JPH03200952A - Method and apparatus for producing silver halide emulsion - Google Patents

Abstract

PURPOSE:To make stable mass production with good reproducibility by successively effecting particle formation reaction in a specified direction to substantially prevent mingling of the reaction solns. in plural stages of batch wise medium volume reaction vessels disposed in series with each other. CONSTITUTION:The particle formation reaction is effected successively in the specified direction in such a manner that the reaction solns. in plural stages of the batch wise medium volume reaction vessels 2a, 2b, 2c disposed in series do not substantially mix with each other. Thus, the emulsions of the same performance as the performance of the improved emulsions developed by a small-volume device for research are produced immediately in a factory scale stage and particularly the capacity of the reaction vessels for nuclear formation is decreased. The average residence time of the respective emulsion particles in the respective reaction vessels is unified and the silver halides are produced continuously according to a required amt. with the good reproducibility.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention produces halogenated sI (hereinafter referred to as
The present invention relates to a method and apparatus capable of freely producing emulsion crystal grains (denoted as AgX) in small to large quantities with good reproducibility.

[Conventional technology]

Recent methods and equipment for producing silver halide emulsions are as follows: ■ "Silver salt and X-salt aqueous solutions are continuously introduced in the presence of a dispersion medium by a double jet method, and the formation of AgX grains occurs. AgX emulsion continuous production apparatus is characterized in that the AgX emulsion is continuously taken out from the reaction chamber during the continuous production of AgX emulsion, and in a plurality of continuously connected cascade reactors, An apparatus for continuously producing an AgX emulsion, characterized in that the AgX emulsion taken out is used as a feed material for a second reaction chamber.

[L. L. Zelikman and N.M. Levy “Making and Coating Photographic Emulsions”, Focal Press, London (V, L, Zelikmanand S.
M. Levi, “Making and Co.
ating Photographic E+ulsi
on-s”) P, 228 (Focal Pre
ssLondon) (1964), U.S. Patent No. 3,77
Specifications of No. 3,516 and No. 4,046.576, Arigaken-1 Journal of the Photographic Society of Japan.

30, 99 (1967)] ■Characteristic: ``AgX emulsion is continuously poured into a cylinder or a vibrator, and many addition ports for silver salt and X-salt aqueous solution are provided along the way.'' Continuous manufacturing equipment [U.S. Patent 3, 6]
55.166, 3,827.888, West German Patent Application Publication Specification (OLS) 2.755.16
See Specification No. 6], etc.

[Problem to be solved by the invention]

However, since the method and apparatus of (2) continuously extracts the AgX emulsion while continuously forming nuclei, the extracted AgX particles consist of particles with different residence times in the reaction vessel. AgX with wide particle size distribution
It becomes an emulsion, and the size distribution changes over time. If the average residence time of the particles is shortened, the size distribution becomes steady, but this has the disadvantage that the average particle diameter becomes small.

An example can be found, for example, in US Pat. No. 3,801.326.

Furthermore, in the method and apparatus of (2), the residence time of the emulsion at one location is short, so a very long pipeline is required in order to increase the size of the particles. By slowing the flow rate of the emulsion and increasing its residence time, mixing with adjacent liquids is promoted by stirring,
Broader particle size distribution. Furthermore, the stirrer and addition system in a sealed system require measures to prevent liquid leakage at the joints with the pipe, resulting in equipment that is prone to many troubles. In addition, since the device format is different from a small-volume research device, the device constants cannot be matched with that device. Since the pipe length is constant, there is no adaptability to various prescriptions with different prescription times. It has problems such as poor stirring and mixing performance.

In addition, the most primitive problem is a reaction device (hereinafter referred to as a small-volume device) consisting of a small-capacity reaction vessel usually used for research.
If it is possible to develop an AgX emulsion with excellent performance (having a volume of 1 to 51), it is necessary to mass-produce the emulsion (usually in a reaction vessel of 6001 or more) in order to commercialize the emulsion. be.

In this case, there is a first-order problem.

■ A manufactured using the small-volume equipment according to the same manufacturing procedure manual
gX emulsion and a large-capacity reactor (hereinafter).

It is rather rare that the performances of AgX emulsions produced using large-scale equipment are exactly the same. Therefore, in the case of mass production, a part of the manufacturing procedure manual is often modified to match the performance of both products. This work requires a lot of money and time. This problem is particularly serious in the production of tabular emulsion grains having parallel twin planes.

■ When manufacturing a large amount of emulsion at once using a batch method, if the product is of a variety that sells in small quantities, there will be overproduction of emulsion, and some of the emulsion will have to be discarded.

This is because photosensitive materials have an expiration date and cannot be kept in stock. Therefore, it is desired to be able to produce emulsions in the required amount depending on the type of product sold, whether it is a type with a low sales volume or a variety with a large sales volume.

(2) Normally, when mass-producing silver halide emulsions for photographic light-sensitive materials is carried out in batch mode, the process from nucleation to crystal growth reaction takes a long time in one large container, and a large amount of emulsion can be produced at one time. However, if a large amount of emulsion cannot be coated at one time, most of the emulsion is divided into portions and stored in a refrigerator. This increases extra work, increases refrigerator expenses, and increases costs. Further, a step of dissolving the emulsion is also required each time the emulsion is coated. Since the work becomes complicated in this way, a manufacturing method and manufacturing apparatus that can manufacture the necessary amount of emulsion in a short period of time is desired, rather than a large amount of AgX emulsion that is manufactured in a long period of time.

The purpose of the present invention is to solve the above-mentioned problems, to provide a narrow particle size distribution, the ability to arbitrarily increase the average particle diameter, and to provide stable manufacturing conditions with good reproducibility without major changes in the manufacturing conditions of research reactors. It is an object of the present invention to provide a method and apparatus for producing a silver halide emulsion, which can be mass-produced and can also be produced in small quantities if necessary.

(Means and effects for solving the problem) The above objects of the present invention are as follows: (1) A silver salt solution and a halide salt solution are added in the solution, and the grain formation reaction of the silver halide emulsion is arranged in series. In a method for producing a silver halide emulsion by passing the silver halide emulsion through a plurality of reactors arranged in series, each of the plurality of reactors arranged in series is a batch type medium-sized reactor, and the reaction solution in each reaction vessel is without substantially mixing with each other,
A method for producing a silver halide emulsion, characterized by carrying out a grain forming reaction in a certain direction.

(2) Claim (1) characterized in that the crystal grains of the silver halide emulsion are tabular emulsion grains having parallel twin planes.
) A method for producing a silver halide emulsion as described above.

(3) The method for producing a silver halide emulsion according to claim (1), characterized in that the silver salt solution and the halide salt solution are directly added into the solution through a porous body.

(4) An apparatus for producing silver halide emulsion grains by adding a silver salt solution and a halide salt solution into the liquid has a liquid feeding port with an on-off valve, and has two or more batch-type medium-sized devices connected in series by a transfer pipe. After each reactor moves backwards from the last reactor and sends the reacted reaction solution in the reaction container to the next container, the on-off valve of the reaction container is closed.
Next, the on-off valve of the adjacent upstream reaction container is opened to receive the reaction solution in the upstream reaction container, and then the reaction device is operated for a certain period of time. An apparatus for producing a silver halide emulsion, characterized by the following.

(5) Claim (4) characterized in that the silver salt solution and the halogen salt solution are added directly into the liquid through a porous body.
An apparatus for producing the silver halide emulsion described above.

(6) The silver halide according to claim 4 or 5, wherein the nucleation reactor of the batch reactor is composed of two or more parallel nucleation reactors. Emulsion manufacturing equipment.

distantly related to

3-1 Basic idea of the invention 1. The small-scale research device and the manufacturing device of the present invention are compatible with each other in terms of device constants.

That is, if the small-scale research equipment and the manufacturing equipment of the present invention are completely different in form, there is no compensation for AgX emulsion grains having the same characteristics to be prepared by both equipments.

Furthermore, even if AgX emulsion grains with different characteristics are obtained using both apparatuses, it is difficult to analyze the cause of the difference if the forms of the apparatuses are different. Therefore, we considered making the small-volume research device and the manufacturing device of the present invention as close as possible in terms of form and size. In the case of the small-volume research apparatus, in order to prepare a small amount of AgX emulsion under various experimental conditions and investigate its properties, the AgX emulsion is necessarily prepared in a so-called batch mode in a small-capacity reaction vessel. Therefore, the manufacturing apparatus of the present invention also necessarily incorporates the punch system.

2. Be able to respond to various emulsion formulations.

AgX emulsions continue to be improved and the manufacturing recipe is changing. Further, in the case of manufacturing equipment, it is required to be able to manufacture emulsions of various products ranging from small-sized to large-sized particles. Therefore, the manufacturing apparatus of the present invention was designed to have a highly flexible configuration that can meet these demands.

3. The reaction solution should have good homogeneous mixing properties, and the device should be small.

When producing tabular emulsion grains having parallel twin planes, it is necessary to control various supersaturation factors in the reaction solution with high precision while reducing non-uniformity during nucleation. For details, see Japanese Patent Application Nos. 63-315741 and 63-223.
Reference may be made to the descriptions in the specifications and publications of No. 739 and JP-A No. 63-92942. Also, during crystal growth, emulsion grains with better monodispersity can be obtained if the degree of supersaturation during crystal growth is uniformly controlled in the reaction solution.

Also, in the case of mixed crystal growth, it is preferable to control the composition of the reaction solution uniformly, since the halogen ratio in the growth layer can be controlled more precisely as intended. Since the circulation frequency of a small amount of reaction solution in a small container is higher than that of a reaction solution in a small container, more uniform control can be achieved. Therefore, from this point of view, it is preferable that the container capacity is small.

This method is also preferable in that it can be more compatible with small-volume research devices. Also, in terms of cost, it is cheaper to make five reactors with a capacity of 40 (1!) than to make one reactor with a capacity of 20,001.Therefore, in terms of cost, it is cheaper to make a small reactor than a large one. is preferred.

The main objective of the present invention is, in particular, to reduce the volume of the nucleation vessel as much as possible. This is because the nucleation step is particularly important in AgX particle formation.

4. Each device should be functionally separated and simple as possible.

If the device is simple, it will be easy to analyze when an abnormality occurs. In order to simplify the device, it is sufficient to separate the functions of the device. That is, rather than using one device for nucleation, growth, and growth, it is used exclusively for nucleation. This is because by doing so, the performance of the device can be improved by focusing on one point of view: nucleation.

5. The grain size distribution of the resulting emulsion grains is narrow.

Generally, it is preferable that the grain size distribution of the emulsion grains is narrow because the contrast is high and the single layer effect is effective. Therefore, it is essential to obtain emulsion grains with good monodispersity. For this purpose, it is necessary that each emulsion grain has an equal residence time in the reaction vessel.

6. The AgX emulsion must be manufactured continuously in only the required amount.

3-2 Description of the apparatus characterized by the present invention Based on the above ideas 1 to 6, two or more batch-type medium-sized reactors ( He invented a device in which two devices (hereinafter referred to as medium-sized devices) are connected in series. Specific examples include the devices shown in FIGS. 1 to 3 or a combination of two or more of them. The operating procedure will be explained using the case of FIG. 1 as a representative example. Let t be the preparation time of the AgX emulsion. The reaction solution is put into the reaction container 2A of the reaction apparatus A, and particle formation is performed for t/3 hours.Then, the solution is heated in 2. After transferring to a container, add new reaction solution to 2m, and add 2a and 2. The particle formation reaction is carried out for t/3 hours each at 0th order 2.
After transferring the solution of 2A to the 2c container, add the solution of 2A to the 2c container. Move to
After that, a new reaction solution is added to 2A and the particle forming reaction is carried out for L/3 hours each. After that, repeat this operation, for example 2. 2 of the solution
．． After moving to 2. 2. 2. It goes without saying that it is not necessary to start the reaction until the reaction solution is set in 2A. Further, if necessary, a step of cleaning the nuclear reaction vessel can be included after each liquid transfer operation.

In particular, when n≦6, it is preferable to perform a washing process with shower water once or twice, and the temperature of the shower water is 30-30°C.
70°C is preferred, and 35-60°C is more preferred.

In addition, it is more preferable that the positions of the reaction vessels A, B, and C are at the minimum value of the head required to achieve rapid liquid transfer by gravity.

In the present invention, the value of n (the number of medium-sized devices connected in series) is 2 or more in the multi-stage reaction device.

Preferably it is 2-8, more preferably 3-7, and still more preferably 3-4. For example, a case where three 100ffi containers are connected in series and a case where 10 containers are connected in series will be compared. The transfer time is 1 minute for each AgX emulsion preparation recipe for 120 minutes. Also, assuming that the emulsion yield at the final stage is 801, in the former case it is 801! every 42 minutes!
, and in the latter case, 80ffi of emulsion is prepared and delivered every 14 minutes.

The apparatus of the present invention utilizes this to reduce the size of the reaction vessel, particularly the vessel of the nucleation reactor, without changing the amount of emulsion produced/time. Another advantage is that increasing the number n eliminates the need for a cleaning step after each liquid transfer.

The reason is as follows. When n is large, the grain formation time in each reaction vessel becomes short, and the difference in grain size from the emulsion grains in the previous reactor becomes small. Therefore,
If a small amount of emulsion from an adjacent container is mixed in due to residual liquid during liquid transfer, the effect of this on the grain size distribution of the emulsion will be small. Therefore, the cleaning step can be omitted. However, if the number of n is 8 or more, the equipment cost will increase and the size of the entire device will become too large. Also,
When (liquid transfer time/reaction time) increases and the reaction temperature is high, the contribution of Ostwald ripening during liquid transfer increases.

Therefore, also from this point of view, n≦8 is preferable.

The apparatus of the present invention can be used for small grain emulsions to large grain emulsions (i.e.
It can be used to manufacture all types of emulsions (from short-term formulations to long-term formulations). Specifically, in the case of long-term prescriptions, the number of medium-sized devices used may be increased depending on the length of time, and/or the average residence time in each medium-sized device may be lengthened.

For short-term prescriptions, do the opposite. That is, the number n of medium-sized devices and/or the average residence time may be reduced depending on the prescription.

Further, from the viewpoint of reducing the contribution of Ostwald ripening and eliminating wasteful production time, it is desirable to shorten the liquid transfer time as much as possible. For this reason, the wetted parts of each device are preferably made of a material that is resistant to water (contact angle>90°) (for example, Teflon or stainless steel whose surface is coated with Teflon). This is because the interaction between the solution and the vessel wall is small, so the amount of solution remaining after the liquid transfer can be reduced and the liquid can be transferred quickly. others,
If the inner diameter of the liquid feeding pipe is made as large as possible and the length thereof is shortened, the liquid feeding time will be shortened. However, if the inner diameter of the liquid transfer pipe is increased, the amount of liquid remaining in the pipe increases during liquid transfer, so the size is determined by taking this into account. The traveling wave time is preferably within 2 minutes, more preferably within 60 seconds.

In the present invention, the expression that the reaction solutions in each reaction container do not substantially mix means that the amount of residual liquid is preferably 10% or less of the amount of liquid transferred, and more preferably 3% or less.

To explain the embodiment of the present invention using the drawings, in FIGS. 1 to 3, the next reaction container 2
The liquid feeding port 9 is preferably provided with an on-off valve attached to the lowest part of the reaction vessel 2□. This is because it is effective in reducing the amount of liquid remaining after liquid transfer.

Preferably, each medium-sized reactor, particularly the nucleation reactor, is a device that is identical in form to a small-volume research device. Reactor A
It is preferable that the silver salt aqueous solution (Ag'') and the X-salt (X-) aqueous solution be uniformly mixed into the reaction solution 5 quickly after addition.
X- is added directly into the reaction solution 5 through the addition tube 3.4 (that is, directly added under the wave front), and is vigorously stirred by the stirring blade 8 installed near each addition port 6.7. It is preferable to use a material of this type, and it is even more preferable to add the material through a porous body.

Particularly in a large-volume apparatus, the addition flux of aqueous solutions of silver salts and halide salts becomes thicker, and the non-uniformity of solute concentration near the addition port becomes larger. This is one of the reasons for the performance difference that occurs when AgX emulsion production is scaled up. Adding the solution through a porous body greatly improves the non-uniformity.

Here, a porous body has 4 or more pores, preferably 10 or more, more preferably 10" to IQIs pores per one added solution, and the pore diameter is 2 mm or less, preferably 0.5 m.
mφ to 100 people, preferably 0.1 mφ to 0.1 μm
It has a hole of φ. In particular, a hollow tube type porous membrane is particularly preferable because the supporting device is simple and it is easy to use.

For details, reference may be made to the description in Japanese Patent Application No. 78534/1999.

In addition, in the present invention, as a method for supplying solute ions during crystal growth in a large-scale apparatus, an ultrafine grain emulsion (A
Particularly preferred is a method of supplying (gcl, AgBr, 8gl and/or a mixed crystal of two or more thereof). The ultrafine particles mainly dissolve gradually after being uniformly mixed into a large amount of emulsion, and do not cause non-uniform distribution of solutes beyond their equilibrium dissolution. Therefore, it is possible to uniformly grow seed crystals in a mass-volume device.

The ultrafine particles are preferably defect-free particles that do not substantially contain multiple twin grains (particles containing two or more twin planes in one AgX grain) or helical transition grains.

Here, "substantially" means that the proportion of the number of defective particles is 5% or less, preferably 1% or less.For details of the method for preparing the ultrafine particles, see JP-A No. 1-183417 and Japanese Patent Application No. 2-1426.
The descriptions in each publication No. 35 can be referred to.

These methods can be particularly preferably used in the present invention. That is, the production of tabular emulsion grains having parallel twin planes, particularly the parallel double twinned tabular emulsion grains described in JP-A-63-151618 and JP-A-2-838; It can be preferably used for producing the substantially peerless emulsion grains described in Japanese Patent No. 146033.

Regarding these addition systems, stirrers, reaction vessels, baffles, and stirring blades, please refer to Research Disclosure + - (Re
search Disclosure), vol. 166, i
te++116662 (February 1978), patent application Hei 2-
No. 78534, U.S. Pat. No. 3,897,935, U.S. Patent No. 3,
No. 790,386, No. 3,415.650, No. 3,6
No. 92.283, No. 4,289,733, No. 3,78
No. 5,777, JP-A-57-92524, JP-A No. 60-1
17834 description.

You can refer to descriptions in publications, etc.

FIG. 1 is a side sectional view of one embodiment of the apparatus of the present invention, which is generally called a cascade type apparatus. When the valve 9 at the bottom of each reaction vessel 2 is opened, the solution in the vessel is transferred by gravity to the next vessel. Liquid is transferred.

FIG. 2 shows a device called a step type according to an embodiment of the present invention, and (a) shows a side sectional view of the device, and (b) shows a plan view. In the case of this device, the liquid sending pipe 10 is eliminated, and the container side wall 1 is tilted and movable up and down.
3 and the bottom of the container also serve this role. In this type of device, there is no remaining liquid in the liquid sending pipe 10, and the switching valve 1
1. There is an advantage that the wastewater pipe 12 is not required and the liquid can be quickly transferred to the next device. The liquid transfer may be carried out by raising and lowering each vertically movable side wall 13 of the container, or by loading and unloading it in the lateral direction, or by providing an on-off valve at the lower part of the container side wall 13. The device shown in the figure uses a natural head.

This method has the advantage of being low cost and having a small amount of residual liquid because liquid can be transferred quickly by simply opening and closing a valve.

FIG. 3 shows a system in which each medium-sized device is placed in a substantially horizontal position relative to each other, and liquid transfer is performed using a pump 14.

Each device may be an independent device as shown in (a), and ω
), an integrated device may be used, and the device can be selected depending on the purpose. (Other symbols are the same as in Figure 1.2.

The liquid transfer pump 14 used here refers to a machine that receives power from an external source and moves a liquid at a low water level to a high water level.For details, refer to the Chemical Equipment Handbook, edited by the Society of Chemical Engineers.
Chapters 17 and 18, Marukubi (1989) can be referred to.

In the case of the apparatus of the present invention, it is preferable to use a pump that can transfer the AgX emulsion without causing any adverse effects such as pressure build-up. In this respect, diaphragm pumps (a), vacuum suction type pumps (c), and reciprocating pumps (c) as shown in FIG. 4 are preferable. In either case, the pressure inside the liquid transfer pipe is reduced to suck up the emulsion, and then the emulsion is transferred to an adjacent medium-sized container in conjunction with check valves 15 and 16. Figure 4 shows a specific example.

Reference numerals 15 and 16 in Figures (a) to (C) indicate check valves for suction and discharge, respectively. (a) The figure shows an example of a diaphragm pump, and when the bellows-shaped diaphragm 17 is raised, the pressure inside the liquid suction container 18 is reduced, and the reaction liquid is transferred to the suction check valve 1.
When the bellows-shaped diaphragm 17 is lowered, the reaction liquid in the liquid suction container 18 is transferred through the discharge check valve 16. The guard 19 is a guard that prevents the suction liquid from scattering. 0)) The figure shows an example of a vacuum suction type, and when the valve 20 is switched to the vacuum system 21 side, the pressure inside the liquid suction container 18 is reduced, and the reaction liquid is sucked into the liquid suction container 18 through the suction check valve 15. Ru. When the amount of suction exceeds a certain level in the liquid suction container 18, suction stops, the valve 20 switches to atmospheric pressure or the pressurized system 22 side, and the reaction liquid in the liquid suction container 18 passes through the discharge check valve 16. The liquid is transferred. The amount of suction liquid can be adjusted by adjusting the suction time width. Figure (C) shows an example of a reciprocating pump, and when the piston 23 is raised, the pressure inside the cylinder 24 is reduced.
The reaction liquid is sucked up into the cylinder 24 through the suction check valve 15 . Next, when the piston 23 is lowered, the reaction liquid in the cylinder 24 is transferred through the discharge check valve 16. 25 is a backing for preventing air leakage.

In all cases (a) to (C), the AgX emulsion and the movable part of the pump do not come into direct contact with each other, so they are not rubbed or abraded. The length and thickness of each pipe, the position of each check valve, and other device shapes are determined to make the liquid transfer rate as fast as possible and to minimize the amount of residual liquid. In addition, if necessary, each pump can be washed by passing washing water instead of emulsion through each pump.

In the case of (a) and (C), the liquid suction container 18 or cylinder 24 due to the movement of the bellows-type diaphragm 17 or the piston 23
The relationship between the changing volume V, the unchanged volume ■2, and the internal pressure P2 during suction is P+'V+=Pz(V+ +V,
) is given by the relationship. Here, Pl is the pressure before suction. Therefore, by changing the V+/Vt ratio, the suction speed can be selected.

Additionally, the apparatus of the present invention may be equipped with a chondral double jet (C, D, J) control system. Regarding this, F, C1aes and R, Bere.
nds-en Photo, Korr, vol. 101, 3
7 (1965) may be referred to.

Usually, the process in which the grain size of AgX particles is important is the nucleation process, and the performance of the AgX emulsion finally obtained is greatly influenced by what kind of nuclei are formed. Therefore, it is preferable to use the same nucleation conditions as possible in a small-scale research device to produce the same nuclei. Therefore, the reaction vessel can be further miniaturized using the following method.

(2) As shown in A1 to A in FIG. 5, two or more reactors for nucleation, preferably two to five, are installed. In this case, nuclei are formed at A, , A, and A in FIG. 5, and when the nucleation is completed, each is transferred to B, where the next force or crystal growth reaction is performed.

(2) As another embodiment, nuclei are formed in A+, At, and As shown in FIG. 5, and when the nucleus formation is completed, each is transferred to B.

After repeating this once, the solution of B is transferred to C, and crystal growth is performed in C. In this case, one or more reactors A for nucleation are installed, preferably 2 to 5 reactors A. In addition, in order to prevent nuclear changes during storage in B,
It is preferable to keep the temperature of B at a low temperature (10 to 40°C). In this case, the capacity specifications for the small nucleation device A are shown in Table 1. (Table 1 is shown on the next page.) Usually, for nucleation, it is preferable to add a calculated amount of silver salt and X-salt aqueous solution using a precision constant flow pump, rather than adding C, [1, J, to the aqueous solution. This is because the silver potential at the initial stage of nucleation changes to the positive side in an X-salt excessive solution, so controlling the silver potential will conversely make the control PAg value inaccurate.

For details of these and other nucleation conditions, reference may be made to the descriptions in the specifications of Japanese Patent Application Nos. 315741/1980, 223739/1983, and 90089/1999.

In addition, in the case of an embodiment in which medium-sized devices are connected in series as shown in FIGS. 1 to 3, the reaction time between each device must be designed to be approximately equal. (See Table 1) If the times are different, the residence time of the emulsion in each device is
Of these, it is necessary to adjust to the longest stay time, resulting in wasted waiting time. In order to alleviate this, D in Figure 5
Branch reactor D with the same capacity as Dl as shown in D3.
! , I)3 can be provided as appropriate.

Providing one branch reactor can approximately double the reaction time in this step.

The number of branching reactors per one reaction step is preferably 1 to 5, more preferably 1 to 3. This is because if there are five or more reactors, the entire reactor becomes too large and costs increase. To give a specific example, if you want to grow a crystal by the accelerated addition method without pauses while continuously changing the halogen composition during a certain period of crystal growth, and only during a certain period of crystal growth, the temperature is changed to Tl. For example, when you want to grow at T2°C during other periods, and at T2°C for other periods.Also, if one device breaks down, using a branch reaction device has the advantage that you do not have to stop the entire device. It is preferable that the branching reaction device can be moved according to the prescription. For example, it is preferable that the branching reaction device can be moved by moving Dl in FIG. It is also possible to move.In this case, the first.
3.4 Coupling-type connecting pipes that can be easily attached and detached are more preferable for each of the connecting pipes shown in Figure 4. For details on these pipes, check valves, and pipe connections, please refer to Chapter 13, Round Neck, Chemical Equipment Handbook, edited by the Japan Society of Chemical Engineers. (1989) can be referred to.

In the case of nucleation equipment, conventional production equipment typically conducts everything from nucleation reactions to crystal growth in one reaction vessel.

Therefore, in anticipation of an increase in the amount of the solution during crystal growth, the amount of the reaction solution during nucleation is often suppressed to 173 or less of the container capacity. In this case, if vigorously stirred, the reaction solution will become full of bubbles, and the stirring efficiency will deteriorate. However, in the case of the apparatus of the present invention, there is no need to leave this space open, and the amount of reaction liquid can be increased, so that stirring and mixing can be performed more vigorously, and more uniform nuclei can be formed. In addition, more nuclei are formed in the second reaction. A preferable amount of the reaction solution is 30 to 90%, more preferably 50 to 90% of the capacity of the medium-sized container. Therefore, in the apparatus of the present invention, the capacity of each reaction vessel increases as the amount of the reaction solution increases in the order of nucleation→ripening→crystal growth.

Further, since the addition system only needs to be added during nucleation, there is no need to install addition systems with various halogen compositions and concentrations, and the capacity of the addition system may be small, so it is simple and compact. Also, the number and amount of measuring solutions are small.

This also applies to crystal growth equipment.

Additionally, there is no need to raise or lower the temperature of each medium-sized device during the manufacturing period, and the nucleation device can be kept at the nucleation temperature at all times. Therefore, it saves energy and has good temperature controllability. Furthermore, since the nucleation process is separated, there is no need to control the number of stable nuclei. For example, in the conventional method, the number of stable nuclei is reduced by nucleation followed by normal crystal AgX particle formation, but in the case of the device of the present invention, the capacity of the reaction vessel for nucleation is reduced. Since it is possible to reduce the number of stable nuclei, there is also the advantage that such a ripening operation can be omitted.

Continuous production in the AgX emulsion production apparatus of the present invention means:
Refers to a phenomenon in which certain events occur one after the other, such as consecutive home runs. That is, it refers to a phenomenon in which a certain amount of AgX emulsion is repeatedly produced at certain time intervals.

In the present invention, a small-volume device for research and a large-scale device for manufacturing.

The capacity specifications for the reaction vessels of the medium-sized apparatus (the medium-sized apparatus for the first step, and the medium-sized apparatus for the second to final steps) are shown in Table 1.

3-3 Desalting/Concentration Process The emulsion thus repeatedly produced at certain time intervals is desalted and concentrated in the following manner.

■ When the production volume is large, it is poured one after another into a large-volume tank for desalination, and when a certain amount is reached, it is desalted as per conventional methods. The emulsion produced is then placed in a separate desalination bulk tank. Repeat this alternately.

■ If the production volume is medium, the liquid is transferred to a medium-sized container for desalination,
It is desalted and transferred to the next step. Therefore, desalted and concentrated emulsions are produced in medium quantities at certain time intervals.

The following method can be used as a specific desalting method. (1) Method of adding emulsion sedimentation agent, sedimentation and washing with water, (2)
) method of cooling and solidifying the emulsion and washing with cold water, (3) method of desalting using an ultrafiltration membrane, (4) method of desalting using electrodialysis, (5) method of desalting using a centrifuge or liquid cyclone. (6) A desalting method using two or more of the above methods (1) to (5) in combination.

When method (1) is carried out in a large-volume container, the sedimentation time is usually longer than when carried out in a small-volume container. This is because the emulsion near the surface has a longer distance to settle to the bottom of the container. If the sedimentation time becomes longer, the performance of the AgX emulsion may change during the sedimentation process, and the production time becomes longer, which is not preferable. The problem is small when using a medium volume container in the above item (1), but the sedimentation time is a little longer than in a small volume container. The shorter the settling time, the better. This is closely related by reducing the depth of the container. In principle, if the water depth is the same as that of the small volume device, the settling time will also be the same. In this case, by reducing the depth, the reduced container volume can be compensated for by increasing the horizontal area of the container and/or by configuring the shallow containers in a stacked configuration. The preferred water depth is 100 to 10C11, more preferably 60 to 20 cm. For this sedimentation and washing process, a branching device as shown at Dt and Ds in FIG. 5 can be provided. This is because the settling time is arbitrary depending on the type of emulsion, and this can be dealt with.

Method (2) cools and solidifies the emulsion to form dice.

This method involves cutting the noodles into udon-like or somen-like pieces, washing them in cold water, and desalting them. Generally, the larger the surface/volume of the subdivided emulsion, the faster the desalination rate.

As method (3), a porous membrane with a pore size smaller than the diameter of the AgX particles is used to (a) apply pressure to the emulsion side and remove the aqueous solution from the emulsion;
A method of desalting by repeatedly adding water to the emulsion.

(b) A method of desalting by passing the emulsion through a thin hollow tube such as a hollow porous membrane and mainly utilizing salt concentration diffusion, (C) A combination method of (a) and (a) Can be used.

In method (a), desalting and concentration of the emulsion are performed, but (
In method (b), almost no concentration is performed. In that case, a step of concentrating by vacuum degassing, dehydration, etc. may be added as necessary. Typically, the deposition of a concentrated emulsion on the porous membrane surface prevents subsequent dehydration. Therefore, a method is generally used in which the concentrated emulsion is removed and dehydrated by applying pressure in a direction parallel to the surface of the porous membrane and causing the emulsion to flow in that direction. If the porous membrane becomes clogged, the porous membrane may be replaced, the gelatin layer decomposed by enzymatic decomposition, hydrolysis with acid or alkali, and washed and removed. The AgX particles may be dissolved with a hypo AgX solvent and removed by washing.

Regarding method (4), see Arigaken-1 Journal of the Photographic Society of Japan, Volume 31, 9 (196B), Japanese Chemistry Complete Edition, Chemistry Handbook,
The description of Maruzen (1986) in Section 11.16.6 of the Applied Handbook can be referred to.

An example of method (5) is shown in FIG. 6, in which the container and the AgX emulsion are rotated by a rotating shaft 26 at the center of the container. The partition plate 27 increases the rotation efficiency of the emulsion (because the emulsion and the container rotate as one). It is also equipped with two or more Teflon W428 sheets to facilitate redispersion. That is, it rotates in a manner similar to a dehydrator in a washing machine, and the AgX emulsion and water are separated by centrifugal force. The separated water is removed with a pump of the type shown in FIG. 4 previously described. Next, water is added, the Teflon 1i128 is vibrated to re-disperse, and this operation is repeated to desalinate.

This method allows desalting and concentration in the shortest time and at the lowest cost, and since the processing time is constant, it can be preferably used in a system control system such as the present invention.

(For method 1, the pH of the emulsion must be lowered to below the isoelectric point of gelatin (usually pH 3.8 to 4.5).
(2) to (5) have the advantage of not having such restrictions. In addition, since method (2) does not involve concentration of the emulsion, vacuum degassing and dehydration, ultrafiltration, etc. may be used as necessary. It is necessary to add l regression. the above(
For details of 1) to (5), please refer to CG.

F. Duffin “Photographic E
mulsion Chemistry Focal P
ress, London+ 1966), Tokuko Sho 43
-27725 publication, U.S. Patent No. 4,334.012,
4,336°328, 3,326,641, 3.881,934, 396.027, British Patent No. 1,543.322, JP-A-62-11
Publication No. 3137, Research Disclosure + (R
esearch Disclosure+) Volume 102.

item 10208 (October 1972), 13
Volume 1 item 13122 (March 1975), same 1
Volume 76.

item 17643 (December 1978), Arigaken-1 Journal of the Photographic Society of Japan, Volume 31, 9 (1968)
, Complete Japanese Chemistry, Chemistry Handbook, Applied Chemistry WI1.16/6
The description by Setsu and Maruzen (1986) can be referred to.

Regarding the porous membrane, reference may be made to the description in Japanese Patent Application No. 1-76678.

3-4 Chemical sensitization process In research on improving AgX emulsions, the chemical sensitization process of AgX emulsions is usually carried out in a batch reactor. Therefore, when a newly developed AgX emulsion is manufactured in a factory, it is preferable that the chemical ripening process be carried out under conditions as close as possible to research chemical ripening conditions. Therefore, also in the case of the apparatus of the present invention, it is preferable that the AgX emulsion sent out from the desalting/concentration process is chemically sensitized in a batch type reaction apparatus. In this case, the following three steps can be used depending on the amount to be handled.

(1) The emulsion, which has been desalted and concentrated in a large-scale container and sent out, is chemically sensitized in a large-scale container for chemical sensitization.

(2) The emulsion that has been desalted and concentrated in a medium-capacity container and sent out is placed one after another into a large-capacity container, and when a certain amount is reached, the temperature is raised to chemically sensitize it.

(3) The emulsion that has been desalted and concentrated in a medium capacity container and sent out is placed in a medium capacity container for chemical sensitization and chemically sensitized. (3
) method is the most preferable because it solves all problems.

Chemical sensitization varies depending on the type of emulsion and temperature, but is usually carried out for about 10 to 70 minutes after adding a chemical sensitizer. When the chemical ripening time is long, depending on the length of the time,
The chemical ripening process can be divided into two or more stages, and a branch reaction apparatus can be provided as shown in FIG.

As for the method of adding the chemical sensitizer solution, it is preferable to directly add it to the AgX emulsion (that is, directly add it below the liquid surface) and rapidly stir it with a stirring blade installed near the addition port. Moreover, it is more preferable to add this through a porous body. Regarding these addition systems and stirrers, reference can be made to the aforementioned literature regarding reaction vessels. That is, it is possible to preferably use the same type of reaction apparatus as in the case of AgX particle formation.

In addition, AgX
The chemical sensitization modifier can be chemically sensitized while adsorbed to the particles, and the formation location and number/d of chemical sensitization nuclei can be controlled. It can also be added at any time.

Using this chemical sensitization method, the chemical ripening time can be shortened (
This is particularly preferable since it can be carried out (usually for 3 to 15 minutes). Regarding this, Japanese Patent Application No. 63-315741, No. 63
-223739 and Japanese Patent Application No. 1-90089 can be referred to.

3-5 Addition process of photographic additives Here, photographic additives are spectral sensitizing dyes, antifoggants 2
These include color image forming agents, surfactants, hardening agents, etc., and the descriptions and literature described below can be referred to.

In this case, a medium-sized device of the same type as the AgX particle formation and chemical sensitization device described above can be used as the addition/stirring/mixing device for adding the additive to the aqueous solution. Incidentally, the capacity specifications of the medium-sized equipment and the large-scale equipment used in the above-mentioned water washing step, chemical sensitization step, and addition step of the photographic additive are summarized in Table 1. When adding in the form of an oil solution like a color image forming agent, that is, emulsifying and dispersing addition, see Japanese Patent Application Laid-Open No. 63-296035 and Japanese Patent Application No. 1-766.7.
Reference may be made to the descriptions in No. 8 and the documents mentioned below.

3-6 AgX emulsion manufacturing process In the present invention, the steps of desalting, chemical sensitization, and addition of photographic additives can take the following three modes depending on the amount handled.

(1) Desalting (large amount) → chemical sensitization (large N) → addition of additives (large amount) → coating (2) desalting (medium amount) → chemical sensitization (large amount) → addition of additives (large amount) → Coating (3) Desalination (medium amount) → Chemical sensitization (medium amount) → Addition of additives (medium amount) → Coating However, in this process, any of the steps up to the AgX particle formation coating A refrigerator storage step can also be added later. Furthermore, the order of the desalting step and the chemical sensitization step can be reversed. Further, each step is preferably performed in separate containers connected in series.

In the production of photographic light-sensitive materials using the apparatus of the present invention, the most preferred embodiment is that all of the above steps are carried out continuously in a medium-sized container, and that the continuously produced emulsion is
This is a continuous application mode. WI, this is an embodiment in which all processes are continuously and automatically performed without a refrigerator storage process.

1 on one support, like an X-ray photographic film.
~ When coating two types of AgX emulsions, one to two types of A
The gX emulsion production system and the coating process are linked, and in this case, they can be linked economically. That is, fully automatic, unmanned, continuous manufacturing is possible. But like color negative photographic film, 7-10! on one support! ! II A
When gX emulsions are coated simultaneously, 7 to 10 AgX emulsion production systems must be provided in order to link AgX emulsion production and coating processes, which is rather uneconomical. Also,
Moreover, if for example one such system fails, it may halt the entire production and cause significant damage. In such a case, it is preferable to apply the coating after preparing the 7 to 10 types of emulsions. In this case, storage in a refrigerator can be used as appropriate. Others, 3-4 (1), (
If a large amount of emulsion is sent out as in item 2),
It is preferable to divide the emulsion into portions and store them in a refrigerator.

C, D
, control such as start and stop of J control over the entire device,
A control device that sequentially and systematically makes adjustments according to a predetermined order and time schedule. As a control device,
- Can be used for fishing on a boat. For details, see Sawai Zenbe supervised, Sequence Automatic Control Handbook, Ohmsha (1.
971) can be referred to.

Each medium-sized device mentioned above is typically provided with a temperature control device.

Usually, the temperature during AgX emulsion production is 15 to 90°C, and water is used as a heat exchange medium because water has a large heat capacity. For example, temperature can be controlled by attaching a jacket to the outer surface of the reaction vessel and flowing a heat medium through it. In addition, a method in which a pipe is inserted into the reaction solution and a heat exchange medium is circulated within the vibrator can also be used. Others: electric resistance heating, hot plate heating, infrared rays (hot wire)
Heating can be done using eddy current heating from the outside wall of the container and/or from inside the solution.

In addition, regarding temperature control, Nippon Kagaku Complete Edition, Experiment Guidebook, Sections 3, 2, 3 to 3, 2, 4, Marukubi (1984
Year) 9 Edited by the Chemical Society of Japan, New Experimental Chemistry Course (Basic Operations!)
You can refer to Section 2.2, Marukubi (1975), edited by the Society of Chemical Engineers, Chemical Equipment Handbook, Chapter 14, Marukubi (19B9).

Regarding the temperature control and the p, t, o control system of C, D, J @ etc., please refer to the Chemical Engineering Society, Chemical Equipment Handbook, No. 21.
You can refer to the description in Chapter, Marukubi (1989).

Addition systems for adding silver salts and X-salt aqueous solutions include addition systems that add through orifices, meshes, or needle valves using pressurized air or nitrogen gas, diaphragm pumps as exemplified in Figure 4 (a) and (C), and Addition system using plunger pump, others are disclosed in Japanese Patent Application Laid-open No. 182623/1983, Japanese Patent Application No. 6
The method described in specification No. 3-22842, edited by the Society of Chemical Engineers, Chemical Engineering Handbook, Sections 5, 6, and 5, Marukubi (1988)
, Chemical Equipment Encyclopedia, Chapter 1, Kagaku Kogyosha (1976)
You can refer to the description. In principle, JP-A-6
As described in Japanese Patent No. 2-182623, a digital flow rate control system has higher accuracy than an analog system. Further, in the case of the above-mentioned diaphragm pump or plunger pump, the piston action is an immediate solution addition and solution metering action, which is preferable because it is simplified.

Usually used as the material for the parts that come in contact with the AgX emulsion.

It is preferable to use a material that does not adversely affect the AgX emulsion, usually stainless steel (SUS316, 316L, 32
9J), in addition to hard glass, polymeric materials such as polyethylene, polypropylene, and Teflon are used. In addition, composite materials (for example, stainless steel coated with Teflon) are used.

In the case of check valves, Teflon, polyethylene, etc. are used as the material for the ball of a ball lift type valve and the swing of a swing type valve. When opening and closing the valve, it is preferable to perform a smooth pumping operation so as not to give a large impact to the emulsion in the opening/closing part.

The apparatus of the present invention can be used in addition to producing AgX emulsion grains.

It can also be used as an apparatus for general chemical reactions of the same type as the AgX emulsion grain formation.

Conventionally known chemical reaction devices are (1) batch type, (2)
) semi-batch type, and (3) continuous type (A-tube type, B1 type, C multi-stage tank type). Regarding this, see the Chemical Engineering Handbook, Chapter 23, round neck (1988), edited by the Chemical Engineering Society.
You can refer to the description.

According to this, an apparatus using the operation method (continuous multi-stage batch method) of the present invention is not known.

3-8 Other conditions for producing AgX emulsions using the apparatus of the present invention As the dispersion medium used when producing AgX emulsions using the apparatus of the present invention, those commonly used for AgX emulsions can be used. However, various hydrophilic colloids can be used. Generally, gelatin is preferred, and examples of gelatin include alkali-processed gelatin, acid-processed gelatin, derivative gelatin such as phthalated gelatin, low molecular weight gelatin (molecular weight 2,000 to 100,000, enzymatically decomposed gelatin, gelatin hydrolyzed by acid and alkali), and methionine. Gelatin having a content of 50 μmol/g or less (the description in JP-A-62-157024 can be referred to) can be used, or a mixture of two or more thereof can also be used.

Derivative gelatin includes gelatin and various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonate compounds, maleimide compounds, polyalkylene oxides, and epoxy compounds. The product obtained by reacting is used. Other examples include graft polymers of gelatin and other polymers, thioether polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, and boribi G. Synthetic highly hydrophilic compounds such as single or copolymers of alcohol, polyvinyl alcohol partial acetal, poly(1J-N-bi-lpyrrolidone), polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Molecular substances can be used alone or in a mixed system.

Regarding these details, reference can be made to the descriptions in the documents mentioned below.

In order to adjust the degree of supersaturation during nucleation of the AgX particles, to promote ripening during the ripening process, to promote growth during the crystal growth process, and to effectively perform chemical sensitization during chemical sensitization. A halogen base solvent can be used for leveling.

Examples of frequently used halogenated solvents include thiocyanates, ammonia, thioethers, and thioureas. Regarding this, the description in the literature mentioned below can be referred to.

There are no particular restrictions on the additives that can be added from grain formation to coating during the production of AgX emulsions using the apparatus of the present invention. Additives that can be added include AgX solvent (also called force promoter), dopant for AgX particles [Group 8 noble metal compounds, other metal compounds (gold, iron, lead, cadmium, etc.), chalcogen compounds, SCNCN] Chemical dispersion medium, antifogging agent, stabilizer, sensitizing dye (for blue, green, red, infrared, panchromatic, ortho, etc.), supersensitizer, chemical sensitizer (
Chemical sensitizers made by adding sulfur, selenium, tellurium, gold, Group 8 noble metal compounds, and phosphorus compounds alone or in combination, most preferably chemical sensitizers made from a combination of gold, sulfur, and selenium compounds, and stannous chloride. , reduction sensitizers such as thiourea dioxide, thread riabin, and amine borane compounds), fogging agents (organic fogging agents such as hydrazine compounds, inorganic fogging agents), surfactants (antifoaming agents, etc.), emulsion sedimentation agent, soluble silver salt (AgSCN, silver phosphate, silver acetate, etc.), emulsion precipitating agent, latent image stabilizer, pressure desensitization inhibitor, thickener, hardening agent, developer (hydroquinone compound, etc.), development It is a modifier, etc., and for specific compounds, usage methods, etc., the descriptions in the following documents can be referred to.

In addition, for the AgX emulsion, any combination of known techniques and known compounds described in the following documents can be used.

Re5erch Disclosure Vol.
176 (item 17643) (Deces+be
rp 1978), Vol, 184 (ites+
18431) (August.

1979), Vol. 216 (itege
21728) (May, 1982), JCIA Monthly 1984, December issue, P, 18-27,
Journal of the Photographic Society of Japan, Volume 49, 7 (1986), Volume 52
%, 144-166 (1989), JP-A-58-1
13926-11392B, 59-90842, 5
9-142539, 62-253159, 62-9
9751, 63-151618, 62-6251,
62-115035, 63-305343, 62
-269958, 61-1121/12, 62-2
66538, 63-220238, 63-7846
5, Japanese Patent Publications No. 1-131541, No. 1-297649, No. 2-146033, Japanese Patent Applications No. 1983-315741, No. 62
-208241 63-311518, Special Publication 1986-4
3727, U.S. Patent No. 4,705,744, U.S. Patent No. 4+707
+436, T, H, James, The The
ory of ThePhotographic P
rocess, Fourth Edition+
Macmillan+ New York, 1977
, V.L., Zelikman et al., Maki.
ng and Coating Photo-g
rapic ε-ulsion (The F
ocal Press, 1964), P, G1
afkides+ Chi+m1eet Physi
ques Photogra-phiques, Fif
th Editi.

n, Edition de l'Usi-n
e Nouvelle+ Paris+1987, 5th Edition, Paul Mont
el+ Paris+1957, K, R, Ho1l
ister, Journal of Image
, Sci, 31. 148-156 (1987).

〔Example〕

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Comparative Example 1 Tabular AgX emulsion grains having parallel twin planes were prepared using a small-volume research device having the same configuration as the small-sized device shown in FIG. 1 and having a container capacity of 42. First, a gelatin aqueous solution (
H, OIL 1 g of gelatin with an average molecular weight (M) of 20,000, pH
6,0,KBr (4.5 g) was added and the temperature was maintained at 30°C. A g N O using the double jet method while stirring
s aqueous solution (32 g of A g N Os and M in 100 d
= 0.7g of 20,000 gelatin, HNOs (IN) 0
．． 2d) and a KBr aqueous solution (containing 23゜2g of KBr and 0.7g of M = 20,000 gelatin in 10〇)
were simultaneously added by 27.5 m at 25 d/min each. After 1 minute, add 197 id of gelatin aqueous solution (containing 32 g of deionized alkali-treated gelatin).

pH 6,5) was added and mixed uniformly for 1 minute, then 10
The temperature was raised to 75°C over a period of minutes. After raising the temperature and aging for 15 minutes, A g N O3 aqueous solution (15% by weight) 27
11d was added over 3 minutes. Next is NH.

solution (25% by weight) ioIll and NHaNOs aqueous solution (
A mixed solution of 50% by weight) lOae was added and aged for 21 minutes. Next, add 3N HNO, solution, pH 5.5
Then, 10 m of KBr (10% by weight) aqueous solution was added. Next, using an aqueous solution of A g N Os (15% by weight) and an aqueous KBr solution (11% by weight), a silver potential of −20 m
C, D, J for 10 min at 8 d/min at V (vs. saturated calomel electrode) were added.

Add only the A g N O3 solution and increase the silver potential by +5 mV.
I made it. Next, AgNOs (15 layers) solution and
- Salt solution (654- in KBr, 56 g and Kl.

C, D, and J were added at a silver potential of 5 mV. The addition was performed using a linear flow acceleration method for 43 minutes with an initial flow rate of 4 II dl/min and a flow rate acceleration of 0.37 m/min. Next, a KBr aqueous solution (15% by weight) was added to the emulsion to lower the silver potential to -50.
mV, A g N Os aqueous solution (15 layers) and K
8 at 20IR1/min using Br aqueous solution (11% by weight)
C, Il, J was added at this potential for minutes.

The emulsion was then stirred for 3 minutes, then a precipitant was added and the temperature was brought to 30°C. Therefore, the AgX emulsion manufacturing process is A
It took 120 minutes from the beginning of the gX nucleus shape to the addition of the precipitant, and 0.735 mol of tabular AgX emulsion grains were sent to the water washing process.

Nitric acid was added to the emulsion to adjust the pH to 4.1, stirring was stopped, and the emulsion was allowed to settle. The supernatant liquid was removed, 28,001 liters of water was added, stirred, the emulsion was washed with water, stirring was stopped, and the emulsion was allowed to settle again. After doing this one more time, increase the temperature to 40°.
C, add an aqueous gelatin solution (Hgo 700 ad, bone gelatin 70 g) and redisperse to obtain a yield of 1.
II! ,.

The properties determined from a transmission electron micrograph (TEM image) of a replica of the obtained hexagonal tabular emulsion grains were as shown in Table 1.

Next, the temperature of the AgX emulsion was raised to 55°C, and then 5,5° dichloro-9-ethyl-3+ 3' bis (3
83% of the saturated adsorption amount of Na salt (sulfopropyl)-oxacarbocyanine was added, and after 10 minutes, 1. Add only lXl0-'mol/mo IAgX, followed by KSCN at 3x10-'mol/so
Only lAgX was added. After 2 minutes, an aqueous chloroauric acid solution of 8 x 10-'mol/+golAgX was added, and the mixture was aged for 15 minutes.

Next, the temperature of the emulsion was raised to 40°C, and an antifoggant (TAI) was added.
(4-hydroxy-6-methyl 1,3゜3a,7-titraazaindene)] in 7X1 (1-”mol/e+o
Only lAgX was added. After 10 minutes, add gelatin aqueous solution (10% by weight) 25(ld) and 1% by weight solution of coating aid (sodium dodecylbenzenesulfonate) to 26-1 thickener [poly(4-sulfostyrene) sodium salt].
26d of wt% liquid.

A hardener was added and coated with a gelatin protective layer at 2 g/m silver on a cellulose triacetate transparent base and dried. In this case, the steps of AgX emulsion grain formation, washing, chemical sensitization, and addition of additives were carried out in the same medium-sized container.

Comparative Example-2 Using a large-scale apparatus having the same configuration as Comparative Example-1 and a container capacity of 9602, each step of Comparative Example-1 was produced in 250 times the amount. Table 1 shows the results of observing a TEM image of a replica of the emulsion grains obtained. This shows that the grain size distribution was broadened and the hexagonal tabular grain ratio was greatly reduced. It took about 135 minutes from setting the reaction solution to adding the precipitant, and a tabular AgX emulsion of about 184 mol was obtained. 10 minutes to raise the temperature from 30°C to 75°C.

This is because it required extra. The emulsion was then treated in the same manner as in Comparative Example-1 using a bulk container, and 2 g/rrf of silver was deposited on a cellulose triacetate transparent base together with a gelatin protective layer.
It was applied and dried.

Example 1 Using the apparatus of the present invention shown in FIG. 1, the first stage of nucleation was repeated three times using a branch type apparatus, and the AgX emulsion manufacturing recipe of Comparative Example 1 was continuously produced in large quantities.

As shown in Table 2, two devices (AI and A) with container capacities of 2゜l were used for nucleation, and B was used as the second stage of nucleation.
For ripening and crystal growth, use the C-F device (container capacity: 150ffi) (container capacity: C and D are 1504!).
E was 18 (1!, F, G was 2502). Nucleation was performed on a scale 12 times that of Comparative Example-1, and ripening and crystal growth processes were performed on a scale 72 times that of Comparative Example-1. The concentration of the added solution is the same as in Comparative Example-1. Transfer of the reaction solution and shower washing were both performed within 1 minute.

The container temperature of A, , A, , B is always kept at 30''C,
-F vessel temperature was maintained at 75°C. The repetition period of each step is 31 minutes. Each switch switching time is 7
Seconds.

First, using two medium-sized containers of 201, each of Comparative Example-1
Nucleation was carried out with a volume 12 times larger than the recipe. That is,
A gelatin aqueous solution (HzO, 121, M
= 20,000 gelatin 84g.

pH 6.0, KBr54g) was added for 20 seconds and heated at 30°
The mixture was stirred for 4 minutes and 30 seconds while maintaining the temperature at C. Then A[NO,
Aqueous solution and KBr aqueous solution at 300ml/min at the same time
d was added by double jet. After 1 minute, the reaction solution was transferred to B.
The liquid was transferred to B contains gelatin solution 14.18/$d in advance.
is added and stirred. After transferring the liquid, A, and A
! The total time required was 8 minutes and 56 seconds. This was repeated three times each, and 72 times the amount of nuclei (the amount of reaction solution was 90.144 ffi') as in Comparative Example-1 was stored in the container B. This operation was repeated every 31 minutes. After the solution of B was transferred to C, gelatin aqueous solution 14,184af was added to B for 30 seconds, and the mixture was stood by for the next operation. In C, after the liquid transfer and stirring for 22 minutes, 1.944 ml of A g NOs aqueous solution was added over 3 minutes. After 1 minute, the reaction solution was transferred to D. After washing the container C with shower water for 1 minute and draining the water, it was placed on standby for the next operation.

In D, after the liquid transfer, after stirring for 30 seconds, N11lJOi
.

72 (ld) and Nus aqueous solution 72 (ld)
It was added directly to the mixing vessel below the liquid level over a period of seconds. Thereafter, after 21 minutes of PIli, 2.520 ml of a 3N aqueous HNO3 solution was added under the liquid level into the mixing vessel over 30 seconds to adjust the pH to 6.5. After 30 seconds, 720jd of KBr aqueous solution was added into the mixing vessel over 30 seconds.

After stirring for 2 minutes, the reaction solution was transferred to E.
After washing and draining the container with shower water for 1 minute, it was placed on standby for the next operation. In E, after stirring for 30 seconds after the liquid transfer, C, D, and J were added using AgN01 aqueous solution and KBr aqueous solution at a silver potential of -20 mV and a speed of 576 m/min for 10 minutes. AgN0. Only the solution was further added to bring the voltage to +5 mV. After stirring for 30 seconds, AgN0. Aqueous solution and X-
C, D, J at a silver potential of 5 mV using an aqueous salt solution.

Added. lk first 288m/min, flow rate acceleration 26.64
C, D, J were added for 13 minutes at d7 minutes. After addition,
After stirring for 1 minute, the reaction solution was transferred to F. Then E
After washing and draining the container with shower water for 1 minute, it was placed on standby for the next operation. In the container F, after stirring for 30 seconds, AgN0. The aqueous solution and the X-salt aqueous solution are initially 632.32
gf/min, flow rate acceleration 26.6477 molecules: 26 minutes (7) C, D, J were added (sIli position 5 mV). 3
After stirring for 0 seconds, the reaction solution was transferred to G. Next F
After washing the container with shower water for 1 minute and draining it, it was placed on standby for the next operation.

In the container G, after stirring for 30 seconds, AgN0. The aqueous solution and the X-salt aqueous solution were initially added C, D, J for 4 minutes at a rate of 1.326.96 w1/min and a flow rate acceleration of 26.64 d1 min. After stirring for 30 seconds after the addition, an aqueous KBr solution was added to bring the silver potential to -50 mV. After 30 seconds, AgN0
J solution and KBr solution were used at 1,440 d/min for 8 minutes.

C, D, and J were added (50 mV). After stirring for 3 minutes, the reaction solution was transferred to a washing container, and the container G was washed with shower water for 1 minute and drained. Waited for operation. In this case, 52.92 moles of tabular AgX emulsion grains are produced every 31 minutes (211.67 moles/12
4 minutes), with higher productivity than Comparative Example-2, and
This shows that high-performance AgX particles could be produced using a medium-sized device (see Table 4), demonstrating the effectiveness of the present invention.

The container for the washing process was a flat-bottom cylindrical container (44 cm radius) with a depth of 50 cm and a capacity of 8300 f, and the temperature was 30°.
It is kept at C. After stirring for 30 seconds after the liquid transfer, a precipitant was added, and 10 minutes later, nitric acid was added to adjust the pH to 4.1.

Stirring was stopped after 5 minutes and the emulsion was allowed to settle in about 13 minutes.

The supernatant liquid was sucked using the suction pump shown in FIG. 4 (b), water 2001 was added to the removed liquid, and after stirring for 5 minutes, stirring was stopped and the emulsion was allowed to settle in about 13 minutes. Have this again-
After repeating the process, the temperature was raised to 40° C., and an aqueous gelatin solution was added to redisperse the mixture for 10 minutes, resulting in a yield of 179.21. The emulsion was transferred to a container for chemical ripening, washed with shower water, drained, and stood by for the next operation. The total time for this step was 80 minutes. The characteristics determined from the TEM image of the replica of the emulsion grains collected at this point are shown in Table 1, and corresponded well with the results obtained using a small-scale research device.

This specifically reduces the nucleation vessel capacity (20e/960ff
The effect of reducing the amount to i)=1/4B makes a large contribution. The washing container is of a branched type, as shown in D in FIG.
Three units have been installed. Each device was operated on a 93 minute cycle.

The container for chemical ripening is 1204! Two units with a capacity of After the liquid transfer, the mixture was stirred for 10 minutes, and then the same chemical sensitization was applied in an amount 72 times that of Comparative Example 1, and the liquid was transferred to a container for the next step of adding photographic additives. Each device was operated on a 62 minute cycle.

The container is a 120ffi container and the temperature is maintained at 40°C. After the liquid transfer and stirring for 10 minutes, Comparative Example-1
The same additive was added in an amount 72 times that of the total amount, and the solution was transferred to the coating process.

In the coating process, it was coated at 12 g/rrt on a cellulose triacetate transparent base together with a gelatin protective layer and dried.

Example-2 Comparative example-1 using the apparatus shown in Table 3 in the embodiment shown in FIG.
A large-scale continuous production of the following AgX emulsion formulation was carried out. 2A
As 1807! , 2. As 250I! ,,2. A 3201 reaction vessel was used.

In addition, AgN0. The addition of both the liquid and the /2.5 cabinets 2) was used.

Table 3 Each step was carried out on a scale 85 times that of Comparative Example-1. The concentration of the added solution is the same as in Comparative Example-1. Transfer of the reaction solution and shower washing were both performed within 1 minute. The repetition period of each step is 50 minutes. First, add a gelatin aqueous solution (HzO) at 30°C to a 2A container.
851, 595 g of gelatin with average molecular weight M = 20,000, PH
6,0°KBr382.5g) within 30 seconds,
Stirring was carried out for 4 minutes and 30 seconds while maintaining the temperature at 0"C.Next, nucleation was carried out using 85 times the volume of Comparative Example-1, and a gelatin solution was added.
The temperature was raised to 75°C. The temperature rose in about 15 minutes.

After raising the temperature to 75°C and incubating for 15 minutes, AgNo.
Aqueous solution was added. After stirring for an additional 2 minutes, stop stirring; 2. 2. The liquid was transferred to After the liquid transfer, the valve 11 was switched, the 2A container was washed with a hot water shower, and the liquid was drained. The valve was closed and the reactor temperature was lowered to 30°C, waiting for the next operation. The total time required was 50 minutes including waiting time.

On the other hand, 28 is constantly maintained at 75°C, the transferred reaction solution is stirred, and NH4NO is added after 1 minute.

Add the solution and NH, then add the solution and let the amount of mature acid rise for 21 minutes.
3 (3N) solution was added to adjust the pH to 5.5, and then KBr solution was added. Using A g N Os solution and KBr solution,
C, D for 10 min at silver potential -20 mV.

Next, C, D, and J were added at a silver potential of 5 mV for 10 minutes using an AgNO3 solution and an X-salt solution.

The initial flow rate was 340 m11 minutes, and the flow rate acceleration was 31.45 m11 minutes. After the addition, the reaction solution was stirred for 1 minute. 2. The container was rinsed in a hot shower for 1 minute, drained, and then readied for the next operation. The total time required was 50 minutes including waiting time.

2c was always kept at 75°C, the transferred reaction solution was stirred, and after 1 minute, the AgNO2 solution and the X' salt solution were added to the C, D, J, 0gL first 654.5ml for 11 minutes,
The addition was carried out for 33 minutes at a flow rate acceleration of 31.45 ml for 11 minutes. Next, KBr solution was added, the silver potential was set to 50 mV, and AgN0.
C, D, and J were added for 8 minutes at a silver potential of -50 mV using the solution and the KBr solution.

After the addition, after stirring for 2 minutes, the reaction solution was transferred to cooling container 2.
．． The liquid was transferred to 2. The container was rinsed in a hot shower for 1 minute, drained, and ready for further operation.

The total time required was 50 minutes including waiting time.

The 2D is always kept at 35°C, and the emulsion is kept at 38°C.
When the temperature drops below C, the emulsion is transferred to the water washing volume H2E in Figure 6.
The liquid was transferred to 2E is 3607! capacity (depth 50as,
The emulsion was centrifuged using this device, and the separated water was pumped out using a pump of the type shown in FIG. 4 (b). Next, wash water 2307! Added Teflon 5! The screen 28 is vibrated to redisperse the separated emulsion, and the emulsion is again centrifuged and an aqueous gelatin solution is added to redisperse the emulsion. The liquid was transferred to the 2F container for production. The yield of emulsion is 93
It was ゜51. The total time required for the 2D and 2E processes is 50
It was a minute. The properties determined from the TEM image of the replica of the emulsion grains collected at this point are shown in Table 4. Compared to Comparative Example-2, the results were close to those obtained using a small-volume device.

This is because the reaction vessel capacity at the time of nucleation is 9601 of Comparative Example-2.
This is due to the reduction in size from 1801 to 1801 and the effect of the porous membrane addition system.

2F is always kept at 55°C, and the container capacity is 150
It is 1. After the liquid transfer, after stirring for 10 minutes, an additive solution was added in an amount 85 times that of Comparative Example-1, and the temperature was lowered to 40°C after chemical sensitization. Auxiliary agent, thickener.

A hardener was added and the solution was transferred to the coating process. This operation was performed every 50 minutes.

In the coating process, 2 g/rr of silver was coated on a cellulose triacetate transparent base together with a gelatin protective layer and dried.

The samples of Comparative Examples-1 and -2 and Examples-1 and 2 were subjected to zero-order wedge exposure with blue light for 1/10 seconds using a tungsten light source at 5400° and a 419 nm interference filter. Developed with the following developer D-1 (20"C
, 4 minutes) and fixed with fixer F-1, then washed with water and dried.

(Developer D-1) 1-Phenyl-3-pyrazolidone 0.5g Hydroquinone 20.0g Ethylenecyaminetetraacetic acid disodium Potassium sulfite Potassium borate Potassium carbonate Sodium bromide Diethylene glycol Water was added to make 11.

do. ) (Developer F-11) Ammonium thiosulfate Sodium sulfite (anhydrous) Ethylene diamine borate Disodium tetraacetate Aluminum sulfate Add glacial acetic acid water to make 11. (PH is 4°.) (P)l is 10° 2.0 g 60.0 g 4.0 g 20.0 g 5.0 g 30.0 g Adjust to o 200.0 g 20.0 g 8.0 g 0.1 g 15.0 g 2.0 g 22.0 g Adjust to 2 The results of sensitometry are shown in Table 4. Example-1
The results show that they correspond well to the results of Comparative Example-1 in terms of performance.

Table 4 [Effects of the Invention] As explained above, according to the method and apparatus for producing a silver halide emulsion of the present invention, the following effects can be expected.

That is, (1) An emulsion with the same performance as an improved emulsion developed using a small-scale research device can be immediately produced on a factory scale.

In particular, since the capacity of the reaction vessel for nucleation can be reduced, it is particularly effective in producing monodisperse tabular emulsion grains with a high tabular grain ratio.

(2) The average residence time of each emulsion grain in each reaction vessel is the same, and therefore emulsion grains with good monodispersity can be obtained.

(3) The average grain size of each emulsion grain can also be made to any size.

(4) By adjusting the continuous time, small-variety emulsions can be produced in small quantities, and unnecessary overproduction can be eliminated.

(5) It has the advantage that the emulsion as described above can be manufactured continuously with good reproducibility in accordance with the required amount.

Therefore, when linked with the water washing process, chemical sensitization process, additive addition process, and coating process, it is possible to perform fully automatic continuous production from the AgX particle forming process to the coating process, and to store the emulsion in the refrigerator and Since the step of redissolving the emulsion can be omitted, manufacturing costs can be reduced.

(6) Since each device is made with a single function and is small, control performance is improved and automation is easy.
High precision equipment can be achieved.

(7) Since each device is made with a single function and is small in size, the operating rate of the facility is high, so the facility cost for the device as a whole can be reduced.

[Brief explanation of drawings]

Figures 1 to 3 are cross-sectional views of one embodiment of an apparatus for realizing the AgX emulsion manufacturing method of the present invention, and Figure 4 is a cross-sectional view of a specific representative example of the liquid transfer pump shown in Figure 3. is a diaphragm type,
(b) is a vacuum suction type, (C) is a reciprocating pump type, Figure 5 is an arrangement example of each batch type reactor when it has a branched type reactor of the present invention, and Figure 6 is a centrifugal type water washing/desorption type. This is an example of a salt apparatus, in which (a) shows a plan view and Φ) shows a side view. A, B, C,... Apparatus 2^, 2B, 2c... Reaction vessel 3...Ag" addition tube 4...X-addition tube 5...Reaction solution 6...Ag" addition lower ...
Pipe for hemorrhoids 13... Container side wall 14... Circulation pump I5... Suction check valve 16... Discharge check valve 17... Bellows type diaphragm 18... Liquid suction container 19... Guard 20... Switching valve 21... Vacuum system 22... Pressure system
23... Piston 24... Cylinder 25... Air leak prevention backing 26... Rotating shaft 27... Partition plate 28... Teflon net 29... Separated water 30... Separated emulsion (3 idiots) ) Figure (b)

Claims (6)

[Claims] (1) In a method for producing a silver halide emulsion, which is carried out by adding a silver salt solution and a halide salt solution into the liquid, and passing the silver halide emulsion through a multi-stage reaction device arranged in series for grain formation reaction. , each of the plurality of stages of reactors arranged in series is a batch type medium-sized reactor, and the reaction solutions in each reaction vessel are not substantially mixed with each other,
A method for producing a silver halide emulsion, characterized by carrying out a grain forming reaction in a certain direction. (2) Claim (1) characterized in that the crystal grains of the silver halide emulsion are tabular emulsion grains having parallel twin planes.
) A method for producing a silver halide emulsion as described above. (3) The method for producing a silver halide emulsion according to claim (1), characterized in that the silver salt solution and the halide salt solution are directly added into the solution through a porous body. (4) An apparatus for producing silver halide emulsion grains by adding a silver salt solution and a halide salt solution into the liquid has a liquid feeding port with an on-off valve, and has two or more batch-type devices connected in series by a transfer pipe. It consists of a medium-sized reactor, and each reactor works backwards from the last reactor to send the reacted reaction solution in the reaction container to the next container, then closes the on-off valve of that reaction container, and then starts the next reaction. This device has a system control device that repeatedly opens the on-off valve of the upstream reaction container adjacent to the , receives the reaction solution in the upstream reaction container, and then repeatedly operates the reaction device for a certain period of time. An apparatus for producing a silver halide emulsion, characterized by the following. (5) Claim (4) characterized in that the silver salt solution and the halogen salt solution are added directly into the liquid through a porous body.
An apparatus for producing the silver halide emulsion described above. (6) The silver halide according to claim 4 or 5, wherein the nucleation reactor of the batch reactor is composed of two or more parallel nucleation reactors. Emulsion manufacturing equipment.