JPH07244352A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material having high sensitivity and low fog by using an emulsion contg. a specified sulfur-contg. compd. in an emulsion produced by a specified method. CONSTITUTION:This photographic sensitive material has a photographic constituent layer on the base and contains particles produced by a method for forming the outermost layers of silver halide particles by feeding fine silver halide particles after desalting and before chemical or spectral sensitization in a process for producing a silver halide photographic emulsion and a compd. represented by formula I and/or a compd. represented by formula II in the photographic constituent layer. In the formula I, each of R<11>-R<14> is H, alkyl, aryl, alkenyl, cycloalkyl or a heterocyclic group, at least one of R<11>-R<14> is H, A is a protonic acid, n11 is 1 or 2 and n12 is a number of 0-3. In the formula II R<21>-R<24>, A<2>, n21 and n22 have the same meanings as R<11>-R<14>, A<1>, n11 and n12, respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a chemically sensitized silver halide photographic light-sensitive material. Particularly, it relates to a silver halide photographic light-sensitive material having high sensitivity and low fog.

[0002]

2. Description of the Related Art In recent years, performance requirements for silver halide light-sensitive materials for photography have become more and more severe, and higher level requirements have been made for various photographic characteristics such as sensitivity, fog and graininess. There is. Particularly in recent years, with the spread of compact zoom cameras and lens-equipped films generally called disposable cameras, high sensitivity has become an essential condition for photographic light-sensitive materials.

Therefore, various improvement techniques have been developed for the photosensitive silver halide photographic light-sensitive material. In particular, as a conventional technique for increasing the sensitivity in a silver halide emulsion, an internal high iodine core / shell type silver halide emulsion represented by a multi-structure grain disclosed in JP-A-60-14331 is used. is there. In this technique, a high iodide phase (which means a phase having a high silver iodide content; the same in the present specification) is positioned inside the grain, and a low iodide phase (iodinated than the high iodide phase is used. By coating with a phase having a low silver content, which is the same in the present specification), it is intended to improve both the light absorption efficiency for blue light and the development activity.

However, the above technique is effective for increasing the absorption efficiency of visible light contained in the intrinsic absorption band of silver halide, that is, blue light, but visible light not contained in the intrinsic absorption band, that is, The effect cannot be expected for red light and green light.

Generally, in a silver halide color light-sensitive material, a dye called a spectral sensitizer is adsorbed to silver halide in order to have sensitivity to red light and green light which are not absorbed by silver halide grains. I am letting you.

The spectral sensitizing dye plays a role of absorbing light in a specific wavelength band (in some cases, an intrinsic absorption band) which is not originally absorbed by silver halide, and donating generated photoelectrons to silver halide. There is. However, when the adsorption power between the spectral sensitizing dye and the silver halide grains is weak, the dye is desorbed during storage of the light-sensitive material (this tendency is particularly remarkable under high temperature and high humidity conditions), and the sensitivity is lowered. It may happen. Therefore, increasing the adsorptive power between the spectral sensitizing dye and the silver halide grains not only enhances the storage stability but also increases the effective adsorption amount of the sensitizing dye. It is thought to lead to improvement of

As a means for improving the adsorption of the spectral sensitizing dye and the intrinsic desensitization, a method of increasing the silver iodide content on the grain surface is known. For example, JP-A 1-183646 discloses core / shell type grains having a silver iodide content of 6 mol% or more in the shell portion as a light-sensitive material having high sensitivity and less intrinsic desensitization. However, in order to accelerate development, the core portion preferably has a silver iodide content of 5 mol% or less, particularly 3 mol% or less. Further, all the emulsions described in Examples are core / shell type grains having a low internal iodine, which is a technique limited to core / shell type grains having a low internal iodine. Further, JP-A 2-12142 discloses a photosensitive material having high sensitivity, low intrinsic desensitization, and low pressure and stress fog, which has an outermost shell having a higher silver iodide content than an inner core. Disclosed is a silver halide grain having an outer shell having a silver iodide content of 6 mol% or more and having at least one intermediate shell between the inner core and the outermost shell and having an aspect ratio of less than 8. As is well known in the art and as specified in the patent, grains having a high silver iodide content on the surface significantly delay the development, and are not preferable as a photographic light-sensitive material for color negatives. This is because the color development is surface development, and the development is suppressed by the iodine of the grain surface.

However, when the sensitivity and the intrinsic desensitization are evaluated in the examples, black-and-white development (total development) in which development suppression due to iodine has little effect is used, and the performance evaluation as a color light-sensitive material is performed. Is not at all.

Further, when color development is performed, only the intrinsic sensitivity is evaluated because the spectral sensitizing dye is not adsorbed. Further, in this case, no comparison is made with core / shell type grains having high internal iodine.

As described above, in the color photographic light-sensitive material using the internal low iodine core / shell type emulsion, satisfactory improvement in sensitivity and reduction in fog have not been achieved.

JP-A-63-10745 discloses an internal high-iodity core / surface containing 5 mol% or more of silver iodide as a light-sensitive material excellent in color sensitization and having little performance deterioration under high humidity conditions. Shell-type particles are disclosed. As one of the methods for introducing silver iodide to the grain surface, the patent specification describes a method of adding fine silver iodide grains of 0.1 μm or less or fine silver halide grains having a high silver iodide content. There is. However, the introduction of silver iodide on the surface of the grains in all the examples is a double jet method,
Alternatively, an aqueous potassium iodide solution is used. or,
A method of using fine silver halide grains as a method of forming the core portion and the shell portion is not described, and in the examples, the silver halide grains are prepared by the control double jet method.

The present inventors have found that this technique has a small degree of improvement in sensitivity and color sensitization, and that the effect that the present inventors cannot satisfy cannot be obtained.

Furthermore, the most legitimate method for achieving high sensitivity is to reduce the inefficiency of the silver halide crystal during the exposure process and improve the quantum efficiency. Conventionally, as a means for improving the quantum efficiency, a chemical sensitizing nucleus composed of silver sulfide or gold sulfide or a mixture thereof which functions as a photosensitizing center for capturing photoelectrons is formed and imparted on the surface or inside of the silver halide crystal. It is performed and is generally known as sulfur sensitization or gold sulfur sensitization.

However, when the conventional chemical sensitization method is used to form the chemical sensitizing nuclei having a high electron trapping efficiency, a large number of the chemical sensitizing nuclei are formed, and the chemical sensitizing nuclei are formed in the photosensitizing process. It is known that the competition for capturing photoelectrons causes a decrease in latent image forming efficiency, that is, a decrease in sensitivity.

Further, the size and physicochemical properties of each of the plurality of chemically sensitized nuclei formed on the surface or inside of the silver halide grain are not necessarily uniform. Moreover, there are differences in the size, number, distribution state, and properties of the chemically sensitized nuclei among the grains contained in the emulsion.
It is known that the optimum state is not necessarily obtained from the viewpoint of sensitization efficiency and sensitivity-fogging relationship.

As a means for improving such drawbacks of the conventional method, there is a technique for controlling the chemical sensitization nucleation process by allowing a so-called chemical sensitization control agent or chemical sensitization modifier to be present in the chemical sensitization step. Proposed. For example, JP-A-58-126526, JP-A-1-201651, US Pat. Nos. 2,131,038, 3,411,914, and 3,554,757 and Daffin's "Photoemulsion Chemistry", published by Focal Press (1966), pages 138-143, etc. It is described in. As another improvement measure, various methods for selectively growing chemical sensitization at specific sites on a silver halide crystal are disclosed in JP-A-61-93447.
No. 64-40938, No. 64-62631, No. 64-62632, No. 1-158425, No. 1-1201651, No. 2-345, No. 2-298935.
No., etc.

[0017]

However, as a result of our study, it has been found that the recent demand for higher sensitivity cannot be sufficiently achieved by these improvement measures.

Accordingly, it is an object of the present invention to provide a silver halide photographic light-sensitive material having high sensitivity and low fog.

[0019]

The above object of the present invention can be achieved by any one of the following constitutions.

In a silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, in at least one of the photographic constituent layers, after desalting in the production process of the silver halide photographic emulsion, and Before chemical sensitization or spectral sensitization, grains prepared by a method of forming the outermost layer or at least a part of the outermost layer of silver halide grains by supplying fine silver halide grains and represented by the following general formula [I] And / or at least one selected from the compounds represented by the following general formula [II].

[0021]

[Chemical 3]

In the formula, R ^{11 to} R ¹⁴ represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group, and at least one of R ^{11 to} R ¹⁴ always represents a hydrogen atom. R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ can form a 5- or 6-membered heterocycle. A ¹ represents a protonic acid, n ₁₁ represents 1, 2 or 3 and n ₁₂ represents 0, 1, 2 or 3.

[0023]

[Chemical 4]

In the formula, R ^{21 to} R ²⁴ have the same meanings as R ^{11 to} R ^14, and A ² has the same meaning as A ¹ . n ₂₁ has the same meaning as n _11, and n ₂₂ has the same meaning as n ₁₂ .

In a silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, in at least one of the photographic constituent layers, after desalting in the production process of the silver halide photographic emulsion, and It contains at least one of a grain and a selenium compound produced by a method of forming an outermost layer or at least a part of the outermost layer of silver halide grains by supplying fine silver halide grains before chemical sensitization or spectral sensitization. A silver halide photographic light-sensitive material characterized by the above.

In a silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, in at least one of the photographic constituent layers, after desalting in the production process of the silver halide photographic emulsion, and It contains at least one of a grain and a tellurium compound produced by a method of forming an outermost layer or at least a part of the outermost layer of silver halide grains by supplying fine silver halide grains before chemical sensitization or spectral sensitization. A silver halide photographic light-sensitive material characterized by the above.

That is, the object of the present invention is: (1) In a silver halide photographic light-sensitive material having a photographic constituent layer on a support, at least one of the photographic constituent layers is a silver halide emulsion layer, and the photographic constituent is By supplying fine silver halide grains to at least one of the layers after desalting in the process for producing a silver halide photographic emulsion and before chemical sensitization or spectral sensitization, the silver halide photographic In the emulsion produced by the method of forming at least a part of the outermost surface layer of the silver halide grains contained in the emulsion or the outermost shell layer including the outermost surface layer, a compound represented by the above general formula [I] and / or Alternatively, a silver halide photographic light-sensitive material comprising an emulsion containing at least one selected from the group of sulfur-containing compounds consisting of the compound represented by the general formula [II].

(2) General formula [I] in the above (1)
The silver halide according to the above (1), characterized in that an emulsion containing at least one of selenium compounds is used in place of the compound represented by and / or the compound represented by the general formula [II]. Photographic material.

(3) General formula [I] in the above (1)
The silver halide according to the above (1), characterized in that an emulsion containing at least one of tellurium compounds is used in place of the compound represented by and / or the compound represented by the general formula [II]. It has been found to be achieved by any of the photographic light-sensitive materials.

The present invention will be described in more detail below.

The silver halide grains contained in the silver halide photographic emulsion of the present invention may have a regular crystal form such as a cube, octahedron or tetradecahedron, or may have a spherical or plate shape. It may have an irregular crystal form. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed. Twinned silver halide grains having two parallel twin planes facing each other can be used, but in that case, tabular silver halide grains are preferred.

A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the article Photographiesche Correspondents. (Photographische Korresponden
z] Volume 99, page 99, volume 100, page 57.

In the present invention, when tabular silver halide grains are used, the total amount of tabular silver halide grains based on all silver halide grains in the silver halide photographic emulsion containing the tabular silver halide grains is not limited. The proportion of the projected area is preferably 60% or more, more preferably 70% or more.

In the present invention, when tabular silver halide grains are used, the average ratio of grain size to grain thickness (also referred to as aspect ratio) is preferably 1.3 or more and less than 5.0, and 1.5 or more and 4.5 or less. Less, more preferably 2.0 or more and less than 4.0. The average aspect ratio is obtained by averaging the ratio of grain size to thickness of all tabular grains.

The twin plane can be observed by a transmission electron microscope. The specific method is as follows. First,
A silver halide photographic emulsion is coated on a support so that the main planes of the tabular silver halide grains contained therein are oriented substantially parallel to the support to prepare a sample. This is cut with a diamond cutter to obtain a thin section with a thickness of about 0.1 μm. The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

The average grain size of the silver halide grains of the present invention is 0.
It is preferably 1 μm or more and 5.0 μm or less, more preferably 0.2 μm or more and 3.0 μm or less, and most preferably 0.3 μm or more and 2.0 μm or less.

In the present invention, the average particle size is defined as the particle size ri when ni × ri ³ of the frequencies ni and ri ^{3 of} particles having the particle size ri is maximum. (3 significant digits, rounded down to the nearest digit.) (The number of measured grains shall be indiscriminately 1,000 or more.) The grain size ri here means the tabular silver halide grains. It is the diameter when a projected image when viewed from a direction perpendicular to the principal plane is converted into a circular image having the same area. In the case of silver halide grains having a shape other than tabular silver halide grains, the silver halide is It is the diameter when a projected image of a particle is converted into a circular image of the same area.

The grain size ri can be obtained by taking an image of a tabular silver halide grain with an electron microscope at a magnification of 10,000 to 70,000 and measuring the grain diameter on the print or the area at the time of projection. it can.

The silver halide photographic emulsion according to the present invention may be any one such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution, but a monodisperse emulsion is preferred.

A monodisperse emulsion is defined as the width of distribution (%) = (standard deviation / average grain size) × 100, and the width of distribution is 20%.
It is as follows.

The average particle diameter and standard deviation are obtained from the particle diameter ri defined above.

In the silver halide photographic emulsion of the present invention, any silver halide such as silver iodobromide, silver iodochloride, silver chloroiodobromide and the like used in ordinary silver halide emulsions can be used. However, silver iodobromide and silver chloroiodobromide are particularly preferable.

The average silver iodide content of the silver halide grains contained in the silver halide photographic emulsion of the present invention is 2 mol% or more.
It is less than 30 mol%, preferably 3 mol% or more and less than 20 mol%, more preferably 3 mol% or more and less than 15 mol%.

The average silver iodide content of the outermost layer of silver halide grains contained in the silver halide photographic emulsion of the present invention is I
_{When 1} (mol%) and the average iodide content of the silver halide grains is I ₂ (mol%), I ₁ <I ₂ ,
Preferably I ₁ <0.8 × I ₂ , more preferably I ₁ <0.6 ×
It is I ₂ .

In the silver halide grains contained in the silver halide photographic emulsion of the present invention, it is preferable that a high silver iodide content phase is present inside the grains. The silver iodide content in the high silver iodide content phase is preferably 5 mol% or more and the solid solution limit or less, more preferably 10 mol% or more and the solid solution limit or less, and most preferably 15 mol% or more. It is below the melting limit.

In the present invention, the average silver iodide content of silver halide grains is determined by the EPMA method (Electron Probe Micro Ana
lyzer method). Specifically, a sample was prepared in which silver halide grains were well dispersed so that they did not come into contact with each other, and the sample was irradiated with an electron beam while being cooled to −100 ° C. or lower with liquid nitrogen, and emitted from each silver halide grain. The silver iodide content of the individual silver halide grains can be determined by determining the characteristic X-ray intensities of silver and iodine, which are measured for at least 50 silver halide grains and their average is determined.

Core / shell type grains can also be preferably used in the silver halide grains contained in the silver halide photographic emulsion of the present invention. The core / shell type particles are particles composed of a core and a shell covering the core, and the shell is formed by one layer or more layers. It is preferable that the core and the shell have different silver iodide contents.

In the present invention, the solid solution limit is represented by the maximum mol% of iodide which can exist as a solid solution in silver halide. Specifically, “The Theory of Photo” edited by TH James
Graphic Process ”, 4th edition (published by Macmillan), can be determined by the method described on page 4. In the case of silver iodobromide, Imax (mol%) = 34.5 + 0.165 (t-25) (t is It can be calculated by the temperature (Celsius).

The average silver iodide content I ₁ (mol%) of the outermost layer of the silver halide grains contained in the silver halide photographic emulsion of the present invention is preferably more than 0 mol% and not more than 10.0 mol%, and It is preferably more than 0 mol% and not more than 8.0%, and most preferably not less than 0 mol% and not more than 6.0 mol%.

In the silver halide grains contained in the silver halide photographic emulsion of the present invention, the inside of the silver halide grains means
In the case of using seed grains for the production of the silver halide grains, the seed grains are inside the grain size corresponding to 97% by volume of the silver halide grains and at the portion excluding the outermost layer of the silver halide grains. And in the silver halide grains, the portion excluding the portion occupied by the seed grains is preferably inside the grain size corresponding to 90% by volume of the silver halide grains, and A portion of the silver halide grain excluding the outermost layer and a portion of the silver halide grain excluding the portion occupied by the seed grain, and more preferably 70% by volume of the silver halide grain. Which is inside the grain size, and which is a portion excluding the outermost layer of the silver halide grain, and in the silver halide grain,
It is a part excluding the part occupied by the seed grains, most preferably the part inside the grain size corresponding to 50% by volume of the silver halide grains and excluding the outermost layer of the silver halide grains. And in the silver halide grain,
It is a portion excluding the portion occupied by the seed particles.

In the silver halide grains contained in the silver halide photographic emulsion of the present invention, the inside of the silver halide grains means
In the case where the silver halide grains of the present invention are continuously grown from the nucleation without using seed grains in the production of the silver halide grains, the nuclei formed by the nucleation in the silver halide grains are Is a portion excluding the portion occupied by and which is inside the grain size corresponding to 97% by volume of the silver halide grains, and is the portion excluding the outermost surface layer of the silver halide grains. Is a portion of the silver halide grains excluding the portion occupied by the nuclei formed by the nucleation, and 90% by volume of the silver halide grains.
%, Which is inside the grain size corresponding to% and is the portion excluding the outermost layer of the silver halide grains, and more preferably the portion occupied by the nuclei formed by the nucleation in the silver halide grains. The removed portion, and inside the grain size corresponding to 70% by volume of the silver halide grain,
And the portion excluding the silver halide portion, and most preferably the portion excluding the portion occupied by the nuclei formed by the nucleation in the silver halide grain, and in the silver halide grain volume. This is a portion inside the grain size corresponding to 50% and excluding the outermost layer of the silver halide grains.

The outermost layer referred to in the present invention is the outermost layer of the grain including the outermost surface of the silver halide grain, and has a depth of up to 50Å from the outermost surface of the grain.

The silver halide composition of the outermost layer of the present invention is XP
It is obtained as follows by the S method (X-ray Photoelectron Spectroscopy).

That is, the sample is cooled to -110 ° C. or less in an ultrahigh vacuum of 1 × 10 ^-8 torr or less, and M
Irradiate gKα with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA to obtain Ag3
Measure on d / 5/2, Be3d, and I3d3 / 2 electrons. The integrated intensity of the measured peak is the sensitivity factor (Sensitivity Factor).
And the halide composition of the surface is obtained from these intensity ratios.

The XPS method has hitherto been used as a method for determining the silver iodide content on the surface of silver halide grains.
No., etc. However, when the measurement was performed at room temperature, the accurate silver iodide content in the outermost layer could not be obtained because the sample was destroyed by the X-ray irradiation. We have succeeded in accurately determining the silver iodide content of the surface layer by cooling the sample to a temperature at which no destruction occurs. As a result, particularly for particles such as core / shell particles having a different composition between the surface and the interior or particles having a high iodine layer or a low iodine layer localized on the outermost surface, the measured value at room temperature is X-ray. It was revealed that the composition differs greatly from the true composition due to decomposition of silver halide by irradiation and diffusion of halide (particularly iodine). The XPS method used here is as follows.

Emulsion with proteolytic enzyme (pronase) 0.05
A weight% aqueous solution was added, and the mixture was stirred at 45 ° C for 30 minutes to decompose gelatin. This is centrifuged to precipitate the emulsion particles, and the supernatant is removed. Next, distilled water is added to disperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant. The emulsion particles are redispersed in water and thinly coated on a mirror-polished silicon wafer to obtain a measurement sample. The surface iodide was measured by XPS using the sample thus produced. To prevent the sample from being destroyed by X-ray irradiation, the sample is XP
It cooled to -110-120 degreeC in the chamber for S measurement. As the X-ray for the probe, MgKα ray was irradiated at an X-ray source voltage of 15 kV and an X-ray power source current of 40 mA, and the Ag3d5 / 2, Br3d, and I3d3 / 2 electrons were measured. The integrated intensity of the measured peak was corrected with a sensitivity factor (Sensitivity Factor), and the halide composition of the surface was determined from the intensity ratio of these.

When seed grains are used to form the silver halide grains contained in the silver halide photographic emulsion of the present invention, the seed grains are regular crystals such as cubic, octahedral and tetradecahedral. It may have a shape, or may have an irregular crystal shape such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Also, it may have a composite form of these crystal forms,
Particles of various crystal forms may be mixed. The seed grains are preferably twinned silver halide seed grains having two opposing parallel twin planes, and monodisperse spherical seed grains are also preferably used. It is most preferable to use twin seed particles described in JP-A-3-341164.

The silver halide photographic emulsion of the present invention is prepared by the acidic method,
Although it may be produced by any of the neutral method and the ammonia method, an acidic method or a neutral method in which the growth of silver halide grains is performed without using an ammonium compound is preferable,
The silver halide emulsion of the present invention was most effectively achieved by the neutral method carried out without the ammonium compound. In the present invention, the ammonium compound refers to a compound that releases ammonium ions in an aqueous solution in general, and refers to ammonia water, an ammonia compound, an ammonium salt, an ammonia complex salt, an ammonium oxide, and the most widely used ammonia water. Is.

In the present invention, a known silver halide solvent such as thioether or thiourea can be used except the ammonium compound.

In the production of the silver halide photographic emulsion of the present invention, the halide ion and the silver ion may be mixed at the same time, or while one of them is present, the other may be mixed. Also, considering the critical growth rate of silver halide crystals,
Further, halide ions and silver ions can be added successively or simultaneously by controlling pAg and pH in the mixing vessel. The conversion method may be used in any step of silver halide formation to change the silver halide composition of the silver halide grains.

In the production of the silver halide photographic emulsion of the present invention, a cadmium salt, a zinc salt, a lead salt, a thallium salt and an iridium salt (including a complex salt are included in the process of forming and / or growing the silver halide grain. ), A rhodium salt (including a complex salt) and an iron salt (including a complex salt), at least one metal ion is added to contain these metal elements inside and / or on the surface of the silver halide grain. be able to.

In the production of the silver halide photographic emulsion of the present invention, the dispersion medium is gelatin or other substance capable of forming a protective colloid.

In the present invention, when gelatin is used as the dispersion medium, the gelatin may be lime-treated or acid-treated. Details of the method for producing gelatin are described in "The Macromolecular Chemistry of Gelatin" by Arthur Weiss (Academic Press, 1964). Examples of substances that can form protective colloids other than gelatin include, for example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate. , Sugar alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-n-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, etc. A variety of synthetic or semi-synthetic hydrophilic polymeric substances such as coalescence can be mentioned. In the present invention, it is preferable to use gelatin as the dispersion medium.

In the present invention, the protective colloid aqueous solution in which silver halide grains are grown is an aqueous solution in which silver halide grains are grown and is protected by gelatin or another substance capable of forming a hydrophilic colloid. A colloid is formed in the aqueous solution, preferably an aqueous solution containing colloidal protective gelatin.

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may be contained therein. When removing the salts, Research Disclosure (Re
search Disclosure Hereinafter abbreviated as RD. ) No. 17643, page 11, can be performed.

In the silver halide photographic emulsion of the present invention, the average silver iodide content I ₁ (mol%) of the outermost surface layer of the silver halide grains contained in the silver halide photographic emulsion is the average of the silver halide grains. As a specific method for reducing the silver iodide content I ₂ (mol%), a halogen is used after desalting in the production process of the silver halide photographic emulsion and before chemical sensitization or spectral sensitization. It can be produced by a method of forming at least a part of the outermost surface layer of the silver halide grains contained in the silver halide photographic emulsion or the outermost shell layer including the outermost surface layer by supplying silver halide fine grains.

When silver halide fine grains are used in the present invention, the silver halide fine grains may be prepared in advance prior to the preparation of the silver halide photographic emulsion, or in parallel with the preparation of the silver halide photographic emulsion. You may prepare it. When the latter is prepared in parallel, JP-A 1-183417 and 2-44
As shown in No. 335, a method of producing fine silver halide grains by using a mixer separately provided outside the reaction vessel in which the silver halide grains are formed can be used. As described in JP-A-314891, it is desirable to provide a preparation container after the formation of fine particles, and to supply the silver halide fine grain emulsion to the reaction container while preparing it according to the growth environment in the reaction container. .

As a method for preparing the fine silver halide grains, a production method in which the grains are formed in an acidic to neutral environment (pH ≦ 7) is preferable.

To produce the silver halide fine grains, a water-soluble silver salt containing silver ions and a water-soluble alkali halide containing halide ions may be mixed while appropriately controlling the supersaturation factor. Regarding the control of the supersaturation factor, the description in JP-A-63-92942 or 63-311244 can be referred to.

The pAg forming the silver halide fine particles used in the present invention is preferably 3.0 or more, more preferably 5.0 or more, in order to suppress the generation of reduced silver nuclei in the silver halide fine particles themselves. It is preferably 8.0 or more.

The temperature for forming the silver halide fine grains is preferably 50 ° C. or lower, preferably 40 ° C. or lower, and more preferably 35 ° C. or lower. In addition, usual polymeric gelatin can be used as a protective colloid when forming silver halide grains using this method.

When the silver halide fine particles are formed at a low temperature, Ostwald ripening after the formation of the silver halide fine particles can be further suppressed, but gelatin is likely to coagulate at a low temperature. It is preferable to use low molecular weight gelatin, a synthetic molecular compound having a protective colloid action on silver halide grains, or a natural polymer compound other than gelatin, as described in JP-A-166442. The concentration of the protective colloid is preferably 1% by weight, more preferably 2% by weight, still more preferably 3% by weight or more.

The silver halide fine grains supplied to the aqueous solution containing the protective colloid in which the silver halide grains are formed grows the silver halide grains due to the Ostwald ripening effect. Since the fine silver halide grains have a fine grain size, they are easily dissolved and become silver ions and halide ions again to cause uniform growth.

When silver halide fine grains are used in the present invention, the size of the silver halide fine grains is preferably 0.1 μm or less, more preferably 0.05 μm or less.

When the fine silver halide grains are used in the present invention, a method of dispersing the fine silver halide grains in an aqueous solution containing a protective colloid and then adding the fine grains is preferably used.

The fine silver halide grains can be added by funnel addition or function addition using a pump or the like.
It may be added in two or more portions, and after the addition of the silver halide fine particles, ripening may be carried out if necessary.

In the production of the silver halide photographic emulsion according to the present invention, the conditions other than the above are described in JP-A-61-664.
No. 3, No. 61-14630, No. 61-112142, No. 62-157024,
62-18556, 63-92942, 63-151618, 63-16
Appropriate conditions can be selected with reference to 3451, 63-220238, 63-311244 and the like.

Next, the compounds represented by the general formulas [I] and [II] according to the present invention will be described.

In the general formula [I], R ^{11 to} R ¹⁴ , R ²¹
Examples of the alkyl group represented by R ²⁴ include methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, hexyl group, octyl group, 2-ethylhexyl group, dodecyl group, pentadecyl group and eicosyl group. Can be mentioned. These groups include those having a substituent,
Examples of the substituent include a halogen atom (for example, chlorine,
Bromine, iodine, fluorine etc.), aryl group (eg phenyl group, naphthyl group etc.), heterocyclic group (eg pyridyl group,
Thienyl group, thiazolyl group, pyrrolidyl group, imidazolyl group, etc.), carboxy group, nitro group, hydroxyl group, mercapto group, amino group (for example, amino group, diethylamino group,
Hydroxyethylamino group, etc.), alkyloxy group (eg methyloxy group, ethyloxy group, butyloxy group, isopropyloxy group, octyloxy group, dodecyloxy group etc.), aryloxy group (eg phenyloxy group, naphthyloxy group etc.) , Carbamoyl group (eg, aminocarbonyl group, nonylcarbamoyl group, phenylcarbamoyl group, viridylcarbamoyl group, etc.), amide group (eg, methylamide group, benzamide group, etc.), sulfamoyl group (eg, methylsulfamoyl group, phenylsulfamoyl group) Group, octylsulfamoyl group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, etc.), Finyl group (eg methylsulfinyl group, phenylsulfinyl group etc.), alkyloxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group, isopropyloxycarbonyl group, octyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxy Carbonyl group, naphthyloxycarbonyl group, etc., alkylthio group (eg, methylthio group, isopropylthio group, octylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkylcarbonyl group (eg, methylcarbonyl group, isopropylcarbonyl group) , Octylcarbonyl group, etc.), allylcarbonyl group (eg, phenylcarbonyl group, naphthylcarbonyl group, etc.), cyano group, ureido group (eg, methylureido group) Phenylureido group), a thioureido group (e.g., methyl thioureido group include a phenyl thioureido group).

Examples of the alkenyl group represented by R ^{11 to} R ¹⁴ and R ^{21 to} R ²⁴ include a vinyl group, an aryl group, a 1-propenyl group, a 1,3-butadienyl group and a 2-pentenyl group. You can These groups include those having a substituent, and examples of the substituent include an alkyl group and R ¹¹ to
The thing mentioned as a substituent of the alkyl group represented by R < ¹⁴ >, R < ²¹ > -R < ²⁴ > can be mentioned.

Examples of the cycloalkyl group represented by R ^{11 to} R ¹⁴ and R ^{21 to} R ²⁴ include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. These groups include those having a substituent, and as the substituent,
The substituents of the alkyl group and the alkyl groups represented by R ^{11 to} R ¹⁴ and R ^{21 to} R ²⁴ can be exemplified.

Examples of the aryl group represented by R ^{11 to} R ¹⁴ and R ^{21 to} R ²⁴ include a phenyl group and a naphthyl group, and these groups include those having a substituent. Is an alkyl group and the aforementioned R ^{11 to} R ¹⁴ , R ^{21 to} R
^The groups mentioned as the substituents of the alkyl group represented by ²⁴ can be mentioned.

The heterocyclic group represented by R ^{11 to} R ¹⁴ includes a pyridyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a thienyl group, a furyl group, a pyrrolyl group, a pyrimidinyl group, a pyrazinyl group, a purinyl group and a pyridazinyl group. , Isoxazolidinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, morpholyl group, tetrazolyl group and the like. These groups include those having a substituent, and examples of the substituent include the alkyl group and the groups mentioned as the substituents of the alkyl group represented by R ^{11 to} R ¹⁴ and R ^{21 to} R ^24. .

Examples of the heterocyclic group represented by R ^{21 to} R ²⁴ include pyridyl group, oxazolyl group, thiazolyl group, imidazolyl group, thienyl group, furyl group, pyrrolyl group, pyrimidinyl group, pyrazinyl group, purinyl group, Examples thereof include a pyridazinyl group, an isoxazolidinyl group, a selenazolyl group, a sulforanyl group, a piperidinyl group, a pyrazolyl group, a morpholyl group and a tetrazolyl group. These groups include those having a substituent, and examples of the substituent include the alkyl group and the groups mentioned as the substituents of the alkyl group represented by R ^{11 to} R ¹⁴ and R ^{21 to} R ^24. .

As the protonic acid represented by A ¹ and A ² ,
A wide range of organic acids and inorganic acids can be used.

Preferred protonic acids include, for example, hydrochloric acid, hydrobromic acid, sulfuric acid, carbonic acid, phosphoric acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, pyromellitic acid, trinitrophenol and the like. .

The hetero ring formed by R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ²¹ and R ^22, and R ²³ and R ²⁴ is a pyrrole ring, an imidazole ring, a pyrazole ring, an isoindole ring or an indole ring. , Indazole ring, purine ring, carbazole ring, isothiazole ring, isoxazole ring, phenoxazine ring, pyrroline ring, imidazolidine ring, pyrazolidine ring, pyrazoline ring, morpholine ring, piperazine ring, indoline ring and the like, These groups include those having a substituent, and examples of the substituent include the groups exemplified as the substituent of the alkyl group and the substituent of the alkyl group represented by R ^{11 to} R ¹⁴ and R ^{21 to} R ^24. be able to.

Specific examples of the compound represented by the general formula [I] and the compound represented by the general formula [II] are shown below. However, the present invention is not limited to these.

[0089]

[Chemical 5]

[0090]

[Chemical 6]

[0091]

[Chemical 7]

[0092]

[Chemical 8]

[0093]

[Chemical 9]

[0094]

[Chemical 10]

The compounds represented by the general formulas [I] and [II] are described in, for example, Chem. Rev., Vol. 55, 181 (1955) and Chem. Be.
r., 63 , 208 (1930) and J. Org. Chem., 36 , 3895 (197
1) or the method described in J. Chem. Soc., 2999 (1957), etc., can be used for easy synthesis.

The sulfur compound, selenium compound and tellurium compound used in the present invention may be used as a sensitizer. Hereinafter, a sulfur compound, a selenium compound, and a tellurium compound are designated as a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer.

The amount of the sulfur-containing compound represented by the general formula [I] or [II] used in the present invention is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions and the like. , Usually 1 × per mole of silver halide
It is preferably 10 ⁻⁴ to 1 × 10 ⁻⁸ mol. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The selenium sensitizers used in the present invention include a wide variety of selenium compounds. For example, in this regard, U.S. Pat.Nos. 1,574,944, 1,602,592, 1,623,49
9, JP 60-150046, JP 4-25832, 4-10924
No. 0, No. 4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N,
N'-triethylselenourea, N, N, N'-trimethyl-N'-
Heptafluoroselenourea, N, N, N′-trimethyl-N′-
Heptafluoropropylcarbonyl selenourea, N, N,
N′-trimethyl-N′-4-nitrophenylcarbonyl selenoureas, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarbons Acids and selenoesters (eg 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg tri-p-
Triselenophosphate, etc.) and selenides (dimethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenoketones.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patent specifications. U.S. Patent No. 1,57
4,944, 1,602,592, 1,623,499, 3,297,4
66, 3,297,447, 3,320,069, 3,408,196
No. 3,408,197, 3,442,653, 3,420,670,
No. 3,591,385, French Patent No. 2,693,038, No. 2,093,
No. 209, Japanese Patent Publication No. 52-34491, No. 52-34492, No. 53-295
No. 57-22090, JP-A-59-180536, and 59-185330.
No. 59-181337, 59-187338, 59-192241,
No. 60-150046, No. 60-151637, No. 61-246738, JP-A No. 3-4221, No. 3-24537, No. 3-111838, No. 3-116132.
No. 3, No. 3-148648, No. 3-237450, No. 4-16838, No. 4-2
5832, 4-32831, 4-96059, 4-109240, and
4-140738, 4-140739, 4-147250, 4-149437
No. 4, No. 4-184331, No. 4-190225, No. 4-191729, No. 4-
195035, British Patents 255,846, 861,984, HE
Spencer et al., Journal of Photographic Science, 31
, 158-169 (1983) and other research papers.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used.

The temperature of chemical ripening using the selenium sensitizer in the present invention is preferably in the range of 40 to 90 ° C. More preferably, it is 45 ° C or higher and 80 ° C or lower. The pH is 4-9, pAg
Is preferably in the range of 6 to 9.5.

The tellurium sensitizer (tellurium compound) and the sensitizing method used in the present invention are described in US Pat. No. 1,623,
No. 499, No. 3,320,069, No. 3,772,031, No. 3,531,289
No. 3,655,394, British Patent No. 235,211, 1,121,46
No. 9, No. 1,295,462, No. 1,396,696, Canadian Patent No. 80
No. 0,958, JP-A No. 4-20464, and the like. Examples of useful tellurium sensitizers include telluroureas, telluroamides and the like.

The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

The amounts of selenium sensitizer and tellurium sensitizer used are
Although it varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., it is usually from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁹ mol per mol of silver halide. preferable. Further, preferably 1 × 10 ^-5 mol to 1 × 10 ^-8
It is a mole.

In the chemical ripening of the present invention, the addition amount of the selenium sensitizer and / or tellurium sensitizer is set to the number of sulfur atoms released from the sulfur sensitizer in the chemical ripening step. The amount is equal to or less than the number of selenium and / or tellurium atoms that can be released. For example, from one molecule of selenium sensitizer to 2
When a selenium sensitizer capable of releasing one selenium and forming two silver selenide molecules and a sulfur sensitizer capable of forming one silver sulfide molecule are used in combination, the former addition amount is On the other hand, the amount is 1/2 mol or less. On the contrary, when a sulfur sensitizer capable of releasing two or more sulfur atoms is used, it may be smaller than the addition amount (mol) of the selenium sensitizer and / or the tellurium sensitizer. . The preferable addition amount of the selenium sensitizer and / or tellurium sensitizer is such that the number of selenium and / or tellurium atoms is 1/3 or less with respect to the number of sulfur atoms released in the chemical ripening step. is there.

In the chemical sensitization of the present invention, the sensitivity can be further increased by using gold sensitization together. Examples of useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like, U.S. Patent Nos. 2,597,856, 5,049,484, and 5,
049,485, JP-B-44-15748, JP-A-1-147537, 4
Examples include gold complexes of organic compounds disclosed in No. 70650 and the like.

The above-mentioned various sensitizers can be added by adding them by dissolving them in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent depending on the properties of the compound to be used, or by adding gelatin. A method of mixing with a solution in advance and adding it may be a method disclosed in JP-A-4-140739, that is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

When a color photographic light-sensitive material is formed by using the silver halide photographic emulsion of the present invention, the silver halide photographic emulsion used is one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No.17643, No.18716 and N.
o.308119 (Respectively RD17643, RD18716 and RD30811
(Abbreviated as 9)). The following shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Silver halide of the present invention Known photographic additives that can be used when a color photographic light-sensitive material is constructed using a photographic emulsion are also described in the above Research Disclosure. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators / coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developer (included in light-sensitive material) Item 1011 XXB Color photographic light-sensitive using the silver halide photographic emulsion of the present invention Various couplers can be used in constructing the material, specific examples of which are described in Research Disclosure above. The relevant locations are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC-G item Magenta coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-D item VIIC-G item Colored coupler 1002 Item VII-G Item VIIG Item DIR coupler 1001 Item VII-F Item VIIF Item BAR coupler 1002 Item VII-F Other useful residues Release coupler 1001 Item VII-F Alkali-soluble coupler 1001 Item VII-E Silver halide photograph of the present invention Additives used in constructing a color photographic light-sensitive material using an emulsion can be added by the dispersion method described in RD308119XIV.

When a silver halide photographic emulsion of the present invention is used to form a color photographic light-sensitive material, the above-mentioned RD17643 28 is used.
The supports described on page RD18716 pp. 647-8 and RD308119 XVII can be used.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can be provided with auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned item RD308119VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above item RD308119VII-K.

The silver halide photographic emulsion of the present invention is used in various color photographic light-sensitive films 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. It can be preferably applied to materials.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described in RD17643, pages 28 to 29, RD18716 61.
Development can be carried out by a usual method described on page 5 and XIX of RD308119.

[0117]

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

Example 1 (Preparation of twinned seed emulsion (T-1)) A seed having two parallel twin planes was prepared by the following method with reference to the description of Japanese Patent Application No. 3-341164. An emulsion (T-1) was prepared.

(Solution A) Ocein gelatin 80.0 g Potassium bromide 47.4 g HO (CH ₂ CH ₂ O) m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) nH 10% by weight methanol Solution (m ± n = 9.77) 0.48ml 8000.0ml with water (B solution) Silver nitrate 1200.0g 1600.0ml with water (C solution) Ocein gelatin 32.2g Potassium bromide 790.0g Potassium iodide 70.34g Water with 1600.0ml (D Liquid) Ammonia water 470.0 ml Using the stirring device described in JP-A-62-160128, liquid B and liquid C were added to liquid A that was vigorously stirred at 40 ° C for 7.7 minutes by the double jet method to generate nuclei. I did. During this time, pBr
Kept at 1.60. Then, the temperature was lowered to 20 ° C. over 35 minutes. Furthermore, the D liquid was added in 1 minute, and the aging was continued for 5 minutes. The KBr concentration during aging was 0.03 mol / l and the ammonia concentration was 0.66 mol / l. After aging, pH
Was adjusted to 6.0, and desalting was performed according to a conventional method. When the seed emulsion grains were observed with an electron microscope, the average grain size of the seed emulsion grains was 0.225 μm, and the ratio of double parallel twin planes was 75% in terms of the number of all grains.

(Preparation of emulsion (Em-1)) 5 shown below
An emulsion (Em-1) was prepared using the various solutions.

(Solution A-1) Ocein gelatin 66.5 g Distilled water 3227 ml HO (CH ₂ CH ₂ O) m [CHCH ₃ CH ₂ O] _19.8 (CH ₂ CH ₂ O) nH 10% by weight methanol solution (m ± n = 9.77) 2.50 ml Seed emulsion (T-1) 98.5 g Finish with distilled water to 3500 cc (Solution B-1) 3.5N silver nitrate aqueous solution 4702.0 ml (Solution C-1) Potassium bromide 2499.0 g Distilled water to 6000 cc Finishing (Solution D-1) Fine grain emulsion consisting of 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm) (preparation method is shown below) 1897.0 g 6.0% by weight containing 0.06 mol of potassium iodide 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 5000 ml of the gelatin solution of (2) over 10 minutes.
The temperature during fine particle formation was controlled at 40 ° C. The finished weight is
It was 12.53 kg.

(Solution E-1) 1.75N Potassium Bromide Aqueous Solution Necessary amount Solution A-1 was added to a reaction vessel and stirred vigorously.
Solutions B-1 to D-1 were added according to the combination shown in Table 1 by the simultaneous mixing method to grow seed crystals and prepare a core / shell type silver halide emulsion.

Here, the addition rate of (1) solution B-1, solution C-1 and solution D-1 and (2) addition rate of solution B and solution C were respectively set to the critical growth rate of silver halide grains. As appropriate, the function was changed in a function-like manner with respect to time, and the addition rate was controlled so as to prevent generation of small particles and polydispersion due to Ostwald ripening other than the growing seed crystal.

The temperature of the solution in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. pA
Solution E-1 was added as needed for g control. The pH was not controlled but was maintained in the pH range of 5.0-6.0 throughout grain growth.

Table 1 also shows the amount of silver added at that time and the silver iodide content of the silver halide phase during formation with respect to the addition time of the addition solution.

After grain growth, desalting treatment was performed according to the method described in Japanese Patent Application No. 3-41314 to obtain a 20% by weight gelatin aqueous solution.
Add 1.19 liters and disperse at 50 ° C for 30 minutes, then at 40 ° C
The pH was adjusted to 5.80 and the pBr was adjusted to 3.55.

The silver halide grains contained in the obtained silver halide emulsion are monodisperse tabular silver halide grains having an average grain size of 1.34 μm (diameter in terms of projected area circle), an average aspect ratio of 2.6 and a grain size distribution of 18%. Met.

[0128]

[Table 1]

(Preparation of Emulsion (Em-2)) Emulsion (Em-
In the preparation of 1), after grain growth, desalting treatment was performed according to the method described in Japanese Patent Application No. 3-41314, 1.19 liter of 20% by weight gelatin aqueous solution was added, and the mixture was dispersed at 50 ° C. for 15 minutes.
The pBr was adjusted to 1.5 with a 3.5N potassium bromide aqueous solution at 50 ° C., and the following solution H- was added to the stirring silver halide emulsion.
The emulsion (Em-2) was prepared in exactly the same manner except that 0 was added for 30 seconds, the mixture was stirred for 20 minutes, and then pH was adjusted to 5.80 and pBr to 3.55 at 40 ° C. The history of pH in the reaction vessel was as follows.

Time (minutes) from the start of addition of Solution B-1 to Solution D-1 52.47 76.48 150.13 176.09 239.00 pH 8.00 7.51 6.40 6.36 5.84 (Solution H-0) 3 wt% gelatin And a fine grain emulsion consisting of silver bromide particles (average particle size 0.04 μm) (preparation method is shown below) 0.212 mol 0.06 mol potassium bromide 6.0% by weight gelatin solution 5000 ml, 7.06 mol silver nitrate, 2000 ml each of an aqueous solution containing 7.06 mol of potassium bromide was added over 10 minutes.
The temperature during fine particle formation was controlled at 30 ° C. During particle formation
The pH was controlled to 3.0 using nitric acid, and after forming fine particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

(Preparation of emulsion (Em-3)) 7 shown below
The octahedral twin monodisperse emulsion EM-3 was prepared using various types of solutions.

(Solution A-2) Ocein gelatin 268.2 g Distilled water 4.0 l Polyisopropylene-polyethyleneoxy-succinic acid ester sodium salt 10% methanol solution 1.5 ml Seed emulsion (T-1) 0.341 mol 28 wt% ammonia Aqueous solution 528.0 ml 56 wt% acetic acid aqueous solution 795.0 ml 0.001 Methanol solution containing 1 mol of iodine 50.0 ml Distilled water to 5930.0 ml (Solution B-2) 3.5N ammoniacal silver nitrate aqueous solution (however, pH was adjusted to 9.0 with ammonium nitrate) (Solution C-2) 3.5N potassium bromide aqueous solution containing 4.0% by weight of gelatin (Solution D-2) A fine grain emulsion comprising 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) (preparation method) 0.844 mol 0.06 mol of potassium iodide in a 6.0% by weight gelatin solution of 5000 ml, 7.06 mol of silver nitrate and 7.06 mol of potassium iodide in an aqueous solution of 20 ml each. 00 ml was added over 10 minutes. The pH during the formation of fine particles is 2.0 using nitric acid, and the temperature is 40
Controlled to ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

(Solution E-2) From silver iodobromide grains (average particle size 0.04 μm) containing 1 mol% of silver iodide prepared in the same manner as the silver iodide fine grain emulsion described in Solution D, However, the temperature during the formation of the fine particles was controlled to 30 ° C. (Solution F-2) 1.75N potassium bromide aqueous solution (Solution G-2) 56% by weight acetic acid aqueous solution It was kept at 70 ° C in the reaction vessel. Solution A-2, solution B-2,
Solution C-2 and solution D-2 were added by the simultaneous mixing method over a period of 163 minutes, followed by addition of solution E-2 to 12
The seed crystal was grown to 1.349 μm by constant rate addition alone in a minute.

Here, the addition rates of the solution B-2 and the solution C-2 were changed in a function-like manner with respect to time so as to correspond to the critical growth rate, and the generation of small particles other than the growing seed crystal and It was added at an appropriate addition rate so as not to cause polydispersion due to Ostwald ripening. The solution D-2, that is, the silver iodide fine grain emulsion was supplied, by changing the rate ratio (molar ratio) with the aqueous ammoniacal silver nitrate solution with respect to the particle size (addition time) as shown in Table 2, a multiple structure was formed. A core / shell type silver halide emulsion having the above was prepared.

By using solutions F-2 and G-2, pAg and pH during crystal growth were controlled as shown in Table 2. The pAg and pH were measured using a silver sulfide electrode and a glass electrode according to a conventional method.

After grain formation, desalting treatment was carried out according to the method described in Japanese Patent Application No. 3-41314, and gelatin was added and redispersed to adjust pH to 5.80 and pAg to 8.06 at 40 ° C. From the scanning electron micrograph of the obtained emulsion grains, the average grain size was 1.
It was confirmed to be an octahedral twin dispersion emulsion having a distribution of 10.3% with a width of 28 μm.

[0137]

[Table 2]

(Preparation of Emulsion (Em-4)) Emulsion (Em-
In the preparation of 3), after grain growth, desalting treatment was performed according to the method described in Japanese Patent Application No. 3-41314, 1.19 liter of 20% by weight gelatin aqueous solution was added, and the mixture was dispersed at 50 ° C. for 15 minutes.
Adjust pBr to 1.5 with 3.5N potassium bromide aqueous solution at 50 ℃,
Solution H-1 shown below was added to the stirred silver halide emulsion.
After 30 minutes, 10 minutes later, the following solution I-1 was added for 30 seconds, 10 minutes later, the following solution J-1 was added for 30 seconds, and after stirring for 20 minutes, the pH was 5.80 at 40 ° C. , PBr 3.55
Emulsion (Em-4) in the same manner except that
Was prepared.

(Solution H-1) 3% by weight of gelatin and a fine grain emulsion (**) consisting of silver bromide grains (average particle size 0.04 μm) 0.127 mol (Solution I-1) 3% by weight of gelatin, Fine grain emulsion composed of silver bromide grains (average grain size 0.04 μm) (**) 0.127 mol (solution J-1) 3 wt% gelatin and fine grain emulsion consisting of silver bromide grains (average grain size 0.04 μm) ( **) 0.127 mol ** 5000 ml of a 6.0% by weight gelatin solution containing 0.06 mol of potassium bromide, 5000 ml of 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium iodide, respectively, 10 ml Added over minutes. The temperature during fine particle formation was controlled at 30 ° C. The pH during fine particle formation was controlled to 3.0 using nitric acid, and the pH was adjusted to 6.0 using an aqueous sodium carbonate solution after particle formation.

The emulsions (Em-1) to (Em-4) were optimally chemically sensitized by adding sulfur, selenium or tellurium compounds as shown in Tables 3 and 4, respectively. Each of these emulsions was designated as (Emulsion A) and used in the following sample formulation.

Multi-layer color photographic light-sensitive material samples 1 to 30 were prepared by sequentially forming each layer having the following composition on the triacetyl cellulose film support from the support side.

Unless otherwise specified, the addition amount is the number of grams per 1 m ² . The silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in the number of moles per mole of silver.

First layer; antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point organic solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer Compound (SC-1) 0.15 High boiling point Organic solvent (Oil-2) 0.17 Gelatin 1.27 Third layer; low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size) 0.27 μm, silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD- ⁴ ) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point Solvent (Oil-1) 0.53 Gelatin 1.30 4th layer; Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol% ) 0.62 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 ^-4 Sensitizing dye (SD-2) 1.2 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD- ⁴ ) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer; high-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.0 μm, silver iodide content 8.0 mol% ) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored Cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 6th layer; Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Gelatin 0.80 7th layer; Low sensitivity green Sensitive layer Silver bromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.61 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD-4 ) 7.4 × 10 ^-5 Sensitizing dye (SD- ⁵ ) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling solvent (Oil-- 2) 0.75 Gelatin 1.95 Eighth layer; Medium-sensitive green sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.87 Sensitizing dye (SD-6) 2.4 × 10 ^-4 increase Dye (SD-7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D─ 3) 0.002 High boiling point solvent (Oil-2) 0.50 Gelatin 1.00 9th layer; High sensitivity green sensitive layer Silver iodobromide emulsion (Emulsion A) 1.27 Sensitizing dye (SD-6) 1.4 ^10-4 Sensitizing dye (SD─7) 1.4 × 10 ^-4 Magenta coupler (M─2) 0.084 Magenta coupler (M─3) 0.064 Colored magenta coupler (CM─1) 0.012 High-boiling solvent (Oil─1) 0.27 High boiling point solvent (Oil-2) 0.012 Gelatin 1.00 10th layer; Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 11th layer; Intermediate layer Formalin scavenger (HS-1) 0.20 Gelatin 0.60 12th layer; Low sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 0.38 µm, silver iodide content 8.0 mol%) 0.22 Iodour Silver halide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.03 Sensitizing dye (SD-8) 4.9 × 10 ^-4 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High Boiling point solvent (Oil-2) 0.30 Gelatin 1.20 13th layer; Medium sensitivity blue feeling Functional layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.30 Sensitizing dye (SD-8) 1.6 × 10 ^-4 Sensitizing dye (SD-9) 7.2 × 10 ^-5 Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer; High-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 1.0 μm, iodine Silver halide content 8 mol%) 0.85 Sensitizing dye (SD-8) 7.3 × 10 ^-5 Sensitizing dye (SD-9) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling solvent (Oil-2) ) 0.046 Gelatin 0.80 15th layer; 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 UV absorber (UV-2) ) 0.10 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 16th layer; 2nd protective layer Alkali-soluble matting agent (average) Diameter 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid Su-2, viscosity adjustment Agent, hardener H-1, H-2, stabilizer ST-1, antifoggant AF-1, weight average molecular weight: 1
Two types of AF-2 with 000 and weight average molecular weight of 1,100,000
And the preservative DI-1 was added. The amount of DI-1 added is 9.
It was 4 mg / m ² .

The structures of the compounds used in the above samples are shown below.

[0145]

[Chemical 11]

[0146]

[Chemical 12]

[0147]

[Chemical 13]

[0148]

[Chemical 14]

[0149]

[Chemical 15]

[0150]

[Chemical 16]

[0151]

[Chemical 17]

[0152]

[Chemical 18]

These samples were exposed to sensitometry with white light and processed in the following processing steps to evaluate sensitivity and fog.

[Treatment process (38 ° C)] Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying treatment The composition of the treatment liquid used in the process is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.0.

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted with ammonia water.
Adjust to 6.0.

[Fixing Solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (Konica Corporation) 7.5 ml Water is added to make 1 liter.

The sensitivity (S) is the relative value of the reciprocal of the amount of received light that gives a density of fog +0.1, and is the relative when the green sensitivity of the sample (No. 1) processed immediately after exposure is 100. Shown by value. The fog is shown as a relative value when the fog density of the green photosensitive layer of the sample (No. 1) is 100.

Tables 3 and 4 show the evaluation results of sensitivity and fog of samples (No. 1) to (No. 30).

[0161]

[Table 3]

[0162]

[Table 4]

[0163]

[Chemical 19]

From Tables 3 and 4, samples (No. 9) to (No. 14) and (No. 23) using the silver halide photographic emulsion of the present invention were used.
It can be seen that (No. 30) to (No. 30) have excellent photographic performance with respect to sensitivity and fog with respect to the comparative sample.

[0165]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and low fog can be provided.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, wherein at least one of the photographic constituent layers has been subjected to desalting in the step of producing a silver halide photographic emulsion. , And before chemical sensitization or spectral sensitization, by supplying silver halide fine particles, a grain prepared by a method of forming the outermost layer or at least a part of the outermost layer of silver halide grains and the following general formula [I]
And / or at least one compound selected from the compounds represented by the following general formula [II]. [Chemical 1] [In the formula, R ^{11 to} R ¹⁴ represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group, and at least one of R ^{11 to} R ¹⁴ always represents a hydrogen atom. R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ can form a 5- or 6-membered heterocycle. A ¹ represents a protonic acid,
n ₁₁ represents a number of 1, 2, or 3, and n ₁₂ represents a number of 0, 1, 2, or 3. ] [Chemical 2] [In the formula, R ^{21 to} R ²⁴ have the same meanings as R ^{11 to} R ¹⁴ ,
A ² has the same meaning as A ¹ . n ₂₁ has the same meaning as n _11, and n ₂₂ has the same meaning as n ₁₂ . ] 2. A silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, wherein at least one of the photographic constituent layers has been subjected to desalting in the process for producing a silver halide photographic emulsion. , And before chemical sensitization or spectral sensitization, at least one of a grain and a selenium compound produced by a method of forming an outermost layer or at least a part of the outermost layer of silver halide grains by supplying fine silver halide grains. A silver halide photographic light-sensitive material characterized by containing. 3. A silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, wherein at least one of said photographic constituent layers has been subjected to desalting in the step of producing a silver halide photographic emulsion. And before chemical sensitization or spectral sensitization, at least one of a grain and a tellurium compound produced by a method of forming an outermost layer or at least a part of the outermost layer of a silver halide grain by supplying fine silver halide grains. A silver halide photographic light-sensitive material characterized by containing.