JPH0243535A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain the title emulsion with excellent sensitivity, gradation, graininess, sharpness, resolving power, covering power, shelf-life, stability of a latent image and pressure resistant property by composing the emulsion of a dispersion medium and a specified tabular silver halide particle. CONSTITUTION:At least 50% of the total projected area of silver halide particles is occupied by the tabular silver halide particle having a mean aspect ratio of >=3, and the tabular silver halide particle contains a silver halide phase having >=10mol.% of silver chloride, and the distribution of the silver chloride contd. in the silver halide particle is completely uniform. Namely, when the transmission image of the silver halide particle is observed with a cooling and transmission type electron microscope, a microscopic line due to microscopic ununiformity of silver chloride in a tabular silver halide particle contg. silver chloride is at most, 2 lines, preferably one line with a distance of 0.2mum, and further preferably does not present. Thus, the silver halide emulsion which has a less tendency for generating a fog, and the high sensitivity and the improved graininess, sharpness and covering power, and the excellent shelf-life and pressure resistant property, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a light-sensitive silver halide emulsion useful in the field of photography, and in particular to a silver halide emulsion comprising a dispersion medium and tabular silver halide grains, and the production thereof. Regarding the method.

(Prior Art) Tabular silver halide grains containing parallel twin planes (hereinafter referred to as "tabular grains") have photographic properties such as: l) a large ratio of surface area to volume (hereinafter referred to as specific surface area); sensitizing dyes can be adsorbed onto the surface. As a result, the color sensitization sensitivity is relatively high compared to the inherent sensitivity.

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

3) In X-ray photography systems, when a sensitizing dye is added to tabular grains, they become halogenated! ! The extinction coefficient of the dye is larger than the extinction coefficient of the it(AgX) indirect transition, so that crossover light can be significantly reduced and deterioration of image quality can be prevented.

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

5) Since the sensitivity to blue light is low, the yellow filter can be removed from the emulsion when used in a green or red light-sensitive layer.

etc. can be mentioned.

Because of these many advantages, it has been used in highly sensitive commercially available light-sensitive materials.

Regarding silver bromide and silver iodobromide tabular grains, for example, JP-A-58-113926, JP-A No. 58-113927,
No. 5B-113928 discloses milk-scarred grains having an aspect ratio of 8 or more.

The aspect ratio referred to here is indicated by the ratio of the diameter to the thickness of the tabular grain. Furthermore, the diameter of a grain refers to 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. Further, the thickness is indicated by the distance between two parallel planes constituting a tabular silver halide grain.

On the other hand, light-sensitive silver halide photographic emulsions containing silver chloride are known and offer the following advantages.

For example, it is more soluble than other photographically useful silver halides so that development and fixing can be accomplished in a shorter time. Silver chlorobromide emulsions containing silver chloride are of particular use in applications requiring high contrast, such as graphic arts, and applications requiring rapid processing, such as black-and-white negative shadow materials, X-ray films, and color printing products. sex is obtained.

Furthermore, as color photographic materials become more and more popular, the color development process is becoming simpler and faster, while high-quality images and uniform finishing quality are required.

It is generally known that silver iodobromide emulsions containing 4 to 20 mol % of silver iodide are used for photographic color light-sensitive materials, and silver chlorobromide emulsions are used for color printing materials. Silver chlorobromide emulsions have higher sensitivity and are more difficult to obtain high quality images than silver iodobromide emulsions, but they may be useful in speeding up color development processing.

U.S. Pat. No. 4,399,215 discloses a silver chloride content of 50
The tabular grains of silver chlorobromide and silver chloride of mol% or more do not contain silver bromide and silver iodide inside, and have a pA and g of 6.5 to 10.
It is described that particles can be formed by using ammonia while maintaining the pH in the range of 8 to IO. U.S. Pat. No. 4,400,463 describes that a tabular silver halide emulsion having a silver chloride content of at least 50% can be obtained by forming grains in the coexistence of an aminoazaindene and a veptizer containing a thioether bond. ing. U.S. Patent No. 4713323
The publication describes that tabular grains of silver chloride and silver chlorobromide can be obtained by using gelatin as a dispersion medium with a methionine content of 30 μ5 ole/g or less. JP-A-58-111936 describes silver chlorobromide tabular grains having an average molar ratio of chloride to promide up to at least 2:3, which increases the molar ratio of chloride to promide ions in the reaction vessel. It is described that the halogen ions can be obtained by double jet while maintaining the ratio of +, S:t to 258:1 and the total concentration of halogen ions in the reaction vessel to the regulation o, i fi'y O,LO. These patents disclose silver chlorobromide tabular grains with various silver chloride contents or methods for producing the same, but the silver chlorobromide emulsions described above are less sensitive than the silver iodobromide emulsions. Moreover, it does not solve the drawbacks of instability of the obtained sensitivity and the tendency to cause fogging.

On the other hand, several methods have been proposed to solve these problems.

For example, JP-A No. 48-51627, JP-A No. 49-469
32, etc., a method of adding water-soluble bromide ions or iodide ions after adding a sensitizing dye to a silver halide emulsion; JP-A-58-108533, JP-A-60-222845 A method of simultaneously adding bromide ions and daughter ions to silver halide grains with a high silver chloride content to form a layer of silver bromide of 60 mol% or more on the surface of the grains, as described in Similarly, a method in which a layer of 10 mol% to 50 mol% silver bromide is provided on the surface of the grains, either entirely or partially; Japanese Patent Publication No. 50-36978, Japanese Publication No. 5B
-24772, U.S. Patent No. 4471050 and 0LS-
3229999, etc., by adding bromide ions to silver halide with a high silver chloride content or by simultaneously adding bromide ions and silver ions to produce halogen-converted core-shell double structure particles or bonded particles. Methods for producing particles with multiphase structures such as structured particles are known.

All of these methods fall short of their targets in terms of sensitivity and the like.

The content described in these patents is to vary the content of silver bromide in each silver chlorobromide grain depending on the location (particularly on the inside or outside of the grain, or on the surface of the grain), thereby, The aim is to obtain better photographic characteristics.

For example, in JP-A-58-111935, 50 mol%
In tabular silver halide emulsion grains in which is chloride,
A photographic emulsion is disclosed which is characterized in that the central region contains at least one of bromide and iodide.

The topography of silver chloride-containing locations (or silver bromide gold [1)] in these silver chlorobromide tabular grains was observed using analytical electron microscopy #1 (analytical electrons+1).
8 For example, the results of investigating the topography of the silver iodide content in silver iodobromide tabular grains are known as King (M, ^5King).
), Lorretto (71, H,), MaLernaghan (T, J, MaLernaghan) and Belli (F, J).

Berry) 'The Investigation of Iodide Distribution by Analytical Electron Microscopy' Progress in Basic Principles of Imaging Systems, International Conductors of Photographic Science Cologne (Ktfln), 1
986.

Here, it was shown that even if silver iodobromide tabular grains were grown with a constant silver iodide content, the silver iodide content was higher in the periphery than in the center. In other words, in the formation of the silver iodobromide phase, grains were grown so that the iodide content remained constant, but this was not actually the case.

On the other hand, Tan (Y, T, Tan) and Bella Old (R
,C.

Baetzold calculated the energy state of silver halide and proposed at the 5PSE 41st Annual Meeting that iodine in silver iodobromide crystal grains tends to form clusters. The distribution of silver iodide in the above-mentioned tabular silver bromide grains is a change in silver iodide content at different locations in units of at least 300 to 1000 Å, but tan (Y).

T, Tan) and BaeLzo (R,C, BaeLzo)
As expected, a more microscopic (100 or less) non-uniform distribution of silver iodide is confirmed in the silver iodobromide crystals.

These findings were confirmed in tabular silver iodobromide grains, but they are also the same in silver chlorobromide tabular grains, so-called mixed crystal grains consisting of two or more different types of halogens. )
The inventors have confirmed that this is a common problem in the above-mentioned microscopic silver chloride distribution. This microscopic silver chloride distribution (silver iodide distribution in the case of silver iodobromide) refers to completely uniform particles.
Tabular silver halide grains with a completely uniform distribution of silver chloride, which can be confirmed by a cooled transmission electron microscope and which is disclosed in the Zero patent, have not been obtained to date.

(Objective of the Invention) The object of the present invention is to provide a negative-working tabular silver halide with low fog, high sensitivity, improved graininess, sharpness, and covering power, and excellent storage stability and pressure resistance. An object of the present invention is to provide a photographic emulsion comprising grains.

(Disclosure of the Invention) The object of the present invention is to provide a silver halide photographic emulsion comprising a dispersion medium and silver halide grains, in which at least 50% of the total projected area of the silver halide grains has an average aspect ratio of 3 or more. dominated by tabular silver halide grains,
and the tabular grains contain a silver halide phase containing 8110 mol% or more of chloride, and the silver halide containing the silver chloride has a completely uniform distribution of silver chloride. It was done.

The tabular silver chlorobromide grains of the present invention having a silver chlorobromide phase having a completely uniform silver chloride distribution will now be described. The term "completely uniform silver chloride distribution" here refers to a more microscopic distribution of silver chloride (or silver chloride distribution) in silver chlorobromide grains, which is completely different from the silver chloride distribution that has been handled up to now. As a means of measuring silver oxide distribution, an analytical electron microscope (Analytical Electron Mic
For example, in the above-mentioned ``Study of Coud Distribution Using Analytical Electron Microscopy'' by King (M., A., N.), et al. , it is stated that in reality, the electron beam spreads due to elastic scattering of electrons, and the diameter of the electron beam spot irradiated onto the surface of the sample becomes approximately 300 Å or more. Therefore, this method cannot measure a finer-grained silver chloride distribution.
In JP-A-58-113927, the silver iodide distribution in silver iodobromide grains was measured using the same method, but the size of the electron beam spot used was 0.2 μ.

Therefore, depending on these measurement methods, more microscopic (30
It is impossible to clarify the distribution of silver chloride (locational variations on the order of 0 or less).

This microscopic silver chloride distribution is, for example, Hamiltonian (
J, F, 1lasilton) Photographic Science and Engineering ltS, t
967 p, p, 57 and Takeshi Shiozawa Photographic Society of Japan 3
Vol. 5, No. 4, 1972, p. The silver oxide particles are placed on a mesh for electron microscopic observation, and the specimen is cooled with liquid nitrogen or liquid helium to prevent damage (printout, etc.) caused by the electron beam, and then observed using a transmission method.

Here, the higher the accelerating voltage of the electron microscope, the clearer the transmitted image can be obtained, but up to a particle thickness of 0.25 μm, the
lL, for particle thicknesses larger than 1000 k
The better the voltage and the higher the accelerating voltage, the greater the damage to particles caused by the irradiated electron beam, so it is more desirable to cool the sample with liquid helium than with liquid nitrogen.

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

When a transmission electron micrograph of silver chlorobromide tabular grains is taken in this manner, a very fine annual ring-like striped pattern is observed in the silver chlorobromide phase. An example of this is shown in FIG.

The silver chlorobromide tabular grains shown here contain 35% silver chloride, and as shown in FIG. 1, very fine annual ring-like striped patterns can be clearly seen. It can be seen that the spacing between these striped patterns is very fine, on the order of 100 people or less, indicating extremely microscopic non-uniformity. Although this very fine striped pattern indicates non-uniformity of silver chloride distribution, it can be revealed by various methods, but more directly, this tabular grain indicates the movement of chloride ions within the silver halide crystal. This can be clearly concluded from the fact that this striped pattern completely disappears when annealing is performed under certain conditions (for example, 250° C. for 3 hours).

The ring-like striped pattern showing the non-uniformity of silver iodide distribution in tabular silver iodobromide is described in Japanese Patent Application Laid-Open No. 1139-1983 cited above.
It is clearly observed in the transmission electron micrograph attached to 27, and is also clearly shown in the transmission electron micrograph in the study by King et al. cited above. Furthermore, Japanese Patent Application No. 7852/1983 discloses transmission electron micrographs showing the non-uniformity of silver iodide distribution in tabular iodobromide grains having a silver iodide content of 10 mol %.

There have been no cases in which the tree-ring-like striped pattern described above, which indicates microscopically uneven distribution of silver chloride in tabular silver halide grains containing silver chloride, such as silver chlorobromide tabular grains, has been observed. This was discovered for the first time by the inventor.

Due to these facts, silver chlorobromide grains that have been prepared so far to obtain a substantially uniform distribution of silver chloride have a very microscopic non-uniform distribution of silver chloride, which is completely contrary to the intention of the manufacture. Until now, no technology for uniformizing the uniformity has been disclosed, nor has a method for producing the same been disclosed.

As mentioned above, the tabular silver halide grains with "completely uniform silver chloride distribution" of the present invention can be obtained by observing the transmission image of the grains using a cooled transmission electron microscope. can be clearly distinguished from silver halide grains. That is, the tabular silver halide grains containing silver chloride of the present invention have at most two, preferably one, microscopic lines at intervals of 0.2 μm due to microscopic non-uniformity of silver chloride.
The lines constituting the ring-like stripes, which indicate this microscopic inhomogeneity of silver chloride, which is more preferably absent, occur perpendicular to the direction of grain growth, and as a result these lines Distributed concentrically from the center of the particle.

For example, in the case of the tabular grain shown in Figure 1, the lines constituting the annual ring-like striped pattern, which indicates the non-uniformity of silver chloride, are perpendicular to the growth direction of the tabular grain, and as a result, they are parallel to the edge of the grain. and the direction perpendicular to them points toward the center of the particle, and is distributed concentrically around the center of the particle.

Of course, if the silver chloride content changes rapidly during grain growth, the boundary line will be observed as a line similar to that described above using the above observation method, but such a change in silver chloride content is simply It only consists of one line, and can be clearly distinguished from one consisting of multiple lines resulting from microscopic non-uniformity of silver chloride. Furthermore, the line derived from such changes in silver chloride content is
The silver chloride content on both sides of this line can be clearly confirmed by measuring it with the analytical electron microscope mentioned above. Such a line due to a change in silver chloride content is completely different from a line resulting from microscopic non-uniformity of silver chloride as referred to in the present invention, and indicates a ``macroscopic silver chloride distribution J''.

Furthermore, if the silver chloride content is changed substantially continuously during grain growth, the above line showing the macroscopic change in silver chloride content will not be observed because there will be no sudden change in the silver chloride content. figure,
Therefore, if there are at least three lines at intervals of 0.2 μm, this means that there is microscopic non-uniformity in the silver iodide content.

Thus, the silver halide grains of the present invention with completely uniform silver chloride distribution have microscopic particles at intervals of 0.2 am in the direction perpendicular to the line in a transmission image of the grains obtained using a cooled transmission electron microscope. It is a silver halide grain having at most two lines, preferably one line, and more preferably no such line, and such grains account for a small proportion of the total grains. The silver halide grains account for both 40%, preferably at least 60%, and more preferably at least 80%.

Tabular silver halide grains, which have been called tabular silver halide grains containing uniform silver chloride, are simply double-layered with silver nitrate and a halide mixture of a constant composition (constant iodide content) during grain growth. The particles were simply added to the reaction vessel by a jet method, and although the macroscopic silver chloride distribution in such particles is certainly constant, the microscopic silver chloride distribution is not uniform.

In the present invention, such grains are referred to as "tabular grains having a fixed halogen composition J" and are clearly distinguished from the tabular grains shown in the present invention which are completely uniform.

Next, the method for producing the tabular silver halide grains of the present invention will be described. The method for producing 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 nuclei are generated as shown in Japanese Patent Application No. 61-29155, other fine grains (especially octahedral and -heavy twinned) are formed at the same time, and by subsequent ripening, tabular grains are formed. By eliminating grains other than the core, only the core of the tabular grain can be obtained. Therefore, in the formation of tabular grains, the nucleation process includes two processes: tabular nucleation and ripening.8 Nucleation is not the subject of the present invention, and therefore, the resulting tabular grains are processed using a cooling type transmission method. In a transmission image obtained using an electron microscope, the central part of the particle, which indicates the nucleus, is outside the scope of the present invention. The position of the nucleus is determined by the fact that after nucleation is complete, if a new layer is added using it as a nucleus to cause growth, the boundary line between the nucleus and the growth phase can be observed as a line in the transmission image! ! In particular, if there is a difference in halide composition between the nucleus and the growth phase, it can be confirmed even 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; ,
The position within the grain of the phase containing silver chloride, which is preferably silver iodochlorobromide, may be in the center of the tabular grain, may be throughout the grain, or may be present in the outer portion. In addition, the number of phases containing silver chloride may be one or more. In general, phases containing silver chloride often form a ring structure due to the mechanism of grain growth. For example, by utilizing the difference in properties between the edges and corners of tabular grains, it is possible to form a silver chloride phase only at the edges or only at a part of the corners. Further, by forming a shell outward from the grain, tabular silver halide grains having silver chloride at specific points without an annular structure inside the grain can be produced.

Specifically, an example can be given in which, after nucleation, grain growth is performed using the configuration shown below.

First coating layer Second coating layer 1 "Uniform^gBrc 1 2 AgBr uniform-AgBrC13 uniform-A
gBrCI AgBr4 Uniform-AgBrC15AgBr 6 # Unequal-AgBrC17 Uniform-AgB
rC12AgBr 3 Heterogeneous-AgBrC! ! tt9 〃
Uni-AgBrCj! IO-AgBrCj!
Non-uniform - AgBrC1 "uniform" in the present invention means "completely uniform -j third coating layer AgBr uniform -AgBrC12 uniform 8gBrc I AgBr".

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

In the present invention, the average -AgB occupying in one tabular grain
rCj! The proportion of is 5 to 99 mol%, preferably,
It is 20-99%, more preferably 50-99%.

The silver chloride content contained in the silver chlorobromide phase contained in the emulsion grains of the present invention is 10 mol% to 90 mol%, preferably 20 mol%.
~80 mol%. As mentioned above, it is difficult to obtain high sensitivity with silver chlorobromide emulsions, and fogging is likely to occur, which is particularly noticeable as the content of silver chloride increases. Therefore, if the silver chloride content is less than 10%, even if there is microscopic non-uniformity of silver chloride, the width of its distribution is substantially small and does not cause much inconvenience. However, when the silver chloride content in the outermost layer containing silver chloride exceeds 10 mol%, conventional grains with a microscopic non-uniform distribution of silver chloride have low sensitivity even when chemically sensitized, especially when sulfur When gold sensitized, fogging is likely to occur and sensitivity is also less likely to occur.

In other words, conventional grains with a "constant silver chloride content but microscopic non-uniform silver chloride distribution" interfere with chemical sensitization. Therefore, in this case, it is not possible to take advantage of the rapid processability that is a characteristic of silver chlorobromide.However, if the silver halide of the present invention having a "completely uniform" silver chloride distribution is in the outermost layer, the above-mentioned chemical It has no effect on sensitivity and can take advantage of all the benefits of containing silver chloride. It has a high development speed and stable speed, high sensitivity, low fog, good graininess, and high sharpness that were previously unattainable. It is possible to obtain tabular silver chlorobromide (or silver chloroiodobromide) with a molten metal.

The reason why a grain surface with a non-uniform silver chloride distribution hinders chemical sensitization, and a grain surface with a completely uniform silver chloride distribution does not hinder chemical sensitization is that the lattice constant of the grain crystal surface is The uniform distribution of silver chloride is not constant, and as a result, the composition and size of the chemically sensitized particles formed thereon become non-uniform, making it impossible to obtain optimal chemical sensitization conditions. On the other hand, in the case of a surface with a completely uniform silver chloride distribution, the chemical sensitizing nuclei will have a uniform composition and size, making it possible to perform optimal chemical sensitization, but this remains to be studied in the future. have to wait.

Furthermore, when silver halide containing silver chloride is present inside the grain, the sensitivity is increased because the phase is "completely homogeneous". In other words, it is thought that the more uneven the distribution of silver chloride contained inside, the more traps there are for electrons generated by light, making it impossible to effectively concentrate photoelectrons. This also requires further consideration. As mentioned above, several proposals have been made as means for increasing the sensitivity of silver chlorobromide grains (particularly those containing high silver chloride content).

For example, JP-A No. 48-51627, JP-A No. 49-469
32, etc., a method of adding water-soluble bromide ions or iodide ions after adding a sensitizing dye to a silver halide emulsion; JP-A-58-108533, JP-A-60-222845 As described in et al., a method of simultaneously adding bromide ions and silver ions to silver halide grains with a high silver chloride content to form a layer of silver bromide of 60 mol% or more on the grain surface; Similarly, a method in which a layer of 10 mol % to 50 mol % silver bromide is provided on the surface of the grains, either entirely or partially; Japanese Patent Publication No. 50-36978, Japanese Publication No. 5B
-24772, U.S. Patent No. 4471050 and 0LS-
3229999, etc., by adding bromide ions to silver halide with a high silver chloride content or by simultaneously adding bromide ions and silver ions to produce halogen-converted core-shell double structure particles or bonded particles. Methods for producing particles with multiphase structures such as structured particles are known.

Of course, these techniques also show their effects on tabular silver chlorobromide grains or tabular silver chloroiodobromide grains, but in this case, the silver chlorobromide grains (
By making the distribution of silver chloride in the silver chloroiododobromide grains "completely uniform", high sensitivity and low fog can be obtained compared to conventional non-uniform grains. Furthermore, as mentioned above, in these techniques, it is essential for high sensitivity and low fog that the distribution of silver chloride in the phase outside the grains be "completely uniform." The reason why the microscopic uniformity of the silver chloride in tabular grains containing silver chloride is important is that the electrons generated by light are more uniform in completely uniform grains than in grains with non-uniform distribution. This is thought to be due to the fact that it is easier to move and the principle of concentration of the latent image can be applied more efficiently.

The total silver chloride content of the emulsion grains of the present invention is at least lo-T nil%, but more effective is at least 20 mol%. More preferably, the content is 30 mol% or more.The size of the tabular silver halide grains having a completely uniform silver chloride distribution according to the present invention is not particularly limited, but the average projection plane equivalent diameter of an ellipse is 0.5 μm or more. is preferable, and more preferably 1.0
The effect is greater when the thickness is 1.5 μm or more, particularly 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 monodisperse in shape and grain size is preferred. As described in , 70% or more of the total projected area is a hexagon in which the ratio of the length of the side with the maximum length to the length of the side with the minimum length is 2 or less, and parallel A silver halide emulsion is preferred in which the hexagonal tabular silver halide grains are monodisperse, and are dominated by tabular silver halide grains having two outer surfaces. The coefficient of variation is 20% or less, preferably 15% or less.

The tabular grains of the present invention are composed of opposing parallel main surfaces consisting of (111) planes, have an average aspect ratio of 2 or more, preferably 3 to 20, more preferably 3 to 15, and have a grain size of 0. It is 4 μ or more, preferably 0.4 to 4 tI.

Here, the average aspect ratio (r) is defined as the average aspect ratio (r) when the tabular silver halide grains are oriented so that the two main faces facing each other on a plane are horizontal to this plane. When the diameter of a circle having an area equal to the projected area of a silver halide grain is D+, and 11 of the grains in the direction perpendicular to the two main planes are ti, it is defined as follows. However, N is a necessary and sufficient number to give the average aspect ratio of the silver halide grains, and the value of N is usually N≧600 (2). Equation (1) above indicates that T is given by the average of the aspect ratios Tm of each silver halide grain. ≦N)・・・・・・(3)
or, if there is a real increase, /l, Yu DJ / t j (i\j; i, j≦N)... (4), then γ' defined as has a real increase in γ exactly equal.

Therefore, the average aspect ratio may be given by T, as long as it is within acceptable precision in particle measurements.

Next, we will describe the details of the method for producing tabular silver halide grains of the present invention. The method for producing tabular silver halide grains of the present invention consists of nucleation (tabular nucleation and ripening) and grain growth. As the present invention relates to grain growth, nucleation follows conventional methods.

1. Regarding nucleation when the nucleation nucleus is silver bromide or silver iodobromide, as shown in Japanese Patent Application No. 61-299155, PBrl is maintained at 0 to 2.5 in an aqueous solution containing a dispersion medium. This is carried out by adding an aqueous solution of a water-soluble silver salt and an aqueous solution of an alkali halide.

Tabular silver halide grains have one parallel twin plane inside them.
The formation of twin planes is a so-called nucleation process. Therefore, the nucleation conditions are determined by the frequency at which twin planes are formed, and are 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 rotation speed, Cod content in the halogen alkali aqueous solution to be added,
Halogenated! (solvent amount, pH salt concentration, etc.), which is illustrated in Japanese Patent Application No. 61-238808.

By controlling this nucleation condition, it is possible to change the shape of the core particle (the number of twin planes per particle) and the number of particles (which determines the particle size after growth). In particular, the temperature during nucleation is 15° to 39°C, and the gelatin concentration is 0.05 to 1.
When the amount is 6% by weight, it is possible to form nuclei of fine particles with a uniform particle size distribution.

When carrying out nucleation of silver chlorobromide tabular grains, JP-A-58
As shown in No. 111936, silver, chloride, and promide salts are simultaneously introduced into a reaction vessel containing a dispersion medium, and at this time, the molar ratio of chloride ions to promide ions in the reaction vessel is maintained at tent~2581, and the halogen in the vessel is The total concentration of ions may be maintained within the range of 0.1θ to 0.90 normal.

U.S. Pat. No. 4,399,215 discloses a silver chloride content of 50
The tabular grains of silver chlorobromide and silver chloride of mol% or more do not contain silver bromide or silver iodide, have a pAg in the range of 6.5 to 10, and have a pH in the range of 8 to 10. It is described that particles can be obtained by holding the particles at a temperature of 1000 ml and forming particles using ammonia.

U.S. Pat. No. 4,400,463 describes that a tabular silver halide emulsion having a silver chloride content of at least 50% can be obtained by forming grains in the coexistence of an aminoazaindene and a pebutizer having a thioether bond. has been done. US Pat. No. 4,713,323 describes that tabular grains of silver chloride and silver chlorobromide can be obtained by using gelatin having a methionine content of 30 μ5 ole/g or less as a dispersion medium.

2 As shown in Japanese Patent Application No. 61-299155, minute tabular grain nuclei are formed during nucleation, but at the same time many other fine grains (especially octahedral and -heavy twinned grains) are formed. Before starting the growth process described below, it is necessary to eliminate grains other than tabular grain nuclei to obtain grains that are to become tabular grains. A specific method of ripening to make this possible follows the method described in Japanese Patent Application No. 61-299155.

3. After the formation of growth nuclei, an aqueous solution of a water-soluble silver salt and an alkali halide is added to the reaction vessel in order to grow the nuclei so as to prevent new nucleation. In the conventional method, an aqueous solution of silver salt and halide salt is added during the reaction day under efficient stirring. At this time, when growing silver halide with a single halide composition (for example, silver bromide, silver chloride), the silver halide phase is completely uniform, and even when observed using a transmission electron microscope, there is no difference in the silver halide phase. , no microscopic heterogeneity is observed.

If the composition is originally a single halide, nonuniform growth (apart from dislocations) will not occur in principle, and therefore,
In the growth of pure silver bromide and pure silver chloride, the nonuniformity referred to in the present invention is impossible regardless of the preparation conditions. However, in the growth of silver halide with a composition of multiple halides (so-called mixed crystal), In this case, non-uniform growth in halogen composition becomes a serious problem. It has already been mentioned that the non-uniform distribution of silver iodide can be clearly confirmed by transmission electron microscopy.

On the other hand, various studies have been made to obtain uniform growth of silver halide. It is known that the growth rate of silver halide grains is greatly influenced by the silver ion concentration, halide 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, the growth rate will vary depending on each concentration, and non-uniform growth will occur. As a method to improve this local concentration bias, US Pat.
415650, UK Patent 1323464, US Patent 36
The technique disclosed in No. 92283 is known. These methods include a reaction vessel filled with an aqueous colloid solution, a hollow rotating mixer having a slit in the wall of a medium-thick cylinder (the inside is filled with an aqueous colloid solution, and more preferably the mixer is moved up and down by a disk). ) is installed so that its axis of rotation is vertical, and a halogen salt aqueous solution and a silver salt aqueous solution are fed from its upper and lower open ends through supply pipes into a mixer rotating at high speed. (If there is an upper and lower separation disc, the halogen salt aqueous solution and silver salt aqueous solution supplied to the upper and lower chambers are diluted by the colloid aqueous solution filled in each chamber, respectively, and then the mixer This is a method in which silver halide particles are grown by rapidly mixing and reacting near the output loss lift), and silver halide particles produced by centrifugal force generated by the rotation of a mixer are discharged into an aqueous colloid solution in a reaction vessel. However, even with this method, the non-uniform distribution of silver chloride could not be completely resolved, and tree-ring-like striped patterns indicating non-uniform distribution of silver chloride were clearly observed using a cooling transmission electron microscope.

On the other hand, Japanese Patent Publication No. 55-10545 discloses a technique for preventing non-uniform growth by improving local concentration deviation. In this method, a halogen salt aqueous solution and a silver salt aqueous solution are separately supplied through supply pipes from the lower end of a mixer into which a colloid aqueous solution is dropped in a reaction vessel filled with a colloid aqueous solution. Both reaction solutions were rapidly stirred and mixed by a lower stirring blade (turbine blade) installed in the mixer to grow silver halide, and immediately grown by an upper stirring blade installed above the stirring blade. This is a technique in which silver halide particles are discharged from the opening of an upper mixer into an aqueous colloid solution in a reaction vessel. However, even with this method, the non-uniform distribution of silver chloride could not be solved at all, and tree-ring-like stripes 8 indicating non-uniform distribution of silver chloride were clearly confirmed.

Thus, it is clear that completely uniform silver chloride distribution cannot be realized by the techniques disclosed so far.As a result of intensive research, the inventors have found that in the growth of silver halide tabular grains containing chloride, In this case, the ions and halide ions (chloride ions, bromide ions, and iodine ions) that form particles are added to the reaction vessel in an aqueous solution (without adding them), and 1 il of fine halides with the desired halide composition is added.
vI! It has been found that by supplying silver chloride in the form of grains and allowing the tabular grains to grow, the annual ring-like stripes 1g4 completely disappear and a completely uniform distribution of silver chloride can be obtained. This is a surprising technique that cannot be achieved using conventional methods. A more specific method is ■ Addition of fine grain emulsion containing silver chloride prepared in advance. Fine silver halide grains (silver chlorobromide, chloride iodine) having the same silver chloride content as the target tabular grains are added in advance. An emulsion containing silver bromide, silver iodochloride) was prepared in advance, and only this fine grain emulsion was supplied to the reaction vessel to form tabular grains, without supplying the entire solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide to a reaction vessel. Let it grow.

■Method for supplying silver halide fine particles from a mixer outside the reaction vessel As an efficient method for supplying fine particles, a powerful and efficient mixer is installed outside the reaction vessel, and an aqueous solution of water-soluble silver salt and water-soluble silver salt are mixed in the mixer. An aqueous halide solution and a protective colloid aqueous solution are supplied and mixed rapidly to generate extremely fine silver halide grains which are immediately supplied to the reaction vessel. At that time■
As in the method, an aqueous solution of a water-soluble root salt and an aqueous solution of a water-soluble halogen salt are not supplied to the reaction vessel at all.

U.S. Patent No. 2,146,938 describes the growth of a coarse grain emulsion by mixing coarse particles that have not adsorbed an adsorbent with fine particles that have not also adsorbed an adsorbent, or by slowly adding a fine grain emulsion to a coarse grain emulsion. A method is disclosed. However, here we only deal with silver iodobromide.

U.S. Pat. Nos. 3,317,322 and 3,206,313 disclose that a silver halide grain emulsion serving as a core is chemically sensitized to have an average grain size of at least 0.8 μm, and is chemically sensitized to have an average grain size of 0.4 μm or less. A method for preparing a silver halide emulsion having a high internal sensitivity by mixing untreated silver halide grain emulsions and ripening to form a shell is disclosed. That patent concerns silver bromide and low silver iodide content silver iodobromide, which is quite different from the present invention, which concerns tabular grains containing silver chloride. JP-A-58-111936 discloses that ``Instead of introducing silver and halide salts as an aqueous solution, silver and halide salts are introduced initially or during the growth stage in the form of fine silver halide grains suspended in a dispersion medium. The zero grain size that can be obtained is such that it will easily Ostwald ripen onto the larger grain nuclei that may be present when introduced into the reactor. Silver bromide, silver chloride and/or mixed silver halide grains are introduced. It is possible to do so.” However, these are general descriptions of silver halide growth and do not contain any teaching of specific manufacturing methods or specific examples necessary to prepare the completely uniform tabular silver halide grains referred to in this patent. do not have.

Next, each method will be explained in detail.

■About the method In this method, tabular grains that serve as nuclei or cores are made to exist in a reaction vessel in advance, and then an emulsion containing fine-sized grains prepared in advance is added and the fine grains are dissolved by so-called Ostwald ripening. ,
Its deposition in the nucleus or core causes particle growth. The halide composition of the fine grain emulsion contains silver chloride that is the same as the silver chloride content of the target tabular grains, and is silver chlorobromide, silver chloroiodobromide, and silver iodochloride.

The average diameter of the particles is preferably 0.1 m or less, more preferably 0.06 μm or less. In the present invention, the dissolution rate of these fine particles is important, and in order to increase the dissolution rate, a halogenated II solvent is used. Examples of silver halide solvents which are preferably used include water-soluble bromides, water-soluble chlorides, thiocyanates, ammonia, thioethers, thioureas, and the like.

For example, thiocyanate (U.S. Pat. No. 2.222°264)
No. 2,448.534, No. 3゜320.06
9, etc.), ammonia, thioether compounds (for example, U.S. Pat. No. 3.271,157, U.S. Pat. No. 3.574.6)
No. 28, No. 3.704.130, No. 4.297.
439, 4.276.347, etc.), thione compounds (for example, JP-A-53-144319, JP-A-53-8)
No. 2408, No. 55-77737, etc.), amine compounds (e.g., JP-A-54-100717, etc.), thiourea derivatives (e.g., JP-A-55-2982), imidazole! II (e.g., JP-A-54-100717), substituted mercaptotetrazoles (e.g., JP-A-57-20253);
1), etc.

The temperature at which tabular grains are grown is 50°C or higher, preferably 60°C or higher, more preferably 70°C or higher. Further, the fine grain emulsion for crystal growth may be added at one time or in portions, but it is preferably supplied at a constant flow rate, and more preferably the addition rate is increased.

In this case, how to increase the addition rate depends on the concentration of coexisting colloids, the solubility of silver halide crystals, the size of silver halide fine particles, the degree of agitation in the reaction vessel, the size of crystals present at each point, and concentration, 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 target crystal particle size and its distribution, and can be easily determined by routine experimental methods.

Regarding (2), the crystal growth method disclosed in the present invention, as described above, supplies silver ions and halide ions (including chloride ions) necessary for silver halide crystal growth by adding their aqueous solutions as in the conventional method. Therefore, the growth of tabular grains is achieved by adding fine silver halide crystals and utilizing their high solubility to cause Ostwald ripening. The growth rate of the particles depends on how quickly the fine particles dissolve and supply silver ions and halide ions into the reaction vessel. On the other hand, as silver halide grains become smaller in size, their solubility increases and they become very unstable, causing Ostwald ripening to occur on their own, resulting in an increase in grain size.

James (J, H, Ja+wos) + The Theory of the Photographic Process, 4th edition, contains Lippmann emulsion as fine grains.
[! Kasumi ulsion) is cited, and its average size is 0.
It is stated that the thickness is 0.05 μm.

Although it is possible to obtain fine particles with a particle size of 0.05 μm or less, even if they are obtained, they are unstable and the particle size easily increases due to Ostwald ripening. However, the dissolution rate also decreases accordingly, which is contrary to the intention of the present invention.

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

■ Immediately after forming the microparticles in the mixer, add them to the reaction vessel.

Fine grains are formed in advance to obtain a fine grain emulsion, which is then redissolved, and the dissolved fine grain emulsion is added to a reaction vessel that holds silver halide grains serving as cores and in which a silver halide solvent is present. I mentioned in ■ what causes growth. However, once generated, extremely fine particles undergo Ostwald ripening during the particle formation process, water washing process, redispersion process, and redissolution process, resulting in an increase in particle size. This Ostwald ripening was prevented by providing a mixer very close to the reactor and shortening the residence time of the additive in the mixer, thereby immediately adding the formed fine particles to the reaction vessel.

Specifically, the residence time of the liquid added to the mixer is calculated as follows.

t False a+b+g ■; Volume of reaction chamber of mixer (Ml) a; Addition of silver nitrate solution! (d/m t n )b: Addition amount of halogen salt solution Cdl/m1n) C: Addition amount of protective colloid solution (td/m1n) 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, still more preferably 20 seconds or less. The fine particles thus obtained in the mixer are immediately added to the reactor without their particle size increasing.

■ Perform powerful and efficient stirring with a mixer.

James (T, H, James) The Theory of the Photographic Process P, P, 93
``Along with Ostwald ripening, another form is coalescence.In coalescence ripening, crystals that were previously far away come into direct contact,
There is a sudden change in particle size as larger crystals are formed. Both Ostwald ripening and Coreffense ripening occur not only after the end of deposition, but also during deposition.

J The core reflex ripening described here is particularly likely to occur when the particle size is very small, and is particularly likely to occur if stirring is insufficient, and in extreme cases it may even create coarse, clumpy particles. In the present invention, as shown in Figure 2, a closed type mixer is used, so the stirring blades in the reaction chamber can be rotated at a high rotational speed, unlike conventional open type reaction vessels. (With the open type, when the stirring blades are rotated at high speeds, the liquid is blown away by centrifugal force,
It is not practical due to the problem of foaming. ) Strong and efficient stirring and mixing can be performed, the above-mentioned core reflex ripening can be prevented, and as a result, fine particles with a very small particle size can be obtained. In the present invention, the rotation speed of the stirring blade is , p, - or more, preferably 200
0 r, p, ta or more, more preferably 3000 r, p
, at or more.

■ Injecting the protective colloid aqueous solution into the mixer The aforementioned core reflex ripening can be significantly prevented by the protective colloid of silver halide fine particles. In the present invention, the protective colloid aqueous solution is added to the mixer in the following manner. Depends on the method.

■ Inject the protective colloid aqueous solution alone into the mixer.

The concentration of the protective colloid is 1% by weight or more, preferably zff
i amount% is good, and the flow rate is at least 20%, preferably at least 50% of the sum of the flow rates of the silver nitrate solution and the aqueous halide solution.
, more preferably 100% or more.

■ Add a protective colloid to the halogen salt aqueous solution.

The concentration of the protective colloid is 1% by weight or more, preferably 2M% or more.

■ Add a protective colloid to the silver nitrate aqueous solution.

The concentration of the protective colloid is at least 1% by weight, preferably at least 2% by weight. When using gelatin as a protective colloid, gelatin silver is made from silver ions and gelatin, and silver colloid is produced by photolysis and thermal decomposition, so it is better to mix the nitric acid ml solution and the protective colloid solution immediately before use.

Further, the above-mentioned methods [Phase] to O may be used alone or in combination, or three may be used at the same time. As the protective colloid used in the present invention,
Usually gelatin is used, but other hydrophilic colloids can also be used, specifically Research Disclosure Vol. 176, Tane 17643 (December 1978).
Month) is listed in ■.

Thus, the particle size of the fine particles obtained by techniques A to C can be confirmed by placing the particles on a Messier and using a transmission electron microscope at a magnification of 20,000 to 40,000 times. The particle size of the present invention is 0.06 μm or less, preferably 0.0 μm or less.
3μm or less, more preferably 0. Ol, um or less.

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

Although the method no longer requires the use of silver halide emulsions, 1 silver halide emulsions may be used if desired to obtain higher growth rates or for other purposes.

The silver halide solvent is as described in Method (2).

According to this method, the supply rate of silver ions and halide ions to the reaction vessel can be freely adjusted to 1ill JTg. Although a constant feeding rate may be used, it is preferable to increase the addition rate.The method is described in JP-A-48-3689.
0, 52-16364. Other ■
As stated in the law. Furthermore, according to this method, the halogen composition during growth can be freely controlled; for example, it is possible to maintain a constant silver chloride content during the growth of tabular grains, to continuously increase or decrease the silver chloride content, or to change the silver chloride content at a certain point in time. It becomes 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.At a reaction temperature of 35°C or lower, ordinary gelatin tends to coagulate. It is preferred to use low molecular weight gelatin (average molecular ffi 30,000 or less).

The low molecular weight gelatin used in the present invention can usually be made as follows.
Dissolve 100,000 g of gelatin in water, add gelatin-degrading enzyme, and enzymatically decompose the gelatin molecules. This method is described in R, J. Cox+r'photographic
Gelatin II, Academic Pre
ss+Lor++fon, 1976,
The descriptions of P, 233-251 and P, 335-346 can be referred to. In this case, since the bonding positions that the enzyme decomposes are fixed, a low molecular weight gelatin with 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 becomes. Others, low pH (pH 1-3) or high pH (pH 10-12)
There is also a method of heating and hydrolyzing in an atmosphere.

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

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number of layers (13) and the order of the layers of the non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the arrangement may be reversed, or the positional order may be such that different photosensitive layers are placed within the same color-sensitive layer.

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

The intermediate layer includes JP-A-61-43748 and JP-A-59-3.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing prevention agent.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 12751, No. 62-200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (11()) / low sensitivity green sensitive layer (GL )/high sensitivity red sensitive layer (RH)/low sensitivity red sensitive layer (RL), or B H/B L/G L/G H/RH/R
In order of L, or B H/B L/GH/CL/R1,/
They can be installed in the order of RH, etc.

Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of R11/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer is arranged in the order of /C, L/RL/G H/RH from the side farthest from the support. You can also do that.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer with a low degree of strength is disposed and is composed of 3Ms having different sensitivities, the sensitivities of which are successively lowered toward the support. Even in the case where 311 is composed of 311 with different photosensitivity, as described in JP-A-59-202464, medium-openness emulsions are added from the side remote from the support in the same color-sensitive layer. They may be arranged in the order of W4/high sensitivity emulsion M/low sensitivity emulsion layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure Seed 17.
643 and Sou F. 816, 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 descriptions are shown in the table below.

Masu dish dish dish dish dish U gong LRJ11JLufL1 Chemical stimulant Page 23 Page 648 Right column 2 Demonic stimulant
Same as above 3 Spectral aggravating agents, pages 23-24
Page 648 right column - Superchromic multiplier Page 649 right column 4 Brightener Page 24 5 Anti-fogging agent Page 24-25 Page 649 Right column - and stabilizer 6 Light absorber, Page 25-26 Page 649 Right column ~Filter dye, page 650 left column UV absorber 7 Stain inhibitor page 25 right column page 650 left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 right column 12 Coating aid, pages 26-27 Page 650 right side surface active agent 13 Sukchinoku page 27 Same as above Patch agent Also, photographic performance improvement with formaldehyde gas In order to prevent deterioration, US Patent No. 4,411,987 and US Pat.
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Seed No. 17643, ■-C to G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4.022.620, No. 4.3
No. 26.024, No. 4.401,752, No. 4.
248.961, Japanese Patent Publication No. 58-10739, British Patent No. 1.425.020, British Patent No. 1,476.760, U.S. Patent No. 3,973.968, British Patent No. 4.314,
No. 023, No. 4,511.649, European Patent No. 24
9.473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0.619, European Patent Box No. 4,351,897, European Patent Box No. 73.636, US Patent No. 3,061,432, US Patent No. 3°725,064, Research Disclosure) JQ2422 (June 1984) month), Japanese Patent Application Publication No. 1986-
No. 33552, Research Disclosure k 24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4゜500.630, No. 4,540.654
No. 4.556.630, No. (PCT) 8B
Particularly preferred are those described in No. 104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4,146.396, No. 4,228,23
No. 3, No. 4,296,200, No. 2.369.9
No. 29, No. 2.801.171, No. 2.772.
No. 162, No. 2.895.826, No. 3.772
．． No. 002, No. 3,758.308, No. 4,33
4.011, 4.327.173, West German Patent Publication No. 3゜329.729, European Patent Box 121,365
No. A, No. 249°453A, U.S. Patent No. 3,446
．． No. 622, No. 4,333.999, No. 4,75
No. 3,871, No. 4,451,559, No. 4,4
No. 27,767, No. 4.690,889, No. 4,
Preferred are those described in No. 254.212, No. 4,296.199, and Japanese Patent Application Laid-Open No. 61-42658.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4.004,929, U.S. Patent No. 4.138,258, British Patent No. 1,146.36
The one described in No. 13 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, European Patent Box 96.570 and German Patent Publication No. 3.234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,367.282, No. 4,409.32
No. 0, No. 4,576°910, British Patent No. 2.102
．． It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
．． The patent described in paragraphs 1 and 1, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4,248,96
The one described in No. 2 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

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, U.S. Pat. , DIR redox compound releasing couplers, DIR coupler releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc.,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Box 173°3
R, D, Na 11449, 24241, a bleaching accelerator releasing coupler described in JP-A-61-201247, etc., U.S. Patent No. 4.553; Examples thereof include ligand-releasing couplers described in JP-A-63-75747, etc., and leuco dye-releasing couplers described in JP-A-63-75747.

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

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

The boiling point at normal pressure used in the oil-in-water dispersion method is 175"
Specific examples of high boiling point organic solvents of C or higher include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-L-amylphenyl) phthalate) , bis(2,4-di-t-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (
Trifel phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexylbosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.)
, ammonium, -franic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p
-hydroxybenzoate, etc.), amide li (N,
N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.),
Aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-diptyl-2-butoxy-54crt- octylaniline, etc.) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). Further, as the auxiliary T8, organic solvents having a boiling point of about 30°C or more, preferably 50°C or more and about 160"C or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Examples include cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

The present invention can be applied to various colored fluorescent materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, 17643, page 28, and Nα18716, page 647, right column to page 648, left column.

The color photographic light-sensitive material according to the present invention can be developed by the usual method described in the above-mentioned RD, pages 28 to 29 of 17643, and 615 left column to right column of Nα18716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although aminophenol compounds can be used as the color developing agent, p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-H-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pHil buffers such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds, or fogging agents. It is best to include an inhibitor. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo(2,2,2)octane), etc. 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 poron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifying agents, aminopolycarboxylic acids, aminopolymer Various chelating agents typified by phosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and 1-hydroxyacetic acid. Siechiriden-
1,1-diphosphonic acid, nitriloN,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N,N-
Tetramethylenephosphonic acid, ethylene diamine di(0
-hydroxyphenylacetic acid) and their salts are representative examples.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or amine phenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is 32 g or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be less than ajt. In order to reduce replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

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

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (Ill), cobalt (III), chromium (IV), and m(n), peracids, quinones, and nitro compounds.

Typical bleaching agents include ferricyanide; dichromate; iron (I) or cobalt (I),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (I [I) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. [[) Complex salts are particularly useful in both bleach and bleach-fix solutions. The pn of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron cm>t=salts is usually 5.5 to 8, but in order to speed up the processing, it may be processed at an even lower pH. can.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2.059.988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Nα17129 (July 1978), etc.; Thiazolidine derivatives described in No.
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3,706.561
Thiourea derivatives described in West German Patent No. 1.127.7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent No. 966.410, West German Patent No. 2.748.430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-42,434, 49-59.644, 53-
No. 94.927, No. 54-35.727, No. 55-2
Compounds described in No. 6, No. 506 and No. 58-163.940; bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, compounds having a mercapto group or a disulfide group are preferable, and in particular, compounds having a mercapto group or a disulfide group are preferred.
No. 8, West Patent No. 1゜290.812, JP-A-53-9
Preferred are the compounds described in US Patent No. 4.552.830;
These bleach accelerators may be added to the printing press, and are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. As the preservative for the bleach-fix solution that can be used for #, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

It is preferable that the silver halide color photographic material of the present invention undergoes a water washing and/or stabilization process after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
own-al of the 5ociety or
Motion Picture and Te1e-
Vision Engineers Volume 64, P, 2
48-253 (May 1955 issue),
You can ask for it.

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of anti-dent and fungicide" written by Hiroshi Horiguchi, "Microbial Sterilization, sterilization, and anti-mildew techniques" and the Japanese Society of Antibacterial and Antifungal Research, "Encyclopedia of Antibacterial Agents" can also be used.

The po of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is in the range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 5B-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent Division 3,342.59
Indoaniline compound described in No. 7, No. 3.342,
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13,924, U.S. Patent No. 3
．． Metal salt complex described in No. 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 5B-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Usually, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

Also, photosensitive materials! West German Patent No. 2.2 for Ifff Silver
26,770 or U.S. Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photoluminescent material of the present invention is disclosed in U.S. Patent No. 4,
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Left below) Effects of the Present Invention The thus obtained silver halide emulsion of the present invention has tabular silver halide grains having a silver chloride-containing silver halide phase with a completely uniform silver chloride distribution, and has high sensitivity and high sensitivity. gradation, graininess,
It is an object of the present invention to provide a silver halide emulsion that has excellent properties in terms of sharpness, resolution, covering power, storage stability, latent image stability, and pressure resistance, and has a high development speed and fixing speed, and therefore can be processed quickly. can.

The present invention will be further explained below with reference to Examples.

Example 1 Silver chlorobromide fine grain emulsion 1-A 2.3% by weight gelatin aqueous solution containing O, OIM potassium bromide and 0.05 M sodium chloride 1°3j
! Then, while stirring, use the double jet method to
M silver nitrate aqueous solution, 0.72 M potassium bromide and 1.
600 d of each halogen salt aqueous solution containing sodium chloride of OM was added over 25 minutes. During this time, the gelatin solution in the reaction vessel was maintained at 35°C.

After this, the emulsion was washed using the conventional flocculant thinning method.
Add 30g of gelatin and adjust the pH to 6.5 after dissolving.
11ffL, the obtained silver chlorobromide fine particles (silver chloride content 4
0%) had an average particle size of 0.09 μm.

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

The thus formed core silver bromide tabular grains (hereinafter referred to as seed crystals) were washed by a conventional flochieration method and heated to H6.0 at 40°C.

It was adjusted to have a PAg of 8.5. The average projection surface ellipse equivalent diameter of the obtained tabular grains was 0.4 μm.

Tabular Silver Chlorobromide Emulsion 1-C (Comparative Emulsion) Tens of the above seed crystals were dissolved in a 1N solution containing 3% by weight of gelatin and maintained at a temperature of 75°C. 20% sodium chloride 3
0cc and 3,6-cythioctane-I,8-diol 0
．． 5 g was added, and immediately an aqueous solution containing 150 g of silver nitrate, 63 g of potassium bromide, and 31 g of sodium chloride were added by double jet in 100 minutes.

Thereafter, the emulsion was cooled to 35°C, washed by a conventional flochieracin method, and then heated to pH 6°5 and P at 40°C.
It was adjusted to have an A g of 8.0. These particles have an average projected area circle equivalent diameter of 2. Ott m, average thickness was 0.32 μm, and the outside of the core was silver chlorobromide tabular grains containing 60% silver bromide and 40% silver chloride.

Tabular silver chlorobromide emulsion 1-D <This invention> Seed crystal emulsion 1-B
A tenth of the sample was dissolved in a solution 12 containing 3% by weight gelatin and the temperature was maintained at 75°C. Then 30 cc of 20% sodium chloride and 3.6-cynaoctane-1,8-
0.5 g of diol was added, and immediately dissolved fine grain emulsion 1-A was added using a pump. The fine grain emulsion was added over 100 minutes at an addition rate of 50 g in terms of silver nitrate. At this time, 10.4 g of sodium chloride was dissolved in advance in the fine grain emulsion. After this, emulsion 1-
Wash with water in the same manner as C, and at 40°C, pH 6, 5p A g
Adjusted to 8.0. The average projected area circle equivalent diameter of these tabular grains is 2.1 μm, and the average grain thickness is 0.1 μm.
It was 31 μm.

Tabular silver chlorobromide emulsion 1-E This invention> Emulsion except for the following! -Prepared in the same manner as C. Here, as shown in Figure 2, seed crystal particle growth was carried out in a powerful and efficient mixer installed near the reaction vessel for 100 minutes with 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 loj! An aqueous solution of f% low molecular weight gelatin (average molecular weight 10,000) was added using a triple jet. Ultrafine particles (average size 0.02 μm) produced by stirring and reaction in the mixer were immediately and continuously introduced into the reaction vessel from the mixer. During this time, the temperature of the mixer was maintained at 27°C.

Thereafter, the emulsion was washed with water in the same manner as Emulsion 1-C and adjusted to pH 6.5 and pA g 8.0 at 40°C. The average projected area circle equivalent diameter of these tabular grains is 2.1 tt m
, the average thickness of the particles was 0.32 μm.

Tabular Silver Chlorobromide Emulsion 1-F <Comparative Example> The emulsion was exactly the same as Emulsion 1-C except that 3.6-guthioctane-1,8-diol was not added.

The average equivalent circular diameter of the resulting tabular grains is 2.3 μm.
The average thickness was 0.27 μm.

Tabular silver chlorobromide emulsion 1-G (present invention) Emulsion 1 except that 36-guthioctane-1,8-diol was not added.
-Made exactly the same as E.

The average equivalent circle diameter of the resulting tabular grains is 2,211
The average thickness was 0.27 μm.

Tabular Silver Chlorobromide Emulsion 1-H (Reference Example) The emulsion was exactly the same as Emulsion 1-D except that 3.6-guthioctane-1,8-diol was not added.

In this case, all of the added fine particles were not dissolved, and the fine particles remained even after the addition was completed.

Grains of emulsions 1-C, 1-D, 1-E, 1-F, and 1-G were each sampled, and their transmission images were observed using a νoft transmission electron microscope at 200 mL while cooled with liquid nitrogen. . As a result, clear annual ring-like striped patterns were observed in emulsions 1-C and IF, but in emulsions 1-D and IF of the present invention,
No striped pattern was observed in Samples 1-E and 1-G, indicating that the present invention produced tabular silver chlorobromide emulsions with completely uniform silver chloride distribution.

Comparing emulsions 1-D and 1-H, the average size of fine grains 1-A is 0 when using the pre-prepared fine grain emulsion addition method.
．． 09 μm, indicating that a silver halide solvent is required to dissolve it. (here 3.6
-cythioctane-1°8-diol) However, as shown in the example of emulsion 1-G, in the method using a mixer, such a silver halide solvent is no longer necessary because the size of the fine grains is very small. As a result, an emulsion with a small grain thickness (and thus a high aspect ratio) and a narrow grain size distribution is obtained.This method, combined with a completely uniform silver chloride distribution, makes it an ideal method for growing tabular grains. It is easily understood that

These 1-C to 1-G emulsions (pH 6.5, pAg
Sodium sulfuric acid, potassium chloroaurate, and potassium thiocyanate were added to 8°C, and optimal chemical sensitization was carried out at 60°C. 4-hydroxy-6-methyl-1 after chemical sensitization
After adding ,3,3a,7-chitrazaindene, 3 g/
It was coated on a polyethylene terephthalate support to give a silver content of I.

Next, for these samples, a 2854 ” K tungsten light source was applied with a 419 nm interference filter to reduce the
After exposure to blue light for 10 seconds, developer D-1 below
The film was developed (20° C. for 4 minutes), fixed with fixer F-1, washed with water, and dried.

[Developer D-1] 1-phenyl-3-pyrazolidone hydroquinone ethylene diamine tetraacetic acid disodium potassium sulfite potassium borate potassium carbonate sodium bromide 0.5 g 20, 0 g 2.0 g 60, 0 g 4.0 g 20, 0 g 5.0 g Diethylene glycol 30.0 g Add water and stir * (pH adjust 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
2.0g glacial acetic acid
Add 22.0 g of water to make 1N. (The pH was adjusted to 4.2.) The results of sensitometry are shown in Table 1.

Example 2 Silver chlorobromide fine grain emulsion 2-A 1.21% by weight gelatin solution containing O, OIM potassium bromide and 0.06 M sodium chloride was added to 1.21% by double jet with strong stirring. By the method, 600 d of each of halogen salt aqueous solutions containing 1.2 M silver nitrate aqueous solution, 0.6 M potassium bromide, and 1.2 M sodium chloride were added to
Added over 0 minutes. During this time, the solution in the reaction vessel was maintained at 35°C.

After this, the emulsion was washed by a conventional flocculation method, 20 g of gelatin was added and dissolved, and the pH was adjusted to 181 to 6°5.
Manufactured. Obtained silver chlorobromide fine particles (silver chloride content 50%)
The average size was 0.08 μm.

Tabular silver bromide core emulsion 2-B 0,09 M into a 2% by weight gelatin solution containing 11 M potassium bromide by the double-jet method while stirring it with a 1.5 M silver nitrate solution <1.5 M Add 100 cc of potassium bromide solution. During this time, the reaction solution was kept at 40°
It was kept at C. After addition, heat to 75°C and add gelatin to 40°C.
After adding PBr, add 1.0M silver nitrate solution.
2.5, then over 60 minutes 150 g of silver nitrate was added at an accelerated flow rate (the flow rate at the end was 10 times that at the beginning) and at the same time potassium bromide was added by double jet to P B
It was added so that r was 2.5.

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

Tabular silver chlorobromide emulsion 2-C (comparative emulsion) 10 with silver nitrate
Emulsion 2-B containing silver bromide equivalent to 0 g was dissolved in 12 parts of water, the temperature was brought to 70''C, and 5 parts of a 20% sodium chloride aqueous solution was added.
Immediately after the addition of 0 cc, a solution containing 50 g of silver nitrate aqueous solution, 17.5 g of potassium bromide, and 13 g of sodium chloride was added in a double jet for 100 minutes.

Thereafter, the emulsion was cooled to 35°C, washed by the conventional flocculage method, and then tested at 40°C for p I! 6.5P A
g Adjusted to 8.1. These particles have an equivalent diameter for average projected area of 2.4 μm, an average thickness of 0.22 μm, and the outside of the core is 11i bromide! The silver chlorobromide tabular grains were 50% chloride and 50% chloride.

Tabular silver chlorobromide emulsion 2-D (this invention) 100 with silver nitrate
Emulsion 2-A corresponding to 1 g was dissolved in 12 g of water, and the temperature was adjusted to 70 g.
50 cc of 20% NaCl solution was added thereto, and immediately fine grain emulsion 2-A dissolved at 40° C. was added using a pump. The fine grain emulsion was added over 100 minutes at an addition rate of 50 g in terms of silver nitrate. At that time, 4.4 g of sodium chloride was dissolved in advance in the fine grain emulsion. After this, the emulsion was washed with water in the same manner as in 1-C, and then heated at 40°C.
H6.5, pA g was adjusted to 8.1.

The average projected area equivalent diameter of the tabular grains was 2.3 μm, and the average thickness of the grains was 0.24 μm.

Tabular Silver Chlorobromide Emulsion 2-E (Invention) Same as Emulsion 1-C except for the following. Here, particle growth was measured by adding 3.5 g of an aqueous solution containing 50 g of silver nitrate for 100 minutes to a powerful and efficient mixer installed near the reaction vessel, as shown in Figure 2.
An aqueous solution containing 5 g of potassium bromide and 13 g of sodium chloride and a 3% by weight gelatin (fl-gelatin, average molecular weight 100,000) aqueous solution were added by triple jet.

Ultrafine particles generated in the mixer (average size 0.02 μm1
50% silver bromide, 50% silver chloride) were immediately and continuously introduced into the reaction vessel from the mixer. Mixer temperature is 25°C
After this, the emulsion was washed with water in the same way as in 1-C and heated at 40°.
The pH was adjusted to 6.5 and ρA g to 8.1 using C. The equivalent diameter for average projected area of this tabular grain is 2.4μ
m, and the average thickness was 0.22 μm.

As in Example 1, particles of emulsions 2-Cl2-D and 2-E were each sampled, and their transmission images were observed using a 200 Kvolt transmission electron microscope while being cooled with liquid nitrogen. These emulsion grains have cores of AgBr and shells of chlorobromide'Wi (silver chloride content 50%), which can be clearly distinguished from this transmission image. A ring-shaped striped pattern was observed, but this striped pattern was not observed in the 2-D and 2-H emulsion grains of the present invention, and the present invention produced a tabular salt with a completely uniform silver chloride distribution. It can be seen that silver bromide emulsion grains were obtained.

After optimally chemically sensitizing emulsions 2 to Cl2-D and 2-E at 60°C with sodium thiosulfate, chloroauric acid and potassium thiocyanate, the following sensitizing dyes were added at a concentration of 200IIIg/Ag1 mol for sensitization. After exposing the light source to 1/I for 0 seconds at 5400' with respect to the light source with a filter that cuts light of wavelengths shorter than 500 nm (minus blue exposure), the developer D-1 described in Example 1 above was applied. The film was developed (20° C. for 4 minutes), fixed with the above-mentioned fixer F-1, washed with water, and dried.

The sensitometry results are shown in Table 2.

Table-2 (C1b) 5sOs (CHZ) 5sOxN
a then 4-hydroxy=6-methyl-1,3゜3a,
7-chitrazaindene was added (however, the amount of 2-C emulsion added was adjusted so that the total amount added was the same as that of the other emulsions). These samples of zero order coated on terephthalate support As noted above, the emulsions of the present invention have higher sensitivity than the comparative emulsions at the same fog.

Example 3 Tabular silver chlorobromide emulsion 3-A (comparative emulsion) 0, 47 M
3 containing potassium chloride and 0.01M potassium bromide
Weight % gelatin solution 1. (while stirring it to l.
Using a double jet method, 13 cc of each solution containing a 2M silver nitrate aqueous solution, 1.7M potassium bromide L, and 1.3M potassium chloride was added over 5 minutes. During this time, the solution was kept at 55°C.
was maintained. After aging for 20 minutes, the temperature was raised to 70°C and 2M silver nitrate aqueous solution, 1.2M potassium bromide and 1
．． A solution containing 8M potassium chloride was mixed with a double jet for 3
20 cc was added over 80 minutes.

Thereafter, the emulsion was cooled to 35 DEG C., washed with water by a conventional flokyl-thin method, and 60 g of gelatin was added thereto, dissolved at 40 DEG C., and adjusted to pH 6.5 and pA g 7.8. These silver chlorobromide tabular grains have a core silver chloride content of 15%, a shell silver chloride content of 40%, and an average equivalent circular diameter of 2 μm.
The m5 particle thickness was 0.2 μm.

Tabular silver chlorobromide emulsion 3-B This invention>0.47M potassium chloride and 0.47M potassium chloride and 0.47M potassium chloride A solution containing 2M silver nitrate aqueous solution, 1.7M potassium bromide and 1.3M potassium chloride was added to a 3 wt% gelatin solution containing potassium bromide in OIM using a double jet method while stirring it. 1 each
3CC was added over 5 minutes. During this time the solution was kept at 55°C. After aging for 20 minutes, the temperature was raised to 70°C.
Silver chlorobromide fine grain emulsion 1-A (silver chloride content 40%) was added using a pump. The amount of added soumaro is 109g in terms of silver nitrate.
Fine grain emulsion 1-A was added over 80 minutes so that At that time, 23.9 g of potassium chloride was added in advance to the fine grain emulsion. Thereafter, the emulsion was washed with water in the same manner as Emulsion 3-A, and adjusted to pH 6.5 and pAg 7.8 at 40°C. The average projected area circle-equivalent diameter of the tabular grains was 2.2 μm, and the average grain thickness was 0.3 am.

Tabular Silver Chlorobromide Emulsion 3-C <Invention> Same as Emulsion 3-3 except for the following. Here, as shown in Figure 2, particle growth was carried out in a powerful and efficient mixer installed near the reaction vessel for 80 minutes with 2M silver nitrate aqueous solution, 1.2M potassium bromide, and! , 320 cc of a mixed aqueous solution of 8 M potassium chloride and 10% low molecular weight gelatin (
500 cc of an aqueous solution (average molecular f5000) was added by triple jet. The ultrafine particles (average size 0°011Im silver bromide 60%, w chloride 140%) produced in the mixer were immediately and continuously introduced into the reactor from the mixer.

The temperature of the mixer was maintained at 15°C. After this, emulsion 1
．． - Wash with water in the same way as B. p 11 G, 5, p A g
Adjusted to 7.8. The average projected area circle equivalent diameter of the tabular grains was 2.2 μm, and the grain thickness was 0.3 μm.

To these emulsions 3-A, 3-8, and 3-C were added sensitizing dye (2) shown below at 60"C in an amount of 250 μ/1 mole of Ag, and
After a few minutes, sodium thiosulfate and potassium chloroaurate were added for optimal chemical sensitization.

After chemical sensitization, 10% each of emulsions 3-A, 3-B, and 3-C
0 g (containing 0.08 mol of Ag) was dissolved at 40°C, and the following ① to ② were added in sequence with stirring to prepare a solution.

■ 4-Hydroxy-・6-methyl-1,3゜3a,7
-Chitrazaindene 3% 2cc ■ C+, Hss-0-(CHzCHO)zs-82%
2.2 cc 503K n-ca, 3000 surface retention 1
! Coating solution i was added to ① to ① in sequence at 40° C. with stirring to prepare a solution according to the following procedure.

■ 14% gelatin aqueous solution 56.8 g ■
Polymethyl methacrylate fine particles (average particle size 3
．． 0μm) 3.9g■ Emulsion gelatin 10% 4.248CToCO
OCHgCII(C!lls)CJwNaOsS-CH
COOCIIzCI (CxHs) C4H910, 6
K ■ 11□0 68.8 cc After developing with developer D-2 at 20°C for 7 minutes, fixing with fixer F-1, washing with water, and drying.

[Developer D-2] Metol 2g Sodium sulfite 100g Hydroquinone
5g Borax・5HxO1
, 53 g of water was added, and the results of Il sensitometry are shown in Table 3.

Table 3 4.3% 3cc Together with the emulsion coating solution and the surface protective layer coating solution obtained as above, the volume ratio when coating each was 103= on a cellulose triacetate film support by co-extrusion method.
It was applied so that it became 45.

The amount of coating S is 3. Ig/rrf. 2001ux with a light source with a color temperature of 2854° for these samples.
, 1/10 second web exposure, the emulsions of the present invention have significantly higher sensitivity and lower fog than the comparative emulsions, as shown in Table 3 below. Furthermore, the emulsion of the present invention had higher gradation than the comparative emulsion.

Example 4 Samples 401 to 405, which are multilayer color light-sensitive materials each having the composition shown below, were prepared on a subbed cellulose triacetate film support.

(Composition of the photosensitive layer) The coating meter measures the amount of silver in g/rr (units) for silver halide and colloidal silver, and the amount in g/nr (small units) for coupler additives and gelatin.
Regarding the sensitizing dye, the number of moles is expressed per mole of silver halide in the same layer. Further, the chemical structural formulas or chemical names of the compounds used in the present invention are summarized in Table 6 below.

1st J? ! (Haresh town prevention layer) Black colloidal silver...0.2 gelatin...bow. 3 Colored coupler〇-1...0.06 Ultraviolet absorber UV-1・
...0.1 Same as above UV-2...0.2 Dispersion oil 0il-1...0.01 Same as above 0
il-2 2nd layer (intermediate layer) Fine grain silver chloride (average grain size 0.07μ) Gelatin colored coupler C-2 Dispersion oil 0il-1 3rd layer (first red-sensitive emulsion W4) Emulsion (average grain size 0.07μ) 4μ, Sensitizing dye! Sensitizing dye ■ Sensitizing dye ■ Coupler C-3 Coupler C-4 Coupler C-8 Coupler C-2 Dispersion oil O Same as above 0 ...0.01 ...0.15 ... 1.0...0.02...0.l AgBrC1 (silver chloride 35%)...vA+, 0...], 5X10-'...3.5X10''4...1.5X10 -' ...0.48 ...0.48 ...0.08 ...0.08 11-1 ...0.30+1-3
...0.04 4th layer (second red-sensitive emulsion layer) Emulsion (+) Gelatin sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Coupler C-6 Cobra-C-7 Dispersion oil 0il-1 Same as above 0i1 -2 5th layer (intermediate layer) Gelatin compound CPd-A Dispersed oil Of+-1 6th layer (1st green emulsion layer) Emulsion (average particle size 0.4u, AgBrC1 Sensitizing dye■ Listed in Table 4 ...Grudge 1.0 ...1.0 ...lXl0-' ...3 X 10-'...lXl0-' ...0.05 ...0.1 ...0.01 ...0.05 ...0.1 ...0.03 ...0.05 (wi chloride 35%) ...Silver 0.8 ...5X10-' Sensitizing dye V Coupler C-9 Coupler C-1 Coupler C-10 Coupler C-5 Dispersion oil 0il-1 7th layer (second green emulsion layer) Emulsion (2) Gelatin sensitizing dye■ Enhanced dye V Coupler C-11 Coupler C-12 Coupler C -13 Coupler C-1 Coupler C-15 Dispersion oil 0il-1 Same as above 0i1-2 8th layer (yellow filter layer) ...2X10-' ...0.50 ...0.06 ...0. 03...0.02...0.4 Listed in Table 4...Silver 0.85...1.0...3.5X10-'...1.4X10-'... 0.Ol ...0.03 ...0.20 ...0.02 ...0.02 ...0.20 ...0.05 Gelatin yellow colloidal silver compound Cpd-8 Dispersion oil 0il -1 9th layer (first blue-sensitive emulsion layer) Emulsion (average grain size 0.4I, AgBrCj! Gelatin sensitizing dye ■ Coupler C-14 Coupler C-5 Dispersion oil 0il-1 10th layer (second blue-sensitive emulsion layer) Emulsion layer) Emulsion (3) Gelatin sensitizing dye ■ Coupler C-14 Dispersion oil Of+-1 ...1.2 ...0.08 ...0.1 ...0.3 (Silver chloride 35% )...Silver 0.4...1.0...2X10-'...0.9...0.07...0.2 Listed in Table 4...Grudge 0.5 ...0.6 ...lXl0-' ...0.25 ...0.07 11th R (first protection W4) Gelatin ...0.8 Ultraviolet absorber UV-1 ...O, I Same as above UV-2...0.2 Dispersion oil Oi l -1-0,01 Dispersion oil Oi + -2-0,01 12th layer (second protective layer) Fine particle silver chloride (average particle size 0.07μ ) ...0.5 Gelatin ...0.45 Polymethyl methacrylate 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 ingredients, each layer contains a surfactant. Sample 30 is a sample prepared as above with addition of coating aid.
It was set to 1.

Table 4 Sample 401 Sample 402 Sample 403 Sample 404 Sample 405
(Comparison) (Present invention) (Comparison) (Present invention) (Present invention) Fourth
Layer emulsion (1) 1-CI-[! 3-＾ 3-
8, 3-C9146M emulsion (2) 1-CI-
[! 3-A 3-8 3-C 10th layer bill split (3) 1-CI-E 3-^ 3-B
3-C Note that the chemical sensitization of each emulsion is adjusted to suit each layer.
Optimal chemical sensitization was performed for each.

25CMS L using a tungsten light source for these photographic elements and adjusting the color temperature to 4800@K with a filter.
After exposure for /100 seconds, development was performed at 38° C. according to the following processing steps.

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

(Color developer) Diethylenetriaminepentaacetic acid 1.0 gl-Hydroxyedylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0 g potassium bromide
1.4g hydroxylamine sulfate 2.4
3 4-(N-ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1. Olp [1
10,0 (bleaching solution) ethylenediaminetetraacetic acid ferric ammonium salt 100,
0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water
1. This is the relative sensitivity calculated at pH 6.0.

Table 5 Relative Sensitivity (Fixer) Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0Id Sodium bisulfite 4.6g Add water 1.0N pH 6, (i ( Stabilizer) Formalin (40%) 2.0 dPolyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) As is clear from Table 5, the emulsion of the present invention has higher sensitivity than the comparative emulsion.

The concentrations of samples 401 to 405 treated with 1.0ffi by adding 0.3 g of water were measured using red light, green light, and blue light. The obtained results are shown in Table 5, and the sensitivity is shown in Table V-1 COOCII□C11JC0 COOCil at the lowest concentration +0.2.

[NoV-2 il tricresyl phosphate dibutyl phthalate Bisphthalate (2 ethylhexyl) (n)Csll* Cs1l++(t) CI+1 C(CIls)s C-9 OCR, CII□5CII□C00I+C11゜ C00Call* OI wk.

Approximately 20,000 C,H.

iI Js pdA pdB Sensitizing dye ■ Sensitizing dye ■ (C1b) 3 (Clli, l 03Na Sensitizing dye ■ SO, Na CIb=CH-5Ox-C1lt-CONH-CHlC
Snow ll Cl1-SQ, -C11, -CONH-Cll
.

Exacerbating pigment■ Sensitizing dye■

[Brief explanation of the drawing]

FIG. 1 is a transmission electron micrograph showing the crystal structure of conventional silver halide grains in which the silver chloride distribution of silver chlorobromide is not completely uniform, and the magnification is 15,000 times. FIG. 2 schematically shows one of the emulsion manufacturing methods according to the present invention, in which fine silver halide grains are supplied from a mixer outside the reaction vessel. Patent applicant: Fuji Photo Film Co., Ltd. 1961/Monday d

Claims (1)

[Claims] In a silver halide photographic emulsion comprising a dispersion medium and silver halide grains, at least 50% of the total projected area of the silver halide grains is occupied by tabular silver halide grains having an average aspect ratio of 3 or more. and the tabular grains contain a silver halide phase containing 10 mol % or more of silver chloride, and the silver halide containing the silver chloride has a completely uniform distribution of silver chloride. Photographic emulsion.