JP5221287B2 - Method for producing barium titanate and barium calcium titanate using a microreaction apparatus - Google Patents

Description

The present invention relates to a method for producing barium titanate and barium calcium titanate.

  Since barium titanate has a high dielectric constant, it is widely applied to electronic devices such as multilayer ceramic capacitors as a main component of the capacitor. For example, it is manufactured using a manufacturing method as disclosed in Patent Documents 1 to 4. Has been made.

  Patent Document 1 discloses a method for producing barium titanate by a solid phase reaction method in which barium carbonate powder and titanium dioxide powder are mixed and heated to around 1000 ° C. to produce barium titanate powder.

Patent Document 2 discloses a barium titanate powder by a hydrothermal synthesis method for producing a barium titanate powder at a few hundred degrees Celsius under high pressure from a barium salt and a titanium salt and a method for producing the same.
Patent Document 3 discloses a method for producing a barium titanate powder by a sol-gel method for producing a barium titanate powder by hydrolyzing a metal alkoxide solution.

In Patent Document 4, a metal alkoxide having a composition of Ba (OC ₂ H ₅ ) ₂ is dissolved in a mixed solution of methanol and 2-methoxyethanol (6: 4 by volume) at room temperature to obtain 1.0 mol / L. A high concentration precursor solution is prepared, and the precursor solution is hydrolyzed with water vapor at 0 ° C., for example, and then subjected to aging treatment at 0 to 60 ° C. for 1 to 480 hours to obtain barium titanate (BaTiO _3). ) Is produced, and this is charged into, for example, 2-methoxyethanol, and uniformly dispersed while being finely pulverized using ultrasonic waves.
JP 2002-255552 A JP 2002-221926 A JP-A-5-116943 JP 2002-275390 A

  However, in such a conventional method for producing barium titanate, for example, the production method described in Patent Document 1 described above requires calcining at 1000 ° C. or higher, and barium titanate produced by calcining. Aggregation of the powders occurs, and it is necessary to pulverize mechanically. In addition, mechanical pulverization has pulverization limits, and at the same time, there are particles that are not sufficiently pulverized or excessively pulverized, so the particle size distribution becomes wide, and inconveniences such as deterioration in reliability occur when used for capacitor layers. Met.

  In addition, in the manufacturing method described in Patent Document 2, although a fine powder is obtained, residual functional groups such as OH groups exist in the particles of the powder and the crystallinity becomes low, so that heat treatment at around 1000 ° C. is performed again. There was a problem that it was necessary.

Furthermore, in the sol-gel method described in Patent Document 3, crystals cannot be obtained at the synthesis stage.
The dried gel powder had to be calcined at around 1000 ° C. and crystallized.
The production method using alkoxide as a raw material described in Patent Document 4 is a so-called batch-type synthesis method, which is unsuitable for mass production. Also, this production method has a problem that the amount of water and the atmosphere (oxygen) at the time of reaction are constantly required, which increases the burden of operation and cost.

Thus, since the conventional method for producing barium titanate has the above-described problems, further simplification of the process has been demanded.
An object of the present invention is to provide a method for producing barium titanate and the like, which can efficiently produce, for example, barium titanate powder having fine particles and high crystallinity applicable as a dielectric material for electronic devices at room temperature. The purpose is to do.

The first invention in this application is:
A first fluid injection path for injecting a first fluid from the outside;
A second fluid injection path for injecting a second fluid from the outside,
A plurality of first fluid inlets in communication with the first fluid injection path for inflowing a first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of first fluid inflow channels as one channel;
A plurality of second fluid inlets for communicating with the second fluid injection path, formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path, and for inflowing a second fluid;
An induction channel that is formed at an end opposite to the outlet side end of the first fluid inflow channel in the fluid collecting path, and that flows out the combined fluid of the first fluid and the second fluid;
A confluence channel connected to the guide channel;
A micromixing chip having
First fluid pressurizing means connected to a first fluid inlet of the micromixing chip via a first fluid injection path;
Second fluid pressurizing means connected to the second fluid inlet of the micromixing chip via a second fluid injection path;
A fluid discharge path connected to the confluence channel;
A reaction vessel installed on the outlet side of the fluid discharge path;
A method for producing barium titanate using a microreaction apparatus comprising:
The first fluid pressurizing means injects a first fluid made of a mixture of barium alkoxide and titanium alkoxide into the first fluid inlet through the first fluid injection path of the micromixing chip, and a plurality of first fluid inflow channels. Allowing the first fluid to flow into,
Injecting a second fluid made of a hydrous solvent into the second fluid inlet through the second fluid injection path of the micromixing chip by the second fluid pressurizing means;
The first fluid and the second fluid are merged in the fluid collecting path to form a laminar flow of the first fluid and the second fluid, and the first fluid and the second fluid are maintained while maintaining the laminar flow state. Discharging the merged fluid with the fluid from the merged channel to the fluid discharge channel via the induction channel;
Hydrolyzing barium alkoxide and titanium alkoxide contained in the mixed solution discharged through the fluid discharge passage outside the micromixing chip with water contained in the hydrous solvent;
It is a manufacturing method of barium titanate characterized by having.

The second invention in this application is:
A first fluid injection path for injecting a first fluid from the outside;
A second fluid injection path for injecting a second fluid from the outside,
A plurality of first fluid inlets in communication with the first fluid injection path for inflowing a first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of first fluid inflow channels as one channel;
A plurality of second fluid inlets for communicating with the second fluid injection path, formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path, and for inflowing a second fluid;
An induction channel that is formed at an end opposite to the outlet side end of the first fluid inflow channel in the fluid collecting path, and that flows out the combined fluid of the first fluid and the second fluid;
A confluence channel connected to the guide channel;
A micromixing chip having
First fluid pressurizing means connected to a first fluid inlet of the micromixing chip via a first fluid injection path;
Second fluid pressurizing means connected to the second fluid inlet of the micromixing chip via a second fluid injection path;
A fluid discharge path connected to the confluence channel;
A reaction vessel installed on the outlet side of the fluid discharge path;
A method for producing barium titanate using a microreaction apparatus comprising:
The first fluid pressurizing means injects a first fluid made of a mixture of barium alkoxide and titanium alkoxide into the first fluid inlet through the first fluid injection path of the micromixing chip, and a plurality of first fluid inflow channels. Allowing the first fluid to flow into,
Injecting a second fluid made of a hydrous solvent into the second fluid inlet through the second fluid injection path of the micromixing chip by the second fluid pressurizing means;
Before the first fluid and the second fluid are merged in a fluid collecting path to form a laminar flow of the first fluid and the second fluid, and before the amorphous gel is generated by hydrolysis of the alkoxide, Discharging the merged fluid of the first fluid and the second fluid from the merged channel to the fluid discharge channel via the induction channel;
Hydrolyzing barium alkoxide and titanium alkoxide contained in the mixed solution discharged through the fluid discharge path outside the micromixing chip with water contained in the hydrous solvent,
The flow rate of the mixture (first fluid) of barium alkoxide and titanium alkoxide sent to the first fluid inlet through the first fluid injection path by the first fluid pressurizing means is in the range of 2 to 50 ml / min. ,
The flow rate of the water-containing solvent (second fluid) sent to the second fluid inlet through the second fluid injection path by the second fluid pressurizing means is in the range of 2 to 50 ml / min. It is a manufacturing method of barium titanate.

The third invention in this application is:
The method for producing barium titanate according to the first invention or the second invention, wherein the hydrous solvent contains 15 to 80 mol% of a polar organic solvent.

The fourth invention in this application is:
The method for producing barium titanate according to any one of the first to third inventions, wherein aging is performed following the hydrolysis.

The fifth invention in this application is:
Following the aging, one or more treatments selected from 1) dispersion, 2) solvent substitution, 3) filtration or 4) drying are performed. The method for producing barium titanate according to the fourth invention It is.
The sixth invention in this application is:
The cross-sectional area of the first fluid inflow channel is in the range of 0.01 to 1 mm ² , and the total length thereof is in the range of 5 to 20 mm;
A cross-sectional area of the first fluid injection path is in a range of 1.0 to 9.0 mm ² ;
A cross-sectional area of the second fluid injection path is in a range of 1.0 to 9.0 mm ² ;
The shortest distance from the first fluid inflow channel side end of the fluid collecting channel to the guide channel is in the range of 10 to 20 mm,
In the range where the cross-sectional area of the guide channel is 1.0 to 9.0 mm ² and the total length is 5 to 50 mm,
The cross-sectional area of the confluence channel is in the range of 1.0 to 9.0 mm ² ;
The method for producing barium titanate according to the second aspect of the present invention.
The seventh invention in this application is:
The cross-sectional area of the first fluid injection path introduction portion in the first fluid injection path is in the range of 1.0 to 9.0 mm ² , and the cross-sectional area of the first fluid injection path communication portion is 1.0 to 9.0 mm ² . Range, the total length is in the range of 10-30 mm,
In the second fluid injection path, the cross-sectional area of the second fluid injection path introduction part is in the range of 1.0 to 9.0 mm ² , and the cross-sectional area of the second fluid injection path communication part is 1.0 to 9.0 mm ^2. In the range of 10 to 30 mm in total length,
The method for producing barium titanate according to the sixth aspect of the invention.

The eighth invention in this application is:
A first fluid injection path for injecting a first fluid from the outside;
A second fluid injection path for injecting a second fluid from the outside,
A plurality of first fluid inlets in communication with the first fluid injection path for inflowing a first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of first fluid inflow channels as one channel;
A plurality of second fluid inlets for communicating with the second fluid injection path, formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path, and for inflowing a second fluid;
An induction channel that is formed at an end opposite to the outlet side end of the first fluid inflow channel in the fluid collecting path, and that flows out the combined fluid of the first fluid and the second fluid;
A confluence channel connected to the guide channel;
A method for producing barium calcium titanate using a microreaction apparatus comprising:
The first fluid pressurizing means injects a first fluid made of a mixture of barium alkoxide, titanium alkoxide, and calcium alkoxide through the first fluid injection path of the micromixing chip into the first fluid inlet, and a plurality of first fluids Flowing the first fluid into the inflow channel;
Injecting a second fluid made of a hydrous solvent into the second fluid inlet through the second fluid injection path of the micromixing chip by the second fluid pressurizing means;
The first fluid and the second fluid are merged in the fluid collecting path to form a laminar flow of the first fluid and the second fluid, and the first fluid and the second fluid are maintained while maintaining the laminar flow state. Discharging the merged fluid with the fluid from the merged channel to the fluid discharge channel via the induction channel;
Hydrolyzing barium alkoxide, titanium alkoxide, and calcium alkoxide contained in the mixed solution discharged through the fluid discharge path outside the micromixing chip with water contained in the hydrous solvent;
It is a manufacturing method of barium calcium titanate characterized by having.

The ninth invention in this application is:
A first fluid injection path for injecting a first fluid from the outside;
A second fluid injection path for injecting a second fluid from the outside,
A plurality of first fluid inlets in communication with the first fluid injection path for inflowing a first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of first fluid inflow channels as one channel;
A plurality of second fluid inlets for communicating with the second fluid injection path, formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path, and for inflowing a second fluid;
An induction channel that is formed at an end opposite to the outlet side end of the first fluid inflow channel in the fluid collecting path, and that flows out the combined fluid of the first fluid and the second fluid;
A confluence channel connected to the guide channel;
A micromixing chip having
First fluid pressurizing means connected to a first fluid inlet of the micromixing chip via a first fluid injection path;
Second fluid pressurizing means connected to the second fluid inlet of the micromixing chip via a second fluid injection path;
A fluid discharge path connected to the confluence channel;
A reaction vessel installed on the outlet side of the fluid discharge path;
A method for producing barium calcium titanate using a microreaction apparatus comprising:
The first fluid pressurizing means injects a first fluid made of a mixture of barium alkoxide, titanium alkoxide, and calcium alkoxide through the first fluid injection path of the micromixing chip into the first fluid inlet, and a plurality of first fluids Flowing the first fluid into the inflow channel;
Injecting a second fluid made of a hydrous solvent into the second fluid inlet through the second fluid injection path of the micromixing chip by the second fluid pressurizing means;
Before the first fluid and the second fluid are merged in a fluid collecting path to form a laminar flow of the first fluid and the second fluid, and before the amorphous gel is generated by hydrolysis of the alkoxide, Discharging the merged fluid of the first fluid and the second fluid from the merged channel to the fluid discharge channel via the induction channel;
Hydrolyzing barium alkoxide, titanium alkoxide and calcium alkoxide contained in the mixed solution discharged through the fluid discharge path outside the micromixing chip with water contained in the water-containing solvent,
The flow rate of the mixture (first fluid) of barium alkoxide, titanium alkoxide and calcium alkoxide sent to the first fluid inlet through the first fluid injection path by the first fluid pressurizing means is 2 to 50 ml / min. Range,
The flow rate of the water-containing solvent (second fluid) sent to the second fluid inlet through the second fluid injection path by the second fluid pressurizing means is in the range of 2 to 50 ml / min. This is a method for producing barium calcium titanate.

The tenth invention in this application is:
The method for producing barium calcium titanate according to the eighth or ninth invention, wherein the hydrous solvent contains 15 to 80 mol% of a polar organic solvent.

The eleventh invention in this application is
The method for producing barium calcium titanate according to any one of the eighth to tenth aspects, wherein aging is performed following the hydrolysis.

The twelfth invention in this application is
Following the aging, 1) dispersion, 2) solvent substitution, 3) Filtration and 4) barium titanate according to the eleventh invention, wherein the performing one or more processes selected from the group consisting of drying It is a manufacturing method of calcium.
The thirteenth invention in this application is
The cross-sectional area of the first fluid inflow channel is in the range of 0.01 to 1 mm ² , and the total length thereof is in the range of 5 to 20 mm;
A cross-sectional area of the first fluid injection path is in a range of 1.0 to 9.0 mm ² ;
A cross-sectional area of the second fluid injection path is in a range of 1.0 to 9.0 mm ² ;
The shortest distance from the first fluid inflow channel side end of the fluid collecting channel to the guide channel is in the range of 10 to 20 mm,
In the range where the cross-sectional area of the guide channel is 1.0 to 9.0 mm ² and the total length is 5 to 50 mm,
The cross-sectional area of the confluence channel is in the range of 1.0 to 9.0 mm ² ;
The method for producing barium calcium titanate according to the ninth aspect of the invention.
The fourteenth invention in this application is
The cross-sectional area of the first fluid injection path introduction portion in the first fluid injection path is in the range of 1.0 to 9.0 mm ² , and the cross-sectional area of the first fluid injection path communication portion is 1.0 to 9.0 mm ² . Range, the total length is in the range of 10-30 mm,
In the second fluid injection path, the cross-sectional area of the second fluid injection path introduction part is in the range of 1.0 to 9.0 mm ² , and the cross-sectional area of the second fluid injection path communication part is 1.0 to 9.0 mm ^2. In the range of 10 to 30 mm in total length,
The method for producing barium calcium titanate according to the thirteenth aspect of the invention.

  According to the method for producing barium titanate according to the present invention, hydrolysis of an alkoxide is not limited to a low temperature of 2 ° C., but can be performed at a low temperature or a room temperature or higher, and further at a 1000 ° C. level. It was possible to produce barium titanate with a high degree of crystallinity without performing the heat treatment.

  In particular, according to the production method of the present invention, the mixture of barium alkoxide and titanium alkoxide and the water-containing solvent are completely contained in the fluid collecting path, the guiding path and the merging path of the micromixing chip used for preparing barium titanate. It does not mix, the clogging of the flow path associated with the formation of amorphous gel does not occur in the fluid collecting path, the guiding flow path, and the merging flow path of the micromixing chip. Thus, it was possible to efficiently prepare a large amount of barium titanate continuously.

  In the method for producing barium calcium titanate according to the present invention, the same effect as described above can be obtained.

Hereinafter, embodiments (examples) of the present invention will be described in more detail with reference to the drawings.
FIG. 1 is a schematic view showing the configuration of a trace reaction apparatus according to the present invention.
The present invention relates to a method for producing barium titanate and barium calcium titanate, a micromixing chip suitable for the preparation of barium titanate and barium calcium titanate, and a microreaction apparatus including the same.

In addition, about the micro mixing chip | tip shown in FIG. 1, it is the cross-sectional view seen from the upper surface direction. Furthermore, the line indicated by the symbol A indicates the flow of the first fluid, and the line indicated by the symbol B indicates the flow of the second fluid. Moreover, the arrow in a figure shows the direction of the flow of each fluid.
FIG. 2 is a schematic view showing another configuration of the trace reaction apparatus of the present invention. The symbols in the figure mean the same contents as in FIG.

<Configuration of Trace Reaction Device 10>
The microreaction apparatus 10 according to the present invention supplies two types of reactive fluids separately to a flow path in a closed system at a high speed to generate a laminar flow of both fluids. It was designed with the aim of discharging this laminar flow out of the closed system before the product is produced, and then obtaining the invention product.

Specifically, the microreaction apparatus 10 according to the present invention includes a micromixing chip 20 that provides the closed system, two fluid pressurizing units 30 and 40 for supplying fluid to the micromixing chip 20, and the micromixing chip 20. Along with the accompanying injection paths 32 and 42 for feeding liquid, a fluid discharge path 50 for discharging a laminar flow composed of two kinds of fluids to the outside of the micromixing chip 20 and a reaction container 52 for receiving the discharged fluid are included.
Hereinafter, each member which comprises the apparatus 10 for trace reaction is demonstrated.

<Fluid pressurizing means (feed pump) 30, 40>
The fluid pressurizing means (liquid feed pumps) 30 and 40 can be used as long as they can supply the fluids 31 and 41 into the micromixing chip 20 at 2 to 50 ml / min. Usually, liquid pump 3
0 and 40 are equipped with syringes or tanks, from which fluids 31 and 41 to be injected are supplied.

  The liquid feed pumps 30 and 40 are connected to the micromixing chip 20 directly or via the injection paths 32 and 42. The flow rates of the fluids 31 and 41 may be determined from the flow rate display of the liquid feed pumps 30 and 40 themselves, or may be determined by providing a flow meter in a part of the injection paths 32 and 42.

In order to supply the two kinds of reactive fluids 31 and 41 to the micromixing chip 20, it is usually necessary to provide two liquid feed pumps 30 and 40. This is not the case when using a mechanism having a mechanism capable of supplying 41.
About the material of the injection paths 32 and 42 used for liquid feeding, the material with sufficient tolerance with respect to the fluid to apply is preferable. Usually, fluororesin, glass, metal, etc. are used.

<First form of micromixing chip>
The two kinds of fluids 31 and 41 are supplied into the micromixing chip 20 and form a laminar flow there, and in a laminar flow state (a state where the fluid 31 and the fluid 41 are not completely mixed), outside the closed system ( In this embodiment shown in FIG. 1, it is discharged into the reaction vessel 52).

  The micromixing chip 20 is formed of a molded body made of a material that is sufficiently resistant to an applied fluid or a reaction product thereof. Usually, a metal molded body in which three plate-like bodies are overlapped is suitably applied. Examples of such metals include titanium alloys and stainless steel, but are not limited as long as the above conditions are satisfied.

  As shown in FIG. 1, the micromixing chip 20 includes a first fluid injection path 32 for injecting a first fluid 31 from the outside and a second fluid injection path 42 for injecting a second fluid 41 from the outside. And a plurality of first fluid inlets 21 through which the first fluid 31 flows and a plurality of first fluid inlets 21 and a plurality of first fluid inlets 21 are provided in parallel with each other. A plurality of first fluid inflow channels 22, a plurality of partition walls 23 formed between the channels 22 and the plurality of first fluid inflow channels 22, and a plurality of first fluid inflow channels The first fluid inflow flow of the fluid collecting path 24 is connected to the outlet side of the path 22 and communicates with the fluid collecting path 24 and the second fluid injecting path having the plurality of first fluid inflow channels 22 as one channel. A second fluid inlet 2 that is formed at the outlet side end of the passage 22 and into which the second fluid 41 flows. And a guide channel 43 that is formed at the end of the fluid collecting channel 24 opposite to the outlet side end of the first fluid inflow channel 22 and that flows out the combined fluid of the first fluid 31 and the second fluid 41. , And a confluence channel 26 connected thereto.

  Here, the first fluid inlet 21 communicates with the outside of the micromixing chip 20 through the first fluid injection path 32 and is usually connected to the first fluid pressurizing means 30 through the first fluid injection path 32. The

  The second fluid inlet 25 communicates with the outside of the micromixing chip 20 through the second fluid injection path 42 and is normally connected to the second fluid pressurizing means 40 through the second fluid injection path 42. .

The merging flow path 26 communicates with the outside of the micromixing chip 20 through the fluid discharge path 50, and the fluid discharge path 50 is normally connected to the reaction vessel 52.
The micromixing chip 20 preferably has a plate-like three-layer structure for manufacturing reasons and cleaning reasons. In addition, in the case where each plate-like body is brought into close contact by means such as bolting, three plate-like bodies having a three-layer structure are provided for the purpose of improving the adhesion and preventing the plate-like body from being damaged by bolting. It is possible to form four or five layers by stacking a plate-like body on the outer side.

  For a three-layer structure, for example, a lower plate-like body (third plate-like body) in which a plurality of grooves serving as injection paths are formed on the upper surface, a plurality of grooves serving as flow paths are formed on the upper surface, A hole serving as a fluid inlet is formed, and a middle plate (second plate) forming an injection path serving as a lid of the groove of the third plate and a merging channel A structure in which a hole is formed and an upper plate (first plate) that is a lid of the groove of the second plate and constitutes the flow path is overlapped and integrated. can do.

  In addition to the above, regarding the position of the merging flow path 26, a fluid discharge path 50 is provided from the side surface of the third plate-like body, and the fluid discharge is provided at the end of the guide flow path 43 of the second plate-like body. It is also possible to provide an opening communicating with the path 50.

  Each plate-like body can be brought into close contact by means such as bolting to form the micromixing chip 20, but the close contact means is not particularly limited, and a liquid-tight flow path can be formed. Any means may be used as long as it is.

  The external dimensions of the micromixing chip 20 are not limited as long as the predetermined first fluid injection path 32, the fluid collecting path 24, the guide channel 43, and the merging channel 26 described later can be provided. There is usually no range of 40 to 100 mm in width, 60 to 200 mm in length, and 20 to 60 mm in thickness when the first plate, the second plate, and the third plate are brought into close contact with each other. Recommended.

  The shape of the micromixing chip 20 is not particularly limited as long as it can provide a predetermined first fluid injection path 32, fluid collecting path 24, guide channel 43, and merging channel 26 described later. Usually, a rectangular shape is used.

  Regarding the thicknesses of the first plate-like body, the second plate-like body, and the third plate-like body, considering the depth of the groove provided on the plate-like body, the first plate-like body or the second plate-like body About a plate-shaped object, the thickness of the range of 5-20 mm is preferable. Moreover, about the 3rd plate-shaped object, the thickness of the range of 10-30 mm is preferable.

  As for the shape of the first fluid inflow channel 22 in the micromixing chip 20, as described above, in the case where the first fluid inflow channel 22 is constituted by three plate-like bodies, since the processing is easy, the upper surface of the second plate-like body is formed. Since the concave groove is provided and the first plate-like body is covered, it is preferable that the first fluid inflow channel 22 finally has a mouth-like structure. In the micromixing chip of the present invention, a V-shaped or U-shaped groove may be provided on the upper surface of the second plate-like body as desired. The number of the first fluid inflow channels depends on the channel width, but is usually preferably in the range of 5 to 35.

About the cross-sectional area of a 1st fluid inflow channel, the cross-sectional area has the preferable range of 0.01-1 mm < ² >. By injecting the liquid into the first fluid inflow channel in the cross-sectional area range at a flow rate of 2 to 50 ml / min, a laminar flow between the first fluid and the second fluid is easily formed.

Usually, the shape of the first fluid inlet is preferably a circular hole. The range of the cross-sectional area of the first fluid inlet 21 is the same as the cross-sectional area of the first fluid inflow channel 22.
Moreover, about the range of the cross-sectional area of a 1st fluid injection path, the range of 1.0-9.0 mm < ² > is desirable.

It is technically difficult to provide the first fluid inflow channel having a cross-sectional area of less than 0.01 mm ² on the micromixing chip. In addition, when the cross-sectional area exceeds 1 mm ² , it is desirable to form a laminar flow of two types of liquid and perform a small amount of reaction, because the amount of liquid that flows in may be excessive and may obstruct the formation of a laminar flow. Absent.

About the full length of the 1st fluid inflow channel 22, the range of 5-20 mm is preferred. If the total length is within this range, the first fluid 31 injected at a flow rate of 2 to 50 ml / min forms a laminar flow with the second fluid 41 that merges at a flow rate of 2 to 50 ml / min at the second fluid inlet 25. It becomes easy to do.

  When the total length is less than 5 mm, a case where a laminar flow composed of the two types of fluids 31 and 41 is not formed in the fluid collecting path 24 is likely to occur. When the total length exceeds 20 mm, it is not always necessary.

  At the end of each first fluid inflow channel 22 on the second plate-like body on the side opposite to the fluid collecting channel 24, holes serving as the first fluid inlet 21 are provided. All the first fluid inlets 21 need to be provided at positions where they communicate with the first fluid injection path 32 when the second plate body and the third plate body are overlapped to form the micromixing chip 20.

  The second fluid inlet 25 is formed at the outlet side end of the first fluid inflow channel 22 of the fluid collecting path 24, and more specifically, the second fluid inlet 25 is the first fluid inflow of the fluid collecting path 24. It is desirable to be provided at the outlet side end portion of the flow path 22 and at the front end position of the partition wall portion 23 that does not overlap the outlet of each first fluid inflow flow path 22.

About the cross-sectional area of the 2nd fluid injection path 42, the cross-sectional area has the preferable range of 1.0-9.0 mm < ² >. A laminar flow between the second fluid 41 and the first fluid 31 is easily formed by injecting the fluid 41 into the second fluid injection path 42 in the cross-sectional area range at a flow rate of 2 to 50 ml / min.

  Normally, the shape of the second fluid inlet 25 is the same as the cross-sectional shape of the second fluid injection path 42, so the range of the cross-sectional area of the second fluid inlet 25 is also the cross-sectional area of the second fluid injection path 42. And the same range. Note that when the second plate-like body and the third plate-like body are overlapped to form the micromixing chip 20, the position of the second fluid injection path 42 needs to be provided at a position where it can communicate with the second fluid inlet 25. is there.

  Regarding the length of the fluid collecting path 24 in the fluid traveling direction, the shortest distance from the end of the fluid collecting path 24 on the first fluid inflow channel 22 side to the end connected to the guide channel 43 is in the range of 10 to 20 mm. Preferably there is. When it is in this range, the fluids 31 and 41 injected at a flow rate in the above range merge to form a laminar flow, and then the fluids 31 and 41 are mixed before the formed laminar flow disappears. The fluids 31 and 41 can reach the reaction vessel 52 through the fluid collecting passage 24, the guide passage 43, and the fluid discharge passage 50. When it is less than 10 mm, it becomes difficult to form a laminar flow composed of the fluid 31 and the fluid 41. On the other hand, when it exceeds 20 mm, it is not necessarily required.

  Regarding the shape and the cross-sectional area of the fluid collecting passage 24, the width and the vertical width that allow the first fluids 31 coming from all the first fluid inflow channels 22 to merge at the portion connected to the plurality of first fluid inflow channels 22. And the cross-sectional area is necessary, but the lateral width gradually decreases so that the laminar flow formed in the fluid collecting passage 24 can be discharged from the guide flow path 43 and the merge flow path 26 without disappearing. A structure that is connected to the guide channel 43 at a narrowed portion is preferable.

Specifically, a structure in which the width of the fluid collecting path 24 is the maximum width on the side in contact with the first fluid inflow channel 22 and the minimum width is in the portion connected to the guide channel 43 is preferable.
The shape of the fluid collecting path 24 is preferably bilaterally symmetrical so that the formation of laminar flow by the first fluid 31 and the second fluid 41 is not hindered.

  In particular, when the fluid collecting path 24 has a bowl shape, high-speed laminar flow is easily discharged out of the micromixing chip 20 without stagnation. Note that the fluid collecting path 24 communicates with all the first fluid inflow channels.

About the cross-sectional area of the induction | guidance | derivation flow path 43, the range of 1.0-9.0 mm < ² > is preferable normally. The cross-sectional area of the merging flow path 26 is preferably larger than the cross-sectional area of the first fluid inflow flow path 22 or the second fluid injection path 42 although it depends on the flow rates of the fluids 31 and 41. The shape of the guide channel 43 is the same as that of the first fluid inflow channel 22. About the full length of the induction | guidance | derivation flow path 43, the range of 5-50 mm is desirable. Moreover, it is preferable that the induction | guidance | derivation flow path 43 is linear in order to discharge | emit a fluid rapidly.

  When the confluence channel 26 is provided above the end of the guide channel 43, in the first plate-like body, at a position where it can communicate with the end of the guide channel 43 on the second plate-like body, It is provided with a hole. Further, when the confluence channel 26 is provided below the end portion of the guide channel 43, a hole is made in the end of the guide channel 43 on the second plate-like body, and further, the side surface of the third plate-like body is formed. A hole-like channel is formed from the hole, and an outlet opening of the hole-like channel is provided at a position where it can communicate with a hole provided at the end of the guide channel 43 on the upper surface of the second plate-like body.

  The cross-sectional area of the merge channel is the same as that of the guide channel 43. About the length of the confluence | merging flow path 26, the length until it reaches the exterior of the micro mixing chip | tip 20 is needed. The shape of the merging channel 26 is not particularly limited, but the shape of a square or cylindrical pipe is preferable.

  Each of the second fluid inlets 25 provided at the respective end positions of the partition walls 23 communicates with the second fluid injection path 42 and is supplied from the second fluid pressurizing means (liquid feed pump) 40. It becomes the outlet of the two fluid 41.

  The first fluid 31 that has flowed through the plurality of first fluid inflow passages 22 at high speed is another second fluid that is supplied from the second fluid inlet 25 at high speed near the end point of the first fluid inflow passage 22. 41, moves through the fluid collecting path 24 at a high speed, and is discharged to the outside (in this embodiment, the reaction vessel 52) through the guide flow path 43 and the combined flow path 26 through the fluid discharge path 50.

<Second Embodiment of Micromixing Chip>
In addition to the first aspect described above, the micromixing chip according to the present invention may be a second aspect described below.

  That is, in the micromixing chip 20 of the first aspect, as shown in FIG. 2, the first fluid injection path 32 further includes a first fluid injection path communication portion 32 b that communicates with the plurality of first fluid inlets 21. The first fluid injection path introduction section 32a is connected to the first fluid injection path communication section 32b from the outside.

  Also, the second fluid injection path 42 is introduced from the outside to the second fluid injection path communication section 42b, and the second fluid injection path communication section 42b communicating with the plurality of second fluid inlets 25. It can be set as the micro mixing chip | tip 20 formed by connecting the part 42a.

  More specifically, with respect to the micromixing chip 20, a first plate-like body located at the top, a second plate-like body located at the middle, and a third plate-like body located at the bottom are overlapped. Is formed.

The first fluid inflow channel 22, the fluid collecting channel 24, and the guide channel 43 form a substantially concave channel in the upper surface of the second plate-like body, and the first fluid inlet 21 and the second fluid channel 21. The fluid inlet 25 forms a hole penetrating the second plate-like body, and a first fluid having a substantially concave cross section that communicates with all of the first fluid inlet 21 on the lower surface of the second plate-like body. A second fluid injection channel communication portion 42b having a substantially concave cross section is formed to communicate with all of the injection channel communication portion 32b and the second fluid inlet 25.

  The first fluid injection path introducing portion 32a forms a hole-like flow path from the side surface of the third plate-like body, and is an opening communicating with the first fluid injection path communication portion 32b on the upper surface of the third plate-like body. The second fluid injection path introduction section 32a forms a hole-like flow path from the side surface of the third plate-like body, and the second fluid injection path communication section 42b is formed on the upper surface of the third plate-like body. The merging flow path 26 has a hole-like flow path from the side surface of the third plate-like body and a hole communicating with the end of the guide flow path 43 on the upper surface of the second plate-like body. The structure having the above structure is preferably used.

  The cross-sectional area of each flow path in the second aspect of the micromixing chip 20, the total length thereof, the shortest distance from the end of the fluid collecting path on the first fluid inflow flow path 22 side to the guide flow path 43, and the like in the first aspect Defined similarly to the micromixing chip 20.

  On the other hand, the first fluid injection path 32 includes a first fluid injection path introduction part 32a and a first fluid injection path communication part 32b connected to the first fluid injection path introduction part 32a, and the second fluid injection path 42 is a second fluid injection path introduction part 42a. And a second fluid injection path communicating portion 42b connected to the second fluid injection path.

Here, the cross-sectional area of the first fluid injection path inlet portion 32a is preferably in the range of 1.0~9.0mm ^2. The cross-sectional area of the first fluid injection path communicating portion 32b is in the range of 1.0 to 9.0 mm ² and the total length is preferably in the range of 10 to 30 mm.

Further, the range of 1.0～9.0Mm ² for the cross-sectional area of the second fluid injection path inlet portion 42a is preferred. In the range of 1.0～9.0Mm ² for the cross-sectional area of the second fluid injection path communicating portion 42b, it is preferable that its length is in the range of 10 to 30 mm.

<Method for producing barium titanate>
In the method for producing barium titanate according to the present invention, a mixture of barium alkoxide and titanium alkoxide is injected into the first fluid inlet 21 of the micromixing chip 20 by the first fluid pressurizing means 30 using the trace reaction device 10. A step of flowing the mixture into the plurality of first fluid inflow channels 22, a step of injecting a hydrous solvent into the second fluid inlet 25 of the micromixing chip 20 by the second fluid pressurizing means 40, and the mixture And the water-containing solvent are combined in a state where the liquid mixture and the water-containing solvent are not completely mixed in the fluid collecting path 24, and before the formation of amorphous gel by hydrolysis, A step of discharging the hydrous solvent from the merging channel 26 to the fluid discharge channel 50, and the merged mixed solution and the hydrated solvent discharged through the fluid drain channel 50 are And a step of hydrolysis in Kishinguchippu 20 outside.

[Mixture of barium alkoxide and titanium alkoxide (first fluid 31)]
About the kind of barium alkoxide used as a raw material, it is not specifically limited, For example, barium methoxide, barium ethoxide, barium propoxide, barium butoxide etc. can be mentioned. Of these, Ba (OC ₂ H ₅ ) ₂ is particularly preferably used. Further, the type of titanium alkoxide as a raw material is not particularly limited, and examples thereof include titanium methoxide, titanium ethoxide, titanium propoxide, and titanium butoxide. Of these, Ti (O—iC ₃ H ₇ ) ₄ is particularly preferably used.

In addition to these alkoxides, composite alkoxides can also be used. Examples of such include barium titanium methoxide, barium titanium ethoxide, barium titanium propoxide, barium titanium butoxide and the like.

[Precursor (first fluid 31)]
The compounding ratio of barium alkoxide and titanium alkoxide in the precursor (first fluid 31) used in the production method according to the present invention is an equimolar reaction, so the molar ratio is 1: 1.00 to 1: 1.01. The range of is preferable.

  In the production method according to the present invention, barium alkoxide and titanium alkoxide are used after being dissolved in an organic solvent. (In this specification, such an alkoxide dissolved in an organic solvent is referred to as a “precursor”.) As the type of the organic solvent, alcohol-based (for example, methanol, ethanol, etc.), ketone-based Organic solvents such as (methyl ethyl ketone, acetone, etc.) can be used alone or mixed to form a mixed solvent. Specifically, for example, a precursor (first fluid 31) can be obtained by dissolving in a mixed solvent of special grade methanol and 2-methoxyethanol (volume ratio 3: 2).

  The solid content (barium alkoxide and titanium alkoxide) concentration in the precursor is preferably 0.1 mol / L or more. When the solid content concentration of the precursor is less than 0.1 mol / L, the crystallinity of the finally obtained barium titanate particles tends to be insufficient.

  The solid content concentration of the precursor is more preferably 0.25 mol / L or more. More desirably, 1.0 mol / L or more is recommended. In preparing the precursor, since it is necessary to prevent the hydrolysis reaction from proceeding, it is preferably performed in an atmosphere not containing water. As an atmosphere to be used, inert atmospheres, such as nitrogen, argon, helium, can be mentioned, for example.

[Hydrophilic solvent (second fluid 41)]
As the water-containing solvent (second fluid 41) used for the hydrolysis of the precursor, a water-containing solvent containing a polar organic solvent at a concentration of 15 to 80 mol% is preferable. When the concentration of the polar organic solvent is 15 mol% or more, a self-association cluster structure of the polar organic solvent is formed in which the polar organic solvent molecules are surrounded around the water molecules, so that when the precursor and the hydrous solvent are in contact with each other, The alkoxide and water are preferably prevented from coming into direct contact with each other, and as a result, uniform hydrolysis can be performed.

  When the concentration of the polar organic solvent is less than 15 mol%, since the self-association cluster structure is difficult to form, the alkoxide and water are easily hydrolyzed immediately, so that the particle size control is not easy.

  The upper limit of the ratio of the polar organic solvent contained in the water-containing solvent is not limited as long as moisture is present and the required hydrolysis efficiency can be maintained. Usually, the concentration of the polar organic solvent is 80 mol. % Or less is preferable. If it exceeds 80 mol%, the hydrolysis reaction may not proceed effectively.

  The concentration of the polar organic solvent contained in the water-containing solvent is desirably 20 to 80 mol%. More desirably, a range of 25 to 77 mol% is recommended. Specific examples of the water-containing solvent include a water-containing solvent having a volume ratio of 1: 1 between pure water and special grade methanol (methanol content 31 mol%).

[Specific manufacturing method]
A method for preparing barium titanate using the micromixing chip 20 shown in FIG. 1 will be described below.

  The precursor (first fluid 31) is injected from the syringe pump (first fluid pressurizing means 30), and the precursor (first fluid 31) is pressurized by the syringe pump (first fluid pressurizing means 30), Through the first fluid injection path 32, the first fluid inlet 21, and further through the first fluid inflow path 22, reach the merging path 26.

  Further, the water-containing solvent (second fluid 41) is injected from the syringe pump (second fluid pressurizing means 40), pressurized by the syringe pump (second fluid pressurizing means 40), and passed through the second fluid injection path 42. The fluid collecting path 24 is reached via the second fluid inlet 25.

  In the vicinity of the second fluid inlet 25, the flow of the precursor (first fluid 31) and the flow of the water-containing solvent (second fluid 41) are maintained at a predetermined flow rate and the laminar flow state (the precursor and the water-containing solvent are completely separated). In the state of not being mixed with each other, and proceeds through the fluid collecting path 24 as it is, and flows out from the merging flow path 26 while maintaining the laminar flow state.

  The laminar flow state is a state in which a unique flow of the precursor and the hydrous solvent can be detected, and the precursor and the hydrous solvent are not in a completely mixed state. For this reason, in the merging channel 26, the precursor and the water-containing solvent are mixed to the extent that they pass through the same channel, but excessive contact between the alkoxide and water is limited, and hydrolysis of the alkoxide is limited. Does not progress excessively. As a result, in the merging channel 26, the amorphous gel generated by the hydrolysis of the alkoxide is not coarsened, and a phenomenon that blocks the merging channel 26 does not occur.

  The barium alkoxide and titanium alkoxide used in the present invention are extremely reactive compounds, and when they come into contact with water, they rapidly undergo hydrolysis and produce an amorphous gel.

  Therefore, the laminar flow referred to here can be said to be a combined state of the precursor and the hydrous solvent that does not produce an amorphous gel that closes the inside of the combined flow path by hydrolysis of the alkoxide. As described above, such a laminar flow is appropriately determined in the micromixing chip 20 as the channel length of the first fluid inflow channel 22, the shape and size of the fluid collecting channel 24, the position of the merging channel 26, and the like. In addition, as described later, it can be formed and maintained by appropriately determining the feeding speed of the precursor and the water-containing solvent.

  Thereafter, the precursor and the water-containing solvent pass through the fluid discharge channel 50 and reach the reaction vessel 52 outside the micromixing chip 20, where barium alkoxide and titanium in the precursor are caused by the action of water contained in the water-containing solvent. Hydrolysis of the alkoxide proceeds.

[Liquid feeding speed]
Regarding the liquid feeding speed of the precursor, that is, the mixture of barium alkoxide and titanium alkoxide, in the micromixing chip having the above preferred dimensions, it is in the range of 2-50 ml / min, and the liquid feeding speed of the hydrous solvent is also 2-50 ml / min. A range of minutes is preferred. In any liquid feeding speed, when it is less than 2 ml / min, the merge flow path 26 or the fluid discharge path 50
As a result of hydrolysis of alkoxide and water, an amorphous gel is formed, and the fluid discharge passage 50 may be blocked.
About the liquid feeding speed of the precursor, a range of preferably 10 to 30 ml / min is recommended,
A range of 15 to 25 ml / min is recommended for the feeding speed of the water-containing solvent.

[Temperature at liquid feeding]
In the method for producing barium titanate according to the present invention, the flow path 22, 24 in the micromixing chip 20 has a high speed of 2-50 ml / min of the precursor (first fluid 31) and the water-containing solvent (second fluid 41). In addition, the hydrous solvent forms a self-associative cluster structure of the polar organic solvent as described above, so that the hydrolysis in the vicinity of the merging channel 26 or in the fluid discharge channel 50 is performed. The generation of an amorphous gel based on the above is suppressed, and hydrolysis is performed outside the micromixing chip 20.

  For this reason, in the method for producing barium titanate according to the present invention, it is not necessary to suppress the hydrolysis by cooling to about −30 ° C. as seen in the conventional production method, and the precursor and water-containing solvent are fed at room temperature. It is possible to carry out liquid. Specifically, the precursor (alkoxide) and water-containing solvent (water) can be fed in the range of 2 to 40 ° C.

〔Hydrolysis〕
In the present invention, hydrolysis of the alkoxide proceeds outside the micromixing chip, so there is no need to consider channel blockage during hydrolysis. About a hydrolysis temperature, it can carry out in the range of 1 to 80 degreeC, for example.

  About the mixture of the precursor (alkoxide) discharged | emitted from the micromixing chip | tip, and inject | poured into the reaction container 52 with a water-containing solvent (water), it is room temperature-200 degreeC in the range of 1 to 150 hours as needed after hydrolysis. Aging is performed in the range of. Generation of barium titanate crystals proceeds by aging. Furthermore, if desired, the particle formation of barium titanate crystals can be promoted by ultrasonic irradiation during aging. As the ultrasonic generator, a device having a transmitter such as an ultrasonic cleaner, an ultrasonic disperser, or a homogenizer can be used.

[Distributed processing]
In the produced barium titanate dispersion after completion of hydrolysis, since the barium titanate particles are aggregated, a dispersion treatment is performed as necessary. Usually, the barium titanate particles are dispersed using a high-pressure dispersion device. Examples of the high-pressure dispersion device include “Nanomizer” (trade name) manufactured by Nanomizer, and an ultrahigh-pressure homogenizer “Microfluidizer” (trade name) manufactured by Microfluidics Corporation. These devices are devices that make ultrafine pressure collide with each other and put the solution in the device into fine particles, and can make fine particles in a short time. Usually, these devices are distributed about 1 to 10 times.

[Solvent substitution]
Depending on the application, solvent substitution of the produced barium titanate dispersion can be performed. The solvent is preferably a low boiling point solvent. Here, the low boiling point solvent means a solvent having a boiling point lower than 130 ° C.

  Specifically, ester solvents such as ethyl acetate (boiling point 77 ° C.), butyl acetate (boiling point 126 ° C.), isobutyl acetate (boiling point 118 ° C.), propylene glycol monomethyl ether (boiling point 120 ° C.), ethylene glycol monomethyl ether (common name) Ether solvent such as “Methicello”, boiling point 124 ° C., methanol solvent (boiling point 65 ° C.), butanol (boiling point 117 ° C.), ethanol (boiling point 78 ° C.), propyl alcohol (boiling point 97 ° C.) Boiling point 56 ° C), methyl ethyl ketone (boiling point 80 ° C), ketone solvents such as methyl isobutyl ketone (boiling point 118 ° C), n-hexane (boiling point 69 ° C), heptane (boiling point 98 ° C), cyclohexane (boiling point 81 ° C), etc. Aliphatic solvents; aromatic solvents such as toluene (boiling point 111 ° C.). Of these, ethylene glycol monomethyl ether (commonly called “methicello”) is particularly preferable in consideration of dispersibility.

〔filtration〕
Examples of the filtration method include filtration separation using a filter cloth, filtration separation by centrifugal separation, and ceramic filtration separation.

[Dry]
If desired, a barium titanate powder is dried. The drying conditions are not particularly limited as long as the solvent can be removed, but usually a method of drying at 120 to 150 ° C. for 1 to 10 hours is employed.

<Method for producing barium calcium titanate>
In the method for producing barium calcium titanate according to the present invention, barium alkoxide, titanium alkoxide, and calcium alkoxide are supplied to the first fluid inlet 21 of the micromixing chip 20 by the first fluid pressurizing means 30 using the trace reaction device 10. A step of injecting the mixture to cause the mixture to flow into the plurality of first fluid inflow channels 22, and a step of injecting the hydrous solvent into the second fluid inlet 25 of the micromixing chip 20 by the second fluid pressurizing means 40. And the mixture and the water-containing solvent are combined in a state where the liquid mixture and the water-containing solvent are not completely mixed in the fluid collecting path 24, and this is combined before the amorphous gel is formed by hydrolysis. A step of discharging the mixed liquid and the water-containing solvent from the merging channel 26 to the fluid discharging channel 50, and the merging flow discharged through the fluid discharging channel 50. The mixture liquid and the water-containing solvent, and a step of hydrolyzing outside micromixing chip 20.

[A mixture of barium alkoxide, titanium alkoxide and calcium alkoxide (first fluid 31)]
About the kind of barium alkoxide used as a raw material, it is not specifically limited, For example, barium methoxide, barium ethoxide, barium propoxide, barium butoxide etc. can be mentioned. Specific examples include dimethoxybarium, diethoxybarium, dipropoxybarium, and dipropoxybarium. Of these, diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] is particularly preferably used.
The kind of titanium alkoxide used as a raw material is not particularly limited, and examples thereof include titanium methoxide, titanium ethoxide, titanium propoxide, and titanium butoxide.

Specific examples include tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, and tetrabutoxytitanium. Of these, tetraisopropoxytitanium [Ti (O—iC ₃ H ₇ ) ₄ ] is particularly preferably used.

The kind of calcium alkoxide used as a raw material is not particularly limited, and examples thereof include dimethoxy calcium, diethoxy calcium, dipropoxy calcium, dipropoxy calcium and the like. Of these, diethoxycalcium [Ca (OC ₂ H ₅ ) ₂ ] is particularly preferably used.

  In addition to these alkoxides, composite alkoxides can also be used. Examples of such include barium titanium methoxide, barium titanium ethoxide, barium titanium propoxide, barium titanium butoxide and the like.

[Precursor (first fluid 31)]
The compounding ratio of barium alkoxide, titanium alkoxide and calcium alkoxide in the precursor (first fluid 31) used in the production method according to the present invention is an equimolar reaction, so that the molar ratio is 1: M: N (M is 0.80 to 1.20, N is 0.01 to 0.20
) Is preferred.

  In the production method according to the present invention, barium alkoxide, titanium alkoxide and calcium alkoxide are used after being dissolved in an organic solvent. (In this specification, such an alkoxide dissolved in an organic solvent is referred to as a “precursor”.) As the type of the organic solvent, alcohol-based (for example, methanol, ethanol, etc.), ketone-based Organic solvents such as (methyl ethyl ketone, acetone, etc.) can be used alone or mixed to form a mixed solvent. Specifically, for example, a precursor (first fluid 31) can be obtained by dissolving in a mixed solvent of special grade methanol and 2-methoxyethanol (volume ratio 3: 2).

  The solid content (barium alkoxide, titanium alkoxide and calcium alkoxide) concentration in the precursor is preferably 0.1 mol / L or more. When the solid content concentration of the precursor is less than 0.1 mol / L, the crystallinity of the finally obtained barium calcium titanate particles tends to be insufficient.

The solid content concentration of the precursor is more preferably 0.25 mol / L or more. More desirably, 1.0 mol / L or more is recommended.
In preparing the precursor, since it is necessary to prevent the hydrolysis reaction from proceeding, it is preferably performed in an atmosphere not containing water. As an atmosphere to be used, inert atmospheres, such as nitrogen, argon, helium, can be mentioned, for example.

[Hydrophilic solvent (second fluid 41)]
As the water-containing solvent (second fluid 41) used for the hydrolysis of the precursor, a water-containing solvent containing a polar organic solvent at a concentration of 15 to 80 mol% is preferable. When the concentration of the polar organic solvent is 15 mol% or more, a self-association cluster structure of the polar organic solvent is formed in which the polar organic solvent molecules are surrounded around the water molecules, so that when the precursor and the hydrous solvent are in contact with each other, The alkoxide and water are preferably prevented from coming into direct contact with each other, and as a result, uniform hydrolysis can be performed.

  When the concentration of the polar organic solvent is less than 15 mol%, since the self-association cluster structure is difficult to form, the alkoxide and water are easily hydrolyzed immediately, so that the particle size control is not easy.

  The upper limit of the ratio of the polar organic solvent contained in the water-containing solvent is not limited as long as moisture is present and the required hydrolysis efficiency can be maintained. Usually, the concentration of the polar organic solvent is 80 mol. % Or less is preferable. If it exceeds 80 mol%, the hydrolysis reaction may not proceed effectively.

  The concentration of the polar organic solvent contained in the water-containing solvent is desirably 20 to 80 mol%. More desirably, a range of 25 to 77 mol% is recommended. Specific examples of the water-containing solvent include a water-containing solvent having a volume ratio of 1: 1 between pure water and special grade methanol (methanol content 31 mol%).

[Specific manufacturing method]
A method for preparing barium calcium titanate using the micromixing chip 20 shown in FIG. 1 will be described below.

The precursor (first fluid 31) is injected from the syringe pump (first fluid pressurizing means 30), and the precursor (first fluid 31) is pressurized by the syringe pump (first fluid pressurizing means 30), First
Through the fluid injection path 32, the first fluid inlet 21, and further through the first fluid inflow path 22, reach the merging path 26.

  Further, the water-containing solvent (second fluid 41) is injected from the syringe pump (second fluid pressurizing means 40), pressurized by the syringe pump (second fluid pressurizing means 40), and passed through the second fluid injection path 42. The fluid collecting path 24 is reached via the second fluid inlet 25.

  In the vicinity of the second fluid inlet 25, the flow of the precursor (first fluid 31) and the flow of the water-containing solvent (second fluid 41) are maintained at a predetermined flow rate and the laminar flow state (the precursor and the water-containing solvent are completely separated). In the state of not being mixed with each other, and proceeds through the fluid collecting path 24 as it is, and flows out from the merging flow path 26 while maintaining the laminar flow state.

  The laminar flow state is a state in which a unique flow of the precursor and the hydrous solvent can be detected, and the precursor and the hydrous solvent are not in a completely mixed state. For this reason, in the merging channel 26, the precursor and the water-containing solvent are mixed to the extent that they pass through the same channel, but excessive contact between the alkoxide and water is limited, and hydrolysis of the alkoxide is limited. Does not progress excessively. As a result, in the merging channel 26, the amorphous gel generated by the hydrolysis of the alkoxide is not coarsened, and a phenomenon that blocks the merging channel 26 does not occur.

  The barium alkoxide, titanium alkoxide, and calcium alkoxide used in the present invention are extremely reactive compounds, and when they come into contact with water, they are rapidly hydrolyzed to produce an amorphous gel.

  Therefore, the laminar flow referred to here can be said to be a combined state of the precursor and the hydrous solvent that does not produce an amorphous gel that closes the inside of the combined flow path by hydrolysis of the alkoxide. As described above, such a laminar flow is appropriately determined in the micromixing chip 20 as the channel length of the first fluid inflow channel 22, the shape and size of the fluid collecting channel 24, the position of the merging channel 26, and the like. In addition, as described later, it can be formed and maintained by appropriately determining the feeding speed of the precursor and the water-containing solvent.

  Thereafter, the precursor and the water-containing solvent pass through the fluid discharge path 50 and reach the reaction vessel 52 outside the micromixing chip 20, where barium alkoxide and titanium in the precursor are caused by the action of water contained in the water-containing solvent. Hydrolysis of alkoxide and calcium alkoxide proceeds.

[Liquid feeding speed]
Regarding the liquid feeding speed of the precursor, that is, the mixture of barium alkoxide, titanium alkoxide and calcium alkoxide, in the micromixing chip having the above preferred dimensions, the liquid feeding speed of the water-containing solvent is also 2 A range of ˜50 ml / min is preferred. For any liquid feeding speed, if it is less than 2 ml / min, the merge channel 2
6 or hydrolysis of the alkoxide and water proceeds in the fluid discharge path 50, whereby an amorphous gel is generated, and in particular, the fluid discharge path 50 may be blocked.
About the liquid feeding speed of the precursor, a range of preferably 10 to 30 ml / min is recommended,
A range of 15 to 25 ml / min is recommended for the feeding speed of the water-containing solvent.

[Temperature at liquid feeding]
In the method for producing barium calcium titanate according to the present invention, the flow paths 22 and 24 in the micromixing chip 20 have a precursor (first fluid 31) and a water-containing solvent (second fluid 41) of 2 to 50 ml / min. By flowing in a laminar flow at a high speed, and further, the hydrous solvent forms a self-associative cluster structure of a polar organic solvent as described above. Generation of an amorphous gel based on decomposition is suppressed, and hydrolysis is performed outside the micromixing chip 20.

  For this reason, in the method for producing barium calcium titanate according to the present invention, it is not necessary to suppress the hydrolysis by cooling to about −30 ° C. as seen in the conventional production method. It is possible to perform liquid feeding. Specifically, the precursor (alkoxide) and water-containing solvent (water) can be fed in the range of 2 to 40 ° C.

〔Hydrolysis〕
In the present invention, hydrolysis of the alkoxide proceeds outside the micromixing chip, so there is no need to consider channel blockage during hydrolysis. About a hydrolysis temperature, it can carry out in the range of 1 to 80 degreeC, for example.

  About the mixture of the precursor (alkoxide) discharged | emitted from the micromixing chip | tip, and inject | poured into the reaction container 52 with a water-containing solvent (water), it is room temperature-200 degreeC in the range of 1 to 150 hours as needed after hydrolysis. Aging is performed in the range of. Generation of barium calcium titanate crystals proceeds by aging. Further, if desired, the generation of particles of barium calcium titanate crystals can be promoted by ultrasonic irradiation during aging. As the ultrasonic generator, a device having a transmitter such as an ultrasonic cleaner, an ultrasonic disperser, or a homogenizer can be used.

[Distributed processing]
In the barium calcium titanate dispersion produced after the hydrolysis, the barium calcium titanate particles are agglomerated, so that a dispersion treatment is performed as necessary. Usually, the barium calcium titanate particles are dispersed using a high-pressure dispersing device. Examples of the high-pressure dispersion device include “Nanomizer” (trade name) manufactured by Nanomizer, and an ultrahigh-pressure homogenizer “Microfluidizer” (trade name) manufactured by Microfluidics Corporation. These devices are devices that make ultrafine pressure collide with each other and put the solution in the device into fine particles, and can make fine particles in a short time. Usually, these devices are distributed about 1 to 10 times.

[Solvent substitution]
Depending on the application, solvent substitution of the produced barium calcium titanate dispersion can be performed. The solvent is preferably a low boiling point solvent. Here, the low boiling point solvent means a solvent having a boiling point lower than 130 ° C.

  Specifically, ester solvents such as ethyl acetate (boiling point 77 ° C.), butyl acetate (boiling point 126 ° C.), isobutyl acetate (boiling point 118 ° C.), propylene glycol monomethyl ether (boiling point 120 ° C.), ethylene glycol monomethyl ether (common name) Ether solvent such as “Methicello”, boiling point 124 ° C., methanol solvent (boiling point 65 ° C.), butanol (boiling point 117 ° C.), ethanol (boiling point 78 ° C.), propyl alcohol (boiling point 97 ° C.) Boiling point 56 ° C), methyl ethyl ketone (boiling point 80 ° C), ketone solvents such as methyl isobutyl ketone (boiling point 118 ° C), n-hexane (boiling point 69 ° C), heptane (boiling point 98 ° C), cyclohexane (boiling point 81 ° C), etc. Aliphatic solvents; aromatic solvents such as toluene (boiling point 111 ° C.). Of these, ethylene glycol monomethyl ether (commonly called “methicello”) is particularly preferable in consideration of dispersibility.

〔filtration〕
Examples of the filtration method include filtration separation using a filter cloth, filtration separation by centrifugal separation, and ceramic filtration separation.

[Dry]
If desired, a barium calcium titanate powder is dried. The drying conditions are not particularly limited as long as the solvent can be removed, but usually a method of drying at 120 to 150 ° C. for 1 to 10 hours is employed.

Barium titanate and barium calcium titanate prepared by the production method according to the present invention are known compounds. These compounds have a high insulation resistance after firing, and can be, for example, a ceramic capacitor with little decrease in insulation resistance with time change in a high-temperature load test.
Preferred embodiments of the present invention are listed below.

<Preferred embodiment 1>
A first fluid injection path introduction section for injecting a first fluid from the outside, and a first fluid injection path communication section connected to the first fluid injection path introduction section;
A second fluid injection path introduction section for injecting a second fluid from the outside and a second fluid injection path communication section connected thereto;
A plurality of first fluid inlets for communicating with the second fluid injection path communicating portion and for flowing in the first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of fluid channels as one channel;
A plurality of second fluid inlets configured to communicate with the second fluid injection path communicating portion and formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path;
An inductive channel that is formed at an end of the first fluid inflow channel opposite to an outlet side end of the first fluid inflow channel and that flows out of the merged fluid of the first fluid and the second fluid, and a confluence that connects to the guide channel A micromixing chip having a flow path.

<Preferred embodiment 2>
A first fluid injection path for injecting a first fluid from the outside;
A second fluid injection path for injecting a second fluid from the outside,
A plurality of first fluid inlets in communication with the first fluid injection path for inflowing a first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of first fluid inflow channels as one channel;
A plurality of second fluid inlets for communicating with the second fluid injection path, formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path, and for inflowing a second fluid;
An induction channel that is formed at an end opposite to the outlet side end of the first fluid inflow channel in the fluid collecting path, and that flows out the combined fluid of the first fluid and the second fluid;
A confluence channel connected to the guide channel,
Furthermore, the first fluid injection path is introduced until the first fluid injection path is connected to the first fluid injection path communication section communicating with the plurality of first fluid inlets and the first fluid injection path communication section from the outside. The part is connected to the
A second fluid injection path communicating section in which the second fluid injection path communicates with the plurality of second fluid inlets; and a second fluid injection path introducing section extending from the outside to the second fluid injection path communicating section. Are connected to each other,
The width of the fluid collecting path is the maximum width on the side in contact with the first fluid inflow channel, and takes the minimum width in the portion connected to the guide channel,
The second fluid inlet is formed at a position on the outlet side end of the first fluid inflow channel of the fluid collecting path and not overlapping with the outlets of the plurality of first fluid inflow channels. A micromixing chip characterized by being configured as described above.

Measurement of crystallite diameter of barium titanate As a method for measuring the crystallite diameter of the barium titanate particles prepared in the following examples, an equal amount of the prepared samples were taken out into powders, and an X-ray small angle scattering measurement device ( X-ray diffraction measurement (XRD) was carried out under the conditions of X-ray source: CuKα, tube voltage: 50 KV, tube current; 240 mA, 2θ range: 20 ° to 90 °. The results are shown in Table 1.

[Example 1]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. The precursor (first fluid) was added and mixed at room temperature such that the molar ratio was 1: 1 and the total concentration of diethoxybarium and tetraisopropoxytitanium was 1 mol / l.

In addition, a 1: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).
Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed at room temperature in the reaction vessel 52, aging was performed under the conditions shown in Table 1, and further, the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. Liquid passing treatment (fine dispersion treatment) was performed 5 times with "Nanomizer" (trade name) to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 2]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. The precursor (first fluid) was added and mixed at room temperature such that the molar ratio was 1: 1 and the total concentration of diethoxybarium and tetraisopropoxytitanium was 1 mol / l. In addition, a 1: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 3]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. The precursor (first fluid) was added and mixed at room temperature such that the molar ratio was 1: 1 and the total concentration of diethoxybarium and tetraisopropoxytitanium was 1 mol / l.

  Moreover, a 0.33: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid). Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 4]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. The precursor (first fluid) was added and mixed at room temperature such that the molar ratio was 1: 1 and the total concentration of diethoxybarium and tetraisopropoxytitanium was 1 mol / l. Moreover, a 0.33: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 5]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. ] At a room temperature so that the total concentration of diethoxybarium and tetraisopropoxytitanium is 0.50 mol / l in a molar ratio to obtain a precursor (first fluid). Moreover, a 0.33: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 6]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. ] At a room temperature so that the total concentration of diethoxybarium and tetraisopropoxytitanium is 0.50 mol / l in a molar ratio to obtain a precursor (first fluid). Further, a 0.143: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 7]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. ] At a room temperature so that the total concentration of diethoxybarium and tetraisopropoxytitanium is 0.50 mol / l in a molar ratio to obtain a precursor (first fluid). In addition, a 1: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 8]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. ] At a room temperature so that the total concentration of diethoxybarium and tetraisopropoxytitanium is 0.25 mol / l in a molar ratio to give a precursor (first fluid). Further, a 0.143: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 9]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. ] At a room temperature so that the total concentration of diethoxybarium and tetraisopropoxytitanium is 0.25 mol / l in a molar ratio to give a precursor (first fluid). Further, a 0.143: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 10]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. ] At a room temperature so that the total concentration of diethoxybarium and tetraisopropoxytitanium is 0.25 mol / l in a molar ratio to give a precursor (first fluid). Moreover, a 0.33: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 11]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. ] At a room temperature so that the total concentration of diethoxybarium and tetraisopropoxytitanium is 0.25 mol / l in a molar ratio to give a precursor (first fluid). Further, a 0.143: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 12]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. ] At a room temperature so that the total concentration of diethoxybarium and tetraisopropoxytitanium is 0.50 mol / l in a molar ratio to obtain a precursor (first fluid). Moreover, a 0.173: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 13]
A mixed solvent of methanol: 2-methoxyethanol in a volume ratio of 3: 2 was prepared, and diethoxybarium [Ba (OC ₂ H ₅ ) ₂ ] and tetraisopropoxy titanium [Ti (O—iC ₃ H ₇ ) ₄ were prepared there. ] At a room temperature so that the total concentration of diethoxybarium and tetraisopropoxytitanium is 0.50 mol / l in a molar ratio to obtain a precursor (first fluid). Moreover, a 0.173: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is used as the second fluid. Injected from the pressurizing means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 14]
2 and methoxyethanol diethoxy barium [Ba (OC ₂ H _{5) 2]} diethoxy calcium [Ca (C ₂ H _{5) 2]} and the titanium tetraisopropoxide _{[Ti (O-iC 3 H 7} ) 4 ] Was added and mixed at room temperature so that the molar ratio was 0.95: 0.05: 1 to obtain a precursor (first fluid). Moreover, a 0.33: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid). Under the conditions described in Table 1, the precursor (first fluid) is injected from the first fluid pressurizing means 30 of the trace reaction apparatus shown in FIG. 1, and the hydrous solvent (second fluid) is added to the second fluid. Injected from the pressure means 40.

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

[Example 15]
2 and methoxyethanol diethoxy barium [Ba (OC ₂ H _{5) 2]} diethoxy calcium [Ca (C ₂ H _{5) 2]} and the titanium tetraisopropoxide _{[Ti (O-iC 3 H 7} ) 4 ] Was added and mixed at room temperature so that the molar ratio was 0.9: 0.1: 1 to obtain a precursor (first fluid). Moreover, a 0.33: 1 (volume ratio) mixture of pure water and high-purity methanol was prepared and used as a hydrous solvent (second fluid).

  After the precursor was hydrolyzed in the reaction vessel 52, hydrolysis and aging were performed under the conditions shown in Table 1, and the solvent was replaced with ethylene glycol monomethyl ether using a rotary evaporator. With “Nanomizer” (trade name), liquid passing treatment (fine dispersion treatment) was performed 5 times to prepare a barium titanate solution. Subsequently, it was dried at 140 ° C. for 1 hour to obtain a barium titanate powder. The results of XRD analysis of this barium titanate are shown in Table 1.

〔微量反応用装置の説明〕
図２に示した構成を有する微量反応用装置１０を用いて、チタン酸バリウムを調製した。
マイクロミキシングチップ外寸５０ｍｍ×７９ｍｍ×３０ｍｍ
第１流体流入流路２２の長さ９ｍｍ
第１流体流入流路２２の断面積０．２５ｍｍ²
第１流体流入流路２２の幅０．５ｍｍ
第１流体入口２１の内径０．５ｍｍ
第１流体注入路導入部３２ａの内径２ｍｍ
第１流体注入路連通部３２ｂの内径２ｍｍ、全長１２．２ｍｍ
第２流体入口２５の内径０．５ｍｍ
第２流体注入路導入部４２ａの内径２ｍｍ
第２流体注入路連通部４２ｂの内径２ｍｍ、全長１２．２ｍｍ
流体集合路２４の長さ（第１流体流路との接続部分から、誘導流路との接続部分までの最短距離）１４ｍｍ
誘導流路４３の長さ６ｍｍ
誘導流路４３の幅１．５ｍｍ
合流流路２６内径２ｍｍ
流体排出路５０の内径２ｍｍ
マイクロミキシングチップ２０の材質：ＳＵＳ
流体注入路・流体排出路を形成する送液管の材質：フッ素樹脂

[Explanation of trace reaction equipment]
Barium titanate was prepared using the trace reaction apparatus 10 having the configuration shown in FIG.
Micro mixing chip outer dimensions 50mm x 79mm x 30mm
9 mm length of the first fluid inflow channel 22
The sectional area of the first fluid inflow channel 22 is 0.25 mm ^2.
The width of the first fluid inflow channel 22 is 0.5 mm.
Inner diameter 0.5 mm of the first fluid inlet 21
Inner diameter 2 mm of the first fluid injection path introducing portion 32a
Inner diameter 2 mm, total length 12.2 mm of the first fluid injection path communicating portion 32 b
Inner diameter of second fluid inlet 25 0.5 mm
2 mm inner diameter of the second fluid injection path introducing portion 42a
2nd inner diameter of the second fluid injection path communicating portion 42b, total length 12.2mm
Length of fluid collecting path 24 (shortest distance from the connecting portion with the first fluid flow path to the connecting portion with the guide flow path) 14 mm
6 mm length of the guide channel 43
The width of the guide channel 43 is 1.5 mm.
Confluence channel 26 inner diameter 2 mm
Inner diameter of fluid discharge passage 50
Micromixing chip 20 material: SUS
Material of the liquid supply pipe that forms the fluid injection path / fluid discharge path: Fluororesin

  As mentioned above, although the preferable form of this invention was demonstrated, this invention is not limited to said form, For example, the micro mixing chip | tip concerning this invention is two liquids with high reactivity like barium titanate. The present invention can be suitably applied to a compound preparation method including the above reaction.

FIG. 1 is a schematic view showing the configuration of a trace reaction apparatus according to the present invention. FIG. 2 is a schematic view showing another configuration of the trace reaction apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Micro-reaction apparatus 20 Micro mixing chip 21 1st fluid inlet 22 1st fluid inflow channel 23 Partition part 24 Fluid collecting channel 25 Second fluid inlet 26 Merge channel 30 1st fluid pressurization means (liquid feeding pump)
31 First fluid (precursor)
32 1st fluid injection path 32a 1st fluid injection path introduction part 32b 1st fluid injection path communication part 40 2nd fluid pressurization means (liquid feed pump)
41 Second fluid (hydrous solvent)
42 2nd fluid injection path 42a 2nd fluid injection path introduction part 42b 2nd fluid injection path communication part 43 Guidance flow path 50 Fluid discharge path 52 Reaction vessel A Flow of 1st fluid B Flow of 2nd fluid

Claims (14)

A first fluid injection path for injecting a first fluid from the outside;
A second fluid injection path for injecting a second fluid from the outside,
A plurality of first fluid inlets in communication with the first fluid injection path for inflowing a first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of first fluid inflow channels as one channel;
A plurality of second fluid inlets for communicating with the second fluid injection path, formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path, and for inflowing a second fluid;
An induction channel that is formed at an end opposite to the outlet side end of the first fluid inflow channel in the fluid collecting path, and that flows out the combined fluid of the first fluid and the second fluid;
A confluence channel connected to the guide channel;
A micromixing chip having
First fluid pressurizing means connected to a first fluid inlet of the micromixing chip via a first fluid injection path;
Second fluid pressurizing means connected to the second fluid inlet of the micromixing chip via a second fluid injection path;
A fluid discharge path connected to the confluence channel;
A reaction vessel installed on the outlet side of the fluid discharge path;
A method for producing barium titanate using a microreaction apparatus comprising:
The first fluid pressurizing means injects a first fluid made of a mixture of barium alkoxide and titanium alkoxide into the first fluid inlet through the first fluid injection path of the micromixing chip, and a plurality of first fluid inflow channels. Allowing the first fluid to flow into,
Injecting a second fluid made of a hydrous solvent into the second fluid inlet through the second fluid injection path of the micromixing chip by the second fluid pressurizing means;
The first fluid and the second fluid are merged in the fluid collecting path to form a laminar flow of the first fluid and the second fluid, and the first fluid and the second fluid are maintained while maintaining the laminar flow state. Discharging the merged fluid with the fluid from the merged channel to the fluid discharge channel via the induction channel;
Hydrolyzing barium alkoxide and titanium alkoxide contained in the mixed solution discharged through the fluid discharge passage outside the micromixing chip with water contained in the hydrous solvent;
A method for producing barium titanate, comprising: A first fluid injection path for injecting a first fluid from the outside;
A second fluid injection path for injecting a second fluid from the outside,
A plurality of first fluid inlets in communication with the first fluid injection path for inflowing a first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of first fluid inflow channels as one channel;
A plurality of second fluid inlets for communicating with the second fluid injection path, formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path, and for inflowing a second fluid;
An induction channel that is formed at an end opposite to the outlet side end of the first fluid inflow channel in the fluid collecting path, and that flows out the combined fluid of the first fluid and the second fluid;
A confluence channel connected to the guide channel;
A micromixing chip having
First fluid pressurizing means connected to a first fluid inlet of the micromixing chip via a first fluid injection path;
Second fluid pressurizing means connected to the second fluid inlet of the micromixing chip via a second fluid injection path;
A fluid discharge path connected to the confluence channel;
A reaction vessel installed on the outlet side of the fluid discharge path;
A method for producing barium titanate using a microreaction apparatus comprising:
The first fluid pressurizing means injects a first fluid made of a mixture of barium alkoxide and titanium alkoxide into the first fluid inlet through the first fluid injection path of the micromixing chip, and a plurality of first fluid inflow channels. Allowing the first fluid to flow into,
Injecting a second fluid made of a hydrous solvent into the second fluid inlet through the second fluid injection path of the micromixing chip by the second fluid pressurizing means;
Before the first fluid and the second fluid are merged in a fluid collecting path to form a laminar flow of the first fluid and the second fluid, and before the amorphous gel is generated by hydrolysis of the alkoxide, Discharging the merged fluid of the first fluid and the second fluid from the merged channel to the fluid discharge channel via the induction channel;
Hydrolyzing barium alkoxide and titanium alkoxide contained in the mixed solution discharged through the fluid discharge path outside the micromixing chip with water contained in the hydrous solvent,
The flow rate of the mixture (first fluid) of barium alkoxide and titanium alkoxide sent to the first fluid inlet through the first fluid injection path by the first fluid pressurizing means is in the range of 2 to 50 ml / min. ,
The flow rate of the water-containing solvent (second fluid) sent to the second fluid inlet through the second fluid injection path by the second fluid pressurizing means is in the range of 2 to 50 ml / min. A method for producing barium titanate. The method for producing barium titanate according to claim 1 or 2 , wherein the hydrous solvent contains 15 to 80 mol% of a polar organic solvent. The method for producing barium titanate according to any one of claims 1 to 3 , wherein aging is performed following the hydrolysis. 5. The barium titanate according to claim 4 , wherein the aging is followed by one or more treatments selected from the group consisting of 1) dispersion, 2) solvent substitution, 3) filtration, and 4) drying. Production method.   A cross-sectional area of the first fluid inflow channel is 0.01 to 1 mm. ² The total length is in the range of 5 to 20 mm,
  A cross-sectional area of the first fluid injection path is 1.0 to 9.0 mm. ² In the range
  A cross-sectional area of the second fluid injection path is 1.0 to 9.0 mm. ² In the range
  The shortest distance from the first fluid inflow channel side end of the fluid collecting channel to the guide channel is in the range of 10 to 20 mm,
  The cross-sectional area of the guide channel is 1.0 to 9.0 mm ² In the range of 5 to 50 mm in total length,
  The cross-sectional area of the confluence channel is 1.0 to 9.0 mm ² Range,
  The method for producing barium titanate according to claim 2, wherein:   A cross-sectional area of the first fluid injection path introduction portion in the first fluid injection path is 1.0 to 9.0 mm. ² In the range, the cross-sectional area of the first fluid injection path communicating portion is 1.0 to 9.0 mm ² The total length is in the range of 10-30 mm,
  A cross-sectional area of the second fluid injection path introduction portion in the second fluid injection path is 1.0 to 9.0 mm. ² In the range, the cross-sectional area of the second fluid injection path communicating portion is 1.0 to 9.0 mm ² In the range of 10 to 30 mm in total length,
  The method for producing barium titanate according to claim 6. A first fluid injection path for injecting a first fluid from the outside;
A second fluid injection path for injecting a second fluid from the outside,
A plurality of first fluid inlets in communication with the first fluid injection path for inflowing a first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of first fluid inflow channels as one channel;
A plurality of second fluid inlets for communicating with the second fluid injection path, formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path, and for inflowing a second fluid;
An induction channel that is formed at an end opposite to the outlet side end of the first fluid inflow channel in the fluid collecting path, and that flows out the combined fluid of the first fluid and the second fluid;
A confluence channel connected to the guide channel;
A micromixing chip having
First fluid pressurizing means connected to a first fluid inlet of the micromixing chip via a first fluid injection path;
Second fluid pressurizing means connected to the second fluid inlet of the micromixing chip via a second fluid injection path;
A fluid discharge path connected to the confluence channel;
A reaction vessel installed on the outlet side of the fluid discharge path;
A method for producing barium calcium titanate using a microreaction apparatus comprising:
The first fluid pressurizing means injects a first fluid made of a mixture of barium alkoxide, titanium alkoxide, and calcium alkoxide through the first fluid injection path of the micromixing chip into the first fluid inlet, and a plurality of first fluids Flowing the first fluid into the inflow channel;
Injecting a second fluid made of a hydrous solvent into the second fluid inlet through the second fluid injection path of the micromixing chip by the second fluid pressurizing means;
The first fluid and the second fluid are merged in the fluid collecting path to form a laminar flow of the first fluid and the second fluid, and the first fluid and the second fluid are maintained while maintaining the laminar flow state. Discharging the merged fluid with the fluid from the merged channel to the fluid discharge channel via the induction channel;
Hydrolyzing barium alkoxide, titanium alkoxide, and calcium alkoxide contained in the mixed solution discharged through the fluid discharge path outside the micromixing chip with water contained in the hydrous solvent;
A process for producing barium calcium titanate, comprising: A first fluid injection path for injecting a first fluid from the outside;
A second fluid injection path for injecting a second fluid from the outside,
A plurality of first fluid inlets in communication with the first fluid injection path for inflowing a first fluid;
A plurality of first fluid inflow passages that are in communication with the plurality of first fluid inlets and are arranged substantially in parallel;
A plurality of partition walls formed between each of the plurality of first fluid inflow channels; and
A fluid collecting path that communicates with an outlet side of the plurality of first fluid inflow channels, and uses the plurality of first fluid inflow channels as one channel;
A plurality of second fluid inlets for communicating with the second fluid injection path, formed at an outlet side end portion of the first fluid inflow channel of the fluid collecting path, and for inflowing a second fluid;
An induction channel that is formed at an end opposite to the outlet side end of the first fluid inflow channel in the fluid collecting path, and that flows out the combined fluid of the first fluid and the second fluid;
A confluence channel connected to the guide channel;
A micromixing chip having
First fluid pressurizing means connected to a first fluid inlet of the micromixing chip via a first fluid injection path;
Second fluid pressurizing means connected to the second fluid inlet of the micromixing chip via a second fluid injection path;
A fluid discharge path connected to the confluence channel;
A reaction vessel installed on the outlet side of the fluid discharge path;
A method for producing barium calcium titanate using a microreaction apparatus comprising:
The first fluid pressurizing means injects a first fluid made of a mixture of barium alkoxide, titanium alkoxide, and calcium alkoxide through the first fluid injection path of the micromixing chip into the first fluid inlet, and a plurality of first fluids Flowing the first fluid into the inflow channel;
Injecting a second fluid made of a hydrous solvent into the second fluid inlet through the second fluid injection path of the micromixing chip by the second fluid pressurizing means;
Before the first fluid and the second fluid are merged in a fluid collecting path to form a laminar flow of the first fluid and the second fluid, and before the amorphous gel is generated by hydrolysis of the alkoxide, Discharging the merged fluid of the first fluid and the second fluid from the merged channel to the fluid discharge channel via the induction channel;
Hydrolyzing barium alkoxide, titanium alkoxide and calcium alkoxide contained in the mixed solution discharged through the fluid discharge path outside the micromixing chip with water contained in the water-containing solvent,
The flow rate of the mixture (first fluid) of barium alkoxide, titanium alkoxide and calcium alkoxide sent to the first fluid inlet through the first fluid injection path by the first fluid pressurizing means is 2 to 50 ml / min. Range,
The flow rate of the water-containing solvent (second fluid) sent to the second fluid inlet through the second fluid injection path by the second fluid pressurizing means is in the range of 2 to 50 ml / min. A method for producing barium calcium titanate. The method for producing barium calcium titanate according to claim 8 or 9 , wherein the hydrous solvent contains 15 to 80 mol% of a polar organic solvent. The method for producing barium calcium titanate according to any one of claims 8 to 10 , wherein aging is performed following the hydrolysis. The barium calcium titanate according to claim 11 , wherein the aging is followed by one or more treatments selected from the group consisting of 1) dispersion, 2) solvent substitution, 3) filtration, and 4) drying. Manufacturing method.   A cross-sectional area of the first fluid inflow channel is 0.01 to 1 mm. ² The total length is in the range of 5 to 20 mm,
  A cross-sectional area of the first fluid injection path is 1.0 to 9.0 mm. ² In the range
  A cross-sectional area of the second fluid injection path is 1.0 to 9.0 mm. ² In the range
  The shortest distance from the first fluid inflow channel side end of the fluid collecting channel to the guide channel is in the range of 10 to 20 mm,
  The cross-sectional area of the guide channel is 1.0 to 9.0 mm ² In the range of 5 to 50 mm in total length,
  The cross-sectional area of the confluence channel is 1.0 to 9.0 mm ² Range,
  The method for producing barium calcium titanate according to claim 9.   A cross-sectional area of the first fluid injection path introduction portion in the first fluid injection path is 1.0 to 9.0 mm. ² In the range, the cross-sectional area of the first fluid injection path communicating portion is 1.0 to 9.0 mm ² The total length is in the range of 10-30 mm,
  A cross-sectional area of the second fluid injection path introduction portion in the second fluid injection path is 1.0 to 9.0 mm. ² In the range, the cross-sectional area of the second fluid injection path communicating portion is 1.0 to 9.0 mm ² In the range of 10 to 30 mm in total length,
  The method for producing barium calcium titanate according to claim 13.

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