WO1989006830A1 - Silver halide photographic material and process for its preparation - Google Patents

Abstract

A photographic material prepared by using a silver halide emulsion containing silver halide grains wherein a halide distribution is microscopically completely uniform and/or which comprise a core part not containing reduced silver formed upon formation of the grains and a shell part different from the core part in a halide composition, and a process for its preparation are disclosed. This material has excellent properties with respect to sensitivity, gradation, graininess, sharpness, resolving power, covering power, preservability, latent image stability and pressure effect.

Description

 Specification

 C. α-silver photographic light-sensitive material and method for producing the same [Technical field]

 The present invention relates to a silver halide photographic material useful in the field of photography and a method for producing the same. More specifically, the microscopic halide distribution inside each silver halide mixed crystal is completely uniform, and / or the inside of the silver halide crystal also contains reduced silver generated during grain formation. The present invention relates to a photographic light-sensitive material using a silver halide emulsion having silver halide grains and a method for producing the same.

 (Background technology)

In recent years, there has been an increasing demand for improved performance of silver halide photographic light-sensitive materials.In particular, it has been desired to increase the sensitivity and increase the developing speed while minimizing deterioration of graininess and sharpness. I have. In order to satisfy these demands, a so-called core-shell type emulsion in which the halide composition of the inside and the surface layer of silver halide grains is changed has been developed. In the silver iodobromide emulsion, the inside of the grain (core) is silver iodobromide, which has a high silver iodide content, and the surface (shell) is silver iodobromide or pure silver bromide, which has a lower silver iodide content. It has been disclosed. These are described in JP-A-57-15432, JP-A-60-14331, JP-A-60-138538, JP-A-60-147727, JP-A-61-245151 and JP-A-61-14363. The technology is disclosed in the issue. Also, with respect to the Coaschul emulsion having silver chloride or silver chlorobromide on the grain surface, JP-A-58-9137, JP-A-58-9573, JP-A-59-48755, JP-A-61-215540, The technique is disclosed in Japanese Patent Application Laid-Open No. 62-69261. In addition, the particle surface is higher than the inside The technique of the coachul emulsion having a silver iodide content is disclosed in JP-A-56-78831 and JP-A-62-19843.

 In these core shell emulsions, an increase in light absorption, an increase in the efficiency of latent image formation due to the formation of a layer structure of the core and the shell, and an improvement in the development speed have been achieved. It has been found that such a microscopic uneven distribution of halide in particles exists, which hinders the movement of electrons generated by exposure and lowers the efficiency of latent image formation. It needed to be improved.

 Generally, silver halide grains are produced by reacting an aqueous silver salt solution and an aqueous halide salt solution in an aqueous colloid solution in a reaction vessel. In a reaction vessel, a protective jet such as gelatin and an aqueous solution of a halogen salt are placed, and while stirring, an aqueous solution of a silver salt is added thereto for a certain time, or a gelatin aqueous solution is placed in the reaction vessel. A double-jet method in which an aqueous solution of a halogen salt and an aqueous solution of a silver salt are added for a certain period of time is known. Comparing the two, the double jet method gives silver halide grains with a narrower grain size distribution, and the halide composition can be freely changed as the grains grow.

It is also known that the growth rate of silver halide grains varies greatly depending on the concentration of silver ion (halogen ion) in the reaction solution, the concentration of the silver halide solvent, the distance between grains, the grain size, and the like. ing. In particular, the non-uniformity of silver ion or halogen ion concentration created by the aqueous silver salt solution and the aqueous solution of haegent salt added to the reaction vessel causes the growth rate to differ depending on each concentration, and as a result It causes unevenness in the silver halide emulsion that emerges. For this purpose, the silver ion or halogen solution in the reaction vessel should be uniformly mixed, and the silver salt aqueous solution and the hacogen salt solution should be mixed rapidly. It is necessary. In the conventional method of adding an aqueous solution of a halogen salt and an aqueous solution of a silver salt to the surface of an aqueous solution of a colloid in a reaction vessel, the concentration of the halogen ion and the silver ion in the vicinity of the addition position of each reaction solution is determined. High portions were formed, and it was difficult to produce uniform silver halide grains. As a method of improving the local density, techniques disclosed in U.S. Pat. No. 3,415,650, British Patent No. 1323464, and U.S. Pat. No. 3,692,283 are known. In these methods, a reaction vessel filled with an aqueous solution of colloid has a slit on the wall of a medium-thick cylindrical shape. Φ empty face-to-face mixer (the interior is filled with an aqueous solution of colloid). More preferably, the mixer is divided into two upper and lower chambers by means of a disc), and the vertical axis of the image is set vertically. The aqueous solution and the silver salt aqueous solution are supplied into the mixer rotating at high speed through the supply pipe, and are rapidly mixed and reacted. (If there are upper and lower separation disks, the aqueous solution of the halogen salt is supplied to the upper and lower two chambers. The aqueous silver salt solution was diluted with the aqueous colloid solution filled in each chamber and rapidly mixed and reacted near the exit slit of the mixer), and was generated by the centrifugal force generated by rotation of the mixer. , Silver halide grains in the reaction vessel It is a method of growing by discharging into an aqueous solution.

On the other hand, Japanese Patent Publication No. 55-10545 discloses a technique for improving the local concentration density to prevent uneven growth. This According to the method, a halogen salt aqueous solution and a silver salt aqueous solution are introduced into a reactor filled with a colloid aqueous solution from the open lower end of a mixer filled with the colloid aqueous solution. The reaction solutions are separately supplied through a supply pipe, and the reaction solutions are rapidly stirred and mixed by a lower stirring blade (turbine blade) provided in a mixer to grow silver halide. There is a technique in which silver halide grains grown by an upper stirring blade provided above are discharged from the opening of the upper mixer into an aqueous solution of copper in a reaction vessel.

 Japanese Patent Application Laid-Open No. 57-92523 similarly discloses a production method for improving the nonuniformity of the concentration. According to this method, a halogen salt aqueous solution and a silver salt aqueous solution are separated from the open lower end of a mixer filled with a colloid aqueous solution in a reaction vessel filled with the colloid aqueous solution. The two reaction solutions are diluted with the aqueous colloid solution, and the reaction solutions are rapidly stirred and mixed by a lower stirring blade provided in the mixer, and immediately above the mixer. In a manufacturing method or an apparatus for discharging silver halide grains grown from the open part of the reaction vessel into the aqueous solution of the coide, both reaction solutions diluted with the aqueous solution of the coide are mixed with each blade of the stirring blade. Without passing through the gap between the inner wall of the mixer and the gap formed outside the tip of the blade of the agitating blade, the two reaction liquids are rapidly sheared and mixed in the gap, and the reaction is performed. Generates silver halide particles Forming method and apparatus is disclosed.

However, the manufacturing methods and equipment that have been arrested so far do not guarantee that the local concentrations of silver ions and halogens in the reaction vessel are uneven. Although it can be completely eliminated, this concentration unevenness still exists in the mixer, especially near the nozzle that supplies the silver salt aqueous solution and the halogen salt aqueous solution, the lower part of the stirring blade, and the stirring. There is a fairly large concentration distribution in the part. Furthermore, the silver halide grains supplied to the mixer together with the protective colloid pass through such a place having an uneven concentration distribution, and most importantly, the silver halide grains Growing rapidly in parts. In other words, in these production methods and devices, the concentration distribution exists in the mixer, and since the grain growth occurs rapidly in the mixer, the silver halide grows uniformly without the concentration distribution. Has not achieved its purpose.

In order to eliminate the non-uniform distribution of silver ion and nodrogen ion concentrations due to more thorough mixing, the reaction vessel and the mixer were separated from each other, and the silver salt aqueous solution and the halogen were added to the mixer. Attempts have been made to grow silver halide grains by supplying an aqueous salt solution and mixing rapidly. For example, in JP-A-53-37414 and JP-B-48-21045, an aqueous protective chloride solution (containing silver halide particles) in a reaction vessel is circulated from the bottom of the reaction vessel by a pump, and the circulation system is used. A manufacturing method and apparatus are disclosed in which a mixer is provided in the middle of the process, an aqueous solution of silver salt and an aqueous solution of hagen are supplied to the mixer, and both aqueous solutions are rapidly mixed by the mixer to grow silver halide particles. Have been. U.S. Pat. No. 3,897,935 discloses that a protective colloid aqueous solution (containing silver halide grains) in a reaction vessel is circulated by a pump from the bottom of the reaction vessel. A method of injecting a silver salt aqueous solution by a pump is disclosed. JP-A Sho 53 In 47397, an aqueous solution of protective colloid (containing a silver halide emulsion) in the reaction vessel was circulated from the reaction vessel by a pump, and an aqueous solution of alkali metal halide was first added to the circulation system. A production method and apparatus characterized in that silver halide grains are formed by injecting and mixing an aqueous silver salt solution into this system after injecting and diffusing until it is uniform, has been proposed. I have. Indeed, with these methods, the flow rate of the aqueous solution in the reaction vessel flowing into the circulation system and the stirring efficiency of the mixer can be independently changed, and the particles can be grown under a more uniform concentration distribution. In the end, the silver halide crystals sent from the reaction vessel together with the aqueous solution of protective colloid will grow rapidly at the inlet of the aqueous silver salt solution and the aqueous halide solution. Therefore, it is theoretically impossible to eliminate the concentration distribution near the mixing portion or the injection port, as described above.In other words, it is possible to achieve the purpose of uniformly growing Haguchi silver halide without the concentration distribution. Absent.

It is an object of the present invention to completely disperse the microscopic halide distribution inside the grain (core) in the core shell emulsion grains having different halide compositions. Uniformity and / or uniformity of reduced silver in the grains, resulting in low fog, high sensitivity, improved granularity, sharpness, and covering power, and excellent storage stability and pressure When to provide a method of manufacturing a wafer port Gen halide photographic material and the photosensitive material having I ¹

 [Disclosure of the Invention]

 The object of the present invention has been achieved by the following. That is

(1) At least one silver halide emulsion layer on the support In a silver halide photographic light-sensitive material, the photosensitive silver halide grains contained in the silver halide emulsion layer may contain at least two kinds of silver halides. It is composed of at least one phase, its halide distribution is completely uniform, and the surface of the particles is silver halide having a different halide composition from the interior of the grains adjacent to the surface. Silver halide photo-sensitive material.

 (2) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the photosensitive silver halide grains contained in the silver halide emulsion layer are formed. By adding a previously prepared fine-sized silver halide to a reaction vessel for causing nucleation and / or crystal growth of the grains, nucleation and Z or crystal growth are performed in the reaction vessel. A silver halide photographic light-sensitive material, characterized in that the silver halide grains have silver halides having different halide compositions outside of the silver halide grains.

 (3) A water-soluble silver salt is placed in a mixer provided outside a reaction vessel for causing nucleation and / or crystal growth of photosensitive silver halide grains by using fine-sized silver halide grains. And an aqueous solution of a water-soluble halide are formed by mixing, and supplied into the reaction vessel immediately after the formation to form nucleation and / or crystal growth of the photosensitive silver halide grains. Forming silver halide having a different halide composition from the outside.

The method for producing a silver halide photographic light-sensitive material according to (2).

The silver halide grains of the present invention have a so-called corenosil structure, and its core portion has a completely uniform halide distribution. It is a sign.

 The shell portion only needs to have a different halogen composition from the core portion adjacent to the shell portion, and the halide distribution of the shell portion does not need to be completely uniform. The halide composition may be a single composition or a so-called mixed crystal.

 Tabular silver iodobromide grains having a silver iodobromide phase will be described as an example of the silver halide emulsion grains having a “completely uniform halide distribution” in the present invention.

The term “perfectly uniform silver iodide distribution” here is completely different from the silver iodide distribution that has been treated so far, and refers to a more microscopic distribution. Conventionally, an analytical electron microscope (Analytical Electron Microscopy) is often used as a means for measuring the distribution of silver iodide in silver iodobromide grains. For example, King (M. King), π-let (MHLorretto M. Nanotern (T. J. Maternaghan) and F. Berry (FJ Berry), "analytical electron microscopy. Research on the distribution of singularities (investigations, observations, distributions, analysis, electronics, microscopy), “Progress, Invasive, and Principles” In Imaging Systems, International Congress of the Science of Cologne (Κδΐη), 1986, the content of silver iodide in flat silver bromide particles was measured. The size of the electron beam irradiation probe used in this study is 50 mm, but the electron beam is actually scattered due to elastic scattering of electrons. Has spread, and the sample table The diameter of the spot of the electron beam irradiated on the surface is about 300 people. Therefore, this method cannot measure the finer silver iodide distribution. The same method was used to measure the silver iodide distribution in JP-A-58-113927, but the size of the electron beam spot used was 0.2.

 Therefore, it is not possible to clarify the more microscopic (100 A order or less spatial change) silver iodide distribution by these methods. This microscopic distribution of silver iodide is described, for example, in Hamilton (JF Hamilton), Photographic Science and Engineering, Vol. 11, 1967. It can be observed by a direct method using a low-temperature transmission electron microscope described in P. P57, Takeshi Shiozawa, The Photographic Society of Japan, Vol. 35, No. 4, 1972, P. P213. That is, the silver halide grains taken out under safe light are placed on a mesh for electron microscopic observation so that the emulsion grains do not print out so as to prevent damage by electron beams (such as printouts). Observe by the transmission method with the sample cooled with liquid nitrogen or liquid helium.

 Here, the higher the accelerating voltage of the electron microscope, the sharper the transmission image can be obtained, but up to a particle thickness of 0.25, particles of 200 K volt and more! : For that, lOOOKvo l t is good. The higher the accelerating voltage, the greater the damage of the particles by the irradiation electron beam. Therefore, it is desirable to cool the sample with a liquid helium rather than liquid nitrogen.

 The imaging magnification can be changed as appropriate depending on the particle size of the sample, but it is 20,000 to 40,000.

Thus, transmission electron micrographs of silver iodobromide tabular grains were obtained. When photographing Shin, a very detailed annual ring-shaped stripe pattern is observed in the area of Ginkgo Bromide. An example of this is shown in FIG. The tabular grains shown here consist of silver bromide tabular grains as the core and a silver iodobromide shell of 10 mol% silver iodide formed outside the core. Can be clearly seen in this transmission electron micrograph. In other words, a part of the core is silver bromide, which is of course uniform, so that only a uniform flat image can be obtained.On the other hand, the silver iodobromide phase has a very fine annual ring shape. Stripes can be clearly seen. It can be seen that the spacing of the stripes is very fine, on the order of 100 A to less, indicating very microscopic non-uniformity. Various methods can be used to show that this very fine grain pattern shows non-uniformity in the distribution of silver iodide, but more directly, this tabular grain is formed by silver halide crystals. It is clear that this striping disappears completely when annealing (eg, 250 hours, 3 hours) under conditions that allow you to move inside.

The annual ring-shaped stripes, which indicate the uneven distribution of silver iodide in the silver bromide emulsion grains of the tabular plate described above, are referred to in the above-cited Japanese Patent Application Laid-Open No. 58-113927. This is clearly seen in the transmission electron micrographs, as well as in the transmission electron microscopy photographs in the study of King et al. Cited above. Based on these facts, to date, iodine bromide particles prepared with a constant amount of silver iodide in order to obtain a uniform silver iodide distribution have been extremely contradictory to their intended use. It has a microscopic non-uniform distribution of silver iodide, and no technology for homogenizing it has been disclosed. No production method is disclosed. The present invention discloses a core-shell emulsion having a core portion in which the microscopic silver iodide distribution is completely uniform, and a method for producing the same.

 As described above, silver halide grains having a “completely uniform halide distribution” can be obtained by observing the transmission image of the grains using a cooled transmission electron microscope. It can be clearly distinguished from particles. In other words, inside the silver halide grains of the present invention, for example, in the case of the above silver iodobromide, a microscopic line caused by the microscopic unevenness of the silver iodide becomes a line. There are at most two, preferably one, at 0.2 intervals in the orthogonal direction, and more preferably none. The lines ′ that form the annual ring-shaped stripes, which indicate the microscopic unevenness of silver iodide, are generated perpendicular to the direction of grain growth, and consequently these lines are concentric from the grain center. Distribute in a shape. For example, in the case of the tabular grains shown in Fig. 5, the line forming the annual ring-shaped stripe pattern indicating the unevenness of silver iodide is orthogonal to the growth direction of the tabular grains. The direction parallel to ヂ and perpendicular to them has a direction toward the center of the particle, and is distributed concentrically around the center of the particle.

Of course, if the silver iodide content is changed rapidly during grain growth, the boundary will be observed as a line similar to that described above in the above observation method. The change in the amount of silver only constitutes a single line, which can be clearly distinguished from a line composed of multiple lines derived from the microscopic unevenness of silver iodide. Furthermore, a line derived from such a change in silver iodide content can be clearly confirmed by measuring the amount of silver iodide on both sides of the line by the above-mentioned diffraction electron microscope. Can be. The line due to such a change in the silver iodide content is completely different from the line derived from the microscopic unevenness of the silver iodide referred to in the present invention, and shows a “macroscopic silver iodide distribution”. .

 In addition, when the amount of silver iodide is changed substantially continuously during the growth of grains, there is no sharp change in the silver iodide content. No line of change is observed, so if there are at least three lines at 0.1 intervals, there is a microscopic unevenness in the silver iodide content. become.

 Thus, the “halogen silver halide core particles having a completely uniform halide distribution” of the present invention are mixed crystals having at least two kinds of silver halides. In the transmission image of the particles obtained using the method, the core particles have at most two lines exhibiting a microscopic halide distribution at 0.2 intervals in a direction perpendicular to the lines, and preferably have one line. More preferred are silver halide core grains free of such lines. Further, it is desirable that such particles having a uniform interior make up at least 60%, preferably at least 80%, and more preferably at least 90% of the total particles.

Until now, conventional silver halide grains, for example, which have been called silver halide grains containing uniform silver iodide, simply contain silver nitrate and a halogen of a certain composition (a certain amount of iodide) during grain growth. The salt mixture was only added to the reaction vessel by the double jet method, and in such particles the macroscopic silver iodide distribution is indeed constant.The microscopic silver iodide distribution is not uniform. Absent. In the present invention, such a particle is called a particle having a “constant halogen composition” and is clearly distinguished from a “perfectly uniform” particle shown in the present invention. Although the above description has been made taking silver iodobromide silver halide grains as an example, the problem of microscopic halide composition is that silver halides such as silver chlorobromide, silver chloroiodobromide, and silver chloroiodide are used. It is all about mixed crystals.

 The uniformity of the microscopic halide distribution of the silver halide mixed crystal can be further measured using X-ray diffraction.

 It is well known to those skilled in the art to determine the halogen composition using an X-ray diffractometer (diffractometer). The principle is briefly described as follows. By measuring the Bragg angle in X-ray diffraction, the lattice constant a can be determined from the following Bragg equation.

 2 d hki sin Θ hki = λ λ: X-ray wavelength

Θ hki: Bragg angle from (hk £) plane d _{hk t} = ^a ― d _hk i: spacing between (hk £) planes

• h ² + k ² + £ ² a: lattice constant By the way, T, H. James, “The Theory of the Process” by The James, “The Theory of the Process” (Photographic Process) 4th edition Macmillan Co., New York (Chapters 1) Relationship of lattice constant a to silver composition for silver iodobromide, silver chlorobromide and silver iodochloride It is shown. Thus, when the lattice constant (halogen composition) is different, the diffraction peak position is different. Therefore, silver halide grains having excellent uniformity of the halogen composition distribution have a small variation in lattice constant, and the half width of the profile is narrow. In the measurement of the folding profile, the source is preferably a Ko line having a high intensity and a good monochromaticity over a K line. Note that the Κ line is a double line !? Using the achinger method to obtain a single profile It is possible to determine the price range.

 For the sample, use powdered particles obtained by removing gelatin from the emulsion, or use C.Fa in the Journal of Photographic Science, Vol. 24, 1976, 1976, page 24 of the Journal of Photographic Science. Immersion in 50% glycerin solution for 20 minutes according to GC Farnell, R. J. Jenkins and LR Solraan A coated emulsion film can be used in which the pressure applied to the grain surface is removed by the gelatin inside. In order to accurately determine the angle of the bent profile, a method of mixing Si powder or NaCl powder with a known diffraction angle with the sample is used. Further, it is known that a diffraction profile having a large diffraction angle from a high index plane is preferably used in order to accurately measure the diffraction angle and the line width of the profile. Therefore, in this patent, the K or line of the copper target is used to convert the diffraction profile of the (420) plane into a plane bending angle (twice the Bragg angle) of 7 mm. The measurement was performed in the area of Γ. -In the X-ray diffraction measurement, the accuracy of measurement was higher for the coated emulsion film than for the powder, and the measurement was also performed on the coated emulsion film in Examples described later.

By the way, the half width of the profile of a system without distortion due to external stress as in the state of the sample described in this patent is determined not only by the halogen composition distribution but also by other factors. This also includes the half-width due to the diffractometer optical system and the half-width due to the size of the crystallite (crystallite) of the sample. Therefore, in order to obtain the half width due to the halogen composition distribution, it is necessary to subtract the half width contribution of the former two. is there. The half value width obtained by the optical meter of the folding meter can be obtained as the half value width of the diffraction profile of a single crystal having a grain size of 25 ^ π or more without distortion (no variation in lattice constant). Such a trial

 .≤ tied x

 The number of crystals is 25 to 44 (500 mesh 350 mesh under).

 The use of annealed quartz with an 80-wave angle is the science of general university

 Niki by Electric Corporation X

 て い る It is described in the revised Handbook of X-Ray Diffraction, Ch. 2, Sec. S i particle or S i A simple. Can be used for crystal wafers, etc.

 9:).

 Noh. The value of the half-A value measured by the optical meter depends on the diffraction angle.

 }

 It is necessary to find the half width at half point for the diffraction profile of the point.

 value

Perform the outer and inner steps as necessary to obtain the half value width by the optical system for the diffraction angle of the system being measured. On the other hand, the half width according to the crystallite size is described by the following equation.

 Κ λ 180

 D c os 6 π '

Subtracting the half-width by the optical system and the half-width by the crystallite size obtained in this way from the measured half-width of the diffraction profile gives the half-width by the halogen composition distribution. The half-width of the mixed crystal grain to be measured now is the half-width due to the optical system and the half-width due to the crystallite size. The halogen composition distribution with the same crystallite size as the particle of interest is uniform (with constant lattice constant). ) Is equivalent to the half width of the diffraction profile of the silver halide grain. In general, in the absence of external stress, particles without lattice defects The size of the particle (side length, equivalent volume sphere equivalent diameter, etc.) matches the size of the crystallite. This is not a defractometer but a photographic method.However, the size of AgBr crystallites and the size of particles obtained from the diffraction line width agree with each other. It was reported by FW Killets in the British Journal of Applied Physics, Volume 16 of 1965, page 323. In this report, the photographer selected 1.44 as the Schiller constant using the profile standard deviation instead of the half width. In our measurement system, the size of the crystallite and the particle size obtained from the half-width obtained by subtracting the half-width obtained by the optical system obtained using a Si single crystal were subtracted from the force using a diffractometer. It has been found that the size is in good agreement with AgBr particles prepared by balanced double jet. -In other words, the half-width of the mixed crystal emulsion particles due to the optical system and the half-width due to the size of the crystallites are the same as those of the mixed crystal emulsion particles, and the fracture profile of AgBr, AgCl, and AgΙ particles is the same. It can be obtained as the half width of the file.

 The half-width of the mixed crystal emulsion particles based on the Haguchi composition distribution alone is determined by the measured half-width of the profile of the profile of the AgBr, AgCl, and AgI particles of the same particle size as the particles of interest. It can be obtained by subtracting the half width of the folding door file.

The preferred half width of the profile of the X-ray diffraction profile of the silver halide emulsion grains having a uniform microscopic halogen composition according to the present invention is shown in FIG. 1 for silver chlorobromide. Figure 2 shows silver bromide. In Fig. 1 and Fig. 2, The uniformity of the grains of the composition is indicated by the value obtained by subtracting the half-width of pure silver chloride or pure silver bromide of the same grain size from the half-width of X-ray diffraction of each grain. The particles of the present invention have a half width not more than the half width shown by the curve A, and preferably smaller than the half width shown by the curve B. The halide composition of the core part and the sur part can be measured by X-ray diffraction.

 An example of the application of X-ray diffraction to silver halogen particles is described in H. Hirsch's literature, Jiannano 'Ob' Photographic * Science, Volume 10, (1962), pages 129 et seq. When the lattice constant is determined by the halogen composition, a peak of the fold occurs at a fold angle that satisfies the Bragg condition (2 d sin 5 = n A).

 The details of the X-ray diffraction measurement method are described in the Basic Analysis Chemistry Course 24 “X-ray analysis” (Kyoritsu Shuppan) and “Guide to X-ray diffraction” (Rigaku Denki Co., Ltd.). The standard method is to use Cu as a target and obtain the diffraction curve of the (220) plane of silver halide using a Cu line as the source (tube voltage 40 V, tube current 60 mA). It is. To increase the resolution of the measuring instrument, select the width of the slit (divergence slit, light receiving slit, etc.), the time constant of the device, the scanning speed of the goniometer, and the recording speed appropriately. It is necessary to confirm the measurement accuracy using standard samples such as

 When the diffraction intensity versus diffraction angle curve of the (220) plane of silver halide is obtained using the K K line of Cu, when the diffraction peaks corresponding to a part of the core and the shell part are detected in a clearly separated state May overlap with each other and not separate into two distinct peaks.

A method for decomposing a diffraction curve consisting of two diffraction components Is well known and is described, for example, in Experimental Physics Course 11 Lattice Defects (Kyoritsu Shuppan).

 It is also useful to assume a curve curve as a function such as a Gaussian number or a Lorentz function and use a curve analyzer manufactured by DuPont to solve the curve.

 The silver halide grains used in the present invention may or may not clearly separate the beak corresponding to the core portion and the shell portion. Even in the case of an emulsion having two types of grains having different halogen compositions and having no distinct layered structure, two peaks appear in the X-ray diffraction.

 Such emulsions cannot exhibit the excellent photographic performance obtained in the present invention.

 Is the silver halide emulsion the emulsion according to the present invention 'or the above-mentioned? In addition to X-ray diffraction, the EPMA method (Electron-Probe) must be used to determine whether the silver halide grains have no distinct layered structure and coexist with two types of silver halide grains. This is possible by using the Micro Analyzer method.

 According to this method, a sample in which emulsion grains are well dispersed so as not to contact with each other is prepared and irradiated with an electron beam. X-ray diffraction by electron beam excitation makes it possible to perform elemental analysis of extremely small parts.

 By determining the characteristic X-ray intensity of silver and halogen emitted from each grain by this method, the halogen composition of each grain can be determined.

When the halogen composition of at least 50 grains is confirmed by the EPMA method, it is determined whether the emulsion is the emulsion according to the present study. I can judge.

 In the emulsion of the present invention, it is preferable that the distribution of the halogen composition between grains, particularly the distribution of the halogen composition between grains in the core portion of the grains, is more uniform. When the distribution of the halogen composition between grains (for example, the distribution of silver iodide content in silver iodobromide or the distribution of silver bromide content in silver chlorobromide) was measured by the EPMA method, the relative standard of the halogen content was measured. The deviation is preferably 50% or less, more preferably 35% or less, particularly preferably 20% or less.

 When the overlap between the diffraction peaks corresponding to the core and the shell is very large, or the ratio of the shell to the particles is very small, the diffraction peak corresponding to the shell is weak and the seal is harsh. If the halide composition cannot be determined, measure the halide composition on the particle surface '.

 The halide composition on the particle surface is measured by the X-ray photon spectroscopy (XPS) surface diffraction method (the measured depth is said to be about 50A).

 Regarding the principle of the XPS method used for the analysis of the amount of Haguchigen particles near the surface of Haguchigenide grains, Junichi Aihara et al., “Electron Spectroscopy,” Kyoritsu Library, 16, Kyoritsu B version, (Showa 53).

The standard method for measuring XPS is to use Mg— as the excited X-rays, and to obtain halogen and silver (Ag) photoelectrons (usually C1-2P, This method measures the intensity of Br-3d, I-3d5 _{/ 2} , Ag-3d5 _{/ 2} ).

For example, to determine the amount of iodine, the amount of iodine is known. Using several standard samples, a calibration curve is created for the intensity ratio of photoelectrons of iodine (I) and silver (Ag) (intensity (I) and intensity (Ag)), and the calibration curve is used to determine this. be able to. In silver halide emulsions, XPS must be measured after gelatin adsorbed on the surface of silver halide particles is decomposed and removed with a protease.

 Embodiments of the silver halide grains of the present invention are as follows.

① If the core has two or more phases, it means the core adjacent to the sur part. The halide composition of the seal is 5 It is desirable that there be a difference of at least 10 mol%, preferably at least 10 mol%, more preferably at least 20 mol%. For example, if the pay-de species _ό The core and the shell Ru Kotodea 'because when silver chloride in Complex free silver chlorobromide the silver chloride content is the above difference in Koa-shell are different It is desirable that the amount of the different halides be at least 3 mol%, preferably at least 6 mol%, more preferably at least 10 mol%. For example, when the shell is AgBr and the core is AgBrCl, it means that the amount of silver chloride in the core follows the above.

 (2) The molar ratio of the core part to the shell part is arbitrary, but the molar ratio of the shell is preferably 50 mol% or less, more preferably 30 mol% or less, and further preferably 10 mol% or less.

 ③ The microscopic halide composition of the core part is completely uniform, and the microscopic halide composition of the swell part may be completely uniform or non-uniform.

コ ア The core may be a single phase or may be composed of two or more layers. Secondly, the microscopic halide composition inside the silver halide mixed crystal of the present invention is completely uniform and / or the inside of the silver halide crystal does not have reduced silver generated at the time of grain formation. The method for producing silver halide core grains will be described.

 By adding silver halide of a fine size prepared in advance to a reaction vessel which causes nucleation and crystal growth of the grains or crystal growth, nucleation and formation of the halogenated core grains in the reaction vessel. Alternatively, crystal growth is performed.

 In the present invention, fine particles of silver halide prepared in advance are added to the reaction vessel to form nuclei of the particles in the reaction vessel and allow further crystal growth.

 Alternatively, crystal nuclei can be grown by previously forming nuclei of grains in a reaction vessel by a conventionally known method and adding the fine silver halide.

 More specific methods for adding fine silver halide include the following.

 (1) Method of supplying silver halide particles from a mixer outside the reaction vessel

 In a mixer provided outside the reaction vessel for causing nucleation and Z or crystal growth, fine particles formed by mixing an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are immediately subjected to the reaction. By supplying it into a container, nucleation and crystal growth of silver halide core grains are performed (hereinafter referred to as method A).

The system of such a particle forming method is shown below by taking FIG. 3 as an example. In Fig. 3, first, the reaction vessel 1 has an aqueous solution 2 of a protective core solution. are doing. The aqueous solution of the protective colloid is stirred and mixed by the propeller 3 attached to the turning shaft. A silver salt aqueous solution, a halogen salt aqueous solution, and a protective π-ide aqueous solution are introduced into the mixer outside the reaction vessel with the addition systems 4, 5, and 6, respectively. (At this time, the aqueous solution of the protective colloid may be added to the aqueous solution of the halogen salt and the aqueous solution of Z or silver salt.) These solutions are rapidly and vigorously mixed in the mixer, and the system is immediately Introduce into Reaction Vessel 1 by 8. FIG. 4 illustrates details of the mixer 7. In the mixer 反 応, a reaction chamber 10 is provided therein, and in the reaction chamber 10, a stirring blade 9 attached to a contra-rotating shaft 11 is provided. The silver salt aqueous solution, the halogen salt aqueous solution and the protective colloid aqueous solution are added to the reaction chamber 10 through three inlets (4, 5, and the other inlet is omitted from the drawing). Rapid and powerful mixing by rotating the rotary shaft at high speed (l OOO r.p.m or more, preferably 2000 r.p.m or more, more preferably 3000 r.p.m or more) The resulting solution containing the extremely fine particles is immediately discharged from the outlet 8 to the outside. Thus, the extremely fine particles produced in the mixer are introduced into the reaction vessel, and after being introduced into the reaction vessel, the particle size is very small, so that they are easily dissolved and become silver ions and halogen ions again. Causes nucleation and / or particle growth. The halide composition of the extremely fine grains should be the same as the halide composition of the target silver halide grains. The ultrafine particles introduced into the reaction vessel are dispersed in the reaction vessel by stirring in the reaction vessel, and the halogen ions and silver ions having the desired halide composition are released from the individual fine particles. . Here, the particles produced by the mixer are extremely fine, and the number of particles is In many cases, such a large number of grains emit silver ions and halogen ions (in the case of mixed crystal growth, the target halogen ion composition is obtained), and these grains are emitted. Since it occurs over the entire protective colloid in the reaction vessel, quite uniform particle growth can occur. It is important that silver ion and halogen ion should not be added to the reaction vessel as an aqueous solution except for pAg adjustment, and the protective solution in the reaction vessel should be circulated to the mixer. Don't do it. Here, completely different from the conventional method, this method has a surprising effect on the uniform growth of silver halide grains.

 The fine particles formed in the mixer have a very high solubility due to the fine particle size, and when added to the reaction vessel, dissolve and become silver ions and halogen ions again to form nuclei. Alternatively, the particles are deposited on particles already present in the reaction vessel and cause particle growth.At this time, since the fine particles have high solubility, so-called Ostwald ripening is caused by the fine particles together before being added to the reaction vessel. Increase. As the size of the particles increases, the solubility decreases, the dissolution in the reaction vessel slows down, the rate of particle growth decreases significantly, and in some cases, Rather, on the contrary, it grows itself as a core.

 In the present invention, this problem has been solved by the following three techniques.

 ① Immediately after the fine particles are formed in the mixer, add them to the reaction vessel.

In the present invention, a mixer is provided very close to the reaction vessel, and By shortening the residence time of the additive liquid in the mixer, the fine particles produced by the addition were immediately added to the reaction vessel to prevent the occurrence of this ripening. Specifically, the residence time t of the liquid added to the mixer is expressed as follows.

 V V: Volume of reaction chamber of mixer (m

 t = a: Addition amount of silver nitrate solution (Zmin)

 a + b + cb: Addition amount of halide salt solution (Zmin) c: Addition amount of protective colloid solution (ffig min) In the production method of the present invention, t is 10 minutes or less, preferably 5 minutes or less. Below, more preferably less than 1 minute and even more preferably less than 20 seconds. The fine particles obtained in the mixer are immediately added to the reaction vessel without increasing the particle size.

 ② Perform strong and efficient stirring in the mixer.

TH James The Theory of the Photographic Process pp93 states, "Along with Ostwald ripening, another form is coalescence. Coalescence. In the ripening process, the crystal size changes suddenly because the crystal that was far away is directly in contact with and adheres to the crystal, causing a sudden change in the particle size. It occurs not only after the sedimentation is completed, but also during the sedimentation. ”Coalescence maturation, which occurs here, tends to occur especially when the particle size is very small, especially when the stirring is insufficient. easy. In extreme cases, it can even produce coarse, massive particles. In the present invention, as shown in FIG. 4, a closed mixer is used, so that the stirring blades of the reaction chamber can be rotated at a high number of revolutions, which is impossible with a conventional open-type reaction vessel. (In the open type, the rotor is rotated at high speed. If it is inverted, the liquid will be dislodged by the centrifugal force, and foaming will be a problem, making it impractical. ) Powerful and efficient stirring and mixing can be performed, and the above-mentioned coalescence ripening can be prevented. As a result, fine particles having a very small particle size can be obtained. In the present invention, the rotation speed of the stirring blade is lOOOr.pm or more, preferably 2000r.pm or more, and more preferably 3000rpm.

 ③ Inject protection colloid solution into mixer

 The aforementioned coalescence ripening can be remarkably prevented by the protection cohesion of the silver halide fine grains. In the present invention, the protective colloid aqueous solution is added to the mixer by the following method.

 ③ Inject the protective colloid solution into the mixer alone.

 The concentration of the protective colloid should be at least 0.2% by weight, preferably 0.5% by weight, and the flow rate should be at least 20% of the sum of the flow rates of the silver nitrate solution and the aqueous solution of the halogen salt: preferably It is at least 50%, more preferably more than 100%.

 ® Make protective colloids available in an aqueous solution of halogen salt.

 The concentration of the protective colloid is at least 0.2% by weight, preferably at least 0.5% by weight.

 © Add protective colloid to silver nitrate solution.

 The concentration of the protective colloid is at least 0.2% by weight, preferably at least 0.5% by weight. When using gelatin, silver nitrate solution and protective colloid solution are mixed immediately before use because silver gelatin is formed from silver ion and gelatin, and photodecomposition and thermal decomposition produce silver colloid. It is better to do. .

Further, the above methods (1) to (3) may be used alone or separately. These may be combined, or three may be used at the same time. (2) Method of adding a previously prepared silver halide fine grain emulsion

 In the present invention, a method in which a fine grain silver halide emulsion having fine grains prepared in advance is added to a reaction vessel to carry out nucleation and grain growth or grain growth can be used (hereinafter, referred to as "hereafter").

In this case, the smaller the grain size of the previously prepared emulsion, the better is the same as described above. Also in this method, a reaction that causes nucleation and / or grain growth occurs No aqueous solution of a water-soluble silver salt or an aqueous solution of a water-soluble halide is added to the reaction container except for adjusting the p Ag of the emulsion in the reaction container. Before washing, it may be washed and Z or solidified in advance.

 In method A, the temperature of the mixer is 40 ° C or lower, preferably 35 ° C or lower, and the temperature of the reaction vessel is 50 ° C or higher, preferably 60 ° C or higher, and more preferably 70 ° C or higher.

 In Method B, the grain formation temperature of the fine grain emulsion prepared in advance is 40 ° C or less, preferably S5 ° C or less, and the temperature of the reaction vessel to which the fine grain emulsion is added is 50 ° C or more, preferably 60 ° C or less. Above 'C, and more preferably above 70 ° C.

 The fine particle size of the silver halide used in the present invention can be confirmed by a transmission electron microscope with the grains placed on a mesh, and the magnification is preferably 20,000 to 40,000. The size of the fine particles of the present invention is 0.1 or less, preferably 0.06 or less, more preferably 0.03 / OT or less.

The halide composition of the core grain emulsion obtained by the present invention is as follows: Any of silver bromide, silver chlorobromide, silver chloroiodobromide and silver chloroiodide can be used. According to the present invention, the microscopic distribution of halide is uniform, that is, A "uniform" silver halide mixed crystal grain is obtained.

 Further, the method of the present invention is very effective also in producing core particles composed of pure silver bromide and pure silver chloride. According to the conventional manufacturing method, the local distribution of silver ions and halogen ions in the reaction vessel is unavoidable, and the silver halide grains in the reaction vessel are inevitable. Passing through the non-uniform part will result in a different environment from other homogeneous parts, which will cause non-uniform growth, of course.For example, in the high concentration part of silver ion, reduced silver Alternatively, capri silver is produced. Therefore, in silver bromide and silver chloride, there is certainly no non-uniform distribution of halide, but the other non-uniformity described above occurs. This problem can be completely solved by the method of the present invention. Accordingly, the core grains obtained by the method of the present invention include silver halide having a single composition. Further, it is preferable that such reduced silver has no distribution even between core grains. .

 In the present method, when a silver halide solvent is added to a reaction vessel and used, a higher dissolution rate of fine particles and a higher growth rate of grains in the reaction vessel can be obtained.

 Examples of the silver halide solvent include water-soluble bromide, water-soluble chloride, thiocyanate, ammonia, thioether, and thiourea.

 For example, thiocyanates (U.S. Pat. Nos. 2,222,264;

Nos. 2, 448, 53, 3, 320, 069, etc.), ammonia, Ter compounds (for example, U.S. Pat. Nos. 3,271,157, 3,574,628, 3,704,130, 4,297,439, 4,276,347, etc.); Compounds (for example, JP-A-53-144319, JP-A-53-82408, JP-A-55-77737), amine compounds (for example, JP-A-54-1007Π), and thiourea derivatives (for example, JP-A-55-1007Π). No. 2982), imidazoles (for example, JP-A-54-100717), and substituted mecaptotetrasol (for example, JP-A-57-202531). .

 The obtained completely uniform silver halide emulsion grains are not particularly limited, but are preferably at least 0.3, more preferably at least 0.8, particularly preferably at least 1.4. The shape of the silver halide grains according to the present invention may have a regular crystal form (normal crystal grains) such as a hexahedron, an octahedron, a dodecahedron, a tetrahedron, a 24-hedahedron, and a 48-hedahedron. It may be irregular or crystalline, such as spherical or potato-shaped, and particles of various shapes having one or more twin planes, especially two or three parallel twin planes Hexagonal tabular grains and triangular tabular twin grains may be used.

Next, a method for forming the seal of the present invention will be described. A squeeze is formed following the formation of the core described above, and the method A and the method B can be applied to the method of manufacturing the squeeze. The details are as already described. For the shell formation of the present invention, a particle formation method known hitherto can be used. That is, a silver salt water solution and a haegent water solution are added to a reaction vessel having an aqueous solution containing a core silver halide particle and a protection core under efficient stirring. As a specific method, see Chemie et Phisique by P. Glafkides. Photographique (Paul Montel, 1967) ヽ G, F, Duff in Photographic Emulsion Chemistr (The Focal Press, 1966) V, shi- Ze ikmari eta 1 Making and Coating Photographic Emulsion (The Focal Press, 1964) and the like. That is, any method such as an acidic method, a neutral method, and an ammonia method may be used, and the method of reacting a soluble silver salt with a soluble halide salt includes a one-sided mixing method, a double-mixing method, and a combination thereof. Either may be used.

 It is also possible to use a method in which a seal is formed under an excess of silver ion (a so-called reverse mixing method). As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used.

 In the course of the formation or physical ripening of the coresil emulsion grains of the present invention, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron Salts or iron complex salts may coexist.

Also, as described in British Patent Nos. 1,535,016, JP-B-48-36890, and JP-B-52-1636, the addition rate of silver nitrate or an aqueous halide halide solution is changed according to the grain growth rate. And rapid growth in a range not exceeding the critical supersaturation by using a method of changing the concentration of the aqueous solution as described in US Pat. No. 4,242,445, JP-A-55-158124, etc. It is preferable to let them do so. These methods are preferably used because renucleation does not occur and each core silver halide particle is uniformly coated. In the core-shaped particles of the present invention, the shape of the core portion and the entire shape with the shell may be the same or different, specifically, the core portion has a cubic shape, The shape of the particles with a seal may be cubic or octahedral. Conversely, the core part may be octahedral, and the particles with a sur may have a cubic or octahedral shape. In addition, although the core is a well-defined regular particle, the particle with a shell may be slightly deformed or irregularly shaped. It is not just a double structure, but a triple structure or a multilayer structure as disclosed in JP-A-60-222844, and the surface of a core-shell double structure particle differs. It can be used to thinly apply silver halide having a composition.

In order to give the structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonded structure can be produced. Examples of these are disclosed in JP-A-59-133540, JP-A-58-108526, EP 199290 A2, JP-B-58-24772, JP-A-59-16254 and the like. The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a different composition from that of the host crystal. Such a bonded crystal can be formed even if the host crystal is uniform in terms of the haegen composition or has a core-shell structure. Combinations of competitors are of course possible, but silver salt compounds, such as silver rodan and silver carbonate, that do not have a rock salt structure can be combined with silver halide to form a bonded structure. Also A non-silver salt compound such as PbO may be used as long as it can form a junction structure.

 In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, conversely, The grains may have a low silver iodide content in the core and a high shell. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. .

 In addition, a boundary portion having a different halogen composition in a grain having such a structure may be a clear boundary or an unclear boundary formed by a mixed crystal due to a difference in composition. It may be one with continuous structural changes.

 The silver halide emulsion used in the present invention may be prepared by subjecting the grains to a rounding treatment as disclosed in EP-0096727 B1, EP-0064412 B1, etc., or DE-2306447 C2, JP-A-60-221320. Surface modifications as disclosed may be made.

 The silver halide emulsion used in the present invention is preferably a surface latent image type, but an internal latent image type emulsion may be used by selecting a developing solution or development conditions as disclosed in JP-A-59-133542. be able to. Also, a shallow internal latent image type emulsion covered with a thin shell can be used according to the purpose.

In the present invention, it is extremely important to perform chemical sensitization represented by reduction sensitization, sulfur sensitization, and gold sensitization. Where chemical sensitization is performed depends on the composition, structure, and shape of the emulsion grains, and the emulsion is used. It depends on the intended use. When a chemical sensitization nucleus is embedded in the inside of a grain, when it is embedded at a shallow position from the grain surface, or when a chemical sensitizer is formed on the surface. Although effective in the case of the effects of the present invention, etc., it is particularly preferable to form a chemical nucleus near the surface. In other words, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

 The emulsion of the present invention is generally spectrally sensitive. -Methine dyes are generally used as the spectral sensitizing dyes used in the present invention. These include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex melocyanine dyes, and holopolar cyanine dyes. And hemicyanine dyes, styryl dyes, and hemioxanol dyes. Any of nuclei usually used in cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole sodium, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, viridin nucleus, etc .; A nucleus in which an alicyclic hydrocarbon ring is fused to the nucleus; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenin nucleus, a benzindrenine nucleus, an indole nucleus, a benzoxadol nucleus, A naphthoxadr nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include pyrazolin-15-one nuclei and thiohi Dantoin nucleus, 2-thioxazolidin-1,2,4-dione nucleus, thiazolidin-1,2,4-56-membered heterocyclic nucleus such as dione nucleus, rhodanine nucleus, and thiobarbituric acid nucleus Can be applied.

 The amount of the sensitizing dye added during the preparation of a silver halide emulsion cannot be unambiguously stated depending on the type of additive, the amount of silver halide, etc., but is almost equal to the amount added by a conventional method. The amount can be used.

That is, the amount of preferred correct sensitizing dye is per mol of silver halide 0,001 100 mmol, is rather to favored is et 0.01; a 10 1 _c

 The sensitizing dye is added after or before chemical ripening. The sensitizing dye is most preferably added to the silver halide grains of the present invention during chemical ripening or before chemical ripening (for example, during grain formation or physical ripening).

 Along with the sensitizing dye, a dye that does not itself have a spectral effect or a substance that does not substantially absorb visible light and that exhibits supersensitization may be included in the emulsion. For example, amino still compounds substituted with a nitrogen heterocyclic group (for example, US Patent No.

2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensate (for example, described in US Pat. No. 3,743,510), cadmium salt, azaindene compound It may be a house. U.S. Patent Nos. 3,615,613, 3,615,641,

The combinations described in 3,617,295 and 3,635,721 are particularly useful.

Silver halide emulsions are usually chemically sensitized. Chemical sensitization For example, H. Frieser ed., D'Darn Dragel-Dell. Photographieschen. Protesse Mitt-Sinorebenorenoro 0 * Niden Die Grund 1 agen der

 Pho tographis en Prozesse mit Silber alogeniden), and the method described in Mitsushi Ferraglus Gesersakto ί968) pp. 675-734 can be used.

 That is, sulfur-containing compounds that can react with active gelatin and silver '

(E.g., thiosulfates, thioureas, mercapto compounds, π

—Danins) with sulfur sensitizers; reducing substances (eg, stannous salts, amines, hydrazine derivatives, formamide sulphate)

A-acidic acid, silane compound); noble metal compound

(For example, besides gold salts, complex salts of Group I of the periodic table such as Pt, Ir, and Pd) can be used alone or in combination with a noble metal sensitization method.

The photographic emulsion used in the present invention contains various compounds for the purpose of preventing the capri during the manufacturing process, storage or photographic processing of the photographic material and stabilizing the photographic performance. Can be done. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted); Compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazols (especially 11-phenyl-15-mercaptototrazol) , Melcapto pyrimidines; water-soluble compounds such as galboxyl and sulfone groups The above-mentioned heterocyclic mercapto compounds having a functional group; thioketo compounds such as oxazolinthione; azandenes such as tetrazindene (especially 4-hydroxysubstituted (1,3,3a, Many compounds known as anti-capri agents or stabilizers can be added, such as 7-tetrazandene); benzenesulfonates; benzenesulfinate; and the like.

 The timing of adding these anti-Capri agents or stabilizers is usually performed after chemical sensitization, but can be more preferably selected during chemical ripening or before chemical ripening. That is, during the silver halide emulsion grain formation process, even during the addition of the silver salt solution or during the period from the addition to the start of chemical ripening, during chemical ripening (preferably 50% from the start during the chemical ripening time). Or more preferably within 20% of the time).

 The emulsion of the present invention can be used for a photographic light-sensitive material having an arbitrary layer constitution irrespective of whether the emulsion layer has one layer or two or more layers. .

 The silver halide multilayer color photographic light-sensitive material using the emulsion of the present invention has a multilayer structure in which a binder for separately recording blue, green and red light and an emulsion layer having silver halide grains are superposed. Each emulsion layer is composed of at least a high-sensitivity layer and a low-sensitivity layer. Particularly practical layer constitutions include the following.

 (1) B H / B L / G H / G L / R H / R L / S

 (2) BH / BM / BL / GH / GM / GL / RH / RM /

 R L / S

Described in U.S. Pat.No. 4,184,876. (3) BH / BL / GH / R HXG L / RLS

 RD-22534, JP-A-59-Π7551, and JP-A-59-177552.

 (4) B H G H / R H / B L / G L / R L / S

This is a layer configuration.

 Where B is the blue-sensitive layer, G is the green-sensitive layer, R is the red-sensitive layer, 'H is the highest-sensitive layer, M is the medium-sensitive layer, L is the low-sensitive layer, and S is the support, and The recording of non-photosensitive layers such as layers, filter layers, intermediate layers, anti-halation layers and undercoat layers is omitted.

 Of these, preferred layer configurations are (1), (2) and (4).

 In addition, Japanese Patent Application Laid-Open No. 61-34141 describes

 (5) B H / B L / C L / G H / G L / R H / R L / S

 (6) B H / B L / G H / G L / C L / R H / R L / S

Is also preferable.

 Here, CL is a layer effect imparting layer, and the others are as described above. Further, the high-sensitivity layer and the low-sensitivity layer having the same color sensitivity may be arranged in reverse.

 The silver halide emulsion of the present invention can be applied to light-sensitive light-sensitive materials as described above. However, the light-sensitive material may have one or more emulsion layers, for example, X-ray light-sensitive material, black-and-white photographing. It can also be applied to photosensitive forestry materials, photosensitive materials for plate making, photographic paper, etc.

Various additives of the silver halide emulsion of the present invention, such as binders, chemical sensitizers, spectral sensitizers, stabilizers, gelatin hardeners, surfactants, antistatic agents, polymer latex, matte Agents, color couplers, UV absorbers, anti-fading agents, dyes and their milks There are no particular restrictions on the support, coating method, exposure method, development processing method, etc. of the photosensitive material using the agent. For example, Research 'Disclosure, Vol. 6, Item 17643 (RD-17643), The descriptions in Vol. 187, Item 18716 (RD-18716) and Vol. 225, Item 22534 (RD-22534) can be referred to.

 The descriptions of these research * discs are shown in the table below. Additive type RD 17643 RD 18716 RD22534

1 Chemical sensitizer page 23 page 648 right column page 24

2 Sensitivity enhancer Same as above

 3 Spectral sensitizer, page 23-24, right column, page 648-page 24-28 Supersensitizer, right column, page 6.49

 4 Brightener page 24

 5 Antifoggant page 24-25 page 649 right column-page 24, page 31 and stabilizer

 6 Light absorber, pages 25-26, page 649, right column

 Filter dye, page 650, left column

 UV absorber

 7 Stain inhibitor 25 pages right column 650 pages left to right column

 8 Dye image stabilizer page 25 page 32

9 Hardener Page 26 Page 651 Left column Page 28

10 binder page 26 Same as above

 11 Plasticizers and lubricants Page 27 Page 650 Right column

 12 Coating aids, pp. 26-27

 Surfactant

 13 Static page 27 Same as above

 Inhibitor

14 Characters Page 25 Page 649 Page 31 Gelatin hardeners include, for example, active halogen compounds (2,4-dichloro-16-hydroxy-1,3,5-triazine and its sodium salt) and active bur compounds (1,2,3-triazine and sodium salts thereof). 3—Bis vinylsulfuryl 2- 1-fluoro-nor, 1,2-bis (vinylinolesulfonyl amide) ethane or vinyl-based poly (vinylsulfone) with vinylsulfonyl group Are preferred because hydrophilic colloids such as gelatin cure quickly and provide stable photographic properties. N—Carnomoylpyridinium salt (1—Morpholinocarbonyl 3-pyridino) Methansulfonate, etc. ゃ Haloa midinium salt (1—1—1-chloropipermethylene) (Pyrrolidine 2-naphthalene sulfonate) also has a fast curing rate and is excellent.

 No. 17643, pages 28 to 29, and No. 18716, 651 left column to right column described in RD. No. 17643. It can be developed according to the method.

 The photographic light-sensitive material using the silver halide photographic emulsion of the present invention is usually subjected to a washing treatment or a stabilization treatment after development, bleach-fixing or fixing. One

 In the water washing process, two or more tanks are generally countercurrently washed to save water. As a stabilization treatment, a multi-stage countercurrent stabilization treatment as described in JP-A-57-8543 may be mentioned as a typical example instead of the washing step.

 [Brief description of drawings]

Fig. 1 and Fig. 2 show the uniformity of silver halide grains. The vertical axis represents the half-width of the X-ray profile, and the horizontal axis represents the Haguchi composition of the silver halide grains.

 FIG. 3 schematically shows the method of the present invention.

 1: & fc, content s

 2.Aqueous protective colloid solution

 3: Propeller

 : Halogen salt aqueous solution addition system

 5: Silver salt aqueous solution added system

 6: Protective colloid addition system

 7: Mixer

 FIG. 4 is a detailed view of the mixer according to the present invention.

 4, 5, 6, and 7 are the same as those in FIG.

 8: Introduction system to reaction vessel

 9: stirring blade

 10: Reaction chamber

 FIG. 5 is a transmission electron micrograph showing the crystal structure of conventional tabular silver halide grains in which the distribution of silver iodobromide phases is not completely uniform. The magnification was 37,000. It is twice.

 [Best mode for carrying out the invention]

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

Example 1 1

 Silver iodobromide fine grain emulsion 1 A

A 2.6% 2.0% by weight gelatin solution containing 0.126 M potassium bromide was stirred by a double jet method with a 1.2 M silver nitrate solution, 0.9 M potassium bromide and 0.3 M with stirring. M iodide A 1200 ml aqueous solution of Haguchigen salt was added over 15 minutes. During this time the gelatin solution was kept at 35. Thereafter, the emulsion was washed by a conventional flocculation method, added with 30 g of gelatin, dissolved, and adjusted to PH 6.5 and _P Ag 8.6. The resulting silver iodobromide fine particles (silver iodide content 25%) had an average particle size of 0.05 ^. Silver bromide octahedral core emulsion 1 B <The present invention>

 1.5% by weight of a 1.5% gelatin solution having a bromide rim of 0.05M was added to 1.2 pounds of the solution while stirring, and 60% of 0.5% 3,6-dithiaoctane-1,8-diol was added thereto and kept at 75'C. Nucleation was performed by adding an emulsion prepared by adding 270 water to 100 g of silver iodobromide fine grain emulsion (containing silver equivalent to 10 g of silver nitrate) in a reaction vessel over 10 minutes. Was. The obtained silver iodobromide octahedral core particles were 0.4 ^.

 Fine grain emulsion 1 One AlOOO g (silver nitrate containing 100 g of silver) was continuously added to the reaction vessel over 100 minutes. Thereafter, the emulsion was cooled to 35, washed with water by a conventional flocculation method, and adjusted to PH 6.2 and pAg 8.8 by adding 70 g of gelatin. The obtained core emulsion grains were octahedral silver iodobromide emulsions having an average projected area of 1.2 ^ <2> (equivalent content of 25 mol%).

 Silver bromide octahedral core emulsion 1

To a 1.5% by weight gelatin solution containing 0.05M of bromide having a concentration of 0.05M was added, while stirring, 20% of 0.5% 3,6-dithiaoctane-1,8-diol was added, and the reaction vessel was brought to 75'C. Kept. Mixer located beside reaction vessel contains 0.59 M silver nitrate aqueous solution 100 and 0.44 M lithium bromide and 0.148 M potassium iodide 100 ml of an aqueous solution of a halogen salt and 300 ml of a 2% by weight aqueous solution of gelatin were added by a triple-jet method over 5 minutes. The temperature of the mixer was 20 and the rotation speed of the stirring blade was 6000 rpm. The obtained fine particles were confirmed by a direct transmission electron microscope at a magnification of 20,000 times to be 0.01. The fine particles generated by the mixer were continuously introduced into a reaction vessel maintained at 75 ° C. The obtained silver bromide octahedral nuclei (25 mol% of silver iodide) were 0.4 ·. Subsequently, at 75, a 1 M silver nitrate aqueous solution 600, a solution containing 0.75 M bromide rim, 0.25 potassium iodide and 2 wt% gelatin 800 were mixed in a triple jet with a mixer. Was added. The formed fine particles were continuously added to the reaction vessel at a size of. At this time, the mixer was kept at 20'C. The emulsion was washed with water in the same manner as in Emulsion 1-1B and adjusted to the same pH and pAg. The obtained core emulsion grains were octahedral silver iodobromide emulsions having an average projected area circle equivalent diameter of 1.2 ^ (silver iodide content: 25 mol%).

 Silver bromide octahedral core emulsion 1 D <Comparative emulsion>

To a 3.0% by weight gelatin solution 1.2 containing 0.06 M bromide, 0.5% 3.6-dithiaoctane-1,8-diol solution 50 was added while stirring, and the mixture was heated to 75'C. 50cc of 0.3M silver nitrate solution, 50cc of 0.063M potassium iodide and 0.19M bromide solution of haguchigen salt solution in a maintained reaction vessel for 3 minutes by double jet method And added. As a result, nucleation was performed by obtaining silver iodide bromide grains having a projected area circle equivalent diameter of 0.4 and a silver iodide concentration of 25 mol%. Subsequently, similarly at 75 ° C, a 1 M silver nitrate aqueous solution 600, 0.75 M potassium bromide and 0.25 M calcium iodide were added. 溶液 Add the solution 600) containing the solution to the reaction vessel in a double-jet and wash it in the same way? The pH was adjusted to the same value as p. The obtained core emulsion grains were octahedral silver bromide emulsions having an average projected area circle equivalent diameter of 1.2 (silver iodide content: 25 mol%).

 Emulsion 1-1 To examine the microscopic distribution of iodine in B, 1 — C, and 1 — D, the X-ray diffraction of the (420) plane was measured using the Kor line described earlier, and the size was the same. X-ray diffraction measurement of the pure silver bromide emulsion was also performed. Table 1 shows the results.

 table 1

 Emulsion

 Half width 1 1 B 1 1 C 1 1 D

 A Half width: 0.14. 0.13 ° 0.22 °

 B Half width of pure AgBr 0.08 ° 0.08 ° 0.08 °

(A-B) 0.06. 0. 05 ° 0.14. Table one 1 (A- B) emulsion grains 1 first value are present invention indicates a non-uniform distribution of ® c de of B, 1 - C if half width as compared with Comparative Emulsion 1 one D is rather small, ^l It turns out that it is / _z or less.

Example 1 2

 A core of pure AgBr was formed on the core-emulsion obtained in Example 11 at 60 ° C. and at a pAg of 9.0 by double jet. Table 2 shows the details of the seal formation.

 Table 1 Emulsion name 2-A 2-B 2-C 2-D 2-B 2-F Core milk 1-B (invention) 1-C (invention) 1-D (comparison)

C / S ratio (mol%) 3/2 9/1 3/2 9/1 3/2 19/1 The obtained emulsions 2 — A to 2 — F were optimally chemically sensitized with sodium thiosulfate and chloroauric acid or potassium thiocyanate, and the following compounds were added to form an undercoat layer. Triacetyl cellulose film was coated on a support.

 (Ϊ) Emulsion layer

 . Emulsion ... Emulsion shown in Table 2

 . Coupler

Π 1 1 then 5 0

¹ '"CS

Tri-Crystal Fute

 i sosensen 5-black 5 '-feneru 4-echiru 3

 3 '-(3—Sulfopropyl) oxacarrubinannaminium

 Stabilizer 4—Hydroxy 6—Methyl—1,3,3a, 7—Tetrazaindene

 44-Coating aid sodium dodecylbenzenesulfonate

(2)

2,4—Dichloro mouth 6—Hydroxy s—Triazine . gelatin

 These samples were subjected to sensitometric exposure and subjected to the following color development processing.

 The density of the treated sample was measured with a green filter. Table 3 shows the obtained photo performance results.

 The development processing used here was performed at 38 ° C under the following conditions.

 1. Power color development 2 minutes 45 seconds

 2. Bleaching-6 minutes 30 min

 3. Rinse-3 minutes 15 seconds

 4. Fixed arrival 6 minutes 30 seconds

 5. Rinse for 3 minutes 15 seconds

 6. Stable --- 3 minutes 15 seconds

 The composition of the processing solution used in each step is as follows.

Color developer

 Sodium triacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Bromide 1.4 g Hydroxylamin sulfate 2.4 g 4 1 (N-ethyl-N- i5 Hydroki Shechill

 Amino) 1-2-methyl aniline sulfate 4.5 g Add water and add 1 ϋ

 15 Bleach,

Ammonia bromide. 1 600 g Ammonia water (28%). 25. Ethylenediaminetetraacetic acid sodium salt 130 g Glacial acetic acid 14 Add water and fixer 1

 Sodium tetratetraphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 g Sodium bisulfite 4.6 g Stable at 1 £ with water Liquid

 Formalin 8.0 id with water 1

 Table 1 3

 As can be seen from the results shown in Table 13, the emulsion of the present invention has higher sensitivity than the comparative emulsion.

Example 1 3

Silver chlorobromide fine grain emulsion 3 — A (L 2.3 M bromide power with 0.05 M sodium chloride, 2.3 M% gelatin solution containing 1.3 M with 1.3 M silver nitrate aqueous solution by double-jet method while stirring it to 1.3 £. A bromide power of 0.72 M and an aqueous solution of a halogen salt containing 1.0 M of sodium chloride were each added over 600 minutes over a period of 25 minutes while the gelatin solution in the reaction vessel was kept at 35 ° C. Thereafter, the emulsion was washed by a conventional flocculation method, 30 g of gelatin was added, and after dissolution, the pH was adjusted to 6.5. The _obtained silver chlorobromide fine particles (silver chloride amount: 40%) The average particle size was 0.09 ^.

 Silver chlorobromide cubic grain emulsion 3-B (Comparative emulsion)

 A 3.0% by weight gelatin solution containing 0.065 M potassium bromide and 0.3 M sodium chloride was stirred into 1.2 pounds of 1% N—N′-dimethylimidazoline. 2 — Add 5 thione solutions and add 50 cc of 0.3 M silver nitrate solution and 50 cc of 0.18 M potassium bromide and 0.8 M sodium chloride in a reaction vessel kept at 75 ° C. 50 cc of a halogen salt aqueous solution Was added by the double jet method over 3 minutes.

 Thus, nucleation was performed by obtaining silver chlorobromide particles having a silver chloride concentration of 0.2 mol and a mol ratio of 40 mol%. Subsequently, a double jet of 800 cc of an aqueous solution containing 150 g of silver nitrate and 63 g of lithium bromide and 43 g of sodium chloride in 75 minutes at 75 ° C for 100 minutes. At the same time. Thereafter, the emulsion was cooled to 35'C, washed with water by a conventional flocculation method, and adjusted to pH 6.2 and Pg to 8. by adding 70 g of gelatin. These grains were cubic silver chlorobromide grains having a silver chloride content of L1 of 40 mol%.

Silver chlorobromide cubic grain emulsion 3 — C (this invention) 0.5% by weight aqueous gelatin solution containing 0,065 M potassium bromide and 0.3 M sodium chloride 1% N—N'—dimethylimidazoline 1 2 —Thion solution was added at 4.5 / ^, and Fine Emulsion 3-A was added to the reaction vessel by pump at 75'C. The addition rate was such that a fine grain emulsion corresponding to 5 g in terms of the amount of silver nitrate was added over 10 minutes.

 Then, at 75, the fine grain emulsion 3-A was added to the reaction vessel by pump. The fine grain emulsion was added over a period of 100 minutes so that the addition rate was 150 g in terms of the amount of silver nitrate. At that time, 20 g of sodium chloride was previously dissolved in the fine grain emulsion. Thereafter, the emulsion was washed with water in the same manner as in Emulsion 11B, and adjusted to pH 6.5 and pAg 7.8 with 40. The obtained grains were silver chlorobromide cubic grains having a silver chloride content of 1.1 ^ of 40 mol%. '

 Silver chlorobromide octahedral grain emulsion 3 — D <The present invention>

 After nucleation in the same manner as for emulsion 11C, the seed crystal growth was transferred to a powerful and efficient mixer located near the reaction vessel as shown in Fig. 1 for 150 g for 100 minutes. Aqueous solution containing 800 cc of silver nitrate and 63 g of bromide rim and 43 g of sodium chloride 800 cc of an aqueous solution containing 10 g of low molecular weight gelatin (average molecular weight of 20,000) 800 cc was added in triple jut. The ultrafine particles (average size 0.02) produced in the reaction by stirring in the mixer were immediately and continuously introduced into the reaction vessel from the mixer. During this time, the temperature of the mixer was kept at 25'C, and the temperature of the reaction vessel was kept at 75 ° C.

Thereafter, the emulsion was washed with water in the same manner as Emulsion 1-B, and adjusted to pH 6.5 and pAg 7.8. This grain has a silver chloride content of 1.1 and 40 mol% It was silver chlorobromide cubic grains.

 Emulsion 3 — B, 3 — C, 3 — D was coated on a film base support at 3 g silver / ir, and the above K line was examined to examine the microscopic distribution of halide. The (420) plane was used to measure X-ray diffraction. At that time, X-ray diffraction of pure silver chloride and pure silver bromide of the same size was also performed. Table 4 shows the results.

 Table 1 4

 The value of (A-B) in Table 1 indicates the microscopic nonuniformity of halides (silver chloride, silver bromide). Emulsion grains 3 — C and 3 — D of the present invention are comparative emulsions 3 — The half width is much smaller than that of B, and it is close to that of silver bromide (silver chloride).

Example 1 4

The core emulsion obtained in Example 13 was kept in a reaction vessel at 60 ° C., and a 1M silver nitrate aqueous solution and a 1M aqueous bromide aqueous solution were added with a double jet while stirring, and a silver bromide shell was added. Was formed. Table 5 shows the details of shell formation. Table 5

The resulting emulsions 4 — A to 4 — F were optimally chemically sensitized with sodium thiosulfate and potassium chloroaurate and potassium thiocyanate. Coated samples were prepared in the same manner as described in Example 12. Produced. Table 6 shows the results obtained by performing the same sensitometry as in Example-2. Table 1 6

As can be seen from the results in Table 1, the emulsion of the present invention has higher sensitivity than the comparative emulsion.

 [Industrial applicability]

The silver halide photographic light-sensitive material having the silver halide emulsion of the present invention thus obtained is characterized in that the silver halide silver halide grains contained in the emulsion have a completely uniform halide distribution. Has, sensitivity, gradation, granular It has excellent properties in terms of image quality, sharpness, resolution, force balling power, storage stability, latent image stability and pressure characteristics.

Claims

The scope of the claims

 1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the photosensitive silver halide grains contained in the silver halide emulsion layer are: A grain whose interior is composed of at least one phase having at least two kinds of silver halides, and whose halide distribution is completely uniform, and whose surface is adjacent to the surface; A silver halide photographic light-sensitive material characterized in that it is a silver halide having a different halide composition from the interior of the silver halide photographic material.

2) In a silver halide photographic material having at least one silver halide emulsion layer on a support, photosensitive silver halide grains contained in the silver halide emulsion layer form nuclei of the grains. And / or by adding a previously prepared fine-sized silver halide to a reaction vessel in which crystal growth is caused, the nucleation and the growth of silver halide grains formed in the reaction vessel. A silver halide photographic light-sensitive material characterized by comprising grains having silver halides having different halide compositions on the outside.

 3) A small-sized silver halide is mixed with an aqueous solution of a water-soluble silver salt in a mixer provided outside a reaction vessel that causes nucleation and growth of photosensitive silver halide grains or crystal growth. The photosensitive silver halide grains are nucleated and / or crystal-grown by forming an aqueous solution of a photosensitive halide by mixing and supplying the mixture to the reaction vessel immediately after the formation. 3. The method for producing a silver halide photographic light-sensitive material according to claim 2, wherein silver halide having a different halide composition is formed.