c
28.2 cc of KBr (containing 1.1 g of cBr) was added at 80.6 cc / min. After stirring for 3 minutes, the Ag-1 solution and the X-1 solution were simultaneously added at 62.4 cc each at 46.8 cc. After stirring for 2 minutes, 203c gelatin aqueous solution
c (gelatin-1 13 g, NaCl 1.3 g, pH
(Including NaOH necessary for adjusting the temperature to 6.5) is added to adjust the potential to 80 mV, and then the temperature is raised to 75 ° C. to set the potential to 100.
Aged for 3 minutes according to mV. Then Ag-2 liquid (1
350cc AgNO in 00cc) and X-3 liquid (1
Includes 16.9 g of NaCl and 1.4 g of KBR in 00 cc. ) To C. D. J (controlled do)
It was added at a constant flow rate for 41 minutes until the added amount of the Ag-2 solution reached 375 cc by keeping the same at 140 mV.

Then, a precipitating agent was added, and after a normal desalting step, an aqueous gelatin solution was added and redispersed. At 38 ° C., the pH was adjusted to 6.2 and the silver potential was adjusted to 80 mV. The silver halide emulsion thus prepared has an average equivalent spherical diameter of 0.87 μm.
m, and the average silver chloride content was 97.8 mol%, and contained 76% by number of tabular grains having an aspect ratio of 2 or more. The average aspect ratio of the tabular grains was 7.6. 70% of the total projected area of the tabular grains consisted of grains having an adjacent side length ratio of 2 or less to the main plane. The main plane of the tabular grains was the (100) plane. This emulsion was chemically sensitized as follows. The temperature of the emulsion was raised to 57 ° C., AgBr fine particles having an average equivalent spherical diameter of 0.05 μm were added in an amount of 0.2 mol% per mol of silver halide,
After aging for about 10 minutes, sodium thiosulfate 7.4 x 10
^-6 mol / mol Ag, potassium chloroauric acid 3.0 × 10 ^-6 mol / mol Ag, potassium thiocyanate 0.9 × 10 ^-3 mol / mol Ag, N, N-dimethylselenourea 1 × 10
Optimal chemical sensitization was achieved by adding ^-6 mol / mol Ag. 1- (3-acetamidophenyl) -5 immediately before the completion of chemical sensitization
-Mercaptotetrazole 7 × 10 ^-4 mol / mol Ag
Was added.

Preparation of Emulsion A-2 In the step of Emulsion A-1, after adding 1- (3-acetamidophenyl) -5-mercaptotetrazole, silver chloride fine particles were added in an amount of 0.01 mol per mol of tabular grains by the following method. Was added so that the ratio would be. The silver chloride fine particles are continuously produced in a separate small reaction vessel as shown below and added directly to the reaction vessel containing the tabular grains. That is, in a well-stirred small reaction vessel having a volume of 30 cc, an aqueous solution containing 11.3 g of AgNO in 100 cc, 3.5 g of NaC and 0.5 g of gelatin in 100 cc.
Is continuously added, and the overflow is directly added to the reaction vessel containing the tabular grains.

Preparation of Emulsions A-3 to A-7 The addition amount of silver chloride fine particles was 0.
Emulsions A-3 to 7 were prepared by adding 07 mol, 0.19 mol, 0.25 mol, 0.33 mol and 0.5 mol, respectively.

Preparation of Emulsion A-8 Cubic grains of silver chloride having a spherical equivalent diameter of 0.90 μm were prepared by a known method. The temperature of the emulsion was raised to 57 ° C., 0.2 mol% of AgBr fine particles having an average equivalent spherical diameter of 0.05 μm was added per mol of silver halide, and the mixture was ripened for about 10 minutes, then sodium thiosulfate and potassium chloroaurate were added. , Potassium thiocyanate and N, N-dimethylselenourea were added in optimum amounts for chemical sensitization. Just before the end of chemical sensitization 1- (3
- acetamidophenyl) -5-mercaptotetrazole 7 × added 10 ^-4 mol / mol Ag.

Preparation of Emulsion A-9 In the step of Emulsion A-8, after adding 1- (3-acetamidophenyl) -5-mercaptotetrazole, silver chloride fine particles were added in an amount of 0.01 to 1 mol of cubic grains by the following method.
It was added in a molar ratio. The silver chloride fine particles are continuously produced in a separate small reaction vessel as shown below and added directly to the reaction vessel containing the tabular grains. That is, in a well-stirred small reaction vessel having a volume of 30 cc, 100 cc of an aqueous solution containing 11.3 g of AgNO and 100 cc of 3.5 g of NaC and 0.5 g of gelatin.
An aqueous solution containing g is continuously added, and the overflow is directly added to the reaction vessel containing the tabular grains.

Preparation of Emulsions A-10 to A-14 The addition amount of silver chloride fine particles was 1 mol of cubic grains.
0.07 mol, 0.19 mol, 0.25 mol, 0.33
Emulsions A-3 to 7 were prepared by adding 0.5 mol and 0.5 mol, respectively. Emulsions A-1 to A-14 were coated on a cellulose triacetate film support having an undercoat layer under the coating conditions shown in Table 1 below to prepare Samples 101 to 114. However, immediately before coating, each emulsion was kept at 40 ° C., 0.2 mol / mol Ag of potassium iodide was added, and the mixture was allowed to stand for 10 minutes. ^10-4 mol / mol Ag, 1.6 × ^10-5 mol /
Mol Ag was added at 5.2 × 10 ⁻⁴ mol / mol Ag.

[0059]

[Table 1]

Further, the depth of the latent image was obtained by the method described in the text. Table 2 shows the results. These samples 101 to 10
No. 7 was imagewise exposed with white light at a shutter speed of 1/100 ″ to 10 ″, and color development processing described in the following processing method was performed. Processing method Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ℃ 45ml 10 liters Bleach 1 minute 00 seconds 38 ℃ 20ml 4 liters Bleach fixing 3 minutes 15 seconds 38 ℃ 30ml 8 liters Washing with water (1) 40 Second 35 ℃ (2) to (1) F 4 liters Countercurrent piping system Washing with water (2) 1 minute 00 seconds 35 ℃ 30 ml 4 liters Stability 40 seconds 38 ℃ 20 ml 4 liters Dry 1 minute 15 seconds 55 ℃ Replenishment Quantity is 35mm per 1m length

Next, the composition of the treatment liquid will be described. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1 3.0 3.2-Diphosphonic acid Sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 2.8 4- (N-ethyl-N-β-hydro 4.5 5. 5 xylethylamino) -2-methyl aniline sulphate Add water 1.0 liter 1.0 liter pH 10.05 10.10

(Bleaching Solution) Common to mother liquor and replenisher (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleach acceleration agent _{{(CH 3) 2 N-} CH 2 CH 2 -S} 2 · 2HCl 0.005 mole ammonia water (27%) 15.0 ml water to make 1.0 l pH 6.3 (bleach-fixing solution) mother liquor Common replenisher (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27% ) Add 6.0 ml water to 1.0 liter pH 7.2

(Washing liquid) common to mother liquor and replenisher tap water is prepared by using H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Water was passed through the packed mixed-bed column to adjust the concentration of calcium and magnesium ions to 3 mg / liter or less, and then 20 mg / liter of sodium diisocyanurate dichloride and 0.15 g / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5. (Stabilizer) Mother liquor, replenisher common (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water 1.0 liter is added and Table 2 shows granularity and sensitivity. Granularity is (fog +
The RMS granularity measured by the G filter of the sample exposed with the exposure amount giving the color image density of 0.3) is represented by a relative value with the value of the sample 101 being 100. Sensitivity is (fog +0.
Sample 1 is defined as the reciprocal of the exposure dose that gives the color image density of 2).
The value of 01 is expressed as a relative value with 100 as the value.

[0064]

[Table 2]

From Table 2, "latent image depth" is 2 nm or more 1
It can be seen that when the thickness is less than 00 nm, the sensitivity is high and the graininess is excellent. Further, it can be seen that the tabular grains are superior in both sensitivity and granularity to the cubic grains. Further, when the "latent image depth" is 50 nm or more and less than 100 nm, the sensitivity is extremely high and the graininess is excellent, and the difference from the cube is significantly large.

Example 2 Preparation of Emulsion B-1 A tabular plate made of silver bromide by a known method, having a main plane of (111) plane, a sphere-equivalent diameter of 0.87 μm and an aspect ratio of 2 or more. An emulsion containing 85% by number of grains was prepared. The average aspect ratio of the tabular grains was 7.8. After the completion of grain formation, the temperature was lowered to 40 ° C., an aqueous solution containing an anionic precipitant was added to bring the total volume to 3 liters, and then the pH was lowered using sulfuric acid until the silver halide precipitated. Next, 85% of the total volume of the supernatant was removed (first washing with water). Further, the same amount of distilled water as that removed was added, and then sulfuric acid was added until silver halide precipitated. Again 85% of total volume
The supernatant liquid was removed (second washing with water). The same operation as the second washing with water was repeated once more (third washing with water) to complete the desalting process. Gelatin 80g and phenol (5%) 85cc
And 242 cc of distilled water were added. The pH was adjusted to 6.2 and pAg 7.5 with caustic soda and silver nitrate solution. In this way, pure silver chloride was obtained, which had a mean spherical equivalent diameter of 0.85 μm, an average thickness of 0.12 μm, and a main plane of (111) plane. Subsequently, chemical sensitization was performed. The emulsion was kept at 55 ° C. and the following operations were performed. Sensitizing dye ExS-4, which will be described later,
5 and 6 are 3.7 × 10 ⁻⁵ mol / mol Ag and 8.
1 × 10 ^-5 mol / mol Ag, 3.2 × 10 ^-4 mol / mol Ag was added, and after 5 minutes to 4-hydroxy-6-methyl-1,3,3a, 7- tetrazaindene the 6 × 10 ^-4
Mol / mol silver was added. Subsequently, sodium thiosulfate 4.4 × 10 ⁻⁶ mol / mol silver and selenium compound-1 were added to 2.
2 × 10 ⁻⁶ mol / mol silver, 0.2 × 10 ⁻⁵ mol / mol silver chloroauric acid and 1 × 10 ⁻⁵ mol / mol silver potassium thiocyanate were added, and after 60 minutes, the mixture was cooled to 35 ° C.

Preparation of Emulsion B-2 In the preparation step of Emulsion B-1, after chemical sensitization, the mixture was cooled to 35 ° C., and subsequently, in an ordinary double jet method, silver and halogen were added in equimolar amounts in 100 cc. AgN
Aqueous solution containing 11.3 g of O and KB in 100 cc
An aqueous solution containing r7.9 g and gelatin 0.5 g was added for shelling. The silver halide attached to the shell was adjusted to 0.01 mol with respect to 1 mol of the original tabular grains. Preparation of Emulsions B-3 to B-7 0.07 mol, 0.19 mol, 0.25 mol, based on 1 mol of the tabular grain based on the silver halide attached to the shell,
Emulsions B-3 to 7 were prepared with 0.33 mol and 0.5 mol.

Preparation of Emulsion C-1 In 1.68 liters of water, 3.8 g of sodium chloride, 3 mmol of crystal habit controlling agent-1 shown below and 10 parts of inert gelatin were added.
28.8 cc of silver nitrate aqueous solution (7.34 g of silver nitrate) and 28.8 cc of sodium chloride aqueous solution (2.71 g of sodium chloride) with stirring in a container kept at 30 ° C.
Was added by the double jet method in 1 minute. Two minutes after the addition was completed, 188 g of 10% aqueous solution of inactive gelatin was added. The temperature of the reaction vessel was raised to 75 ° C. in the next 15 minutes. After aging at 75 ° C for 12 minutes, aqueous silver nitrate solution 480
cc (122.7 g of silver nitrate) and aqueous sodium chloride solution were added over 39 minutes at an accelerated flow rate. During this period, the potential was kept at +100 mV against the saturated calomel electrode. After the addition was completed, the temperature was lowered to 40 ° C., an aqueous solution containing an anionic precipitating agent was added to bring the total volume to 3 liters, and then the pH was lowered using sulfuric acid until the silver halide precipitated. Next, 85% of the total volume of the supernatant was removed (first washing with water). Further, the same amount of distilled water as that removed was added, and then sulfuric acid was added until silver halide precipitated. The supernatant liquid of 85% of the total volume was removed again (second water washing). The same operation as the second washing with water was repeated once more (third washing with water) to complete the desalting process. 80 g of gelatin, 85 cc of phenol (5%) and 242 cc of distilled water were added. The pH was adjusted to 6.2 and pAg 7.5 with caustic soda and silver nitrate solution. Thus, an emulsion containing pure silver chloride containing 85% of grains having an average sphere-equivalent diameter of 0.85 μm and an aspect ratio of 2 or more was prepared. The principal planes of the tabular grains were (111) planes and had an average aspect ratio of 7.6.

Subsequently, chemical sensitization was performed. 55 emulsion
The following operation was performed while keeping the temperature at ℃. First, sphere equivalent diameter 0.0
Pure silver bromide fine particles of 5 μm are added to 0.01 mol per mol of silver chloride.
Mole was added. After 10 minutes, potassium iodide 1.0 × 1
0^-FiveMol / mol Ag was added. After a further 5 minutes,
Sensitizing dyes ExS-4, 5 and 6 of 3.7 × 10
^-FiveMol / mol Ag, 8.1 × 10^-FiveMol / mol Ag,
3.2 x 10^-FourMol / mol Ag was added, and 5 minutes later, 4
-Hydroxy-6-methyl-1,3,3a, 7-tetra
6x10 Azaindene^-FourMol / mol silver was added. Further
Was added with 0.5 g of calcium chloride aqueous solution. Continue to
Sodium sulphate 4.4 x 10^-6Mol / mole Silver and selenium
Compound-1 was 2.2 x 10^-6Mol / mol silver and chloroauric acid
1.0 x 10 ^-Five30 minutes after adding mol / mol silver, 35 ° C
And cooled.

Preparation of Emulsion C-2 In the preparation process of Emulsion C-1, after chemical sensitization, the mixture was cooled to 35 ° C., and subsequently, 100 cc under the condition of equimolar addition of silver and halogen by a normal double jet method. AgN
An aqueous solution containing 11.3 g of O and Na in 100 cc
An aqueous solution containing 3.5 g of Cl and 0.5 g of gelatin was added for shelling. The silver halide attached to the shell was adjusted to 0.1 mol per mol of the original tabular grains. Preparation of Emulsions C-3 to C-7: 0.07 mol, 0.19 mol, 0.25 mol, based on 1 mol of the tabular grain based on the silver halide attached to the shell,
Emulsions C-3 to 7 were prepared with 0.33 mol and 0.5 mol.

Emulsions B-1 to B-7 and C-1 to C-7 were coated under the same coating conditions as in Example 1 to prepare samples 201 to 214. Furthermore, the depth of the latent image was obtained by the method described in the text. The results are shown in Table 3. These samples 201 to 214
Then, imagewise exposure was performed with white light at a shutter speed of 1/100 ″ to 10 ″, and the same color development processing as in Example 1 was performed. Table 3 shows the graininess and the sensitivity. As for graininess, the RMS graininess measured by a G filter of a sample exposed with an exposure amount giving a color image density of (fog + 0.3)
The value is expressed as a relative value with the value of 1 as 100. Sensitivity is (fog +
The value is defined as the reciprocal of the exposure amount that gives the color image density of 0.2), and is expressed as a relative value with the value of Sample 201 as 100.

[0072]

[Table 3]

From Table 3, when the halogen composition of the base grain is silver bromide, when the "latent image depth" is 2 nm or more and less than 100 nm, the sensitivity is high and the graininess is excellent. It can be seen that it is significantly smaller than the obtained size.
Further, when the "latent image depth" is 50 nm or more and less than 100 nm, a greater effect can be obtained in the case of silver chloride, but desensitization is unfavorable in the case of silver bromide, which is not preferable.

(Example 3) Emulsion A-prepared in Example 1
1-A-14 was used for the 5th layer and the multilayer coating sample sample 301-314 was created. 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
0 parts by weight and Tinuvin P. as an ultraviolet absorber. 3
26 (manufactured by Ciba-Geigy) and 2 parts by weight were dried, melted at 300 ° C., extruded from a T-die, and stretched longitudinally 3.3 times at 140 ° C., followed by 130 ° C. The film is stretched 3.3 times in the direction of
After heat fixing for 6 seconds, a PEN (polyethylene naphthalate) film having a thickness of 90 μm was obtained. The PEN film had a blue dye, a magenta dye and a yellow dye (I-1 described in the publication technique: Japanese Patent No. 94-6023,
I-4, I-6, I-24, I-26, I-27, II-
5) was added in an appropriate amount. Further, the support was wound around a stainless steel winding core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled. 2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and Soudium α-sulfodi-2 on each surface. −
Ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g
/ M ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO)
₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² An undercoat liquid was applied (10 cc / m ² , using a bar coater), and the undercoat layer was applied to the high temperature surface side during stretching. Provided. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat. 3-1) Coating of antistatic layer Tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm which is a dispersion of fine particle powder (secondary aggregated particle size of about 0.08 μm). .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH
₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.00
Coated with 5 g / m ² and resorcin. 3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g; Long axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 emu
/ G, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06
g / m ² of diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out by an open kneader and a sand mill), and C ₂ H ₅ C (CH ₂ OCONH-C
0.3 g / m ² of ₆ H ₃ (CH ₃ ) NCO) ₃ was applied with a bar coater using acetone, methyl ethyl ketone and cyclohexanone as a solvent to obtain a 1.2 μm-thick magnetic recording layer. Silica particles (0.3μ
m) and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) treated and coated with aluminum oxide (0.15 μm) as an abrasive at a concentration of 10 mg / m ^2. did. 115 for drying
It was carried out at 6 ° C. for 6 minutes (115 ° C. for all the rollers and conveyance devices in the drying zone). The color density increase of D ^B of the magnetic recording layer by the X-light (blue filter) was about 0.1, the saturation magnetization moment of the magnetic recording layer was 4.2 emu / g, and the coercive force was 7.3 × 10 ⁴ A. / M, the squareness ratio was 65%. 3-3) Adjustment of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ C
H (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg
/ M ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1
/ 1) melted at 105 ° C, poured into and dispersed in propylene monomethyl ether (10 times amount) at room temperature to prepare,
It was added after being made into a dispersion (average particle diameter 0.01 μm) in acetone. Silica particles (0.3 μm) as matting agent
And aluminum oxide (0.15 μm) coated with 3-poly (polymerization degree 15) oxyethylenepropyloxytrimethoxysilane (15% by weight) as a polishing agent, 15 mg /
It was added so as to be m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). The sliding layer has a dynamic friction coefficient of 0.06 (stainless hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a kinetic friction coefficient of 0.12 between an emulsion surface and a sliding layer described later. Excellent characteristics.

4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in a multi-layered manner to prepare a color negative film. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye (specific compounds are described below, numerical values are given after symbols, and chemical formulas are listed after them). The numbers corresponding to the respective components are g / m ² units. The coating amount is expressed by and the coating amount in terms of silver is shown for silver halide. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer. Table 4 below shows the outline of the silver halide emulsions a to l. First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02 Second layer (intermediate layer) 0.07 μm Silver bromide emulsion Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver chlorobromide emulsion a Silver 0.25 Silver chlorobromide emulsion b Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87 Fourth layer (medium-speed red-sensitive emulsion layer) Silver chlorobromide emulsion c Silver 0.70 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.8 × 10 ^{− 5} ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.06 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion prepared in Example 1 Silver 1.40 ExS-1 2.5 × 10 ⁻⁴ ExS-2 9.8 × 10 ⁻⁵ ExS-3 3. 5 × 10 ⁻⁴ ExC-1 0.10 ExC-3 0.040 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1. 10 6th layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10 7th layer (low sensitivity green sensitive emulsion layer) ) Silver chlorobromide emulsion e Silver 0.15 Silver chlorobromide emulsion f Silver 0.10 Silver chlorobromide emulsion g Silver 0.10 ExS-4 3.0 × 10 ⁻⁵ ExS-5 2.1 × 10 ^{− 4 ExS-6 8.1 × 10 -4} ExM-2 0.33 ExM 3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion h Silver 0.80 ExS-4 3.2 × 10 ⁻⁵ ExS-5 2.1 × 10 ⁻⁴ ExS-6 8.5 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY- ⁴ 0.010 ExY-5 0.040 HBS-1 0.13 HBS-34 0.0 × 10 ⁻³ Gelatin 0.80 9th layer (high-sensitivity green-sensitive emulsion layer) Silver chlorobromide emulsion m Silver 1.25 ExS-4 4.2 × 10 ⁻⁵ ExS-5 4.1 × 10 ^{− 4} ExS-6 8.5 × 10 ⁻⁴ ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 polyethyl acrylate Latex 0.15 Gelatin 1.33 10th layer (yellow filter ) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0. 60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver chlorobromide emulsion i Silver 0.09 Silver chlorobromide emulsion j Silver 0.09 ExS-7 8.6 × 10 ⁻⁴ ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20 12th layer (high-sensitivity blue-sensitive emulsion layer) Silver chlorobromide emulsion k Silver 0.09 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.020 Cpd-2 0.10 Cpd-3 1.0 × 10 ⁻³ HBS-1 0.070 Gelatin 0.70 13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1. 8 14th layer (2nd protective layer) 0.07 μm Silver bromide emulsion Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1. 7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 70

[0080]

[Table 4]

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 used in the above light-sensitive material was dispersed by the following method. That is, 21.7 cc of water, 3 cc of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethane sulfonate, and 0.5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were placed in a 700 cc pot mill. , Dye ExF-2 5.
0g and zirconium oxide beads (diameter 1mm) 500c
c was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the content was taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm. Similarly, solid dispersions of ExF-3, 4, and 6 were obtained. The average particle size of the fine dye particles is 0. 24 μm, 0.4
It was 5 μm and 0.52 μm. ExF-5 is EP-5
49,489A Microprecipitation as described in Example 1 (Micr
It was dispersed by the dispersion method. The average particle size was 0.06 μm. Samples 301 to 314 in which the emulsion of the fifth layer was changed to A-1 to A-14 were prepared. However, to the emulsions A-1 to A-14, 0.2 mol / mol Ag of potassium iodide was added immediately before coating, and the emulsion was mixed for 4 minutes for 10 minutes.
Aged at 0 ° C.

After exposing Samples 301 to 314 in a white imagewise manner, the following developing treatment was carried out. Processing process Temperature Time Replenishment amount Tank capacity Color development 38.5 ℃ 45 seconds 73ml 500ml Bleaching fixing 30-35 ℃ 45 seconds 60ml 500ml Rinse 30-35 ℃ 20 seconds 500ml Rinse 30-35 ℃ 20 seconds 500ml Rinse 30-35 ℃ 20 seconds 370ml 500ml Dry 70-80 ℃ 60 seconds * Replenishment amount per 1m ² of light-sensitive material (Rinse is 3 tank countercurrent method to →)

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Sodium triisopropylene (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 3.0g 3.0g 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5g 0.5g Triethanolamine 12.0g 12.0g Potassium chloride 6.5g-Potassium bromide 0.03g-Potassium carbonate 27.0g 27.0g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical Co., Ltd.) 1.0g 3.0g Sodium sulfite 0.1g 0.1g Disodium-N , N-bis (sulfonate ethyl) hydroxylamine 10.0 g 13.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 11.5 g Water was added 1000 ml 1000 ml pH (25 ℃) 10.0 11.0

Bleach-fixing solution (same as tank solution and replenisher) Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Nitric acid (67) %) 30 g Water was added to 1000 ml pH (25 ° C.) (with acetic acid and ammonia water) 5.8

Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less) Before and after the continuous treatment, the following sensitometry was performed using a sample having the same sample NO. as the sample used for each continuous treatment. Using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., light source color temperature: 3200 K), the photosensitive material was exposed through a color separation filter and a gradation wedge, and then developed. After processing, the density is measured with an R filter to give a density of (fog + 0.3), which is defined as the reciprocal of the exposure amount, and (fog +
The RMS value of the concentration of 0.2) was obtained. Table 5 shows the results. The sensitivity and RMS value were expressed as relative values with the value of Sample 301 as 100. It is clear that the sample using the emulsion of the present invention has high sensitivity and excellent graininess.

[0087]

[Table 5]

(Example 4) In Sample 301, the silver chloride emulsions m, ExS-4, 5 and 6 of the ninth layer were removed, and instead, the emulsions B-1 to 7 and C-1 to 1 prepared in Example 2 were replaced. 7 was added so that the amount of coated silver was equal, and samples 401 to 414 were prepared. After exposing the samples 401 to 414 in a white imagewise manner,
The same development process as in Example 3 was performed. The density is measured with the G filter, and the sensitivity is defined by the reciprocal of the exposure amount giving the density of (fog + 0.3), and (fog + 0.2)
The RMS value of the concentration was determined. Table 6 shows the results. sensitivity,
The RMS value was expressed as a relative value with the value of Sample 401 as 100.

[0089]

[Table 6]

It is apparent that the sample using the emulsion of the present invention has high sensitivity and excellent graininess.

(Embodiment 5) In Embodiment 3, only the development process is changed to the same process as in Embodiment 1. As a result, the same conclusion as in Example 3 was obtained. (Example 6) In Example 4, only the developing process was changed to the same process as in Example 1. As a result, the same conclusion as in Example 4 was obtained. The compounds used in the examples are summarized below.

[0092]

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[0093]

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[0094]

[Chemical 12]

[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

[Chemical 21]

[0104]

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[0105]

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[0106]

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[0107]

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Claims (2)

[Claims] 1. A tabular silver halide grain having an aspect ratio of 2 or more has a grain number of 50% or more, an average silver chloride content of at least 50 mol% and a latent image depth of 2.
A photosensitive silver halide photographic emulsion characterized by having a size of not less than 100 nm and less than 100 nm. 2. The photosensitive silver halide photographic emulsion according to claim 1, wherein the latent image has a depth of 50 nm or more and less than 100 nm.