JP2673037B2 - Silver halide emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention has a high spectral sensitivity due to a sensitizing dye, and
The present invention relates to a tabular silver halide emulsion having a good granularity.

(Prior Art) With the widespread use of photographing devices in recent years, the opportunities for taking photographs tend to increase. This inevitably brings about diversification of photography, and due to this diversification, silver halide photographic light-sensitive materials are strongly required to have higher image quality and higher sensitivity. As is well known in the art, it is the characteristics of silver halide grains that dominate these two basic performances of a silver halide photographic light-sensitive material. Generally, if the amount of silver in a silver halide light-sensitive material is constant, the smaller the size of silver halide grains, the greater the number of grains per unit volume of the light-sensitive material, resulting in high image quality. However,
A simple reduction in particle size results in reduced sensitivity. That is,
Higher sensitivity and higher image quality of silver halide light-sensitive materials are in a conflicting relationship, and in order to satisfy the requirements for these two silver halide light-sensitive materials at the same time, the sensitivity / size ratio per silver halide grain Must be improved. Use of tabular silver halide grains is one of the techniques for improving the sensitivity / size ratio.
108,525, 58-111,935, 58-111,936, 58
-113,937, 58-113,927, 59-99,433 and the like. The tabular silver halide grains have a large surface area in the same volume as the well-known regular hexahedron, regular octahedron, regular tetradecahedron or agglomerated silver halide grains. A large amount of dye can be adsorbed on silver halide grains, increasing the amount of light absorption,
It can be said that it is very advantageous for improving the size ratio. Most of the silver halides of practical silver halide light-sensitive materials are used after being spectrally sensitized by adsorbing a sensitizing dye. Therefore, it can be said that the tabular silver halide grains are extremely advantageous for actually achieving high sensitivity and high image quality of the silver halide light-sensitive material.

The tabularization rate of tabular silver halide grains is increased to increase the surface area /
Increasing the body weight ratio has favorable results as described above. However, increasing the surface area / weight ratio leads to the following inefficiency factors for the silver halide sensitization process. That is, Berry (CR), Journal of Photographic Science (Journal of
According to Photographic Science), Volume 21, 1973, p.202, the average diffusion length of photoelectrons generated in silver halide by light absorption is 4 μm at room temperature in the case of AgBr. On the other hand, since the size of silver halide grains used in a usual silver halide light-sensitive material is about 0.1 to 10 μm, extremely increasing the surface area / body weight ratio is obviously disadvantageous for latent image formation. That is, there will be some suitable surface area / volume ratio. Therefore, U.S. Pat.Nos. 4,434,226, 4,439,520, 4,386,156, British Patent 2,110,83
Aspect ratio (a value obtained by dividing the diameter of a circle having an area equal to the projected area of a tabular silver halide grain by the thickness of the tabular silver halide grain) as disclosed in No. 0-A and the like is 8 or more. In principle, the very thin tabular grains of ## STR3 ## often deviate from the above-mentioned optimum surface area / volume ratio region.

Further, as the aspect ratio increases, the solubility at the edges of the tabular silver halide grains increases, and the stability of the emulsion in the solution state in the actual manufacturing process tends to deteriorate.

In general, when silver halide is adsorbed with a sensitizing dye, the sensitivity peculiar to silver halide is often lower than when it is not adsorbed, and this tendency becomes remarkable when the light absorbing region of the sensitizing dye becomes a long wavelength region. This is a well-known fact.
Further, generally, the degree of this sensitivity decrease increases as the amount of the sensitizing dye adsorbed increases. The spectral sensitization sensitivity of the silver halide sensitizing dye is reduced by the amount corresponding to the reduction in the sensitivity specific to silver halide. This means that if the inefficiency factor peculiar to the silver halide caused by adsorbing the sensitizing dye by some method can be eliminated, the spectral sensitization sensitivity of the silver halide can be increased accordingly. It means that. That is, it is possible to realize high-sensitivity image quality. This situation applies to silver halide in general, and tabular silver halide is no exception. In particular, it can be said that elimination of the inefficiency factors described here is indispensable in order to make full use of the features of the tabular grains described above.

As a technique for improving the inefficiency due to the sensitizing dye by making the crystal structure of silver halide special, for example, a cavity having a maximum depth of 60 lattices is provided on the surface of silver halide. The technique of burying chemically sensitized nuclei therein is disclosed in West German Patent No. 2,306,447-C. However, in this method, the latent image formed in the vicinity of the chemically sensitized nuclei to be developed is not present on the surface of the silver halide grain but is present on the inner side. Therefore, the surface is processed with a commonly used surface developer for color negative or black and white negative. In this case, there is a drawback that the development is delayed and the development is not sufficiently performed within a predetermined time. In particular, this goes against the trend of recent simple rapid processing. Furthermore, such a structure is a technology that is premised on the stable existence of atomic-order minute holes on the surface, but such a structure is thermodynamically unstable, and This hole is apt to be buried by recrystallization of the silver halide after a certain period of time in the solution state of the emulsion, which must be inevitably passed in the production of silver halide. In this case, it is believed that the chemically sensitized nuclei will either be embedded in the silver halide or rearrange on the recrystallized silver halide surface. When the former phenomenon occurs, development becomes extremely difficult with a normal surface developing solution. When the latter development occurs, the chemically sensitized nuclei appear outside the hole, contrary to the intended design. In any case, the silver halide emulsion having such a structure has poor storage stability in a solution state of the emulsion and poor production suitability.

Further, a technique for preventing desensitization by a sensitizing dye by chemically sensitizing silver halide in the presence of a polyvalent metal salt and a sensitizing dye is disclosed, for example, in JP-A-61-160,739. However, when the silver halide is chemically sensitized in the presence of such a polyvalent metal salt, the adsorption of the sensitizing dye is significantly hindered in the addition amount region where the effect appears. Therefore, the substantial increase in spectral sensitivity is extremely small.

A technique for preventing desensitization by a sensitizing dye by adding various additives to a silver halide emulsion is disclosed, for example, in JP-A-61-169,831. However,
A technique for preventing desensitization by a sensitizing dye by adding such an additive is such that the additive desorbs the sensitizing dye, particularly in an emulsion system in which a sensitizing dye having a weak adsorptivity for silver halide is used. Or change the association state of the dye. The former causes a decrease in spectral sensitization sensitivity, and the latter causes an obstacle that is an obstacle to the production of a photographic light-sensitive material such that the spectral sensitization property as designed cannot be obtained. Therefore, such an additive generally exhibits competitive effects by adsorbing with the sensitizing dye, so that the adsorption of the sensitizing dye is significantly inhibited in the addition amount region where the effect is exhibited. Therefore, the substantial increase in spectral sensitivity is extremely small.

As described above, when a silver halide light-sensitive material to be put to practical use is manufactured by a conventionally known technique, a technical principle problem that conflicts with the intended purpose occurs as described above, and it is impossible to realize. Met.

(Problems to be Solved by the Invention) The object of the present invention is to stabilize a high spectral sensitization sensitivity even when spectrally sensitized with a sensitizing dye whose absorption is in the visible region while being adsorbed on silver halide. Another object of the present invention is to provide a tabular silver halide emulsion for photography obtained as described above.

(Means for Solving the Problems) It was found that the objects of the present invention can be achieved by a silver halide photographic emulsion having the following features.

(1) 50 of the total projected area of all silver halide grains in the emulsion
% Or more is occupied by tabular silver halide grains having a diameter of 0.4 μm or more, and these tabular silver halide grains having a diameter of 0.4 μm or more have an average of 10 dislocation lines per grain,
An emulsion having an average aspect ratio of 3 or more and less than 8, wherein this emulsion is used per mol of silver halide. A tabular silver halide emulsion characterized in that it comprises a nitrogen-containing heterocyclic compound having a mercapto group and formed in the presence of a compound represented by the following general formula.

General formula: in X (QCN) _n formula, X is an n-valent cation, n represents a number from QCN groups bonded to the n-valent cation. Where Q is S
Or Se.

(2) The silver halide emulsion according to (1) above, wherein the nitrogen-containing heterocyclic compound having a mercapto group is represented by the following general formula (II).

General formula (II) In the formula, R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, which is substituted with at least one —COOM or —SO ₃ M, and M is a hydrogen atom, an alkali metal, a quaternary ammonium or a quaternary group. Represents phosphonium.

 Next, embodiments of the present invention will be described in detail.

(1) Detailed Aspect of Average Aspect Ratio In the present invention, the diameter of the tabular silver halide grain means that the tabular silver halide grains are oriented so that two main planes facing each other are horizontal to the plane. It means the diameter of a circle that has an area equal to the projected area on this plane. Here, the two main planes facing each other mean, among the surfaces constituting the tabular grains, the surfaces parallel to each other and having the largest area. Hereinafter, the diameter of tabular silver halide grains may be referred to as "diameter" for the sake of simplicity, unless otherwise specified.

The average aspect ratio, r, is defined as: I-th
When the diameter of the th grain is D _i and the thickness of the tabular silver halide grain in the direction orthogonal to the two main planes facing each other is t _i , r is r = (ΣD _i / t _i ) / N [1]. However, the sum Σ is i = 1 to N for grains having a diameter of 0.4 μm or more, and N is a number sufficient to give the average aspect ratio of the tabular silver halide grains. In the above formula [I], r is such that each silver halide grain is substantially t _i t _j (i ≠ j; i, j ≦ N) [2] or substantially D _i / t _i D _j If / t _j (i ≠ J; i, j ≦ N) [3], then r ′ defined as r ′ = (ΣD _i ) / (Σt _i ) [4] is substantially equal to r. However, the sum Σ is i = 1 to N for particles with a diameter of 0.4 μm or more.
Take up to Therefore, the average aspect ratio may be given by r ', as long as the error is within the range of acceptable accuracy in particle size measurement.

That is, an electron micrograph of silver halide grains is taken, and the diameter and thickness of each grain in the photograph are measured. Of these, the average aspect ratio is calculated for all particles having a diameter of 0.4 μm or more.

Sum of individual projected areas of particles with a diameter of 0.4 μm or more (S
t) and the total projected area of particles with a diameter of less than 0.4 μm (Sn)
From this, the ratio σ = (St / (St + Sn)) × 100% of the grains having a diameter of 0.4 μm or more to the whole emulsion grains can be calculated [5]. The value of σ may be 50% or more, preferably 80% or more, and particularly preferably 90% or more.

The tabular silver halide grains having a diameter of 0.4 μm or more may have an average diameter of 0.4 μm or more, preferably 0.5 μm or more and 4 μm or less, and particularly preferably 0.6 μm or more and 3 μm or less.

The tabular grains having a diameter of 0.4 μm or more may have an average aspect ratio of 3 or more and less than 8, but preferably 4 or more and less than 7.8, and particularly preferably 5 or more and less than 7.5.

(2) Detailed modes of dislocation lines As for dislocation lines, tabular silver halide is prepared by intentionally introducing a controlled recrystallization process of silver halide grains in the preparation of silver halide emulsion grains as shown below. It can be incorporated into particles. There are various methods for observing dislocation lines, for example, the Japan Institute of Metals, new edition, `` Dislocation theory-its application to metallurgy '', Maruzen, 1971, p.
Direct observation with an electron microscope as described in 627-645 is possible. Regarding the number of dislocation lines, James (TH) “Theory of Photographic Process (The Theory of the Photographic Process)”, 3rd edition, New York, Macmillan, 1967, p.17, "The number of dislocation lines found in emulsion crystals is usually small, from 5
It is ten. However, in some silver halide precipitations, the number is zero. "a. In the present invention, an average of 10 or more dislocation lines are incorporated into each grain having a diameter of 0.4 μm or more which occupies 50% or more of the total projected area of all silver halide grains in the emulsion by the following emulsion preparation method. I was able to. Regarding the number of dislocation lines, an average of 10 or more dislocation lines per grain having a diameter of 0.4 μm or more, which occupies 50% or more of the total projected area of all silver halide in the emulsion, may be averaged per grain. It is preferable to have 20 or more dislocation lines, and it is particularly preferable to have an average of 30 or more dislocation lines per grain.

To introduce dislocation lines into a silver halide crystal, it is necessary to disorder the periodic structure of the crystal aperiodically. That is, a foreign ion or an organic compound different from the halogen ion and silver ion used for the growth of silver halide is introduced in the middle of the crystal growth process so that the lattice constant changes discontinuously at a certain position of the crystal lattice. Alternatively, dislocation lines can be introduced by supplying halogen ions and silver ions so that the halogen composition changes abruptly. If an organic compound is added for this purpose, it is preferred that it interacts in some way with the silver halide. Specifically, sensitizing dyes and stabilizers commonly used in the art can be used for this purpose. As a method of rapidly changing the composition of silver halide, for example, a method of adding a KI solution during the formation of AgBr particles, or AgI or AgCl during the formation of AgBr particles.
Are grown and then aged, or subsequently further AgBr grain formation is added. A specific method of introducing dislocation lines will be shown in the following examples. In short, when the silver halide minimizes the formation energy of the crystal lattice during the growth process, the lattice constant suddenly changes in a certain region of the crystal lattice. Crystallization may be performed so as to be stabilized at.

(3) Compound X (QCN) _n The general formula of the compound used in the present invention is X
(QCN) given by _n . However, X is an atom or molecule that produces an n-valent cation, and n represents the number of QCN groups bonded to the n-valent cation. For example, when n = 1, X is NH ₄ ,
K, Na, etc. The value of n may be 1 or more, preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. Q is S or Se. The addition amount of X (QCN) _n is as described below. The amount of X (QCN) _n added in the process of grain formation of silver halide is 1 mol per mol of silver halide. If you like, Is preferred, Is particularly preferred.

The position _where X (QCN) _n is added is preferably after the stage where 80% or more of the total Ag amount used for silver halide grain formation has been added, and at the stage where 90% or more and less than 100% have been added. Position is particularly preferred. Thus, such use of X (QCN) _n in the present invention is added at the stage when the growth of silver halide grains has been sufficiently performed. The method of adding the compound in order to monodisperse silver halide grains generally known in the art from the nucleation stage to the main growth stage of silver halide grain formation and the addition method of the present invention are Totally different. Furthermore, it is completely different from the method which is commonly used in the art and which uses the compound as a gold ligand during gold sulfur sensitization.

Among the X (QCN) _n described in this section, it is already known to use, for example, KSCN in the field of photography. For example, JP-A-63-106,746, JP-A-63-316,847, JP-A-2-123,34
No. 5 shows that high sensitivity and improved pressure resistance can be achieved by using KSCN in the latter stage of silver halide grain formation. However, from these use techniques, the effect of the tabular silver halide emulsion according to the embodiment of the present invention on the improvement of the high image quality of the photographic light-sensitive material was completely unexpected.

Here, it was totally unexpected in the following sense that the compound is made to act on silver halide grains containing a high-density dislocation line of 10 or more per grain to obtain high-sensitivity image quality. . That is, in general, a solid containing dislocation lines has a structurally weak point at which the dislocation line intersects with the solid surface and has a property of being dissolved specifically and selectively by a chemical treatment. This easy-to-melt location is called an etch pit. A description of this property can be found, for example, in "Dislocation theory-its application to metallurgy-" in the description, p.83-84 and edited by Akiya Okawa, "Advances in the study of lattice defects", Agne, 1964, p.277
~ 278 and W. Shockley, JH Hollomon, R. Maurer, F. Seit
z), "Imperfecfions in Nearly
Perfect Crystals ”, John Wiley & Sons, New York
k) found on pages 403-406. Also, especially for silver halide etch pits, JC Fisher (Fish
er), WG Johnston R. Thomson (Thom
son), T. Breeland, Jr. (Vreeland, Jr.)
Volume "Dislocation and Mechanical Properties of Crystals (Dislocation and Mech
anical Properties of Crystals) -An International Conference Held Out Lake
Placido (An International Confrernce held at Lake
Placid) SEPTEMBER 6-8, 1956. John Wiler & Sons (New York), p.69-91. Therefore, the use of the compound having a solvent effect on silver halide grains having a high density of dislocations in a large amount region as defined in the present invention causes dissolution of dislocation lines and remarkable grain deformation in the ordinary grain formation method. However, it was expected that the resulting reduction in photographic sensitivity of silver halide would result. However, as a result of intensive studies, we have found a method for achieving a higher image quality without deteriorating the photographic characteristics of silver halide having a high-density dislocation line according to the embodiment of the present invention. .

(4) Detailed Aspect of Nitrogen-Containing Heterocyclic Compound Having Mercapto Group The nitrogen-containing heterocyclic compound having a mercapto group may be added at any step of the process for producing a silver halide emulsion. For example, it may be added at the time of nucleation, which is the initial stage of grain formation, or may be added prior to chemical sensitization or after chemical sensitization. Further, it may be added just before coating. Regarding the addition in the coating step, when the compound is diffusible, it may be added to the same layer as the emulsion of the present invention, or to another layer to be coated in multiple layers, which has a water permeability relationship. Also,
Either of them can achieve the object of the present invention. Although it is necessary to select a preferable amount of the compound, the silver halide 1
A range of 10 ⁻⁶ to 10 ⁻² mol per mol is preferred.

In the present invention, the nitrogen-containing heterocyclic compound is preferably a compound represented by the following general formula (I), more preferably a compound represented by the general formula (II).

General formula (I) In the general formula (I), Z represents a nonmetal atomic group necessary for forming a nitrogen-containing heterocycle, and M represents a hydrogen atom, an alkali metal, a quaternary ammonium or a quaternary phosphonium.

General formula (II) In the general formula (II), R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, which is substituted with at least one —COOM or —SO ₃ M, and M has the same meaning as in the formula (I). .

Hereinafter, the nitrogen-containing heterocyclic compound represented by the general formulas (I) and (II) used in the present invention will be described in more detail.

Specific examples of the aliphatic group represented by R ¹ in the general formula (II) include a linear or branched alkyl group having 1 to 20 carbon atoms (eg methyl, propyl, hexyl, dodecyl, isopropyl), 1 carbon atom. To 20 cycloalkyl groups (for example, cyclopropyl, cyclohexyl) and aromatic groups, specifically, aryl groups having 6 to 20 carbon atoms (for example, phenyl,
Naphthyl) and a heterocyclic group, specifically, 1
A 5-membered ring containing more than one nitrogen, oxygen or sulfur atom,
6-membered or 7-membered heterocyclic ring (eg, morpholine, piperidine, pyridine), which further forms a condensed ring at an appropriate position (eg, quinoline ring, pyrimidine ring, isoquinoline ring) .

Also, the linear or branched alkyl group, cycloalkyl group, aryl group and heterocyclic group in addition to -COOM or -SO ₃ M, may further have a substituent. Specific examples of these substituents include halogen atoms (F, Cl, B
r), an alkyl group (eg, methyl, ethyl), an aryl group (eg, phenyl, p-chlorophenyl), an alkoxy group (eg, methoxy, methoxyethoxy), an aryloxy group (eg, phenoxy), a sulfonyl group (eg, methanesulfonyl, p- Toluenesulfonyl), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), sulfamoyl group (eg, diethylsulfamoyl, unsubstituted sulfamoyl), carbamoyl group (eg, unsubstituted carbamoyl, diethylcarbamoyl), amide group (eg, acetamido, Benzamide), ureido group (eg, methylureide, phenylureide), alkoxycarbonylamino group (eg, methoxycarbonylamino), aryloxycarbonylamino group (eg, phenoxy Carbonylamino), alkoxycarbonyl group (eg methoxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group (eg unsubstituted amino, dimethylamino), Examples thereof include an alkylsulfinyl group (for example, methoxysulfinyl), an arylsulfinyl group (for example, phenylsulfinyl), an alkylthio group (for example, methylthio), and an arylthio group (for example, phenylthio), and two or more of these substituents are substituted. And the substituents may be the same or different.

Among the nitrogen-containing heterocyclic compounds represented by the general formulas (I) and (II), the compounds represented by the general formula (III) are particularly preferable.

General formula (III) R ^{2 in the} general formula (III) represents a phenyl group substituted with at least one —COOM or —SO ₃ M, and this phenyl group is substituted with another substituent other than —COOM or —SO ₃ M. It may have been done. Specific examples of other substituents include
The same as the substituents of the linear or branched alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ¹ can be mentioned. Here -COOM, it may be the same or different when SO ₃ M is 2 or more. M means the same as those represented by the general formulas (I) and (II).

The compound can be easily synthesized by using a reaction between isothiocyanate and sodium azide, as is generally well known. References and patents relating to these synthetic methods are listed below for reference.

U.S. Pat.No. 3,266,897, Japanese Patent Publication No. 42-21842, JP-A-5
6-111,846, British Patent 1,275,701, DA Berges (B
erges) etc., Journal of Heterocyclic
Chemistry (Journal of Heterocyclic Chemistry) 1
Volume 5, p.981 (1978), RG Dubenko, V.
D. Panchenko, "Khimiia Ge
terotsiklicheskikh Soedinenii) ", Part 1, (Azole
oder Jhas chie Geterotsikly, 1967, p.199-20
1).

The silver halide emulsion of this compound may be added in the usual manner as a photographic emulsion additive. For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water or a mixed solvent thereof, and added as a solution.

The use of compounds of the above formula (I) in the photographic field is already known. For example, JP-A-62-89,952 describes a combination of a nitrogen-containing heterocyclic compound having a mercapto group and a cyanine dye, and shows prevention of fogging and high sensitivity. However, from these use techniques, the stabilizing effect on the photographic light-sensitive material using the tabular silver halide emulsion according to the embodiment of the present invention was completely unexpected.

Tabular silver halide emulsions are described by Cagnac and Chateau "Evolution of the Morphology of Silver Bromide Crystals During・ Physical Lipping) "Science & Industry Photography, Volume 33, No.2 (19
62), p.121-125, Duffin, "Chemistry of Photographic Emulsions (Fetographic Emulsion Chemistry)", New York, 1966, p.66-72, APH Tribelli (Trivelli), WF Smith (Smith) ), Photographic Journal, 80
Vol., P. 285 (1940), etc.
It can be easily prepared by referring to the methods described in 8-127,921, 58-113,927, 58-113,928, and U.S. Pat. No. 4,414,310. The size of tabular silver halide grains is
It can be adjusted by adjusting the temperature, selecting the type and amount of the silver halide solvent, and controlling the addition rate of the silver salt and halide used during grain growth. Also, the aspect ratio can be easily adjusted by adjusting pAg and / or using a silver halide solvent in combination.

In particular, the preparation of tabular silver halide emulsion having a well-balanced grain size is described, for example, in JP-A-63-151,618, U.S. Pat.
54, West German Patent 3,707,135-A1, and JP-A-2-838 can be referred to.

The general formula of the silver halide emulsion grains according to the present invention can be represented by AgBr _1-xy I _x Cl _y . Here, x and y can take the following values.

0 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.5 Preferably 0 ≦ x ≦ 0.4, 0 ≦ y ≦ 0.3 Especially preferably 0 ≦ x ≦ 0.2, 0 ≦ y ≦ 0.05.

The silver halide emulsion according to the present invention can be chemically sensitized if necessary. As the chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. No. 2,445,060
No. 3,320,069) or a sensitization method with a metal such as iridium, platinum, rhodium, palladium (for example, US Pat.Nos. 2,448,069, 2,566,245, 2,566,263) or a sulfur sensitization method using a sulfur-containing compound (for example, US Patent No.
2,222,264) or a reduction sensitization method using tin salts, polyamines and the like (for example, US Pat. Nos. 2,487,850 and 2,518,698).
No. 2,521,925), or a combination of two or more thereof. From the viewpoint of high sensitivity, the silver halide emulsion of the present invention is preferably chemically sensitized by the combined use of gold sensitization and sulfur sensitization.

In the process of silver halide grain formation or physical ripening or chemical ripening of the present invention, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt, a palladium salt or a complex salt thereof, an iron salt, an iron complex salt or the like is allowed to coexist. Good.

The silver halide emulsion of the present invention has a photosensitive material production process,
Prevent fog during storage or photo processing and /
Alternatively, various compounds may be incorporated for the purpose of stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles. , Nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines, thioketo compounds such as oxazolithione;
Azaindenes, for example triazaindenes; tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazaindenes; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfone Many compounds known as antifoggants or stabilizers such as acid amides and the like can be added. For example, U.S. Patents 3,954,474, 3,982,927, Japanese Patent Publication No. 52-
Those described in No. 28,660 can be used.

The silver halide emulsions of this invention can be spectrally sensitized with methine dyes and the like. 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 for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like;
A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole A nucleus, a benzoselenazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

In a merocyanine dye or a complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazolidione-2,4-dione nucleus, rhodanine nucleus or thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often preferably used for supersensitization and optimum setting of spectral sensitivity.

The silver halide emulsion in the present invention is effective in any wavelength region when spectrally sensitized with a sensitizing dye having an absorption peak at a wavelength of 400 to 700 nm which is usually used in a light-sensitive material. The effect of the present invention is remarkable when spectrally sensitized using a sensitizing dye having an absorption peak in the 500 to 700 nm region, and further, when a sensitizing dye having a series peak in the wavelength range of 600 to 700 nm is used. The effect of the present invention is extremely remarkable.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, an aminostilbene compound substituted with a nitrogen-containing heterocyclic group (for example, those described in U.S. Pat.Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate (for example, those described in U.S. Patent 3,743,510), It may contain a gadmium salt, an azaindene compound or the like. U.S. Patent 3,615,61
The combinations described in Nos. 3, 3,615,641, 3,617,295, and 3,635,721 are particularly useful.

The antifoggant, stabilizer and sensitizing dye described above may be added in the process of forming silver halide grains or in the process of chemical sensitization, or may be added at the time of coating.

Particularly as a method of adding a sensitizing dye during silver halide emulsion grain formation, U.S. Pat.Nos. 4,225,666 and 4,828,972,
Reference can be made to JP-A-61-103,149. Further, as a method of adding a sensitizing dye in a desalting step of a silver halide emulsion, European Patent 291,339-A, JP-A-64,
-52,137 can be referred to. Also, a method of adding a sensitizing dye in the chemical sensitization step is disclosed in JP-A-59-48,
You can refer to No. 56.

A color-forming coupler can be added to the photographic emulsion layer of the photographic light-sensitive material containing the silver halide emulsion of the present invention. That is, a compound capable of forming a color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in color development processing is used, for example, as a magenta coupler, a 5-pyrazolone coupler or a pyrazolobenz. There are imidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers include naphthol couplers and phenol couplers. Etc. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, it may be a colored coupler having a color correction effect, or a coupler releasing a development inhibitor upon development (so-called DIR coupler).

In addition to the DIR coupler, a non-colored DIR coupling compound, which is a colorless product of the coupling reaction and releases a development inhibitor, may be contained.

The tabular silver halide emulsion according to the present invention has the following formula (C).
It is particularly preferable to use in combination with a coupler represented by

Formula (C) In formula (C), R ₁ is -CONR ₄ R ₅ , -SO ₂ NR ₄ R ₅ , -NHC.
_{OR 4, -NHCOOR 6, -NHSO 2} R 6, -NHCONR 4 R 5 or -NHSO
₂ NR ₄ R ₅ , R ₂ is a group that can be substituted on a naphthalene ring, 1 is 0
R ₃ represents a substituent, X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However, R ₄ and R ₅ may be the same or different, and a hydrogen atom, an alkyl group,
An aryl group or a heterocyclic group, and R ₆ represents an alkyl group, an aryl group or a heterocyclic group. When representing l2 or 3,
Plural R _{2 s} may be the same or different and may be bonded to each other to form a ring. R ₂ and R ₃ or R ₃ and X may be bonded to each other to form a ring.

The coupler represented by the formula (C) is represented by R ₁ , R ₂ , R ₃ or X.
In, a dimer or a multimer or more (polymer including a polymer in which a coupler is bonded) is bound to each other via a divalent or divalent group may be formed.

In the present invention, the alkyl group may be linear, branched or cyclic, and even if it contains an unsaturated bond, it is a substituent (for example, a halogen atom, an aryl group, a heterocyclic group, an alkoxy group, an aryl group). Oxy group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, acyloxy group, acyl group).

Even if the aryl group is a condensed ring (for example, a naphthyl group), a substituent (for example, a substituent of the above alkyl group, an alkyl group, a cyano group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group) ,
It may have an alkoxycarbonylamino group).

The heterocyclic group is a 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one heteroatom of O, N, S, P, Se, and Te in the ring, and a substituent (for example, In addition to the substituent of the aryl group, it may have a hydroxyl group, a carboxyl group, a nitro group, an amino group, an aryloxycarbonyl group).

R ₁ is preferably 1 to 30 in total number of carbon atoms (hereinafter referred to as C number).
A carbamoyl group (for example, Nn-butylcarbamoyl, Nn-hexadecylcarbamoyl, N- [3-
(2,4-di-t-pentylphenoxy) propyl] carbamoyl, N- (3-n-dodecyloxypropyl) carbamoyl, N- (3-n-dodecyloxy-2-methylpropyl) carbamoyl), N- [ 3- (4-t-octylphenoxy) propyl] carbamoyl) or C
A sulfamoyl group of the number 0 to 30 (for example, N- (3-n-dodecyloxypropyl) sulfamoyl, N- [4-
(2,4-di-t-benzylphenoxy) butyl] sulfamoyl), and particularly preferably a carbamoyl group.

1 is preferably 0 or 1, particularly preferably 0. R ₂ is preferably a halogen atom (F, Cl, Br, I, the same applies hereinafter), a cyano group, an alkyl group having 1 to 12 C, an alkoxy group, a carbonamido group or a sulfonamide group.

R ₃ is preferably _{-COR 7, -SO 2 R 8,} -CO 2 R 8, Wherein R ₇ has the same meaning as R ₄ and R ₈ has the same meaning as R ₆ . R ₃ is particularly preferably —COR ₇ having a C number of 1 to 30 (eg acetyl, trifluoroacetyl, pivaloyl, benzoyl), —SO ₂ R ₈ having a C number of 1 to 30 (eg methylsulfonyl, n-butylsulfonyl, p -Trisulfonyl)
Alternatively, it is —CO ₂ R ₈ having a C number of 2 to 30 (eg methoxycarbonyl, isobutoxycarbonyl, 2-ethylhexyloxycarbonyl), and —CO ₂ R ₈ is more preferred.

X is preferably a hydrogen atom, a halogen atom, or a C number of 1 to 30.
An alkoxy group (for example, 2-hydroxyethoxy, 2-
(Carboxymethylthio) ethoxy, 3-carboxyethoxy, 2-methoxyethoxy, an aryloxy group having a C number of 6 to 30, (for example, 4-methoxyphenoxy, 4-
(3-carboxypropanamide) phenoxy), an alkylthio group having 2 to 30 C atoms (for example, carboxymethylthio, 2-carboxyethylthio, 2-hydroxyethylthio, 2,3-dihydroxypropylthio) or a C number 6
To 30 arylthio groups (eg, 4-t-butylphenylthio, 4- (3-carboxypropanamide) phenylthio), and particularly preferably hydrogen atom, chlorine atom, alkoxy group or alkylthio group.

Table A given below shows specific examples of the cyan coupler represented by the formula (C).

Specific examples of the cyan coupler represented by the formula (C) other than the above and / or methods for synthesizing these compounds are described in, for example, U.S. Pat. No. 4,690,889, JP-A-60-237448, and 61-15364.
No. 0, No. 61-145557, No. 63-208042 and West German Patent No. 3
No. 823049A.

The total addition amount of the cyan coupler represented by the formula (C) is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more of the total cyan couplers.

The cyan coupler represented by the formula (C) is preferably used in combination of two or more kinds. When the same color-sensitive layer is divided into two or more layers having different sensitivities, a 2-equivalent cyan coupler is used in the highest sensitivity layer. It is preferable to use a 4-equivalent cyan coupler in the lowest sensitivity layer. It is preferable to use one or both of them in the same color-sensitive layer other than the above.

Other constitutions of the emulsion layer of the silver halide photographic light-sensitive material of the present invention are not particularly limited, and various additives can be used as needed. For example, Research Disclosure Volume 176, p.22-2
8, binders, surfactants, described in December 1978,
Dyes, ultraviolet absorbers, hardeners, coating aids, thickeners, plasticizers and the like can be used.

The surface of the photographic light-sensitive material of the present invention is gelatin or a water-soluble polyvinyl compound or a natural polymer (for example, U.S. Pat. Nos. 3,142,568, 3,193,386 and 3,062,674).
No.) as a main component. The surface protective layer may contain a surfactant, an antistatic agent, a matting agent, a slip agent, a curing agent, a thickening agent, etc., in addition to gelatin or another polymer substance.

The photographic light-sensitive material of the present invention may further include an intermediate layer,
It may have a filter layer, an antihalation layer and the like.

In the photographic light-sensitive material of the present invention, the photographic emulsion and other layers are coated on a flexible support such as a plastic film, paper or cloth usually used for photographic light-sensitive materials. What is useful as a flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate (PET), and polycarbonate.
It is a paper or the like coated or laminated with a baryta layer or an α-olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored using a dye or a pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with the photographic emulsion layers.
The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

In the present invention, the method of coating an emulsion layer containing silver halide grains, a surface protective layer and the like on the support is not particularly limited, but for example, U.S. Patents 2,761,418 and 3,508,947
No. 2,761,791 and the like can be preferably used.

The layer structure of the photographic light-sensitive material of the present invention is not particularly limited. That is, the silver halide emulsion according to the present invention has only to be present between the support and the surface protective layer, and the photographic light-sensitive material is optimally constructed according to its main purpose of use. A layer or the like containing an ultraviolet absorber or a dye is also appropriately used. These layers may be on only one side or both sides of the support. The silver halide emulsion layer may be composed of a plurality of silver halide emulsion layers spectrally sensitized to different or the same wavelength, or may be composed of a single layer.

The silver halide photographic light-sensitive material of the present invention is specifically a color photographic light-sensitive material such as a color negative film, a color reversal film, a color paper, a color diffusion transfer light-sensitive material, a black and white negative film, an X-ray light-sensitive material (indirect). For X-ray,
(For direct X-rays), lith-type photosensitive materials, black-and-white photographic photosensitive materials such as black-and-white printing paper, and the like.

For the photographic processing of the light-sensitive material of the present invention, any one of known methods and known processing solutions as described in Research Disclosure, No. 176, p. 28-30 (RD-17643) may be applied. You can This photographic process is a photographic process that forms a dye image according to the purpose (color photographic process),
Alternatively, any of photographic processing (color photographic processing) for forming a silver image may be used. The treatment temperature is usually selected from 18 ° C to 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C.

When a dye image is formed, an ordinary method can be applied. For example, the negative-positive method (eg, Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion
Picture and Television Engineers) Volume 61, 1953,
p.667-701. Color reversal to obtain a positive dye image by developing with a developer containing a black-and-white developing agent to form a negative image, followed by at least one uniform exposure or other suitable fog treatment, followed by color development. Method: A silver dye bleaching method is used in which a photographic emulsion layer containing a dye is exposed and then developed to form a silver image, and the dye is bleached using this as a bleach catalyst.

The color developer generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 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-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Meta-methanesulfoamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline) can be used.

In addition, LFA Mason Photographic Processing Chemistry (Photographic Pro
cessing Chemistry) (Focal Pres
s), 1966), p.226-229, U.S. Pat.
Those described in JP-A-2,592,364 and JP-A-48-64,933 may be used.

To the color developing solution, a pH buffer, a development inhibitor, an antifoggant, a water softener, a preservative, an organic solvent, a development accelerator, a carboxylic acid chelating agent, etc. can be added to the color developing solution, if necessary. . Specific examples of these additives are
Disclosure (RD-17,643) and US Patent 4,08
No. 3,723, West German Open (OLS) No. 2,622,950, etc.

Developers used in black-and-white photographic processing can contain commonly known developing agents. As a developing agent, dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3-
Pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol) and the like can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, etc., and if necessary, dissolution aids, color toning agents, development accelerators (eg, quaternary ammonium salt, hydrazine). , Benzyl alcohol), a surfactant, an antifoaming agent, a water softener, a film hardening agent (eg, glutaraldehyde), a viscosity imparting agent, and the like.

As a special form of development processing, the developing agent in the photosensitive material,
For example, a method may be used in which the photosensitive material is contained in the emulsion layer and the photosensitive material is processed in an alkaline aqueous solution for development. Among the developing agents, hydrophobic ones are contained in the emulsion layer by various methods described in Research Disclosure, 169 (RD-16,928), US Patent 2,739,890, British Patent 813,253 or West German Patent 1,547,763. be able to. Such a development treatment may be combined with a silver salt stabilization treatment with thiocyanate.

As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixer may contain a water-soluble aluminum salt as a hardener.

Examples of the present invention will be shown below, but the present invention is not limited to the following examples.

[Example 1] A silver halide emulsion of the present invention and a comparative silver halide emulsion were prepared as follows.

(Preparation of Seed Crystal Emulsion A) With reference to JP-A-63-151,618, US Pat. No. 4,797,354 and West German Patent 3,707,135-A1, the following double structure of silver iodobromide tabular silver halide seed crystal is prepared. Emulsion A was prepared.

Core: 13.3% of total seed crystal silver / iodine content = 0 Zero Shell: 86.7% of total seed silver / average iodine content = 10.9
mol% As shown in the following examples, the manifestation of the effects of the present invention is not directly related to the content of seed crystal formation, and the finally formed silver halide emulsion satisfies the requirements of the present invention. I wish I had it.

(Preparation of Seed Crystal Emulsion B) A silver bromide tabular plate having substantially the same size but a high aspect ratio was prepared in the same manner as in Seed Crystal Emulsion A except that the iodine content of the shell of Seed Crystal Emulsion A was set to zero. -Like silver halide seed crystal emulsion B was prepared.

(Emulsion EM-1: Emulsion of the present invention) While stirring seed crystal emulsion A (containing 167.6 g of silver in terms of AgNO ₃ and 39 g of gelatin) kept at 40 ° C. (solution 1-1a)
And (1-1b solution) were added simultaneously over 5 minutes.

(1-1a solution) AgNO ₃ 8.2g H ₂ O 200cc (1-1b solution) KI 6.1g H ₂ O 200cc Next, while maintaining pAg at 9.7, (1-2a solution) and (1-2b solution)
Liquid) was added simultaneously over 36 minutes.

(1-2a solution) AgNO ₃ 66g H ₂ O 300cc (1-2b solution) KBr 46.2g H ₂ O 300cc Next, (1-3 solution) was added and pAg was adjusted to 9.4,
While maintaining this value, (1-4a solution) and (1-4b solution) were simultaneously added over 10 minutes.

(1-3 solution) KSCN (1N) 32cc (1-4a solution) AgNO ₃ 19.5g H ₂ O 200cc (1-4b solution) KBr 13.7g H ₂ O 200cc Then, after desalting according to the usual method, gelatin Was optimally sensitized with chloroauric acid and sodium thiosulfate. This silver halide emulsion is designated as Emulsion EM-1.

(Emulsion EM-2: Emulsion according to the present invention) In the preparation of the emulsion EM-1, (1-4b solution) was added to (2-
Silver halide grains were formed in the same manner as in Emulsion EM-1 except that the liquid 4b) was used.

(Solution 2-4b) KI 0.95 g KBr 13.0 g H ₂ O 200 cc Thereafter, desalting was performed in the same manner as in the emulsion EM-1, gelatin was added, and gold-sulfur sensitization was further optimally performed. This silver halide emulsion is designated as Emulsion EM-2.

(Emulsion EM-3: Emulsion according to the present invention) In the preparation of the emulsion EM-1, (1-4b solution) was added to (3-
Silver halide grains were formed in the same manner as in Emulsion EM-1 except that the liquid 4b) was used.

(Solution 3-4b) KI 1.91 g KBr 12.3 g H ₂ O 200 cc Thereafter, desalting was performed in the same manner as in the emulsion EM-1, gelatin was added, and optimal gold sulfur sensitization was performed. This silver halide emulsion is designated as Emulsion EM-3.

(Emulsion EM-4: Emulsion for comparison) Silver halide grains were formed in the same manner as in Emulsion EM-2 except that (1-3 Solution) was prepared in the preparation of Emulsion EM-2.

After this, gelatin was added after desalting in the same manner as Emulsion EM-2, and gold-sulfur sensitization was further optimally performed. At the time of this gold sulfur sensitization, 5.0 × 10 ^-6 mol of KSCN was added to Ag. This silver halide emulsion is designated as Emulsion EM-4.

(Emulsion EM-5: Emulsion for comparison) In the preparation of the emulsion EM-2, (1-1a solution) and (1-
Silver halide grains were formed in the same manner as Emulsion EM-2 except for 1b solution).

After this, gelatin was added after desalting in the same manner as Emulsion EM-2, and gold-sulfur sensitization was further optimally performed. This silver halide emulsion is designated as Emulsion EM-5.

(Emulsion EM-6: Emulsion for comparison) In the preparation of the emulsion EM-2, seed crystal emulsion A was seed crystal emulsion B (containing 167.6 g of silver in terms of AgNO ₃ and 39 g of gelatin).
Silver halide grains were formed in the same manner as in Emulsion EM-2 except that the above was used.

After this, gelatin was added after desalting in the same manner as Emulsion EM-2, and gold-sulfur sensitization was further optimally performed. This silver halide emulsion is designated as Emulsion EM-6.

(Emulsion EM-7: Emulsion according to the present invention) In the preparation of the emulsion EM-1, (1-3 solution) was added to (1-
Solution 2a) and solution (1-2b) were added 13 minutes and 30 seconds after the start of addition. At this point the pAg was changed to 9.4. In addition, (1-4a
Solution) and (1-4b solution) were removed. Except for this, silver halide grains were formed in the same manner as Emulsion EM-1.

After that, gelatin was added after desalting in the same manner as in the emulsion EM-1, and gold-sulfur sensitization was optimally performed. This silver halide emulsion is designated as Emulsion EM-7.

(Emulsion EM-8: Emulsion according to the present invention) In the preparation of the emulsion EM-1, (1-3 solution) was added to (1-
22 minutes and 19 seconds after the start of addition of (2a solution) and (1-2b solution), the pAg was changed to 9.4. From this point (8-1 solution)
Was added until the addition of (1-2a solution) and (1-2b solution) was completed. Further, (1-4a solution) and (1-4b solution) were removed. Except for this, silver halide grains were formed in the same manner as Emulsion EM-1.

(Solution 8-1) KI 1.23 g H ₂ O 40 cc Thereafter, desalting was carried out in the same manner as in the emulsion EM-1, gelatin was added, and gold sulfur sensitization was further optimally carried out. This silver halide emulsion is designated as Emulsion EM-8.

(Emulsion EM-9: Emulsion according to the present invention) In the preparation of the emulsion EM-1, (1-3 solution) was added to (1-
The solution (2a) and the solution (1-2b) were added 29 minutes and 9 seconds after the start of addition, and the pAg was further changed to 9.4. From this point (8-1 solution)
Was added until the addition of (1-2a solution) and (1-2b solution) was completed. Further, (1-4a solution) and (1-4b solution) were removed. Except for this, silver halide grains were formed in the same manner as Emulsion EM-1.

After that, gelatin was added after desalting in the same manner as in the emulsion EM-1, and gold-sulfur sensitization was optimally performed. This silver halide emulsion is designated as Emulsion EM-9.

(Emulsion EM-10: Comparative Emulsion) Silver halide grains were formed in the same manner as in Emulsion EM-8 except that (1-3 Solution) was removed from the preparation of Emulsion EM-8.

After that, gelatin was added after desalting as in the case of Emulsion EM-8, and gold-sulfur sensitization was optimally performed. For this gold-sulfur sensitization, 5.0 × 10 ⁻⁶ mol of KSCN was added to 1 mol of Ag. This silver halide emulsion is designated as Emulsion EM-10.

(Emulsion EM-11: Emulsion for comparison) In the preparation of the emulsion EM-8, (1-1a solution) and (1-
Silver halide grains were formed in the same manner as Emulsion EM-8 except that the 1b solution) was removed.

After that, gelatin was added after desalting as in the case of Emulsion EM-8, and gold-sulfur sensitization was optimally performed. This silver halide emulsion is designated as emulsion EM-11.

(Emulsion EM-12: comparative emulsion) Emulsion EM-8 except that seed crystal emulsion A was replaced with seed crystal emulsion B containing the same amount of silver and gelatin as seed crystal emulsion A in the preparation of emulsion EM-8. Similarly, silver halide grains were formed.

After that, gelatin was added after desalting as in the case of Emulsion EM-8, and gold-sulfur sensitization was optimally performed. This silver halide emulsion is designated as Emulsion EM-12.

 The characteristics of these emulsions EM-1 to 12 are shown in Table 1.

In Table 1, “average number of dislocation lines per grain” and “average aspect ratio” are average values for grains having a diameter of 0.4 μm or more. The SCN content in Table 1 is a value obtained by quantitatively analyzing the silver halide emulsion after the desalting process and after chemical sensitization by an ion chromatography method or a gas chromatography method.

When the average grain diameters of Emulsions EM-1 to 12 were measured, the average diameters of grains having a diameter of 0.4 μm or more were substantially the same (about 1.4 μm) within the error of measurement.

Next, each layer having the composition shown below was multilayer-coated on the undercoated cellulose triacetate film support to prepare a sample as a multilayer color light-sensitive material.

Shows the coating amount expressed in units of number g / m ² for the nuclear component,
For silver halide, the coating amount is expressed in terms of silver. However, with respect to the sensitizing dye, the coating amount per mol of silver halide in the same layer is shown in mol unit.

(Detailed layer structure) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 Second layer (intermediate layer) 2,5-t-pentadecylhydroquinone 0.18 EX-1 0.070 EX-3 0.020 EX-12 2.0 × 10 ^-3 U-1 0.060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 Sensitizing dye I 6.9 × 10 ^-5 sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 3.1 × 10 ^-4 EX-2 0.34 EX-10 0.020 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0.060 Gelatin 0.87 4th Layer (second red-sensitive emulsion layer) Emulsion G Silver 1.00 Sensitizing dye I 5.1 × 10 ⁻⁵ Sensitizing dye II 1.4 × 10 ⁻⁵ Sensitizing dye III 2.3 × 10 ⁻⁴ EX-2 0.40 EX-3 0.050 EX− 10 0.015 U-1 0.070 U-2 0.050 U-3 0.070 Gelatin 1.30 Fifth layer (third red emulsion layer) Emulsion D Silver 1.60 Sensitizing dye I 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 EX-2 0.097 E X-3 0.010 EX-4 0.080 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80 7th layer (1st green sensitive emulsion layer) Emulsion A Silver 0.15 Emulsion B Silver 0.15 Sensitizing dye IV 3.0 × 10 ^-5 Sensitizing dye V 1.0 × 10 ^-4 Sensitizing dye VI 3.8 × 10 ^-4 EX-1 0.021 EX-6 0.26 EX-7 0.030 EX-8 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63 Eighth layer (second green emulsion layer) Emulsion C Silver 1.45 Sensitizing dye IV 2.1 × 10 ^-5 Sensitizing dye V 7.0 × 10 ^-5 Sensitizing dye VI 2.6 × 10 ^-4 EX -6 0.094 EX-7 0.026 EX-8 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.50 9th layer (3rd green emulsion layer) Emulsion E Silver 1.20 Sensitizing dye IV 3.5 × 10 ^-5 Sensitizing dye V 8.0 × 10 ^-5 Sensitizing dye VI 3.0 × 10 ^-4 EX-1 0.025 EX-11 0.10 EX-13 0.015 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 10th layer (yellow filter layer) Yellow colloidal silver Silver 0.050 EX-5 0.080 HBS-1 0.030 Gelatin 0.95 11th layer The first blue-sensitive emulsion layer) Emulsion A silver 0.080 Emulsion B silver 0.070 Emulsion F silver 0.070 Sensitizing dye ^{VII 3.5 × 10 -4 EX-8} 0.042 EX-9 0.72 HBS-1 0.28 Gelatin 1.10 12th layer (2nd blue-sensitive Emulsion layer) Emulsion G Silver 0.45 Sensitizing dye VII 2.1 × 10 ^-4 EX-9 0.15 EX-10 7.0 × 10 ^-3 HBS-1 0.050 Gelatin 0.78 13th layer (3rd blue sensitive emulsion layer) Emulsion H Silver 0.77 increase Sensitizing dye VII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.070 Gelatin 0.69 14th layer (first protective layer) Emulsion I Silver 0.20 U-4 0.11 U-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00 No. 15 layers (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Furthermore, preserved in all layers W-1, in order to improve heat resistance, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property,
W-2, W-3, B-4, B-5, F-1, F-2, F
-3, F-4, F-5, F-6, F-7, F-8, F-
9, F-10, F-11, F-12, F-13, and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

In particular, from the standpoint of storability, in accordance with the regulations of the present invention, in the emulsions to which the emulsions EM-1 to EM-12 shown in this example are applied, F-
2, F-3 3.0 × 10 ^-4 mol / mol Ag, 4.0 × 10 ^-4
mol / mol Ag was added.

The contents of Emulsions A to I used for preparing the samples are shown in Table 2.
The chemical structural formulas of various compounds are shown in Table B below.

The coated samples thus obtained correspond to emulsion numbers EM-1 to 12 and are designated as sample SP-1 to 12. For these samples,
A 20 cms, 1/100 sec wedge exposure was applied with a light source having a color temperature of 4800 ° K. After that, development processing was performed according to the following processing steps.

The four types of color phenomenon processing are shown below, but the samples of the present invention and the comparative sample exhibited substantially the same photographic performance in any of the color development processings of A to D below.

Processing method (A) Process processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ℃ 25ml 10 Bleach 45 seconds 38.0 ℃ 5ml 5 Fixing (1) 45 seconds 38.0 ℃ -5 Fixing (2) 45 seconds 38.0 ℃ 30ml 5 Stable (1) 20 seconds 38.0 ℃ -5 Stable (2) 20 seconds 38.0 ℃ -5 Stable (3) 20 seconds 38.0 ℃ 40ml 5 Dry 1 minute 55 ℃ Replenishment amount is 35mm width 1m ² Fixing is (2 )-(1) Counter-current method Fixing is (3)-(1) counter-current method The amount of developer brought into the bleaching process and the amount of fixer brought into the stabilizing process are 35 mm wide. The photosensitive materials were 2.5 ml and 2.0 ml per 1 m length, respectively.

 The composition of the treatment liquid is shown below.

(Fixer) Mother liquor and replenisher (g) Ethylenediaminetetraacetic acid disodium salt 1.7 Sodium sulfite 14.0 Sodium bisulfite 10.0 Ammonium thiosulfate aqueous solution (70% weight / volume) 210.0 ml Ammonium thiocyanate 163.0 Thiourea 1.8 Add water 1.0 pH 6.5 (stabilizer) common to mother liquor and replenisher (g) Surfactant 0.5 Surfactant 0.4 Triethanolamine 2.0 1,2-Benzisothiazolin-3-one Methanol 0.3 Formalin (37%) 1.5 Add water 1.0 pH 6.5 (Wash water) Mother liquor and replenisher common Tap water is H type strong acid cation exchange resin (Amberlite 1R-120B manufactured by Rohm and Haas) and OH type strong basic anion exchange resin (Amberlite 1RA-400). Water is passed through a packed mixed bed column to reduce the concentration of sulphium and magnesium ions to 3 mg / or less, followed by 20 mg of sodium diisocyanurate dichloride and 150 mg of sodium sulfate.
/ Was added. The pH of this solution was in the range of 6.5-7.5.

(Stabilizer) Common to mother liquor and replenisher (Unit: g) Formalin (37%) 1.2 ml Surfactant 0.4 Ethylene glycol 1.0 Addition of water 1.0 pH 5.0-7.0 Processing method (C) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 1 minute 00 seconds 38 ℃ Bleaching fixing 3 minutes 15 seconds 38 ℃ Washing with water (1) 40 seconds 35 ℃ Washing with water (2) 1 minute 00 seconds 35 ℃ Stabilization 40 seconds 38 ℃ Drying 1 minute 15 seconds 55 ℃ Next, write the composition of the treatment liquid.

(Color developing solution) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N-β-hydroxyethylamino]
2-Methylaniline sulfate 4.5 Add water 1.0 pH 10.05 (bleaching solution) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0 ml Add water 1.0 pH 6.3 (Bleach fixer) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70 %) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 pH 7.2 (Aqueous solution) Tap water is exchanged with H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange. Water was passed through a mixed-bed column packed with resin (Amberlite IR-400) to treat calcium and magnesium ions at a concentration of 3 mg / or less, followed by sodium diisocyanurate dichloride 20 mg / and sodium sulfate 0.15 g / Was added. The pH of this solution is in the range 6.5-7.5.

(Stabilizer) (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 is added to 1.0 pH 5.0-8.0 Treatment method (D) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 6 minutes 30 seconds 38 ℃ Water wash 2 minutes 10 seconds 24 ℃ Settling 4 minutes 20 seconds 38 ℃ Water wash (1) 1 minute 05 seconds 24 ℃ Washing with water (2) 1 minute 00 seconds 24 ° C Stability 1 minute 05 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C Next, the composition of the treatment liquid is described.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxyamine sulfate 2.4 4- [N- Ethyl-N-β-hydroxyethylamino]
2-Methylaniline sulfate 4.5 Add water 1.0 pH 10.05 (bleaching solution) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water ( 27%) 6.5 ml Water 1.0 pH 6.0 (fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170.0 ml Water 1.0 pH 6.7 (Stabilizer) (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 is added to 1.0 pH 5.0-8.0 Third The table shows the photographic sensitivity of samples SP-1 to SP-12. Third
The sensitivity S in the table is expressed as follows using the exposure amount E (cms) corresponding to the position of the optical density of the fog on the sensitomer curve plus the optical density of 0.2.

S _x = (E _s / E _x ) × 100 where E _x is the exposure amount that gives the above-mentioned sensitivity point of the sample x. E _s is the exposure dose that gives the above-mentioned sensitivity point of the sample having the lowest sensitivity among the samples SP-1 to SP-12. Therefore, in this sensitivity definition, the sensitivity is expressed as a relative sensitivity to the sample showing the lowest sensitivity, and the higher the sensitivity, the larger the value is displayed. The B sensitivity, G sensitivity, and R sensitivity are sensitivities measured through the B filter, G filter, and R filter as shown in FIG.
It corresponds to the sensitivity evaluation of silver halide emulsions applied to the green-sensitive emulsion layer and the red-sensitive emulsion layer. In FIG. 1, the horizontal axis represents the wavelength of light and the vertical axis represents the transmittance.

From Table 3, the samples using the silver halide emulsion according to the present invention are the main blue-sensitive emulsion layers of the silver halide color light-sensitive material,
It can be easily seen that both the green-sensitive emulsion layer and the red-sensitive emulsion layer exhibit higher sensitivity than the sample using the comparative silver halide emulsion. Further, looking at Table 3 in detail, in particular, the effect of the present invention is more remarkable in the green-sensitive emulsion layer than in the blue-sensitive emulsion layer, and more remarkable in the red-sensitive emulsion layer. I know there is.

Among the factors that define the effect of the present invention, the above-mentioned emulsion EM-4 and emulsion EM-10 are compounds X (QCN) _n [specifically (1- 3 liquid)] is not added, the multilayer color light-sensitive materials SP-4 and SP-10 using them cannot exhibit the effect of the present invention. However, when SP-4 and SP-10 are respectively coated on a support in multiple layers, coating solutions of emulsions A to I, that is, emulsion EM-4 or emulsion EM-10, which is an emulsion of all emulsion layers in the light-sensitive material 1 x 10 ^-3 mol of KSCN or 1 x 10 ^-3 mol of Na per mol of silver halide when preparing the coating solution
A multilayer color light-sensitive material was prepared by adding SCN. These coated samples were made to correspond to emulsion numbers EM-4 and EM-10, and SP-
4 ', SP-10'. When the photographic characteristics of SP-4 'and SP-10' were examined under the above-mentioned exposure and processing conditions, similar results to those of SP-2 and SP-8 were obtained. That is, even if the (1-3 solution) is not used in the grain formation of a silver halide emulsion, the total amount of silver halide in all emulsion layers in the light-sensitive material is finally averaged to 1 mol of silver halide. On the other hand, it can be seen that the effect of the present invention can be obtained when the SCN is contained in the specified amount or more.

The effects of the present invention were exhibited regardless of the method of adding the sensitizing dye, and substantially the same results as the results shown in Table 3 were obtained. That is, for example, after the silver halide grains are formed, before the chemical sensitization, the above-mentioned corresponding sensitizing dye is completely adsorbed in advance and then chemically sensitized, or a part of the sensitizing dye is chemically sensitized. Adsorption and then chemical sensitization followed by the addition of the remaining sensitizing dye gave substantially the same results as in Table 3.

Example 2 A silver halide emulsion according to the present invention and a comparative silver halide emulsion were prepared as follows.

(Emulsion EM-13: Emulsion according to the present invention) In the preparation of the emulsion EM-1, (1-1b solution) was added to (13-
1b solution), replace (13-2 solution) with (1-1a solution), (13-1b
Solution) It was added 2 minutes and 30 seconds after the start of addition. (1-1a solution),
After the addition of (13-1b solution) was completed, pAg was adjusted to 9.7.

(13-1b solution) KBr 5.7g H ₂ O 200cc (13-2 solution) KI 6.1g H ₂ O 100cc Silver halide grains were formed in the same manner as the emulsion EM-1 except for the above.

After that, gelatin was added after desalting in the same manner as in the emulsion EM-1, and gold-sulfur sensitization was optimally performed. This silver halide emulsion is designated as Emulsion EM-13.

(Emulsion EM-14: Emulsion according to the present invention) In the preparation of the emulsion EM-13, (13-2 solution) was added to (14-
Silver halide grains were formed in the same manner as in Emulsion EM-13 except that the first liquid was used.

Then, after desalting in the same manner as in Emulsion EM-13, gelatin was added to perform optimum gold sulfur sensitization. This silver halide emulsion is designated as Emulsion EM-14.

(14-1 solution) KI 8.0g H ₂ O 100cc (emulsion EM-15: emulsion according to the present invention) (13-2 solution) was replaced with (1-
Silver halide grains were formed in the same manner as in Emulsion EM-13, except that 1a solution) and (13-1b solution) were added 1 second after the start of addition.

Then, after desalting in the same manner as in Emulsion EM-13, gelatin was added to perform optimum gold sulfur sensitization. This silver halide emulsion is designated as Emulsion EM-15.

(Emulsion EM-16: Emulsion according to the present invention) In the preparation of the emulsion EM-13 (solution 1-1a), (13-
(1b solution) 10 seconds after the addition is completed, (1-2a solution), (1-2a solution)
Silver halide grains were formed in the same manner as Emulsion EM-13 except that (13-2 solution) was added before the addition.

Then, after desalting in the same manner as in Emulsion EM-13, gelatin was added to perform optimum gold sulfur sensitization. This silver halide emulsion is designated as emulsion EM-16.

(Emulsion EM-17: Comparative Emulsion) Silver halide grains were formed in the same manner as Emulsion EM-13 except that (13-2 Solution) was not added in the preparation of Emulsion EM-13.

Then, after desalting in the same manner as in Emulsion EM-13, gelatin was added to perform optimum gold sulfur sensitization. This silver halide emulsion is designated as Emulsion EM-17.

(Emulsion EM-18: Comparative Emulsion) Silver halide grains were formed in the same manner as in Emulsion EM-13 except that (1-3 Solution) was not added in the preparation of Emulsion EM-13.

Then, after desalting in the same manner as in Emulsion EM-13, gelatin was added to perform optimum gold sulfur sensitization. For this gold-sulfur sensitization, 5.0 × 10 ⁻⁶ mol of KSCN was added to 1 mol of Ag. This silver halide emulsion is designated as Emulsion EM-18.

When the average grain diameters of the emulsions EM-13 to 18 were measured, the average diameters of the grains having a diameter of 0.4 μm or more were substantially the same (about 1.4 μm) within the error of measurement.

 The characteristics of these emulsions EM-13 to 18 are shown in Table 4.

In Table 4, "average number of dislocation lines per grain" and "average aspect ratio" are average values for grains having a diameter of 0.4 µm or more. The SCN content in Table 1 is a value obtained by quantitatively analyzing the silver halide emulsion after the desalting process and after chemical sensitization by an ion chromatography method or a gas chromatography method.

Using these emulsions EM-13-18, Example 1 shown above
A coated sample of a multilayer color light-sensitive material was prepared in the same manner as in. These coated samples correspond to emulsion numbers EM-13 to 18, and
-13 to 18 These samples were exposed and color-developed in the same manner as in Example 1. Sample SP-13-18
Shows substantially the same photographic performance in any of the four types of color development processing A to D shown in Example 1.

 Table 5 shows the photographic sensitivity of Samples SP-13 to 18.

The optical density measurement of the sample was performed in the same manner as in Example 1, and the sensitivity notation was performed in the same manner as in Example 1.

From Table 5, samples using the silver halide emulsion according to the present invention are the main blue-sensitive emulsion layers of the silver halide color light-sensitive material,
It can be easily seen that both the green-sensitive emulsion layer and the red-sensitive emulsion layer exhibit higher sensitivity than the sample using the comparative silver halide emulsion. Further, looking at Table 5 in detail, in particular, the effect of the present invention is more remarkable in the green-sensitive emulsion layer than in the blue-sensitive emulsion layer, and more remarkable in the red-sensitive emulsion layer. I know there is.

Among the factors that determine the effect of the present invention, the above-mentioned emulsion EM-18 contains compound X (QCN) _n [specifically (1-3 solution)] of the present invention in the process of forming silver halide emulsion grains. Since they are not added, multi-layer color photosensitive materials SP using them
-18 failed to exhibit the effect according to the present invention. However, when SP-18 is coated on a support in a multi-layered manner, a halogenated liquid is prepared when preparing coating liquids of emulsions A to I, that is, emulsions of all emulsion layers in a light-sensitive material containing emulsion EM-18. 1 × 10 ^-3 mol of KSCN or 1 × 10 ^-3 mol per mol of silver halide
NaSCN was added to make a multilayer color light-sensitive material. These coated samples are designated as SP-18 ', corresponding to emulsion number EM-18. When the photographic characteristics of SP-18 'were examined under the above-mentioned exposure and processing conditions, similar results to SP-13 were obtained.
That is, in the grain formation of a silver halide emulsion (1-3
Even if the specified amount of (solution) is not used, SCN is contained in an amount not less than the specified amount of the present invention per 1 mol of silver halide finally averaged over the total amount of silver halide in all emulsion layers of the light-sensitive material. For example, it can be seen that the effects of the present invention can be obtained.

The effects of the present invention were exhibited regardless of the method of adding the sensitizing dye, and substantially the same results as those shown in Table 5 were obtained. That is, for example, after the silver halide grains are formed, before the chemical sensitization, the above-mentioned corresponding sensitizing dye is completely adsorbed in advance and then chemically sensitized, or a part of the sensitizing dye is chemically sensitized. Adsorption and then chemical sensitization followed by the addition of the remaining sensitizing dyes gave substantially the same results as in Table 5.

[Brief description of the drawings]

FIG. 1 is a diagram showing the spectral transmittance curves of the B filter, G filter, and R filter used in the examples.

Claims (2)

(57) [Claims] 1. A tabular silver halide grain having a diameter of 0.4 μm or more occupies 50% or more of the total projected area of all silver halide grains in an emulsion, and these tabular silver halide grains having a diameter of 0.4 μm or more. For an average aspect ratio of 3 to less than 8 having an average of 10 dislocation lines per grain. A tabular silver halide emulsion characterized in that it comprises a nitrogen-containing heterocyclic compound having a mercapto group and formed in the presence of a compound represented by the following general formula. General formula: in X (QCN) _n formula, X is an n-valent cation, n represents a number from QCN groups bonded to the n-valent cation. Here, Q is S or Se. 2. The silver halide emulsion according to claim 1, wherein the nitrogen-containing heterocyclic compound having a mercapto group is represented by the following general formula (II). General formula (II) In the formula, R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, which is substituted with at least one —COOM or —SO ₃ M,
M represents a hydrogen atom, an alkali metal, a quaternary ammonium or a quaternary phosphonium.