JPH06142478A - Uniform mixing method for solution - Google Patents

Abstract

PURPOSE:To prevent foaming, to enable vigorous stirring and mixing and to rapidly and uniformly mix liquids by forming a reaction vessel of a uniform mixing method as a hermetic type and making its volume reversibly increasable. CONSTITUTION:A dispersion medium soln. is put into the vessel by an opening/ closing cock 15 and air in the vessel is substantially completely removed through an air vent valve 14. A silver salt soln. and an X<-> salt soln. are then added under stirring through liquid feed pipes 16, 17 which are independent from each other, into the soln. in the vessel. An elastic rubber film 20 elongates to push up the front surface with an increase in the volume of the solns. in the vessel so that the volume thereof can be reversibly increased to >=0.15 times the original volume at this time. More than 10% of the area of the soln. surface in the vessel is covered by a floating cap. The solns. are vigorously stirred and mixed if the solns. are mixed in such a manner and, therefore, AgX emulsion particles, etc., having excellent photographic characteristics are produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for uniformly mixing two or more solutions containing a solute into a uniform solution. Furthermore, the present invention relates to a chemical reaction method in which two or more solutions containing a solute are uniformly mixed and chemically reacted to produce a product. Further, it relates to a method for producing silver halide (hereinafter referred to as "AgX") emulsion grains useful in the field of photography. Furthermore, it relates to a method for adding a chemical sensitizer to an AgX emulsion. Furthermore, it relates to a method for adding photographically effective additives to AgX emulsions and further to those devices.

[0002]

2. Description of the Related Art The operation of rapidly and uniformly mixing two or more solutions containing a solute is an important basic operation often used in the field of chemistry. Especially silver salt solution and halide salt (hereinafter
A rapid homogenization is required in the chemical reaction in which the Ag-emulsion emulsion grains are mixed by mixing the solutions (described as X ^- salts).
Further, when a chemical sensitizer is added to an AgX emulsion to form uniform chemical sensitized nuclei between AgX grains, rapid uniform mixing is required. Further, when adding a photographically effective additive to the AgX emulsion, rapid uniform mixing is required. In order to achieve uniform mixing rapidly, the rotation speed of the stirring blade is usually increased. However, above a certain level, the container solution begins to foam. In particular, in a container solution containing a dispersion medium, the generated medium does not disappear and the bubbles accumulate because the dispersion medium acts as a surfactant. Since the foam portion is not stirred and mixed, the stirring and mixing efficiency is extremely poor. Therefore, conversely, the stirring and mixing efficiency decreases. In order to prevent this, it is known to add an antifoaming agent or use a baffle together. Regarding the defoaming agent, for example, the Chemical Dictionary, "Defoaming Agent", Kyoritsu Shuppan (1960), The Chemical Dictionary, "Antifoaming Agent", and Tokyo Kagaku Dojin (1989) are included. Is, for example, the World Science Dictionary, "Mixing and stirring", Kodansha (1
The description in 977) can be referred to.

However, the antifoaming agent shows only an effect of slightly reducing the accumulation of bubbles, and it introduces an unnecessary chemical species into the container solution, so that its side effects are often a problem. Further, even in the case of a baffle plate, if it violently collides with the rotating solution, foaming will occur at the baffle plate part, and this will not be the fundamental solution.
Further, decreasing the rotation speed of the solution also decreases the uniform mixing speed, and there is a dilemma. Therefore, these conventionally known methods and devices have not been the fundamental solution. Further, a method is also known in which another mixing box is provided inside or outside the reaction container to improve the stirring and mixing efficiency.
For example, JP-A-51-72,994 and JP-A-57-92,52
4, Japanese Patent Publication No. 48-21,045, US Pat. No. 3,415,
650 and 4,289,733 can be referred to. This method is intended to hermetically stir the stirring / mixing part to prevent foaming and vigorously stir in the hermetically sealed box, but the foaming prevention is incomplete, and the stirring and mixing outside the mixing box becomes weak. There is also a drawback.

[0004]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a method of stirring and mixing a container solution and an additive solution to rapidly and uniformly mix them, to prevent foaming more completely and to vigorously stir the whole container solution. It is an object of the present invention to provide a method that enables mixing and enables more rapid uniform mixing. Furthermore, in the method of producing AgX emulsion grains by adding a silver salt solution and / or a halide salt (hereinafter referred to as X ^- salt) solution to a dispersion medium solution, more photographic properties (sensitivity, fog,
It is an object of the present invention to provide a method for producing AgX emulsion grains having excellent graininess. Another object of the present invention is to provide a method for performing chemical sensitization which is more excellent in the photographic property. It is another object of the present invention to provide a method for adding and mixing photographically effective additives that can obtain an AgX emulsion having more excellent photographic properties.

[0005]

The objects of the present invention have been achieved by the following items. (1) In a homogeneous mixing method in which at least one additive solution containing a solute is added to a solution or a dispersion medium solution (container solution) that is being stirred in a container and homogeneously mixed, the reaction container is hermetically sealed. A method for uniform mixing of a solution, characterized in that it is a mold and is a variable volume type container whose volume can be reversibly increased to 1.05 times or more of the original volume with an increase in the amount of solution in the container. . (2) In a method in which at least one additive solution containing a solute is added to a solution stirred in a container or a dispersion medium solution (container solution) to uniformly mix, the container solution surface has at least its surface radius. A method for uniform mixing of a solution, characterized in that it is covered by 25% or more of the floats.

(3) The above-mentioned (1) or (2), wherein the stirring is driven by a non-contact magnetic coupling drive and the magnet in the container is rotated in non-contact with the container. A method for uniformly mixing the solution of. (4) The solution in the container contains at least a dispersion medium and water, one additive solution contains at least a silver salt and water, and the other additive solution contains at least a halide salt and water. The method for uniformly mixing a solution according to (1), (2) or (3) above, wherein the substance is a silver halide emulsion grain. (5) The solution in the container contains at least a dispersion medium, water, and silver halide emulsion grains, the added solution contains at least a chemical sensitizer, and / or a photographically effective addition other than the chemical sensitizer. The method for uniformly mixing a solution according to (1), (2) or (3) above, which further comprises an agent.

Other preferred embodiments will be described in the next section. (6) Uniformity of the solution according to (1) above, characterized in that the volume is a variable volume type container capable of reversibly increasing 1.1 to 6 times the original volume as the volume of the solution in the container increases. Mixing method. (7) The above-mentioned (1), (3), wherein the uniform mixing is performed in the absence of gas in the container.
(4), (5) or the homogeneous mixing method of the solution described above. (8) Dissolved oxygen concentration in the container solution is measured potentiometrically, the dissolved oxygen concentration is controlled to a specified value by the detected potential difference value (1), (2),
(3), (4), (5), (6) or (7) The homogeneous mixing method of the solution described in (7). (9) An electrode enters the container solution, and a potential of −0.2 to 1.5 V with respect to the standard hydrogen electrode potential is applied to the electrode (1), (2), (3), (4), (5),
(6) A method for uniformly mixing the solution according to (7) or (8).

(10) The above-mentioned (1), (2), (3), (4), (5), (6), characterized in that the internal pressure of the container is not less than atmospheric pressure.
(7) A method for uniformly mixing the solution according to (9). (11) H ₂ to the vessel _{solution, O 3, Cl 2, Br} 2, I 2
At least one of the gases has an equilibrium partial pressure of 10
^- (1), which is introduced at ^-3 atm or higher,
(2), (3), (4), (5), (6), (7), (8), (9) or the homogeneous mixing method of the solution according to (10). (12) The above (1), (2), (3), wherein H ₂ O ₂ is present in the container solution in an amount of 10 ^-7 mol / liter or more.
(4), (5), (6), (7), (8), (9), (10) or (11)
A method for uniformly mixing a solution as described. (13) The dissolved oxygen concentration in the container solution is 1.1 times or more, or 0.9 times or less of the standard dissolved oxygen concentration, (1), (2), (3), ( 4), (5), (6), (7),
(8), (9), (10), (11) or (12), wherein the solution is uniformly mixed. (14) The above (1), (2), (3), (4), (5), (6), (7),
An apparatus using the method for uniformly mixing a solution according to (8), (9), (10), (11), (12) or (13).

The present invention will be described in more detail below. A. Basic idea of the present invention When a container solution is vigorously stirred by a stirring blade, the container solution foams because an interface between the container solution and air exists and the container solution and air are vigorously mixed. Therefore, if the container is hermetically closed and the interface is eliminated, foaming does not occur. However, if the system is made into a closed container by a system of stirring while adding the additive solution, the additive solution does not enter the container. Therefore, in the first aspect of the present invention, a volume-variable reaction vessel in which the volume of the vessel can be reversibly increased to 1.05 times or more of the original volume with an increase in the volume of the solution in the vessel, and at the time of uniform mixing, Homogeneous mixing is performed in a manner that air is substantially absent in the container.
In the second aspect of the present invention, a float is installed on the surface of the container solution to minimize the interface area between the container solution and air. In addition, the position of the floating lid for the increase of container solution,
Corresponding by increasing in accordance with the increase.

B. Volume-variable reaction vessel In the present invention, the volume-variable reaction vessel means that the volume of the vessel is 1.05 times or more the original volume in response to an increase in the volume of the vessel solution,
It preferably refers to a reaction vessel capable of increasing 1.1 to 6 times, and more preferably 1.3 to 4 times. As a concrete example of a container that enables this, 1. A mode in which a part or all of the wall of the reaction vessel is made of a rubber elastic film. 2. A mode in which a part or all of the reaction vessel wall is made of a flexible film, for example, a bellows film. 3. A mode in which the reaction vessel is a plunger type vessel, A combination of two or more of them can be used. Next, these aspects will be described in detail.

1. As a specific example of the rubber elastic membrane type reaction container, 1) the mode of FIG. 1 (a) is shown. In FIG. 1 (a), the upper portion 20 of the reaction vessel is composed of a rubber elastic body film, and as the vessel solution increases and the pressure in the vessel increases, the elastic body membrane expands upward and the vessel volume increases. To do. In this case, the rubber elastic film is a film that undergoes reversible elastic deformation to a length exceeding 5% of the original length in a temperature range of use, that is, a linear elastic limit elongation% of 5 or more, preferably It refers to a membrane of 20 to 800, more preferably 60 to 600. The Young's modulus of the rubber elastic film can be appropriately selected and used, but is usually 10 ⁵ to 10 ¹⁰ dyn / cm ² , and preferably 10 ⁶ to 10 ⁹ dyn / cm ² . Japanese Patent Application No. 2-
No. 326222, edited by Japan Society of Polymer Science, New Polymer Material One Poi
nt 19, Elastomer, Kyoritsu Shuppan (1989), Hideo Kaneko, Applied Rubber Chemistry 12 lectures, Taiseisha (1977), Kaneko Hideo, Applied Rubber Physical Theory 20 lectures, Taiseisha (198)
5), Encyclopedia of World Science, "Rubber", Kodansha (197)
7), Handbook of Chemistry, Applied Chemistry, Chapters 8 and 15, Maruzen (1
986), Handbook of Elastmer, Marcel Dekker In
The description in c., New York (1988) can be referred to.

In terms of the molecular structure, the random coil-like long-chain polymer chains have a structure in which they are cross-linked by a vulcanization method or a non-vulcanization method, and when extended, the cross-linking prevents slippage between the molecular chains. Therefore, when the external force is removed, the elongated long chain returns to its original structure. Usually useful rubber is considered to be a composite of hard and soft parts, the main soft part has flexibility and a small number of hard parts (crosslinks, crystalline or hard polymers, reinforcing fillers). The agent serves to maintain the shape of the complex for a long time or at high temperature. Specific examples of the rubber elastic body include natural rubber, isoprene rubber, butadiene rubber,
1,2-polybutadiene, styrene-butadiene rubber,
Chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene,
Acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorine rubber and urethane rubber can be mentioned.

In the case of AgX emulsion production, S, Se and Te impurities are not preferable because they have a great influence on photographic characteristics. The vulcanization method is a method in which a simple substance of S, Se or Te, an inorganic compound or an organic compound is added and heated, and the photographic property may be affected. Therefore, the non-vulcanized rubber elastic body is preferable to the vulcanized rubber elastic body. Examples of the non-vulcanization method include organic peroxides, metal oxides, organic polyvalent amines, phenols, quinoid crosslinking agents, resin crosslinking agents, crosslinking by addition of isocyanates, and crosslinking by irradiation. .

As the impurities, a rubber elastic body from which metal ions and halogen ions are not eluted is preferable.
Further, it is preferably corrosion resistant and heat resistant under the conditions of use. In the case of AgX emulsion production, the operating temperature is usually 5 to 15
0 ° C, more often 20-90 ° C, pH 1-12, more often 2-10. Preferred rubber elastic bodies in this respect are fluororubber (vinylidene fluoride type, fluorosilicone type, tetrafluoroethylene-propylene type, fluorophosphazene type, perfluoro type), ethylene-propylene rubber, butyl rubber, acrylic rubber, ethylene. -Acrylic rubber and silicone rubber can be mentioned, more preferably fluororubber.
In addition, pigments (carbon black, zinc oxide, inorganic reinforcing agents such as silica, calcium carbonate powder and various types of viscosity, etc.), protective agents (oxidizing agents, etc.) are used depending on the purpose in order to improve the properties of the rubber elastic body. It is possible to add optimal amounts of anti-aging agents, anti-aging agents, anti-ozone agents, ultraviolet absorbers, etc.).

The dispersion medium solution is put in through the opening / closing cock 15 shown in FIG. 1 (a), and the air in the container is substantially completely removed through the air vent valve 14. Next, the silver salt solution and the X ^- salt solution are added to the container solution through liquid feed pipes 16 and 17 independent of each other while stirring. As the amount of solution in the container increases, the rubber elastic film 2
0 extends like 20 in FIG. 1 (b). Furthermore, the state before the start of addition can be raised such that the upper surface is concave as shown in FIG. Larger volume change (△
V) is possible, which is more preferable. For example, a weight may be placed on the rubber elastic film and the container solution may be set before the addition is started. In the case of FIG. 1 (b), when the membrane is greatly stretched and the support of the expansion part is unstable, it is preferable to provide the upper side wall 10. The support is strengthened and preferred. Figure 1
(B) and (c) are the same devices as (a), but the illustration of other attachments is omitted for simplification.

In FIG. 1A, since the end of the shaft 22 of the stirring blade is supported by the bearing 19, the shaking of the stirring shaft is small, and the shield of the shaft sealing portion 18 is more reliable. Therefore, this aspect can be preferably used. Since the bearing 19 has a shaft-sealing structure described later, the container solution does not substantially enter the inside of the bearing. More specifically, rubber packing seals the rotating shaft. The rubber packing is a rubber elastic body, and the above description can be referred to.

In addition, 2) a mode in which the side wall portion 23 of the reaction container is made of a rubber elastic film to increase the diameter of the reaction container, 3) a mode in which the entire reaction container expands, 4) a mode in which the reaction container bottom extends downward, and 5) Two or more of them can be combined.

In the case of 2), a belt-shaped spring can be arranged around the body of the reaction container to strengthen the support of the reaction container.
However, an aspect in which the container bottom portion extends upward or laterally is more preferable than an aspect in which the container bottom portion extends downward. The reason is as follows. (1) The bottom of the container properly supports the weight of the container solution, but the rubber elastic membrane usually has a low capacity for supporting heavy objects. (2)
A heating bath jacket is usually installed at the bottom, but in the embodiment where the bottom extends downward, a larger jacket must be installed. (3) The ΔV becomes small because the film has already stretched due to the weight of the container solution.

2. Flexible Membrane Reaction Container For example, as shown in FIG. 2, a mode in which the upper part of the side wall of the reaction container is a bellows membrane can be mentioned. Opening and closing cock 1 in Figure 2
Put the dispersion medium solution from 5 and remove the air in the container from the air vent valve 1
Eliminate practically all from 4. Next, the silver salt solution and the X ^- salt solution are added to the container solution through liquid feed pipes 16 and 17 independent of each other while stirring. The bellows portion 25 extends upward as the container solution amount increases. Specific examples include a bellows-type camera and a folding chin. When the bellows membrane bends, the inside of the bent part shrinks,
The outside stretches. The opposite is true when stretching. Therefore, the bent portion always accompanies both elongation and contraction. Therefore, as the bent portion, the rubber elastic film or the flexible film described later is used. The film other than the bent portion may be a film other than those and is not limited.

The structure of the bellows part can be classified into a mode composed only of a membrane like a bellows type camera and a mode composed of a bone part and a membrane part like a chin. The bellows membrane having a bone portion is preferable because it has a larger supporting force for the container solution and the reproducibility of the container shape is good. The bone part may be a ring-shaped bone or a lateral line-shaped bone. The bone part can be installed in the inner side of the membrane, in the outer side, or in the inner side, but the outer side is more effective in supporting the container solution and is preferable. . Moreover, since the bellows membrane has elasticity, the bellows part may shake due to vibration. In order to support this, it is preferable to provide a support frame 26 around it as shown in FIG. 2, for example.

When the bellows membrane is folded to the lowest position, the solution between the membranes has very poor stirring and mixing efficiency. Therefore,
It is preferably used in a folding range that does not affect stirring and mixing properties. When the lowest is 0 and the position where the bellows membrane is extended to the highest is 100, the range of use is 10 to 10
0 is preferable, 20 to 100 is more preferable, and 30 to 1
00 is more preferable. In addition, regarding folding folding paper, Encyclopedia of World Encyclopedia, "Tachin", Heibonsha (196
The description in 7) can be referred to.

In addition, a mode in which the film 20 of FIG. 1 (a) is composed of a flexible film such as a paper balloon, a balloon and a volleyball ball can be mentioned. In the case of a paper bag or the sphere, when air is blown into the film, the film changes from a dented state as shown in FIG. 1 (c) to a bulged state as shown in FIG. 1 (b). That is, FIG. 1 (a)
Alternatively, when the added solution is added to the container solution with stirring after being set in the state of FIG. 1 (c), the flexible membrane approaches the state of FIG. 1 (b) as the amount of the container solution increases.

Here, the flexible film means a bendable plastic film. As a specific example, a film formed of a synthetic fiber resin can be mentioned. For example, a copolymer of vinylidene chloride and one or more of vinyl chloride, vinyl acetate, acrylonitrile, acrylic ester, allyl ester, unsaturated ether, styrene and the like can be mentioned. These undergo intramolecular plasticization and have good miscibility with a plasticizer. In addition, a polymer having more branches is more plastic than one long-chain polymer because crystallization is prevented. The plastic polymer film is usually prepared by 1) adding a plasticizer (a low molecular weight solvent), 2) reducing the molecular weight of the polymer, and 3) copolymerizing different monomers. 4) Obtained by using a polymer with a large number of branches. What they have in common is to widen the space between the polymers to weaken the bonding force between the polymers and facilitate micro Brownian motion. In the case of a perfect elastic body, when the force that deforms the substance is removed, the substance completely returns to its original shape. That is, it is reversible. In the present invention, the film in this case has the above-mentioned 1. are categorized. In the present invention, a film with so-called sparse deformation that does not completely return to the original state is 2. Classify into.

Specific examples of the plasticizer include phthalic acid ester,
Examples thereof include phosphoric acid ester and fatty acid ester. More specifically, mention is made of a single example of many synthetic polymers such as polystyrene and polyethylene, (nitrocellulose + camphor), (thermoplastic resin having a high glass transition point, a combination of a cellulose derivative and the plasticizer) and leather. You can In addition, a silicone resin can be used. For details of these plastic polymer films, see Chemical Handbook, Chapter 8, Chapter 15, Chapter 20, Maruzen (1966),
Seizo Okamura et al., Introduction to polymer chemistry, Kagaku Dojin (1970),
OJ Sweeting, The Science and Technology of Po
lymer Films, John Wiley & Sons, Inc. (1968),
CR Oswin et al., Plastic Films and Packaging, Appli
ed Science Publishers LTD, London (1975), J.
H. Briston et al., Platic Films, Longman Scientific &
The description in Technical, Harlow, England (1988) can be referred to.

3. Plunger type reaction vessel FIG. 3 shows an example of a plunger pump type reaction vessel. Figure 3
The dispersion medium solution is put in through the opening / closing cock 15 of (a), and substantially all the air in the container is removed through the air vent valve 14. Next, the silver salt solution and the X ^- salt solution are added to the container solution through liquid feed pipes 16 and 17 independent of each other while stirring. The plunger head 32 rises as the amount of solution in the container increases.
In this case, since the load of the plunger on the container solution is constant, the pressure on the upper part of the container solution is kept substantially constant. The shield packing 31 is attached to the plunger to prevent leakage of the container solution between the plunger and the cylinder. The shield packing 31 is made of a rubber elastic body, and the description of the rubber elastic body can be referred to. A rubber elastic body that does not affect photographically is preferable. The plunger support tube 33 forces the plunger to move straight up and down.

FIG. 3 (b) shows a mode in which a weight 35 for constant load is installed on the plunger and the pressure inside the reaction vessel is adjusted to a constant value. In this case, the weight of the weight is set such that the internal pressure of the container is not less than 1.05 of the body pressure, more preferably 1.1 to
It is 10 times the weight. The shield packing 31 is
It is attached to the plunger and moves with it. In addition to its role, 31 prevents container solution from entering between the plunger cylinder 36 and the cylinder cylinder 34. When the container solution enters in the meantime, the stirring and mixing property of the solution in the gap is extremely poor. Therefore, it is more preferable that the container solution does not enter the gap. A mode in which the shield packing is not used, such as a syringe, can be mentioned, but a mode in which the shield packing is contained is more preferable.
FIG. 3C shows a mode in which the plunger head 32 moves laterally as the container solution increases. Furthermore, FIG.
It is possible to provide a mode in which the left wall portion of (c) is also provided with a plunger so that the plunger moves in both side directions.

4. Combined type reaction container For example, if the upper plate 27 of FIG. 2 is made of a rubber elastic film, an example of the combined type container of type 1 and type 2 can be obtained. If the reaction vessel wall 37 shown in FIG. 3C is a bellows membrane extending in the lateral direction, an example of the above-mentioned type 2 and type 3 combination type vessel can be obtained. The homogeneous mixing is carried out in the absence of a gas in the reaction vessel, and the term "substantially" means that the volume of the vessel is preferably 30% or less, more preferably 15% or less, further preferably 5% or less, Most preferably it refers to 0% volume. If there is no air in the reaction vessel, no bubbles will be generated. Even if some air remains, it is difficult for the residual air to reach the stirring blades because it is a closed system. Further, even when vigorously stirred, there is no foaming exceeding the amount of residual air, and the generated foam is also dispersed in the container solution and stirred together with the container solution. However, the smaller the remaining air amount, the smaller the amount of bubbles generated. Therefore, it is preferable to reduce the remaining air amount as much as possible.

Usually, the stress with respect to the increase of the container volume in the same manner is (rubber elastic film> bellows film). This is because the rubber elastic film accompanies elongation of the entire film, whereas the bellows film causes a large change in container volume by bending a part of the film. In this respect, the bellows membrane is more preferable than the rubber elastic membrane. This is because the change in the internal pressure of the container with respect to the same change in the volume of the container is small and the operation is simple. More generally, the stress can be said to be (rubber elastic film> flexible film). In the case of the variable volume type container, the internal pressure increases due to an increase in the amount of the container solution, and the container volume increases. In the case of the 1st type, the increase value of the internal pressure can be adjusted by selecting the Young's modulus and the film thickness of the rubber elastic film. The higher the Young's modulus and the thicker the film thickness, the larger the increase value. Furthermore, the greater the rate of increase in the amount of solution in the container, the greater the increase. In the case of the above-mentioned type 3, the higher the weight of the plunger to be lifted (weight / cm ² ) and the higher the pressure with which the sealing rubber packing 31 is pressed against the vessel wall, the greater the rise value. In the case of the type 2, the higher the stress with respect to the bending of the film, the larger the increase value. In these cases, the increase value is preferably 10 times or less of the atmospheric pressure P ₀ , more preferably 0.01 to 5 times, and 0.1 to 5 times.
3 times is more preferable. When the uniform mixing operation is completed, the on-off valve 21 is opened, the container solution is transferred to the next step, and the inside of the container is washed with rinsing water.

C. Floating lid-type reaction vessel When the rotation speed of the vessel solution is increased by the rotation of the stirring blade, the vessel solution is pressed against the peripheral portion of the vessel by the centrifugal force, and the vicinity of the central portion of the solution surface is dented. When the dent reaches the stirring blade, it foams violently. If this dent is prevented from occurring, foaming is prevented. By installing a floating lid on the surface of the solution where the dent occurs, the occurrence of the dent is prevented. The size of the float is 10% or more, preferably 25 to 99%, more preferably 50 to 9 of the area of the solution surface.
The size is 8%, more preferably 80 to 98%. The center point of the floating lid is preferably installed so as to be located on the dent portion, and more preferably installed so as to be located on the center point of the dent portion. The dent position changes depending on the installation position of the stirring blade and the direction of the axis of the stirring blade. For example, when the shaft is vertical and placed at a position eccentric from the center of the solution surface and stirred, the dent usually occurs at a position eccentric to the side opposite to the shaft. Therefore, it is preferable to stir without floating caps, confirm the position of the center point of the dents, and then determine the installation position of the floating caps. Here, the center point of the floating lid refers to the intersection of two lines that divide the surface area of the floating lid into two equal parts.

Here, the floating lid is a plate that is impermeable to air. When a floating lid is installed and the container solution is rotated, the indentation-occurring portion a ₁ is in a depressurized state, but since the floating lid does not allow air to pass through, the a ₁ portion cannot entrap air. The depressurizing part sucks the solution in the peripheral part and improves the circulation of the solution.
The specific gravity G ₁ of the float is smaller than the specific gravity G ₀ of the container solution, preferably 0.9 or less of G ₀ , more preferably 0.8 to 0.1, further preferably 0.7 to 0.15. Is. Since the float must always float on the surface of the container solution, at least G ₀ > G ₁ is necessary. The float is drawn into the solution by the decompression unit. The pull-in increases as the degree of pressure reduction in the pressure reducing unit increases. At this time, it is preferable that the floating lid does not sink into the solution. That is, it is preferable that the container solution does not exist above the floating lid.

When the thickness of the floating end is b ₁ and the thickness of the floating end submerged in the solution is b ₂ , (b ₂ / b ₁ ) = b ₀ during stirring is 98% or less. Is preferred, 90-
10% is more preferable, and 70 to 15% is further preferable.
Further, during stirring, the thickness of the portion where the floating end is exposed in the air is preferably V ^1/3 mm or more, when the container solution amount is V liter, 2 × V ^1/3 to 15 × V ^{1 / 3} mm is more preferred.
The most preferable value can be selected according to each purpose. The larger the coating ratio a _{0 by} which the floating lid covers the surface of the solution in the container, the more the solution is sealed and vigorous stirring is possible, which is preferable. However, the end of the floating lid and the container wall of the container must be in close contact with each other, and the floating lid must not be able to move. Therefore, it is preferable to select the a ₀ within a range in which the floating lid can be raised without trouble as the amount of the solution increases. The a ₀ is 10
When it approaches 0%, it approaches the plunger type reaction vessel mode. However, in the case of a float, the a ₀ is smaller than 100%, and the pressure on the surface of the container solution is atmospheric pressure.

As the structure of the float, the following structures can be mentioned. 1) A single plate with a homogeneous structure. 2) A concave structure having a liquid barrier 41 on the periphery of the plate, for example, a petri dish-like floating pig or a bowl-like floating pig of tableware shown in FIG. 3) A single plate having a shield portion 45 on the surface and a hollow portion 44 inside. For example, FIG. 4B. 4) As shown in FIG.
A mode in which an opening / closing pig 46 is provided on the upper part of 3).

In the case of the structure of 2), the specific gravity of the floating lid is
Total weight of the lid (g)] / [entire lid including the levee
Body floor area x height (cm³)]. In the case of 1) structure,
The G ₁The only factor that can control the is the choice of plate material.
At least a material lighter than water is required, other cork of wood,
Examples of materials that have non-open cells such as Styrofoam
be able to. Material containing open cells such as sponge
Is not preferable because it allows air to pass through. G in the content rate of the bubbles
₁You can control the value. On the other hand, 2) -4)
In the case of construction, a material with a higher specific gravity than water, such as stainless steel
Can also be used, and the range of choice of materials can be widened.
Is preferred. In the structure of 2), the solution is
When entering the section, the float may sink.

On the other hand, the structures 1), 3) and 4) are more preferable because such trouble does not occur. Compared to the structure of 1), the structures of 3) and 4) have a wider selection of materials, and
It is more preferable because a float having a smaller G ₁ value can be produced. For example, when the float of the structure of 3) is made from the material of 1), G ₁ becomes smaller in the structure of 3). This is because when vigorous stirring is performed, the float is strongly sucked and the b ₀ value increases, so that a float having a smaller G ₁ value is required. In the case of 3), in order to increase the mechanical strength of the float, one or more, preferably two or more partitions can be provided inside. The structure of 4) has the same advantages as 3) and has the advantage that the value of G ₁ can be adjusted to the optimum value in each case by, for example, pouring water into the cavity. More preferable.

The shape of the float is not particularly limited, but FIG.
In addition to the simple flat plate shape shown in (a) to (c), a so-called top type in which the central portion of the bottom surface bulges downward as shown in (d) can be mentioned. In this case, the smoothness of the stirring flow of the solution in the vicinity of the floating end is (d)> (a)
~ (C). That is, the type (d) of FIG. 4 provides the smoothest stirring flow. Usually, (a) to (c) from the (e) type of FIG.
The mold is preferable, and the (d) mold is more preferable than the (a) to (c) molds. The types (a) to (c) have an intersection angle C between the bottom surface and the end surface.
₀ is 85 ≦ C ₀ ≦ 95 °, and the (d) type is 95 ° <C ₀ <
160 °, preferably 97 ° <C ₀ <130 °.
The type (e) indicates C ₀ <85 °. To describe the type (d) more generally (thickness D ₁ of the central portion of the floating lid / thickness D ₂ of the peripheral portion of the floating lid) = D ₀ > 1.0, preferably D
₀ ≧ 1.2, more preferably 7 ≧ D ₀ ≧ 1.5.
Compared to the types (a) to (c), the type (d) has a smaller suction pressure applied to the float, and thus the sink of the float can be prevented. Furthermore, as in the case of a boat, it is stable and does not easily turn over even when vigorously stirred. Furthermore, the entire solution flow becomes smooth. Therefore, it is more preferable.

As the material of the bottom surface of the float, a non-deformable solid and a deformable solid can be more preferably used.
Here, the non-deformable solid is a solid having a linear system elongation% d ₀ of less than 5% with respect to the original length of the bottom surface of the floating lid when the floating lid is placed and stirred under use conditions. Point to. On the other hand, a metamorphic solid has a d ₀ value of 5% or more, preferably 20.
˜200% of rubber elastic film. Regarding the rubber elastic film, the above description can be referred to. For example, 2)
When the bottom surface of the floating lid is composed of a deformable solid and the peripheral portion is composed of a non-deformable solid in the form Has the effect of reducing the b ₀ value of the floating lid. Therefore, this aspect can be preferably used.

Even when the bottom surface of the floating lid is made of a deformable solid and the other portions are made of a non-deformable solid in the modes 3) and 4), the bottom surface has a suction pressure of the stirring flow. Accordingly, the elongation rate is lower than that of the above 2) mode. This is because the inner cavity of the float is a closed system. When the upper lid is opened in the mode of 4), the elongation rate of the bottom becomes the same as in 2) above. Therefore, this aspect can also be preferably used. The bottom shape of the floating lid is set to the above-mentioned D ₁
When the aspect of> D ₂ is adopted, the effect of alleviating the suction force becomes larger, which is preferable. In addition, you can get a baffle effect by attaching a protrusion to the bottom of the floating lid.

The floating pig may be rotated on the surface of the solution, but it is more preferable not to rotate or move in the horizontal direction. In order to prevent the movement of the floating pig, it is preferable to adopt a mode having a movement restraining portion 43 as shown in, for example, FIGS. 4 (a) and 5 (a). The number of 43 is preferably 1 or more, more preferably 2 or more, still more preferably 2 to 8 per reaction vessel. The 45 is fixed in the reaction vessel and stops the rotational movement of the float. As other specific examples, the modes of (b) and (c) of FIG. 5 can be mentioned. In this case, the movement range of the floating lid can be controlled smaller in the modes (a) and (b) than in the mode (c), which is preferable. The rotational movement angle range of the float with respect to the rotational direction is preferably 50 ° or less, more preferably 30 ° or less, and further preferably 10 ° or less.

The motion restraint portion is preferably a hollow tube. This is because it is possible to pass a liquid feed pipe for the added solution, and necessary substances such as a pH meter, a silver electrometer, and a thermometer through the hollow tube. That is, since the surface of the solution is covered with the float, the empty space on the surface for putting them in the container is reduced. The installation position of the 45 depends on the size of the float, but at least it must be installed at a position where the rotational movement of the float can be stopped. The shaft of the stirring blade can be passed through the motion restricting portion 43, the container wall and the empty space at the end of the floating lid, or the container wall as described later. , The axis is installed at a position eccentric from the center of the solution surface.

D. Stirring Blade and Mixing Device In the case of a variable-capacity reaction vessel, since it is a closed reaction vessel, it is necessary to stir with a shield type stirring mechanism.
The following mechanism can be given as the shield type stirring mechanism in this case. 1) Magnetic coupling method, for example, when permanent magnets are placed inside and outside the container so as to face each other and the permanent magnets outside the container are rotated, the magnets inside the container also rotate. It refers to a mechanism for transmitting external rotational power into the container by using the principle of such magnetic coupling. Usually, a permanent magnet is installed in the reaction container, a permanent magnet is installed outside the reaction container so as to face it, and a permanent magnet outside the reaction container is rotated. You can also do it. The Curie point temperature Q of the permanent magnet installed in the reaction vessel needs to be higher than the reaction solution temperature T ₀ ,
The temperature is preferably 5 ° C. or higher and more preferably 20 ° C. or higher. The magnetic coupling can be installed under the reaction vessel, on the top, around the reaction vessel, or a combination of two or more thereof. It is preferable that the magnet used has a large coercive force Hc, a residual magnetic flux density Br, and a magnetic energy product B · H, its magnetism is thermally, mechanically, and electromagnetically stable, has high durability, and is inexpensive. As a specific example, alloy magnets containing Fe and Co as main components (MK steel, alnico magnet, Fe-
Cr-Co, Cu-Ni-Fe, etc., compound magnets (oxide magnets such as barium ferrite, Sm-Co, Mn-)
Al, etc.) can be used.

For details of the types of permanent magnets, their Curie temperatures, etc., see the Chemical Society of Japan, Chemical Handbook, Applied Chemistry, P. 1
019 to 1032, Maruzen (1986), Electric / Electronic Materials Handbook, Chapter IV, Asakura Shoten (1987), edited by Noboru Ichinose, New Development of Magnet Materials, Industrial Research Society (1988). The vessel wall material of the magnetic coupling portion is preferably a non-ferromagnetic material, more preferably a non-magnetizable material. Specific examples thereof include organic polymer materials, ceramic materials, and corrosion resistant materials such as stainless steel and aluminum. For details, reference can be made to the description given later and the references given in the references of the magnets. It is more preferable that the surface of the magnet installed in the reaction vessel is covered with a corrosion resistant material. Specifically, for example, a fluororesin such as tetrafluoropolyethylene can be used, and the details can be referred to the description of the literature described later.

The non-contact magnetic coupling method has the advantage that there is no liquid leakage even if the pressure in the container is high because it does not have a penetrating portion of the connecting shaft for transmitting the driving force, and therefore it is most preferably used. it can. For a specific installation example, for example, FIG. 3A can be referred to. In FIG. 3A, permanent magnets 38 are arranged on both sides of the container, and two permanent magnets 39 are arranged in the container by coupling with them. The permanent magnets 38 on both sides are connected to the same drive system and rotate in the same phase with each other. The bearing 19 has a shaft-sealing structure similar to the above. The non-contact magnetic coupling drive referred to in the present invention refers to a mode in which the magnet inside the container and the magnet outside the container are not directly connected by the connecting shaft, and therefore the container wall does not have a penetrating portion for transmitting the driving force. . In the present invention, it is preferable that the magnet in the container rotates without contacting the container wall.
This is because when the AgX particles are rubbed by the magnet and the vessel wall that are attracted to the vessel wall, the photographic properties such as fogging change.

2) A method using a through shaft seal device. Examples of the shaft seal device include a gland seal method, a mechanical seal method, and an oil seal method, and preferably a gland seal method and a mechanical seal method. The material used for the shaft seal portion is preferably a material that does not affect the photographic properties of the AgX emulsion. For example, when using rubber packing, it is preferable to use the rubber packing formed of the non-vulcanized rubber elastic body. The shaft seal part,
For details of the bearings, refer to Mechanical Engineering Dictionary, "Shaft Sealing Section", Asakura Shoten (1988), Kazuo Yamamoto et al., Stirrer, Chapter 4, Chapter 5, Chemical Industry Co. (1979), World Science University. The dictionary, "Bearing", and Heibonsha (1977) can be referred to.

In the shaft sealing method, the probability of liquid leakage from the shaft sealing portion increases as the internal pressure of the container increases. Therefore, it is preferable to design the shaft sealing portion so that the pressure difference ΔP inside and outside the container is small. The ΔP value is smaller when the penetrating portion is provided on the side surface portion than when it is provided on the lower portion of the container, and further when it is provided on the upper portion.
Therefore, the most preferable position of the penetrating portion can be selected according to each case. Usually, the stirring blade is installed near the bottom of the container away from the air interface. This is because when it is installed near the air interface, it foams violently. However, in the case of the present invention, since foaming is suppressed, that restriction is removed. Therefore, for example, as shown in FIG. 1A, a stirring blade can be installed in the entire container. That is, it is possible to preferably adopt a mode in which the stirring blades are present on both sides of 1/3, preferably 1/2 of the height of the container solution. The entire solution is more homogeneously mixed, which is preferred.

The chemical reaction apparatus, AgX emulsion grain forming apparatus, chemical sensitization reaction apparatus, apparatus for adding photographic additives, or the method for adding them can be applied to the method of the present invention, and they are conventionally known or will be used in the future. It can be applied to any known apparatus, and in particular, can be preferably applied to an apparatus for producing AgX emulsion grains, an apparatus for chemical sensitization reaction, an apparatus for adding photographic additives or a method for adding the same, and more preferably applied by an apparatus for forming AgX emulsion particles. it can. A baffle plate can be used in combination with these devices in order to increase the stirring efficiency. In addition to the conventionally known baffle plate, a porous flow control plate described in JP-A-4-283741 can be preferably used. As a stirring and mixing method for the uniform mixing method or apparatus of the present invention, in addition to rotation of a stirring blade, jet mixer, shaking tow, application of AC electric field, ultrasonic stirring, etc. can be used alone or in combination.

For details of these devices, see Japanese Patent Laid-Open No.
21339, 3-155555, 3-2009
No. 52, No. 4-193336, and Japanese Patent Application No. 3-13951.
No. 6, No. 3-202967, No. 3-224377,
No. 3-48315, No. 4-147438, No. 4-1.
70972, 4-240283, and JP-A-51
-72994, 57-92524, 60-11
No. 7834, ResearchDisclosure Volume 176, Item17
643, December, 1978, same volume 307, Item 307
105, November, 1989, U.S. Pat. No. 3,785,7
No. 77, No. 3,415, 650, No. 3,692, 28
No. 3, No. 3,790,386, World Science Dictionary, "Mixing and Mixing", Kodansha (1977), Kohei Koike, Mixing / Mixing Technology, IPC (1988), Actual Mixing Technology, Technology Reference can be made to the description of Information Society (1989), Kazuo Yamamoto et al., Stirring device, Chapters 4 and 5, Chemical Industry Co. (1979).

E. Addition system As a method of limiting the addition flow rate of the addition liquid, the following method can be given, for example. 1) A method in which a gas pressure is applied to the addition system, an orifice is inserted in the liquid transfer pipe, and the gas pressure is controlled by a pressure reducing valve or the like to control the flow rate. 2) A method of controlling the liquid supply flow rate using a positive displacement pump. A positive displacement pump is a type of pump that fills a closed space of a certain volume with a liquid or empties it repeatedly to deliver a liquid. The rotary type used can be mentioned. Reciprocating pump (plunger pump, piston pump,
Diaphragm pump) is a generic name, piston pump is a type of plunger pump. It is preferable to use two or more reciprocating pumps in combination in order to smooth the liquid transfer and further to reduce the pump capacity. Further, a digitally controlled plunger pump (a system in which the plunger is driven by a pulse motor and the liquid supply flow rate is controlled by pulse / minute) is more preferable.

In particular, in the case of the reaction vessels of the above-mentioned B clauses 1 and 2, the vessel internal pressure increases as the volume of the vessel solution increases. In the case of 1), the flow rate of the additive liquid is adjusted in consideration of the increase in the internal pressure,
The pressure applied to the addition system must be adjusted. On the other hand, in the case of the method of 2), there is no influence of the pressure fluctuation on the addition flow rate. Therefore, as the addition system of the present invention, the method of 2) is preferable to the method of 1), the digitally controlled plunger pump is more preferable, and it is more preferable to use two or more plunger pumps in combination. Item B 1,
The same applies to the methods other than 2, and the method 2) is more preferable.

Regarding the liquid delivery pumps in general, the Chemical Equipment Handbook, Chapter 8, Maruzen (1989), '90 / '91 Scientific Equipment Guide, Chapters 1-6, Tokyo Scientific Equipment Association (1990),
JP-A-3-21339, JP-A-4-193336, and JP-A-3-2
The description of Japanese Patent Application Laid-Open No. 009552 and the description of Japanese Patent Laid-Open No. 3-246534 can be referred to for the plunger pump. The addition solution can be added to the reaction solution by introducing a liquid feeding tube into the reaction vessel and adding it from the open end, but addition through a porous body, more preferably a hollow tubular rubber elastic body porous membrane. More preferably. The addition can be performed continuously or in a pulsed manner. Increase the degree of supersaturation of the solute in the container solution,
AgX grain growth can be grown by a growth method that greatly contributes to diffusion-controlled growth. In this case, the degree of supersaturation is preferably 20 to 100% of the critical point at which new nuclei start to be generated, and more preferably 35 to 97%. In this case, the addition rates of Ag ⁺ and X ⁻ are increased as the particles grow, and examples of the method include a flow rate acceleration method, a concentration increasing method, and a combination method of both.

Further, AgX fine particles may be formed in advance and the fine grain emulsion may be added to the reaction solution, or may be used in combination with the solution addition method. Regarding these details, JP-A-3-21339, JP-A-4-193336, JP-A-2-146033, JP-A-3-246534, and JP-A-4-345.
44, ibid. 1-183417, Japanese Patent Application No. 4-147438,
4-170972, 4-240283, 3-36
582, U.S. Pat. Nos. 4,242,445 and 3,650,
757, Research Disclosure, Volume 307 (Item 307105, 1989) can be referred to.

Further, the halogen composition with respect to the grain formation time
X when forming mixed crystals with different ^-How to add salt solution
As Cl^-, Br^-And I^-Each salt solution
A method of controlling the flow rate through independent adding holes, C
l^-, Br^-And I^-Salt solution in one tube or mixed
After extruding into a ply box to mix with each other, pass through the porous membrane.
Then, the method of adding to the reaction solution can be mentioned.
It It should be noted that Japanese Patent Application No. 2-3262 was added to the addition hole portion to the mixing portion.
No. 22, 4-240283, and JP-A-3-21339.
It is preferable to use the porous membrane addition system described. these
For details, see JP-A-59-45438 and JP-A-3-
Refer to the descriptions of No. 21339 and No. 4-193336.
be able to. Better method in terms of uniform composition
Good

F. Control of Dissolved Oxygen Concentration and Oxidation Potential of Container Solution 1) Control of Dissolved Oxygen Concentration In the method of the present invention, the reaction solution is carried out substantially without contact with air. Therefore, the process of feeding oxygen O ₂ in the air into the reaction solution by stirring is stopped. Then, the dissolved O ₂ concentration in the reaction solution may decrease, and the oxidation potential of the container solution may change. Usually, when an electrolyte is added to a pure water solution and its pH is changed with stirring, the Pt electrode potential of the solution changes as described in JP-A-2-146033. The potential is the hydrogen standard electrode potential (hereinafter referred to as NHE).
In contrast, about 0.8 V at pH 2 and 0.15 at pH 12
It is 0.2 V, and changes about 59 mV with respect to pH change. Examples of aqueous solution reactions involved in the potential region include a) to c) in Table 1.

These reactions are reactions involving dissolved O ₂ , and when the dissolved O ₂ concentration decreases, the oxidation potential of the aqueous solution shifts to the reducing agent. Therefore, when AgX emulsion grains are produced under the same conditions as in conventional open systems, fogging may occur in AgX grains. Therefore, a more preferred embodiment of the present invention is an embodiment in which a dissolved O ₂ concentration meter is installed. Dissolved O
_{The 2} densitometer refers to a device for measuring the dissolved concentration of O ₂ dissolved in a solution. The dissolved O ₂ concentration meter is a potentiometric measuring device mainly using the diaphragm electrode method. For details, see Fujishima et al., Electrochemical measuring method, Chapter 11, Gihodo Publishing (1
984), '90 / '91 Scientific Instruments Guide, Section 4-2,
The description of the Tokyo Scientific Instruments Association (1990) can be referred to.

[0054] concentration of dissolved O ₂ is determined by the O ₂ partial pressure and the liquidus temperature of the gas phase in contact with the liquid phase. It is preferable that the dissolved O ₂ concentration is measured by a potentiometric method with a dissolved O ₂ concentration meter and the dissolved O ₂ concentration is maintained at a specified value by using the detected potential difference value. In this case, as a method of introducing O ₂ into the container solution, the following method can be mentioned. (1) A gas containing O ₂ is put in a reaction vessel as a residual gas in advance. In the case of the plunger type container, it is more preferable because the internal pressure of the container can be kept constant. The residual gas amount complies with the above-mentioned regulations.
(2) A gas introduction pipe is provided in the reaction vessel, and O ₂ gas is introduced when the O ₂ concentration in the solution becomes a certain set value or less.

(3) The electrode is placed in a container solution and the O
₂If the concentration falls below a certain set value, the electrode will discharge water.
It decomposes and O₂Generate. Dissolved O₂The concentration increases
If so, the electrode potential is shifted to the reducing agent and O₂Reduce
Then O₂You can reduce the concentration. In these cases, the B,
The device described in C is preferable, and the device described in B is more preferable.
Good This is because the contact with air is cut off more completely. Well
Dissolved O₂The concentration control value is usually the standard dissolved oxygen concentration value.
(Dissolved O in an open reaction aqueous solution in equilibrium with atmospheric pressure ₂Dark
1/50 to 50 times the amount) is preferred.
/ 10 to 10 times the amount is more preferable.

When adjusting the dissolved O ₂ concentration, an inert gas (nitrogen gas, argon gas, etc.) was blown in before the reaction was started, or O ₂ gas was introduced under pressure to set the dissolved O ₂ concentration to a desired value. Afterwards, the bubbles can be removed and the reaction system can be set up. Alternatively, the dissolved O ₂ concentration can be adjusted by the above method after setting the reaction system. The O ₂ gas can be blown into the container solution, or the dissolved O ₂ concentration can be increased by increasing the partial pressure of O ₂ in the gas phase in contact with the container solution. The former can raise the dissolved O ₂ concentration more quickly, but foams. Dissolved O ₂ is shown in Table 1 for example.
Of a) and b) reaction in subjected to reduction, but is reduced H ₂
When O ₂ is generated, the reaction of i) in Table 1 is involved, and the oxidizability is further increased.

2) Controlling the Oxidation Potential of the Container Solution The dissolved O ₂ concentration in the solution is controlled in order to prevent fluctuations in the oxidation potential of the solution. A method of keeping the electrode potential constant can be mentioned. In this case, the control potential of the electrode is NH
With respect to E, −0.2 to 1.5 V is preferable, and 0.2 to
1.0 V is more preferable. The electrodes 1) and 2) are preferably materials that do not elute at the electrode potential used and are inert to the photographic properties. Specific examples include Group VIII noble metals such as platinum and palladium, carbon, gold, silver, copper, and Nesa electrodes (In ₂
Semiconductor electrodes such as O ₃ , SnO ₃ ), Si, and TiO ₂ can be cited, and platinum, palladium, carbon, silver, nesa electrode, Si, and TiO ₂ are more preferable.

The electrodes may be one or more, preferably three or more rod-shaped electrodes, as well as wire-mesh-shaped electrodes. The installation place is in the container solution, and three or more electrodes are scattered in the container solution. More preferably. In addition, a mode in which a circulation circuit for the container solution is provided and the electrode is installed in the circulation circuit can be mentioned. Regarding the circulation circuit, for example, the description in JP-A-48-21045 can be referred to.
In addition, it is preferable to provide a porous film around the electrodes to prevent the AgX particles from directly contacting the electrodes. In this case, the pore diameter of the porous membrane is 3 times or less the particle diameter of the existing AgX particles, preferably the particle diameter or less, more preferably 1/2 or less of the particle diameter, and water molecules and ions can freely pass therethrough. The pore size.

In this case, in order to promote the mixing of the inner solution of the porous membrane and the outer solution of the porous membrane, pressure and pressure can be repeatedly applied to the inner side of the porous membrane. Usually, the pressure is preferably 1.1 to 10 times the atmospheric pressure, more preferably 1.2 to 5 times. Reduced pressure is preferably 0.98 times the atmospheric pressure or less,
It is more preferably 0.9 to 0.01 times. The potential can be applied to the electrode continuously or in a pulsed manner. In the conventional reactor in which dissolved O ₂ exists, the reactions of a) and b) of Table 1 are involved on the low pH side,
The oxidation potential of the solution cannot be lowered. raise the pH,
By reducing the H ⁺ concentration, the oxidation potential of the solution can be lowered. However, if the pH of the solution is raised, AgO
The generation probability of H also increases. Therefore, it may be desirable to lower the oxidation potential at low pH. In this case, it is necessary to reduce the dissolved O ₂ concentration.

In the method of the present invention, since the dissolved O ₂ concentration can be controlled, the oxidation potential can be further lowered at low pH.
The dissolved O ₂ concentration in this case is 90 times the standard dissolved O ₂ concentration.
% Or less is preferable, 0.1 to 70% is more preferable, and 1
-30% is more preferable. The low pH at this time is p
H9 or less, preferably 1 to 8, more preferably 2 to 6. In this case, the oxidation potential of the solution is lowered due to the removal of the reaction particularly in a) of Table 1. Furthermore, the oxidation potential of the container solution can be lowered by increasing the dissolved H ₂ concentration in the container solution. In order to increase the dissolved H ₂ concentration, the electrode potential may be lowered below the standard hydrogen electrode potential to generate hydrogen, or H ₂ gas may be introduced into the reaction vessel from the outside. In this case, gas phase H _{2 in} contact with the liquid phase
The partial pressure is preferably 10 ⁻³ atm or higher, more preferably 10 ⁻² to 10 atm. The dissolved H ₂ concentration range refers to the concentration range in equilibrium with the partial pressure. Furthermore, Cl ₂ gas, Br ₂ gas,
I ₂ gas can also be introduced into the reaction vessel from the outside. The partial pressure range is the same as in the case of H ₂ . These gases may be introduced alone or in combination of two or more.

FIG. 6 shows various types when the pH of the aqueous solution is changed.
The change in oxidation potential under the standard conditions of the reaction is shown. AgX
When forming emulsion grains, Ag⁺, AgCl, AgBr,
The reduction reaction of AgI particularly affects the photographic properties of the produced AgX particles.
To do. Here, the standard conditions mean that the solute in the logarithmic part in Table 1
Indicates the condition where the activity is 1.0. In addition, Ag⁺Is [A
g⁺] ・ [OH^-] = K₀, [AgOH] / [Ag⁺]
・ [OH^-] = K₁Because of the additional restrictions,
gOH and Ag₂O is generated and is represented by the straight line m in FIG.
Thus, the potential changes. Where K₀Is the solubility product,
10 at 25 ° C ^-7.71, K₁Is the complex stability constant,
10 at 25 ° C^2.3Is. Also, for example, [Ag⁺] Is
Ag⁺Activity = (concentration mol / liter) x (activity coefficient)
Represent.

For details of these electrochemistry in general, see A.
J. Bard et al., Standard Potentials in Aqueous Solut
Ion, Marcel Dekker, Inc., New York (1985), Electrochemical Handbook (4th edition), and Maruzen (1985) can be referred to. On the other hand, there are cases where it is desired to raise the oxidation potential of the solution to make it more oxidizing atmosphere. Especially pH 2
As described above, more preferably 4 or more, it may be desired to suppress the reduction reaction. This is because AgX particles are more likely to fog at higher pH. In this case, the dissolved O ₂ concentration is the standard dissolved O ₂
The concentration is preferably 1.1 times or more, more preferably 1.2 to 50 times. In addition, it is preferable to add H ₂ O ₂ . In this case, the H ₂ O ₂ concentration in the container solution is preferably 10 ⁻⁷ mol / liter or more, more preferably 10 ⁻⁶ mol / liter or more, and further preferably 10 ⁻⁴ to 10 mol / liter. For example, reactions such as i) in Table 1 are involved and the oxidation potential is further increased.

In addition, ozone (O₃) Can also be added
It is valid. In this case, add O ₃The equilibrium partial pressure of
Usually 10^-3-10 atm, 10^-2~ 5 bar is better
Good Dissolved O₃O in the vapor phase, which is in contact with the liquid phase₃Minute
Determined by pressure and liquidus temperature. In this case, for example, Table 1
The reaction such as j) is involved and the oxidation potential is further increased. That
Other, NO in the container solution₃ ^-Exists, k) in Table 1
Reactions are also involved.

[0064]

[Table 1]

G. Chemical sensitizer, addition of photographically effective additive other than chemical sensitizer The homogeneous mixing method of the present invention is a method for chemically sensitizing AgX emulsion grains by adding a chemical sensitizer to AgX emulsion. It can also be used. When a chemical sensitizer is added to an AgX emulsion using the method of the present invention, all the AgX grains in the AgX emulsion are chemically sensitized uniformly, and an AgX emulsion with low fog and high sensitivity is obtained. The chemical sensitized nucleus formed by the chemical sensitization is a chemical sensitized nucleus composed of sulfur, selenium, tellurium, gold and a noble metal compound or phosphorus compound of Group VIII, a reduced silver nucleus, or a combination of two or more species, preferably Is a gold-chalcogenide sensitized nucleus, and the details can be referred to the description of the literature described later.

Specific examples of chemical sensitizer compounds include io
C Sodium thiosulfate and thiourea compounds for sensitization
(Eg triethylthiourea, allyl-thiourea, etc.),
-Danine compounds (eg 5-benzylidene-3-ethylrhod
anine), thione compounds (eg 3-allyl-4-oxa-ox)
azolidine-2-thione etc.), Na₂S, thioamide, poly
Sulfa compounds, their Se-based compounds and Te-based compounds
The gold sensitizer is HAuCl.
_Four, KAu (SCN)₂, Na₃Au (S₂O₃)₂,
Au₂There is S colloid, etc., and as a Group 8 noble metal compound
Is A₂PtX₆, A₂PtX_Four, A₂IrX_Four, A₃
IrX₆, A₂PdX_Four, A₂PdX₆, A₂OsX₆
Etc. Where A is K, Na, NH_FourX is C
l^-, Br ^-Refers to. The addition amount of these chemical sensitizers is 1
0^-2-10^-8Mol / mol AgX is preferred and 10^-3~ 1
0^-7More preferred is mol / mol AgX. Temperature during chemical sensitization
The degree is usually 30 ° C or higher, preferably 40 to 80 ° C.

For details of these compounds and examples of other compounds, see the following documents and Canadian Patent 800,9.
58, U.S. Pat. No. 3,442,653, Japanese Patent Application No. 2-13
0,976, 2-2-229,300, 3-53,69
3, the same 3-82,929, the same 2-333,819, the same 3
-131,598 and 3-53,693 can be referred to. The method of the present invention can also be used as a method in which a photographically effective additive is added to an AgX emulsion for uniform mixing. For example, spectral sensitizing dyes, antifoggants, fogging agents (organic fogging agents such as hydrazine compounds, inorganic fogging agents), supersensitizers, reduction sensitizers, latent image stabilizers, pressure desensitization prevention At least one compound selected from the group consisting of agents, developers and photographic property improving agents. For specific examples of these photographically effective additives, reference can be made to the descriptions in the following documents. The addition amount of these is 10 ^-2
-10 ^-8 mol / mol AgX is preferred.

H. Others The capacity of the reaction vessel of the present invention is not limited, but the effect of the present invention is greater when the final volume is 10 liters or more, preferably 100 liters or more, more preferably 300 liters or more. This is because a larger volume requires more vigorous agitation and more foaming countermeasures. The reaction solution temperature is not particularly limited and is 0 ° C or higher, preferably 10 ° C or higher,
More preferably, it can be used at 15 to 150 ° C.
In the case of a conventional open-type reaction vessel, it was difficult to use the solution at a temperature of 80 ° C. or higher because the solution was extremely vaporized.
In particular, in the case of the closed container of the item B, the effect is large at 80 ° C. or higher, preferably 90 to 150 ° C., and it can be preferably used. Also in the case of the float type, the effect is large at 75 ° C. or higher, preferably 80 to 100 ° C. In the case of a closed container, the boiling point of the reaction solution can be adjusted by adjusting the internal pressure of the container. Therefore, it is preferable to adjust the internal pressure of the container so that the temperature of the reaction solution is 3 ° C or lower, preferably 10 ° C or lower than the boiling point. Regarding the relationship between the boiling point and the internal pressure of the container, the description in Japanese Patent Application No. 3-343180 can be referred to. Normally, when heated in a closed system, water evaporates, the internal pressure rises, the boiling point rises, and it naturally falls to the balance point at that temperature. In these cases, specifically, the pressure in the closed container is equal to or higher than atmospheric pressure, preferably 1.
1 to 10 times, more preferably 1.2 to 5 times.

Regarding the temperature control method of the container solution, Japanese Patent Application No.
-160395 and JP-A-3-196836 can be referred to. The container wall materials other than the expandable part of the container are corrosion-resistant metal materials (stainless steel, aluminum, etc.),
A ceramic material, an organic polymer material, and a composite material of two or more kinds thereof can be mentioned, and an embodiment in which the stainless steel surface is covered with a fluororesin is more preferably used. Regarding the details of the wall material, Japanese Patent Application No. 3-16
Reference can be made to the description of 0395, Handbook of Anticorrosion Technology, and Nikkan Kogyo (1986). The internal pressure in the case of the closed container of the item B can be set to the atmospheric pressure or more within the above range even in the case of 0 to 100 ° C. In this case, the atmospheric pressure is preferably 1.1 to 10 times, more preferably 1.2 to 5 times.
Double. This is because cavitation due to vigorous stirring can be prevented.

Although the residual gas is substantially absent in the closed container of the above item B, when the residual gas is present,
The oxygen partial pressure in the residual gas is preferably different from that in the atmosphere. That is, the oxygen partial pressure is preferably 1.1 times or more, more preferably 1.2 times or more of atmospheric pressure. Or 0.
It is preferably 9 times or less, more preferably 0.7 times or less. The pH value of the container solution during particle formation can be kept constant or can be controlled to follow a predetermined function with respect to the particle formation time. For example, the pH of the latter half of the particle formation can be lower than that of the first half, or can be higher. The most preferable pattern can be selected and used according to each case. In order to control the pH value, for example, the pH value may be measured potentiometrically and controlled by the output potential value.

In addition, according to the method of the present invention, AgX fine particles are previously formed and the fine particle emulsion is added to the container solution.
It can also be used for forming gX fine particles. The average particle size of the fine particles is preferably 0.15 μmφ or less,
mφ or less is more preferable, and 0.01 to 0.06 μmφ is further preferable. The ratio of particles having double or more multiple twin planes or screw transition defects is preferably 5% or less, and 1%.
The following is more preferable, and 0.1% or less is further preferable.

As the dispersion medium used in the production of AgX particles, any dispersion medium known for AgX photographic light-sensitive materials can be used, and gelatin is usually preferable, and gelatin from which impurity ions and impurities have been removed is more preferable.
Examples of gelatin include alkali-treated gelatin, acid-treated gelatin, derivative gelatin such as phthalated gelatin, low molecular weight gelatin (molecular weight of 1,000 to 100,000, specifically, oxygen-dispersed gelatin, hydrolyzed with acid and / or alkali). Examples thereof include gelatin, heat-decomposed gelatin, and high-molecular weight gelatin (molecular weight 10).
10,000 to 300,000), gelatin having a methionine content of 50 μmol / g or less, oxidized gelatin, and gelatin in which methionine is inactivated by alkylation or the like can be used. It is also possible to use a mixture of two or more thereof.
The concentration of the dispersion medium is usually 0.1 to 10% by weight, more preferably 0.3 to 5% by weight.

Also, the silver salt and / or X ^{− to be} added.
The dispersion medium can be included in the salt solution. The concentration of the dispersion medium is preferably 0 to 5% by weight, and 0.1 to 3% by weight.
Is more preferable, and 0.3 to 2% by weight is further preferable. In this case, low-molecular weight gelatin (molecular weight 1000 to 40,000) does not gel even if the concentration is high, so high-concentration side (1.6 to 5
(% By weight) is particularly preferable. In order to increase the uniformity of gelatin concentration in the vicinity where the solution is added,
A more uniform nucleation is possible. Therefore, it is more preferable.
The details of these dispersion media can be referred to the description of the literature described later. There is no limitation on the AgX particles that can be produced using the method of the present invention, and any conventionally known or future known AgX particles can be produced. The particle size of AgX particles is preferably 10 μmφ or less,
0.1 to 5 μmφ is preferable. Regarding this, for example, the descriptions in Japanese Patent Application No. 2-326222 and the documents mentioned later can be referred to. There is no particular limitation on the concentration of the additive solution,
Depending on the purpose, it is possible to select and use from 10 ⁻³ mol / liter to the solubility limit concentration of the solute. Usually, 95% or less of the solubility limit concentration is preferable. The temperature of the addition solution is preferably (room temperature-10) ° C to (room temperature +30) ° C.

P of the container solution during the AgX particle formation process
Ag is usually in the range of 1 or more, preferably 2 to 12, while pH is usually in the range of 1 to 12, preferably 2 to 11, and the most preferable combination value can be selected and used. Additives that can be added to these emulsions from the grain formation to the coating step and their addition amounts are not particularly limited, and any conventionally known photographic additives can be added. For example, an alkali halide, an AgX solvent, a dopant for AgX particles (for example, a Group 8 noble metal compound, other metal compounds, chalcogen compounds, SCN compounds, etc.), a dispersion medium, an antifoggant, and a sensitizing dye (blue, green, Red, infrared, panchromatic, ortho), supersensitizers, chemical sensitizers (sulfur, selenium, tellurium, gold and Group 8 noble metal compounds, phosphorus compounds, rhodan compounds, reduction sensitizers alone and (A combination of two or more thereof), a fogging agent, an emulsion precipitation agent, a surfactant, a hardening agent, a dye, a color image forming agent, a color photographic additive,
Examples thereof include soluble silver salts, latent image stabilizers, developers (hydroquinone compounds, etc.), pressure desensitizing agents, matting agents and the like.

The AgX emulsion produced by the method of the present invention can be subjected to sedimentation washing of the emulsion by adding a precipitation agent in the same container, or can be transferred to another container and desalted. . As the desalination treatment method, in addition to sedimentation washing method, centrifugal separation washing method, ultrafiltration washing method, Nudel washing method, natural sedimentation washing method, electrochemical dialysis desalting method, etc. Any desalting method can be used. For details of these, reference can be made to the description of the literature described below. The AgX emulsion produced by the method of the present invention may be subjected to a desalting step next, or may be subjected to chemical sensitization before the desalting step. As the chemical sensitization method, in addition to the conventional chemical sensitization method, a method of adsorbing an adsorbent on AgX particles and then adding the chemical sensitizer to perform chemical sensitization can be preferably used. In this case, the location and number / cm ² of chemically sensitized nuclei on the AgX grains are limited, and it is more preferable because latent image dispersion is prevented. For details of these, JP-A-2-838, 2-146033, and 2-2863.
No. 8, Japanese Patent Application Nos. 3-115872 and 3-73266 can be referred to. Most preferably, the AgX emulsion produced by the method of the present invention is chemically sensitized by the method of the present invention, and a photographically effective additive such as a spectral sensitizer or an antifoggant is added by the method of the present invention. JP-A-3-2009
It is more preferable to use the serial batch method described in 52.

The AgX emulsion prepared by the method of the present invention can be used in any conventionally known photographic light-sensitive material. For example, black-and-white silver halide photographic light-sensitive material (for example, X-ray sensitive material, printing sensitive material, photographic paper, negative film, microfilm, direct positive sensitive material, ultrafine particle dry plate sensitive material (for LSI photomask, shadow mask) , Liquid crystal masks)], color photographic light-sensitive materials (eg negative film, photographic paper, reversal film, direct positive color light-sensitive material, silver dye bleaching method photographs, etc.)
Can be used for. Furthermore, diffusion transfer photosensitive materials (eg color diffusion transfer elements, silver salt diffusion transfer elements), photothermographic materials (black and white, color), high density digital recording photosensitive materials,
Examples include holographic sensitive materials. The silver coating amount can be selected to be a preferable value of 0.01 g / m ² or more. AgX emulsion production method (grain formation, desalting, chemical sensitization, spectral sensitization, photographic additive addition method, etc.) and apparatus, AgX grain structure, support, undercoat layer, surface protective layer,
There is no limitation on the constitution of the photographic light-sensitive material (eg, layer constitution, silver / color former molar ratio, silver amount ratio between layers), product form and storage method, emulsion dispersion of photographic additives, exposure, development method, etc. , Any technology that has become known in the past or in the future,
Embodiments can be used. For details of these, the descriptions in the following documents can be referred to.

Research Disclosure
Disclosure), Volume 176 (Item 17643) (12
Mon, 1978), volume 307 (item 30710)
May, November, 1989), Duffin, Photographic Emulsion Chemistry, Focal
Press, New York (1966), by Bill (EJBirr),
Stabilization of photographic silver halide emulsions
otographic Silver Halide Emulsion), Focal Press, London (1974), James (TH James), The Theory of Photography
Photographic Process 4th Edition, Macmilla
n), New York (1977)

P. Glafkides, Chemistry and Physics of Photography (Chimie et Physique Photographique), No. 5.
Edition, Edition
UsineNouvelle, Paris (1987), second edition, Paul Montell, Paris (1957), Zelikmann et al. (V.
L. Zelikman et al.), Preparation and coating of photographic emulsions (Makinga
nd Coating Photographic Emulsion), Focal Press
(1964), KR Hollister, Journal of Imaging Science (Journal of Imagi
ng science), Volume 31, p.148-156 (1987)
Year), Muskasky (JE Maskasky), Volume 30, p.24.
7-254 (1986), 32 volumes, 160-177.
(1988), 33 volumes, 10-13 (1989).

Freezer et al. Ed., The basics of the silver halide photographic process (Die Grundlagen Der Photographischen Prozesse
Mit Silverhalogeniden), Akademische Verlaggesellschaft,
Frankfurt (1968). JCIA Monthly Report 1984
December issue, p.18-27, Journal of the Photographic Society of Japan, 49
Volume, 7-12 (1986), 52 volumes, 144-16
6 (1986), 52 volumes, 41-48 (1989).
Year), JP-A-58-113926 to 113928, and JP-A-58-113926.
9-90841, 58-111936, 62-
99751, 60-143331, 60-14
No. 3332, No. 61-14630, No. 62-6251
issue,

JP-A-1-131541 and JP-A-2-838.
No. 2, No. 2-146033, No. 3-15539, No. 3-200952, No. 3-246534, and No. 4-3.
No. 4544, No. 2-28638, No. 4-109240
No. 2-73346, Japanese Patent Application No. 2-326222,
AgX photography other Japanese patents, US patents, European patents, World patents, Journal Image Science, Journal of Photographic Science
Science, Photographic Science and Engine
ering), Journal of the Photographic Society of Japan, Proceedings of the Photographic Society of Japan, In
ternational Congress of Photographic Science and The International East-West Symposium on the Fa
Collection of lectures by ctors Influencing Photographic Sensitivity. U.S. Pat. No. 3,442,653, Japanese Patent Application No. 2-13
0976, 2-229300, 3-53693.
No. 3, No. 3-82929, No. 2-333819, No. 3
No. 131,598, No. 3-53693, No. 4-195.
036, 4-145031, 4-77261.
No. JP-A-51-88017, Canadian Patent 800,9
No. 58, Japanese Patent Publication No. 64-8323.

[0081]

EXAMPLES The present invention will now be described in more detail by way of examples, but the embodiments of the present invention are not limited thereto. Example 1 An aqueous gelatin solution (H ₂ O 100
0 ml, gelatin 40 g, pH 9.0, KBr 0.3 g)
Was added and the temperature was raised to 60 ° C. Ag-1 aqueous solution (containing 0.9 g of AgNO ₃ in 100 ml) and KBr with stirring.
The aqueous solution was added simultaneously with a precision constant flow pump at 4 ml / min for 10 minutes, followed by 20 ml / min for 10 minutes. The pH and pBr value were constant during this addition. Next, a KBr aqueous solution was added to adjust the silver potential (to a saturated calomel electrode) to -40.
It was set to mV. Next, Ag-2 aqueous solution (A in 100 ml)
gNO ₃ (including 15 g) and an aqueous KBr solution at the potential of C.I.
D. J. Was added. The Ag-2 solution was added at a flow rate of 4 ml / min for 3 minutes, followed by 0.4 ml / min linear flow rate accelerated addition and 560 ml. 1 minute after the addition is completed, then A
g-3 aqueous solution (100 ml contains 30 g of AgNO ₃ )
Initial flow rate of Ag-3 solution is 12ml using
/ Min, 340 ml at a linear flow rate acceleration of 0.2 ml / min, C.I. D. J. Was added. The pH was maintained at 9.0 during grain formation. Next, the emulsion was transferred to a vessel for washing with sedimentation water, a precipitating agent was added, the temperature was lowered to 30 ° C., and the emulsion was desalted by the sedimentation washing method. The emulsion was redispersed at 40 ° C. A transmission electron micrograph image (TEM image) of the obtained replica of the AgX particles was observed, and the characteristic results are shown in Table 2. The coefficient of variation of the particle size distribution refers to the value obtained by dividing the variation (standard deviation) of the particle size represented by the circle-converted diameter of the projected area of the particles by the average particle size.

The emulsion was transferred to the chemical sensitizer of the present invention,
The temperature was raised to 55 ° C. After the dye 1 was adsorbed by 60% of the saturated adsorption _{amount, Na 2 S 2 O 3 ·} 5H as sulfur sensitizer
₂ O was added in an amount of 2.8 × 10 ⁻⁵ mol / mol AgX, followed by gold-thiocyanate complex (chloroauric acid: NaSCN = 1: 1).
The solution was added in an amount of 1.4 × 10 ⁻⁵ mol / mol AgX, and the mixture was aged for 50 minutes. Next, the temperature was lowered to 40 ° C, and the antifoggant TAI (4-hydroxy-6-methyl-1,3,3a, 7
-Tetraazaindene) was added (5 × 10 ⁻³ mol / mol AgX) and a coating aid to coat (coated silver amount: 1.5 g / m ² , base: triacetyl cellulose film), and dried. The coated film was subjected to wedge exposure (minus blue exposure) for 1/100 seconds and developed with a MAA-1 developer at 20 ° C. for 10 minutes. Table 2 shows the sensitivity, fog and gamma obtained from the special curve obtained after fixing, washing with water and drying.

[0083]

[Chemical 1]

Comparative Example 1 AgBr particles were formed in the same pattern as in Example 1 by using the device described in JP-B-55-10545 (device B). Next, the emulsion was transferred to a vessel for washing with sedimentation water, and the emulsion was washed in Example 1
It was desalted in the same manner as above and redispersed. A TEM image of a replica of the obtained particles was observed, and the characteristic results are shown in Table 2. The emulsion was transferred to the apparatus B, and dye 1 was adsorbed and chemically sensitized in the same manner as in Example 1. Further, TAI and a coating aid were added and coated, and dried. The coated film was exposed and developed under the same conditions as in Example 1. The fog and gamma obtained from the characteristic curve obtained after fixing, washing with water and drying are shown in Table 2.

Example 2 The emulsion obtained in Example 1 was transferred to the apparatus B, and the same treatment as in Comparative Example 1 was performed thereafter. The fog and gamma obtained from the obtained characteristic curve are shown in Table 2. According to the results in Table 2, the particle size distribution of AgX particles manufactured using the method of the present invention is narrower than the size distribution of AgX particles manufactured using the apparatus B. The preferred order of the photographic properties of the emulsion-coated film was as follows: Example 1> Example 2> Comparative Example 1. Therefore, it was confirmed that the AgX grain formation and chemical sensitization methods according to the method of the present invention were excellent in terms of uniformity, sensitivity, fog and gamma of each grain. However, as the apparatus of the present invention, the apparatus of FIG. 3A was used for both grain formation and chemical sensitization, and the residual air volume ratio was 3% or less.

[0086]

[Table 2]

H. Effects of the Invention (1) When the rotation speed of the stirring blade is increased, foaming becomes more severe at a certain level or higher. Therefore, conventionally, it has been impossible to further increase the rotation speed. In the present invention, since the foaming can be suppressed by reducing the contact area between the container solution and air, vigorous stirring and mixing can be performed. Therefore, AgX particles with low fog and high sensitivity can be obtained. Furthermore, (2) in the conventional open system, it was difficult to freely control the dissolved oxygen concentration in the container solution, but since the method of the present invention carries out the reaction in a closed system, the dissolved oxygen concentration in the solution is Can be controlled to any value. Increasing the dissolved oxygen concentration increases the oxidation potential of the solution, and decreasing it decreases the potential.

(3) In the conventional open system, the inside of the container is at atmospheric pressure, but in the closed container described in the above item B, the internal pressure of the container can be adjusted to atmospheric pressure or higher. Therefore, the reaction at 76 ° C. or higher becomes possible. (4) Usually a small volume for research (usually 1-5 liters)
When an AgX emulsion with excellent performance can be developed with a reaction device (small volume device) consisting of a reaction container, a large amount of the emulsion (usually a reaction container capacity of 100 liters or more) is manufactured for commercialization. Need to do. However, when the emulsion is produced according to the same production recipe, it is rare that the two performances are completely the same. Therefore, in the case of mass production,
Often, a part of the prescription is changed to match the performance of both. This job is expensive and difficult. When the method of the present invention is used, the stirring and mixing properties of a large-scale apparatus are improved, so that the performances of the two can be made substantially the same with the same formulation.

[Brief description of drawings]

FIG. 1 is a front view. A specific example of the rubber elastic film type variable volume container of the present invention will be described. The figure (a) shows an example of a state before the addition is started, and the figure (b) shows an example of a state during the addition or after the addition. (C) The figure shows another example of the state before the start of addition.

FIG. 2 is a front view. A specific example of a flexible membrane-type variable volume container will be shown.

FIG. 3 is a front view. A specific example of the plunger pump type variable volume container will be shown. In FIGS. (A) and (b), the plunger moves upward as the container solution increases, and in FIG. (C) moves to the right.

FIG. 4 is a front view. (A) The figure shows a specific example of a uniform mixing container whose container solution surface is covered with floating lids. (B) is a specific example of a float having a hollow inside, and (c) is a specific example of a float having a hollow inside and an opening / closing lid at the top,
(D) The figure shows a specific example of a spinning top-shaped float in which the central portion of the bottom of the float bulges downward. (E) The figure shows a specific example of a float with an intersection angle C ₀ between the bottom surface and the end surface of C ₀ <85 °.

FIG. 5 is a top view. An example of a uniform mixing container having a restraining portion 45 that restrains the rotational movement of the float.

FIG. 6 shows changes in redox potential under standard conditions of various reactions when the pH of an aqueous solution is changed.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 ... Upper side wall of container 11 ... Container wall 12 ... Container solution 13 ... Stirring blade 14 ... Air vent valve 15 ... Open / close cock 16 ... Silver salt solution delivery pipe 17 ... X ^- Salt solution delivery pipe 18 ... Shaft seal Part 19 ... Bearing 20 ... Rubber elastic film 21 ... Transfer valve 22 ... Stirring blade shaft 23 ... Reaction container side wall 25 ... Bellows membrane 26 ... Bellows membrane support frame 27 ... Container top plate 31 ... Shield packing 32 ... Plunger head 33 ... Plunger support cylinder 34 ... Cylinder cylinder 35 ... Load weight 36 ... Plunger cylinder 37 ... Reactor vessel wall 38 and 39 ... Permanent magnet 41 ... Liquid bank 42 ... Float The lid 43 ... Motion stop portion 44 ... The hollow portion of the floating lid 45 ... The shield portion of the floating lid 46 ... The open / close lid 47 ... The edge of the container upper portion. The straight lines ah in FIG. 6 are the straight lines representing the oxidation potential under the standard conditions of the reactions ah in Table 1. m is Ag ⁺ + e ⇔
It is a straight line showing the oxidation potential of Ag in the high pH region.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 28, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

[0005]

The objects of the present invention have been achieved by the following items. (1) In a homogeneous mixing method in which at least one additive solution containing a solute is added to a solution or a dispersion medium solution (container solution) that is being stirred in a container and homogeneously mixed, the reaction container is hermetically sealed. A method for uniform mixing of a solution, characterized in that it is a mold and is a variable volume type container whose volume can be reversibly increased to 1.05 times or more of the original volume with an increase in the amount of solution in the container. . (2) In the method of adding at least one additive solution containing a solute to a solution stirred in a container or a dispersion medium solution (container solution) to homogenize the mixture, the surface of the container solution is at least its surface radius. The method for uniform mixing of a solution is characterized in that it is covered with 10% or more of the floats.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

Other preferred embodiments will be described in the next section. (6) Uniformity of the solution according to (1) above, characterized in that the volume is a variable volume type container capable of reversibly increasing 1.1 to 6 times the original volume as the volume of the solution in the container increases. Mixing method. (7) The above-mentioned (1), (3), wherein the uniform mixing is performed in the absence of gas in the container.
The method for uniformly mixing the solution according to (4), (5) or (6).
(8) Dissolved oxygen concentration in the container solution is measured potentiometrically, the dissolved oxygen concentration is controlled to a specified value by the detected potential difference value (1), (2),
(3), (4), (5), (6) or (7) The homogeneous mixing method of the solution described in (7). (9) An electrode enters the container solution, and a potential of −0.2 to 1.5 V with respect to the standard hydrogen electrode potential is applied to the electrode (1), (2), (3), (4), (5),
(6) A method for uniformly mixing the solution according to (7) or (8).

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

(10) The above-mentioned (1), (2), (3), (4), (5), (6), characterized in that the internal pressure of the container is not less than atmospheric pressure.
(7) A method for uniformly mixing the solution according to (8) or (9). (11) H ₂ to the vessel _{solution, O 3, Cl 2, Br} 2, I 2
At least one of the gases has an equilibrium partial pressure of 10
^- (1), which is introduced at ^-3 atm or higher,
(2), (3), (4), (5), (6), (7), (8), (9) or the homogeneous mixing method of the solution according to (10). (12) The above (1), (2), (3), wherein H ₂ O ₂ is present in the container solution in an amount of 10 ^-7 mol / liter or more.
(4), (5), (6), (7), (8), (9), (10) or (11)
A method for uniformly mixing a solution as described. (13) The dissolved oxygen concentration in the container solution is 1.1 times or more, or 0.9 times or less of the standard dissolved oxygen concentration, (1), (2), (3), ( 4), (5), (6), (7),
(8), (9), (10), (11) or (12), wherein the solution is uniformly mixed. (14) The above (1), (2), (3), (4), (5), (6), (7),
An apparatus using the method for uniformly mixing a solution according to (8), (9), (10), (11), (12) or (13).

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

Here, the floating lid is a plate that is impermeable to air. When a floating lid is installed and the container solution is rotated, the indentation-occurring portion a ₁ is in a depressurized state, but since the floating lid does not allow air to pass through, the a ₁ portion cannot entrap air. The depressurizing part sucks the solution in the peripheral part and improves the circulation of the solution.
The specific gravity G ₁ of the float is smaller than the specific gravity G ₀ of the container solution, preferably 0.9 or less of G ₀ , more preferably 0.8 to 0.1, still more preferably 0.5 to 0.1. , And most preferably 0.3 to 0.1. Since the float must always float on the surface of the container solution, at least G
₀ > G ₁ is required. The float is drawn into the solution by the decompression unit. The pull-in increases as the degree of pressure reduction in the pressure reducing unit increases. At this time, it is preferable that the floating lid does not sink into the solution. That is, it is preferable that the container solution does not exist above the floating lid.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

When the thickness of the floating end is b ₁ and the thickness of the floating end submerged in the solution is b ₂ , (b ₂ / b ₁ ) = b ₀ during stirring is 98% or less. Is preferred, 90-
10% is more preferable, 60 to 10% is further preferable,
30 to 10% is the most preferable. Further, during stirring, the thickness of the portion where the floating end is exposed in the air is preferably V ^1/3 mm or more, when the container solution volume is V liter, and 2 × V ^1/3 to 1
5 × V ^1/3 mm is more preferable. The most preferable value can be selected according to each purpose. The larger the coating ratio a _{0 by} which the floating lid covers the surface of the solution in the container, the more the solution is sealed and vigorous stirring is possible, which is preferable. However, the end of the floating lid and the container wall of the container must be in close contact with each other, and the floating lid must not be able to move. Therefore, it is preferable to select the a ₀ within a range in which the floating lid can be raised without trouble as the amount of the solution increases. When the a ₀ approaches 100%, it approaches the plunger type reaction vessel mode. However, in the case of a float, the a ₀ is smaller than 100%, and the pressure on the surface of the container solution is atmospheric pressure.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

2) A method using a through shaft seal device. Examples of the shaft seal device include a gland seal method, a mechanical seal method, and an oil seal method, and preferably a gland seal method and a mechanical seal method. The material used for the shaft seal portion is preferably a material that does not affect the photographic properties of the AgX emulsion. For example, when using rubber packing, it is preferable to use the rubber packing formed of the non-vulcanized rubber elastic body. In addition, a sealing liquid sealing method can be used. The shaft sealing device is more preferable because it can withstand larger pressurization and depressurization. For details of the sealing liquid sealing method, the magnetic coupling method, the shaft sealing portion, and the bearing, a mechanical engineering dictionary, "Shaft sealing portion", Asakura Shoten (1988), Kazuo Yamamoto et al., A stirrer, Chapters 4 and 5, Chemical Industry Company (1979), Encyclopedia of World Science, "Bearing", Heibonsha (1977) General Survey of Scientific Instruments, '92 / '93, Sections 1.5, Tokyo Scientific Instruments Association (1992), 4th edition, Experimental Chemistry Lecture 2, Part 2.5,
The description of Maruzen (1990) can be referred to. Other examples of the floating lid include the floating lids of the above 3) type and 4) type formed by using an organic polymer film having a thickness of preferably 1 mm or less, more preferably 10 to 500 μm. It is more preferable because a float having a smaller specific gravity G ₁ can be produced. Other than the above 1) to 4) types, a floating lid (for example, funnel shape) that is close to the hollow shape of the liquid surface formed at the time of stirring can be mentioned, but the absorption power for sucking the surrounding liquid into the center is weak. Therefore, the effect of promoting circulation is weakened. Therefore, the above 1) to 4) types are more preferable. In addition, when the stirrer is installed in the container through the space between the float and the container wall, a flexible stirrer (a stirrer in which a rotary drive force is transmitted to a stirring blade by using a flexible wire) is preferably used. it can. By passing the flexible wire portion through the gap, the installation position and installation direction of the stirring blade in the container can be freely selected. An example of the preferable installation mode is shown in FIG.
It was shown to. For details of the flexible stirrer, reference can be made to the description in the Scientific Equipment Guide.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a front view. A specific example of the rubber elastic film type variable volume container of the present invention will be described. The figure (a) shows an example of a state before the addition is started, and the figure (b) shows an example of a state during the addition or after the addition. (C) The figure shows another example of the state before the start of addition.

FIG. 2 is a front view. A specific example of a flexible membrane-type variable volume container will be shown.

FIG. 3 is a front view. A specific example of the plunger pump type variable volume container will be shown. In FIGS. (A) and (b), the plunger moves upward as the container solution increases, and in FIG. (C) moves to the right.

FIG. 4 is a front view. (A) The figure shows a specific example of a uniform mixing container whose container solution surface is covered with floating lids. (B) is a specific example of a float having a hollow inside, and (c) is a specific example of a float having a hollow inside and an opening / closing lid at the top,
(D) The figure shows a specific example of a spinning top-shaped float in which the central portion of the bottom of the float bulges downward. (E) The figure shows a specific example of a float with an intersection angle C ₀ between the bottom surface and the end surface of C ₀ <85 °.

FIG. 5 is a top view. An example of a uniform mixing container having a restraining portion 45 that restrains the rotational movement of the float.

FIG. 6 shows changes in redox potential under standard conditions of various reactions when the pH of an aqueous solution is changed.

FIG. 7 is an example of a uniform mixing container having a float and a flexible stirrer. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 28, 1994

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 7

[Correction method] Added

[Correction content]

[Figure 7]

Claims (5)

[Claims] 1. A homogeneous mixing method in which at least one additive solution containing a solute is added to a solution or a dispersion medium solution (container solution) which is being stirred in a container, and homogeneously mixed,
A homogeneous mixing of a solution, characterized in that the reaction vessel is a closed type, and the volume is a variable volume type vessel capable of increasing to 1.05 times or more of the original volume with an increase in the volume of solution in the vessel. Method. 2. A method of adding at least one additive solution containing a solute to a solution or a dispersion medium solution (container solution) which is being stirred in a container to uniformly mix the solution, and A method for uniformly mixing a solution, characterized in that 10% or more is covered by a float. 3. The uniform solution according to claim 1, wherein the stirring is driven by a non-contact magnetic coupling drive, and the magnet in the container is rotated in non-contact with the container. Mixing method. 4. The in-container solution contains at least a dispersion medium and water, and one additive solution contains at least a silver salt and water, and the other additive solution contains at least a halide salt and water. 4. The method for uniformly mixing a solution according to claim 1, 2 or 3, wherein the produced substance is a silver halide emulsion grain. 5. The solution in the container contains at least a dispersion medium, water, and silver halide emulsion grains, the added solution contains at least a chemical sensitizer, and / or a photographically effective material other than the chemical sensitizer. The method for uniformly mixing a solution according to claim 1, 2 or 3, further comprising a different additive.