JPH0778600B2 - Silver halide photographic emulsion - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive silver halide emulsion useful in the field of photography, and particularly to a silver halide emulsion comprising a dispersion medium and tabular silver halide grains and its production. Regarding the method.

(Prior Art) Tabular silver halide grains containing parallel twin planes (hereinafter referred to as "tabular grains") have the following photographic characteristics: 1) ratio of surface area to volume (hereinafter referred to as specific surface area)
Is large, and a large amount of sensitizing dye can be adsorbed on the surface. As a result, the color sensitization sensitivity is relatively high with respect to the intrinsic sensitivity.

2) When an emulsion containing tabular grains is coated and dried, the grains are arranged parallel to the surface of the support, so that the coating layer can be thin and the sharpness is good.

3) In the X-ray photography system, when a sensitizing dye is added to the tabular grains, the extinction coefficient of the dye is larger than the extinction coefficient of the indirect transition of silver halide (AgX), and crossover light can be significantly reduced. , It is possible to prevent deterioration of image quality.

4) An image with high resolution can be obtained with little light scattering.

5) Due to its low sensitivity to blue light, the yellow filter can be removed from the emulsion when used in the green or red photosensitive layer.

Etc.

Because of these many advantages, they have been used in high-sensitivity commercial light-sensitive materials.

Regarding silver bromide and silver iodobromide tabular grains, emulsion grains having an aspect ratio of 8 or more are disclosed in, for example, JP-A Nos. 58-113926, 58-113927 and 58-113928.

The aspect ratio mentioned here is represented by the ratio of the diameter to the thickness of the tabular grains. Further, the grain diameter means the diameter of a circle having an area equal to the projected area of the grain when the emulsion is observed with a microscope or an electron microscope. The thickness is indicated by the distance between two parallel noodles forming the tabular silver halide grain.

On the other hand, a light-sensitive silver halide photographic emulsion containing silver chloride is known and provides the following advantages. For example, it is more soluble than other photographic-effective silver halides, so that development and fixing can be accomplished in less time. Silver chlorobromide emulsions containing silver chloride have particular utility in applications requiring high contrast such as graphic arts and in applications requiring rapid processing such as black and white negative photographic materials, x-ray films and color printing products. Has been obtained.

In addition, as color photographic materials have become more and more popular, the color development processing has become simpler and faster, and on the other hand, high quality images and uniformity of finish quality are required.

Generally, 4 to 20 mol% of silver iodide is used in a color photosensitive material for photographing.
It is known that a silver iodobromide emulsion as described above and a silver chlorobromide emulsion are used for color print materials. The silver chlorobromide emulsion is more sensitive than the silver iodobromide emulsion and it is difficult to obtain a high quality image, but it may be advantageous for speeding up the color development processing.

In U.S. Pat.No. 4,399,215, tabular grains of silver chlorobromide and silver chloride having a silver chloride content of 50 mol% or more do not contain silver bromide and silver iodide therein, and have a pAg of 6.5 to 10. Range and pH
Is maintained in the range of 8 to 10 to form particles by using ammonia. U.S. Pat.No. 4,400,463 discloses that tabular silver halide emulsions having a silver chloride content of at least 50% can be obtained by grain formation in the presence of aminoazaindene and a peptizer having a thioether bond. ing. U.S. Pat. No. 4,713,323 describes obtaining tabular grains of silver chloride and silver chlorobromide by using as a gelatin dispersion medium having a methionine content of 30 μmole / g or less. JP-A-58-111936 describes silver chlorobromide tabular grains having an average molar ratio of chloride to bromide of at least 2: 3, which is the molar ratio of chloride ion to bromide ion in the reaction vessel. Is maintained at 1.6: 1 to 258: 1, and the total concentration of halogen ions in the reaction vessel is maintained at 0.10 to 0.90 N, while it is obtained by a double jet. Although these patents disclose silver chlorobromide tabular grains having various silver chloride contents or a method for producing the same, the above-mentioned silver chlorobromide emulsion is less sensitive than silver iodobromide emulsion. And, it does not solve the instability of the obtained sensitivity and the drawback of easy fog.

On the other hand, some methods have been proposed for solving these problems.

For example, a method of adding a sensitizing dye to a silver halide emulsion and then adding a water-soluble bromine ion or iodine ion as described in JP-A-48-51627 and JP-B-49-46932.
As described in JP-A-58-108533, JP-A-60-222845, etc., bromine ions and silver ions are simultaneously added to silver halide grains having a high silver chloride content to form a grain surface. A method of providing a silver bromide layer of 60 mol% or more; and a method of providing a silver bromide layer of 10 mol% to 50 mol% on the surface of the grain in whole or in part; JP-B-50-36978; Japanese Patent Sho 58
No. -24772, U.S. Pat.No. 4471050, OLS-3229999, etc., halogen conversion is carried out by adding bromine ion to silver halide having a high silver chloride content or by simultaneously adding bromine ion and silver ion. 2 core and shell
A method for producing particles having a multi-phase structure such as heavy structure particles or bonded structure particles is known. Either of these methods
It does not reach the target due to sensitivity.

The content of these patents is to change the content of silver bromide in each silver chlorobromide grain depending on the location (especially inside or outside of the grain or on the surface of the grain). It seeks to obtain good photographic characteristics.

For example, JP-A-58-111935 is characterized in that tabular silver halide emulsion grains having a chloride content of 50 mol% contain at least one of bromide and iodide in the central region. Photographic emulsions are disclosed.

The topography of the silver chloride content (or silver bromide content) in these tabular grains of silver chlorobromide can be known by using analytical electron microscopy. For example, the results of examining the topography of the content of silver iodide in the tabular grains of silver iodobromide show that King (MAKing), Loret (MHLorretto), Matanahan (TJMaternaghan) and Berry (FJBerry) "Iodine distribution by analytical electron microscope". Research (The Investigation of Iodide Distribution by Analytical Electron Microscopy) "Progress Inbasic Principles of Imaging Systems, International Congress of Photographic Science Cologne (Kln), 1986.

Here, it was shown that even if the tabular grains of silver iodobromide were grown with a constant silver iodide content, the silver iodide content was higher in the peripheral portion than in the central portion. That is, in the formation of the silver iodobromide phase, it was shown that the grain growth was performed so that the iodine content was constant, but this was not the case.

Meanwhile, Tan (YTTan) and Beth Old (RCBaetzol
(d) presented the expectation that the energy state of silver halide was calculated and that iodine in silver iodobromide crystal grains tended to form clusters at the 41st Annual Meeting of SPSE. The distribution of silver iodide in the tabular silver iodobromide grains described above is a change in the silver iodide content at different places of 300 to 1000 Å or more, even though it is at least small, but tan (YTTan) and bezold (RCBaetzold) As expected, a more microscopic (100Å or less) non-uniform distribution of silver iodide is confirmed in the silver iodobromide crystal.

Although these findings were confirmed in tabular silver iodobromide grains, they are the same in tabular silver chlorobromide grains, so-called mixed crystal grains (Mixed Crystal) composed of two or more different halogens. It was confirmed by the present inventor that it is a common problem in Grain). The tabular silver halide grains having a completely uniform silver chloride distribution disclosed in this patent mean that the above-mentioned microscopic silver chloride distribution (in the case of silver iodobromide, silver iodide distribution) is completely Refers to uniform particles. This microscopic silver chloride distribution can be confirmed by a cooling transmission electron microscope, and tabular silver halide grains having a completely uniform distribution of silver chloride disclosed in this patent have not been obtained so far. It is a thing.

(Object of the Invention) An object of the present invention is a negative tabular silver halide having low fog, high sensitivity, improved graininess, sharpness and covering power, and excellent storage stability and pressure resistance. It is to provide a photographic emulsion composed of grains.

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion comprising a dispersion medium and silver halide grains, wherein at least 50% of the total projected area of the silver halide grains has an average aspect ratio of 3 or more. The tabular grains are occupied by certain tabular silver halide grains, and the tabular grains contain a silver chloride phase having a silver chloride content of 10 mol% to 90 mol%, and the silver chloride phase has a completely uniform distribution of silver chloride. Was achieved by a silver halide photographic emulsion.

The silver chloride phase having a completely uniform silver chloride distribution of the present invention, and a tabular silver chlorobromide grain having a silver chlorobromide phase as a typical example, will be described below. The “completely uniform silver chloride distribution” mentioned here is a microscopic distribution, which is completely different from the silver chloride distributions that have been dealt with so far. As a means for measuring the silver chloride distribution (or silver bromide distribution) in silver chlorobromide grains, an analytical electron microscope (Analytical Elect
ron Microscopy) is often used. For example, in the study of iodine distribution by analytical electron microscope (MAKing) cited above, the probe for electron beam irradiation has a size of 50 Å, but in reality the electron beam spreads due to elastic scattering of electrons. It is described that the diameter of the electron beam spot irradiated on the surface of the sample becomes about 300 Å or more. Therefore, this method cannot measure a finer silver chloride distribution. JP-A-58-113
The silver iodide distribution in silver iodobromide grains was also measured for 927 using the same method, but the size of the electron beam spot used was 0.2μ.

Therefore, some of these measurements are more microscopic (300
It is impossible to clarify the silver chloride distribution. This microscopic silver chloride distribution can be found, for example, in JF Hamilton Photographic Science and Engineering.
Volume 11, 1967 pp57 and Takeshi Shiozawa Japan Society of Photography 35
It can be observed by a direct method using a transmission electron microscope at low temperature described in No. 4, 1972 pp213.
That is, put the silver halide grains taken out under safe light on a mesh for electron microscope observation so that emulsion grains do not print out, and use liquid nitrogen or liquid helium to prevent damage (printout, etc.) from electron beams. In the cooled state, observation is performed by the transmission method.

Here, the higher the accelerating voltage of the electron microscope, the clearer the transmission image can be obtained, but 200 kvolt is preferable up to a particle thickness of 0.25 μm, and 1000 kvolt is preferable for a particle thickness of more than 0.25 μm. The higher the accelerating voltage is, the more the particles are damaged by the irradiation electron beam. Therefore, it is preferable to cool the sample with liquid helium rather than liquid nitrogen.

The photographing magnification can be appropriately changed depending on the particle size of the sample, but is 20,000 to 40,000 times.

Thus, when a transmission electron micrograph of the silver chlorobromide tabular grains is taken, a very fine annual ring-shaped striped pattern is observed in the silver chlorobromide phase portion. An example of this is shown in FIG.
The silver chlorobromide tabular grains shown here contain 35% of silver chloride, and as shown in FIG. 1, a very fine annual ring-shaped striped pattern can be clearly confirmed. It can be seen that the spacing of this striped pattern is very fine and is in the order of 100Å or less, indicating very microscopic non-uniformity. It can be clarified by various methods that this very fine striped pattern shows non-uniformity of silver chloride distribution, but more directly, chlorine or ions move this tabular grain in the silver halide crystal. If you anneal under the conditions that you can (for example, 250
(° C, 3 hours), this striped pattern disappears at all, so it can be concluded clearly.

The ring-shaped stripe pattern showing the non-uniformity of silver iodide distribution in tabular silver iodobromide is clearly observed in the transmission electron micrograph attached to the above-mentioned JP-A-58-113927. Similarly, it is clearly shown in the transmission electron microscope photograph in the study of King et al. Cited above. Japanese patent application
63-7852 contains transmission electron micrographs showing the non-uniformity of silver iodide distribution in tabular silver iodobromide grains having a silver iodide content of 10 mol%.

1 shows a microscopic non-uniform distribution of silver chloride in tabular silver halide grains containing silver chloride, such as tabular silver chlorobromide grains. The annual ring-shaped striped pattern described so far has not been observed, and it is the first discovery by the inventor this time.

From these facts, the silver chlorobromide grains prepared so far to obtain a substantially uniform silver chloride distribution have a very microscopic uneven distribution of silver chloride, which is completely contrary to the intention of the production. It has, and so far, neither the technique of homogenizing it nor the manufacturing method thereof has been disclosed.

As described above, the tabular silver halide grain having the "completely uniform silver chloride distribution" of the present invention is obtained by observing a transmission image of the grain by using a cooling transmission electron microscope. It can be clearly distinguished from conventional silver halide grains. That is, in the tabular silver halide grains containing silver chloride of the present invention, at most two microscopic lines due to microscopic nonuniformity of silver chloride are present at 0.2 μm intervals, preferably one microscopic line.
More preferably not present. The lines forming the annual ring-shaped striped pattern showing microscopic non-uniformity of silver chloride occur in a form orthogonal to the grain growth direction, and as a result, these lines are distributed concentrically from the center of the grain. To do. For example, in the case of the tabular grains shown in FIG. 1, since the line forming the annual ring-shaped striped pattern showing the nonuniformity of silver chloride is orthogonal to the growth direction of the tabular grains,
As a result, the direction parallel to the edges of the particles and orthogonal to them has a direction toward the center of the particles, and is distributed concentrically around the center of the particles.

Of course, if the silver chloride content is changed abruptly during grain growth, the boundary line is observed as a line similar to that described above by the above observation method, but such a change in the silver chloride content is not observed. It is possible to clearly distinguish it from a plurality of lines derived from the microscopic inhomogeneity of silver chloride only by forming one line. Further, the line resulting from such a change in the silver chloride content can be clearly confirmed by measuring the silver chloride contents on both sides of this line by the above-mentioned analytical electron microscope. The line resulting from such a change in the silver chloride content shows a "macroscopic silver chloride distribution", which is completely different from the line derived from the microscopic inhomogeneity of silver chloride in the present invention. Further, when the silver chloride content was changed substantially continuously during the growth of the grains, there was no sudden change in the silver chloride content, and thus the line showing the macroscopic change in the silver chloride content was observed. No, so if there is 0.
The presence of at least 3 lines at 2 μm intervals is a microscopic nonuniformity of silver chloride content.

Thus, the silver halide grains having a completely uniform silver chloride distribution according to the present invention are microscopic silver chloride grains at 0.2 μm intervals in the direction orthogonal to the line in the transmission image of the grains obtained by using a cooling transmission electron microscope. A grain having at most two lines showing a distribution, preferably one, more preferably a silver halide grain free of such lines, and such grains having at least 40% of the total grains. , Preferably at least 60%,
More preferably, it is a silver halide grain occupying at least 80%.

The tabular silver halide grains, which have hitherto been called tabular silver halide grains containing uniform silver chloride, are simply doubled with silver nitrate and a constant (constant iodide content) halide mixture during grain growth. Only added by jet method to the reaction vessel, the macroscopic silver chloride distribution is indeed constant in such grains, but the microscopic silver chloride distribution is not uniform. In the present invention, such a grain is referred to as a tabular grain having a "constant halogen composition" and "completely uniform".
It is clearly distinguished from the tabular grains shown in the present invention.

Next, the method for producing the tabular silver halide grains of the present invention will be described. The manufacturing method for obtaining the grains of the present invention relates to the growth of tabular grains and conventional techniques are used for nucleation. Nucleation of tabular silver halide grains consists of two processes, tabular grain nucleation and ripening.
That is, when tabular grain nucleation is carried out as shown in Japanese Patent Application No. 61-29155, other fine particles (especially octahedron and single twin) are formed at the same time, followed by aging to form tabular grain nuclei. Only the nuclei that become tabular grains can be obtained by eliminating the grains other than. Therefore, in tabular grain formation, the nucleation process includes two processes of tabular nucleation and ripening. In the present invention, nucleation is not a target, and therefore, in the transmission image obtained by photographing the completed tabular grains with a cooling transmission electron microscope,
The central part of the particle showing a nucleus is out of the scope of the present invention. The position of the nucleus can be confirmed by observing the boundary line between the nucleus and the growth phase as a line in the transmission image when the growth is started by adding a new layer using the nucleus as a nucleus after the completion of the nucleation, and especially the nucleus If there is a difference in halide composition in the growth phase,
It can be confirmed more clearly.

In the present invention, the composition of the tabular silver halide grains having a completely uniform silver chloride distribution may be any of silver chlorobromide, silver iodochloride and silver iodochlorobromide. It is preferably silver iodochlorobromide. The position of the phase containing silver chloride in the grain may be at the center of the tabular grain, the whole grain, or the outer portion. The phase in which silver chloride is present may be one or plural. In general, the phase containing silver chloride often forms a ring structure due to the mechanism of grain growth, but it may be a specific portion. For example, it is possible to form a silver chloride phase only at the edge or only at the corner portion by utilizing the difference in properties between the edge and the corner of the tabular grain. Further, by forming a shell on the outside thereof, tabular silver halide grains having silver chloride at a specific point having no ring structure inside the grain can be prepared.

Specifically, an example can be given in which after each formation, particles are grown with the following constitution.

Further, in the case of silver iodochlorobromide, silver iodide may be contained in the above, and the silver iodide containing layer may be any of the first coating layer, the second coating layer and the third coating layer.

Uniform AgBrCl in one tabular grain in the present invention
Is preferably 5 to 99 mol%, preferably 20 to 99%,
It is more preferably 50 to 99%.

In the present invention, the silver chloride content in the silver chloride phase contained in the emulsion grains is 10 mol% to 90 mol%, preferably 20 to 80 mol%. As described above, it is difficult to obtain a high sensitivity in a silver chlorobromide emulsion and fog is liable to occur, which is remarkable especially as the content of silver chloride increases. Therefore, if the silver chloride content is less than 10%, even if microscopic nonuniformity of silver chloride is present, the width of the distribution is practically small, and such a disadvantage is not caused. However, if the silver chloride content of the outermost layer containing silver chloride is 10 mol% or more, the sensitivity is low even with chemical sensitization with conventional grains having a microscopically non-uniform distribution of silver chloride, especially sulfur plus. When gold sensitization is performed, fog is likely to occur and sensitivity is less likely to occur. In other words, the conventional grains having a "constant silver chloride content but a microscopic nonuniform silver chloride distribution" interfere with the chemical sensitization. Therefore, this cannot take advantage of the rapid processability characteristic of silver chlorobromide. However, if the silver halide having the "completely uniform" silver chloride distribution of the present invention is in the outermost layer, there is no interfering action of the above chemical sensitization and all the advantages including silver chloride can be utilized. It is possible to obtain tabular silver chlorobromide (or silver chloroiodobromide) which has a high developing speed and a stable speed that could not be reached and has high sensitivity, low fog, good graininess, and high sharpness. .

The reason why the grain surface having a non-uniform silver chloride distribution hinders chemical sensitization and the grain surface having a completely uniform silver chloride distribution does not hinder chemical sensitization is that the lattice constant of the grain crystal surface is
The non-uniform silver chloride distribution is not constant, and therefore the composition and size of the chemically sensitized nuclei formed on it become non-uniform, so optimal chemical sensitization conditions can be obtained. On the other hand, in the case of a surface having a completely uniform silver chloride distribution, it is considered that the composition and size of the chemically sensitized nuclei become uniform and optimal chemical sensitization can be carried out. I have to wait for consideration.

Further, when silver halide containing silver chloride is present inside the grain, the sensitivity is increased due to the "completely uniform" phase. In other words, if the distribution of silver chloride contained in the inside is non-uniform, it is considered that there are many electron traps generated by light, and effective concentration of photoelectrons cannot be performed. This matter also needs further study. As mentioned above, several proposals have been made as means for increasing the sensitivity of silver chlorobromide grains (especially high silver chloride content).

For example, a method of adding a sensitizing dye to a silver halide emulsion and then adding a water-soluble bromine ion or iodine ion as described in JP-A-48-51627 and JP-B-49-46932.
As described in JP-A-58-108533, JP-A-60-222845, etc., bromine ions and silver ions are simultaneously added to silver halide grains having a high silver chloride content to form a grain surface. A method of providing a silver bromide layer of 60 mol% or more; and a method of providing a silver bromide layer of 10 mol% to 50 mol% on the surface of the grain in whole or in part; JP-B-50-36978; Japanese Patent Sho 58
No. -24772, U.S. Pat.No. 4471050, OLS-3229999, etc., halogen conversion is carried out by adding bromine ion to silver halide having a high silver chloride content or by simultaneously adding bromine ion and silver ion. 2 core and shell
A method for producing particles having a multi-phase structure such as heavy structure particles or bonded structure particles is known.

These techniques are of course effective for tabular silver chlorobromide grains or tabular silver chloroiodobromide grains, in which case silver chlorobromide grains (silver chloroiodobromide) serving as a host or a core are used. "Completely uniform" distribution of silver chloride
With this, high sensitivity and low fog can be obtained with respect to conventional non-uniform particles. Furthermore, as described above, in these techniques, it is essential that the distribution of silver chloride in the outer phase of the grain is "completely uniform" for high sensitivity and low fog. The reason why the microscopic homogeneity of silver chloride is important in tabular grains containing silver chloride is that grains having completely uniform electrons generated by light have a nonuniform distribution. It is considered that the principle of concentration of latent images can be activated more easily and more efficiently.

The total silver chloride content of the emulsion grains of the present invention is 10 mol% or more, but 20 mol% or more is more effective. More preferably, it is 30 mol% or more. The size of the tabular silver halide grains having a completely uniform silver chloride distribution of the present invention is not particularly limited, but the average projected area circle equivalent diameter is 0.5 μm.
Or more, more preferably 1.0 μm or more, especially
The effect is greater when the thickness is 1.5 μm or more.

The size distribution of the tabular silver halide emulsion grains in the present invention may be monodisperse or polydisperse, but it is preferable that the form and grain size are monodisperse. That is, as described in Japanese Patent Application No. 61-299155, 70% or more of the total projected area has a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 2 or less. A silver halide emulsion which is hexagonal and which is occupied by tabular silver halide having two parallel outer surfaces as outer surfaces, and in which the hexagonal tabular silver halide grains are monodispersed is preferable. The monodispersion as used herein means that the coefficient of variation of particle size is 20% or less, preferably 15% or less.

The tabular grains of the present invention are composed of (111) faces which are parallel main surfaces facing each other and have an average aspect ratio of 2 or more, preferably 3 to 20, and more preferably 3 to 15. The particle size is 0.4 μ or more, preferably 0.4 to 4 μ.

Here, the average aspect ratio () means the i-th halogen when the tabular silver halide grains are oriented so that two principal planes facing each other on a plane are horizontal to this plane. Let Di be the diameter of a circle with an area equal to the projected area of a silver halide grain, and ti be the thickness of the grain in the direction perpendicular to the two principal planes. Is defined as However, N is a number necessary and sufficient to give the average aspect ratio of the silver halide grains, and usually, N600 ... (2) is often used as the value of N. Although the above formula (1) shows that is given by the average of the aspect ratio γ _i of each silver halide grain, the silver halide grain is substantially t _i t _j (i ≠ j; i, j ≦ N) (3) or substantially D _i / t _i D _j / t _j (i ≠ j; i, j ≦ N) (4), Is defined as 'Is substantially equal to.

Therefore, the average aspect ratio may be given by ', as long as it is within the range of acceptable accuracy in particle measurement.

The details of the method for producing the tabular silver halide of the present invention are described below. The method for producing tabular silver halide grains of the present invention comprises nucleation (tabular nucleation and ripening) and grain growth. As mentioned above, the present invention relates to grain growth, and nucleation follows conventional methods. .

1. Nucleation Regarding nucleation when the nuclei are silver bromide or silver iodobromide, as shown in Japanese Patent Application No. 61-299155, while maintaining PBr 1.0 to 2.5 in an aqueous solution containing a dispersion medium, It is carried out by adding an aqueous solution of a water-soluble silver salt and an aqueous solution of an alkali halide. The tabular silver halide grains have at least one parallel twin plane inside, and this twin plane formation is a so-called nucleation process. Therefore, this nucleation condition is determined by the frequency of twin plane formation, which is determined by various supersaturation factors (temperature during nucleation, gelatin concentration, addition rate of silver salt aqueous solution and alkali halide aqueous solution, Br ~ concentration, Stirring speed, iodine content in the added halogen-alkali aqueous solution, silver halide solvent amount, pH salt concentration, etc.)
It is illustrated in Japanese Patent Application No. 61-238808. By controlling the nucleation conditions, the shape of the nuclear particles (the number of twin planes per particle) and the number of particles (the particle size after growth is determined)
Can be changed. Especially the temperature during nucleation is 15 °
Nucleation with fine particles and a uniform particle size distribution can be carried out by carrying out at ~ 39 ° C and a gelatin concentration of 0.05 to 1.6% by weight.

When nucleation of tabular grains of silver chlorobromide is carried out, JP-A-58-1
Silver in a reaction vessel containing a dispersion medium as shown in No. 11936,
Chloride and bromide salt were introduced simultaneously, and the molar ratio of chloride ion to bromide ion in the reaction vessel was 1.6:
Keep the total concentration of halogen ions in the container at 1 to 258: 1.
It suffices to keep it within the specified range of 0.10 to 0.90. U.S. Patent No. 43
In No. 99215, tabular grains of silver chlorobromide and silver chloride having a silver chloride content of 50 mol% or more do not contain silver bromide and silver iodide inside, and pAg is in the range of 6.5 to 10, Further, it is described that it can be obtained by carrying out particle formation using ammonia while maintaining the pH in the range of 8 to 10. US Patent 440046
No. 3 describes that a tabular silver halide emulsion having a silver chloride content of at least 50% can be obtained by forming grains in the presence of a peptizer having an aminoazaindene and a thioether bond. US Patent 471332
No. 3 describes that tabular grains of silver chloride and silver chlorobromide are obtained by using gelatin having a methionine content of 30 μmole / g or less as a dispersion medium.

2. Aging As shown in Japanese Patent Application No. 61-299155, fine tabular grain nuclei are formed by nucleation, but a large number of other fine grains (especially octahedron and single twin) are simultaneously formed. Before starting the growth process described below, it is necessary to eliminate grains other than tabular grain nuclei to obtain grains that should become tabular grains. Aging is performed to make this possible. The specific method is Japanese Patent Application Sho 61
-Follow the method described in 299155.

3. Growth After the formation of nuclei, an aqueous solution of a water-soluble silver salt and an alkali halide is added to the reaction vessel in order to grow nuclei so that no new nucleation occurs. In the conventional method, an aqueous solution of a silver salt and a halogen salt is added to the reactor under efficient stirring. At this time, when growing a silver halide having a single halogen composition (for example, silver bromide, silver chloride), the silver halide phase is completely uniform, and even if it is observed by using a transmission electron microscope, nothing happens. , No microscopic non-uniformity is observed. In the case of a single halide composition, non-uniform growth (aside from transition) does not occur in principle, and therefore, in the growth of pure silver bromide or pure silver chloride, it depends on the preparation conditions. Therefore, the nonuniformity referred to in the present invention is not possible. However, in the growth of silver halide (so-called mixed crystal) having a plurality of halide compositions, nonuniform growth in halogen composition becomes a serious problem. As already mentioned, the non-uniform distribution of silver chloride can be clearly confirmed by a transmission electron microscope.

On the other hand, various studies have been made so far in order to obtain uniform growth of silver halide. It is known that the growth rate of silver halide grains is greatly affected by the silver ion concentration, halogen salt concentration and equilibrium solubility in the reaction solution.
Therefore, if the concentrations (silver ion concentration, halide ion concentration) in the reaction solution are non-uniform, it is considered that the growth rate varies depending on the respective concentrations, and non-uniform growth occurs. As a method for improving this local concentration bias, US Pat.
The techniques disclosed in 15650, British Patent 1323464, and US Patent 3692283 are known. In these methods, a reaction vessel filled with an aqueous colloid solution has a hollow rotating mixer having a slit in the wall of a medium-thick cylinder (the inside is filled with the aqueous colloid solution, and more preferably, the mixer is moved up and down by a disc. Is divided into two chambers) so that its rotation axis is vertical, and an aqueous solution of a halogen salt and an aqueous solution of a silver salt are supplied from upper and lower open ends thereof through a supply pipe into a mixer which is rotating at a high speed. Supply and mix rapidly to react (if there are upper and lower separation disks, the aqueous solution of halogen salt and the aqueous solution of silver salt supplied to the upper and lower two chambers are diluted by the colloidal solution filled in each chamber, and mixed. The reaction is carried out by rapidly mixing near the exit slit of the), and the silver halide grains generated by the centrifugal force generated by the rotation of the mixer are discharged into the colloid aqueous solution in the reaction vessel. It is a method to. However, even with this method, the nonuniform distribution of silver chloride could not be solved at all, and a ring-shaped striped pattern showing a nonuniform distribution of silver chloride was clearly observed in the cooled transmission electron microscope.

On the other hand, Japanese Examined Patent Publication (Kokoku) No. 55-10545 discloses a technique for improving the local concentration bias to prevent uneven growth. In this method, in a reaction vessel filled with an aqueous colloid solution, a halogen salt aqueous solution and a silver salt aqueous solution are separately supplied from a lower end of a mixer filled with the colloid aqueous solution through a supply pipe, The reaction solution was rapidly stirred and mixed by a lower stirring blade (turbine blade) provided in the mixer to grow silver halide, and immediately grown by an upper stirring blade provided above the stirring blade. This is a technique in which silver halide grains are discharged into the colloidal aqueous solution in the reaction vessel through the opening of the upper mixer. However, even with this method, the uneven distribution of silver chloride could not be solved at all, and the annual ring-shaped striped pattern showing the uneven distribution of silver chloride was clearly confirmed.

Thus, it is clear that the techniques disclosed thus far do not allow for a complete homogenization of the silver chloride distribution. As a result of earnest research by the inventor, in the growth of silver halide tabular grains containing chloride, silver ions and halide ions (chlorine ion, bromine ion, and iodide ion) which form the grain are deposited in a reaction vessel in an aqueous solution. By supplying it in the form of fine silver halide fine particles having the desired halide composition without any addition and growing tabular grains, the annual ring-shaped striped pattern disappeared completely, and a completely uniform silver chloride It has been found that a distribution can be obtained. This is an unachievable and surprising technique that cannot be achieved by conventional methods. More specifically, a method of adding a fine grain emulsion containing silver chloride prepared in advance. Fine silver halide grains (silver chlorobromide, chloroiodo odor, etc.) having the same silver chloride content as that of the target tabular grain are prepared in advance. Silver halide, silver iodochloride) is prepared in advance, and only this fine grain emulsion is supplied to grow tabular grains without supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide solution to the reaction vessel at all. .

Method for supplying fine silver halide particles from a mixer outside the reaction vessel As an efficient method for supplying fine particles, a powerful and efficient mixer is provided outside the reaction vessel and an aqueous solution of a water-soluble silver salt and a water-soluble halide are provided in the mixer. The above aqueous solution and the protective colloid aqueous solution are supplied and rapidly mixed to generate extremely fine silver halide grains, which are immediately supplied to the reaction vessel. In that case, similarly to the method, neither the aqueous solution of the water-soluble silver salt nor the aqueous solution of the water-soluble halogen salt is supplied to the reaction vessel at all.

U.S. Pat.No. 2146938 describes the growth of a coarse grain emulsion by mixing coarse particles not adsorbing adsorbate and fine grains not adsorbing adsorbate, or slowly adding a fine grain emulsion to a coarse grain emulsion. A method of doing is disclosed. However, we are only dealing with silver iodobromide here.

U.S. Pat. Nos. 3,317,322 and 3,206,313 disclose that a core silver halide grain emulsion, which has been chemically sensitized with an average grain size of at least 0.8 μm, is chemically sensitized with an average grain size of 0.4 μm or less. It discloses a method of preparing a silver halide emulsion having a high internal sensitivity by forming a shell by mixing and ripening a non-existing silver halide grain emulsion. The patent is concerned with silver bromide and silver iodobromide having a low silver iodide content, which is quite different from the present invention relating to tabular grains containing silver chloride. In JP-A-58-111936, "Instead of introducing the silver and halide salts as an aqueous solution, the silver and halide salts are initially introduced in the form of fine silver halide grains suspended in a dispersion medium or at the growth stage. The grain size is such that it is readily Ostwald ripened onto the larger grain nuclei that may be present when introduced into the reactor .. Introducing silver bromide, silver chloride and / or mixed silver halide grains. It is possible. ” However, these are general descriptions of silver halide growth and are not intended to have the teachings of the particular method of preparation and the particular examples required to prepare the perfectly uniform tabular silver halide grains referred to in this patent. Absent.

Next, each method will be described in detail.

Regarding the method In this method, tabular grains serving as nuclei or cores are allowed to exist in a reaction vessel in advance, and then emulsions having fine particles prepared in advance are added to the so-called Ortowald ripening to dissolve fine particles,
Grain growth occurs by its deposition in the nucleus or core. The halide composition of the fine grain emulsion contains the same silver chloride content as the intended tabular grain silver chloride, which is silver chlorobromide, silver chloroiodobromide or silver iodochloride. The average particle diameter of the particles is preferably 0.1 μm or less, more preferably 0.06 μm or less. In the present invention, the dissolution rate of the fine particles is important, in order to increase the speed,
The use of silver halide solvents is preferred. Examples of the silver halide emulsion include water-soluble bromide, water-soluble chloride, thiocyanate, ammonia, thiotheter, thioureas and the like.

For example, thiocyanate (U.S. Pat.
2,448,534, 3,320,069, etc.), ammonia, thioether compounds (e.g., U.S. Pat.Nos. 3,271,157, 3,574,628, 3,704,130, 4,297,439,
No. 4,276,347, etc.), thione compounds (for example, JP-A-5
3-144319, 53-82408, 55-77737, etc.), amine compounds (for example, JP-A-54-100717), thiourea derivatives (for example, JP-A-55-2982), imidazoles (for example, Kakai No. 54-100717) and substituted mercaptotetrazoles (for example, JP-A No. 57-202531).

The temperature for growing tabular grains is 50 ° C or higher,
The temperature is preferably 60 ° C or higher, more preferably 70 ° C or higher. The fine grain emulsion in crystal growth may be added at one time or dividedly, but it is preferable to supply it at a constant flow rate, more preferably to increase the addition rate. In this case, how to increase the addition rate is
Concentration of coexisting colloid, solubility of silver halide crystals,
Size of fine silver halide grains, degree of stirring in reaction vessel,
Size and concentration of coexisting crystals at each time point, hydrogen ion concentration (pH), silver ion concentration (pA) of the aqueous solution in the reaction vessel
It is determined from the relationship between g) and the like and the size and distribution of the target crystal particles, but can be simply determined by routine experimental methods.

With respect to the crystal growth method disclosed in the present invention, as described above, silver ions and halide ions (including chlorine ions) necessary for silver halide crystal growth are conventionally supplied by adding an aqueous solution thereof. Instead, fine silver halide crystals are added and Ostwald ripening is carried out by utilizing the high solubility thereof to grow tabular grains. At that time, the rate-determining step of the system is not the growth rate of tabular grains but how quickly the fine particles are dissolved and silver ions and halide ions are supplied into the reaction vessel. In the case of preparing an emulsion of fine grains in advance as in the method, grains as small as possible are desired, while silver halide grains become more unstable as the size becomes smaller and the solubility increases. Immediately, Ostwald ripening occurred on its own,
This results in an increase in particle size.

JHJames, The Theory of the
Lippmann Emulsion is cited as fine grains in the fourth edition of the Photographic Process, and it is described that its average size is 0.05 μm.

It is possible to obtain fine particles having a particle size of 0.05 μm or less, but even if they are obtained, they are unstable and easily increase in particle size by Ostwald ripening. When the adsorbate is adsorbed, this Ostwald ripening can be prevented to some extent, but the dissolution rate is also reduced accordingly, which goes against the intention of the present invention.

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

Immediately after forming the fine particles in the mixer, add it to the reaction vessel.

After forming fine grains in advance and re-dissolving it after obtaining a fine grain emulsion, the dissolved fine grain emulsion is added to a reaction vessel in which a silver halide grain serving as a core is held and a silver halide solvent is present, It is said that it can bring about growth. However, the extremely fine particles once produced undergo Ostwald ripening during the particle formation process, water washing process, redispersion process, and re-dissolution process, and the particle size increases. In this method, the Ostwald ripening occurs by providing a mixer in the immediate vicinity of the reaction vessel and shortening the residence time of the added liquid in the mixer, and thus immediately adding the produced fine particles to the reaction vessel. I tried not to. Specifically, the residence time t of the liquid added to the mixer is represented below.

V: Volume of mixed gas reaction chamber (ml) a: Addition amount of silver nitrate solution (ml / min) b: Addition amount of halogen salt solution (ml / min) c: Addition amount of protective colloid solution (ml / min) In the production method of the present invention, t is 10 minutes or less, preferably 5
Minutes or less, more preferably 1 minute or less, further preferably 20
It is less than a second. The fine particles thus obtained in the mixer are immediately added to the reactor without increasing their particle size.

(2) Perform strong and efficient stirring with a mixer. James The Theory of the Photographic Process pp93 states that, along with Ostwald ripening, another form is coalescence. During coalescence aging, crystals that were far apart in direct contact were in direct contact. , The grain size suddenly changes as it deposits and produces larger crystals. Both Ostwald and coalescence aging occur not only after the end of deposition, but also during the deposition. ” The coalescence aging is likely to occur especially when the particle size is very small, and particularly when the stirring is insufficient. In extreme cases, it may even form coarse, agglomerated particles. In the present invention, since the mixer of the closed type is used as shown in FIG. 2, the stirring blade of the reaction chamber can be rotated at a high rotational speed, which is not possible with the conventional open type reaction vessel. (In the open type, when the stirring blade is rotated at a high speed, the liquid is spattered by the centrifugal force, which causes problems of foaming and is not practical.) Strong and efficient stirring and mixing can be performed. Coalescence aging can be prevented, and 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 1000 rpm or more, preferably 2000 rpm or more, more preferably 3000 rpm or more.

(C) Injection of protective colloid aqueous solution into the mixer The aforementioned coalescence ripening can be remarkably prevented by the protective colloid of silver halide fine grains. In the present invention, the addition of the protective colloid aqueous solution to the mixer is carried out by the following method.

Pour the protective colloid solution alone into the mixer.

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

A protective colloid is added to the aqueous solution of halogen salt.

The concentration of the protective colloid is 0.2% by weight or more, preferably 0.5% by weight or more.

A protective colloid is added to the silver nitrate aqueous solution.

The concentration of protective colloid is 0.2% by weight or more, preferably 0.5
It is more than weight%. When gelatin is used as the protective colloid, it is better to mix the silver nitrate solution and the protective colloid solution immediately before use, because gelatin silver is formed from silver ions and gelatin and photo-decomposed and thermally decomposed to form a silver colloid.

The above methods (1) to (3) may be used alone or in combination, or three methods may be used at the same time. As the protective colloid used in the present invention, gelatin is usually used, but other hydrophilic colloids can also be used. Specifically, it is described in Research Disclosure, Vol. 176, No. 17643 (December 1978). It is described in Section IX.

Thus, the particle size of the fine particles obtained by the techniques of (a) to (c) can be confirmed by placing the particles on a mesh and directly using a transmission electron microscope at a magnification of 20,000 to 40,000. The size of the fine particles of the present invention is 0.06 μm or less, preferably 0.03 μm or less, more preferably 0.01 μm or less.

In this way it becomes possible to supply particles of extremely fine size to the reaction vessel, a higher dissolution rate of the fine particles,
Therefore, a higher growth rate of tabular grains in the reaction vessel can be obtained.

Although the use of silver halide emulsions is no longer essential by this method, silver halide solvents may be used as necessary to obtain higher growth rates or for other purposes.

The silver halide solvent is as described in the method.
According to this method, the supply rates of silver ions and halide ions to the reaction vessel can be freely controlled. The feed rate may be constant, but preferably the addition rate is increased. The method is described in JP-A-48-36890 and 52-16364. Others are as described in the law. Further, according to the present method, the halogen composition during growth can be freely controlled, for example, while maintaining a constant silver chloride content during the growth of tabular grains, continuously increasing or decreasing the silver chloride content, at a certain point of time. It is possible to change the silver chloride content.

The reaction temperature in the mixer is preferably 60 ° C or lower, preferably 50 ° C or lower, more preferably 40 ° C or lower. 35 ° C
At the following reaction temperatures, normal gelatin easily coagulates, so low molecular weight gelatin (average molecular weight 30,000
It is preferable to use the following).

The low molecular weight gelatin used in the present invention can be usually prepared as follows. Commonly used average molecular weight
100,000 gelatin is dissolved in water and gelatin degrading enzyme is added to enzymatically decompose gelatin molecules. For this method, see RJ Cox, Photographic Gelatin II, Academic Pres.
s, London, 1976, P.233-251, P.335-346 can be referred to. In this case, since the binding position at which the enzyme decomposes is determined, a low molecular weight gelatin having a relatively narrow molecular weight distribution can be obtained, which is preferable. In this case, the longer the enzymatic decomposition time, the lower the molecular weight. In addition, low pH (pH
1 to 3) or under high pH (pH 10 to 12) atmosphere,
There is also a method of hydrolysis.

Next, a light-sensitive material using the emulsion of the present invention will be described.

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support, and a silver halide emulsion. There is no particular limitation on the number of layers and the order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of positions may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

A non-photosensitive layer such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748, 59-113438 and 5
No. 9-113440, No. 61-20037, No. 61-20038 may contain a coupler as described in the specification, DIR compounds and the like, may also contain a color mixing inhibitor as is commonly used Good.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of high-speed emulsion layer and low-speed emulsion layer as described in No.
A layer structure can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57-112751 and 62-20
As described in 0350, 62-206541, 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL
It can be installed in the order of / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-6
As described in 3936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree of sensitivity is arranged, and the sensitivities are gradually lowered toward the support.
An example is an array composed of layers. Even in the case of being composed of three layers having different sensitivities as described above, JP-A-59-20246
As described in No. 4, in the same color-sensitive layer, intermediate emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support.

As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure No.176.
43 and No. 17816, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 to a light-sensitive material.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,401,7
No. 52, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Patent No. 3,973,96.
No. 8, No. 4,314,023, No. 4,511,649, European Patent No. 2
Those described in No. 49,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,61
No. 9, No. 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, No. 3,725,064, Research Disclosure No. 2422 (June 1984), Japanese Patent Laid-Open No. 60-33552.
Issue, Research Disclosure No. 24230 (June 1984
Mon), JP-A-60-43659, 61-72238, 60-35730
No. 55-118034, No. 60-185951, U.S. Pat.No. 4,500,
No. 630, No. 4,540,654, No. 4,556,630, WO (PCT)
Those described in 88/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and U.S. Pat.
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453A.
U.S. Pat.Nos. 3,446,622, 4,333,999, and 4,
753,871, No. 4,451,559, No. 4,427,767, No. 4
Those described in 4,690,889, 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable.

Colored couplers to correct unwanted absorption of colored dyes are Research Disclosure No. 17643 VII-
Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No. 1,
Those described in No. 146,368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, 4,576,910, British Patent 2,10
2, 173, etc.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD17643, VII to F patents, JP-A-57-151944 and JP-A-57-154234.
No. 60-184248, No. 63-37346, U.S. Patent No. 4,248,962
Those described in No. 10 are preferable.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,13.
Those described in 1,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-18
5950, DIR redox compound releasing coupler described in JP-A-62-24252, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, recoloring after separation described in European Patent 173,302A RD No. 11449, a coupler that releases a dye
24241, bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No. 4,553,477, couplers releasing a leuco dye described in JP-A-63-75747, etc. Can be mentioned.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid ester Kinds (trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amylphenol), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2) -Butoxy-5-tert
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably an organic solvent of 50 ℃ or more and about 160 ℃ or less can be used, as a typical example, ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (0LS) 2,541,274 and 2,541,230.

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

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.
Development can be carried out by a usual method described on pages 28 to 29 of 643 and 615, left column to right column of No. 18716.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, Hydrochloride or p-toluene sulfonic acid salt etc. are mentioned. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. , 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, Representative examples include N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developer, a known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol is used alone. Alternatively, they can be used in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 l or less per 1 m 2 of the light-sensitive material and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
No. 53-32736, No. 53-57831, No. 53-37418,
53-72623, 53-95630, 53-95631, 53-104
No. 232, No. 53-124424, No. 53-141623, No. 53-28426
Issue, Research. Compounds having a mercapto group or a disulfide group described in Disclosure No. 17129 (July 1978); thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506 and JP-A-52-20832 Issue 5
3-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide salts described in Japanese Patent Laid-Open No. 58-16,235; West German Patents 966,410, 2,748,430 Oxyethylene compounds; polyamine compounds described in JP-B-45-8836; other JP-A-49-42,434,
49-59,644, 53-94,927, 54-35,727, 55-
Compounds described in Nos. 26,506 and 58-163,940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858 and West Patent 1,290,812.
And the compounds described in JP-A-53-95,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is the most widely used. Can be used for As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in Jour.
nal of the Society of Motion Picture and Televisio
n Engineers Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is a solution,
The method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No.
All known methods described in Nos. -8543, 58-14834, and 60-220345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff's base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, metals described in U.S. Pat.No. 3,719,492. Salt complex, JP-A-5
The urethane compounds described in 3-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64339, JP-A-57-144547, and JP-A-58-1154.
No. 38 etc. are listed.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The silver halide light-sensitive material of the present invention is described in US Pat.
0,626, JP-A-60-133449, 59-218443, 61-23
It can also be applied to the photothermographic materials described in 8056 and European Patent 210,660A2.

EFFECTS OF THE INVENTION The thus obtained silver halide emulsion of the present invention has tabular silver halide grains having a silver chloride-containing silver halide phase having a completely uniform silver chloride distribution, sensitivity, gradation and graininess. sex,
It is possible to provide a silver halide emulsion having excellent characteristics in sharpness, resolution, covering power, storability, stability of latent image and pressure property, and having a high developing rate and a high fixing rate, and therefore capable of rapid processing. .

The present invention will be further described below with reference to examples.

Example 1 Silver chlorobromide fine grain emulsion 1-A To 1.3 l of a 2.3% by weight gelatin aqueous solution containing 0.01 M potassium bromide and 0.05 M sodium chloride, 1.2 M silver nitrate was added by a double jet method with stirring. 600 ml of an aqueous solution and an aqueous solution of halogen salt containing 0.72 M potassium bromide and 1.0 M sodium chloride were added over 25 minutes. During this time, the gelatin solution in the reaction vessel was kept at 35 ° C. After that, the emulsion was washed with a conventional flocculation method to obtain gelatin 30
After g was added and dissolved, the pH was adjusted to 6.5. The obtained silver chlorobromide fine particles (silver chloride content 40%) had an average particle size of 0.09.
was μm.

Tabular silver bromide core grains 1-B 2.0 M by double jet method while stirring it in 1.3 l of 0.8% by weight gelatin solution containing 0.08 M potassium bromide.
150 cc of the silver nitrate solution of and the 2.0 M potassium bromide solution are added. During this time, the gelatin solution was kept at 30 ° C. 70 after addition
The temperature was raised to ℃ and 30 g of gelatin was added. It was then aged for 30 minutes.

The silver bromide tabular grains (hereinafter referred to as seed crystals), which are cores thus formed, were washed by a conventional flocculation method and adjusted to pH 6.0 and pAg 8.5 at 40 ° C. . The average projected area circle equivalent diameter of the obtained tabular grains was 0.4.
was μm.

Tabular Silver Chlorobromide Emulsion 1-C <Comparative Emulsion> Tenths of the above seed crystals were dissolved in Solution 1 containing 3% by weight of gelatin, and the temperature was kept at 75 ° C. 20% sodium chloride 30 cc and 3,6-dithioctan-1,8-diol 0.5 g
Immediately after that, an aqueous solution containing 150 g of silver nitrate and an aqueous solution containing 63 g of potassium bromide and 31 g of sodium chloride were added by a double jet for 100 minutes.

Then, the emulsion was cooled to 35 ° C., washed by a conventional flocculation method, and adjusted to have a pH of 6.5 and pAg 8.0 at 40 ° C. This particle has an average projected area circle equivalent diameter of 2.0
The average thickness is 0.32 μm in μm, and the outside of the core is silver bromide.
The grains were tabular grains of 60% silver chloride and 40% silver chloride.

Tabular Silver Chlorobromide Emulsion 1-D <Invention> One-tenth of seed crystal emulsion 1-B was dissolved in solution 1 containing 3% by weight of gelatin and the temperature was kept at 75 ° C. afterwards
30% of 20% sodium chloride and 0.5 g of 3,6-dithioctan-1,8-diol were added and immediately dissolved Fine grain emulsion 1-
A was pumped in. The fine grain emulsion was added over 100 minutes so that the addition rate was 150 g in terms of the amount of silver nitrate. At that time, 10.4 g of sodium chloride was previously dissolved in the fine grain emulsion. Thereafter, the emulsion was washed with water in the same manner as Emulsion 1-C and adjusted to have a pH of 6.5 pAg 8.0 at 40 ° C. The average projected area circle-equivalent diameter of this tabular grain was 2.1 μm, and the average grain thickness was 0.31 μm.

Tabular Silver Chlorobromide Emulsion 1-E <Invention> Other than the following, it was prepared in the same manner as Emulsion 1-C. Here, as shown in Fig. 2, the grain growth of seed crystals was carried out in a powerful and efficient mixer provided near the reaction vessel for 100 minutes in an aqueous solution containing 150 g of silver nitrate, 63 g of potassium bromide and 31 g of sodium chloride. And an aqueous solution containing 10% by weight of low molecular weight gelatin (average molecular weight 10,000) were added by a triple jet.
The ultrafine particles (average size 0.02 μm) produced by the reaction with stirring in the mixer were continuously introduced into the reaction vessel immediately from the mixer. During this time, the temperature of the mixer was kept at 27 ° C.

After that, the emulsion was washed with water in the same manner as Emulsion 1-C, and then at 40 ° C.
The pH was adjusted to 6.5 and pAg8.0. The average projected area circle equivalent diameter of the tabular grains was 2.1 μm, and the average thickness of the grains was 0.32 μm.

Tabular silver chlorobromide emulsion 1-F <Comparative example> Emulsion 1-C was prepared in the same manner as emulsion 1-C except that 3,6-dithiooctane-1,8-diol was not added. The resulting tabular grains have an average equivalent circle diameter of 2.3 μm and an average thickness of 0.27 μm.
Met.

Tabular silver chlorobromide emulsion 1-G <Invention> The same as emulsion 1-E except that 3,6-dithiooctane-1,8-diol was not added. The resulting tabular grains have an average equivalent circular diameter of 2.2 μm and an average thickness of 0.27 μm.
Met.

Tabular silver chlorobromide emulsion 1-H <Reference example> Emulsion 1-D was prepared in the same manner as emulsion 1-D except that 3,6-dithiooctane-1,8-diol was not added. Here, the added fine particles were not all dissolved, and the fine particles remained after the addition was completed.

Emulsion 1-C, 1-D, 1-E, 1-F, and 1-G grains were sampled and cooled with liquid nitrogen, and their transmission images were observed with a 200 kvolt transmission electron microscope. As a result, a clear annual ring-shaped striped pattern was observed in Emulsions 1-C and 1-F.
No striped pattern was observed in E and 1-G, and it was found that a tabular silver chlorobromide emulsion having a completely uniform silver chloride distribution was obtained by the present invention.

Comparing emulsions 1-D and 1-H, the average size of fine particles 1-A was 0.
It is 09 μm, which means that a silver halide solvent is necessary to dissolve it. (Here, 3,6-dithiooctane-1,8-diol) However, as the example of Emulsion 1-G shows, in the method using the mixer,
Such a silver halide solvent is no longer required because the size of the fine grains is very small, resulting in an emulsion with a small grain thickness and thus a high aspect ratio and a narrow grain size distribution. It is easily understood that this is an ideal tabular grain growth method, together with the complete homogenization of distribution.

Sodium thiosulfate, potassium chloroaurate and potassium thiocyanate were added to these 1-C to 1-G emulsions (pH 6.5, pAg 8.0), and optimum chemical sensitization was performed at 60 ° C. After completion of the chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added and then coated on a polyethylene terephthalate support so that the silver amount was 3 g / m ² .

Next, these samples were exposed to blue light for 1/10 seconds with a 2854 ° K tungsten light source through a 419 nm interference filter, and then developed (20 ° C for 4 minutes) with the following developing solution D-1 to give a fixing solution. After fixing with F-1, it was washed with water and dried.

[Developer D-1] 1-Phenyl-3-pyrazolidone 0.5g Hydroquinone 20.0g Ethylenediaminetetraacetic acid disodium 2.0g Potassium sulfite 60.0g Boric acid 4.0g Potassium carbonate 20.0g Sodium bromide 5.0g Diethylene glycol 30.0g Add water Set to 1. (The pH is adjusted to 10.0.) [Fixer F-1] Ammonium thiosulfate 200.0 g Sodium sulfite (anhydrous) 20.0 g Boric acid 8.0 g Disodium ethylenediaminetetraacetate 0.1 g Aluminum sulfate 15.0 g Sulfuric acid 2.0 g Glacial acetic acid 22.0 g Water In addition, it is set to 1. (PH is adjusted to 4.2.) The results of sensitometry are shown in Table 1.

Example 2 Fine grain silver chlorobromide emulsion 2-A A 1.2M silver nitrate aqueous solution was prepared by a double jet method in 1.2L of a 1.5% by weight gelatin solution containing 0.01M potassium bromide and 0.06M sodium chloride while vigorously stirring it. Then, 600 ml of an aqueous halogen salt solution containing 0.6 M potassium bromide and 1.2 M sodium chloride was added over 20 minutes. During this time, the solution in the reaction vessel was kept at 35 ° C.

After that, the emulsion was washed by a conventional flocculation method, 20 g of gelatin was added and dissolved, and then the pH was adjusted to 6.5. The obtained silver chlorobromide fine particles (silver chloride content 50%) have an average size of 0.
It was 08 μm.

Tabular silver bromide core emulsion 2-B To a 2% by weight gelatin solution 1 containing 0.09 M potassium bromide, a 1.5 M silver nitrate solution and a 1.5 M potassium bromide solution were prepared by a double jet method while stirring it. And 100cc
Added. During this time, the reaction solution was kept at 40 ° C. After addition 75
After raising the temperature to ℃ and adding 40 g of gelatin, 1.0 M silver nitrate solution was added to adjust PBr to 2.5, and then 150 g of silver nitrate was accelerated in 60 minutes (the flow rate at the end was 10 Times)
At the same time, potassium bromide is PB by double jet
r2.5 was added.

Thereafter, the emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method, 60 g of gelatin was added and dissolved at 40 ° C., and the pH was adjusted to 6.5 and pAg 8.7. The tabular silver bromide grains were monodisperse tabular grains having an average equivalent circle diameter of 2.2 μm and a grain thickness of 0.18 μm and a coefficient of variation of equivalent circle diameter of 18%.

Tabular silver chlorobromide emulsion 2-C <Comparative emulsion> Emulsion 2-B containing silver nitrate equivalent to 100 g of silver nitrate was added to water 1
Dissolve in water and adjust the temperature to 70 ℃, and add 20% sodium chloride solution.
After adding 50 cc, 100 g of silver nitrate aqueous solution and 1
A solution containing 7.5 g potassium bromide and 13 g sodium chloride was added with a double jet.

Then, the emulsion was cooled to 35 ° C., washed by a conventional flocculation method, and adjusted to pH 6.5 pAg 8.1 at 40 ° C. This grain had an average projected area circle equivalent diameter of 2.4 μm and an average thickness of 0.22 μm, and the outside of the core was a silver chlorobromide tabular grain having 50% silver bromide and 50% silver chloride.

Tabular silver chlorobromide emulsion 2-D <Invention> Emulsion 2-A corresponding to 100 g of silver nitrate was dissolved in water 1,
Bring the temperature to 70 ° C and add 50cc of 20% NaCl solution.
The fine particle emulsion 2-A dissolved at 0 ° C was added by a pump.
The fine grain emulsion was added over 100 minutes so that the addition rate was 50 g in terms of the amount of silver nitrate. Then sodium chloride
4.4 g was previously dissolved in a fine grain emulsion. After that, the emulsion was washed with water in the same manner as in 1-C and adjusted to have a pH of 6.5 and a pAg of 8.1 at 40 ° C. The average projected area circle equivalent diameter of this tabular grain is
The average thickness of the particles was 2.3 μm and was 0.24 μm.

Tabular silver chlorobromide emulsion 2-E <Invention> The same as emulsion 1-C except for the following. Here, as shown in FIG. 2, the grain growth is carried out in a powerful and efficient mixer provided near the reaction vessel containing an aqueous solution containing 50 g of silver nitrate, 35 g of potassium bromide and 13 g of sodium chloride in 100 minutes. Aqueous solution and 3% by weight gelatin (bone gelatin, average molecular weight
100,000) aqueous solution was added by triple jet.

Ultrafine particles (average size 0.02 μm, silver bromide 50%, silver chloride 50%) produced in the mixer were immediately continuously introduced into the reaction vessel from the mixer. The temperature of the mixer was kept at 25 ° C.
Thereafter, the emulsion was washed with water in the same manner as in 1-C, and the pH was 6.5 at 40 ° C and pAg8.
Adjusted to 1. The average projected area circle-equivalent diameter of this tabular grain was 2.4 μm, and the average thickness was 0.22 μm.

In the same manner as in Example 1, while the emulsion 2-C, 2-D, and 2-E grains were sampled and cooled with liquid nitrogen,
The transmission image was observed with a 200 Kvolt transmission electron microscope. In these emulsion grains, the core was made of AgBr and the shell was composed of silver chlorobromide (silver chloride content 50%), which was clearly distinguished in this transmission image. Although a striped pattern was observed,
This stripe pattern was not observed in the emulsion grains of D and 2-E, and it is understood that tabular silver chlorobromide emulsion grains having a completely uniform silver chloride distribution were obtained by the present invention.

Emulsions 2-C, 2-D and 2-E were optimally chemically sensitized with sodium thiosulfate, chloroauric acid and potassium thiocyanate at 60 ° C, and then the following sensitizing dyes were added so as to be 200 mg / Ag 1 mol. Shi Then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added (however, the addition amount of 2-C emulsion was adjusted so that the total addition amount was the same as that of other emulsions). It was coated on a polyethylene terephthalate support so that the amount of silver was ² g / m ² . Next, apply a filter (minus blue exposure) that cuts light of wavelengths shorter than 500 nm to a 5400 ° K light source for these samples to 1/10
After exposure for a second, the developer D described in Example 1 above
After development with -1 (4 minutes at 20 ° C) and fixing with the above-mentioned fixing solution F-1, washing with water and drying were carried out.

The results of sensitometry are shown in Table 2.

As described above, the emulsion of the present invention has the same fog and is more sensitive than the comparative emulsion.

Example 3 Tabular silver chlorobromide emulsion 3-A (comparative emulsion) containing 0.47M potassium chloride and 0.01M potassium bromide 3
13 cc of a solution containing 2M silver nitrate aqueous solution and 1.7M potassium bromide and 1.3M potassium chloride were respectively added by a double jet method to 1.0 liters of 1.0% by weight gelatin solution for 5 minutes while stirring it. During this time, the solution was kept at 55 ° C. After aging for 20 minutes as it was, the temperature was raised to 70 ° C., and 320 cc of a solution containing 2M silver nitrate aqueous solution, 1.2M potassium bromide and 1.8M potassium chloride was added by a double jet for 80 minutes.

After that, the emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method, added with 60 g of gelatin, dissolved at 40 ° C., and p
Adjusted to H6.5 and pAg7.8. The silver chlorobromide tabular grains had a core silver chloride content of 15%, a shell silver chloride content of 40%, an average equivalent circle diameter of 2 μm, and a grain thickness of 0.2 μm.

Tabular silver chlorobromide emulsion 3-B <Invention> 3 containing 0.47 M potassium chloride and 0.01 M potassium bromide
13 cc of a solution containing 2M silver nitrate aqueous solution and 1.7M potassium bromide and 1.3M potassium chloride were respectively added by a double jet method to 1.0 liters of 1.0% by weight gelatin solution for 5 minutes while stirring it. During this time, the solution was kept at 55 ° C. After ripening for 20 minutes as it is, the temperature is raised to 70 ° C., and silver chlorobromide fine grain emulsion 1-
A (silver chloride content 40%) was added by a pump. Fine grain emulsion 1-A was added so that the addition rate was 109 g in terms of silver nitrate.
Added over 80 minutes. At that time, 23.9 g of potassium chloride was previously added to the fine grain emulsion. This is followed by emulsion 3
It was washed with water in the same manner as in -A and adjusted to have a pH of 6.5 and pAg 7.8 at 40 ° C. The average projected area circle equivalent diameter of this tabular grain is
The average particle thickness was 2.2 μm and was 0.3 μm.

Tabular silver chlorobromide emulsion 3-C <Invention> The same as emulsion 3-B except for the following. Here, as shown in Fig. 2, the grain growth was carried out in a powerful and efficient mixer installed near the reaction vessel with a 2M silver nitrate aqueous solution in a period of 80 minutes.
320cc of a mixed aqueous solution of 2M potassium bromide and 1.8M potassium chloride and 500cc of a 10% by weight low molecular weight gelatin (average molecular weight 5000) aqueous solution were added by a triple jet.
Ultrafine particles produced by mixer (average size 0.01 μm silver bromide
(60%, 40% silver chloride) was continuously introduced into the reactor immediately from the mixer. The temperature of the mixer was kept at 15 ° C. Thereafter, the emulsion was washed with water in the same manner as Emulsion 1-B to adjust the pH to 6.5 and pAg 7.8. The average projected area circle equivalent diameter of this tabular grain is 2.
The particle thickness was 2 μm and the particle thickness was 0.3 μm. These emulsions 3-
Sensitizing dye II shown below is added to A, 3-B and 3-C at 60 ° C.
Optimum chemical sensitization was performed by adding 0 mg / Ag 1 mol and 10 minutes later, adding sodium thiosulfate and potassium chloroaurate.

After chemical sensitization, 100g of emulsions 3-A, 3-B and 3-C respectively
(Including 0.08 mol of Ag) Was dissolved at 40 ° C., and the following were added one by one with stirring to prepare a solution.

The coating solution for the surface protective layer was successively added at 40 ° C. with stirring under the following conditions to prepare a solution.

The emulsion coating solution thus obtained and the coating solution for the surface protective layer were coated on the cellulose triacetate film support by the simultaneous extrusion method so that the volume ratio at the time of coating was 103: 45. The coated silver amount is 3.1 g / m ² . 200lux with a light source of 2854 ° K color temperature for these samples,
After applying 1/10 second wedge exposure, use the following developer D-2.
After developing at 20 ° C. for 7 minutes, the fixing solution F-1 was used for fixing, followed by washing with water and drying.

[Developer D-2] Metol 2 g Sodium sulfite 100 g Hydroquinone 5 g Borax-5H ₂ O 1.53 g Water 1 was added. 1 The result of sensitometry is shown in Table 3.

As shown in Table 3, the emulsion of the present invention has significantly higher sensitivity and lower fog than the comparative emulsion. Furthermore, the gradation of the emulsion of the present invention was higher than that of the comparative emulsion.

Example 4 Samples 401 to 405, which are multilayer color light-sensitive materials having respective layers having the compositions shown below, were prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by. The chemical structural formulas or chemical names of the compounds used in the present invention are shown collectively in Table 6 below.

1st layer (antihalation layer) Black colloidal silver …… 0.2 Gelatin …… 1.3 Colored coupler C-1 …… 0.06 UV absorber UV-1 …… 0.1 Same as above UV-2 …… 0.2 Dispersion oil Oil-1 …… 0.01 Same as above Oil-2 …… 0.01 Second layer (intermediate layer) Fine silver chloride (average particle size 0.07μ) …… 0.15 Gelatin …… 1.0 Colored coupler C-2 …… 0.02 Dispersed oil Oil-1 …… 0.1 Third layer (First red-sensitive emulsion layer) Emulsion (average grain size 0.4μ, AgBrCl (silver chloride 35%) …… Silver 1.0 Sensitizing dye I …… 1.5 × 10 ^-4 Sensitizing dye II …… 3.5 × 10 ^-4 increase Sensitizing dye III …… 1.5 × 10 ^-5 Coupler C-3 …… 0.48 Coupler C-4 …… 0.48 Coupler C-8 …… 0.08 Coupler C-2 …… 0.08 Dispersed oil Oil-1 …… 0.30 Same as above Oil-3 …… 0.04 4th layer (2nd red-sensitive emulsion layer) Emulsion (1) As shown in Table 4 …… Silver 1.0 Gelatin …… 1.0 Sensitizing dye I …… 1 × 10 ^-4 sensitization Dye II …… 3 × 10 ^-4 Sensitizing Dye III …… 1 × 10 ^-5 Coupler C-6 …… 0.05 Coupler C-7 …… 0.1 Dispersed oil Oil-1 …… 0.01 Same as above Oil-2 …… 0.05 No. 5 layers (intermediate layer) Gelatin ...... 0.1 Compound Cpd-A ・ ・ ・ 0.03 Dispersion oil Oil-1 …… 0.05 6th layer (1st green emulsion layer) Emulsion (Average grain size 0.4μ, AgBrCl (silver chloride 35%) ) Silver 0.8 sensitizing dye IV …… 5 × 10 ^-4 Sensitizing dye V …… 2 × 10 ^-4 Coupler C-9 …… 0.50 Coupler C-1 …… 0.06 Coupler C-10 …… 0.03 Coupler C -5 ...... 0.02 Dispersed oil Oil-1 ...... 0.4 7th layer (2nd green emulsion layer) Emulsion (2) As shown in Table 4 ...... Silver 0.85 gelatin ...... 1.0 Sensitizing dye IV ...... 3.5 × 10 ^-4 Sensitizing dye V …… 1.4 × 10 ^-4 Coupler C-11 …… 0.01 Coupler C-12 …… 0.03 Coupler C-13 …… 0.20 Coupler C-1 …… 0.02 Coupler C-15 …… 0.02 Dispersion oil Oil-1 ... 0.20 Same as above Oil-2 …… 0.05 Eighth layer (yellow filter layer) Gelatin …… 1.2 Yellow colloidal silver …… 0.08 Compound Cpd-B …… 0.1 Dispersed oil Oil-1 …… 0.3 Ninth layer (first blue-sensitive emulsion) Layer) Emulsion (average grain size 0.4μ, AgBrCl (35% silver chloride) ...... Silver 0.4 Gelatin ...... 1.0 Sensitizing dye ...... 2 × 10 ^-4 Coupler C-14 ...... 0.9 Coupler C-5 ...... 0.07 Dispersion oil Oil-1 …… 0.2 10th layer (2nd blue-sensitive emulsion layer) Emulsion (3) Table 4 …… Silver 0.5 Gelatin …… 0.6 Sensitizing dye IV …… 1 × 10 ^-4 Coupler C- 14 …… 0.25 Dispersed oil Oil-1 …… 0.07 11th layer (first protective layer) Gelatin …… 0.8 UV absorber UV-1 …… 0.1 Same as above UV-2 …… 0.2 Dispersed oil Oil-1 …… 0.01 Dispersion Oil Oil-2 …… 0.01 12th layer (2nd protective layer) Fine grain silver chloride (average particle size 0.07μ) …… 0.5 Gelatin …… 0.45 Polymethylmethacrelay Particles (diameter 1.5μ) ...... 0.2 Hardener H-1 ...... 0.4 Formaldehyde scavenger S-1 ...... 0.5 Formaldehyde scavenger S-2 ...... 0.5 In addition to the above components, a surfactant is added to each layer. It was added as a coating aid. The sample prepared as described above is sample 301
And

The optimum chemical sensitization of each emulsion was carried out so as to suit each layer.

These photographic elements were exposed to 25 CMS for 1/100 second with a color temperature adjusted to 4800 ° K by a filter using a Tantasten light source, and then developed at 38 ° C according to the following processing steps.

Color development 2 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

(Color developer) Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N) -B-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Water added 1.0l pH10.0 (bleaching solution) Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water In addition 1.0l pH 6.0 (fixing solution) Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water is added 1.0l pH 6.6 (stabilizing solution) Formalin ( 40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g Water-added 1.0 l Samples 401 to 405 were measured for concentration with red light, green light, and blue light . The results obtained are shown in Table 5. The sensitivity is the relative sensitivity calculated at the lowest concentration +0.2.

As is clear from Table 5, the emulsion of the present invention has higher sensitivity than the comparative emulsion.

[Brief description of drawings]

FIG. 1 is a transmission electron micrograph showing a crystal structure of a conventional silver halide grain in which silver chloride distribution of silver chlorobromide is not completely uniform, and its magnification is 15,000 times. FIG. 2 schematically shows a method of supplying silver halide fine grains from a mixer outside the reaction vessel, which is one of the emulsion production methods according to the present invention.

Claims (3)

[Claims] 1. A silver halide photographic emulsion comprising a dispersion medium and silver halide grains, wherein at least 50% of the total projected area of the silver halide grains is a tabular halide having an average aspect ratio of 3 or more. Characterized by the fact that the tabular grains contain a silver chloride phase having a silver chloride content of 10 mol% to 90 mol% and the distribution of silver chloride in the silver chloride phase is completely uniform. And a silver halide photographic emulsion. 2. The silver chloride phase is characterized in that there are at most two microscopic lines at 0.2 μm intervals due to nonuniform transmission images by a cooling transmission electron microscope. A silver halide photographic emulsion as set forth in claim 1. 3. The silver chloride phase has an average grain size of 0.1 μm.
The silver halide photographic emulsion according to claim 1, which is formed by the following fine silver halide grains.