JP2690392B2 - Silver halide photographic emulsion and silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is applicable not only to medium illuminance (10 ^-1 to 10 ^-3 sec) exposure,
The present invention relates to a tabular silver halide photographic emulsion and a silver halide photographic light-sensitive material capable of obtaining high sensitivity even when exposed to high illuminance (10 ^-4 to 10 ^-5 sec).

(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, high sensitivity and high 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 per silver halide grain is The size ratio must be improved. Use of tabular silver halide grains is one of the techniques for improving the sensitivity / size ratio.
58-108,525, 58-111,935, 58-111,936,
58-111,937, 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. It can be said that a large amount of dye can be adsorbed on the silver halide grains, which is very advantageous for improving the sensitivity / 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, the surface area /
The tabular silver halide grains having a large volume ratio can adsorb a large amount of sensitizing dye on the surface thereof, and thus the light absorption amount can be increased. Therefore, it can be said that the tabular silver halide grains are extremely advantageous because they give the silver halide light-sensitive material actually high sensitivity and high image quality.

Also, the tabular silver halide grains are oriented parallel to the support because of their morphological characteristics. Therefore, it is possible to make the silver halide emulsion layer thinner with the same amount of coated silver. As a result, the silver halide light-sensitive material can be provided with desirable properties such as improved rapid processing suitability, improved interlayer effect, and improved sharpness.

The tabularization rate of tabular silver halide grains is increased to increase the surface area /
Increasing the volume ratio has favorable results as described above. However, increasing the surface area / volume ratio causes the following inefficiency factors for the photographic process of silver halide. That is, Berry, CR, Journal of Photographic Science (Jour
nal of Photographic Science), Volume 21, 1973, p.202
According to the report, 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 normal silver halide light-sensitive material is about 0.1 to 10 μm, extremely increasing the surface area / volume ratio obviously has a disadvantageous effect on latent image formation.

As a means for compensating for the above-mentioned drawbacks of tabular silver halide grains, methods of positively introducing dislocation lines into silver halide grains are disclosed in JP-A-63-220,238 and 1-201,649. ing. According to the descriptions of these patents, tabular silver halide grains to which dislocation lines have been introduced to some extent are superior in photographic sensitivity and reciprocity law characteristics to those in which dislocation lines have not been introduced, and these are used in photosensitive materials. Although it is shown that the sharpness and the graininess are excellent, it is not yet satisfactory because the spatial control of the dislocation line introduction is insufficient.

On the other hand, in recent years, there has been an increasing tendency to use a high shutter speed especially for shooting sports scenes. In addition to shooting sports scenes, taking pictures with a high shutter speed reduces shooting failures due to camera shake at the time of shooting and increases focus depth by increasing the depth of field. It leads to the expansion of latitude. However, in general, when a photographic light-sensitive material is exposed at a high speed, high illuminance failure, which is considered to be caused by latent image dispersion, occurs as well known in the art, and the sensitivity decreases. The improvement only in this respect can be carried out by appropriately adjusting the chemical sensitization of the silver halide emulsion, but in this case, it causes a decrease in sensitivity in the low illuminance and medium illuminance exposed areas.

With such conventional silver halide grain forming technology and chemical sensitization adjusting technology, a silver halide emulsion capable of attaining sufficiently high sensitivity in both medium illuminance and high illuminance exposure regions has not been obtained.

(Problems to be Solved by the Invention) An object of the present invention is to sufficiently compensate for the above-mentioned drawbacks of the tabular silver halide emulsion so that high sensitivity can be obtained in both medium illuminance and high illuminance exposure regions. The object is to provide a tabular silver halide photographic emulsion and a silver halide photographic light-sensitive material.

(Means for Solving the Problems) It has been found that the problems of the present invention can be solved by a silver halide photographic emulsion or a silver halide photographic light-sensitive material having the following features.

(1) 50% of the total projected area of all silver halide grains in the emulsion
The above is occupied by tabular silver halide grains having a diameter of 0.4 μm or more, and 80% or more of the number of tabular silver halide grains having a diameter of 0.4 μm or more is substantially a dislocation line concentrated near the apex of the grain. Having an average aspect ratio of 2 or more, and the emulsion is 1 m of silver halide.
per ol A tabular silver halide photographic emulsion characterized in that grains are formed in the presence of the compound represented by the following general formula.

General formula: X (QCN) _{n In the} formula, n is a natural number of 1 to 5, and X represents an n-valent cation. Here, Q is S or Se.

(2) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of these emulsion layers is 50% of the total projected area of all silver halide grains in the emulsion. The above is occupied by tabular silver halide grains having a diameter of 0.4 μm or more, and 80% or more of the number of tabular silver halide grains having a diameter of 0.4 μm or more is substantially a dislocation line concentrated near the apex of the grain. A silver halide containing at least one tabular silver halide photographic emulsion having an average aspect ratio of 2 or more and containing the QCN compound in the general formula described in (1) above in the light-sensitive material. 1mo
A silver halide photographic light-sensitive material containing 1 × 10 ⁻⁵ mol or more per liter.

 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 the orientation of the tabular silver halide grain such 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 follows. The diameter of the i-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
When t _i , r is defined as 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 [1], 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.

The tabular grains preferably have a diameter of 0.4 to 5.0 μm. The thickness of the tabular grains is preferably from 0.05 to 0.5 μm.

The ratio of grains having a diameter of 0.4 μm or more to the whole emulsion grains is calculated from the sum of individual projected areas of grains having a diameter of 0.4 μm or more (S _t ) and the sum of projected areas of grains having a diameter of less than 0.4 μm (S _n ). (S _t / (S _t + S _n )) × 100 (%) [5] can be calculated. The value of σ may be 50% or more, preferably 80% or more, and particularly preferably 90% or more.

The tabular grains having a diameter of 0.4 μm or more may have an average aspect ratio of 2 or more, preferably 4 or more and less than 7.8, and particularly preferably 5 or more and less than 7.5.

(2) Detailed Aspects of Dislocation Lines Regarding the dislocation lines, tabular silver halide grains are prepared by intentionally introducing a controlled recrystallization process of silver halide grains in the preparation of silver halide emulsion grains as described later. Can be incorporated into. 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.

The dislocation lines of the silver halide grains of the present invention are substantially concentrated near the apexes of tabular grains. When a tabular grain has a triangular or hexagonal outer surface in the vicinity of its apex, the direction from the midpoint of the line segment (length l) connecting the center of the tabular grain and each apex to the apex (l / 2 ) A region including the apex of a region surrounded by a straight line drawn perpendicularly to the line segment from the point of xx and two sides, and a three-dimensional region over the entire thickness of the particle. Say. The value of x is preferably 0.5 or more and less than 1, and more preferably 0.7 or more and less than 0.9.

When the tabular grains are rounded, the vertices are ambiguous, but in this case as well, six tangents are obtained with respect to the outer circumference, and a straight line connecting the intersection of each tangent and the center of the tabular grains is obtained. , The point intersecting the outer circumference of the tabular grain can be obtained as the apex.

When the outer surface has a hexagonal shape, there are six vertices, and dislocation lines may be concentrated near each vertex. 6
Even if dislocation lines are concentrated in the vicinity of at least one of the vertices, the effect of the present invention can be obtained.

Here, the dislocation lines are substantially concentrated in the vicinity of the apexes of tabular grains, and the region within one grain including dislocation lines is strictly defined as the vicinity of the apex mentioned above by averaging the silver halide grain system. and the volume V _a of the region, the ratio of the volume V _b of the other dislocation lines containing _{region, V a / (V a +} V b)> 0.8 or where, dislocation lines number in V _a N _a and V the ratio of the dislocation line number N _b in _b is
It means that N _a / (N _a + N _b )> 0.8. However, in this case, V _a / (V _a + V _b )> 0.9 or N _a / (N _a
+ N _b )> 0.9 is preferable, and V _a / (V _a + V _b )>
It is particularly preferred that 0.95 or N _a / (N _a + N _b )> 0.95.

The tabular grains with dislocation lines concentrated near the apex have a diameter of 0.4μ.
It may be 80% or more of the total number of particles of m or more, preferably 90% or more, and particularly preferably 95% or more.

(3) Compound X (QCN) _n The general formula of the compound used in the present invention is X (QCN
N) given by _n . However, X is an atom or molecule that produces an n-valent cation, and n is bonded to the n-valent cation.
Represents the number of QCN groups. n is a natural number of 1 to 5. For example X when n = 1 is NH _4, K, N _a, and the like. n is preferably 1 to 3, and particularly preferably n = 1. Q is S or
S _e . Content is 1 × 10 ^-4 mol per mol of silver halide
The amount is preferably not less than 1 but is preferably 1 × 10 ⁻³ mol or more, particularly preferably 1 × 10 ⁻² mol or more.

The QCN used in the present invention may be present in at least one of the constituent layers on the support of the silver halide light-sensitive material, but is preferably contained in the silver halide emulsion according to the present invention. In the latter case, it is particularly preferable that X (QCN) _n is added during the formation of silver halide emulsion grains.

When a silver halide light-sensitive material having a multi-layer structure is constituted, it is possible that a particular silver halide emulsion layer does not contain QCN, but in such a case, in order to develop without impairing the effect of the present invention, , 1 × 10 ⁻⁵ mol or more, preferably 1 × 10 ^{5 with} respect to 1 mol of silver halide contained in the light-sensitive material
^-4 mol or more, particularly preferably 1.times.10.sup.- ³ mol or more of QCN should be contained. When X (QCN) _n is added to the silver halide emulsion, the addition position is preferably after the stage where 80% or more of the total Ag amount used for silver halide grain formation has been added, and 90% or more and 100% or less. Was added,
Moreover, the addition position before the desalting step is particularly preferable. Thus, such use of X (QCN) _n in the present invention is to add X (QCN) _{n when} the growth of silver halide grains has been sufficiently performed, and it is generally known in the art. The method of adding the compound in order to monodisperse the silver halide grains from the nucleation stage to the main growth stage of silver halide grain formation is completely different from the addition method of the present invention. 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. The preferred or particularly preferred addition position of X (QCN) _n of the present invention is not during chemical sensitization, and the added amount itself is 10% of that used as a gold ligand for ordinary gold sulfur sensitization.
It is about 1000 times, and the way it is used is completely different. Also, as described above, X (QCN) _n has only to be contained as QCN in the light-sensitive material even after chemical sensitization, and thereby the object of the present invention can be achieved.

Further, the use of X (QCN) _n in the present invention is not limited to the so-called host grain as disclosed in JP-A-59-162,540 (US Pat. It is completely different from the one that epitaxially grows the silver salt of. This is because no epitaxial growth of silver salt derived from X (QCN) _n is observed at any stage of the grain formation process of silver halide grains according to the present invention.

Among the X (QCN) _n described here, 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 on the high sensitivity and high image quality of the photographic light-sensitive material using the tabular silver halide emulsion according to the embodiment of the present invention was completely unexpected. Here, it was totally unexpected in the following sense that X (QCN) _n was allowed to act on silver halide grains containing high-density dislocation lines to achieve high sensitivity and high 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 the above-mentioned "Dislocation Theory: Its Application to Metallurgy-", p.83-84, edited by Akiya Okawa, "Advances in the Study of Lattice Defects", Agne, 1964, p.277-278 and W. Shockley, JH Hollomon,
R. Maurer, F. Seitz, “Imperfections in Nearly Perfect Crysta
ls) ”, John Wiley and Sons (John Wil)
ey & Sons), New York, p.403-406
Is found in For silver halide etch pits, see “Dislocation and Jr.” edited by JC Fisher, WG Johnston, R. Thomson, T. Vreeland, Jr.・ Mechanical Properties of Crystals (Dislocations and Mechanical Prop
erties of Crystals) -An International Conference Held at Lake Placid (An
International Conference held at Lake Placid) SEP
TEMBER6-8,1956, John Wiley & Sons (John Wiley & Sons), New York (New York),
See p.69-91. Therefore, the use of X (QCN) _n , which exerts a solvent action on silver halide grains having high-density dislocations, in a large amount range as defined in the present invention is such that the dislocation line portion is dissolved and the grains are remarkably deformed in the ordinary grain formation method. And the resulting reduction in silver halide photographic sensitivity. Particularly, as is well known in the art, since the apex portion of tabular silver halide grains has high solubility, the problem about such solubility is that dislocations occur in addition to the apex portions of tabular silver halide grains. It was expected to be more difficult to solve than with lines. However, as a result of intensive studies, we have found a method for achieving higher sensitivity and higher image quality without impairing the photographic features of silver halide having dislocation lines as in the embodiment of the present invention.

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 (Photographic Emulsion Chemistry)", New York, 1966, p.66-72, APH Triveri, 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 halogenated emulsions in which the grain sizes are well aligned is described, for example, in JP-A-63-151,618 and U.S. Pat.
Reference can be made to No. 3, West German Patent 3,707,135-A1 and JP-A-2-838.

In order to introduce a dislocation line near the apex, silver iodide or silver halide having a high silver iodide content is once bonded to the apex of the tabular grain, and the tabular grain is grown again.

Silver iodide or at least higher than the silver iodide content of the host grains, preferably 80 mol% or more of silver iodide is contained at the apex of the tabular grains, and the rest is silver iodide and / or silver chloride. To join the silver halide moieties with a high silver content, either by direct methods or by indirect methods via halogen conversion.

A method of bonding a guest, which is silver iodide, to a host grain having a face-centered cubic rock salt crystal structure by epitaxial growth,
It is disclosed in a broad sense in JP-A-59-162,540 (US4,463,087). According to this method, it is described that the attachment by epitaxial growth can be performed by selecting a silver salt that is non-isomorphic to the crystal structure of the host grain. However, in the examples, only edge selective growth such as local selective epitaxial growth of silver thiocyanate on octahedral silver bromide grains is disclosed. Only the example in which silver thiocyanate is selectively epitaxially grown on the edge of tabular grains of silver iodobromide (AgI 6 mol%) is disclosed, and a specific example of growing silver iodobromide on the apex of tabular grains is disclosed. Is not specifically disclosed.

As a result of diligent studies, the present inventors have found that tabular grains of silver iodobromide are used as hosts, and 0.5 to 10 mol%, preferably 1 to 6 mol%, of both aqueous solutions of potassium iodide and silver nitrate are rapidly doubled. By adding a jet, direct bonding can be achieved by epitaxially growing silver iodide or silver halide having a high silver iodide content on the apex of tabular grains without using any orientation director (site director). Found out. The addition time is preferably 5 to 0.2 minutes, more preferably 0.5 to 2 minutes.

Next, an indirect method for epitaxially bonding a silver iodide or a silver halide portion having a high silver iodide content to the apex of a tabular grain via halogen conversion will be described.

A method for epitaxially growing silver chloride on the apexes of tabular grains is described in JP-A-58-108,526 (US4,435,501). If the tabular grains of the host consist essentially of at least 8 mol% iodide on their surface, epitaxial growth of silver chloride occurs adjacent to the corner (vertex) even in the absence of an orientation controlling substance, The use of aqueous iodides and adsorptive orientation-controlling substances is also described in order to limit the epitaxial growth more narrowly at the edges.

As described in Example 4 of JP-A-58-108,526, the present inventors have made a tabular grain adsorb a cyanine dye,
It has been found that the method of epitaxially growing silver chloride at a corner is not preferable for achieving the object of the present invention. That is, even if the thus obtained epitaxial grains are converted to halogen with iodide and then tabular grains are grown, dislocation lines are introduced not only in the vicinity of the apex but also in the sides and the main surface. This is presumably because the sensitizing dye itself has a function of introducing dislocation.

The present inventors have found that it is preferable to use a water-soluble iodide as an alignment controlling substance in order to epitaxially grow silver chloride. That is, potassium iodide is typically used. It is preferable to use 0.03 to 3 mol%, preferably 0.5 to 1.5 mol% of potassium iodide with respect to the host tabular grains. This amount preferably corresponds to about 50 to 200% of the surface monoatomic coverage of the tabular grains. After that, when the amount of nitric acid and sodium chloride are added by the double jet method, silver chloride suitable for the purpose of the present invention can be grown on the apexes of tabular grains. The amount of silver nitrate added here is preferably 0.1 to 10 mol% based on the host tabular grains.

The halogen conversion of silver chloride by potassium iodide will be described. Highly soluble silver halide is converted to less soluble silver halide by adding halide ions that can form less soluble silver halide. This process is called halogen conversion and is described, for example, in US Pat. No. 4,142,900. In the present invention, a β-AgI phase is formed at the apex of tabular grains by selectively halogenating silver chloride epitaxially grown with potassium iodide. If the amount of potassium iodide for halogen conversion is too large, dislocation lines are dispersed, and if it is too small, desired dislocation lines disappear due to recrystallization that occurs in the subsequent grain growth stage. Further, in the process, if an appropriate amount of silver chloride phase does not exist in advance, potassium iodide causes halogen conversion with silver bromide, and dislocation lines do not concentrate in the subsequent grain growth. The amount of potassium iodide for halogen conversion is preferably from 0.1 to 10 mol% based on the host tabular grains.

 Next, the growth of dislocation lines will be described.

Directly bonding silver iodide by the direct method,
Substrate (host tabular grains)
Of silver bromide, silver iodobromide, silver chlorobromide, or β-AgI phase having a crystal form different from that of silver chloroiodobromide or a silver halide phase having a high silver iodide content is formed at the apex of tabular grains. To be done. When silver nitrate and potassium bromide or silver nitrate and a mixed solution of potassium bromide and potassium iodide are subsequently added at the same time, the grains grow further. At this time, dislocation lines are introduced starting from the β-AgI phase. Since the β-AgI phase is localized near the apex, dislocation lines are concentrated near the apex. The amount of silver nitrate added at this time is arbitrary as long as it is 5 mol% or more based on the substrate. When a mixed solution of potassium bromide and potassium iodide is added, the mixing ratio is preferably 0 to 0.4 in terms of molar ratio of potassium bromide to potassium bromide.

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. 2,448,060, 2,566,245, and 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,
Various compounds can be incorporated for the purpose of preventing fogging during storage or photographic processing and / or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles. ,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Etc .; mercaptopyrimidines; mercaptotriazines, for example thioketo compounds such as oxolinothione;
Azaindenes such as triazaindenes; tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazaindenes, etc .; benzenethiosulphones, benzenesulfinic acid, benzene Many compounds known as antifoggants or stabilizers such as sulphonic acid amides and the like can be added.
For example, U.S. Patents 3,954,474, 3,982,947, and Japanese Patent Publication No. 52
Those described in -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 ring-raising 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 an absorption 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 ring 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 cadmium 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, an aminophenol derivative, etc.) in color development processing, for example, a magenta coupler such as a 5-pyrazolone coupler or a pyrazolone benzimidazole. There are couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers such as naphthol couplers and phenol couplers. There is. These couplers are preferably non-diffusing couplers 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 couplerd 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, the product of the coupling reaction may contain a colorless DIR coupling compound which is colorless and releases a development inhibitor.

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, 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. Materials useful as flexible supports include cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
It is a film made of a semi-synthetic or synthetic polymer such as polyethylene terephthalate (PET) or polycarbonate, a baryter layer or a paper coated or laminated with a α-olefin polymer (eg polyethylene, polypropylene, ethylene / butene copolymer) or the like. 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 of known methods and known processing solutions such as those described in Research Discosure, No. 176, p. 28-30 (RD-17643) can be applied. be able to. This photographic processing may be either photographic processing for forming a dye image (color photographic processing) or photographic processing for forming a silver image (color photographic processing) depending on the purpose. 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 Moti
on Picture and Television Engineers) Volume 61, 1953
, Pp.667-701); producing a negative image developed with a developer containing a black and white developing agent, and then at least 1
A color reversal method in which a positive dye image is obtained by performing a single uniform exposure or other suitable fog treatment, followed by color development; a photographic emulsion layer containing the dye is exposed and developed to form a silver image, A silver dye bleaching method in which a dye is bleached using this as a bleach catalyst is used.

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 and the like) 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. Hydrophobic developing agents 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 fixing solution may contain a water-soluble aluminum salt as a curing agent.

(Example) Hereinafter, the present invention will be further described with reference to examples.

Example-1 (1) Preparation of Emulsion A. Preparation of Base Emulsion Preparation of Emulsion A-1 A 0.7% aqueous solution of low molecular weight gelatin containing 0.91 mol of potassium bromide was kept at 30 ° C. with stirring and the double jet method was applied thereto. By the same constant flow rate
1.01 molar aqueous solution of potassium bromide and silver nitrate over minutes
A 0.94 molar aqueous solution was added (12.7% of the total silver nitrate was consumed). After adding 400 ml of a 16% deionized gelatin solution, the temperature was raised to 75 ° C. Add 0.88 mol aqueous solution of silver nitrate to add pBr
After adjusting to 2.31 (consuming 3.7% of total silver nitrate), add 14.7N aqueous ammonia solution to adjust pH to 8.3, and after physical ripening, 3
The pH was adjusted to 5.5 again by adding N-nitric acid. Potassium bromide 1.33
A molar aqueous solution and a 0.88 molar aqueous solution of silver nitrate were added simultaneously for 30 minutes while maintaining pBr at 3.02 (consuming 83.6% of total silver nitrate). Then, desalting was carried out by a usual flocculation method to prepare a tabular AgBr emulsion A-1. The silver nitrate used was 156 g.

Emulsion A-2 (Ag of central region, central annular region and peripheral annular region)
Preparation of 16.7 / 67.3 / 16 ratio; silver iodide content in the 3 regions: 0 / 7.5 / 0) Deionized gelatin containing 0.57 mol of potassium bromide.
While maintaining 1.0 liter of 7% aqueous solution (solution A) at 30 ° C,
A 1.95 molar aqueous solution of potassium bromide (solution B) and a 1.9 molar aqueous solution of silver nitrate (solution C) were added thereto at the same constant flow rate for 30 seconds by the double jet method (total silver nitrate solution).
Consumed 2.06%). 8% deionized gelatin solution
After adding 400 ml, the temperature was raised to 75 ° C. A 1.12 molar aqueous silver nitrate solution (solution D) was added to adjust the pBr to 2.13, and a 14.7N aqueous ammonia solution (consuming 1.84% of the total silver nitrate) was added.
After physical aging with H adjusted to 8.3, add 1N nitric acid and adjust the pH to 5.
Adjusted to 5. 1.34 M aqueous potassium bromide solution (Solution E)
And solution D were added simultaneously with increasing the flow rate (final flow rate was 2.5 times the starting flow) while maintaining pBr at 1.56 (12.8% of total silver nitrate was consumed), followed by 1N
NaOH was added to adjust the pH to 9.3. Potassium bromide 1.34
The aqueous solution (solution F) and the solution D containing 0.108 mol of potassium iodide and 0.108 mol of potassium iodide were simultaneously accelerated at a flow rate (the flow rate at the end was 5.5 times that at the start) and the pBr was raised to 1.85 for 28.5 minutes.
Added while keeping at 56 (consumed 67.3% of total silver nitrate). Further, solution D and a 1.34 molar aqueous solution of potassium bromide (solution G) were simultaneously added while accelerating the flow rate (the flow rate at the end was twice that at the start) while maintaining the pBr at 2.42 (16% of total silver nitrate). % Consumed). It is then desalted by the usual flocculation method to obtain flat AgBr
I (AgI = 5.1 mol) Emulsion A-2 was prepared. The silver nitrate used was 156 g. The tabular silver iodobromide grains obtained had a surface silver iodide concentration of 2.6 mol% and an average silver iodide concentration of 5.1 mol%, and the central annular region had a higher silver iodide concentration than the peripheral annular region. Was shown.

Emulsion A-3 (Ag in central region, central annular region and peripheral annular region)
Ratio 16.7 / 67.3 / 16; Preparation of silver iodide content in the 3 regions: 0 / 4.6 / 12) In the method for preparing Emulsion A-2, the composition of solution F contained 1.35 mol of potassium bromide and 0.065 mol of potassium iodide. Solution G, and further changed the composition of solution G to potassium bromide 1.24.
Emulsion A-3 was prepared in the same manner (AgI = 5.0 mol% formulation) except that the aqueous solution contained 0.17 mol of potassium iodide and 0.17 mol of potassium iodide. The tabular silver iodobromide grains obtained showed a surface silver iodide concentration of 10.8 mol% and an average silver iodide concentration of 4.9 mol% (actually measured value)%. It was shown to be the silver concentration.

B. Preparation of grains having dislocation lines concentrated near the apex 50
0g of base emulsion A-1, A-2, A-3 (0.5molAg) and distilled water 35
0 cc was mixed, the temperature was raised to 40 ° C., and the contents were well stirred. While keeping this state, the following procedure was performed.

A potassium iodide solution (concentration 0.04 mol / l) corresponding to 1.2 mol% with respect to the silver amount of the base emulsion was added over 15 minutes.

A silver nitrate solution (concentration: 1.02 mol / l) and a sodium chloride solution (1.58 mol / l) were added by the double jet method in an amount corresponding to 4.0 mol% with respect to the silver amount of the base emulsion, respectively, for 1 minute.

A potassium iodide solution (concentration 0.04 mol / l) corresponding to 1.3 mol% with respect to the silver amount of the base emulsion was added over 8 minutes.

Silver nitrate solution (concentration 1.02 mol / l) and potassium bromide solution (concentration 1.02 mol / l) were added in amounts corresponding to 50 mol% with respect to the silver amount of the base emulsion in 49 minutes while maintaining pBr = 1.73. .

While maintaining pBr at 3.71, 1 × KSCN aqueous solution was added at 2 × 10 ⁻² mol to 1 mol of silver halide and ripened for 10 minutes.

 It was desalted by flocculation method.

Emulsion prepared using Emulsion A-1 as a base emulsion (Emulsion B-
1), an emulsion prepared by using the emulsion A-2 as a base emulsion (emulsion B-2), and an emulsion prepared by using the emulsion A-3 as a base emulsion (emulsion B-3). On the other hand, as comparative emulsions, emulsions which did not undergo the above ripening process were emulsion B-1 and emulsion B.
-Emulsion B-1X, Emulsion B corresponding to -2 and Emulsion B-3 respectively
-2X, Emulsion B-3X. The average aspect ratio and diameter of these silver halide grains are 6.5 and 1.3 μm, respectively.
m. The ratio σ of grains having a diameter of 0.4 μm or more to the whole emulsion grains was 90% or more.

C. Preparation of Grains with Non-Localized Dislocation Lines Among the procedures described in B to, only ,, and were performed. Emulsion prepared from base emulsion A-1 is emulsion C-1, emulsion prepared from emulsion A-2 is emulsion C-
2. The emulsion prepared from emulsion A-3 was designated as emulsion C-3.

D. Preparation of grains without dislocation lines Among the procedures described in B to, only and were performed. An emulsion prepared from the base emulsion A-1 was used as an emulsion D-
1. Emulsion prepared from Emulsion A-2 was Emulsion D-2, Emulsion A
The emulsion prepared from -3 was designated as Emulsion D-3.

The average aspect ratio and diameter of the silver halide grains of the above emulsions C-n and D-n (n = 1 to 3) were 6.7 and 1.4 μm, respectively. The ratio σ of grains having a diameter of 0.4 μm or more to the whole emulsion grains was 90% or more.

Optimal gold-sulfur sensitization was performed on each of the above silver halide emulsions using sodium thiosulfate, chloroauric acid, and KSCN as a ligand for gold. The optimum gold-sulfur sensitization here means the gold-sulfur sensitization condition that gives the highest ultimate sensitivity when exposed at 1/100 ″. KSSCN is used as a gold ligand for 1 mol of silver halide, 2-8 × 10 ^-6 mol
Was added. This amount of KSCN was substantially the optimal amount for gold-sulfur sensitization of the silver halide emulsion described above.

The grain size distribution, grain outline and dislocation linear density and distribution of the silver halide grain system were substantially the same and no change was observed whether or not the above physical ripening process was performed. However, as will be described later, the above physical ripening process is effective for increasing the photographic sensitivity particularly for silver halide grains having dislocation lines concentrated near the apexes. That is, the physical ripening of the present invention is the above dislocation line,
It contributes to an increase in photographic sensitivity while substantially maintaining the morphological characteristics such as grain size, and in particular, the expression of this effect is
This is remarkable for silver halide grains having dislocation lines near the apex regardless of the nature of the base grain.

When the silver halide grains of the emulsions Bn and Bnx (n = 1 to 3) were observed by a transmission electron microscope, the above-mentioned x value was 0.85, which was a mean value of all the emulsion grains. The value was V _a / (V _a + V _b ) = 1, and the dislocation lines were localized only at the apexes. The proportion of dislocation lines localized at the apex of particles with a diameter of 0.4 μm or more is 90
% Or more. On the other hand, in the case of emulsion C-n (n = 1 to 3), the value of x was 0.86 on the basis of all emulsion grains, and V _a / (V _a + V _b ) ≦ 0.75 with respect to this value. It was. Emulsion C-n (n = 1 to 3) has dislocation lines substantially uniformly present at the fringes of tabular silver halide grains, and emulsions B-n and B-nX (n = 1) Localization of dislocation lines in the vicinity of the apex was not observed. Emulsion D-
When the same observation was carried out for nX (n = 1 to 3), dislocation lines were substantially absent in any of the emulsion grains.

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.

The number for each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver.
However, for the sensitizing dye, 1 mol of silver halide in the same layer
The coating amount is shown in mol unit.

(Detailed layer structure) First layer (antihalation layer) Black colloidal silver 0.18 Gelatin 1.40 Second layer (intermediate layer) 2,5-di-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 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 (2nd 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-sensitive 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 EX-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 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-2 0.010 Gelatin 0.63 Eighth layer (second green sensitive emulsion layer) Emulsion C Silver 0.45 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 ( 1 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 emulsion layer) Emulsion H Silver 0.77 Sensitization 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 15th Layer (2nd 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, storability in all layers W-1, in order to improve 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.

The coated sample thus obtained was used as emulsion number B-n, B-nX,
Corresponding to C-n and D-n (n = 1,2,3), samples SP-1 to 12 are used. A light source with a color temperature of 4800 ° K is used for these samples.
A wedge exposure of 20 cms and 1/100 sec was applied. After that, development processing was performed according to the following processing steps.

Four types of color development processing are shown below, but the paint of the present invention and the comparative sample exhibited substantially the same photographic performance regardless of any of the color development processings of A to D below.

The amount of the developer brought into the bleaching process and the amount of the stabilizer brought into the stabilizing process were 2.5 ml and 2.0 ml, respectively, per 1 m length of the light-sensitive material having a width of 35 mm.

 The composition of the treatment liquid is shown below.

(Fixer) Common for mother liquor and replenisher (g) Ethylenediaminetetraacetic acid dinarium 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 l pH 6.5 (stabilizer) common to mother liquor and replenisher (g) Surfactant 0.5 Surfactant 0.4 _{C 10 H 21 -OCH 2 CH 2} O 10 H ] Triethanolamine 2.0 1,2-benzisothiazolin-3-methanol 0.3 Formalin (37%) was added to 1.5 Water 1.0 l pH 6.5 Each of the steps of bleach-fixing and washing was a countercurrent method from (2) to (1), and the overflow of the bleaching solution was all introduced into bleach-fixing (2).

The amount of the bleach-fix solution brought into the washing step in the above process was 2 ml per 1 m length of a 35 mm-wide photosensitive material.

(Wash water) Mother liquor and replenisher common Tap water is H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strong basic anion exchange resin (Amberlite IRA-400). Water was passed through a packed mixed-bed column to treat calcium and magnesium ions at a concentration of 3 mg / l or less, followed by sodium diisocyanurate dichloride 20 mg / l and sodium sulfate 150 mg / l.
l 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 [C ₁₀ H ₂₁ -OCH ₂ CH ₂ O ₁₀ H] Ethylene glycol 1.0 Water 1.0 l pH 5.0- 7.0 Processing method (C) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° C Bleaching fixing 3 minutes 15 seconds 38 ° C Washing (1) 40 seconds 35 ° C Washing (2) 1 minute 00 Second 35 ℃ Stability 40 seconds 38 ℃ Dry 1 minute 15 seconds 35 ℃ Next, describe the composition of the treatment liquid.

(Color developer) (Unit: g) Ethylenetriaminepentaacetic 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 1.0l 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 acceleration Agent 0.005mol Ammonia water (27%) 15.0 ml Add water 1.0 l pH 6.3 (bleach-fixing solution) (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 l pH 7.2 (Washing solution) Tap water is H type strong acid cation exchange resin (Amberlite IR-120B by Rohm and Haas) and OH -Type anion exchange resin (Amberlite IR-400) was passed through a mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg / l or less, followed by 20 mg / l of sodium diisocyanurate dichloride. Sodium sulfate 0.15 g / l 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 1.0l 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 ℃ Washing with water 2 minutes 10 seconds 24 ℃ Settling 4 minutes 20 seconds 38 ℃ Washing with water (1) 1 minute 05 seconds 24 ℃ Washing with water (2) 1 min 00 sec 24 ℃ Stability 1 min 05 s 38 ℃ Dry 4 min 20 s 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 1.0l pH 10.05 (bleaching solution) (Unit: g) Ethylenediaminetetraacetic acid ammonium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 l 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 Add water 1.0 l 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 was added to 1.0l pH 5.0 -8.0 Table 1 shows the photographic sensitivity of SP-1 to SP-12. The sensitivity S in Table 1 is the exposure amount E (c corresponding to the position of the optical density of fog plus the optical density of 0.2 on the sensitometry curve.
ms) and is expressed as follows.

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

From Table 1, 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.

For the samples SP-1 to SP12, the same light source as described above or the _Xe flash lamp was used as the light source, and 10 ^-1 second, 10 ^-3 second, 10
Wedge exposure was performed for ^-4 seconds and 10 ^-5 seconds, respectively, and development processing was performed according to the above-described processing steps. As a result, the relative relationship of photographic sensitivity was substantially the same as in Table 1.

From the above results, it can be seen that the tabular silver halide emulsion according to the embodiment of the present invention achieves high sensitivity in a wide exposure range of medium to high illuminance ranging from 10 ^-1 to 10 ^-5 seconds. It

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 1 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 1.

Example 2 A multi-layer color light-sensitive material having each of the following compositions was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) For silver halide and colloidal silver,
The amounts expressed in units of g / m ^2, and a coupler, the amount for the additives and gelatin, expressed in units of g / m ^2, moles per mole of silver halide in the same layer for Matazo sensitizing dye Indicated by.

First layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.3 UV-1 0.05 UV-2 0.05 UV-3 0.10 UV-4 0.10 Oil-1 0.10 Oil-2 0.10 Second layer (intermediate layer) Gelatin 1.0 Third layer (First red-sensitive emulsion layer) Emulsion A Silver 0.5 Emulsion B Silver 0.5 Gelatin 2.0 S-1 2.8 × 10 ^-4 S-2 2.0 × 10 ^-4 S-3 1.0 × 10 ^-5 Cp-1 0.40 Cp-2 0.040 Cp-3 0.020 Cp-4 0.0020 Oil-1 0.15 Oil-2 0.15 4th layer (second red emulsion layer) Emulsion G Silver 1.20 Gelatin 0.8 S-1 2.0 × 10 ^-4 S-2 1.5 × 10 ^-4 S -3 8.0 × 10 ^-6 Cp-1 0.30 Cp-2 0.03 Cp-3 0.03 Cp-4 0.002 Oil-1 0.12 Oil-2 0.12 Fifth layer (third red emulsion layer) Emulsion D Silver 1.00 Gelatin 1.50 S- 1 1.5 × 10 ^-4 S-2 1.5 × 10 ^-4 S-3 8.0 × 10 ^-6 Cp-1 0.10 Cp-2 0.10 Oil-1 0.05 Oil-2 0.05 6th layer (intermediate layer) Gelatin 0.70 Cpd-11 0.03 Oil-1 0.05 7th layer (1st green emulsion layer) Emulsion A Silver 0.55 Agent B silver 0.55 Gelatin ^{2.50 S-4 2.4 × 10 -4} S-5 2.4 × 10 -4 S-6 1.2 × 10 -4 S-7 5.0 × 10 -5 Cp-5 0.15 Cp-6 0.10 Cp-7 0.03 Cp-8 0.02 Oil-1 0.30 Oil-2 0.30 Eighth layer (second green emulsion layer) Emulsion C Silver 1.10 Gelatin 0.80 S-4 2.0 × 10 ^-4 S-5 1.9 × 10 ^-4 S-6 1.1 × 10 ^-4 S-7 4.0 x 10 ^-5 Cp-5 0.10 Cp-6 0.070 Cp-7 0.030 Cp-8 0.025 Oil-1 0.20 Oil-2 0.20 Ninth layer (third green emulsion layer) Emulsion E Silver 1.20 Gelatin 1.80 S-4 1.3 × 10 ^-4 S-5 1.3 × 10 ^-4 S-6 9.0 × 10 ^-5 S-7 3.0 × 10 ^-5 Cp-6 0.20 Cp-7 0.03 Oil-1 0.20 Oil-2 0.05 10th layer (yellow filter layer) Gelatin 1.2 Yellow colloidal silver 0.08 Cpd-12 0.1 Oil-1 0.3 11th layer (1st blue sensitive emulsion layer) Emulsion A Silver 0.17 Emulsion B Silver 0.14 Emulsion F Silver 0.14 Gelatin 1.75 S-7 ^{1.0 × 10 -4 S-8 2.0} × 10 -4 Cp-9 0.45 Cp-10 0.50 Oil-1 0.20 Oil-2 0.10 12th layer ( 2 blue-sensitive emulsion layer) Emulsion G silver 0.41 Emulsion H silver 0.69 Gelatin ^{1.20 S-7 1.0 × 10 -4} S-8 1.0 × 10 -4 Cp-9 0.25 Oil-1 0.060 Oil-2 0.030 13th layer (first Protective layer) Fine silver iodobromide (average particle size 0.08 μm, AgI2 mol%) 0.40 Gelatin 1.30 UV-1 0.05 UV-2 0.05 UV-3 0.10 UV-4 0.10 UV-5 0.03 Oil-1 0.1 Oil-2 0.1 14th layer (second protective layer) Gelatin 0.50 Surfactant (W-11) 0.1 Polymethylmethacrylate particles 0.2 Sliding agent (B-11) 0.03 H-1 0.4 In addition to the above components, coating aid W-12 , Dispersion aid W-1
3, hardener H-11, H-12, formalin scavenger Cpd
In addition to -13, Cpd-14, Cpd-15 and Cpd-16 as preservatives, stabilizer Cpd-17 and antifoggants Cpd-18 and Cpd-19 were added.

The coated sample thus obtained was used as emulsion number B-n, B-nX,
Samples SP-13 to 24 correspond to Cn and Dn (n = 1,2,3). These samples were subjected to the same wedge exposure as in Example 1, and further developed according to the same processing steps as in Example 1. All four color development processes A to D shown in Example 1 gave substantially similar results.

Table 2 shows the photographic sensitivity of SP-13 to 24. The definition of the sensitivity S is the same as that in the first embodiment. B sensitivity, G sensitivity, and R sensitivity are also defined as physical quantities similar to those in the first embodiment.

From Table 2, the silver halide emulsion according to the present invention was prepared as in Example 1.
It can be seen that substantially the same results can be obtained in a system of a silver halide light-sensitive material having a different constitution. Even when the exposure illuminance was changed as in Example 1, the results substantially similar to those in Table 2 were obtained.

From the above results, the tabular silver halide emulsion according to the embodiment of the present invention, even in the system of the silver halide light-sensitive material having a constitution different from that of Example 1, has a high medium illuminance ranging from 10 ^-1 to 10 ^-5 seconds. It can be seen that high sensitivity has been achieved in a wide exposure area of illuminance.

The curing of the present invention was exhibited regardless of the method of adding the sensitizing dye, and substantially the same results as those shown in Table 2 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 2.

HBS-1 Tricresyl phosphate HBS-2 Di-n-butyl phthalate Oil-1 Tricresyl phosphate Oil-2 Dibutyl phthalate _{H-12 {(CH 2 =} CHSO 2 CH 2) 2 CCH 2 SO 2 (CH 2) 2} 2 N (CH 2) 2 SO 3 K

[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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-63-220238 (JP, A) JP-A-1-201649 (JP, A) JP-A 3-1129 (JP, A) JP-A-1- 100533 (JP, A) JP 64-37545 (JP, A) JP 58-108526 (JP, A)

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. Of 80% or more of the grains having dislocation lines substantially concentrated in the vicinity of the apex of the grain, and having an average aspect ratio of 2 or more, and this emulsion per mol of silver halide A tabular silver halide photographic emulsion characterized in that grains are formed in the presence of the compound represented by the following general formula. General formula: X (QCN) _{n In the} formula, n is a natural number of 1 to 5, and X represents an n-valent cation. Here, Q is S or Se. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of these emulsion layers having a total projected area of all silver halide grains in the emulsion. 50% or more, diameter is 0.4 μm
The tabular silver halide grains described above account for 0.4
At least 80% of the number of tabular silver halide grains having a size of μm or more have dislocation lines substantially concentrated near the apexes of the grains, and at least a tabular silver halide photographic emulsion having an average aspect ratio of 2 or more is used. A silver halide photographic light-sensitive material characterized by containing one kind and the QCN compound in the general formula of claim (1) in an amount of 1 × 10 ^-5 mol or more per mol of silver halide contained in the light-sensitive material. material.