JP2003215740A - Apparatus for preparing silver halide photographic emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To increase the diffusion rate of ions in a silver salt solution and a halide solution and perform a uniform chemical reaction, and to achieve uniform nucleation and growth of silver halide. <P>SOLUTION: By a temperature control device 89 attached to a microreactor 88 for nucleation in which silver halide grains are generated by introducing a silver salt solution and a halide solution and reacting silver ions and halogen ions, the diffusion rate of silver ions and halogen ions can be varied and controlled to have a ≥1.1 time diffusion rate at the temperature of the reactive solutions fed to a reaction section in the microreactor 88, heat transfer is enabled in such a way as to change the temperature of the reactive solutions at ≥5°C/min rate, and a heat exchange range to the reactive solutions is set so as to enable heat exchange within a prescribed short time, thereby, the diffusion rate of silver ions and halogen ions is increased to enable efficient preparation. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion manufacturing apparatus for carrying out reactions, mixing, etc. in a silver halide photographic emulsion manufacturing step by a chemical unit operation.

[0002]

2. Description of the Related Art Generally, a silver halide photographic emulsion used in a photographic light-sensitive material is generally subjected to a nucleation treatment (formation of a fine crystal dispersion of silver halide in a protective colloid solution) and physical ripening (desired grain). (Growth to obtain shape and size) treatment, and a growth treatment to form silver halide photographic emulsion grains of a desired size, shape and structure;
Desalting step to remove unwanted substances (removal of soluble salts from dispersion), and sensitization treatment for enhancing sensitivity of emulsion after desalting (performed in the presence of a sensitizer for increasing sensitivity to light) Heat treatment) and a post-ripening step of adding various agents (sensitizing dyes, stabilizers, etc.) that impart required properties as required, to produce.

Incidentally, in the manufacturing process for the above-described silver halide photographic emulsion, two or more of these processes may be combined into one operation. Further, in the manufacturing process described above, one or more manufacturing steps may be omitted from the manufacturing process. Further, in order to obtain a desired emulsion, a plurality of operations may be repeated in each stage.

Further, in a manufacturing system for mass-producing industrially a silver halide emulsion, a so-called batch type manufacturing system using a large-capacity reaction vessel is usually adopted.

A conventional batch type production system for producing a silver halide emulsion is disclosed in Japanese Patent Laid-Open No. 5-1 shown in FIG.
A device utilizing the tank 10 as a reaction container described in 73267 has been proposed.

The tank 10 is, for example, 1000 l (1
A batch-type reaction tank device equipped with a stirrer capable of producing a large amount of silver halide emulsion such as t) at a time.

In this tank 10, the stirring blade 12 is rotationally driven through a transmission means 14 in which the rotational driving force of a motor 15 is transmitted in a non-contact manner by using magnetic force in order to stir the solution filled inside. The magnetic stirring means 16 having the above configuration is attached.

On the outer peripheral surface of the tank 10, temperature control means 18 for heating or cooling the reaction solution is arranged in order to control the temperature of the solution filled inside. The temperature control means 18 includes, for example, a heat exchange medium (water,
It is configured by using means for heating or cooling by flowing steam, liquid organic matter, flame gas, etc. or means for controlling temperature by installing an element for electrically heating or cooling in the temperature control section.

The tank 10 is constructed so as to be hermetically sealed by mounting a sealing lid 20. Further, an emulsion introduction tube 22 with an opening / closing cock is arranged in the closed lid 20 of the tank 10. Further, a liquid transfer pipe 24 with an opening / closing cock is arranged at the bottom of the tank 10.

In the batch type manufacturing system using the tank 10, at least the dispersion medium and water are introduced into the tank 10 from the emulsion introducing pipe 22 in the nucleation process in the pre-ripening step in manufacturing the silver halide emulsion. A predetermined amount of a dispersion medium aqueous solution containing is added, and then a silver salt solution or a silver salt solution and a halogen salt solution are added under the condition of pBr 2.5 or less, and the magnetic stirring means 16 is stirred for a predetermined time (several minutes), The temperature control means 18 controls the temperature of the reaction solution in the tank 10 so as to keep it within a predetermined temperature range (for example, 5 ° C. to 45 ° C.), and forms nuclei of fine tabular grains including parallel twin planes, for example. .

In this nucleation process, solute ions are randomly walking in the solution when forming nuclei, so that fine tabular grain nuclei and a large number of other fine particles (especially twin-free crystals) are formed inside the tank 10. , Single twin, and non-parallel double twin grains) are simultaneously formed.

Next, in the batch type production system utilizing this tank 10, grains other than tabular grain nuclei are extinguished in the Ostwald ripening process in the ripening process in the pre-ripening process when producing a silver halide emulsion. At the same time, the growth of tabular grain nuclei is promoted.

In the maturing process, the following three maturing methods which have been conventionally used can be utilized. In the first ripening method, after the nucleation, the pBr value of the reaction solution in the tank 10 is adjusted to 2.5 to 1.0, preferably 2.3 to 1.4, and the AgX solvent is fed from the emulsion introducing tube 22. It is added (AgNO ₃ may be added during aging), and the mixture is stirred by the magnetic stirring means 16 and the temperature control means 18 keeps the temperature of the reaction solution in the tank 10 at 10 ° C. or higher with respect to the nucleation temperature. More preferably, it is a method of raising the temperature by 20 ° C. or more and aging for a predetermined number of minutes or more.

The second aging method is that after the nucleation, the pBr of the solution is
Adjust the value to 2.5 or less, preferably 1.0 to 2.0,
First ripening for a predetermined number of minutes or more without AgX solvent, then adding AgNO ₃ from the emulsion introducing tube 22 to raise the pBr value to 0.1 or more, preferably 0.3 or more. And stirred by the magnetic stirring means 16, and the temperature of the reaction solution in the tank 10 by the temperature control means 18 is preferably 10 ° C. or higher with respect to the nucleation temperature,
More preferably, the temperature is raised by 20 ° C. or more for a predetermined number of minutes or more,
This is the second aging method.

The third ripening method is that pBr of the solution is formed after nucleation.
Adjust the value to 2.5 or less, preferably 1.0 to 2.0,
Stirring is carried out by the magnetic stirring means 16 without AgX solvent, and the temperature of the reaction solution in the tank 10 is raised by the temperature control means 18 preferably 10 ° C. or more, more preferably 20 ° C. or more with respect to the nucleation temperature. It is a method of aging for a predetermined number of minutes or longer. There is also a method of adding AgNO ₃ during aging.

Further, in the above-described first to third aging methods, the tank 10 is closed only during aging, and the pressure in the tank 10 during aging is increased to several times the atmospheric pressure or more. There is also a method of utilizing a pressure aging method. Further, there is also a method of aging in the presence of an antifoggant by the above-mentioned first to third aging methods.

Next, in the batch type production system utilizing the tank 10, tabular grain nuclei are grown in the crystal growth process after the ripening process in the pre-ripening process in producing a silver halide emulsion is completed. Try.

In this crystal growth process, a method of adding a silver salt solution and a halogen salt solution as solutes for growing crystals of tabular grain nuclei, a flow rate accelerated addition method, a concentration accelerated addition method, and a combination of two or more thereof are added. Method can be used.

Further, in the batch type production system using the tank 10, even in the crystal growth process in the pre-ripening step when producing a silver halide emulsion, the reaction solution stored in the tank 10 Then, a predetermined amount of a silver salt solution and a halogen salt solution as solutes for growing crystals of tabular grain nuclei are injected from the emulsion introducing tube 22 to the magnetic stirring means 16
While stirring at a predetermined time (several minutes), the temperature control means 1
The temperature is controlled by 8 so that the reaction solution in the tank 10 has a predetermined temperature, and the chemical reaction for properly growing the crystal is promoted.

Regarding the details of these, Japanese Patent Application No. 2-
142635 and 2-43791.

In the batch type manufacturing system using the tank 10, the desalting process is performed after the crystal growth process in the pre-ripening process for manufacturing the silver halide emulsion is completed.

This desalting step is a step of removing unnecessary substances (for example, K and Na) and excessive ions (for example, Ag, Br and Cl) generated in the emulsion grain formation in the pre-ripening step.

In this desalting step, various desalting methods such as a coagulation sedimentation method or a noodle method of washing with water and desalting, or an ultrafiltration method or an electrodialysis method of desalting by separation (membrane) can be used. .

When using, for example, a coagulation sedimentation method in this desalting step, the reaction solution which has undergone the pre-ripening step in the tank 10 shown in FIG. 22 is drawn out from the transfer pipe 24 and transferred to a desalting tank (not shown). Liquid, add a coagulating sedimentation agent to the reaction solution in the desalting tank and adjust the pH to coagulate sedimentation (spontaneous sedimentation) of the emulsion particles together with gelatin, discard the supernatant liquid containing unnecessary substances, and The desalting process is repeated 2 to 3 times by adding washing water to the desalting tank and then adjusting the pH to release the gelatin coagulation.

Further, in this batch type manufacturing system,
After finishing the desalting step in producing the silver halide emulsion, the post-ripening step is carried out. This post-ripening step is a step of sensitizing the emulsion sensitivity, which is low in the reaction solution after desalting, to a sensitivity suitable for practical use.

There are a chemical sensitization method and a spectral sensitization method as the sensitization method in the post-ripening step in this batch type manufacturing system. This chemical sensitization method is a method of increasing the intrinsic sensitivity of the emulsion. There are three types of typical chemical sensitization methods: sulfur sensitization method, gold sensitization method and reduction sensitization method.

When carrying out the process of this chemical sensitization method, the reaction solution which has undergone the desalting step is transferred to a tank having the same structure as the above-mentioned tank 10 as a reaction container (not shown), and is transferred into the tank. The chemical sensitizer is weighed and added to the stored reaction solution from the drug introduction tube, and the temperature is controlled by the temperature control means while stirring well with the stirring blade to make the chemical sensitizer uniform in the emulsion grains. It is processed so that a predetermined chemical reaction is completed evenly.

In the spectral sensitization method which is a sensitization method in the post-ripening step, when the emulsion is used as a color light-sensitive material, the photosensitive wavelength range is from the intrinsic sensitivity range of the emulsion of the reaction solution to that of light.
The primary colors are blue (400-500nm) and green (500-6)
00 nm) and red (600 to 700 nm) wavelength ranges.

This spectral sensitization method is generally carried out by adsorbing a sensitizing dye on an emulsion. Examples of the sensitizing dye used here include an ortho dye (for green) and a panchromatic dye (for red). . The sensitizing dye is dissolved in methanol to form a solution or a gelatin solid dispersion solution and added to the emulsion as a reaction solution.

The gelatin fixed dispersion solution is prepared in the preparatory step, but is temporarily stored in refrigeration and dissolved before use.

When the processing of this spectral sensitization method is carried out, the reaction solution which has undergone the desalting step is transferred to a tank (not shown) having the same structure as the above-mentioned tank 10 as a reaction container, and is transferred into the tank. A solution of a sensitizing dye dissolved in methanol or a gelatin solid dispersion solution of the sensitizing dye is stored in the stored reaction solution. (This gelatin fixed dispersion solution is prepared in the preparation step, but it is stored refrigerated temporarily and dissolved at the time of use. Of the chemical sensitizer is uniformly added to the emulsion grains by controlling the temperature with a temperature control means while thoroughly stirring the mixture with a stirring blade. Process so that it is adsorbed uniformly.

In this batch type manufacturing system, the process of the storing step is executed after finishing the post-ripening step in manufacturing the silver halide emulsion. This storage step is a step of storing the emulsion prepared in batch operation for the purpose of temporary storage for supplying it to the coating step in continuous operation.

Furthermore, at the same time as the function of temporary storage, the function of stopping the progress of ripening by cooling, the function of alleviating the difference between emulsion preparation batches by blending a plurality of batches of emulsions of the same variety, and the physical properties of the prepared emulsions. It also plays the role of quality assurance that measures and guarantees its performance.

Therefore, in the batch type manufacturing system,
The equipment for the storage process will consist of a cooling device, a blend tank, and a storage device. As a cooling device for stopping the progress of aging, there is a cooling device configured by a heat exchanger system using a plate heat exchanger or the like, or a vacuum cooling system cooling by latent heat of vaporization.

[0035]

In this batch type production system, in order to carry out the production process of a silver halide emulsion in one or a plurality of stages, a tank 10 as a batch type reaction tank device equipped with a stirrer is used. A plurality of large amounts of liquid chemicals for emulsion production introduced into the tank 10 by the magnetic stirring means 16 are forcibly mixed.

The tank 10 as a batch reaction tank apparatus equipped with this stirrer is suitable for large-scale emulsion production. However, a new liquid chemical is injected from the emulsion introducing pipe 22 into the liquid chemical for emulsion production stored in the tank 10, and a large number of liquid chemicals for emulsion production are introduced into the tank 10 and a large number of liquid chemicals for emulsion production are mixed with each other. When stirring and mixing with the stirring blade 12, the liquid chemical newly injected from the emulsion introduction pipe 22 stays in the tank 10 near the injection port of the emulsion introduction pipe 22 or circulates in the tank 10.

Therefore, in the initial state in which a large number of liquid chemicals for emulsion production of a plurality of types are agitated by the agitating blades 12 and mixing is started, introduction of emulsion in the liquid chemicals for emulsion production stored in the tank 10 is started. The liquid chemical newly injected from the inlet of the pipe 22 is mixed in high concentration with a part of the liquid chemical for emulsion production existing in the place where the liquid is circulated in the tank 10, and is distant from the inlet of the emulsion introducing pipe 22. It is unavoidable that the mixing concentration of the liquid chemical, which is separated from the newly injected liquid chemical and hits the portion where it is not circulated by the stirring blade 12, becomes low.

Therefore, when a large number of liquid chemicals for emulsion production of a plurality of types are stirred by the stirring blade 12, the newly injected liquid chemicals have begun to be mixed at a high concentration.
There may be a difference in history of chemical changes between the newly injected liquid chemical and the one whose mixing was started at a low concentration, and the compound generated in the entire tank 10 may become non-uniform.

Further, a dead space may be present in the details of the tank 10, or a non-uniform chemical reaction may occur due to a different flow when the emulsion manufacturing liquid chemical is stirred by the stirring blade 12.

At the same time, when a large amount of the liquid chemical for emulsion production in the tank 10 is heated by the temperature control means 18, the temperature control means 18 heats through the wall of the tank 10, so that when the heat treatment is started, the tank 10 is heated. The temperature distribution of the liquid chemicals for emulsion production in the tank 10 varies so that the liquid chemicals for emulsion production in the tank 10 are heated rapidly only near the wall of the tank 10 and the temperature does not rise in the central portion of the tank 10. Therefore, a history change may occur in the chemical change, and the compound produced in the entire tank 10 may become non-uniform.

Further, in the method of forming silver halide grains constituting a silver halide emulsion which is industrially used today, a dispersion medium solution (protective colloid aqueous solution) typified by gelatin may be stirred strongly. Then, there is a step of adding an aqueous silver nitrate solution and a halogenated saline solution and mixing them as rapidly as possible to form silver halide grains.

In the step of forming silver halide grains, the ionic reaction in which silver ions and halogen ions react to form silver halide is very fast. Therefore, in order to carry out a uniform reaction, these two ions It is essential that the solution be rapidly stirred and mixed in a short time.

Here, for example, when the silver salt aqueous solution and the halide aqueous solution are added to the dispersion medium in the tank 10 from the emulsion introducing tube 22 and the mixture is agitated by the stirring blade 12, the dispersion in the tank 10 is performed. A liquid chemical for emulsion production in which an aqueous solution of silver salt and an aqueous solution of halide are added to a medium is swirled by a stirring blade 12 rotating at high speed, and mixing by turbulent flow is performed in the process of subdividing the vortex. It will be.

Even in this case, the nucleus once generated is in the tank 1
It circulates in 0, so-called partial circulation (Local Rec
cycling) and the crystal growth of the nuclei occurs concurrently with the generation of the nuclei, making it difficult to generate monodisperse nuclei.

Further, in the field of silver halide photography, tabular silver halide grains having a large light receiving area are widely used as a photosensitive element. In order to increase the light receiving efficiency, thin tabular silver halide grains are preferred.

However, in the batch type production system using the tank 10 and the stirring blades 12 as described above, when stirring is performed by the stirring blades 12 to produce a silver halide emulsion, a tabular halogenation during growth is performed. The silver grains pass through a highly supersaturated region in the vicinity of the injection port of the emulsion introducing tube 22 to which silver ions or halide ions are added, and the thickness of the tabular grains tends to increase.

The tank 10 and the stirring blade 1 as described above are also provided.
In the batch type manufacturing system using
The shape of the stirring blade 12 is determined and the stirring state in the tank 10 is appropriately adjusted on the assumption that the amount of the silver halide emulsion produced at one time is constant. , If the preparation scale is changed to produce the desired emulsion amount, the emulsion performance may change and the preparation scale cannot be changed. Therefore, a predetermined amount of silver halide emulsion larger than the desired emulsion amount is produced. Therefore, there is a problem in that a loss occurs in that the excessively produced silver halide emulsion is discarded as a result.

On the other hand, when a newly developed silver halide emulsion newly developed using the experimental equipment is scaled up from a small production system using the experimental equipment to a production apparatus for mass production, an experiment for producing a small quantity is carried out. It is necessary to repeat trial production and product test many times in order to set the conditions for producing the same performance as the emulsion performance of the equipment with the new prescription silver halide emulsion produced by the production equipment for mass production. There is a problem that it takes a long time to develop a manufacturing system for production, and there is a large loss of raw materials consumed for product testing.

In view of the above facts, the present invention takes into account the above facts, and a large amount of liquid chemicals for emulsion production are stirred and mixed in a turbulent flow. In order to eliminate the above-mentioned disturbance factors and promote uniform chemical reaction in the liquid chemical for emulsion production, and to prevent the history of chemical changes from being different, all compounds produced have uniform emulsion performance. Alternatively, a silver halide photograph that enables easy scale-up from a small production system using experimental equipment to a production equipment for large-scale production, and enables emulsion production at the optimal production scale that matches the required production volume. The purpose of the present invention is to provide a new emulsion manufacturing apparatus.

[0050]

The apparatus for producing a silver halide photographic emulsion according to claim 1 of the present invention introduces a silver salt solution and a halide solution to produce silver ions and halogen ions. A reaction part in a two-liquid mixing microreactor for nucleation, which produces silver halide grains by a reaction, and a diffusion rate of silver ions and halogen ions in the two-liquid mixing microreactor for nucleation. 1.1 of the diffusion rate at the temperature of the reaction liquid supplied to
The temperature of the reaction liquid can be changed at a rate of 5 ° C. or more, preferably 10 ° C. or more per minute, more preferably 20 ° C. or more. The length of time obtained by dividing the volume calculated from the length and depth of the microchannel in the microreactor for mixing two liquids for nucleation and the flow rate is supplied to the microreactor. The diffusion rate of silver ions and halogen ions is increased by setting the heat exchange range for the reaction solution so that the length of heat exchange time is 5 times or less, preferably 2 times or less of the diffusion time at the temperature of the liquid to be reacted. And a temperature control unit configured to be provided.

With the above-mentioned structure, the diffusion coefficient is related to the temperature, and therefore the diffusion rate can be improved by raising the temperature. Accelerate the diffusion speed to the required speed to enable precise and efficient manufacturing,
Moreover, a silver halide photographic emulsion having uniform emulsion performance can be produced by a microreactor in which the silver halide nucleation reaction is controlled. Further, since a microreactor is used, it is possible to easily scale up from a small production system to a large production system, and further, it is possible to produce an emulsion at an optimal production scale corresponding to the required production amount.

In the apparatus for producing a silver halide photographic emulsion according to the second aspect of the present invention, water or a protective colloid aqueous solution is introduced from one flow path to make it flow in a laminar flow forming a thin layer for rectification, and silver is produced. The salt solution is introduced from the channel 2 to form a laminar flow that forms a thin layer of rectification, and is brought into contact with one contact interface in the laminar flow of water or the protective colloid aqueous solution to flow, and the halide solution is introduced from the channel 3 To make a laminar flow in a thin layer of rectification, and to flow as a thin rectification in a state where it contacts the other contact interface in the laminar flow of water or a protective colloid aqueous solution and does not directly contact the laminar flow of the silver salt solution. By the reaction, silver ions and halogen ions diffuse and move into water or a protective colloid aqueous solution to react with each other to generate silver halide nucleus particles, and a microreactor for three-liquid mixing for nucleation reaction, The diffusion rate of ions and halogen ions is 1.1 times or more, preferably 1.5 times or more, the diffusion rate at the temperature of the reaction solution supplied to the reaction part in the microreactor for mixing two liquids for nucleation. The temperature can be controlled to change to 5 ° C / min or more, preferably 10 ° C / min or more, more preferably 20 ° C / min or more so that the temperature of the reaction solution can be changed so that heat can be transferred, and nucleation is performed. The length of time obtained by dividing the volume calculated from the length and depth of the microchannel in the microreactor for mixing two liquids by the flow rate is 5 times or less than the diffusion time at the liquid temperature supplied to the microreactor. In order to accelerate the diffusion rate of silver ions and halogen ions by setting the heat exchange range for the reaction solution so that the heat exchange time is preferably twice or less. And having a temperature control means forms, the.

By configuring as described above, inside the three-liquid mixing microreactor for nucleation reaction,
Microscopically, by accelerating the diffusion rate of a single silver ion and a single halogen ion dispersed in water or an aqueous solution of protective colloid at an appropriate interval to a required speed, the pair can be precisely and efficiently paired. The silver halide nucleation reaction is controlled so that they meet and combine to form a nucleus. The nuclei of silver halide formed at this time can be spread by water or a protective colloid aqueous solution around the nuclei so that Ostwald ripening can be suppressed, so that nucleation reaction and grain growth reaction do not occur at the same time. As described above, the silver halide nuclei formed by the nucleation reaction are stably taken out, and then the grain growth reaction is appropriately promoted, whereby monodisperse silver halide emulsion grains can be finally produced. To do.
That is, it is possible to narrow the size distribution of the core particles so that only the crystals of the core particles have a desired single crystal structure, and to make the shape, size, and number of the core particles uniform. And the crystal shape and size distribution of the final particles can be made more uniform. Thus, the microreactor makes it possible to produce a silver halide photographic emulsion having uniform emulsion performance. Further, since a microreactor is used, it is possible to easily scale up from a small production system to a large production system, and further, it is possible to produce an emulsion at an optimal production scale corresponding to the required production amount.

The invention described in claim 3 is the apparatus for producing a silver halide photographic emulsion according to claim 1 or 2, wherein a microreactor for mixing two liquids for nucleation reaction,
Alternatively, a micro heat exchanger is connected so as to introduce a reaction liquid treated by a microreactor for mixing three liquids for nucleation reaction, and the reaction liquid introduced into the micro heat exchanger is heated at 5 ° C. or more per minute, preferably every It is characterized in that the aging reaction of nuclei in the reaction solution is stopped by cooling at a rate of 10 ° C. or more per minute, preferably 20 ° C. or more per minute, more preferably 40 ° C. or more per minute.

With the above-mentioned structure, the nucleation reaction of the nuclei in the reaction solution is stopped by the micro heat exchanger so that the nuclei produced are only those having a desired single crystal structure. In addition, the size distribution of the core particles is narrowed so that the size and number of core particles are made uniform. In addition, in the microreactor, the diffusion rate is improved by increasing the temperature of the treatment liquid, and after the ions start to diffuse near the interface where the two liquids come into contact, the ion farthest from this interface is present. It is possible to obtain a more uniform reaction product by reducing the time difference until the completion of diffusion. Furthermore, the temperature control means inside the microreactor heats the treatment liquid to a predetermined temperature to accelerate the diffusion rate of silver ions and halogen ions to a required rate, thereby performing the nucleation treatment precisely and efficiently. Here, the reaction between the silver ion and the halogen ion due to diffusion is a reaction that is performed at a very high speed, and reacts in the order of milliseconds. On the other hand, Ostwald ripening is a ripening reaction in which the resulting fine particles dissolve into molecules and are eaten by larger particles (host particles), and the reaction rate is about an order of magnitude slower than the ionic reaction. It is supposed to be. Therefore, in the microreactor, by heating the treatment liquid by the temperature control means, the nucleation reaction is accelerated and the particle formation time by diffusion is accelerated,
The time from the start of the first reaction to the end of the last reaction can be shortened. The Ostwald ripening reaction also proceeds here, but since the reaction rate is slow, when the reaction in the microreactor for the nucleation reaction and the particle growth reaction is completed, it is sent to the micro heat exchanger to change the temperature of the treatment liquid. It is possible to suppress the apparent Ostwald ripening reaction by performing a cooling process that is rapidly reduced. In this way, by making good use of the difference between the reaction rate of silver ions and halogen ions and the reaction rate of Ostwald ripening,
The nucleation reaction and the particle growth reaction can be performed precisely and efficiently.

According to a fourth aspect of the invention, in the apparatus for producing a silver halide photographic emulsion according to any one of the first to third aspects, a temperature control means or a micro heat exchanger is used.
It is characterized in that heating is possible such that the diffusion rate becomes 1.1 times or more within 5 seconds with respect to the diffusion rate of the reactive ion at the temperature before the reaction.

With the above-described structure, inside the two-liquid mixing microreactor for nucleation reaction or the three-liquid mixing microreactor for nucleation reaction,
Accelerate the silver halide nucleation reaction so that the diffusion rate of silver ion and halogen ion is increased to the required speed to form nuclei by efficiently binding to each other. Can be controlled.

[0058]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the apparatus for producing a silver halide photographic emulsion of the present invention will be described with reference to the accompanying drawings.

FIG. 1 is an overall schematic configuration diagram showing a manufacturing system according to a first embodiment of a silver halide photographic emulsion manufacturing apparatus of the present invention. The manufacturing system according to the first embodiment shown in FIG. 1 is a series in which a pre-ripening process (nucleation process, first growth process, and second growth process), a desalting process, and a post-ripening process are successively performed. As a manufacturing system for

Among these steps, two or more steps may be combined into one operation, one or more steps may be omitted from the manufacturing steps, or in order to obtain a desired emulsion. , So that multiple operations can be repeated during each stage,
You may comprise a 1 series manufacturing system.

In the series of production system for producing the silver halide photographic emulsion shown in FIG. 1, a pre-ripening step (nucleation treatment, first growth treatment and second
The growth process) and the post-ripening process are performed.

Here, when a microreactor is referred to in the present specification, "a microreactor is a three-dimensional structure used for performing mixing or mixing and chemical reaction, and is suitable for microtechnology on a solid substrate. A microreactor is produced by a process, and a microreactor is usually introduced by introducing a fluid from a channel (microchannel) having an equivalent diameter of 500 μm or less per introduction channel into a field where mixing or mixing and a chemical reaction are performed, A mixture or a mixture and a chemical reaction are carried out. "

Further, in the present specification, the microreactor includes a so-called micromixer (having a function of mixing fluids) as long as the structures are the same. Along with this, the term "micromixer" includes a microreactor, and the microreactor and the micromixer are recognized as the same.

In the present specification, the term "heat exchange microreactor" refers to "a heat exchange microreactor is a three-dimensional structure used for performing mixing, or mixing and chemical reaction, and is formed on a solid substrate. The heat exchange microreactor is manufactured by a suitable process of microtechnology, and usually, mixing or mixing and chemical reaction are performed from a flow path (microchannel) having an equivalent diameter of 500 μm or less per introduction path. A fluid is introduced into a place where it is carried out to carry out mixing, or a mixing and a chemical reaction, and further, a means for controlling the temperature of the fluid is provided for the purpose of controlling the mixing or the mixing and the chemical reaction. There is. ”

Further, in the present specification, the term "micro heat exchanger" means "a micro heat exchanger is a three-dimensional structure used for controlling the temperature of a fluid, and is a suitable three-dimensional structure on a solid substrate. The micro heat exchanger, which is manufactured by a process, usually has a flow path (micro channel) having an equivalent diameter of 500 μm or less per introduction path, and controls the temperature of the fluid passing through this flow path. It has a means. ”

As shown in FIG. 1, in one series of production systems for producing this silver halide photographic emulsion, the nucleation treatment in the preripening step is performed by the microreactor A30.

This microreactor A30 is constructed as a micromixer for simultaneously mixing three liquids. This microreactor A30 carries out a nucleation treatment in which a silver nitrate solution, a protective colloid solution and a halogen solution are simultaneously mixed to form a silver halide microcrystal dispersion in the protective colloid solution.

When the nucleation treatment is carried out by using this microreactor A30, microscopically, a single silver ion and a single halogen ion are bonded in a one-to-one relationship. By controlling the generation of heat generated at this time to suppress Ostwald ripening, the reaction for appropriately forming a desired nucleus can be stably performed.

The microreactor A30 is constructed so that it is automatically controlled by the controller based on the detection value detected by a detection sensor (not shown). The automatic control of the microreactor A30 by this controller is
A conventionally used potential control means for nucleation treatment or a means for controlling the nucleation treatment by detecting a physical quantity such as pH can be used.

By this nucleation process, nuclei 40 which are fine crystals of silver halide as shown in FIG. 2 are formed, and the process proceeds to the first growth process in the next pre-ripening step.

In this first growth treatment, the liquid chemical for emulsion production, in which fine crystals of silver halide are dispersed in the protective colloid solution, which is sent from the microreactor A30, is used in a micro control unit having a temperature control means. It is introduced into the heat exchange microreactor A32, which is a reactor, and temperature control and physical ripening are performed to bring the liquid chemical for emulsion production to a predetermined temperature suitable for nucleus growth in the first growth process. The microreactor A32 for heat exchange executes temperature control by exchanging heat between the liquid chemical for emulsion production and the temperature control medium introduced therein.

Using this heat exchange microreactor A32, a liquid chemical for emulsion production, in which silver halide nuclei are dispersed in a protective colloid solution, is introduced into the inside thereof, and heat exchange is performed with a temperature control medium. Thus, when the temperature control is performed, the heat energy is transferred in a trace amount of the liquid chemical for emulsion production forming a thin layer, so that the temperature rapidly changes to the target set temperature.

Therefore, the microreactor A3 for heat exchange is used.
When the temperature control is performed in 2, it can be said that the timing of the temperature change does not deviate between the minute amounts of the liquid chemicals for emulsion production, which form a thin layer. Therefore, it is generated due to the difference in the history of the temperature change. It is possible to prevent differences in the chemical substances used.

Further, the microreactor A3 for heat exchange
When the temperature control is performed at 2, heat energy is exchanged with a small amount of a liquid chemical for emulsion production flowing in a thin layer inside the microreactor A32 for heat exchange to produce an emulsion. The temperature change of the liquid chemical is completed.

Therefore, the microreactor A3 for heat exchange is used.
When the temperature control is performed at 2, it is possible to avoid a waiting time from the start to the completion of the temperature change of the liquid chemical for emulsion production. For example, when a large amount of liquid chemicals for emulsion production is stored in a large tank and heating is performed via the outer peripheral wall of the tank, a large amount of liquid chemicals for emulsion production in the large tank is determined by a predetermined amount. A long waiting time (waiting time on the order of time) is required until the temperature changes, but when the temperature control is executed by the heat exchange microreactor A32, this long waiting time (loss time)
Can be omitted, and the processing time can be greatly reduced. At the same time, when the temperature control is performed in the heat exchange microreactor A32, the speed of changing the temperature of the liquid chemical for emulsion production is high (the response of the temperature change is good), and there is no stagnant flow or reflux. Since the temperature control operation for the liquid chemical for emulsion production can be precisely controlled, it is suitable for use when the temperature is the controlling factor of the chemical change.

At this time, the nucleus 40, which is a fine crystal of silver halide as illustrated in FIG. 2, grows into the nucleus 42, which is a small crystal of silver halide.

Thus, the microreactor A for heat exchange is used.
Core 4 which is a small crystal of silver halide as a so-called host grain, which has been temperature-controlled and physically aged to a predetermined temperature in 32
Liquid chemicals for emulsion production containing 2 are microreactor B
Introduced into 34, a new silver nitrate solution and a halogen solution are mixed at the same time to promote Ostwald ripening, and the nucleus 42, which is a small crystal of silver halide as shown in FIG. The nucleus 44 is grown to proceed to the second growth process in the next pre-ripening step.

In this second growth treatment, the liquid chemical for emulsion production, in which the nucleus 44, which is a medium crystal of silver halide, is dispersed in the protective colloid solution, which is sent from the microreactor B34, is used, if necessary. The liquid chemical for emulsion production is introduced into a heat exchange microreactor (not shown) so that the temperature is controlled so that the liquid chemical for emulsion production has a predetermined temperature suitable for nucleus growth in the second growth treatment, and then introduced into the microreactor C36.

The microreactor C36 is constructed as a micromixer for simultaneously mixing two liquids. The microreactor C36 for mixing the two liquids comprises a liquid chemical for emulsion production in which the nucleus 44, which is a medium crystal of silver halide, is dispersed in the protective colloid solution, and the silver halide produced by the microreactor D38. A protective colloid solution containing microcrystal nuclei 40 is mixed at the same time to further promote Ostwald ripening, and the silver halide microcrystal nuclei 40 are consumed to produce silver halide as illustrated in FIG. A nucleus 44, which is a medium crystal, is grown into a nucleus 46, which is a large crystal of silver halide.

At this time, in the microreactor C36, the liquid chemical for emulsion production in which the nucleus 44 (host grain), which is a medium crystal of silver halide, is dispersed in the above-mentioned protective colloid solution, and the nucleus of this silver halide. Particles (host particles)
The newly supplied silver halide nuclei generated by the microreactor D38 to uniformly grow the silver halide nuclei inside the fine channels in the microreactor C36 (host particles). To cause the Ostwald ripening reaction, and uniformize the conditions until the silver halide nucleus particles (host grains) and the newly supplied silver halide nuclei meet at the same timing to end the reaction. The silver nuclei grains (host grains) can be uniformly grown.

This microreactor D38 has the same structure as the microreactor A30 described above.
Configured as a micromixer that mixes 3 liquids at the same time,
The silver nitrate solution, the protective colloid solution, and the halogen solution are mixed at the same time to perform a nucleation treatment to form a silver halide microcrystal dispersion in the protective colloid solution. The containing protective colloid solution is fed to the microreactor C36.

A liquid chemical for emulsion production, in which the nucleus 46, which is a large crystal of silver halide, is dispersed in the protective colloid solution which has undergone the second growth treatment in the pre-ripening step as described above, is prepared from the microreactor C36 as follows. To the desalination device 48 in the desalination process of FIG.

This desalting apparatus 48 is used in the formation of emulsion grains in a pre-ripening step from a liquid chemical for emulsion production by utilizing a commonly used coagulation-sedimentation method, noodle method, ultrafiltration method or electrodialysis method. A process of removing the unnecessary substances and ions existing in excess is performed. The treatment of the desalting step may be carried out in a microreactor configured to be able to separate unnecessary substances and excess ions.

The liquid chemical for emulsion production in which the nucleus 46, which is a large crystal of silver halide, is dispersed in the protective colloid solution which has been subjected to the desalting step in the desalting apparatus 48, is sent to the post-ripening step.

In this post-ripening step, the liquid chemical for emulsion production, in which the core 46, which is a large crystal of silver halide, is dispersed in the protective colloid solution, which is sent from the desalting apparatus 48, is used as the case requires. A chemical sensitization treatment for increasing the sensitivity of a liquid chemical for emulsion production in which a nucleus 46, which is a large crystal of silver halide, is dispersed by introducing it into a heat exchange microreactor (not shown) to increase its sensitivity to a practical level. The temperature is controlled so that the temperature becomes an appropriate predetermined temperature, and then the micro reactor A50 for addition is introduced.

Microreactor A50 for this addition
Is configured as a microreactor that simultaneously mixes two liquids. The microreactor A50 for this addition is prepared by simultaneously mixing a liquid chemical for emulsion production in which the nucleus 46, which is a large crystal of silver halide, is dispersed in the protective colloid solution and a chemical sensitizer, and halogenating the mixture. Nucleus 4 which is a large crystal of silver
6 is subjected to a sensitization process to form a chemically sensitized silver halide nucleus 52 as shown in FIG.

This chemical sensitization process is executed as a conventional sulfur sensitization process, gold sensitization process or reduction sensitization process.

When the chemical sensitizing process is carried out by doping the silver halide nucleus 46 with the chemical sensitizing agent using the microreactor A50 for addition, a single halogen is microscopically observed. A predetermined amount of each molecule for chemical sensitization is present in each crystal lattice in the silver halide nucleus 46 (for example, 1 for each crystal lattice).
Therefore, appropriate chemical sensitization treatment can be carried out.

Therefore, the microreactor A5 for addition
When 0 is used to carry out the chemical sensitization treatment, a crystal lattice in which the chemical sensitizing molecules are not doped occurs, or a crystal lattice in which the chemical sensitizing molecules are excessively doped occurs, or It is possible to prevent excess molecules for sensitization, and prevent waste of chemical sensitizers.

Further, in the post-ripening step, following the chemical sensitization treatment as shown in FIG. 2, the chemically sensitized silver halide nuclei 52 are dispersed by using a microreactor for addition (not shown). As shown in FIG. 2, the spectral sensitization process is performed to expand the light-sensitivity wavelength range for the liquid chemical for emulsion production from the intrinsic sensitivity range to the wavelength ranges of the three primary colors of light, blue, green, and red. A nucleus 54 of spectrally sensitized silver halide is formed.

This spectral sensitization treatment is a treatment which is conventionally carried out by mixing a solution of a sensitizing dye dissolved in methanol to adsorb the sensitizing dye to the silver halide nucleus 52.

Using this addition microreactor, a liquid chemical for emulsion production in which silver halide nuclei (particles) are dispersed in a protective colloid solution, and a spectral sensitizing dye in methanol When a spectral sensitization process is performed by simultaneously mixing with a sensitizer, the molecules of the spectral sensitizer are more uniform on the surface of a single silver halide nucleus (grain) when viewed microscopically. Therefore, it is possible to carry out an appropriate spectral sensitization process.

Therefore, when the spectral sensitization treatment is carried out using the addition microreactor, silver halide nuclei (particles) in which the spectral sensitization molecules are not adsorbed are generated,
Or nuclei of silver halide (particles in which molecules for spectral sensitization are in an excessively adsorbed state (multimolecular adsorption state in which molecules of spectral sensitizer are adsorbed in multiple layers on the surface of nuclei (particles) of silver halide) ) Is caused, or the molecules for spectral sensitization are not left, and the chemicals for spectral sensitization can be prevented from being wasted.

The solution of the silver halide photographic emulsion which has been subjected to the spectral sensitization treatment utilizes a microreactor for addition or the like (not shown) in the post-ripening step, and a stabilizer or the like is added in order to impart various required characteristics. Added.

In this silver halide photographic emulsion solution, the same action and effect can be obtained by using a mixing microreactor (not shown) and adding a stabilizer or the like to impart required characteristics. can get.

The silver halide photographic emulsion thus produced is subjected to temperature control so as to have a predetermined temperature suitable for storage, and then sent to a storage container (not shown) for refrigeration and a series of halogenation. Finished the production of silver photographic emulsion.

The apparatus for producing silver halide photographic emulsions constructed in series using the microreactor shown in FIG. 1 described above reproduces silver halide photographic emulsions having uniform and continuous performance little by little. It is a device for so-called fine chemicals, which is suitable for manufacturing with good properties.

Therefore, the apparatus for producing a silver halide photographic emulsion using this microreactor is equipped with a variety of silver halide photographic emulsion production apparatuses for studying the formulation in developing a new silver halide photographic emulsion in the laboratory. It is also suitable as an experimental device to be used when manufacturing and evaluating a required small amount by changing the composition of the drug.

Further, as shown in FIG. 19, the apparatus for producing silver halide photographic emulsions constructed in series using the microreactor shown in FIG. 1 has a different nucleation treatment (microreactor). It does not have to be a device utilizing the above), and a liquid chemical for emulsion production in which nuclei 42, which are small crystals of silver halide, are dispersed in a protective colloid solution which is separately prepared in advance. It may be configured such that it is introduced into the microreactor B (not shown) for the treatment, and the work is advanced to the subsequent second growth treatment, desalting step, and post-ripening step.

With such a constitution, a delicate nucleation treatment can be carried out by a special apparatus to form various nuclei as desired, and therefore, the degree of freedom in the method of producing a silver halide photographic emulsion can be increased. Can be expanded.

Further, the apparatus for producing a silver halide photographic emulsion, which is constructed in series using the microreactor according to the first embodiment described above, has a nucleation treatment,
The microreactor may be configured to perform at least one of the growth process, the second growth process, and the post-ripening process. That is, the apparatus for producing a silver halide photographic emulsion according to the first embodiment is a series of series production in which a microreactor and a batch reaction tank apparatus equipped with a stirrer and a temperature control means are mixed. It may be configured as a device.

Specific conditions for the apparatus for producing a silver halide photographic emulsion, which is constructed in series using the microreactor, include the following conditions. 1)
Flow rate range of liquid used for each microreactor 1 per minute
Microliter or more, preferably 1 milliliter or more per minute 2) Temperature range of working solution for each microreactor 5 ° C or more and 95 ° C or less, preferably 5 ° C or more and 75 ° C
3) Processing amount in a silver halide photographic emulsion manufacturing apparatus constructed as one series 1 minute or more per minute, preferably 1 milliliter or more per minute, more preferably 1 minute per minute.
0 ml or more 4) Method of connecting microreactor, micromixer, and micro heat exchanger Even if each microdevice is placed in direct contact with no space, each microdevice is fixed pipe or removable pipe. You may connect and arrange by. The pipe is a pipe made of metal, ceramic, glass, resin, or the like, or a composite material, and may be a pipe that is rigidly fixed or a pipe that can be detached flexibly. 5) Microreactor,
Liquid feeding method to micromixer Either continuous flow type or liquid (liquid plug) type can be used. Driving force can be either electric drive type or pressure drive type. Continuous production of silver halide photographic emulsion. In the case of, a continuous flow type pressure drive system is desirable. In that case, a commercially available ordinary pump can be used (eg, a syringe pump, a plunger pump or the like is used.) Here, as a method for quantitatively delivering liquid without pulsation, for example, JP-A-62-1826 is used.
23, JP-A-8-146543, and JP-A-2001-109.
092, JP 2001-113219 A, JP 2001-A1
The means described in 114397 can be used.

Next, regarding the second embodiment of the present invention,
This will be described with reference to FIGS. 3 to 5.

FIG. 3 is an overall schematic configuration diagram showing a production system according to the first configuration example of the second embodiment in the apparatus for producing a silver halide photographic emulsion of the present invention. This Figure 3
The manufacturing system according to the first configuration example shown in FIG. 2 uses a plurality of microreactors for each of the pre-ripening process (nucleation process, first growth process and second growth process) and post-ripening process. It aims to scale up the production scale. The number of parallel devices is 1 or more and 10000 or less,
Preferably, it is 1 or more and 100 or less.

In the apparatus for producing a silver halide photographic emulsion according to the first configuration example, silver halide is added to a protective colloid solution obtained by nucleating each of a plurality of microreactors (A1 to An) 30. The liquid chemicals for emulsion production in which the microcrystals are dispersed are accumulated in the liquid guiding pipe 56, and then again in the liquid guiding pipe 56, a plurality of microreactor A for heat exchange are used.
32 (the number of parallel devices is 1 or more and 10000 or less,
Preferably, it is distributed to 1 or more and 100 or less) and the temperature control process is executed.

Next, in the production apparatus of the first configuration example, the liquid chemicals for emulsion production, which have been temperature-controlled by the plurality of heat exchanging microreactors A32 and adjusted to a predetermined temperature, are integrated in the liquid guiding tube 56. Then, the liquid is introduced again into the plurality of microreactors (B1 to Bn) 34 by the liquid guiding tube 56, and the first growth process is executed.

Next, in the manufacturing apparatus of the first configuration example, the nucleus 44, which is a medium crystal of silver halide, is dispersed in the protective colloid solution by being subjected to the first growth treatment in the plurality of microreactors (B1 to Bn) 34. The obtained liquid chemicals for emulsion production are accumulated in the liquid guiding tube 56, and then distributed again to the plurality of microreactors (C1 to Cn) 36 by the liquid guiding tube 56 to be generated in the plurality of microreactors (D1 to Dn) 38. The second growth process is performed by mixing the liquid chemical for emulsion production described above.

Next, in the manufacturing apparatus of the first configuration example, the second growth process is performed in the plurality of microreactors (C1 to Cn) 36, and the nucleus 46, which is a large crystal of silver halide, is dispersed in the protective colloid solution. The liquid chemicals for emulsion production thus prepared are accumulated in the liquid guiding pipe 56 and introduced into the desalting device 48, and after desalting treatment is carried out, the liquid guiding pipe 56 is used again to carry out a plurality of addition microreactors (A1 to An). ) Distributor 50 and execute the post-ripening process.

In the apparatus for manufacturing a silver halide photographic emulsion according to the first configuration example thus configured, each of the pre-ripening step (nucleation processing, first growth processing and second growth processing) and the post-ripening step is performed. Since the accumulation and distribution of the liquid chemicals for emulsion production are repeated, the liquid chemicals for emulsion production are mixed and homogenized at the turning points of each step, so that the quality of the silver halide photographic emulsion finally produced is The performance can be made uniform.

The apparatus for producing a silver halide photographic emulsion constructed in this series includes a microreactor (A1 to An) 30, a heat exchange microreactor A32, and a microreactor (B1 to B1). B
n) 34, the microreactors (C1 to Cn) 36, the microreactors (D1 to Dn) 38, or the microreactors (A1 to An) 50 are appropriately set in accordance with the processing capacity, etc. By making the flow rate of the liquid chemical for emulsion production of (1) constant, the production system as a whole can be efficiently processed without stagnation.

Next, a second configuration example of the second embodiment will be described with reference to the overall schematic configuration diagram showing the manufacturing system in FIG. The manufacturing system according to the second configuration example shown in FIG. 4 includes the pre-ripening process (nucleation process, first growth process and second growth process) and the post-ripening process according to the first configuration example described above. In a configuration in which a plurality of microreactors are used to scale up the production scale, some of the steps or treatments can be separated and treated.

In the apparatus for producing a silver halide photographic emulsion according to the second configuration example, a plurality of heat exchanging microreactors A32 are used for temperature control treatment to introduce a liquid chemical for emulsion production adjusted to a predetermined temperature. The liquid is accumulated in the liquid pipe 56 and stored in the storage tank 58.

This storage tank 58 performs temperature control and stirring of the liquid chemical for emulsion production by using the temperature control means and the stirring means of the liquid chemical for emulsion production, if necessary. To be homogenized and can be stored under appropriate conditions.

Next, in the production apparatus of the second configuration example, the liquid chemical for emulsion production stored in the storage tank 58 is transferred to the plurality of microreactors (B1 to Bn) 34 by the liquid guiding tube 56 at a predetermined timing. It is configured to distribute and execute the first growth process.

The storage tank 58 may be installed at a required single or plural place during each process or process.

In the apparatus for producing a silver halide photographic emulsion according to the second configuration example thus configured, as shown in FIG. 4, a storage tank is provided between the nucleation process and the first growth process in the pre-ripening process. By installing 58, only the nucleation process is performed first, and the work is advanced so that the subsequent second growth process, post-ripening process, and desalting process are performed at appropriate times thereafter. You can

In this desalting step, the treatment liquids treated in the plurality of microreactors C36 may be integrated and treated in one desalting apparatus 48, or the individual desalination devices corresponding to the respective microreactors C36 may be treated. You may process with the salt apparatus 48.

The configuration, operation, and effect of the second configuration example of the second embodiment other than those described above are the same as those of the first configuration example of the first embodiment or the second embodiment described above. Therefore, detailed description thereof will be omitted.

Next, a third configuration example of the second embodiment will be described with reference to the overall schematic configuration diagram showing the manufacturing system in FIG. The manufacturing system according to the third configuration example shown in FIG. 5 uses a plurality of silver halide photographic emulsion manufacturing apparatuses configured in series in series using the microreactor shown in FIG. In a configuration for increasing the scale of production, some of the steps or processes can be processed separately.

In the apparatus for producing a silver halide photographic emulsion according to the third configuration example, nucleation processing was performed by a plurality of microreactors A30 provided in parallel, and the emulsion was sent out.
A liquid chemical for emulsion production, in which silver halide microcrystals are dispersed in a protective colloid solution, is introduced into each heat exchange microreactor A32, and each emulsion is subjected to temperature control treatment and adjusted to a predetermined temperature. The liquid chemicals for use are accumulated in the respective liquid guide tubes 56 and stored in the storage tank 58.

This storage tank 58 performs temperature control and stirring of the liquid chemical for emulsion production by using the temperature control means and the stirring means of the liquid chemical for emulsion production, if necessary. To be homogenized and can be stored under appropriate conditions.

Next, in the manufacturing apparatus of the third configuration example, the liquid chemicals for emulsion production stored in the storage tank 58 at a predetermined timing are supplied to the plurality of microreactors (B1 to Bn) 34 through the respective liquid guiding tubes 56. And the first growing process is performed.

The storage tank 58 may be installed in a required single or plural place during each process or process.

In the apparatus for manufacturing a silver halide photographic emulsion according to the third configuration example thus configured, as shown in FIG. 5, a storage tank is provided between the nucleation process and the first growth process in the pre-ripening process. By installing 58, it is possible to perform the work such that only the nucleation process is performed first, and then the second growth process and the post-ripening process are performed at appropriate times thereafter.

Further, in the apparatus for producing a silver halide photographic emulsion according to the third configuration example, a plurality of microreactors A30 provided in parallel and a heat exchange microreactor A32 forming a pair are each divided into a plurality of groups. , Nuclei having different performances are formed in each group, and the liquid chemicals for emulsion production containing the nuclei having different performances are accumulated in the respective liquid guiding pipes 56, accumulated in the storage tank 58, and blended for use.

Further, a uniform emulsion-producing liquid chemical containing nuclei having the same performance accumulated in the storage tank 58,
The plurality of microreactors B34, the microreactor C36, the microreactor D38, the desalting device 48, and the microreactor A50 for addition, which are provided in parallel, are supplied to each of a plurality of groups, and each group has a different second A silver halide photographic emulsion having different performances can be produced by carrying out the growth process, the post-ripening process, and the liquid preparation process.

Further, a plurality of silver halide photographic emulsion manufacturing apparatuses configured in series using the microreactor shown in FIG. 1 described above are used in parallel to increase the scale of production (see FIG. (Not shown), when a plurality of series single series are collected and used as one manufacturing system, the plurality of single series are divided into two or more groups,
The groups may be configured to produce silver halide photographic emulsions or other chemicals having different performances. In this case, the number of parallel sequences in one system is 1 or more and 10000 or less, preferably 1 or more and 100 or less. In addition, the number of parallel systems in multiple systems is 1
The number of lines is from 1 to 100, preferably from 1 to 100.

As a result, a plurality of apparatuses for producing silver halide photographic emulsions constituted in series in series are collected into one production apparatus, and the one production apparatus is divided into two or more groups. By simultaneously producing two or more types of emulsions in, it is possible to efficiently deal with the production of multiple kinds of emulsions.

By constructing the production system as described above, a large number of silver halide photographic emulsion production apparatuses constructed in series and in series can be effectively used.

Further, the manufacturing system is constructed such that only a required part of the manufacturing apparatus of the silver halide photographic emulsion constituted of a large number of series single series constituting the manufacturing system is utilized and only the processing corresponding thereto is performed. Partial effective use of can be achieved.

The configuration, operation and effect of the third configuration example of the second embodiment other than those described above are the same as those of the first configuration example of the first embodiment or the second embodiment described above. Therefore, detailed description thereof will be omitted.

Next, a structure for increasing the scale of production by using a plurality of silver halide photographic emulsion manufacturing apparatuses, which are constituted in series using the microreactor shown in FIG. 1 described above, in parallel (see FIG. (Not shown), the total amount of production can be controlled by the number of silver halide photographic emulsion manufacturing devices configured in series and single series that are used in parallel at the same time, and their operating time. High quality and high performance of photographic emulsion can be kept constant.

Therefore, when a desired amount of silver halide photographic emulsion is produced, for example, when it is desired to produce only a desired amount within a short period of time, a relatively large number of serially arranged single series silver halide photographs corresponding to the desired amount are produced. When it is desired to produce a desired amount within a long period by using an emulsion producing apparatus, a relatively small number of serially arranged single series silver halide photographic emulsion producing apparatuses are used. ,
High quality, high performance and uniform silver halide photographic emulsion can be produced.

In the case of producing a predetermined amount of silver halide photographic emulsion in a predetermined time, the production amount per unit and the predetermined production time in a silver halide photographic emulsion production apparatus constructed in series in a single series From the above, it is possible to determine the total number of silver halide photographic emulsion manufacturing apparatuses configured as a series of single series to be used, and to temporarily or permanently configure a so-called tailor-made manufacturing apparatus that satisfies these conditions. it can.

That is, by adjusting the number of so-called lines simultaneously used in parallel in a silver halide photographic emulsion production apparatus constituted in series of a single series and the production time, an arbitrary production amount can be obtained as a whole. It is possible to construct an assembly of silver halide photographic emulsion producing devices which are compatible and capable of producing a high-quality, high-performance and uniform silver halide photographic emulsion and which are constructed in series and in a single series.

As a result, as in the conventional case where a silver halide photographic emulsion is manufactured by a batch system using a large-capacity tank, only a certain large amount of silver halide photographic emulsion can be manufactured. The waste caused by having to discard the excess silver halide photographic emulsion,
It can be eliminated in the apparatus for producing a silver halide photographic emulsion, which is constituted of a series of single series according to the present embodiment.

Further, as in the conventional case where a silver halide photographic emulsion is manufactured in a batch system using a large capacity tank, the time required to complete one manufacturing operation is constant, In the apparatus for producing a silver halide photographic emulsion constituted by a series of single series according to the present embodiment, the flexibility is provided to shorten or lengthen the production time, and the production line is coordinated with other production lines. As a result, productivity can be improved.

Further, as in the conventional case where a silver halide photographic emulsion is manufactured by a batch system using a large capacity tank, the performance and performance of each silver halide photographic emulsion manufactured in a large capacity tank are improved. Compared with those having slightly different qualities, the apparatus for producing a series of silver halide photographic emulsions according to the present embodiment makes the performance and quality of all produced silver halide photographic emulsions uniform. can do.

Next, regarding the third embodiment of the present invention,
This will be described with reference to FIGS. 6 to 8.

FIG. 6 is a microreactor 60 for nucleation reaction and nucleation growth for carrying out a nucleation treatment in the grain formation of a silver halide emulsion in the pre-ripening step in the apparatus for producing a silver halide photographic emulsion of the present invention. It is a schematic diagram of the microreactor 62 for reaction control (corresponding to the processing of the microreactor A30 of FIG. 1).

A pair of microreactor 60 for nucleation reaction and microreactor 62 for controlling nucleation growth reaction are
To prevent nucleation reaction and grain growth reaction from occurring simultaneously during silver halide grain formation, the nucleation reaction and grain growth reaction during grain formation of the silver halide photographic emulsion are separated as much as possible, and the halogen formed by the nucleation reaction is separated. This is to enable the final production of monodispersed silver halide emulsion grains by appropriately taking out the core grains of the silver halide emulsion and then appropriately promoting the grain growth reaction.

Microreactor 6 for this nucleation reaction
Zero can be constructed by using a general microreactor for mixing two liquids.

Here, a microreactor 60 for nucleation reaction is provided with a first flow path through which a silver salt solution (fluid 1) is passed,
A second flow path is formed through which the halide solution (fluid 2) passes, and a part of these two flow paths is formed in contact with each other.

Further, in the microreactor 60 for the nucleation reaction, these two fluids 1 and 2 (silver salt solution and halide solution) form a substantially thin layer, and the adjacent fluids 1 and 2 ( An open interface is formed between the silver salt solution and the halide solution, and the thin layer thickness of these two fluids 1, 2 (silver salt solution and halide solution) is one layer in the direction normal to the contact interface. It becomes 1 to 900 μm per minute, and silver ions and halogen ions are moved to diffuse at the interface formed by the silver salt solution and the halogen salt solution to react with each other to continuously generate silver halide grains. Configure as a device.

Microreactor 6 for this nucleation reaction
At 0, nucleation is performed while flowing in a laminar flow in one direction,
So-called partial circulation (Local R)
It does not cause ecycling). Therefore, when the nucleation is performed, it is possible to prevent the so-called partial circulation (Local Recycling) in which the nuclei once generated circulate and flow to simultaneously grow.

Microreactor 6 for this nucleation reaction
When nucleation treatment is performed by using 0, microscopically, a single silver ion and a single halogen ion are bonded in a one-to-one relationship. By controlling the generation of heat generated at this time to suppress Ostwald ripening, the reaction for appropriately forming a desired nucleus can be stably performed.

The microreactor 62 for controlling the nucleation growth reaction is constructed as a general microreactor for mixing two liquids, like the microreactor 60 for the nucleation reaction.
A first flow path through which the reaction liquid sent from
A second channel is formed through which water or a protective colloid aqueous solution (fluid 2) is passed, and a part of these two channels is formed in contact with each other.

Further, the microreactor 62 for controlling the nucleus growth reaction is a silver halide nucleation reaction 60 which is caused by diffusion in the microreactor 60 for the nucleation reaction.
%, Preferably 90% or more, the reaction solution is introduced into the nucleation reaction control microreactor 62 so that the nucleation reaction microreactor 60 can be introduced.
It is installed by connecting to the processing solution discharge port.

The microreactor 62 for controlling the nuclear growth reaction is capable of instantaneously mixing the reaction liquid introduced from the first channel with the water or protective colloid aqueous solution introduced from the second channel. Water or a protective colloid aqueous solution is interposed between the core particles formed by the formation reaction to separate the core particles from each other.

As described above, when the distance between the nuclear particles immediately after the nucleation reaction is instantaneously separated by the microreactor 62 for controlling the nucleation reaction, the nucleation reaction and the particle growth reaction are prevented from occurring at the same time. And the grain growth reaction can be separated from each other. Therefore, it is possible to stably take out the core grains of the silver halide emulsion formed by the nucleation reaction, and then lead to the step of appropriately performing the grain growth reaction.

That is, the crystal of the nuclear particles is shown in FIG.
It becomes possible to narrow the size distribution of core particles so that only those having a desired single crystal structure exemplified in B, C, D or E, and to make the shape, size and number of core particles uniform. The growth reaction can be facilitated, and the crystal shape and size distribution of the final particles can be made more uniform.

The nucleation reaction microreactor 60 and the nucleation growth reaction control microreactor 62 perform heat exchange between the target fluid introduced inside and the temperature control medium introduced separately. By doing 3 per minute
The temperature control means is capable of controlling the temperature of the target fluid at a temperature of ℃, preferably 5 ℃ or more.

Thus, the microreactor 60 for nucleation reaction and the microreactor 62 for controlling nucleation growth reaction
In the case where (1) and (2) are configured, it is possible to more appropriately control the silver halide nucleation reaction by appropriately controlling the temperature when performing the silver halide nucleation reaction.

That is, an emulsion in which nuclei of silver halide are dispersed in a protective colloid solution is used by utilizing the microreactor 60 for controlling the nucleation reaction and the microreactor 62 for controlling the nuclei growth reaction provided with the temperature control means. When the liquid chemical for production is introduced into the microreactor 60 for nucleation reaction and heat is exchanged with the medium for temperature control, when the temperature control is performed, the liquid chemical for emulsion production is thin. Since heat energy is transferred in a trace amount forming a layer, the temperature rapidly changes to a target set temperature.

Therefore, when the temperature control means of the microreactor is used to control the temperature, it can be said that the timing of the temperature change does not deviate between the minute amounts of the liquid chemicals for emulsion production which form a thin layer. It is possible to prevent a difference in the chemical substances generated due to the difference in the history of the.

When the temperature control means of the microreactor is used to control the temperature, it can be said that the timing of the temperature change does not deviate between the minute amounts of the liquid chemicals for emulsion production which form a thin layer. It is possible to prevent a difference in the chemical substances generated due to the difference in the history of the. Furthermore, when temperature control is performed by the temperature control means of the microreactor, thermal energy is exchanged with a trace amount of liquid chemical for emulsion production flowing in a thin layer inside the microreactor, The temperature change of the liquid chemical for emulsion production is completed. Therefore, when the temperature control is performed by the microreactor temperature control means, it is possible to prevent a waiting time from the start to the completion of the temperature change of the emulsion manufacturing liquid chemical. For example, when a large amount of liquid chemicals for emulsion production is stored in a large tank and heating is performed via the outer peripheral wall of the tank, a large amount of liquid chemicals for emulsion production in the large tank is set to a predetermined value. Long waiting time before changing to temperature (waiting time of the order)
However, in the case of performing temperature control in a microreactor having a temperature control means, this long waiting time (loss time) can be omitted, and the processing time can be greatly shortened. Along with this, when temperature control is performed by the temperature control means of the microreactor, the rate of changing the temperature of the liquid chemical for emulsion production is high (the response of the temperature change is good), and there is no stagnant flow or reflux, Since the temperature control operation for the liquid chemical for emulsion production can be precisely controlled, it is suitable for use in the nucleation treatment of silver halide in which the temperature is the controlling factor of the chemical change.

Next, a configuration example shown in FIG. 7 in the third embodiment will be described. FIG. 7 is a microreactor 64 for nucleation reaction and a nucleation growth reaction control for performing a nucleation process in the grain formation of a silver halide emulsion in a pre-ripening step in the silver halide photographic emulsion manufacturing apparatus of the present invention. FIG. 3 is a schematic diagram of a microreactor 66 (corresponding to the processing of the microreactor A30 in FIG. 1) for use in the application.

Microreactor 6 for this nucleation reaction
4 is configured as a microreactor for mixing three liquids.

Here, the microreactor 64 for nucleation reaction is provided with a first flow path through which a silver salt solution (fluid 1) is passed,
A second flow path through which a halide solution (fluid 2) passes, and a third flow path through which water or a protective colloid aqueous solution that serves as an intermediate layer for preventing sudden contact between these two solutions (fluid 3) Are formed so that adjacent portions of these three flow paths are in contact with each other.

Furthermore, in the microreactor 64 for the nucleation reaction, these three fluids 1 and 2 (silver salt solution and halide solution) form substantially thin layers, and the adjacent fluids 1 and 2 are 3 (silver salt solution and halide solution and water or protective colloid solution) forms an open interface between adjacent three fluids 1, 2 and 3 (silver salt solution and halide solution and water or protective colloid). The thickness of the thin layer of the aqueous solution) is 1 to 900 μm per layer in the normal direction of the contact interface, and the thickness of the intermediate layer is water or a protective colloid aqueous solution provided between the silver salt solution and the halogen salt solution. The silver ion and the halogen ion are diffused and moved, and the silver ion and the halogen ion react with each other, whereby the silver halide grains are continuously produced.

Microreactor 6 for this nucleation reaction
In No. 4, nucleation is performed while flowing in a laminar flow in one direction,
So-called partial circulation (Local R)
It does not cause ecycling). Therefore, when the nucleation is performed, it is possible to prevent the so-called partial circulation (Local Recycling) in which the nuclei once generated circulate and flow to simultaneously grow.

Microreactor 6 for this nucleation reaction
When the nucleation treatment is carried out by using No. 4, microscopically, a single silver ion and a single halogen ion are bonded one to one. By controlling the generation of heat generated at this time to suppress Ostwald ripening, the reaction for appropriately forming a desired nucleus can be stably performed.

Further, the microreactor 66 for controlling the nucleus growth reaction is the same as that of the silver halide nucleation reaction 60 caused by diffusion in the microreactor 64 for the nucleation reaction.
%, Preferably 90% or more, when the reaction solution is introduced into the microreactor 66 for controlling the nuclear growth reaction, the microreactor 64 for the nucleation reaction.
It is installed by connecting to the processing solution discharge port.

The microreactor 66 for controlling the nuclear growth reaction has the action of instantaneously mixing the reaction solution introduced from the first channel with the water or protective colloid aqueous solution newly introduced from the second channel. Further, a large amount of water or an aqueous protective colloid solution is further interposed between the core particles formed by the nucleation reaction to perform a treatment for separating the core particle distance.

As described above, when the microreactor 66 for controlling the nuclei growth reaction instantly separates the distance between the nuclei particles immediately after the nucleation reaction by a relatively large distance, the nucleation reaction and the particle growth reaction are prevented from occurring at the same time. Since the nucleation reaction and the grain growth reaction can be sufficiently separated, it is possible to stably take out the nuclei grains of the silver halide emulsion formed by the nucleation reaction and then lead to the step of appropriately performing the grain growth reaction. it can.

The nucleation reaction microreactor 64 and the nucleation growth reaction control microreactor 66 exchange heat between the target fluid introduced inside and the temperature control medium introduced separately. By doing 3 per minute
The temperature of the target fluid can be controlled at a temperature of ℃, preferably 5 ℃ or more.

As described above, the microreactor 64 for nucleation reaction and the microreactor 66 for controlling nucleation growth reaction are provided.
In the case where (1) and (2) are configured, it is possible to more appropriately control the silver halide nucleation reaction by appropriately controlling the temperature when performing the silver halide nucleation reaction.

Next, the configuration example shown in FIG. 8 in the third embodiment will be described. FIG. 8 is a microreactor 68 for pretreatment and a nucleation reaction for performing a nucleation treatment in grain formation of a silver halide emulsion in a preripening step in the apparatus for producing a silver halide photographic emulsion of the present invention. FIG. 3 is a schematic diagram of the microreactor 70 (corresponding to the processing of the microreactor A30 in FIG. 1).

A pair of the pretreatment microreactor 68 and the nucleation reaction microreactor 70 is shown in FIG.
As in the case of the constitution shown in FIG. 7, the nucleation reaction and the grain growth reaction during the grain formation of the silver halide photographic emulsion are performed so that the nucleation reaction and the grain growth reaction do not occur simultaneously during the formation of the silver halide grain. It is possible to manufacture monodisperse silver halide emulsion grains by separating them as much as possible, stably extracting the nucleus grains of the silver halide emulsion formed by the nucleation reaction, and then appropriately promoting the grain growth reaction. It is for that.

The pretreatment microreactor 68 and the nucleation reaction microreactor 70 can be constructed by using general microreactors for mixing two liquids.

Here, the pretreatment microreactor 6 is used.
8 forms a first flow path for passing a halide solution (fluid 1) and a second flow path for passing water or a protective colloid aqueous solution (fluid 2), and a part of these two flow paths contact each other. To be formed.

Further, the microreactor 68 for pretreatment
These two fluids 1, 2 (halide solution and water or protective colloid solution) each form a substantially thin layer,
And an open interface is formed between adjacent fluids 1 and 2 (halide solution and water or protective colloid aqueous solution), and a thin layer thickness of these two fluids 1 and 2 (halide solution and water or protective colloid aqueous solution) However, 1 layer to 1 to 900 μm per layer in the normal direction of the contact interface, the halogen salt particles move to the interface formed by the halogen salt solution and water or the protective colloid aqueous solution, and water or the protective colloid aqueous solution is formed between the halogen salt particles. It is configured as a device for interposing and separating the distance between the halogen salt particles to diffuse them.

The microreactor 70 for nucleation reaction is constructed as a general microreactor for mixing two liquids, and is a first through which the mixed liquid (fluid 1) sent from the microreactor 68 for pretreatment is passed. And a second flow path through which the silver salt solution (fluid 2) passes, and the two flow paths are formed so that parts of these two flow paths are in contact with each other.

Further, in the microreactor 70 for the nucleation reaction, the two fluids 1 and 2 (a mixture of a halide solution with water or a protective colloid solution and a silver salt solution) are substantially thin layers. And an open interface is formed between adjacent fluids 1 and 2 (a mixture of a halide solution with water or a protective colloid aqueous solution, and a silver salt solution). A mixture of water or a protective colloid aqueous solution and a thin layer of a silver salt solution) has a thickness of 1 to 900 μm per layer in the normal direction of the contact interface, and the halide solution is mixed with water or a protective colloid aqueous solution. Nuclei formed by the nucleation reaction by moving silver ions and halogen ions so that they migrate to the interface formed by In a state that is interposed water or the aqueous protective colloid solution are pulled apart the distance between the core particles during the child constitutes silver halide grains as a continuously produced devices.

Microreactor 7 for this nucleation reaction
At 0, nucleation is performed while flowing in a laminar flow in one direction,
So-called partial circulation (Local R)
It does not cause ecycling). Therefore, when the nucleation is performed, it is possible to prevent the so-called partial circulation (Local Recycling) in which the nuclei once generated circulate and flow to simultaneously grow.

Further, the pretreatment microreactor 68 and the nucleation reaction microreactor 70 exchange heat between the target fluid introduced inside and the temperature control medium introduced separately. The temperature of the target fluid can be controlled at a rate of 3 ° C./minute, preferably 5 ° C. or more.

As described above, the pretreatment microreactor 6 is used.
When 8 and the microreactor 70 for nucleation reaction are configured, the temperature of the silver halide nucleation reaction is appropriately controlled to more accurately control the silver halide nucleation reaction. be able to.

Next, the chemical matters used in the apparatus for producing a silver halide photographic emulsion of the present invention will be described.

The above-mentioned halide salt solution used in the present invention is usually an aqueous solution of potassium bromide, sodium bromide, potassium chloride, sodium chloride, potassium iodide, sodium iodide and a mixture thereof.

When the silver halide grains obtained by the method of the present invention are used as nuclei, the concentration of the aqueous solution is 4 mole / L.
The following is preferred, 1 mole / L or less is more preferred, and 0.2 mole / L or less is most preferred. When used for crystal growth, it is preferable to use a high-concentration aqueous solution from the viewpoint of productivity. 0.5 mole / L or more 4mo
le / L or less is preferable, and 1.0 mol / L or more is more preferable. The temperature of the aqueous solution is preferably 5 ° C or higher and 95 ° C or lower, more preferably 5 ° C or higher and 75 ° C or lower.

At least one of the silver salt solution and the halide salt solution of the present invention preferably contains gelatin as a protective colloid. Since gelatin has a great influence on the probability of twinning in the silver halide grains produced, the preferred concentration of the aqueous gelatin solution varies depending on the intended use of the fine silver halide grains produced.

When the continuously produced silver halide grains are used as nuclei for the preparation of tabular silver halide grains, a parallel double twin crystal sheet is required, so that a desired twinning probability is achieved. Therefore, it is necessary to adjust the gelatin aqueous solution concentration. When the aqueous silver salt solution and the aqueous halide salt solution are mixed, the amount of gelatin per 1 g of silver is 0.03 g.
The gelatin concentration is preferably selected so as to be 0.4 g or less, more preferably 0.3 g or less.

When silver halide grains that are continuously produced are used as nuclei for preparing normal crystal grains, it is necessary to minimize the probability of twinning, so that it is necessary to increase the gelatin concentration during nucleation. The amount of gelatin per 1 g of silver nitrate is 0.4 g or more (the upper limit is not particularly limited, but is preferably 50 g or less), more preferably 1 g or more, and further preferably 5 g or more.

The fine grain silver halide emulsion obtained by the present invention can be used at the time of crystal growth of silver halide grains. When used for crystal growth, it is preferable that the added silver halide fine particles be rapidly dissolved. For that purpose, it is preferable that the number of twins is small, so that the concentration of the aqueous gelatin solution is preferably high. The concentration of gelatin aqueous solution is 0.2 g or more and 1 g or less with respect to 1 g of silver nitrate added,
The concentration is preferably such that gelatin is added, and
It is more preferably 3 g or more, and most preferably 0.4 g or more.

When the concentration of the gelatin aqueous solution is increased, the viscosity of the gelatin aqueous solution increases and it becomes difficult to add the gelatin aqueous solution. The viscosity can be lowered by lowering the molecular weight of gelatin by a method such as enzymatic decomposition. The molecular weight of gelatin is 50
It is preferably 00 or more and 100,000 or less, more preferably 50,000 or less, and most preferably 30,000 or less. When utilized for crystal growth, gelatin added with silver halide grains affects the thickness of tabular silver halide grains. The effect on thickness can be varied by chemical modification of gelatin. In order to obtain thin tabular silver halide grains, oxidation treatment, succination treatment, and trimellitization treatment can be preferably used.

The mixing for forming the silver halide grains in the present invention is not the above-mentioned conventional mixing by turbulence but the mixing utilizing laminar flow. In the mixing of the present invention, the silver nitrate solution and the halide solution are subdivided into thin layers (Lamela) and brought into contact with each other over a wide area to uniformly diffuse ions in a short time. Achieve faster and more uniform mixing. Ion migration due to diffusion is related to the temporal change in temperature Fi
According to ck's law, the terms of diffusion coefficient and temperature gradient are given by the following equation.

T to dl ² / D where D is the diffusion constant and d
1 represents the thickness of the thin layer, and t represents the mixing time.

From the above equation, the mixing time t is the thin layer thickness dl.
The mixing time can be shortened very effectively by making this layer thin because it is proportional to the square of.

The present invention is based on the IMM (Institute
The expected effect can be realized by using a microreactor manufactured by fur Mikrotechnik Mainz. For more information on microreactors, see “Microre
actor ”(W. Ehrfeld, V. Hesse
1, H. Loewe, 1 Ed. (2000) WILEY
-VCH) in chapter 3 and micro heat exchangers in chapter 4 for details. That is, it has the principle of multi-layer thinning of fluid and subsequent diffusion mixing. The fluids of the silver salt solution and the halide solution are divided into a large number of thin film fluids by passing through slits having a thickness of the order of several tens of microns, and at the outlet of the slits, they are aligned in the normal direction of their traveling direction. The silver ions and the halogen ions are immediately diffused in contact with each other over a wide area, the mixing due to the diffusion is completed within a short time, and silver halide fine particles are formed by an ionic reaction that occurs at the same time.

The reaction in the present invention is carried out while flowing in the channel, that is, in the flow.

The thickness of the thin layer in the present invention is 1 μm or more and 900 μm or less, preferably 1 μm or more and 300 μm or less in the direction normal to the traveling direction. The mixing time in the present invention using laminar flow varies depending on the diffusion time of the reactants, but is within 2 minutes, more preferably within 60 seconds.

The microreactor used in the present invention is an apparatus having channels (microchannels) having an equivalent diameter of 500 μm or less per one introducing channel. In the present invention, the equivalent diameter (equalent diameter)
ter) is also called an equivalent (straight) diameter, and is a term used in the field of mechanical engineering. When a circular pipe equivalent to a pipe having an arbitrary cross-sectional shape (flow hole in the present invention) is assumed, the diameter of the equivalent circular pipe is referred to as an equivalent diameter, A: cross-sectional area of the pipe,
P: deq = 4 using the wet edge length (perimeter) of the pipe
It is defined as A / p. When applied to a circular pipe, this equivalent diameter corresponds to the circular pipe diameter. The equivalent diameter is used to estimate the flow or heat transfer characteristics of the pipe based on the data of the equivalent circular pipe, and represents the spatial scale (representative length) of the phenomenon. The equivalent diameter is deq = 4 for a square tube with one side a.
a ² / 4a = a, deq = a / for an equilateral triangular tube with one side a
3 ^1/2 , flow height h between parallel plates deq = 2h
(Reference: “Mechanical Engineering Encyclopedia” edited by The Japan Society of Mechanical Engineers)
Maruzen Co., Ltd., 1997.

The length of the channel used in the present invention is not particularly limited, but it is preferably 1 mm to 1000 mm,
Particularly preferably, it is 10 mm to 500 mm.

The number of channels used in the present invention does not have to be one, and any number of channels can be arranged in parallel (Numbering-up) to increase the throughput.

The flow channel of the present invention is formed on a solid substrate by microfabrication technique. Examples of materials used include metals, silicon, Teflon (R), glass, ceramics or plastics. When heat resistance, pressure resistance and solvent resistance are required, preferred materials are metals, silicon, Teflon (R), glass or ceramics, but metals are particularly preferred. Examples of the metal include nickel, aluminum, silver, gold, platinum, tantalum, stainless steel, Hastelloy (Ni-Fe alloy) or titanium.
Preferred are stainless steel, hastelloy, and titanium, which have high corrosion resistance. In a conventional batch type reaction apparatus, an apparatus having a metal (stainless steel or the like) surface glass-lined is used when handling an acidic substance, but a microreactor or a metal surface may be glass-coated. Not limited to glass, another metal or another material may be coated on the metal depending on the purpose, or a material other than the metal (for example, ceramic) may be coated with the metal or glass.

As a typical microfabrication technique for forming a flow path, there is L using X-ray lithography.
IGA technology, high aspect ratio photolithography method using EPON SU-8, micro electric discharge machining method (μ-E
DM), deep RIE, high aspect ratio silicon processing method, hot embossing method, stereolithography method,
There are a laser processing method, an ion beam processing method, and a mechanical micro cutting method using a micro tool made of a hard material such as diamond. These techniques may be used alone or in combination.
The preferred microfabrication technique is L using X-ray lithography.
IGA technology, high aspect ratio photolithography method using EPON SU-8, micro electric discharge machining method (μ-E
DM), and mechanical micromachining methods.

Joining techniques are often used in assembling the microreactors of the present invention. Ordinary joining techniques are roughly divided into dendritic joining and liquid joining, and commonly used joining methods include pressure welding and diffusion joining as solid-state joining, welding as eutectic joining, eutectic joining, soldering, Adhesion is a typical joining method. Furthermore, at the time of assembly, it is desirable to use a highly precise bonding method that maintains the dimensional accuracy without damaging the microstructure such as the flow of material due to high temperature heating or the large deformation, and the direct silicon bonding is the technique. Anodic bonding, surface activated bonding, direct bonding using hydrogen bonding, H
There are bonding using F water solution, Au-Si eutectic bonding, and void-free bonding.

The flow path of the microreactor of the present invention may be surface-treated depending on the purpose. Particularly when operating an aqueous solution, adsorption of a sample to glass or silicon may be a problem, so surface treatment is important. For fluid control in micro-sized channels, it is desirable to achieve this without incorporating moving parts that require complex fabrication processes. For example, it becomes possible to create a hydrophilic region and a hydrophobic region in the channel by surface treatment and to manipulate the fluid by utilizing the difference in surface tension acting on the boundary.

In order to introduce and mix reagents, samples, etc. into the micro-sized channel of the microreactor,
Fluid control function is required. In particular, the behavior of the fluid in the micro area has a property different from that of the macro scale, so that a control method suitable for the micro scale must be considered. The fluid control methods include a continuous flow method and a droplet (liquid plug) method when classified by form, and an electric drive method and a pressure drive method when classified by a driving force. These schemes are described in detail below. The most widely used form of handling fluid is the continuous flow system. In continuous flow type fluid control, it is general that the entire flow path of the microreactor is filled with fluid, and the entire fluid is driven by a pressure source such as a syringe pump provided outside. In this case, one advantage is that a control system can be realized with a relatively simple setup, but it is difficult to perform operations involving multiple steps of reaction and sample exchange, and the system configuration has a low degree of freedom, and the behavior is low. Since the medium is a solution itself, there is a drawback that the dead volume is large. As a method different from the continuous flow method, there is a droplet (liquid plug) method. In this method, droplets partitioned by air are moved inside the reactor or in a flow path leading to the reactor, and each droplet is driven by air pressure. At that time, a vent structure that allows air to escape between the droplet and the channel wall or between the droplets as necessary, and a valve structure that keeps the pressure in the branched channel independent of other parts Etc. must be prepared inside the reactor system. Further, in order to control the pressure difference and operate the liquid droplets, it is necessary to construct a pressure control system composed of pressure stagnation and a switching valve outside. In this way, in the droplet method, the device configuration and the reactor structure become slightly complicated,
It is possible to perform multi-stage operations such as operating a plurality of droplets individually and performing some reactions in sequence, and the degree of freedom in system configuration is increased.

As a drive system for controlling fluid, an electric drive method in which a high voltage is applied to both ends of a flow channel (channel) to generate an electroosmotic flow, and thereby a fluid is moved, and a pressure stagnation is prepared outside. Generally, a pressure drive method in which a fluid is moved by applying pressure is widely used. The difference between the two is that, for example, as the behavior of the fluid, the flow velocity profile in the cross section of the flow passage has a flat distribution in the case of the electric drive method, whereas in the pressure drive method, the flow passage has a hyperbolic shape with a central portion of the flow passage. It is known that the distribution is fast and the wall surface has a slow distribution, and the electric drive method is more suitable for the purpose of moving the sample plug while keeping the shape. When the electrical disturbance method is used, it is necessary to fill the inside of the flow path with the fluid, and therefore, there is no choice but to adopt the form of the continuous flow method, but the fluid can be operated by electrical control. Therefore, for example, a relatively complicated process of creating a temporal concentration gradient is realized by continuously changing the mixing ratio of two kinds of solutions.
In the case of the pressure drive system, there is almost no effect on the substrate because it can be controlled regardless of the electric ladle of the fluid and it is not necessary to consider side effects such as heat generation and electrolysis. , Its application range is wide. On the other hand,
It is necessary to automate complicated processing such as having to prepare an external pressure source and changing the response characteristics of the operation according to the size of the dead volume of the pressure system.

The method used as the fluid control method is appropriately selected depending on the purpose, but a continuous flow type pressure drive method is preferable.

The temperature control of the microreactor may be carried out by putting the entire apparatus in a temperature-controlled container, or by heating a metal resistance wire or a heater structure such as polysilicon in the apparatus and heating it. This may be used, and for the cooling, the natural cycle may be used for the thermal cycle. For temperature sensing, another resistance wire, which is the same as the heater, is built in the metal resistance wire, temperature is detected based on the change in the resistance value, and detection is performed using a thermocouple for polysilicon. Also, heating and cooling may be performed from the outside by bringing the Peltier element into contact with the reactor. Which method is used is selected according to the application and the material of the reactor body.

Since the configuration, operation and effect of the third embodiment other than those described above are the same as those of the first embodiment, detailed description thereof will be omitted.

Next, regarding the fourth embodiment of the present invention,
This will be described with reference to FIG.

FIG. 9 shows a side arm charging method for carrying out the nucleation treatment in the grain formation of the silver halide emulsion in the pre-ripening step relating to the apparatus for producing a silver halide photographic emulsion of the present invention. Microreactor 72 and mixer 7
FIG. 4 is a schematic diagram illustrating a configuration in which 4 and 4 are provided.

As shown in FIG. 9, in the side arm charging method, a tank 76 is used as a reaction container (which may be a reaction tank for growing particles). This tank 76
For example, the batch type reaction tank device is equipped with a stirrer capable of processing a large amount of liquid such as 1000 l (1 t) at a time.

The tank 76 is equipped with a stirring blade 80 which is rotationally driven by the rotational driving force of a motor 78 in order to stir the solution filled inside.

Further, on the outer peripheral surface of the tank 76, temperature control means 82 for heating or cooling the reaction solution is arranged in order to control the temperature of the solution filled inside. The temperature control means 82 includes, for example, a heat exchange medium (water, water,
It is configured by using means for heating or cooling by flowing steam, liquid organic matter, flame gas, etc. or means for controlling temperature by installing an element for electrically heating or cooling in the temperature control section.

A circulation system in which the solution in the tank 76 is taken out from the bottom of the tank 76, is sent by the pump 84, is discharged to the liquid surface side of the tank 76 through the mixer 74, and is returned into the tank 76. Then, the side arm conduit 86 is attached.

It is desirable that the side arm conduit 86 be able to completely mix the additive solution with the solution in the tank 76 in the shortest possible time, and it is long enough to mix the additive solution with the solution in the tank 76. It is not preferable that it takes time, the added liquid circulates inside the side arm pipe 86 or the mixer 74, or partially circulates at a certain portion. Therefore, a large-capacity pump 84 is attached to the side arm conduit 86 to allow the solution in the tank 76 to flow at a relatively large flow rate.

The mixer 74 attached to the side arm conduit 86 is a channel for supplying the mixer 74 from the tank 76 in the side arm conduit 86 provided outside the system of the tank 76 and returning to the tank 76 again. A part and a flow path for supplying water or a protective colloid aqueous solution in which nuclei, which are small crystals of silver halide generated in the microreactor 72 for nucleation treatment, are dispersed to a part of this flow path To do.

Further, the mixer 74 uses a mechanical stirring means or a static stirring means (may be configured as a microreactor for mixing), and a halogen solution is added to a solution flowing in a large amount through the side arm conduit 86. A liquid in which nuclei, which are small crystals of silver halide, are dispersed can be mixed on average and instantaneously without causing partial circulation.

The microreactor 72 for the nucleation treatment for supplying the liquid in which the nuclei, which are the small crystals of silver halide, which is the additive liquid, are supplied to the mixer 74 is the nucleation process illustrated in FIG. The microreactor 64 for reaction has the same configuration.

Microreactor 7 for this nucleation reaction
2 is configured as a microreactor for mixing three liquids.

Here, the microreactor 72 for the nucleation reaction is provided with a first flow path through which the silver salt solution (fluid 1) passes,
A second flow path through which a halide solution (fluid 2) passes, and a third flow path through which water or a protective colloid aqueous solution that serves as an intermediate layer for preventing sudden contact between these two solutions (fluid 3) Are formed so that adjacent portions of these three flow paths contact each other.

In order to process the required amount of liquid in the microreactor 72, a plurality of microreactors 72 are used to achieve the required amount of processing.

Furthermore, in the microreactor 72 for the nucleation reaction, these three fluids 1 and 2 (silver salt solution and halide solution) each form a substantially thin layer, and the adjacent fluids 1 and 2 are 3 (silver salt solution and halide solution and water or protective colloid solution) forms an open interface between adjacent three fluids 1, 2 and 3 (silver salt solution and halide solution and water or protective colloid). The thickness of the thin layer of the aqueous solution is 1 to 900 μ in the normal direction of the contact interface.
In the range of m, it is preferably 1 μm or more and 300 μm or less. Silver halide grains are produced by the diffusion and migration of silver ions and halogen ions to the intermediate layer, which is water or a protective colloid solution provided between the silver salt solution and the halogen salt solution, and the silver ions react with the halogen ions. Is configured as a device for continuously generating.

Microreactor 7 for this nucleation treatment
In No. 2, the mixing time using the laminar flow is within 2 minutes, more preferably within 60 seconds.

Microreactor 7 for this nucleation reaction
In 2, nucleation is performed while flowing in a laminar flow in one direction,
So-called partial circulation (Local R)
It does not cause ecycling). Therefore, when the nucleation is performed, it is possible to prevent the so-called partial circulation (Local Recycling) in which the nuclei once generated circulate and flow to simultaneously grow.

When carrying out the growth process of nuclei by this side arm charging method, from the emulsion introduction tube into the tank 76,
A predetermined amount of a dispersion medium aqueous solution containing at least a dispersion medium and water is injected. Further, the motor 78 is driven to drive the stirring blade 80.
The temperature control means 82 drives the reaction solution in the tank 76 to rotate within a predetermined temperature range (for example, 5).
The temperature is controlled so as to keep the temperature within the range of ℃ to 45 ℃), for example, nuclei of fine tabular grains including parallel twin planes can be formed, and the pump 84 is driven to disperse in the side arm conduit 86. Set the circulating aqueous solution.

When performing the nucleation treatment by this side arm charging method, the microreactor 72 for the nucleation treatment is used.
The water or protective colloid aqueous solution in which nuclei, which are small crystals of silver halide, are dispersed by the mixer 74,
Since it is rapidly mixed in the aqueous dispersion medium solution in the tank 76,
By interposing a dispersion medium aqueous solution together with water or a protective colloid aqueous solution between the nuclear particles formed by the nucleation reaction to further separate the distance between the nuclear particles so that the nucleation reaction and the particle growth reaction do not occur at the same time. The formed silver halide emulsion core grains can be stably stored in the tank 76.

As a result, the size distribution of the core particles can be narrowed, and the shape, size, and number of the core particles can be made uniform, the growth reaction can be easily performed in the subsequent processing steps, and the crystal shape of the final particles can be facilitated. The size distribution can be made more uniform. For example, it is possible to obtain a silver halide photographic emulsion having tabular grains having a high aspect ratio and a narrow grain size distribution.

Although not shown, in the fourth embodiment, in place of the microreactor 72 and the mixer 74 for the nucleation treatment described above in the side arm charging method for performing the nucleation treatment, a tank 76 outside the system is used. A flow path 1 for supplying an aqueous solution of a halogen salt as a mixer provided in, a flow path 2 for supplying an aqueous solution of silver nitrate, and a protective colloid in the tank 76 from a flow path supplied to the mixer from the tank 76 and returning to the tank 76 again. It may be configured by using a microreactor for the nucleation treatment by providing the flow path 3 for supplying the solution to be used.

In the fourth embodiment, when the treatment for growing nuclei is performed in the tank 76, the system potential is measured by the pAg measuring device provided in the tank 76 or the side arm conduit 86. However, the potential of the reaction system can be controlled by controlling the flow rate of the silver nitrate aqueous solution and / or the halogen salt aqueous solution added to the microreactor 72 for the nucleation treatment, and thus the growth of nuclei can be controlled.

Further, in the fourth embodiment, the tank 76
If you want to configure the process to grow nuclei in
The pH of the reaction system is measured by the pH measuring device provided in the tank 76 or the side arm conduit 86, and the reaction in the mixer 74 and / or the inside of the tank 76 by adding an acid or alkali into the mixer 74 or the tank 76. It is possible to control the pH of the solution in (1) to a predetermined condition and thus control the growth of nuclei.

Since the configuration, operation, and effect of the fourth embodiment other than those described above are the same as those of the above-described first or third embodiment, description thereof will be omitted.

Next, regarding the fifth embodiment of the present invention,
This will be described with reference to FIGS. 10 to 12.

FIG. 10 shows the nuclei for executing the nucleation treatment in the grain formation of the silver halide emulsion in the pre-ripening step relating to the apparatus for producing a silver halide photographic emulsion of the present invention and starting the next physical ripening treatment. It is a schematic diagram of the microreactor 88 for formation reaction and physical ripening reaction (corresponding to the processing of the microreactor A30 and the microreactor A32 for heat exchange in FIG. 1).

The microreactor 88 for the nucleation reaction and the physical ripening reaction is constructed as a microreactor for mixing three liquids. In addition, you may comprise as a microreactor for two liquid mixing.

Here, the microreactor 88 for the nucleation reaction and the physical ripening reaction has a first passage through which a silver salt solution (fluid 1) passes and a second passage through which a halide solution (fluid 2) passes. And a third flow path (fluid 3) through which water or a protective colloid aqueous solution, which serves as an intermediate layer for preventing the sudden contact between these two solutions, is formed, and adjacent parts of these three flow paths are formed. Are formed so that they contact each other.

Further, the microreactor 88 for the nucleation reaction and the physical ripening reaction comprises the three fluids 1,
2 (silver salt solution and halide solution) each form a substantially thin layer, and between adjacent fluids 1, 2 and 3 (silver salt solution and halide solution and water or protective colloid solution). An open interface is formed and the thickness of the thin layers of these three fluids 1, 2, 3 (silver salt solution, halide solution and water or protective colloid solution) is 1 to 900 μm in the normal direction of the contact interface. , Silver ions and halogen ions diffuse and move to the intermediate layer which is water or a protective colloid aqueous solution provided between the silver salt solution and the halogen salt solution,
It is configured as a device for continuously producing silver halide grains by reacting silver ions and halogen ions.

In the microreactor 88 for the nucleation reaction and the physical ripening reaction, nucleation is performed while flowing in a unidirectional flow in a laminar flow, so that so-called partial circulation (local recycling) in which nuclei circulate does not occur. . Therefore, when performing nucleation, so-called partial circulation (local recycle) in which nuclei once generated circulate and flow.
ing) and unplanned growth can be prevented.

The microreactor 88 for nucleation reaction and physical ripening reaction diffuses silver halide grains into water or a protective colloid aqueous solution. That is, water or a protective colloid solution is interposed between the core particles formed by the nucleation reaction to separate the core particle distance.

As described above, in the microreactor 88 for the nucleation reaction and the physical ripening reaction, the distance between the nuclei particles immediately after the nucleation reaction is instantly separated, so that the nucleation reaction and the particle growth reaction do not occur at the same time. It is possible to separate the formation reaction and the grain growth reaction, form the nucleus grains of the silver halide emulsion formed by the nucleation reaction, and lead them to a process of appropriately performing the grain growth reaction in the subsequent stage.

The microreactor 88 for the nucleation reaction and the physical ripening reaction heats the temperature of the target fluid by exchanging heat between the target fluid introduced inside and the temperature control medium introduced separately. A temperature control unit 89 capable of executing control is provided and configured.

The temperature control means 89 may be constructed so that the temperature of the microreactor 88 for the nucleation reaction and the physical ripening reaction can be controlled by putting it in a temperature-controlled container.

Furthermore, the temperature control means 89 has a heater structure such as a metal resistance wire or polysilicon built in the device of the microreactor 88 for nucleation reaction and physical aging reaction, and uses this for heating. Regarding cooling, a natural cycle may be used for the thermal cycle.

For temperature sensing, another resistance wire, which is the same as the heater, is made in the metal resistance wire, and the temperature is detected based on the change in the resistance value. Polysilicon is detected using a thermocouple. To do.

The temperature control means 89 may be equipped with a Peltier element in contact with the microreactor 88 for the nucleation reaction and the physical ripening reaction so as to be in contact with the reactor, and may be heated and cooled from the outside. The temperature control method to be used is selected according to the application and the material of the main body of the microreactor 88 for the nucleation reaction and the physical aging reaction.

Further, in order to accelerate the diffusion rate of silver ions and halogen ions in the microreactor 88 for the nucleation reaction and the physical ripening reaction, the diffusion rates of these silver ions and the halogen ions are adjusted to those for the nucleation reaction and the physical ripening reaction. The temperature is set to be 1.1 times or more, preferably 1.5 times or more, the diffusion rate at the temperature of the liquid supplied to the reaction portion in the microreactor 88.

That is, the heating is made so that the diffusion rate becomes 1.1 times or more the diffusion rate within 5 seconds with respect to the diffusion rate of the reactive ion at the temperature before the reaction.

Further, the microreactor 88 for the nucleation reaction and the physical ripening reaction has its temperature control means 89.
Is composed of a micro heat exchanger capable of transferring heat at a rate at which the liquid temperature supplied to the reaction part is 5 ° C. or more per minute, preferably 10 ° C. or more per minute, and more preferably 20 ° C. or more. Along with this, in the micro heat exchanger, the heat exchange range is the length of time obtained by dividing the volume (Vh) calculated from the length and depth of the microchannel by the flow rate, and the temperature of the liquid supplied to the microreactor. 5 times or less of the diffusion time (td) in
Preferably, the structure is such that heat can be exchanged in a time of 2 times or less.

When the microreactor 88 for the nucleation reaction and the physical ripening reaction and the temperature control means 89 are specifically configured, the conditions such as specific numerical values when configuring each part are as follows. Can be determined in this way.

Generally, the diffusion rate is a function of concentration, temperature and the like. Here, various estimation methods are introduced as the estimation of the liquid layer diffusion coefficient in the section of transport properties of the Chemical Engineering Handbook.

Among them, the diffusion coefficient introduced by the equation relating to temperature is shown in the following Wilke-Chang.
There is a formula.

D ₁₂ ∞ = 2.946 * 10 ^-11 (βM _{r, 2} )
^1/2 T / (μ ₂ V _{b, 1} ^0.6 ) where D ₁₂ ∞; infinite dilution concentration _{Mr, 2} ; molecular weight of diffusion medium V _{b, 1} ; molar volume β of liquid layer at normal boiling point; diffusion medium Association factor T; temperature μ; liquid viscosity.

As shown in the Wilke-Chang equation, the diffusion coefficient is related to temperature, and the diffusion rate can be improved by raising the temperature.

In the microreactor, when channels of the same length are used, it is possible to increase the throughput by widening the channel width. Therefore, by using the above-mentioned Wilke-Chang equation, under the condition that the channel width is constant, the diffusion rate is improved by increasing the temperature, and the ions start to diffuse near the interface where the two liquids contact each other. After that, it is possible to reduce the time difference between the ion farthest from this interface and the end of diffusion of the ions, and it is possible to obtain a more uniform reaction product.

Therefore, in order to take advantage of the above advantages,
It is advantageous to configure so that the diffusion speed can be increased as much as possible.

When the temperature control means 89 is provided in the microreactor 88 for the nucleation reaction and the physical ripening reaction as described above, the diffusion speed of silver ions and halogen ions can be increased to a required speed to accurately and precisely. The silver halide nucleation and growth reactions can be controlled so that they can be produced efficiently.

Next, the configuration example shown in FIG. 11 in the fifth embodiment of the present invention will be described. FIG. 11 shows that the growth of nuclei is temporarily stopped at the stage where desired nuclei have been formed by the nucleation treatment in the grain formation of the silver halide emulsion in the pre-ripening step relating to the apparatus for producing a silver halide photographic emulsion of the present invention. Then
FIG. 3 is a schematic diagram of a microreactor 88 and a micro heat exchanger 90 for a nucleation reaction and a physical ripening reaction that can lead to the next particle growth reaction.

The microreactor 88 for the nucleation reaction and the physical ripening reaction has the same structure as that shown in FIG.

The micro heat exchanger 90 is constructed as a microreactor for controlling the temperature of the treatment liquid introduced within the shortest possible time to a predetermined temperature, and the temperature of the microreactor 88 for the nucleation reaction and the physical aging reaction described above. The configuration is similar to that of the control means.

This micro heat exchanger 90 is arranged in series with the microreactor 88 for the nucleation reaction and the physical ripening reaction, and is the halogen discharged from the microreactor 88 for the nucleation reaction and the physical ripening reaction. Water or a protective colloid solution in which silver halide particles are diffused is introduced into the micro heat exchanger 90, and the temperature is 10 ° C. or higher, preferably 2 minutes / min.
By performing temperature control (for example, cooling treatment) at a rate of 0 ° C. or higher, more preferably 40 ° C. or higher, and stopping the aging reaction of the nucleus, a desired single substance illustrated in FIG. 13A, B, C, D or E is obtained. It is possible to make only those having a different crystal structure (make the shapes of the core particles uniform), narrow the size distribution of the core particles, and make the size and number of the core particles uniform.

That is, the micro heat exchanger 90 is constructed so as to have a cooling rate of 5 ° C. or more per minute.

As described above, the microreactor 88 for the nucleation reaction and the physical ripening reaction is provided with a temperature control means for heating, and the treatment liquid treated in the microreactor 88 for the nucleation reaction and the physical ripening reaction is further treated. When the micro heat exchanger 90 that can be introduced and rapidly cooled is provided and configured, for example, the temperature control means is used to bring the treatment liquid to a predetermined temperature inside the micro reactor 88 for the nucleation reaction and the physical aging reaction. By heating to accelerate the diffusion rate of silver ions and halogen ions to a required rate, the nucleation treatment is performed precisely and efficiently.

Here, the reaction between the silver ion and the halogen ion is a reaction carried out at a very high speed, and the reaction is performed on the order of milliseconds. On the other hand, Ostwald ripening is a ripening reaction in which the resulting fine particles dissolve into molecules and are eaten by larger particles (host particles), and the reaction rate is about an order of magnitude slower than the ionic reaction. It is supposed to be.

Therefore, in the microreactor for the nucleation reaction and the particle growth reaction, the nucleation reaction is accelerated by heating the treatment liquid by the temperature control means, and the particle formation time due to diffusion is also accelerated so that the first reaction is performed. The time from the start of the reaction to the end of the final reaction can be shortened.

The Ostwald ripening reaction also proceeds here, but since the reaction rate is slow, the liquid is sent to the micro heat exchanger 90 at the time when the reaction in the microreactor 88 for the nucleation reaction and the physical ripening reaction is completed. By performing a cooling process for rapidly lowering the temperature of the processing liquid, it is possible to suppress the apparent Ostwald ripening reaction. In this manner, the difference between the reaction rate of silver ions and halogen ions and the reaction rate of Ostwald ripening can be used effectively, and the nucleation reaction and grain growth reaction can be carried out precisely and efficiently.

Next, a configuration example shown in FIG. 12 in the fifth embodiment of the present invention will be described. FIG. 12 shows that the growth of nuclei is temporarily stopped when the desired nuclei are formed by the nucleation treatment in the grain formation of the silver halide emulsion in the pre-ripening step in the apparatus for producing a silver halide photographic emulsion of the present invention. Then
Microreactor 88 and microheat exchanger 90 for nucleation reaction and physical ripening reaction to continue the next particle growth reaction.
FIG. 3 is a schematic diagram of a microreactor 92 for growing nuclei.

The microreactor 88 for the nucleation reaction and the physical ripening reaction has the same structure as that shown in FIG. Further, the micro heat exchanger 90 has the same structure as that shown in FIG.

Also, a microreactor 9 for growing nuclei
2 has the same configuration as the microreactor B34 shown in FIG.

With this structure, by the same operation as described above, nuclei are formed in the microreactor 88 for nucleation reaction and physical ripening reaction, and temperature control (for example, cooling treatment) is performed by the micro heat exchanger 90. The emulsion thus prepared is introduced into a microreactor 92 for growing nuclei, and a new silver nitrate solution and a halogen solution are simultaneously mixed to promote Ostwald ripening. Subsequent processing can be continuously carried out using a microreactor such that crystals are grown into nuclei and proceed to the next step to produce a silver halide photographic emulsion.

Although not shown, the emulsion whose temperature is controlled (eg, cooled) by the micro heat exchanger 90 is stored in a tank for a growth reaction to produce a silver halide photographic emulsion by a conventional batch production system. You can

In the subsequent processing step, since the growth reaction can be performed from the core particles having a desired single crystal structure, the growth reaction can be facilitated and the crystal shape and size distribution of the final particles can be made more uniform. it can.

Since the configuration, operation, and effect of the fifth embodiment other than those described above are the same as those of the first or third embodiment, the description thereof will be omitted.

Next, a sixth embodiment of the present invention will be described.
This will be described with reference to FIG.

FIG. 14 shows a spectral sensitization treatment of a silver halide emulsion in a post-ripening step relating to the apparatus for producing a silver halide photographic emulsion of the present invention (a poorly water-soluble substance such as a sensitizing dye is added,
It is a schematic diagram of the microreactor 94 for spectral sensitization processing which performs the process (to adjust the absorption wavelength of light).

The microreactor 94 for the spectral sensitization process can be constructed by using a general microreactor for mixing two liquids.

Here, the microreactor 94 for the spectral sensitization treatment is provided with a first flow path through which a liquid chemical (fluid 1) for emulsion production in which silver halide nuclei are dispersed, and a poorly water-soluble substance such as a dye. Forming a second flow path through which the solution (solution such as a sensitizing dye dissolved in methanol) (fluid 2) passes,
The two flow paths are formed so that parts of them are in contact with each other.

Further, the microreactor 94 for the spectral sensitization treatment is composed of these two fluids 1 and 2 (a solution containing a liquid chemical for emulsion production in which silver halide nuclei are dispersed and a poorly water-soluble substance such as a dye). Are substantially thin layers, and an open interface is formed between adjacent fluids.

The microreactor 94 for the spectral sensitization treatment has a thickness of these two thin layers of 10 to 10 per layer.
The thickness of the two thin layers is set to 5000 μm, and the length of the two thin layers is set to 0.
It is configured to have a length corresponding to 6 to 1 time.

As a result, at the interface between the solution for producing a silver halide emulsion and the solution containing a poorly water-soluble substance such as a dye, the sensitizing dye is adsorbed on the silver halide nucleus by mutual diffusion from the contact interface. Thus, the sensitized reaction is continuously caused.

As a method of adding a dye for the spectral sensitization treatment of a silver halide emulsion in the post-ripening step, a method of using a solution in which a dye is dissolved and a solid dispersion of a dye are included. Although there is a method of using a solution, any of these methods can be used in the microreactor 94 for spectral sensitization treatment.

Further, in this microreactor 94 for spectral sensitization processing, in order to improve the diffusion rate of dye molecules, the nucleus of silver halide introduced into and reacted in the microreactor 94 for spectral sensitization processing. The temperature is controlled by heat transfer between a liquid chemical for emulsion production in which is dispersed and a solution containing a poorly water-soluble substance such as a dye, at a rate of 5 ° C / min or more, preferably 10 ° C / min or more, more preferably 20 ° C or more. A micro heat exchanger 96 is mounted as a temperature control means capable of performing the above.

In addition, in the microreactor 94 for the spectral sensitization treatment, the first channel through which the liquid chemical for emulsion production (fluid 1) in which the silver halide nuclei are dispersed and the poorly water-soluble substance such as a dye are contained. A fluid (a solution of a sensitizing dye dissolved in methanol, etc.) (fluid 2) through which the fluid 1 and the fluid 2 are introduced from the inlet for introducing the fluid 1 and the fluid 2, respectively. A rectifying field is provided at a predetermined portion on each flow path up to a position where they contact each other in a part of the flow path, and in this rectifying field, the thin layer in each flow path has a vertical thickness of 10 to 5000 μm per layer. A rectifying structure 100 that regulates the flow for 1 second or more is provided in a state where the pressure and the flow rate are equal to each other in the plurality of channels, and when the flow is regulated by the rectifying structure 100, two fluids are separated. Configured to be in contact are.

At the same time, the microreactor 94 for the spectral sensitization process is provided with a mixing field at a position where a part of the two flow paths forms an open interface where the two flow paths contact each other. Dyes are added to the nuclei of each silver halide by applying mechanical energy such as ultrasonic waves or ultra-high frequency vibrations for rapidly mixing the liquid supplied from the channel or by rapidly mixing by supplying electrical energy such as electromagnetic waves. The forced mixing means 98 for adsorbing is attached.

Further, in the microreactor 94 for this spectral sensitization processing, the micro heat exchanger 96 attached to this is mounted.
Is arranged in one or both of a rectifying field that regulates the flow provided on each channel and a mixing field that rapidly mixes the liquids supplied from each channel, and the introduced liquid is 5 ° C. or more per minute, The temperature may be controlled by transferring heat at a rate of preferably 10 ° C. or more per minute, more preferably 20 ° C. or more per minute, and more precise temperature control may be enabled.

Further, in the microreactor 94 for the spectral sensitization treatment, in order to increase the number of places where the nuclei of silver halide and the poorly water-soluble substance such as the dye in the liquid chemical for emulsion production meet, A plurality of mixing fields in the microreactor 94 may be provided in parallel so that the throughput can be further improved.

The thus constructed microreactor 94 for spectral sensitization treatment introduces the liquid chemical for emulsion production in which the nuclei of silver halide are dispersed from the first channel, and introduces the dye from the second channel. Introduce a solution containing a poorly water-soluble substance,
Each of these liquids is rectified by the rectifying structure 100, and each liquid having a predetermined temperature controlled by the micro heat exchanger 96 is rapidly mixed by the forced mixing means 98. Therefore, each silver halide grain and each dye molecule are mixed. React with each other under more uniform conditions, and the dye molecules can be evenly adsorbed on the surface of all silver halide grains.Therefore, when a poorly water-soluble substance such as an added dye is adsorbed on the surface of silver halide grains, Adsorption unevenness can be improved.

As a result, as in the case of reacting by conventional macro-mixing, a dye or the like is adsorbed on silver halide grains in a multi-molecular manner, a silver halide particle is adsorbed by a single molecule of a dye or the like, or a silver halide grain is It is possible to improve the unevenness of adsorption in which a dye or the like is not adsorbed, and to prevent the photographic performance from changing due to rearrangement of the dye or the like adsorbed on the silver halide grains during storage.

At the same time, the dye molecules can be uniformly adsorbed on the surfaces of all the silver halide grains. Therefore, in order to eliminate those in which the dye molecules are not adsorbed on the surfaces of the silver halide grains, a predetermined halogenation is carried out. Since it is not necessary to add an excessive amount of dye molecules to the amount of silver particles, it is sufficient to add an appropriate amount of dye molecules, reducing the amount of poorly water-soluble substances such as expensive dyes, and reducing manufacturing costs. Can be reduced.

That is, a liquid chemical for emulsion production in which silver halide nuclei (particles) are dispersed in a protective colloid solution using a microreactor for mixing, and a solution in which a spectral sensitizing dye is dissolved in methanol. When the spectral sensitizer is simultaneously mixed with the spectral sensitizer, microscopically, the surface of a single nucleus (grain) of silver halide has more molecules of the spectral sensitizer. Since it can be adsorbed uniformly, an appropriate spectral sensitization process can be performed. Therefore, when the spectral sensitization process is carried out using the microreactor for mixing, silver halide nuclei (particles) in which the spectral sensitizing molecules are not adsorbed are generated, or the spectral sensitizing molecules are not generated. Excessive adsorption state (multi-molecular adsorption state in which molecules of the spectral sensitizer are adsorbed in multiple layers on the surface of silver halide nuclei (particles)) is generated, or silver halide nuclei (particles) are generated or spectral sensitization It is possible to prevent an excess of the molecules for use and to prevent the chemical for spectral sensitization from being wasted.

Further, when the reaction was carried out using the microreactor 94 for spectral sensitization processing according to the sixth embodiment, the adsorption of a poorly water-soluble substance such as a dye on silver halide grains became stronger. Was confirmed. Also,
It was confirmed that the thus-produced silver halide emulsion was remarkably improved in cold storage stability and dissolution storage stability.

The configuration, operation, and effect of the sixth embodiment other than those described above are the same as those of the above-described first or third embodiment, and the description thereof will be omitted.

Next, regarding the seventh embodiment of the present invention,
This will be described with reference to FIGS. 15 to 18.

FIG. 15 is a schematic view exemplifying a reaction tank apparatus for carrying out a nucleation treatment in the grain formation of a silver halide emulsion in a preripening step relating to the apparatus for producing a silver halide photographic emulsion of the present invention.

As shown in FIG. 15, this reaction tank device uses a tank 102 as a reaction container (which may be a reaction tank for growing particles). This tank 102
Is a large amount of liquid such as 1000 l (1 t)
It is configured as a batch-type reaction tank device equipped with a stirrer capable of processing a fixed amount each time.

The tank 102 is equipped with a stirring blade 106 that is rotationally driven by the rotational driving force of the motor 104 in order to stir the solution filled inside.

On the outer peripheral surface of the tank 102, temperature control means 108 for heating or cooling the reaction solution is arranged in order to control the temperature of the solution filled inside. The temperature control means 108 is, for example, a means for flowing a heat exchange medium (water, water vapor, liquid organic matter, flame gas, etc.) into the temperature control part to heat or cool, or an element for electrically heating or cooling the temperature control part. It is configured by using a means for installing and controlling the temperature.

A channel 112 for supplying water or a protective colloid aqueous solution in which nuclei, which are small crystals of silver halide, produced in the microreactor 110 for nucleation treatment are dispersed is connected to the tank 102 from above. .

A microreactor 110 for nucleation treatment for supplying a liquid in which nuclei which are small crystals of silver halide are dispersed is a microreactor for mixing two liquids shown in FIG. 16 or FIG. It is configured as a microreactor for mixing three liquids shown in 18.

The microreactor 110A for mixing two liquids shown in FIG. 16 is constructed as a microreactor chip for carrying out a reaction with two liquids having a Y-shaped groove.

Microreactor 11 for mixing two liquids
0A is the inlet 1 at the tip of the Y-shaped bifurcated groove.
14 and a liquid inlet 116 are provided, and a liquid outlet 118 is provided at the tip of a groove extending in a Y shape.

Microreactor 11 for mixing two liquids
OA is a first flow path from one of the liquid inlets 114 to a portion intersecting with the Y shape to pass a silver salt solution (silver nitrate solution) (fluid 1), and the other liquid inlet 116 has a Y shape. The second flow path through which the halide solution (halogen salt solution) (fluid 2) passes is set up to the intersection.

Microreactor 11 for mixing two liquids
0A is set as a reaction part (microchannel) where a part of the first flow path and a part of the second flow path are in contact with each other from the intersection of the Y-shape to the tip of the groove extending in one line. Where the two fluids each form a substantially thin layer and an open interface is formed between the two fluids, the thickness of the two thin layers being the normal direction of the contact interface. The thickness of each layer is 1 to 900 μm, preferably 1 μm or more and 300 μm or less. Reactive substances (ions, monomers, etc.), such as silver ions and halogen ions, diffuse and move between these two thin layers to form silver. By reacting the ions with the halogen ions, silver halide grains are continuously produced.

Further, the microreactor 110A for mixing the two liquids is constructed so as to be scaled up by using a required plurality of them at the same time and to have a necessary processing capacity.

The two-liquid mixing microreactor 110B shown in FIG. 17 is constructed so that the processing capacity is increased as much as necessary.

In the microreactor 110B for mixing two liquids having a large processing capacity, as shown in the drawing, the liquid salt inlet 114 for the silver salt solution and the liquid inlet 116 for the halide solution are alternately arranged at equal intervals. Then, the first channel and the second channel are arranged in parallel with each other.

Microreactor 11 for mixing the two liquids
In 0B, the middle first passage and the second passage except the first passage or the second passage at both ends thereof are bifurcated and intersect in two Y-shapes. To a reaction part (microchannel) from the end of the groove extending to the end.

By thus combining the Y-shaped grooves, the processing capacity can be increased as much as necessary, and the microreactor 110B for mixing two liquids can be constructed as an integrated structure as a whole as a scale-up.

Next, the three-liquid mixing microreactor 110C shown in FIG. 18, which is capable of forming a system for reacting two reactive liquids, will be described.

The microreactor 110C for mixing three liquids shown in FIG. 18 has a liquid inlet 114 and a liquid inlet 116 at each tip of a groove divided into three parts of inverted E shape at one end as shown. , A liquid inlet 120, and a liquid outlet 118 at the tip of a groove extending toward the other end of the inverted E shape, and configured as a microreactor chip for carrying out a reaction with three liquids. To do.

Microreactor 11 for mixing the three liquids
0C is the first flow path from one of the liquid inlets 114 to the intersection of the inverted E-shapes to pass the silver salt solution (silver nitrate solution) (fluid 1), and the other liquid inlet port 116 has the reverse E shape. Halide solution (halogen salt solution) up to the intersection
(Fluid 2) is used as a second flow path, and both liquids are prevented from suddenly coming into contact with each other from the liquid inlet 120 in the middle to the position intersecting with the inverted E shape, and the reaction of these two liquids. The third flow path is for passing water or a protective colloid aqueous solution (a protective colloid solution typified by gelatin, agar, etc.) (fluid 3) which serves as an intermediate layer for stabilizing the reaction product generated by.

Microreactor 11 for mixing three liquids
0C has a part in each of the first flow path, the second flow path, and the third flow path up to the tip of the groove that extends in one direction toward the other end of the inverted E shape. They are set up as reaction parts (microchannels) in contact with each other, where the three fluids each form a substantially thin layer and an open interface is formed between adjacent ones of these three fluids. The thickness of the thin layers is 1 to 900 μm per layer in the direction normal to the contact interface, and reactive substances (ions, monomers, etc.) such as silver ions and halogen ions are present between these three thin layers. The silver halide grains are continuously produced by diffusing, moving and reacting silver ions and halogen ions while controlling the progress of Ostwald ripening by water or a protective colloid aqueous solution.

Further, the microreactor 110C for mixing three liquids is scaled up by providing a plurality of reaction fields (reaction parts) in one structure, or by using a plurality of required fields at the same time, and as needed. It is configured to have the processing capability of.

Next, an outline of a method for producing the two-liquid mixing microreactor 110A, the two-liquid mixing microreactor 110B, or the three-liquid mixing microreactor 110C configured as described above will be described. Silicon (Si) or glass can be used as the material of these microreactors 110A, 110B or 110C.

For example, microreactors 110A, 1
10B or 110C is a type of silicone rubber P
DMS (polydimetylslloxane)
In the case of using the above method, a method called soft lithography can be used to make it relatively easily.

In this soft lithography, a PDMS microchip is manufactured by molding using a fine structure previously patterned by a normal photolithography process as a template.

Further, the PDMS microchip having the fine structure thus formed is pasted on a substrate such as a flat acrylic plate having a required inlet and outlet in advance, and the microreactors 110A and 110B are attached. Or 110
Configure as C.

The microreactor 110A, the microreactor 110B for mixing two liquids, or the microreactor 110C for mixing three liquids can also be manufactured by the LIGA method which is usually used with glass as a material.

Also, the microreactors 110A, 11
A micro heat exchanger is attached to 0B or 110C.

This micro heat exchanger is constructed, for example, as a cooling mechanism having a flow passage through which a heat medium flows arranged adjacent to a micro channel through which the reaction liquid flows in the microreactor 110A, 110B or 110C. The temperature of each of the previous liquids, the reaction liquids, and the reaction-completed liquids is precisely controlled so as to quickly reach a predetermined temperature.

Also, the microreactors 110A, 11
0B or 110C and a reaction tank device are used to carry out a nucleation treatment or a nucleus growth treatment in the grain formation of the silver halide emulsion in the preripening step in the production step of the silver halide photographic emulsion, a micro Reactor 110A,
By measuring the pAg of the solution during or after the reaction of the halogen salt solution and the silver nitrate solution in 110B or 110C, the respective supply rates of the halogen salt solution and the silver nitrate solution are controlled, thereby obtaining silver halide grains. By controlling the pAg during formation, or by measuring the pH of the liquid during or after the reaction of the halogen salt solution and the silver nitrate solution, and by controlling the pH of the fluid so that the pH during the reaction becomes constant, The production work can be automated.

Since the configuration, action, and effect of the seventh embodiment other than those described above are the same as those of the above-described first or third embodiment, description thereof will be omitted.

[0316]

EXAMPLE Next, in the pre-ripening step in the step of producing a silver halide photographic emulsion by using the microreactor 110A, 110B or 110C and the reaction tank device configured as described above in the seventh embodiment. Specific examples of the case where the nucleation treatment and the nucleus growth treatment in the grain formation of the above silver halide emulsion are carried out will be described.

In this example, the microreactor 110 is used.
A tabular grain of silver iodobromide is prepared using A, 110B or 110C and a reaction tank device.

In the present embodiment, Japanese Patent Laid-Open No. 10-239 is used.
In the system disclosed in FIG. 2 of Japanese Patent No. 787, a comparative example using the mixer (volume of mixer inside 0.5 ml) disclosed in FIG. An example in which tabular grains are prepared as described below using the microreactor 110A, 110B or 110C described above instead of the mixer is shown. (Comparative Example) (Emulsion 1-A) In the reaction vessel, nothing was previously added to the mixer (volume 0.5 m1 in the mixer) shown in FIG. 1 of JP-A-10-239787. 500 ml of 0.021 M silver nitrate aqueous solution and low molecular weight gelatin (average molecular weight 4
10,000) 0.028M KBr aqueous solution containing 0.1% by mass 5
00 ml was continuously added for 20 minutes, and the obtained emulsion was continuously received in a reaction vessel for 20 minutes to obtain a fine grain emulsion of 1000 ml. At that time, the stirring speed of the mixer is 2000.
It was at rpm. (Nucleation) 300 ml of 10% bone gelatin solution containing 95% fucose amino groups and KBr were added to adjust the pBr of the emulsion in the reaction vessel to 2.1, and then the temperature was raised to 75 ° C.
And left for 5 minutes. (Thermal formation) After that, 600 ml of 1.0 M silver nitrate aqueous solution, 600 ml of KBr 0.99 M KBr containing 3 mol% of KI, and 5% low molecular weight gelatin aqueous solution were again added to the mixer.
00 ml was added at a constant flow rate over 60 minutes. The fine grain emulsion produced in the mixer was added to the reaction vessel in a continuous ladle.
At that time, the stirring rotation speed of the mixer was 2000 rpm. (Grain Growth) During grain growth, when 70% of silver nitrate was added, IrC ₆ was added and doped at 8 × 10 ⁻⁸ mol / molAg. Furthermore, the yellow blood salt solution was added to the mixer before the end of particle growth. Yellow blood salt was doped to 3% of the shell portion of the particles (in terms of the amount of added silver) so as to have a local concentration of 3 × 10 ⁻⁴ mol / mol Ag. After the addition is complete, add the emulsion to 3
After cooling to 5 ° C., washing with ordinary flocculation with water, adding 70 g of lime-processed bone gelatin and dissolving it to obtain pAg of 8.
7. After adjusting pH to 6.5, it was stored in a cool dark place. Table-1
Shows the characteristics of tabular grains prepared by conventional means.

(Contents of this Example) (Emulsion 1-B) The same procedure as in Emulsion 1-A of Comparative Example was carried out except that the nucleation was changed as follows.

As the mixer, a halogen salt aqueous solution salt solution was used in the glass microreactor illustrated in FIG. 16, and
The width of the flow path of the silver nitrate solution is 200 μm and the depth is 200.
The shape of the reactor supplied from the flow path of μm is LIGA
A process system capable of continuously forming fine particles is constituted by manufacturing the same by the method and providing a plurality of the same.

Further, in this processing system, the temperature of the reaction liquid was controlled by using a micro heat exchanger at the outlet of the microreactor 110A for mixing two liquids. The aqueous silver nitrate solution and KBr solution were added to the microreactor by a syringe pump.

[0322]

[Table 1] As shown in Table-1, it can be seen that the size distribution of tabular grains is narrowed depending on the example.

Emulsion 1-A, 1 prepared as described above
-B, the following compound of 2.4 × 10 ^-4 mol / mol silver,
The mixture was added at 40 ° C., and sodium thiosulfate, potassium chloroaurate and potassium thiocyanate were added to optimally perform chemical sensitization at 60 ° C.

[0324]

[Chemical 1] (1) Emulsion layer emulsion: various emulsions (silver 3.6 × 10 ^-2 mol / m ² ) The following burrs (1.5 × 10 ^-3 mol / m ² ).

[0325]

[Chemical 2] (Compound) Tricresyl Phosphate (1.10 g / m ² ) Gelatin (2.30 g / m ² ) (2) Protective layer 2,4-dichloro-6-hydroxy-S-triazine sodium salt (0.08 g / m 2). ² ) Gelatin (1.80 g / m ² ) These samples were placed under the conditions of 40 ° C. and 70% relative humidity for 14 days.
After being left for a time, it was exposed for 1/100 seconds through a yellow filter and a continuous wedge, and the following color development was performed. [Color development] Process processing time Processing temperature Issued development 2 minutes 00 seconds 40 ° C Deep white fixing 3 minutes 00 seconds 40 ° C Washing with water (1) 20 seconds 35 ° C Washing with water (2) 20 seconds 35 ° C Stable 20 seconds 35 ° C Drying 50 Second 65 ° C. Next, the composition of the treatment liquid is shown. (Color development) (Unit g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-disulfone Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxyamine sulfate 2 .4 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05 (bleach-fixing solution) (unit: g) Ethylenediaminetetraacetic acid Ferric ammonium dihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate water lacquer solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml

[0326]

[Chemical 3] 1.0 liter PH 6.0 (water washing liquid) was added with water, and tap water was added to H-type cation exchange resin (Amperlite IR-120B manufactured by Rohm and Haas) and OH.
Type anion exchange material fat (the same Amperlite IR-400)
Is passed through a mixed bed column filled with to treat calcium and magnesium ion concentration to 3 mg / liter or less,
Subsequently, 20 dishes g / liter of sodium isocyanurate dichloride and 1.5 g / liter of sodium sulfate were added.

The pH of this liquid is in the range of 6.5 to 7.5. (Stabilizer) (Unit: mg) Formalin (37%) 2.0 ml Polyoxyethylene-P-monononylphenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium 0.05 Water was added 1.0 Liters PH 5.0-8.0 The results are shown in Table-2. The sensitivity was expressed as a relative value of the logarithm of the reciprocal of the exposure amount expressed in lux · second which gives a density of 0.1 in the fog value.

[0328]

[Table 2] As shown in Table-2, the emulsion according to the present invention has a high sulky tone. This is a result of the present invention narrowing the size distribution of tabular grains, thereby increasing the gradation.

Further, in the above-described Examples, a silver halide photographic emulsion which is a high quality reaction product having tabular grains having a high ashtect ratio and a narrow grain size distribution was obtained. (Example of Microreactor) Next, a microreactor device that can be used in each embodiment of the present invention is shown in FIG.
And FIG. 21.

This microreactor device is constructed as a mixing microreactor device 122 having a structure for mixing illustrated in FIG. 20, for example. In this mixing microreactor device 122, a channel member 126 is integrally arranged so as to cross a flow path 124 formed in a fine rectangular groove shape.

This channel member 126 has a flow path 124.
A plurality of microchannels each having a U-shape are formed on a partition plate having a corrugated and wrinkled shape that cuts across the substrate.

A lid member 128 is fixed to the upper surface of the flow path 124 shown in FIG. 20 to form a fine rectangular tubular shape as a whole. The lid member 128 includes a channel member 126.
A slit-shaped lead-out port 130 is bored at a predetermined position corresponding to. The outlet 130 is connected to an outlet for the processing liquid (not shown), and is configured to deliver the mixed processing liquid.

In the mixing microreactor device 122 configured as described above, the two fluids respectively introduced from both sides of the flow path 124 shown in FIG.
Of the two U-shaped channels that form a substantially thin layer, and the two fluids respectively entering the adjacent U-shaped channels of the two adjacent U-shaped channels are adjacent to each other when they enter the slit-shaped outlet 130. An open interface is formed between the two fluids, and the thickness of each thin layer in these two fluids becomes a micrometer size in the normal direction of the contact interface and moves so as to diffuse from the open interface between the fluids. It is a device that continuously causes chemical changes by causing reactions and the like.

This mixing microreactor device 122
Causes a chemical change while flowing in a laminar flow in one direction, so the so-called partial circulation (Local R
No chemical reaction takes place at the place where ecycling occurs.

As a microreactor device having a mixing function, a heat exchange function, and a rectifying function, for example, a multifunctional microreactor device 132 illustrated in FIG. 21 is known.

This multifunctional microreactor device 13
2 is a delay plate 1 provided with a structure for rectifying or delaying supply of a supply fluid below the upper plate 134.
36 are stacked on top of each other, a liquid supply plate 138 is arranged thereunder, two liquids are mixed and reacted underneath, and a reaction plate 140 which controls the temperature by heat exchange with the reaction liquid is arranged. The bottom plate 142 is arranged under the bottom plate 142 and is integrally fastened to form one module.

This multifunctional microreactor device 13
2 introduces two kinds of treatment liquids from the treatment liquid insertion ports (not shown) provided on the upper plate 134 or the bottom plate 142, rectifies them with the delay plate 136, and then to the reaction plate 140 via the liquid supply plate 138. The two kinds of treatment liquids are fed, and the two treatment liquids are temperature-controlled and mixed to react with each other, and the reacted treatment liquid is delivered from a treatment liquid discharge port (not shown) provided on the upper plate 134 or the bottom plate 142.

[0338]

According to the present invention, firstly, in a silver halide photographic emulsion manufacturing apparatus, a silver salt solution and a halide solution are introduced by a microreactor for mixing two liquids for nucleation to obtain a silver halide solution. Silver halide grains are produced by reacting ions with halogen ions, and the diffusion rate of silver ions and halogen ions is controlled by the temperature control means provided in the microreactor for mixing two liquids for nucleation. The temperature of the reaction solution supplied to the reaction part in the microreactor for mixing the two liquids for use in the reaction can be controlled to be 1.1 times or more, preferably 1.5 times or more, the temperature at which the diffusion rate can be changed and controlled every minute. 5 ℃ or more, preferably 10 per minute
Calculated from the length and depth of the microchannel in the microreactor for mixing two liquids for nucleation, which enables heat transfer so that the temperature of the reaction liquid can be changed at a rate of ℃ or more, more preferably 20 ° C or more. The reaction is carried out so that the length of time obtained by dividing the volume by the flow rate is 5 times or less, preferably 2 times or less, the diffusion time at the liquid temperature supplied to the microreactor. The heat exchange range for the liquid is set so that the diffusion speed of silver ions and halogen ions can be increased. This allows
Since the diffusion coefficient is related to the temperature, it is possible to improve the diffusion rate by raising the temperature.Therefore, by heating the processing solution, the diffusion rate of silver ions and halogen ions can be increased to the required rate, and In addition, it is possible to efficiently produce a silver halide photographic emulsion having uniform emulsion performance by a microreactor whose silver halide nucleation reaction is controlled. Further, since a microreactor is used, there is an effect that it is possible to easily scale up from a small production system to a mass production system, and further, it is possible to produce an emulsion at an optimal production scale corresponding to a required production amount.

The present invention is secondly, in a silver halide photographic emulsion producing apparatus, to prepare water or a protective colloid aqueous solution by a microreactor for mixing three liquids for nucleation reaction.
In the laminar flow of water or a protective colloid aqueous solution, and the silver salt solution is introduced from the flow channel of 2 to form a laminar flow of rectifying thin layer. Flowing in contact with one of the contact interfaces, introducing the halide solution from the channel 3 into a laminar flow that forms a thin layer of rectification, contacts the other contact interface in the laminar flow of water or a protective colloid aqueous solution, and By flowing as a rectifier forming a thin layer without directly contacting the laminar flow of the silver salt solution, silver ions and halogen ions diffuse and move with respect to water or the protective colloid aqueous solution to react with each other. The temperature control means provided in the microreactor for mixing three liquids for forming nuclei allows the diffusion rate of silver ions and halogen ions to be adjusted in the microreactor for mixing three liquids for nucleation. The temperature can be controlled to be 1.1 times or more, preferably 1.5 times or more, the diffusion rate at the temperature of the reaction liquid supplied to the reaction part inside, and 5 ° C. or more per minute, preferably 10 minutes per minute. Calculated from the length and depth of the microchannel in the microreactor for three-liquid mixing for nucleation, which enables heat transfer so that the temperature of the reaction solution can be changed at a rate of ℃ or more, more preferably 20 ℃ or more. The reaction is carried out so that the length of time obtained by dividing the volume by the flow rate is 5 times or less, preferably 2 times or less, the diffusion time at the liquid temperature supplied to the microreactor. The heat exchange range for the liquid is set so that the diffusion speed of silver ions and halogen ions can be increased. As a result, inside the microreactor for mixing three liquids for the nucleation reaction, microscopically, a single silver ion and a single silver ion dispersed in water or a protective colloid aqueous solution at appropriate intervals are dispersed. The silver halide nucleation reaction is controlled so that the diffusion rate with the halogen ion is increased to a required speed and the one-to-one encounter is precisely and efficiently to bond with each other to form a nucleus. The nuclei of silver halide formed at this time can be spread by water or a protective colloid aqueous solution around the nuclei so that Ostwald ripening can be suppressed, so that nucleation reaction and grain growth reaction do not occur at the same time. As described above, the silver halide nuclei formed by the nucleation reaction are stably taken out, and then the grain growth reaction is appropriately promoted, whereby monodisperse silver halide emulsion grains can be finally produced. To do. That is, it is possible to narrow the size distribution of the core particles so that only the crystals of the core particles have a desired single crystal structure, and to make the shape, size, and number of the core particles uniform. In addition, the crystal shape and size distribution of the final grains can be made more uniform, and a silver halide photographic emulsion having uniform emulsion performance can be produced.

As described above, there is an effect that a silver halide photographic emulsion having uniform emulsion performance can be produced by the microreactor. Further, since a microreactor is used, there is an effect that it is possible to easily scale up from a small production system to a mass production system, and further, it is possible to produce an emulsion at an optimal production scale corresponding to a required production amount.

The present invention is thirdly the reaction carried out by a microreactor for mixing two liquids for nucleation reaction or a microreactor for mixing three liquids for nucleation reaction in an apparatus for producing a silver halide photographic emulsion. A micro heat exchanger is connected so as to introduce a liquid, and the reaction liquid introduced into the micro heat exchanger is 5 ° C. or more per minute, preferably 10 ° C. or more per minute,
Preferably 20 ° C. or more per minute, more preferably 40 per minute
It is configured to cool at a rate of ℃ or more to stop the aging reaction of nuclei in the reaction solution. As a result, the micro heat exchanger stops the aging reaction of the nuclei in the reaction solution, so that the nuclei produced are only those having a desired single crystal structure and the size distribution of the nuclei particles. Has the effect of making the size and number of core particles uniform. In addition, in the microreactor, the diffusion rate is improved by increasing the temperature of the treatment liquid, and after the ions start to diffuse near the interface where the two liquids come into contact, the ion farthest from this interface is present. There is an effect that a time difference until completion of the diffusion can be reduced and a more uniform reaction product can be obtained. Furthermore, the temperature control means inside the microreactor heats the treatment liquid to a predetermined temperature to accelerate the diffusion rate of silver ions and halogen ions to a required rate, thereby performing the nucleation treatment precisely and efficiently. Here, the reaction between the silver ion and the halogen ion due to diffusion is a reaction that is performed at a very high speed, and reacts in the order of milliseconds. On the other hand, Ostwald ripening is a ripening reaction in which the resulting fine particles dissolve into molecules and are eaten by larger particles (host particles), and the reaction rate is about an order of magnitude slower than the ionic reaction. It is supposed to be. Therefore, in the microreactor, by heating the treatment liquid by the temperature control means, the nucleation reaction is accelerated and the particle formation time due to diffusion is accelerated so that the first reaction starts until the last reaction ends. The time can be shortened. The Ostwald ripening reaction also proceeds here, but since the reaction rate is slow, when the reaction in the microreactor for the nucleation reaction and the particle growth reaction is completed, it is sent to the micro heat exchanger to change the temperature of the treatment liquid. It is possible to suppress the apparent Ostwald ripening reaction by performing a cooling process that is rapidly reduced. In this way, it is possible to precisely and efficiently perform the nucleation reaction and the grain growth reaction by taking advantage of the difference between the reaction rate of silver ions and halogen ions and the reaction rate of Ostwald ripening. There is.

Fourthly, the present invention relates to a silver halide photographic emulsion manufacturing apparatus, wherein the temperature control means or the micro heat exchanger is used within 5 seconds with respect to the diffusion speed of the reactive ions at the temperature before the reaction. Can be heated so that the diffusion rate is 1.1 times or more. As a result, inside the microreactor for mixing two liquids for nucleation reaction or the microreactor for mixing three liquids for nucleation reaction, the diffusion rates of silver ions and halogen ions are increased to the required speeds. Produce a silver halide photographic emulsion with uniform emulsion performance by accelerating the silver halide nucleation reaction so as to bond efficiently to form nuclei, and controlling the silver halide nucleation reaction so as to enable efficient production. There is an effect that it can be possible.

[Brief description of drawings]

FIG. 1 is a schematic configuration explanatory diagram showing the whole of a manufacturing apparatus for a series of silver halide photographic emulsions according to a first embodiment of the present invention.

FIG. 2 is a schematic explanatory diagram showing the processing contents in each manufacturing process in the manufacturing apparatus for a series of silver halide photographic emulsions according to the first embodiment of the present invention.

FIG. 3 is a schematic configuration explanatory diagram showing the overall apparatus for producing a silver halide photographic emulsion, which is a first configuration example according to the second embodiment of the present invention.

FIG. 4 is a schematic configuration explanatory diagram showing an overall apparatus for producing a silver halide photographic emulsion which is a second configuration example according to the second embodiment of the invention.

FIG. 5 is a schematic configuration explanatory diagram showing an overall apparatus for producing a silver halide photographic emulsion which is a third configuration example according to the second embodiment of the invention.

FIG. 6 shows a structural example of a microreactor for a nucleation reaction and a microreactor for controlling a nuclei growth reaction in which two liquids are mixed in a silver halide photographic emulsion manufacturing apparatus according to a third embodiment of the present invention. It is a schematic block diagram.

FIG. 7 shows a structural example of a microreactor for nucleation reaction and a microreactor for controlling nuclei growth reaction in which three liquids are mixed in the apparatus for producing a silver halide photographic emulsion according to the third embodiment of the present invention. It is a schematic block diagram.

FIG. 8 is a structural example of a microreactor for pretreatment for mixing two liquids and a microreactor for nucleation reaction for mixing two liquids in the apparatus for producing a silver halide photographic emulsion according to the third embodiment of the present invention. It is a schematic block diagram showing.

FIG. 9 is a side arm charging method for performing nucleation treatment in grain formation of a silver halide emulsion in a pre-ripening step according to the fourth embodiment of the present invention, in which a microreactor and a mixer for nucleation treatment are used. It is a schematic structure diagram which shows the structure which provided.

FIG. 10 A nucleation reaction and a physical ripening reaction in which a nucleation treatment in the grain formation of the silver halide emulsion in the pre-ripening step according to the fifth embodiment of the present invention is executed and the next nucleus growth treatment is started. FIG. 3 is a schematic configuration diagram showing a microreactor for a vehicle.

FIG. 11: At the stage of forming a desired nucleus by performing a nucleation treatment in the grain formation of a silver halide emulsion in the pre-ripening step according to the fifth embodiment of the present invention, the growth of the nucleus is temporarily stopped, and FIG. 3 is a schematic configuration diagram showing a microreactor and a micro heat exchanger for a nucleation reaction and a physical ripening reaction that can lead to a particle growth reaction.

FIG. 12: At the stage of forming a desired nucleus by performing the nucleation treatment in the grain formation of the silver halide emulsion in the pre-ripening step according to the fifth embodiment of the present invention, the growth of the nucleus is temporarily stopped, and the following steps are performed. It is a schematic block diagram which shows the microreactor for a nucleus formation reaction and physical ripening reaction which continue a physical ripening reaction, a micro heat exchanger, and a microreactor for nucleus growth.

FIG. 13 is a perspective view exemplifying A, B, C, D or E as a crystal structure of nuclei when nuclei are formed by the apparatus for producing a silver halide photographic emulsion of the present invention.

FIG. 14 shows a microreactor for spectral sensitization processing for performing spectral sensitization processing of a silver halide emulsion in a post-ripening step in a silver halide photographic emulsion manufacturing apparatus according to a sixth embodiment of the present invention. It is a schematic structure diagram shown.

FIG. 15 is a schematic view showing a reaction tank device for executing a nucleation treatment in the grain formation of a silver halide emulsion in a pre-ripening step according to a silver halide photographic emulsion manufacturing apparatus according to a seventh embodiment of the present invention. Is.

FIG. 16 is a microreactor chip for mixing two liquids for performing nucleation treatment in the grain formation of the silver halide emulsion in the pre-ripening step in the apparatus for producing a silver halide photographic emulsion according to the seventh embodiment of the present invention. FIG.

FIG. 17 is a constitution capable of expanding the processing capacity for performing the nucleation processing in the grain formation of the silver halide emulsion in the pre-ripening step in the apparatus for producing a silver halide photographic emulsion according to the seventh embodiment of the present invention. FIG. 3 is a plan view showing a microreactor chip for mixing the two liquids.

FIG. 18 is a microreactor chip for mixing three liquids for performing a nucleation treatment in grain formation of a silver halide emulsion in a preripening step in a silver halide photographic emulsion manufacturing apparatus according to a seventh embodiment of the present invention. FIG.

FIG. 19 is a schematic explanatory diagram showing the processing contents in other manufacturing steps in the apparatus for manufacturing a silver halide photographic emulsion of the present invention.

FIG. 20 is an exploded perspective view showing a main part of a mixing microreactor device that can be used in the silver halide photographic emulsion manufacturing apparatus of the present invention.

FIG. 21 is an exploded perspective view showing a main part of a multifunctional microreactor device that can be used in the silver halide photographic emulsion manufacturing apparatus of the present invention.

FIG. 22 is a schematic configuration diagram illustrating an apparatus for producing a silver halide photographic emulsion by a conventional batch type production system.

[Explanation of symbols]

30 Microreactor A 32 Microreactor A for heat exchange A 34 Microreactor B 36 Microreactor C 38 Microreactor D 48 Desalination device 56 Liquid conducting tube 58 Storage tank 88 Microreactor 89 for nucleation reaction and physical aging reaction Temperature control means 90 Micro heat exchanger 92 Micro reactor for nuclei growth

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

[Procedure amendment]

[Submission date] June 27, 2002 (2002.6.2)
7)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

Further, in the method of forming silver halide grains constituting a silver halide emulsion which is industrially used today, a dispersion medium solution (protective colloid aqueous solution) typified by gelatin may be stirred strongly. Then, there is a step of forming a silver halide grain by adding an aqueous solution of silver nitrate and an aqueous solution of halogen salt and mixing them as rapidly as possible.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

However, in the batch type production system using the tank 10 and the stirring blades 12 as described above, when stirring is performed by the stirring blades 12 to produce a silver halide emulsion, a tabular halogenation during growth is performed. Silver particles are silver ions or
A harmful effect that the thickness of the tabular grains increases due to passing through a highly supersaturated region in the vicinity of the injection port of the emulsion introduction tube 22 to which a halide ion is added is likely to occur.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

On the other hand, when a newly developed silver halide emulsion newly developed using the experimental equipment is scaled up from a small production system using the experimental equipment to a production apparatus for mass production, an experiment for producing a small quantity is carried out. It is necessary to repeat the trial manufacture and product test many times in order to set the conditions for producing the same performance as the emulsion performance of the equipment with the newly formulated silver halide emulsion manufactured by the manufacturing equipment for mass production. There is a problem that it takes a long time to develop a manufacturing system for production, and there is a large loss of raw materials consumed for product testing.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

The microreactor A30 is constructed so that it is automatically controlled by the controller based on the detection value detected by a detection sensor (not shown). The automatic control of the microreactor A30 by this controller is
Conventionally used potential control means for nucleation treatment or means for controlling the nucleation treatment by detecting a physical quantity such as pH (pH) can be used.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0147

[Correction method] Change

[Correction content]

The microreactor 62 for controlling the nucleation growth reaction is constructed as a general microreactor for mixing two liquids, like the microreactor 60 for the nucleation reaction.
Form a first flow path through which the reaction liquid (fluid 1) sent from the device and a second flow path through which water or a protective colloid aqueous solution (fluid 2) flows, and a part of these two flow paths contact each other. To be formed.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0154

[Correction method] Change

[Correction content]

[0154] That is, by using the microreactor 62 of the microreactor 60 and the nucleus growth reaction control of the temperature control means for nucleation reaction provided, nuclei of silver halide is dispersed in a protective colloid solution When temperature control is performed by introducing a liquid chemical for emulsion production into the microreactor 60 for nucleation reaction and exchanging heat with the temperature control medium, the liquid chemical for emulsion production is Since the heat energy is transferred in a trace amount forming a thin layer, the temperature rapidly changes to the target set temperature.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0180

[Correction method] Change

[Correction content]

When the silver halide grains obtained by the method of the present invention are used as nuclei, the concentration of the aqueous solution is preferably 4 mol / L or less, more preferably 1 mol / L or less,
Most preferably, it is 0.2 mol / L or less. When used for crystal growth, it is preferable to use a high-concentration aqueous solution from the viewpoint of productivity. The amount is preferably 0.5 mol / L or more and 4 mol / L or less, and more preferably 1.0 mol / L or more.
The temperature of the aqueous solution is preferably 5 ° C or higher and 95 ° C or lower, more preferably 5 ° C or higher and 75 ° C or lower.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0182

[Correction method] Change

[Correction content]

When the continuously produced silver halide grains are used as nuclei for preparing tabular silver halide grains, parallel double twinning nuclei are required, so that a desired twinning probability is achieved. Therefore, it is necessary to adjust the gelatin aqueous solution concentration. When the aqueous silver salt solution and the aqueous halide salt solution are mixed, the amount of gelatin per 1 g of silver is 0.03 g.
The gelatin concentration is preferably selected so as to be 0.4 g or less, more preferably 0.3 g or less.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0183

[Correction method] Change

[Correction content]

In the case of utilizing continuously produced silver halide grains as nuclei for preparing normal crystal grains, twinning is performed.
It is necessary to increase the gelatin concentration at the time of nucleation because it is necessary to reduce the probability of liveness as much as possible, and the amount of gelatin per 1 g of silver nitrate is 0.4 g or more (the upper limit is not particularly limited, but preferably 50 g or less), and more preferably Is 1 g or more, more preferably 5 g or more.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0192

[Correction method] Change

[Correction content]

The microreactor used in the present invention is an apparatus having channels (microchannels) having an equivalent diameter of 500 μm or less per one introducing channel. In the present invention, the equivalent diameter (equalent diameter)
ter) is also called an equivalent (straight) diameter, and is a term used in the field of mechanical engineering. When a circular pipe equivalent to a pipe ( flow path in the present invention) having an arbitrary cross-sectional shape is assumed, the diameter of the equivalent circular pipe is called an equivalent diameter, and A is a cross-sectional area of the pipe,
P: deq = 4 using the wet edge length (perimeter) of the pipe
It is defined as A / p. When applied to a circular pipe, this equivalent diameter corresponds to the circular pipe diameter. The equivalent diameter is used to estimate the flow or heat transfer characteristics of the pipe based on the data of the equivalent circular pipe, and represents the spatial scale (representative length) of the phenomenon. The equivalent diameter is deq = 4 for a square tube with one side a.
a ² / 4a = a, deq = a / for an equilateral triangular tube with one side a
3 ^1/2 , flow height h between parallel plates deq = 2h
(Reference: “Mechanical Engineering Encyclopedia” edited by The Japan Society of Mechanical Engineers)
Maruzen Co., Ltd., 1997.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0195

[Correction method] Change

[Correction content]

The flow channel of the present invention is formed on a solid substrate by a fine processing technique.
It is created by surgery . Examples of materials used include metals, silicon, Teflon (R), glass, ceramics or plastics. When heat resistance, pressure resistance and solvent resistance are required, preferred materials are metals, silicon, Teflon (R), glass or ceramics, but metals are particularly preferred. Examples of the metal include nickel, aluminum, silver, gold, platinum, tantalum, stainless steel, Hastelloy (Ni-Fe alloy) or titanium.
Preferred are stainless steel, hastelloy, and titanium, which have high corrosion resistance. In a conventional batch type reaction apparatus, an apparatus having a metal (stainless steel or the like) surface glass-lined is used when handling an acidic substance, but a microreactor or a metal surface may be glass-coated. Not limited to glass, another metal or another material may be coated on the metal depending on the purpose, or a material other than the metal (for example, ceramic) may be coated with the metal or glass.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0196

[Correction method] Change

[Correction content]

[0196] By way of typical as a fine machining technique for creating a flow path, L using X-ray Risogura Fi
IGA art, EPON SU - 8 high aspect <br/> ratio photolithography Gras Fi method using a micro-electro-discharge machining (mu - E
DM), deep RIE, high aspect ratio silicon processing method, hot embossing method, stereolithography method,
There are a laser processing method, an ion beam processing method, and a mechanical micro cutting method using a micro tool made of a hard material such as diamond. These techniques may be used alone or in combination.
Preferred microfabrication techniques, L using X-ray Risogura Fi
IGA techniques, high aspect ratio photolithography Gras Fi method using EPON SU-8, the micro discharge processing method (mu - E
DM), and mechanical micromachining methods.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0197

[Correction method] Change

[Correction content]

Joining techniques are often used in assembling the microreactors of the present invention. Ordinary joining techniques are roughly divided into solid phase joining and liquid phase joining.Generally used joining methods are pressure welding and diffusion joining as solid phase joining, welding as liquid phase joining, eutectic joining, soldering, Adhesion is a typical joining method. Furthermore, at the time of assembly, it is desirable to use a highly precise bonding method that maintains the dimensional accuracy without damaging the microstructure such as the flow of material due to high temperature heating or the large deformation, and the direct silicon bonding is the technique. Anodic bonding, surface activated bonding, direct bonding using hydrogen bonding, H
Examples include bonding using an F aqueous solution , Au-Si eutectic bonding, and void-free adhesion.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0199

[Correction method] Change

[Correction content]

In order to introduce and mix reagents, samples, etc. into the micro-sized channel of the microreactor,
Fluid control function is required. In particular, the behavior of the fluid in the micro area has a property different from that of the macro scale, so that a control method suitable for the micro scale must be considered. The fluid control methods include a continuous flow method and a droplet (liquid plug) method when classified by form, and an electric drive method and a pressure drive method when classified by a driving force. These schemes are described in detail below. The most widely used form of handling fluid is the continuous flow system. In continuous flow type fluid control, it is general that the entire flow path of the microreactor is filled with fluid, and the entire fluid is driven by a pressure source such as a syringe pump provided outside. In this case, one advantage is that a control system can be realized with a relatively simple setup, but it is difficult to perform operations involving multiple steps of reaction and sample exchange, and the flexibility of system configuration is low Since the medium is a solution itself, there is a drawback that the dead volume is large. As a method different from the continuous flow method, there is a droplet (liquid plug) method. In this method, droplets partitioned by air are moved inside the reactor or in a flow path leading to the reactor, and each droplet is driven by air pressure. At that time, a vent structure that allows air to escape between the droplet and the flow channel wall or between the droplets as needed, and a valve structure that keeps the pressure in the branched flow channel independent of other parts Etc. must be prepared inside the reactor system. Further, in order to control the pressure difference and operate the liquid droplets, it is necessary to construct a pressure control system composed of pressure stagnation and a switching valve outside. In this way, in the droplet method, the device configuration and the reactor structure become slightly complicated,
It is possible to perform multi-step operations such as operating a plurality of droplets individually and performing some reactions in sequence, which increases the degree of freedom in system configuration.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0200

[Correction method] Change

[Correction content]

As a drive system for controlling fluid, an electric drive method in which a high voltage is applied to both ends of a flow channel (channel) to generate an electroosmotic flow, and thereby a fluid is moved, and a pressure stagnation is prepared outside. Generally, a pressure drive method in which a fluid is moved by applying pressure is widely used. The difference between the two is that, for example, as the behavior of the fluid, the flow velocity profile in the cross section of the flow passage has a flat distribution in the case of the electric drive method, whereas in the pressure drive method, the flow passage has a hyperbolic shape with a central portion of the flow passage. It is known that the distribution is fast and the wall surface has a slow distribution, and the electric drive method is more suitable for the purpose of moving the sample plug while keeping the shape. When the electric drive method is used, it is necessary to fill the flow path with the fluid, and therefore, there is no choice but to adopt the continuous flow method, but the fluid can be operated by electrical control. Therefore, for example, to by changing the mixing ratio of two kinds of solutions continuous, it has also been realized relatively complicated processing such make temporal concentration gradient.
In the case of the pressure drive system, there is almost no effect on the substrate because it can be controlled regardless of the electrical properties of the fluid and it is not necessary to consider side effects such as heat generation and electrolysis. , Its application range is wide. On the other hand,
It is necessary to automate complicated processing such as having to prepare an external pressure source and changing the response characteristics of the operation according to the size of the dead volume of the pressure system.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0209

[Correction method] Change

[Correction content]

The solution in the tank 76 is taken out from the bottom of the tank 76 and sent by the pump 84 to the mixer.
The liquid is drained to the liquid surface side of the tank 76 via the tank 74.
A side arm conduit 86, which is a circulation system for returning to the inside, is attached.

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0246

[Correction method] Change

[Correction content]

D ₁₂ ∞ = 2.946 * 10 ^-11 (βM _{r, 2} )
^1/2 T / ( μ ₂ V _{b, 1} ^0.6 ) where D ₁₂ ∞; infinite dilution concentration M _{r, 2} ; molecular weight of diffusion medium V _{b, 1} ; molar volume β of liquid layer at normal boiling point; diffusion medium Association factor T; temperature μ; liquid viscosity.

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0272

[Correction method] Change

[Correction content]

The microreactor 94 for the spectral sensitization treatment has a thickness of these two thin layers of 10 to 10 per layer.
The thickness of the two thin layers is set to 5000 μm and the length of the two thin layers is set to a predetermined temperature of a poorly water-soluble substance such as a dye at a predetermined flow rate.
Of the time required for the fluid 2 to diffuse from one end to the other.
It is configured to have a length corresponding to 6 to 1 time.

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0313

[Correction method] Change

[Correction content]

This micro heat exchanger is constructed, for example, as a cooling mechanism having a flow passage through which a heat medium flows arranged adjacent to a micro channel through which the reaction liquid flows in the microreactor 110A, 110B or 110C. Each of the previous solutions and reaction solutions, as well as the end of the reaction
Precisely control the temperature of the liquid so that it reaches a predetermined temperature quickly.

[Procedure amendment 20]

[Document name to be amended] Statement

[Name of item to be corrected] 0316

[Correction method] Change

[Correction content]

[0316]

EXAMPLE Next, in the pre-ripening step in the step of producing a silver halide photographic emulsion by using the microreactor 110A, 110B or 110C and the reaction tank device configured as described above in the seventh embodiment. Specific examples of the case where the nucleation treatment and the nucleus growth treatment in the grain formation of the above silver halide emulsion are carried out will be described.

[Procedure correction 21]

[Document name to be amended] Statement

[Name of item to be corrected] 0318

[Correction method] Change

[Correction content]

In the present embodiment, Japanese Patent Laid-Open No. 10-239 is used.
In the system disclosed in FIG. 2 of Japanese Patent No. 787, a comparative example using the mixer (volume of mixer inside 0.5 ml) disclosed in FIG. An example in which tabular grains are prepared as described below using the microreactor 110A, 110B or 110C described above instead of the mixer is shown. (Comparative Example) (Emulsion 1-A) In the reaction vessel, nothing was previously added to the mixer (volume 0.5 ml inside the mixer) shown in FIG. 1 of JP-A-10-239787. 500 ml of 0.021M silver nitrate aqueous solution and low molecular weight gelatin (average molecular weight 4
10,000) 0.028M KBr aqueous solution containing 0.1% by mass 5
00 ml was continuously added for 20 minutes, and the obtained emulsion was continuously received in a reaction vessel for 20 minutes to obtain 1000 ml of a fine grain emulsion. At that time, the stirring speed of the mixer is 200.
It was 0 rpm. (Nucleation) 300 ml of 10% bone gelatin solution containing 95% amino groups phthalated and KBr were added to adjust the pBr of the emulsion in the reaction vessel to 2.1, and then the temperature was raised to 75 ° C.
And left for 5 minutes. (Aging) after that and again an aqueous silver nitrate solution 600 ml of 1.0M in the mixer, and KBr600 ml of KBr0.99M containing KI 3 mol%, 5% low molecular weight gelatin aqueous solution 8
00 ml was added at a constant flow rate over 60 minutes. The fine grain emulsion produced in the mixer was continuously added to the reaction vessel.
At that time, the stirring rotation speed of the mixer was 2000 rpm. (Grain Growth) During grain growth, when 70% of silver nitrate was added, IrC ₆ was added and doped at 8 × 10 ⁻⁸ mol / molAg. Furthermore, the yellow blood salt solution was added to the mixer before the end of particle growth. Yellow blood salt was doped to 3% of the shell portion of the particles (in terms of the amount of added silver) so as to have a local concentration of 3 × 10 ⁻⁴ mol / mol Ag. After the addition is complete, add the emulsion to 3
After cooling to 5 ° C., washing with ordinary flocculation with water, adding 70 g of lime-processed bone gelatin and dissolving it to obtain pAg of 8.
7. After adjusting pH to 6.5, it was stored in a cool dark place. Table 1 shows the characteristics of the tabular grains obtained by the conventional means.

[Procedure correction 22]

[Document name to be amended] Statement

[Correction target item name] 0320

[Correction method] Change

[Correction content]

As the mixer, a glass microreactor illustrated in FIG. 16 was used, in which a halogen salt aqueous solution and a reactor having a shape in which a flow path of a silver nitrate solution was 200 μm in width and 200 μm in depth were supplied from the LIGA method. In the same manner as in the comparative example, a processing system capable of continuously forming fine particles is configured by producing a plurality of the above.

[Procedure amendment 23]

[Document name to be amended] Statement

[Name of item to be corrected] 0322

[Correction method] Change

[Correction content]

[0322]

[Table 1] As shown in Table 1 , it can be seen that the size distribution of tabular grains is narrowed according to the examples.

[Procedure correction 24]

[Document name to be amended] Statement

[Name of item to be corrected] 0324

[Correction method] Change

[Correction content]

[0324]

[Chemical 1] (1) Emulsion layer emulsion : various emulsions (silver 3.6 × 10 ⁻² mol / m ² ) couplers shown below (1.5 × 10 ⁻³ mol / m ² ).

[Procedure correction 25]

[Document name to be amended] Statement

[Name of item to be corrected] 0325

[Correction method] Change

[Correction content]

[0325]

[Chemical 2]    (Compound) Tricresyl Phosphate (1.10 g / m²) Gelatin (2.30 g / m²) (2) Protective layer 2,4-dichloro−6−Hydroxy−S−Triazina
Thorium salt (0.08g / m²) Gelatin (1.80 g / m²) 14 these samples under the conditions of 40 ℃, 70% relative humidity
After leaving for a while, put the yellow filter and continuous wedge
Exposure for 1/100 seconds, and perform the following color development
It was [Color development] Process processing time Processing temperature Issue development 2 minutes 00 seconds 40 ° C Deep white fixing 3 minutes 00 seconds 40 ° C Washing with water (1) 20 seconds 35 ° C Washing with water (2) 20 seconds 35 ° C Stable 20 seconds 35 ° C 50 seconds dry 65 ° C Next, the composition of the treatment liquid is shown. (Color development) (Unit: g) Diethylenetriamine pentaacetic acid 2.0 1-hydroxyethylidene−1,1-disulfone   Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5mg Hydroxyamine sulfuric acid 2.4 4- [N-ethyl−N-β-hydroxyethylamino]   -2-Methylaniline sulfate 4.5 1.0 liter with water pH 10.05 (Bleaching fixer) (Unit: g) Ethylenediaminetetraacetic acid ferric ammoniumDihydrate salt      90.0 Ethylenediaminetetraacetic acidDisodium salt                  5.0 Sodium sulfite 12.0 Ammonium thiosulfateAqueous solution(70%) 260.0 ml Acetic acid (98%) 5.0 ml

[Procedure Amendment 26]

[Document name to be amended] Statement

[Name of item to be corrected] 0326

[Correction method] Change

[Correction content]

[0326]

[Chemical 3] 1.0 liter of pH 6.0 (water washing solution) tap water was added with H-type cation exchange resin (Amperlite IR-120B manufactured by Rohm and Haas Co.) and OH.
-Type anion exchange resin (Amperlite IR-400)
Is passed through a mixed bed column filled with to treat calcium and magnesium ion concentration to 3 mg / liter or less,
Subsequently, 20 mg / liter of sodium isocyanurate dichloride and 1.5 g / liter of sodium sulfate were added.

[Procedure Amendment 27]

[Document name to be amended] Statement

[Name of item to be corrected] 0327

[Correction method] Change

[Correction content]

The pH of this liquid is in the range of 6.5 to 7.5. (Stabilizing Solution) (Unit mg) Formalin (37%) 2.0 ml Polyoxyethylene - P- monononylphenyl ether (average polymerization degree: 10) was added 0.3 Disodium ethylenediaminetetraacetate 0.05 Water 1. 0 liter pH 5.0-8.0 The results are shown in Table 2 . The sensitivity was expressed as a relative value of the logarithm of the reciprocal of the exposure amount expressed in lux · second which gives a density of 0.1 in the fog value.

[Procedure correction 28]

[Document name to be amended] Statement

[Name of item to be corrected] 0328

[Correction method] Change

[Correction content]

[0328]

[Table 2] As shown in Table 2 , the emulsion according to the present invention has a high gradation . According to the present invention, the size distribution of tabular grains is narrowed,
As a result, the gradation is increased.

[Procedure correction 29]

[Document name to be amended] Statement

[Name of item to be corrected] 0329

[Correction method] Change

[Correction content]

In addition, in the above-mentioned embodiment, a high aspect ratio is obtained.
It has a Ratio, the silver halide photographic emulsion is obtained which is highly reactive product quality consisting of narrow tabular grain grain size distribution. (Example of Microreactor) Next, a microreactor device that can be used in each embodiment of the present invention is shown in FIG.
And FIG. 21.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Fumiko Shiraishi             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F-term (reference) 2H023 BA07

Claims (4)

[Claims] 1. A microreactor for mixing two liquids for nucleation, which introduces a silver salt solution and a halide solution to produce silver halide grains by reacting silver ions and halogen ions. The diffusion rate of silver ions and halogen ions is 1.1 times or more, preferably 1. times the diffusion rate at the temperature of the reaction solution supplied to the reaction portion in the microreactor for mixing the two solutions for nucleation. It is possible to control the temperature to be 5 times or more, and 5 ℃ or more per minute, preferably 10 ℃ or more per minute,
More preferably, heat can be transferred so that the temperature of the reaction liquid can be changed at a rate of 20 ° C. or more, and the volume calculated from the length and depth of the microchannel in the microreactor for mixing two liquids for nucleation is set to The length of time obtained by dividing by the flow rate is 5 times or less, preferably 2 times or less, of the diffusion time at the temperature of the liquid supplied to the microreactor, so that the time for heat exchange is possible for the reaction liquid. An apparatus for producing a silver halide photographic emulsion, comprising: a temperature control unit configured to set a heat exchange range to accelerate a diffusion rate of silver ions and halogen ions. 2. A layer which forms a thin layer of rectification by introducing water or a protective colloid aqueous solution into the laminar flow to form a thin layer of rectification and introducing a silver salt solution from a channel of 2. The water or the protective colloid aqueous solution in a laminar flow in contact with one of the contact interfaces to allow the halide solution to flow to 3
Of the water or the protective colloid aqueous solution into the laminar flow of the water or the protective colloid aqueous solution, and is not directly contacted with the laminar flow of the silver salt solution. By flowing as a layered rectifier, silver ions and halogen ions diffuse and move with respect to the water or the protective colloid aqueous solution, and react with each other to generate silver halide nucleus particles. The microreactor for liquid mixing and the diffusion rate of silver ions and halogen ions are 1.1 times the diffusion rate at the temperature of the reaction liquid supplied to the reaction part in the microreactor for mixing three liquids for nucleation. Above, it is possible to control the temperature to be preferably 1.5 times or more, and 5 ° C. or more per minute, preferably 10 ° C. or more per minute,
More preferably, heat can be transferred so that the temperature of the reaction liquid can be changed at a rate of 20 ° C. or more, and the volume calculated from the length and depth of the microchannel in the microreactor for mixing three liquids for nucleation is calculated. The length of time obtained by dividing by the flow rate is 5 times or less, preferably 2 times or less, of the diffusion time at the temperature of the liquid supplied to the microreactor, so that the time for heat exchange is possible for the reaction liquid. An apparatus for producing a silver halide photographic emulsion, comprising: a temperature control unit configured to set a heat exchange range to accelerate a diffusion rate of silver ions and halogen ions. 3. A micro heat exchanger is connected to introduce a reaction liquid treated by the two-liquid mixing microreactor for nucleation reaction or the three-liquid mixing microreactor for nucleation reaction, The reaction liquid introduced into the micro heat exchanger is cooled at a rate of 5 ° C. or more per minute, preferably 10 ° C. or more per minute, preferably 20 ° C. or more per minute, more preferably 40 ° C. or more per minute, and The apparatus for producing a silver halide photographic emulsion according to claim 1 or 2, which is configured to stop the ripening reaction of nuclei. 4. The temperature control means or the micro heat exchanger is set so that the diffusion rate becomes 1.1 times or more within 5 seconds with respect to the diffusion rate of the reactive ions at the temperature before the reaction. 4. The apparatus for producing a silver halide photographic emulsion according to claim 1, wherein the apparatus is capable of heating.