JPH09179227A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic emulsion contg. flat platy silver halide particles and a dispersive medium, excellent in sensitivity and graininess, ensuring low fog and undergoing a slight change in performance with the lapse of time by incorporating flat platy silver halide particles having a specified coefft. of variation in surface area. SOLUTION: This photographic emulsion contains flat platy silver halide particles having an average aspect ratio of >=3 and <=30% coefft. of variation of surface area and a dispersive medium. The average silver iodide content of the silver halide particles is >=3mol% and chemical sensitization with an Se or Te compd. has been carried out. The pref. average aspect ratio of the silver halide particles is 3-20, especially 4-15, more especially 5-12.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion (hereinafter also simply referred to as a photographic emulsion and emulsion) and a silver halide photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material), more specifically, sensitivity and graininess. , A silver halide emulsion having improved gradation and a silver halide photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art The basic performance required for a silver halide photographic light-sensitive material is that it has a high sensitivity, a low fog density, fine grains, and excellent photographic gradation. Various efforts have been made to date in order to improve these performances. In recent years, with the widespread use of compact cameras, lens-equipped films, etc., opportunities for photography using silver halide photographic light-sensitive materials have become commonplace. Along with this, demands for improving the performance of silver halide photographic light-sensitive materials are becoming more and more severe, and higher-level performance is required.

The dominant factor of the basic performance of silver halide photographic light-sensitive materials is silver halide grains, and the development of silver halide grains aiming at improvement of sensitivity and image quality has been vigorously tackled. In general, in order to improve the image quality, it is effective to reduce the particle size of the silver halide particles, increase the number of particles per unit silver amount, and increase the number of coloring points (the number of pixels). However, reducing the particle size causes a serious decrease in sensitivity, so there is a limit to satisfying both high sensitivity and high image quality. Techniques for improving the sensitivity / size ratio per silver halide grain have been studied in order to achieve higher sensitivity and higher image quality. One of the techniques is to use tabular silver halide. JP-A-58-
No. 111935, No. 58-111936, No. 58-1
Nos. 11937, 58-113927, 59-99
No. 433, etc.

When these tabular silver halide grains are compared with so-called normal crystal silver halide grains such as hexahedral grains, octahedral grains and dodecahedron grains, the surface area per unit volume of silver halide grains becomes large. In the case of the same volume, tabular grains have the advantage that more spectral sensitizing dyes can be adsorbed on the grain surface, and higher sensitivity can be achieved.

Further, Japanese Patent Laid-Open No. 63-92942 discloses a technique of providing a region having a high silver iodide content inside a tabular silver halide grain, and Japanese Patent Laid-Open No. 63-151618 discloses a hexagonal flat plate. The technology using silver halide grains was adopted,
The effects on sensitivity and graininess are shown respectively. Also, JP-A-63-106746 discloses a tabular silver halide grain having a substantially layered structure in a direction parallel to two principal planes facing each other.
No. 7 has a layered structure divided by planes substantially parallel to two opposing main planes, and the average silver iodide content of the outermost layer is the average iodide of the entire silver halide grain. The techniques for using tabular silver halide grains each having a silver content higher than the silver content by at least 1 mol% or more are described.

In addition to this, in Japanese Patent Application Laid-Open No. 1-183644,
A technique using tabular silver halide grains having a completely uniform silver iodide distribution in a silver halide phase containing silver iodide is described. There have been some reports on the technology focusing on parallel twin planes in tabular silver halide grains.
For example, in JP-A-63-163451, the ratio (b / a) of the longest distance (a) between two or more twin planes and the thickness (b) of a grain is 5 or more. A technique using tabular silver halide grains is further disclosed in
No. 1649 discloses a technique in which the number of dislocation lines existing in tabular silver halide grains is also defined, and effects on sensitivity, graininess and sharpness are reported.

In WO 91/18320, the distance between at least two twin planes is 0.012.
A technique using tabular silver halide grains of less than .mu.m is disclosed in Japanese Patent Application Laid-Open (JP-A) No. 3-353003, in which core / shell type twin silver halide grains having an average distance between the longest twin planes of 10 to 100 DEG are used. Techniques are reported, each describing sensitivity, graininess, or the effect of improving sharpness, pressure characteristics, and graininess.

By the way, among the approaches to silver halide emulsion aimed at improving the sensitivity and image quality of silver halide photographic light-sensitive materials in the industry, halogen is positioned as the most basic and important technology. There is a technology for monodisperse silver halide emulsion. Since the optimum conditions for chemical sensitization are different between large and small silver halide grains, they are optimal for a mixed, ie polydisperse (wide grain size) silver halide emulsion. It is difficult to perform chemical sensitization, and as a result, fog is often increased or sufficient chemical sensitization cannot be performed in many cases.

On the other hand, in the case of a monodisperse silver halide emulsion, optimum chemical sensitization can be easily performed, and a silver halide emulsion with high sensitivity and low fog can be prepared.

A hard gradation characteristic curve can be expected. As a monodispersion technique for tabular silver halide grains, Japanese Patent Application Laid-Open No. HEI-1
No. 213637 describes a technique for improving sensitivity, gradation, graininess and the like with monodisperse silver halide grains having two parallel twin planes. In addition, JP-A-5-173
No. 268 and JP-A-6-202258 disclose a method for producing a tabular silver halide emulsion having a small grain size distribution.

In the monodisperse technique for these tabular grains, the monodisperse silver halide grains mean that the variation in projected area between individual tabular grains is small.
Further, in JP-A-6-258744, the sensitivity, gradation, pressure resistance and latent image storability are improved by using monodisperse tabular silver halide grains having regions having different silver halide compositions inside the grains. Technology has been reported. Monodispersion as referred to in this technique means that the volume variation between individual particles is small.

However, in response to market demands for further improvement in performance, the photographic performances obtained by using various techniques in the above-mentioned tabular silver halide emulsion are exceeded, and in particular, sensitivity, fog, graininess, gradation It has been desired to develop a technique that realizes excellent performance in major photographic elements such as sex. Further, there has been a demand for the development of a technique for keeping the photographic performance stable for a long time, that is, there is little change in the performance immediately after the production of the silver halide photographic light-sensitive material and the performance at the time of using it by general users.

[0013]

The object of the present invention is to provide a silver halide photographic emulsion and a silver halide photographic light-sensitive material which are excellent in sensitivity and graininess, have a low fog and have a small change with time in the performance. Especially.

[0014]

The above object of the present invention is achieved by the following constitution.

1. A tabular silver halide grain comprising a tabular silver halide grain having an average aspect ratio of 3 or more and a dispersion medium, the tabular silver halide grain having a surface area variation coefficient of the silver halide grain of 30% or less. A silver halide photographic emulsion characterized by containing a.

2. 2. The silver halide photographic emulsion as described in 1 above, wherein the average silver iodide content of the silver halide grains is 3 mol% or more.

3. 3. The silver halide photographic emulsion as described in 1 or 2 above, wherein the coefficient of variation of surface area of silver halide grains is 20% or less.

4. The silver halide photographic emulsion according to any one of claims 1 to 3, wherein the silver halide grains have an average aspect ratio of 5 or more.

5. 5. The silver halide photographic emulsion as described in any one of 1 to 4 above, which is chemically sensitized in the presence of a selenium compound or a tellurium compound.

6. A silver halide photographic light-sensitive material characterized in that the light-sensitive silver halide emulsion layer provided on a support contains the silver halide emulsion described in any one of 1 to 5 above.

That is, as a result of intensive studies made by the present inventors on the above-mentioned problems, as a result, a silver halide emulsion containing tabular silver halide grains was used, and tabular halides contained in the emulsion were used. It has been found that the improvement of the photographic performance and the stabilization of the performance which are the objectives of the present invention can be realized by suppressing the variation in the surface area between silver grains (hereinafter, also simply referred to as tabular grains and grains). That is, in the tabular grains, the physical parameters of the silver halide grains to be monodispersed are not the projected areas or grain volumes of the silver halide grains that have been focused on in the prior art, but the individual tabular halogens. It was discovered to be the surface area of silver halide grains.

Hereinafter, the present invention will be described in more detail.

The tabular silver halide grains contained in the silver halide emulsion of the present invention may be simply referred to as the tabular silver halide grains of the present invention. The tabular silver halide grains are crystallographically classified as twins. A twin is a crystal having one or more twin planes in one grain. The morphology of twins in a silver halide grain is classified by Klein and Moiser in a report “Photographipheche”.
Korrespondenz "Vol. 99, p. 99, ibid. 100
Volume 57 page.

The tabular silver halide grain in the present invention is one having one or two or more twin planes parallel to each other in the grain. However, in order to reduce variation in surface area between particles, which is a main feature of the present invention, particles having two parallel twin planes are preferable.

In the present invention, the aspect ratio means the ratio of the diameter and the thickness of particles (aspect ratio = diameter / thickness).

The diameter of a grain is an area equal to the area when the grain is projected perpendicularly to the plane (also referred to as the main plane) having the largest area in the plane forming the surface of the tabular grain. It is represented by the diameter of a circle (also referred to as the projected area diameter).

The grain thickness is the grain thickness in the direction perpendicular to the principal plane and generally corresponds to the distance between the two principal planes.

The average aspect ratio means an arithmetic average value obtained by arbitrarily selecting 500 or more silver halide grains contained in a silver halide emulsion and obtaining the aspect ratio thereof.

The tabular silver halide grain according to the present invention has an average aspect ratio of 3 or more, preferably 3 or more and 20 or less, more preferably 4 or more and 15 or less, and particularly preferably 5 or more and 12 or less. The diameter and thickness of the particles can be obtained by the following method. After preparing a sample coated with silver halide grains on the support so that the latex balls of known particle size to be the internal standard and the main planes are oriented in parallel, after performing shadowing by a carbon vapor deposition method from a certain angle, A replica sample is prepared by the usual replica method. An electron micrograph of the same sample is taken, and the projected area diameter and thickness of each particle are obtained using an image processing device or the like. In this case, the particle thickness can be calculated from the internal standard and the length of the shadow of the particle. In the present invention, the coefficient of variation of the surface area of tabular silver halide grains is a value defined by the following.

(Standard deviation of surface area / average surface area) ×
100 = coefficient of variation of surface area (%) The surface area of each grain in the present invention is equal to the projected area of the tabular silver halide grains and the thickness of the tabular silver halide grains obtained by the above method. It is the value of the surface area of a cylinder having a height. The average surface area of the tabular silver halide grains and the standard deviation are values calculated by arbitrarily selecting 500 or more tabular silver halide grains contained in the silver halide emulsion and calculating their surface areas. .
The variation coefficient of the surface area of tabular silver halide grains of the silver halide emulsion according to the present invention is 30% or less.
25% or less is more preferable, and 20% or less is particularly preferable. This is because the smaller the value, the more remarkable the effect of the present invention.

The composition of the tabular silver halide grains of the present invention is preferably silver iodobromide or silver chloroiodobromide,
Silver iodobromide is more preferred. Further, in any composition, the average silver iodide content of the tabular silver halide grains is preferably 3 mol% or more, and 4 mol% or more and 20 mol% or more.
The following is more preferable, and 5 mol% or more and 15 mol% or less is further preferable.

The composition of the tabular silver halide grains is EPM
It can be investigated using a composition analysis method such as method A and X-ray diffraction method.

The average silver iodide content of the surface phase of the tabular silver halide grains of the present invention is preferably 3 mol% or more, more preferably 5 mol% or more and 30 mol% or less, 7 More preferably, it is not less than 20% by mol.

The average silver iodide content of the surface phase of the tabular silver halide grains referred to in the present invention is a value determined by the XPS method or the ISS method.

For example, the surface silver iodide content by the XPS method can be obtained as follows. The sample was placed at 1 × 10 ^-4 torr
After cooling to -155 ° C. or less in the following ultra-high vacuum, MgKa is irradiated as a probe X-ray at an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d, and I3d3 / 2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the composition such as the silver iodide content of the silver halide surface phase is determined from these intensity ratios.

Further, in the silver halide emulsion of the present invention, it is preferable that the tabular silver halide grains have a more uniform silver iodide content. That is, the variation coefficient of the silver iodide content in the silver halide emulsion is preferably 30% or less, more preferably 20% or less. However, the coefficient of variation referred to here is a value obtained by dividing the standard deviation of the silver iodide content by the average value of the silver iodide content and multiplying by 100, and the silver halide grains contained in the silver halide emulsion. Is a value calculated by arbitrarily selecting 500 or more.

The photographic silver halide grains are fine crystals composed of silver chloride, silver bromide, silver iodide, or solid solutions thereof, and two or more phases having different silver halide compositions are contained in the crystals. It is possible to form. As a grain having such a structure, a grain composed of an inner core phase and an outer surface phase having mutually different silver halide compositions is known, and is generally called a core / shell type grain. The silver halide grains of the present invention preferably have a core / shell type grain structure in which the outer surface phase has a higher silver iodide content than the inner core phase.

The silver halide emulsion of the present invention preferably has dislocation lines inside. There is no particular limitation on the position where the dislocation line exists, but it is preferable that the dislocation line exists near the outer peripheral portion, near the ridge line, or near the vertex of the tabular silver halide grains. In terms of the positional relationship of introduction of dislocations in the whole grain, it is preferable that the dislocation is introduced after 50% of the silver amount in the whole grain, and more preferably between 60% and less than 80%.

The number of dislocation lines is preferably 30% or more (the number) of particles containing 5 or more dislocation lines, more preferably 50% or more, and more preferably 80% or more. More preferable. In each case, it is particularly desirable that the number of dislocation lines is 10 or more.

The dislocation lines possessed by the tabular silver halide grains are described in, for example, J. F. Hamilton, Photo. S
ci. Eng. 11 (1967) 57 and T.I. Shio
zawa, J .; Soc. Photo. Sci. Japan
35 (1972) 213 and can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out carefully so as not to apply pressure enough to generate dislocation lines from the emulsion, put them on an electron microscope mesh to prevent damage (printout, etc.) due to electron beams. The sample is cooled and observed by the transmission method.

At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough, so that the method using a high-voltage electron microscope can be observed more clearly. From the grain photograph obtained by such a method, the position and number of dislocation lines in each grain can be determined.

The tabular grains of the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium. Here, the aqueous solution containing a dispersion medium means an aqueous solution in which a protective colloid is formed by a substance that can form a hydrophilic colloid such as gelatin (a substance that can serve as a binder), and preferably a colloidal protective substance. An aqueous solution containing gelatin.

As a preparation mode of the silver halide emulsion of the present invention, a method known in the art can be appropriately applied. For example, pAg of the reaction solution at the time of forming silver halide grains
, A controlled double jet method or a controlled triple jet method. In addition, a silver halide solvent can be used if necessary. Examples of useful silver halide solvents include ammonia, thioethers, and thioureas. US Pat. No. 3,271,15 for thioethers
No. 7, No. 3,790,387, No. 3,574,628
You can refer to the issues.

The method for preparing the tabular silver halide grains of the present invention is not particularly limited, and an ammonia method, a neutral method without using ammonia, an acidic method or the like can be used. From the viewpoint that fog during formation can be suppressed, the pH (logarithm of the reciprocal of the hydrogen ion concentration) is preferably 5.5 or less, more preferably 4.5.
It is preferable to form the particles in the following environment.

In order to control the silver iodide content between the tabular silver halide grains and within the grains more precisely, at least a part of formation of the silver iodide-containing phase of the tabular silver halide grains is controlled by the halogen. It is desirable to carry out in the presence of silver halide grains having a solubility lower than that of silver halide grains, and it is particularly desirable to use silver iodide as the silver halide grains having a low solubility. Further, for the same reason, at least a part of the silver iodide-containing phase formation of the tabular silver halide grains is
A method of forming by supplying only one or more kinds of silver halide fine particles is also preferable.

The method of introducing dislocation lines into the tabular silver halide grains is not particularly limited. For example, a method of adding an aqueous solution of iodide ions such as potassium iodide and a water-soluble silver salt solution by a double jet, or iodine. A method of adding fine silver halide grains, a method of adding only an iodine ion solution, JP-A-6-
A known method such as a method using an iodide ion-releasing agent as described in No. 11781 can be used to form a dislocation line which is a source of the dislocation line at a desired position.

Among these methods, a method of adding an aqueous solution of iodide ion and a water-soluble silver salt solution by a double jet, a method of adding fine silver iodide grains, and a method of using an iodide ion-releasing agent are preferable.

The average grain size of the silver halide grains of the present invention is preferably 0.1 to 1.2 μm, more preferably 0.25 to 0.8 μm.
Is more preferable. If it is less than 0.1 μm, it is difficult to obtain practical sensitivity, while if it is more than 1.2 μm, the granularity is significantly deteriorated due to the large particle diameter. In the present invention, the particle size of the silver halide grains refers to the length of one side of a cube having the same volume as the silver halide grains. The average grain size means the length of one side of a cube having the same volume as the silver halide grains. Further, the average grain size means an arithmetic mean value calculated from the grain sizes of 500 or more arbitrarily selected silver halide grains contained in the silver halide emulsion.

In the silver halide emulsion of the present invention, Research Disclosure No. 308119
The technique described in (hereinafter abbreviated as RD308119) can be used.

The places described below are shown.

[0051]

[Table 1]

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. Specific examples of selenium sensitizers and their use techniques are disclosed in the following patents. That is, U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, 3,297,446, 3,297,447, 3,320,069, No. 3,408,196, No. 3,408,197, No. 3,442,653, No. 3,420,670, No. 3,591,385, No. 52-34491, No. 52- 34492, 53-295, and 57-22.
No. 090, JP-A-59-180536 and JP-A-59-18.
Nos. 5330, 59-181337, 59-187
No. 338, No. 59-192241, No. 60-1500
No. 46, No. 60-151637, No. 61-24673
No. 8, JP-A-3-42221, JP-A-3-24537, JP-A-3-111838, JP-A-3-116132, and JP-A 3-1.
48648, 3-237450, 4-1683.
No. 8, No. 4-25832, No. 4-25832, No. 4
-32831, 4-96059, 4-1092
No. 40, No. 4-140738, No. 4-147250
No. 4, No. 4-149437, No. 4-184331, No. 4-190225, No. 4-191729, No. 4-1.
95035, 4-271341, 4-34446.
No. 36, No. 5-11385, No. 5-40324, No. 5-224332, No. 5-224333, No. 6-4.
0324, 6-43576, 6-75328.
No. 6, No. 6-110149, No. 6-175258, No. 6-175259, No. 6-180478, and No. 6-2.
08184, 6-208186, 6-2651
No. 18, No. 6-281642, and the like, and the selenium sensitizers and techniques for using them can be used.

The technique concerning selenium sensitization is described in H. E. FIG.
Journalof Photog by Spencer et al.
raphic Science, Vol. 31, 158-1
It is also disclosed in scientific literature such as page 69 (1983).

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N,
N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-
Heptafluoropropylcarbonylselenourea, N,
N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.) Selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides (diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide). Particularly preferred selenium sensitizers are selenoureas, selenophosphates, and selenides.

The selenium compound (selenium sensitizer) preferably used in the chemical ripening of the silver halide emulsion of the present invention is described below.
The following shows a specific example.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

[Chemical 6]

The tellurium sensitizer and sensitizing method used in the present invention will be described. Regarding these, US Pat. No. 1,62
3,499, 3,320,069, 3,77
No. 2,031, No. 3,531,289, No. 3,65
5,394, British Patent Nos. 235,211 and 1,1.
21,496, 1,295,462, 1,39
6,696, Canadian Patent No. 800,958, JP-A-4-204640, 4-271341, and 4-3.
No. 33043, No. 5-303157, No. 6-2757
No. 3, No. 6-175258, No. 6-175259,
6-180478, 6-208184, 6-
No. 208186, and the like. See also
al of Chemical Society Ch
medical Communication, p. 635 (1
980), 645 (1979), 1102 (1979), and Journal of Che.
medical Society Perkin Tran
The techniques described in Saction, 1, 191 (1980) and the like can be used.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-).
Dimethyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, etc.), telluroamides (eg, telluroacetamide, N, N-dimethyltellurobenzamide, etc.), Examples include telluroketones, telluroesters, and isotellurocyanates.

The tellurium compounds (tellurium sensitizers) preferably used in the chemical ripening of the silver halide emulsion of the present invention are described below.
The following shows a specific example.

[0065]

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[0066]

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[0067]

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The amount of the selenium compound and tellurium compound added is not uniform depending on the compound used, the type of silver halide photographic emulsion, the conditions of chemical ripening, etc., but is usually 1 × 10 ^-8 per mol of silver halide. To 1 × 10 ⁻³ mol, and 5 × 10 ⁻⁸ to 1 × 10 ⁻⁴ per mol of silver halide.
Preferably it is in the molar range.

Further, the addition method is, depending on the properties of the selenium compound or tellurium compound used, a method of dissolving in water or an organic solvent such as methanol, ethanol or ethyl acetate, alone or in a mixed solvent, or by mixing with a gelatin solution in advance. Addition method, JP-A-4-14073
As disclosed in No. 9, it is added during chemical sensitization in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

The value of pAg (logarithm of reciprocal of silver ion concentration) at the time of chemical ripening is preferably 6.0 to 10.0, more preferably 6.5 to 9.5. The pH during chemical ripening is preferably 4 to 9, more preferably 4.
0 to 6.5. The temperature during chemical aging is preferably 40
To 90 ° C, more preferably 45 to 85 ° C.

The silver halide emulsion of the present invention can be subjected to physical ripening, other chemical ripening and spectral sensitization according to known methods.

As the additives used in such a process, Research Disclosure No. 17643,
No. 18716 and no. 308119 (respectively,
RD17643, RD18716, RD30811
9) can be used. The places to be described are shown below.

[0073]

[Table 2]

Known photographic additives that can be used in the present invention are also described in the above-mentioned Research Disclosure.
The places to be described are shown below.

[0075]

[Table 3]

Various couplers may be used in the present invention, specific examples of which are described in Research Disclosure above.

The following are relevant description points.

[0078]

[Table 4]

The additive used in the present invention is RD3081.
It can be added by the dispersion method described in 19XIV.

In the present invention, the aforementioned RD17643 is used.
28 pages, RD18716 pages 647-8 and RD308
The support described in 119XIX can be used.

The light-sensitive material of the present invention includes the above-mentioned RD3081.
An auxiliary layer such as a filter layer or an intermediate layer described in Item 19VII-K can be provided.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 08119VII-K can be employed.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. .

The light-sensitive material of the present invention is the above-mentioned RD17643.
Pages 28 to 29, RD18716647 and RD30
Development processing can be performed by the usual method described in 8119XIX.

[0084]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these embodiments.

Example 1 [Preparation of seed crystal emulsion T-1] Two gelatin solutions A-1 shown below were used.
Using the controlled double jet method while maintaining the temperature at 5 ° C. and stirring at a stirring rotation speed of 450 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128.
Solution -1 and Solution C-1 were added at an accelerated flow rate in 76.6 minutes. During this period, the pH of the reaction solution and pBr were both 2.0
And was kept at 2.61. Three minutes after the addition was completed, the pH was adjusted to 5.5 using the D-1 solution, and then desalting was carried out by the ultrafiltration method. This seed crystal emulsion consists of spherical silver halide grains having an average grain size of 0.18 μm.

(A-1) Inert gelatin (average molecular weight 100,000) 99.3 g Potassium bromide 5.2 g 10% by weight methanol solution of the following compound-I 88.5 ml Nitric acid 6% aqueous solution 189.0 ml H ₂ O 9840 .0ml (B-1) Silver nitrate 600.0g nitrate 6% aqueous solution of _{155.0ml H 2 O 3667.5ml (C-} 1) potassium bromide 420.4g inert gelatin (average molecular weight 100,000) 17.7 g of polypropylene - polyethylene Oxy-disuccinate sodium salt 10% ethanol solution 17.7 ml H ₂ O 3777.1 ml (D-1) 10% sodium carbonate aqueous solution Required amount (Compound-I) HO (CH ₂ CH ₂ O) _m [CH ( _{CH 3) CH 2 O] 19.8} (CH 2 CH 2 O) n H (m + n = 9.77) [ preparation of seed emulsion T-2] below zero Chin solution A-1 2
Using a controlled double jet method while maintaining the temperature at 5 ° C. and stirring at a stirring rotation speed of 850 rotations / minute using the mixing and stirring device described in JP-A-62-160128,
Solution B-2 and solution C-2 corresponding to 0.58 mol each were added in 2 minutes. During this period, the pH and pBr of the reaction solution were each 5.8.
And kept at 2.10. After the addition was completed, the reaction solution was heated to 60 ° C. over 65 minutes. During this period, when 55 minutes had elapsed, the D-2 solution was added over 5 minutes. E-2 after heating
After the pH was adjusted to 5.0 using the solution, 2.95 moles of A-2 solution and B-2 solution were added for 42 minutes using the controlled double jet method. During this period, pBr was kept at 1.83. After the addition was completed, the temperature was lowered to 40 ° C., and desalting was performed by an ultrafiltration method. This seed crystal emulsion consists of tabular silver halide grains having an average grain size of 0.18 μm and an average aspect ratio of 4.2.

(A-2) Inert gelatin (average molecular weight 16,000) 12.1 g potassium bromide 5.4 g 10% by weight of compound-I 3.4 ml 10% aqueous nitric acid solution 57.0 ml H ₂ O 4928. 8 ml (B-2) 2.5 N silver nitrate aqueous solution (C-2) 2.5 N potassium bromide aqueous solution (D-2) Inactive gelatin (average molecular weight 100,000) 60.5 g H ₂ O 1020.0 ml (E-2 ) Sodium carbonate 10% aqueous solution Necessary amount [Preparation of seed crystal emulsion T-3] The following gelatin aqueous solution A-3 was kept at 24 ° C, and the stirring speed was 650 using a mixing and stirring apparatus described in JP-A-62-160128. Using the controlled double jet method while stirring at a rotation rate of about 3 minutes, 3.5-3 mol of each of B-3 solution and C-3 solution were prepared.
It was added in the liquid in 26 minutes. During this time, the pH and pBr of the reaction solution were kept at 6.2 and 1.36, respectively. Subsequently, the D-3 solution was added and aged for 3 minutes, and then the reaction solution was heated to 68 ° C. over 45 minutes. After the temperature was raised, the rotation speed was set to 300 rotations / minute, and the pH was adjusted to 9.5 using the E-3 liquid. At this point, the pBr of the reaction solution was 1.83. 5
After aging for 2 minutes, 0.29 mol of F-3 solution was added over 1 minute, and the pH was adjusted to 4.7 using G-3. Then, desalting was performed by an ultrafiltration method using an ultrafiltration membrane having a molecular weight cutoff of 20,000. This seed crystal emulsion consists of tabular silver halide grains having an average grain size of 0.18 μm and an average aspect ratio of 3.2.

(A-3) Inert gelatin (average molecular weight 16,000) 122.0 g potassium bromide 78.3 g 10% by weight of compound-I 1.2 ml H ₂ O 20.9 l (B-3) 1 9.9 N silver nitrate aqueous solution (C-3) 1.9 N potassium bromide aqueous solution (D-3) Inactive gelatin (average molecular weight 100,000) 200.0 g H ₂ O 2416.0 ml (E-3) 28% aqueous ammonia solution Required amount (F-3) 1.41N potassium bromide aqueous solution (G-3) 56% acetic acid aqueous solution Required amount [Preparation of seed crystal emulsion T-4] The following gelatin aqueous solution A-4 was kept at 24 ° C. While stirring at a stirring speed of 650 rpm using the mixing stirrer described in Japanese Patent No. 160128, 3.54 mol of each of B-4 solution and C-4 solution were prepared using the controlled double jet method. 4.
It was added in the liquid in 26 minutes. During this time, the pH and pBr of the reaction solution were kept at 6.2 and 1.36, respectively. Subsequently, the D-4 solution was added and aged for 3 minutes, and then the reaction solution was heated to 68 ° C. over 45 minutes. After the temperature was raised, the rotation speed was set to 300 rotations / minute, and pBr was adjusted to 1.60. Then E-4
The pH of the reaction solution was adjusted to 9.5 using the solution. After aging for 5 minutes, 0.29 mole of F-4 solution was added over 1 minute, and the pH was adjusted to 4.7 using G-4. Then, desalting was performed by an ultrafiltration method using an ultrafiltration membrane having a molecular weight cutoff of 20,000. This seed crystal emulsion has an average grain size of 0.1.
It consists of tabular silver halide grains having a size of 8 μm and an average aspect ratio of 4.4.

(A-4) Inert gelatin (average molecular weight: 16,000) 122.0 g Potassium bromide 78.3 g 10% by weight of compound-I 1.2 ml H ₂ O 20.9 l (B-4) 1 9.9 N silver nitrate aqueous solution (C-4) 1.9 N potassium bromide aqueous solution (D-4) Inactive gelatin (average molecular weight 100,000) 200.0 g 4-hydroxy-6-methyl-1,3,3a, 7-tetra Azaindene 180.0 mg H ₂ O 416.0 ml (E-4) 28% aqueous ammonia solution Required amount (F-4) 1.41N potassium bromide aqueous solution (G-4) 56% acetic acid aqueous solution Required amount [Silver iodide fine particles Preparation of Emulsion SMC-1] 6.0 wt% gelatin aqueous solution containing 0.06 mol of potassium iodide
While vigorously stirring 0 l, 7.06 mol of silver nitrate aqueous solution and 7.06 mol of potassium iodide aqueous solution, 2.0 l each
Was added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles were prepared, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution.
The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is called SMC-1.

[Preparation of Emulsions Em-101 to Em-110] The following gelatin solution A101 containing the seed crystal emulsion T-1 was kept at 75 ° C. and stirred using a mixing and stirring apparatus described in JP-A No. 62-160128. The liquid B101, liquid C101 and liquid D101 were added at an accelerated flow rate by using the controlled triple jet method while stirring at a rotation speed of 650 rotations / minute. During this period, the pAg of the reaction solution was continuously changed from 7.8 to 9.6. Then, the temperature of the reaction solution was lowered to 60 ° C. in 15 minutes, and the pAg was adjusted to 9.8. Subsequently, the F101 liquid, the G101 liquid, and the H101 liquid were added at an accelerated flow rate. During this period, the pAg of the reaction solution was kept at 9.8. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur. The pH of the reaction solution was 4.
I kept it at 0. Solution I101 was used for controlling and adjusting pAg. After the addition was completed, the temperature was lowered to 40 ° C., desalting and washing with water were carried out using an ultrafiltration method, and then gelatin was added to disperse well, and pH was adjusted to 5.8 and pAg was adjusted to 8.1. The obtained emulsion has an octahedral shape and an average grain size of 0.6.
The emulsion was composed of silver halide grains having a surface area variation coefficient of 5 μm and 15.5%. This silver halide emulsion is
m-101.

(A101) Inert gelatin (average molecular weight 100,000) 37.3 g Seed crystal emulsion T-1 0.075 mol 10% by weight solution of compound-I in methanol 0.5 ml H ₂ O 866.0 ml (B101) Silver nitrate Aqueous solution (3.5N) 2.71 mol equivalent (C101) Potassium bromide aqueous solution (3.5N) 2.71 mol equivalent (D101) Silver iodide fine grain emulsion SMC-1 0.054 mol equivalent (F101) Aqueous silver nitrate solution (3.5N) 0.68 mol equivalent (G101) Potassium bromide aqueous solution (3.5N) 0.68 mol equivalent (H101) Silver iodide fine grain emulsion SMC-1 0.014 mol equivalent (I101) ) Potassium bromide aqueous solution (1.75N) Required amount 75 Gelatin solution A102 below containing seed crystal emulsion T-3
B by using the controlled triple jet method while maintaining the temperature at 60 ° C. and stirring at a stirring speed of 650 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128.
Liquid 101, liquid C102, and liquid D101 were added at accelerated flow rates. During this period, the pAg of the reaction solution was kept at 8.3. Then, the temperature of the reaction solution was lowered to 60 ° C. in 15 minutes, and pAg was adjusted to 9.6. Then F101 and G
Solution 101 and solution H101 were added at accelerated flow rates.
During this period, the pAg of the reaction solution was maintained at 9.6. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur. The pH of the reaction solution was kept at 4.0 throughout the particle growth. Solution I101 was used for controlling and adjusting pAg. 40 ℃ after addition
The mixture was cooled to 0 ° C, desalted using an ultrafiltration method, and washed with water, and then gelatin was added to disperse well, and the pH was adjusted to 5.8, pA.
The g was adjusted to 8.1. The obtained emulsion had a hexagonal tabular shape and was composed of silver halide grains having an average aspect ratio of 2.6, an average grain size of 0.65 μm and a surface area variation coefficient of 26.5%. It was This silver halide emulsion is designated as Em-102.

(A102) Inert gelatin (average molecular weight 100,000) 37.3 g Seed crystal emulsion T-3 0.075 mol equivalent amount 10% by weight methanol solution of compound-I 1.0 ml H ₂ O 864.5 ml (C102 ) Potassium bromide aqueous solution (3.5N) (however, containing 10 ml of a 10% by weight solution of compound-I in methanol) 2.71 mole equivalent The following gelatin solution A103 containing seed crystal emulsion T-2 was added:
B by using the controlled triple jet method while maintaining the temperature at 60 ° C. and stirring at a stirring speed of 650 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128.
Liquid 101, liquid C101 and liquid D101 were added at accelerated flow rates. During this period, the pAg of the reaction solution was kept at 8.2. Then, the temperature of the reaction solution was lowered to 60 ° C. in 15 minutes, and pAg was adjusted to 9.6. Then F101 and G
Solution 101 and solution H101 were added at accelerated flow rates.
During this period, the pAg of the reaction solution was maintained at 9.6. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur. The pH of the reaction solution was kept at 4.0 throughout the particle growth. Solution I101 was used for controlling and adjusting pAg. 40 ℃ after addition
The mixture was cooled to 0 ° C, desalted using an ultrafiltration method, and washed with water, and then gelatin was added to disperse well, and the pH was adjusted to 5.8, pA.
The g was adjusted to 8.1. The obtained emulsion had a hexagonal tabular shape and was composed of silver halide grains having an average aspect ratio of 3.5, an average grain size of 0.65 μm and a surface area variation coefficient of 33.6%. It was This silver halide emulsion is designated as Em-103.

(A103) Inert gelatin (average molecular weight: 100,000) 37.3 g Seed crystal emulsion T-2: 0.075 mol equivalent amount: 10% by weight methanol solution of compound-I 0.5 ml H ₂ O 864.5 ml seed crystal The following gelatin solution A104 containing Emulsion T-3 was added to 75
B by using the controlled triple jet method while maintaining the temperature at 60 ° C. and stirring at a stirring speed of 650 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128.
Solution 101, solution C104 and solution D101 were added at accelerated flow rates. During this period, the pAg of the reaction solution was kept at 8.3. Then, the temperature of the reaction solution was lowered to 60 ° C. in 15 minutes, and pAg was adjusted to 9.6. Then F101 and G
Solution 101 and solution H101 were added at accelerated flow rates.
During this period, the pAg of the reaction solution was maintained at 9.6. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur. The pH of the reaction solution was kept at 4.0 throughout the particle growth. Solution I101 was used for controlling and adjusting pAg. 40 ℃ after addition
The mixture was cooled to 0 ° C, desalted using an ultrafiltration method, and washed with water, and then gelatin was added to disperse well, and the pH was adjusted to 5.8, pA.
The g was adjusted to 8.1. The obtained emulsion had a hexagonal tabular shape and was composed of silver halide grains having an average aspect ratio of 3.3, an average grain size of 0.65 μm, and a surface area variation coefficient of 27.7%. It was This silver halide emulsion is designated as Em-104.

(A104) Inert gelatin (average molecular weight 100,000) 37.3 g Seed crystal emulsion T-3 0.075 mol equivalent amount 10% by weight methanol solution of compound-I 0.8 ml H ₂ O 864.5 ml (C104 ) Aqueous potassium bromide solution (3.5N) (however, containing 1.5 ml of a 10% by weight solution of compound-I in methanol) 2.71 mol equivalents The gelatin solution A103 containing the seed crystal emulsion T-2 was 75
B by using the controlled triple jet method while maintaining the temperature at 60 ° C. and stirring at a stirring speed of 650 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128.
Solution 105, solution C105 and solution D105 were added at accelerated flow rates. During this period, the pAg of the reaction solution was kept at 8.2. Then, the temperature of the reaction solution was lowered to 60 ° C. in 15 minutes, and pAg was adjusted to 9.6. Then F105 liquid and G
Solution 105 and solution H105 were added at accelerated flow rates.
During this period, the pAg of the reaction solution was maintained at 9.6. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur. The pH of the reaction solution was kept at 4.0 throughout the particle growth. Solution I101 was used for controlling and adjusting pAg. 40 ℃ after addition
The mixture was cooled to 0 ° C, desalted using an ultrafiltration method, and washed with water, and then gelatin was added to disperse well, and the pH was adjusted to 5.8, pA.
The g was adjusted to 8.1. The obtained emulsion had a hexagonal tabular shape and was composed of silver halide grains having an average aspect ratio of 3.4, an average grain size of 0.65 μm and a surface area variation coefficient of 34.2%. It was This silver halide emulsion is designated as Em-105.

(B105) Silver nitrate aqueous solution (3.5N) 2.67 mol equivalent (C105) Potassium bromide aqueous solution (3.5N) 2.67 mol equivalent (D105) Silver iodide fine grain emulsion SMC-1. 097 mol equivalent (F105) silver nitrate aqueous solution (3.5N) 0.67 mol equivalent (G105) potassium bromide aqueous solution (3.5N) 0.67 mol equivalent (H105) silver iodide fine grain emulsion SMC-10 75% of the gelatin solution A104 containing the seed crystal emulsion T-3.
B by using the controlled triple jet method while maintaining the temperature at 60 ° C. and stirring at a stirring speed of 650 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128.
Solution 105, solution C106 and solution D105 were added at accelerated flow rates. During this period, the pAg of the reaction solution was kept at 8.3. Then, the temperature of the reaction solution was lowered to 60 ° C. in 15 minutes, and pAg was adjusted to 9.6. Then F105 liquid and G
Solution 105 and solution H105 were added at accelerated flow rates.
During this period, the pAg of the reaction solution was maintained at 9.6. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur. The pH of the reaction solution was kept at 4.0 throughout the particle growth. Solution I101 was used for controlling and adjusting pAg. 40 ℃ after addition
The mixture was cooled to 0 ° C, desalted using an ultrafiltration method, and washed with water, and then gelatin was added to disperse well, and the pH was adjusted to 5.8, pA.
The g was adjusted to 8.1. The obtained emulsion had a hexagonal tabular shape and was composed of silver halide grains having an average aspect ratio of 3.3, an average grain size of 0.65 μm, and a surface area variation coefficient of 28.4%. It was This silver halide emulsion is designated as Em-106.

(C106) Potassium bromide aqueous solution (3.5N) (however, containing 10 ml of a 10% by weight solution of compound-I in methanol) 2.67 mol equivalent amount The following gelatin containing seed crystal emulsion T-4: Solution A107 75
B by using the controlled triple jet method while maintaining the temperature at 60 ° C. and stirring at a stirring speed of 650 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128.
Solution 105, solution C107 and solution D105 were added at accelerated flow rates. During this period, the pAg of the reaction solution was kept at 8.3. Then, the temperature of the reaction solution was lowered to 60 ° C. in 15 minutes, and pAg was adjusted to 9.6. Then F105 liquid and G
Solution 105 and solution H105 were added at accelerated flow rates.
During this period, the pAg of the reaction solution was maintained at 9.6. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur. The pH of the reaction solution was kept at 4.0 throughout the particle growth. Solution I101 was used for controlling and adjusting pAg. 40 ℃ after addition
The mixture was cooled to 0 ° C, desalted using an ultrafiltration method, and washed with water, and then gelatin was added to disperse well, and the pH was adjusted to 5.8, pA.
The g was adjusted to 8.1. The resulting emulsion was a silver halide grain having a hexagonal tabular shape, an average aspect ratio of 3.5, an average grain size of 0.65 μm, and a surface area variation coefficient of 18.5%. It was This silver halide emulsion is designated as Em-107.

(A107) Inert gelatin (average molecular weight 100,000) 37.3 g Seed crystal emulsion T-4 0.075 mol equivalent amount 10% by weight methanol solution of compound-I 1.0 ml H ₂ O 864.5 ml (C107 ) Potassium bromide aqueous solution (3.5 N) (however, containing 1.2 ml of 10 wt% methanol solution of compound-I) 2.67 mol equivalent amount The gelatin solution A103 containing the seed crystal emulsion T-2 was 75
B by using the controlled triple jet method while maintaining the temperature at 60 ° C. and stirring at a stirring speed of 650 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128.
Solution 105, solution C105 and solution D105 were added at accelerated flow rates. During this period, the pAg of the reaction solution was kept at 8.35. Then, the temperature of the reaction solution was lowered to 60 ° C. in 15 minutes, and pAg was adjusted to 9.6. Then F105 liquid and G
Solution 105 and solution H105 were added at accelerated flow rates.
During this period, the pAg of the reaction solution was maintained at 9.6. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur. The pH of the reaction solution was kept at 4.0 throughout the particle growth. Solution I101 was used for controlling and adjusting pAg. 40 ℃ after addition
The mixture was cooled to 0 ° C, desalted using an ultrafiltration method, and washed with water, and then gelatin was added to disperse well, and the pH was adjusted to 5.8, pA.
The g was adjusted to 8.1. The obtained emulsion was a silver halide grain having a hexagonal tabular shape, an average aspect ratio of 5.4, an average grain size of 0.65 μm, and a surface area variation coefficient of 36.6%. It was This silver halide emulsion is designated as Em-108.

The following gelatin solution A containing seed crystal emulsion T-4
109 was kept at 75 ° C., and the stirring speed was 650 rpm using the mixing and stirring device described in JP-A-62-160128.
The liquid B105, liquid C109 and liquid D105 were added at an accelerated flow rate by using the controlled triple jet method while stirring for minutes. During this period, the pAg of the reaction solution was kept at 8.4. After that, the temperature of the reaction solution is increased to 6 in 15 minutes.
The temperature was lowered to 0 ° C. and the pAg was adjusted to 9.6. Then F1
Solution 05, solution G105 and solution H105 were added at accelerated flow rates. During this period, the pAg of the reaction solution was maintained at 9.6. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur.
The pH of the reaction solution was kept at 4.0 throughout the particle growth.
Solution I101 was used for controlling and adjusting pAg. After the addition was completed, the temperature was lowered to 40 ° C., desalting and washing were performed using an ultrafiltration method, and then gelatin was added to disperse well and pH was adjusted.
Was adjusted to 5.8 and pAg was adjusted to 8.1. The obtained emulsion has a hexagonal tabular shape and an average aspect ratio of 5.
3, average particle size is 0.65μm, surface area coefficient of variation is 1
The emulsion consisted of 7.2% silver halide grains. This silver halide emulsion is designated as Em-109.

(A109) Inert gelatin (average molecular weight 100,000) 37.3 g Seed crystal emulsion T-4 0.075 mol equivalent amount 10% by weight methanol solution of compound-I 0.5 ml H ₂ O 864.5 ml (C109 ) Potassium bromide aqueous solution (3.5N) (however, containing 1.2 ml of a 10 wt% methanol solution of compound-I) 2.67 mol equivalent amount The gelatin solution A110 containing the seed crystal emulsion T-4 was 75
B by using the controlled triple jet method while maintaining the temperature at 60 ° C. and stirring at a stirring speed of 650 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128.
Liquid 110, liquid C110 and liquid D110 were added at accelerated flow rates. During this period, the pAg of the reaction solution was kept at 8.4. Then, the temperature of the reaction solution was lowered to 60 ° C. in 15 minutes, and pAg was adjusted to 9.6. Then F110 liquid and G
Solution 110 and solution H110 were added at accelerated flow rates.
During this period, the pAg of the reaction solution was maintained at 9.6. The addition rate of each addition solution was appropriately controlled so that Ostwald ripening between growth particles and formation of new nuclei did not occur. The pH of the reaction solution was kept at 4.0 throughout the particle growth. Solution I101 was used for controlling and adjusting pAg. 40 ℃ after addition
The mixture was cooled to 0 ° C, desalted using an ultrafiltration method, and washed with water, and then gelatin was added to disperse well, and the pH was adjusted to 5.8, pA.
The g was adjusted to 8.1. The obtained emulsion had a hexagonal tabular shape and was composed of silver halide grains having an average aspect ratio of 5.1, an average grain size of 0.65 μm and a surface area variation coefficient of 18.8%. It was This silver halide emulsion is designated as Em-110.

(B110) Silver nitrate aqueous solution (3.5N) 2.60 mol equivalent amount (C110) Potassium bromide aqueous solution (3.5N) (however, 10% by weight methanol solution of Compound-I is included in 1.0 ml) 2.60 mol equivalent (D110) silver iodide fine grain emulsion SMC-1 0.166 mol equivalent (F110) silver nitrate aqueous solution (3.5N) 0.63 mol equivalent (G110) potassium bromide aqueous solution (3.5N) ) 0.63 mol equivalent (H110) silver iodide fine grain emulsion SMC-1 0.06 mol equivalent Table 5 shows the characteristics of each emulsion prepared as described above.

[0101]

[Table 5]

[Photosensitive Material Sample No. 101-No. 11
Preparation of 0] A part of the emulsion Em-101 was dissolved by heating at 50 ° C., and 52.6 mg of the sensitizing dyes (SSD-1) and 65.7 (SSD-2) shown later per mol of silver halide.
7 mg, (SSD-3) 85.5 mg were added. 20
After ripening for 2 minutes, add 2.0 mg of sodium thiosulfate per mol of silver halide, and then add 0.6 m of chloroauric acid.
g and 54.3 mg of potassium thiocyanate were added and the mixture was aged for an appropriate time. After aging, 1-phenyl-5-
It was stabilized by adding mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene. The aging time was set so that the fog-sensitivity relationship during 1/100 second exposure was optimized.

Similarly, the above-mentioned emulsions Em-102 to Em-
-110 was spectrally and chemically sensitized. However, the addition amount of various sensitizers used and the aging time are 1 /
Some changes were made so that the fog-sensitivity relationship during 100-second exposure was optimized. Em-101-sensitized
To each emulsion of Em-110, the coupler (MCP-
1) Dissolve 1) in ethyl acetate and tricresyl phosphate and emulsify and disperse in an aqueous solution containing gelatin, add general photographic additives such as spreader and hardener to prepare a coating liquid A color light-sensitive material sample N was coated on a cellulose triacetate film support having been subjected to
o. 101-No. 110 was produced.

[0104]

Embedded image

Immediately after the preparation of these samples,
Wedge exposure was performed through a Toshiba glass filter (Y-48) using a light source with a color temperature of 5400 ° K, and development was performed according to the following processing steps.

(Treatment Step) Treatment Step Treatment Time Treatment Temperature Replenishment Amount Color Development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach 45 seconds 38 ± 2.0 ° C. 150 ml fixation 1 minute 30 seconds 38 ± 2.0 ℃ 830ml stability 1 minute 38 ± 5.0 ℃ 830ml dry 1 minute 55 ± 5.0 ℃ − Replenishment amount is a value per 1 m ² of the light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developing solution and color developing replenisher developing solution replenisher water 800 ml 800 ml potassium carbonate 30 g 35 g sodium hydrogen carbonate 2.5 g 3.0 g potassium sulfite 3.0 g 5.0 g sodium bromide 1.3 g 0.4 g iodide Potassium 1.2 mg-hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g 6.3 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Water was added to make 1 liter, and potassium hydroxide or 20% sulfuric acid was used to adjust the color developing solution to pH 10.06 and the replenisher to pH 10. Adjust to 18.

Bleaching Solution and Bleaching Replenishing Solution Bleaching Solution Replenishing Solution Water 700 ml 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water The pH of the bleaching solution is adjusted to pH 4.4 and the replenishing solution is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

Fixing Solution and Fixing Replenishing Solution Fixing Solution Replenishing Solution Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid was used as a fixing solution at pH 6.2. Adjust the pH of the replenisher to 6.5 and add water to make 1 liter.

Stabilizer and stable replenisher Water 900 ml Ethylene oxide 10 mol adduct of p-octylphenol 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UCC) L-77) 0.1 g ammonia water 0.5 ml After adding water to make 1 liter, the pH is adjusted to 8.5 with ammonia water or 50% sulfuric acid.

The sensitivity, fog and RMS value of the obtained sample,
Gamma was measured using green light. Table 6 shows the obtained results.
Shown in The measuring method and conditions are shown below.

(Relative Sensitivity) For each sample, the reciprocal of the exposure dose giving the density of the minimum density (Dmin) +0.15 was found, It was shown as a relative value with the sensitivity of 101 being 100.

(Relative Fog) In each sample, the density (= Dmin) of the unexposed portion was measured, and the sample No. 101 D
It is shown as a relative value with a min value of 100.

(Relative RMS Value) The measurement position of RMS is the same density (Dmin + 0.15) as the sensitivity measurement point. R
The MS value was obtained by scanning the measurement position of each sample with a microdensitometer (slit width 10 μm, slit length 180 μm) equipped with a Ratten filter (W-99) manufactured by Eastman Kodak Company, and measuring 100 samples for concentration measurement.
It was determined as the standard deviation of density values of 0 or more. The RMS value was calculated for each sample, and the sample No. RMS value of 101 is 10
It was shown as a relative value of 0. The smaller the relative RMS value, the better the graininess.

[0116]

[Table 6]

In the results shown in Table 6, the sample No. 10
1 to No. By comparing 104 with each other, when the tabular silver halide grains contained in the silver halide emulsion are tabular grains having an average aspect ratio of 3 or more and a coefficient of variation of surface area of 30% or less, fog and graininess are It can be seen that the sensitizing effect can be obtained under the same conditions.

Sample No. 103 and No. 105 and sample No. 104 and no. By comparing 106, it can be seen that a higher sensitizing effect can be obtained when the average silver iodide content is 3 mol% or more.

Sample No. 105 and No. 108 and sample No. 107 and No. By comparing 109, it can be seen that a higher sensitizing effect can be obtained when the average aspect ratio is 5 or more.

Similarly, sample No. 105-No. 109
From the comparison, it can be seen that when the coefficient of variation of the surface area is 20% or less, particularly excellent effects can be obtained in improving sensitivity, fog, and graininess.

Sample No. 109 and No. By comparing 110, it is understood that the higher the average silver iodide content, the more remarkable the effect of the present invention.

Example 2 [Photosensitive material sample No. 201-No. Preparation of 210] A part of the emulsion Em-101 was heated and dissolved at 50 ° C., and 1- (m-sulfophenyl)-was added per mol of silver halide.
5-Mercaptotetrazole monosodium salt 11.3
After adding mg and aging for 15 minutes, the sensitizing dye (S
SD-1) 52.6 mg, (SSD-2) 65.77 m
g, (SSD-3) 85.5 mg were added. Then 2
After ripening for 0 minutes, 1.6 mg of sodium thiosulfate per mol of silver halide and the selenium compound (b-1)
0.6 mg was added, and then 0.6 mg of chloroauric acid and 54.3 mg of potassium thiocyanate were added, followed by aging for an appropriate time. After aging, 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,
Stabilization was performed by adding 3,3a, 7-tetraazaindene. The aging time was set so that the fog-sensitivity relationship during 1/100 second exposure was optimized.

Similarly, the above-mentioned emulsions Em-102 to Em-
-110 was spectrally and chemically sensitized. However, the addition amount of various sensitizers used and the aging time are 1 /
Some changes were made so that the fog-sensitivity relationship during 100-second exposure was optimized. Em thus sensitized
-101 to Em-110, the above-mentioned coupler (MCP-1) was dissolved in ethyl acetate and tricresyl phosphate and emulsified and dispersed in an aqueous solution containing gelatin, a spreading agent, a hardener, etc. Of the general photographic additives are prepared to prepare a coating solution, which is coated on an undercoated cellulose triacetate film support according to a conventional method and dried to obtain a color light-sensitive material sample No. 201-No. 210 was produced.

Sample No. 201-No. Immediately after preparing the 210 sample, for each sample and each sample after the forced deterioration test,
Wedge exposure was performed through a Toshiba glass filter (Y-48) using a light source having a color temperature of 5400 ° K, and the same development processing and performance evaluation as in Example 1 were performed. Table 3 shows the results.

The relative sensitivity, relative fog, and relative RMS of each sample after the forced deterioration test are also as shown in Sample No. It is shown as a relative value when the value of 201 is 100.

[0126]

[Table 7]

From the results shown in Tables 6 and 7, the effects of chemical sensitization in the presence of a selenium compound are compared.
It can be seen that the silver halide emulsion of the present invention can obtain a high sensitizing effect with respect to the comparative emulsion without significantly deteriorating fog and graininess. Further, it can be seen that the silver halide emulsion of the present invention shows less change in performance after forced deterioration than the comparative emulsion and is excellent in performance stability.

Example 3 Photosensitive material sample No. 1 of Example 2 described above. 201-No. 21
Photosensitive Material Sample No. 1 was prepared in the same manner as in Preparation No. 0 except that the tellurium compound (c-3) was added in an equimolar amount instead of the selenium compound (b-1). 301-No. 3
The effect of chemically sensitizing No. 10 in the same manner as in Example 2 in the presence of a tellurium compound was compared and evaluated in the same manner as in Example 2. As a result, the same result as in Example 2 was obtained. That is, the halogenated emulsion of the present invention showed less variation in performance after forced deterioration than the comparative emulsion and was excellent in performance stability.

[0129]

INDUSTRIAL APPLICABILITY The silver halide photographic emulsion and the silver halide photographic light-sensitive material according to the present invention are excellent in sensitivity and graininess, have low fog, and have the effect that each performance is little changed with time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication G03C 7/00 530 G03C 7/00 530

Claims (6)

[Claims] 1. A silver halide photographic emulsion comprising tabular silver halide grains having an average aspect ratio of 3 or more and a dispersion medium, wherein the coefficient of variation of the surface area of the silver halide grains is 3.
A silver halide photographic emulsion characterized by containing tabular silver halide grains of 0% or less. 2. The silver halide photographic emulsion according to claim 1, wherein the average silver iodide content of the silver halide grains is 3 mol% or more. 3. The silver halide photographic emulsion according to claim 1, wherein the coefficient of variation of the surface area of the silver halide grains is 20% or less. 4. The silver halide photographic emulsion according to claim 1, wherein the silver halide grains have an average aspect ratio of 5 or more. 5. The silver halide photographic emulsion according to claim 1, which is chemically sensitized in the presence of a selenium compound or a tellurium compound. 6. A silver halide emulsion containing a silver halide emulsion according to any one of claims 1 to 5 in a photosensitive silver halide emulsion layer provided on a support. Photographic material.