JP2012166125A - Method and device for producing dichroic minute droplet - Google Patents

Abstract

Disclosed is a dichroic microdroplet, and a dichroic microdroplet, which can be obtained by using a microdroplet manufacturing apparatus using a microchannel capable of efficiently and mass-producing microdroplets at a lower cost. A method for producing dichroic fine particles can be provided.
A method of manufacturing microdroplets by a microdroplet manufacturing apparatus using a microchannel and a through-hole, the apparatus being used to supply a first and a second dispersed phase to the through-hole in the surface direction of the substrate Having a fine channel formed in
The first dispersed phase and the second dispersed phase are merged in the through-hole portion or the fine flow channel before the through-hole portion, and then the merged first dispersed phase and the second dispersed phase are filled with the continuous phase. A method for producing microdroplets by extruding into a chamber filled with a continuous phase on the opening side of a hole; the first dispersed phase and the second dispersed phase have different hues and the produced droplets Is composed of a first dispersed phase and a second dispersed phase. A method for producing dichroic microdroplets, wherein:
[Selection] Figure 3

Description

  The present invention relates to a method and apparatus for producing dichroic microdroplets, and more particularly, dichroic microdroplets (emulsions) having excellent monodispersibility using microchannels, and dichroism obtained therefrom. The present invention relates to a method for producing fine particles and an apparatus therefor.

  The present inventors have developed an emulsion generation method using the cross shape of microchannels as a method for generating microdroplets (emulsions) with excellent size uniformity (monodispersity) (WO02 / 068104).

  This technology makes it possible to produce uniform-size emulsions, and to control the droplet size and production speed of the emulsion flexibly by manipulating the flow speed in the flow path. And this technique is the production | generation of a multiphase emulsion (Unexamined-Japanese-Patent No. 2004-237177), preparation of spherical solid microparticles (Unexamined-Japanese-Patent No. 2004-059802, Unexamined-Japanese-Patent No. 2004-067953), preparation of colored solid fine particles ( (Japanese Patent Laid-Open No. 2004-197083).

  However, the above-described technique has a problem that there is an upper limit to the flow rate at which droplets can be generated in one micro-channel crossing structure, and the amount that can be processed is small. In order to solve this problem, several examples of development of a device in which a large number of micro flow channels are arranged in parallel have been reported. For example, a total of three layers are attached: (a) a layer for fine phase distribution for dispersed phase, (b) a layer for fine channel for continuous phase liquid distribution, and (c) a layer for Y-shaped fine channel for droplet generation. A combined fine channel substrate has been reported (Japanese Patent Laid-Open No. 2004-243308).

  On the other hand, the inventors of the present invention have disclosed a microchannel having a microchannel substrate in which a large number of intersecting shapes of microchannels for droplet generation are arranged and a hierarchical structure for controlling the distribution of liquid to each microchannel. An apparatus consisting of a holder for holding a substrate has been developed (WO2007 / 026564, Lab Chip, 2008, 8, 287-293).

However, in the above-described micro droplet manufacturing apparatus, since the droplet generators are arranged on the substrate at regular intervals on the circumference, in order to arrange N times the number of droplet generators Must be a circle having a diameter N times, and the substrate area needs to be approximately N ² times. In this case, the number of droplet generation units per unit area is approximately N ⁻¹ times. That is, as the number of droplet generation units is increased, the number of droplet generation units arranged per unit area is reduced, and the area efficiency of the substrate is lowered. For this reason, it is difficult to greatly increase the number of droplet generation units that can be arranged on the substrate. For example, it is difficult to arrange several thousand to several tens of thousands of droplet generation units on a several cm square substrate. It was.

  On the other hand, as a technique for producing a monodisperse emulsion using a fine structure, which is different from the above technique, a film emulsification technique can be mentioned. In this technology, the size of the pores is obtained by press-fitting the dispersed phase (= phase that becomes droplets) into the continuous phase (= phase surrounding the droplets) through a plate having many through-holes of uniform size. It is possible to generate emulsion droplets that reflect the distribution and have small size variations (Japanese Patent Laid-Open Nos. 2-95433 and 2006-110505).

  In the membrane emulsification technology, the production volume can be increased by increasing the number of through-holes on the substrate. However, in order to increase the number of pores arranged at regular intervals by N times, the substrate area Therefore, when the number of pores is increased, the area use efficiency of the substrate does not decrease, and a large number of pores can be efficiently arranged on the substrate.

  However, the types of emulsions produced so far by membrane emulsification technology are limited in principle to single-phase or roughly homogeneous ones. For example, multiple emulsions with different physical and chemical properties, such as two-color droplets. A membrane emulsification technique and a manufacturing apparatus therefor that enable generation of droplets composed of segments have not been proposed.

  In recent years, a wide variety of information has been output to the world for recording, storage, transmission, and display. For example, display (display) on CRT, PDP, LCD, etc., recording, storage, and display on paper (hard copy) by electrophotographic images such as copying machines, facsimiles, and printers, and transmission by mobile phone, DTA, etc. As a display, the output form is also wide-ranging, such as electrophoresing charged black and white colored particles such as PLD to display an image.

  Under such circumstances, Japanese Patent Application Laid-Open No. 64-42683 describes a particle rotation type display device, and disclosed is a method for producing rotating particles for display classified into two colors. Titanium is added, granulated and classified by a spray dryer method, and then carbon black-dispersed alkyd resin enamel is spray-colored on the hemispherical surface of black and white wax particles having an average particle diameter of 50 μm. Also, a rubber lump obtained by dispersing green pigment, red pigment, and blue pigment in wax, granulating and classifying, and dispersing green, blue, and red particles having an average particle diameter of 30 to 150 μm in RTV rubber is 90%. Color-coded display particles are collected from rubber cut into a thin plate after cooling by color-coding under centrifugal force while heating to ℃.

  Japanese Patent Application Laid-Open No. 11-352421 discloses a method of manufacturing rotating particles for display classified into two colors used for display of PLD or the like, by vacuum deposition, sputtering, chemical vapor deposition on a hemisphere of a minute ball. It is described that different colored layers are formed using a thin film preparation method such as a growth method or a spinner coating method.

  Japanese Patent Application Laid-Open No. 2000-122103 describes a rotatable electrophoretic colored ball of black and white, which is rotatable, in a microcapsule. As a method for producing the two-color ball, a method is described in which glass beads and plastic beads filled with black and white titanium dioxide are prepared, and then a mixture of antimony sulfide and magnesium fluoride, which is a black material, is vacuum-deposited on this hemisphere. Has been.

  On the other hand, as described in JP-A-11-352411 and JP-A-2000-122103, there has been proposed a production method in which a hemispherical surface of a white particle prepared in advance is coated with a black component by sputtering or vacuum deposition. ing. Further, the manufacturing method described in JP-A-64-42683 is not a manufacturing method in which dichromation tends to be expensive, such as sputtering and vacuum deposition, but the formation of particles is a spray dryer method. As is well known, the granulated product obtained by this method has a large particle size width and requires classification, and generally the yield and monodispersity of the particles are remarkably inferior. In addition, since the proposed two-color process is very complicated, none of the proposals is a satisfactory method for producing dichroic spherical particles.

WO02 / 068104 JP 2004-237177 A JP 2004-059802 A JP 2004-067953 A Japanese Patent Laid-Open No. 2004-197083 WO2007 / 026564 Japanese Patent Laid-Open No. 2-95433 JP 2006-110505 A JP-A 64-42683 Japanese Patent Laid-Open No. 11-352421 JP 2000-122103 A

Lab Chip, 2008, 8, 287-293

  In view of the above situation, the present invention provides a dichroic microscopic apparatus using a microdroplet manufacturing apparatus that uses microchannels capable of efficiently and mass-producing microdroplets at a lower cost. It is an object of the present invention to provide an apparatus and a method that can stably and efficiently produce droplets and dichroic fine particles obtained therefrom.

  That is, the object of the present invention is to have any two hues selected from character materials, graphic materials, particularly black and white achromatic colors used in various display devices, and chromatic colors such as red, blue, green, purple and yellow. An object of the present invention is to provide a method for producing dichroic fine particles capable of producing colored particles having excellent monodispersibility with a simple production method and with a high yield. In addition, another object of the present invention is, from the viewpoint of display properties in a display device such as a PLD, for example, electric field responsiveness excellent in reversal display properties of colored spherical particles in an electric field display cell or in a magnetic field display cell. It is to provide dichroic fine particles having excellent magnetic field response.

The present invention provides the following inventions in order to solve the above problems.
(1) A method for producing microdroplets by a microdroplet production apparatus using microchannels and through holes,
The apparatus comprises a fine channel / through-hole substrate;
A fine flow path / through-hole substrate includes a plurality of through-holes formed in the thickness direction of the substrate and a fine flow formed in the surface direction of the substrate for supplying the first and second dispersed phases to these through-holes. Has a road;
The first dispersed phase and the second dispersed phase are merged in the through-hole portion or the fine flow channel before the through-hole portion, and then the merged first dispersed phase and the second dispersed phase are filled with the continuous phase. A method for producing microdroplets by extrusion into a chamber filled with a continuous phase on the opening side of a pore;
The dichroic microdroplet is characterized in that the first dispersed phase and the second dispersed phase have different hues, and the produced droplet is composed of the first dispersed phase and the second dispersed phase. Production method.
(2) The method for producing dichroic microdroplets according to (1) above, wherein the first dispersed phase and the second dispersed phase are an oily or aqueous fluid medium containing a polymerizable resin component.
(3) The method for producing dichroic microdroplets according to (2) above, wherein the polymerizable resin component is heat or photocurable.
(4) The method for producing dichroic microdroplets according to any one of (1) to (3), wherein the first dispersed phase and the second dispersed phase are different in chargeability or band magnetism.
(5) A method for producing dichroic fine particles, wherein the dichroic microdroplets according to any one of (1) to (4) are cured to obtain fine particles.
(6) In a microdroplet manufacturing apparatus using microchannels and through-holes that form biphasic microdroplets composed of first and second dispersed phases in a continuous phase.
The apparatus comprises a fine channel / through-hole substrate,
A fine flow path / through-hole substrate is formed with a plurality of through-holes formed in the thickness direction of the substrate, and branched fines formed in the surface direction of the substrate for supplying the first and second dispersed phases to these through-holes. A flow path, an inlet for supplying the first and second dispersed phases to the branched fine flow path, and a through hole provided downstream, for extruding the first and second dispersed phases from the opening side of the through hole With a chamber of
The first dispersed phase and the second dispersed phase are merged in the through-hole portion or the fine flow channel before the through-hole portion, and then the merged first and second dispersed phases are drawn from the through-hole filled with the continuous phase. An apparatus for producing biphasic microdroplets for producing biphasic microdroplets composed of first and second dispersed phases, configured to be extruded into a chamber filled with a continuous phase.
(7) In a microdroplet manufacturing apparatus using microchannels and through-holes that form biphasic microdroplets composed of first and second dispersed phases in a continuous phase,
The apparatus comprises a fine channel / through hole substrate and a holder for holding the fine channel / through hole substrate,
The microchannel / through-hole substrate has a plurality of through-holes in the thickness direction of the substrate formed in a row, and a row of micro-channels that supply the first and second dispersed phases to the through-holes,
The microchannel / through-hole substrate holding holder is formed with a slit portion corresponding to the row of microchannels for supplying the first and second dispersed phases, and a biphasic microdroplet is produced. apparatus.
(8) The cross-sectional area of the microchannel in the section extending from the final branching point of the supply channel of the first and second dispersed phases to the through hole is further upstream of the first and second dispersed phases. The apparatus for producing biphasic microdroplets according to (6) or (7) above, wherein the apparatus is set to be smaller than the cross-sectional area of the supply flow path.
(9) The shape of the through hole is a non-circular shape that causes a non-uniform shearing force to act on the interface of the dispersed phase extruded into the continuous phase, as described in any one of (6) to (8) above A device for producing biphasic microdroplets.
(10) The biphasic microscopic shape according to any one of (6) to (9) above, wherein the shape of the through hole is different between the opening filled with the continuous phase and the dispersed phase supply side Droplet production equipment.
(11) The apparatus for producing biphasic microdroplets according to any one of (6) to (10) above, wherein the number of through holes is 500 / cm ² or more.

  According to the present invention, a dichroic micro-droplet, and a micro-droplet manufacturing apparatus using a micro-channel using a micro-channel capable of producing a micro-droplet at low cost, efficiently and mass-produced, and A method for producing dichroic fine particles obtained therefrom can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS The perspective view (a) and exploded view (b) of the fine flow path and through-hole board | substrate of the manufacturing apparatus of a microdroplet which show one example of this invention. The perspective view (a), top view (b), and back view (c) which show an example of the microchannel / through-hole substrate of FIG. (A)-(d) is an expanded sectional view of a part of a microchannel / through-hole substrate showing changes up to the generation of dichroic microdroplets in the microdroplet manufacturing apparatus showing an example of the present invention. Sectional drawing of the manufacturing apparatus of the micro droplet which shows one example of this invention. The perspective view (a) and exploded view (b) of the microchannel / through-hole substrate and the microchannel / through-hole holding holder of the microdroplet manufacturing apparatus showing another example of the present invention. FIG. 6 is a perspective view (a), a top view (b), and a rear view (c) showing an example of the microchannel / through-hole substrate in FIG. 5. (A) to (e) are microchannels / through-hole substrates and microchannels / penetrations showing changes up to the generation of dichroic microdroplets in the microdroplet manufacturing apparatus according to another example of the present invention. The expanded sectional view of a part of holder for hole substrate holding | maintenance. FIG. 6 is a top view showing another example of the fine channel / through-hole substrate of FIG. 5.

  In the first aspect of the present invention, a microchannel / through-hole chip is used as a device for producing dichroic microdroplets. FIG. 1 (a) is a perspective view of the fine channel / through-hole chip, and FIG. 1 (b) is an exploded view. By attaching the cover substrate 2 to the micro-groove processed surface side of the micro-groove / through-hole substrate 3 preferably, a micro-channel that becomes liquid-tight by introducing the dispersed phase is formed inside the micro-channel / through-hole chip 1. It is formed.

  The internal structure of the fine channel / through-hole chip will be described in detail with reference to FIG. 2A is a perspective view of the fine groove / through hole substrate, FIG. 2B is a top view of the substrate, and FIG. 2C is a rear view of the substrate. The micro-groove / through-hole substrate 3 is provided with a large number of through-holes 9 in the direction perpendicular to the substrate, which are locations where dichroic microdroplets are generated. In order to supply both the first dispersed phase 4 and the second dispersed phase 5 to all the through holes 9, a first dispersed phase supply channel 7 and a second dispersed phase supply channel 8 are provided in the surface direction of the substrate. Each is arranged so as to be connected to all the through holes 9. Furthermore, a first dispersed phase supply port 11 and a second dispersed phase supply port 12 are provided so that two dispersed phases can be supplied from the outside of the chip to the flow path inside the chip.

  By press-fitting the first dispersed phase 4 into the chip from the first dispersed phase supply port 11, the first dispersed phase supply flow path 7 leading to the through hole 9 becomes liquid-tight in the first dispersed phase 4. Similarly, when the second dispersed phase 5 is press-fitted into the chip from the second dispersed phase supply port 12, the second dispersed phase supply flow path 8 leading to the through hole 9 becomes liquid-tight in the second dispersed phase 5. Become. By further pressurizing the two dispersed phases, dichroic microdroplets are generated from the openings of the through holes 9 on the back surface of the chip shown in FIG.

  The generation process of the dichroic microdroplet will be described in detail with reference to FIG. First, in the state shown in FIG. 3A, the continuous phase 6 is filled in the through hole 9 and the chamber 20, the first dispersed phase 4 is filled in the first dispersed phase supply flow path 7, and the second It is assumed that the dispersed phase supply flow path 8 is filled with the second dispersed phase 5.

  From this state, when the pressure acting on the first dispersed phase and the second dispersed phase is increased, the first dispersed phase 4 and the second dispersed phase 5 enter the through-hole 9 as shown in FIG. 3 (b). To form a two-phase parallel flow. When this two-phase parallel flow is pushed into the continuous phase 6 in the chamber 20 as shown in FIG. 3 (c), the two-color parallel flow is separated from the two-phase parallel flow as shown in FIG. 3 (d). A microdroplet 10 is obtained.

  FIG. 4 is a cross-sectional view of an apparatus for producing dichroic microdroplets used in the present invention. The apparatus for producing dichroic microdroplets of the present invention is configured by assembling a plurality of parts to a microchannel / through-hole chip 1. The microchannel / through-hole tip 1 is connected to a tip holder 14 having a first dispersed phase supply pipe 17, a second dispersed phase supply pipe 18, a continuous phase supply pipe 19 and a discharge pipe 21, The second disperse phase introduction ports 12 are placed so that the positions thereof are matched, and are fixed by the holder cover 13. A transparent plate 15 made of a glass plate or a plastic plate is fixed to the chip holder 14 with a window-holding press 16 on the opposite side of the micro-channel / through-hole chip 1 across the chip holder 14 to assemble the device. This forms a chamber 20 that becomes liquid-tight when the continuous phase is introduced.

  In the manufacturing apparatus, first, the continuous phase is introduced through the continuous phase supply pipe 19, whereby the chamber 20 becomes liquid-tight with the continuous phase. Next, by introducing the first dispersed phase from the first dispersed phase supply pipe 17 and the second dispersed phase from the second dispersed phase supply pipe 18, the first dispersed phase becomes the first dispersed phase inlet 11, the second dispersed phase The phase is supplied to the inside of the fine channel / through-hole chip through the second dispersed phase introduction port 12, and dichroic microdroplets are generated from the through-hole 9 toward the inside of the chamber 20 filled with the continuous phase. . The generated dichroic microdroplet can be taken out of the apparatus from the discharge pipe 21 by continuously feeding the continuous phase, and can be transferred to subsequent processes such as a curing process.

  In the manufacturing apparatus, the inside of the chamber 20 can be optically observed through the transparent plate 15. That is, it is possible to observe the state of the dichroic microdroplet immediately after generation and the state of the generation of the dichroic microdroplet from the through hole 9. Further, when a transparent member made of a glass plate or a plastic plate is used as the chip cover 2, it is possible to observe the state of the fine flow path inside the chip. When a transparent member is used for both the chip cover 2 and the fine channel substrate 3, the inside of the chamber 20 can be observed from the chip side.

  In a second aspect of the present invention, an apparatus for producing dichroic microdroplets comprises a microchannel / through-hole substrate and a microchannel / through-hole substrate holding holder, The substrate has a plurality of through holes for generating dichroic microdroplets and fine grooves connected in the surface direction of the substrate to supply the first and second dispersed phases to these through holes. On the other hand, the holder for holding the microchannel / through hole substrate corresponds to the position of the microchannel for supplying the first dispersed phase and the second dispersed phase connected to the plurality of through holes that generate dichroic microdroplets. The slit part to be formed is formed. FIG. 5b to be described later shows an example of such a slit portion (each slit portion is independent). For example, a plurality of slit portions (slit 24 or slit 25) through which the same liquid flows are connected to each other. For example, it may be a U-shape joined at the end.

Next, the second aspect of the present invention will be described in more detail with reference to FIGS. FIG. 5 is a perspective view of the fine channel / through-hole substrate and the substrate holding holder during assembly (a) and disassembly (b).
The dichroic microdroplet manufacturing apparatus is composed of a microchannel / through-hole substrate 22 and a microchannel / through-hole substrate holding holder 23,
The fine flow path / through-hole substrate 22 is a fine flow path for supplying a plurality of through-holes arranged on a matrix formed in the thickness direction of the substrate and the first and second dispersed phases connected to the through-holes. Have
The fine channel / through-hole substrate holding holder 23 includes a slit-like channel 24 for supplying a first dispersed phase and a slit-like channel 25 for supplying a second dispersed phase corresponding to the position of the fine channel of the substrate. Have

  The structure of the fine channel / through-hole substrate will be described in detail with reference to FIG. FIG. 6 is a side view (a), a top view (b), and a rear view (c) showing an example of the fine channel / through-hole substrate. The microchannel / through-hole substrate 22 supplies a plurality of through-holes 26 arranged in a matrix formed in the thickness direction of the substrate, and the first and second dispersed phases connected to each of the through-holes 26. A fine flow path 27 is provided on one side of the substrate.

  The first and second dispersed phases are supplied to the through-hole 26 from the fine flow path 27 and further pressurized to the two dispersed phases, whereby the first and second dispersed phases are first introduced from the opening of the through-hole 26 on the back surface of the chip shown in FIG. And dichroic microdroplets constituted by the second dispersed phase.

  The generation process of the dichroic microdroplet will be described in detail with reference to FIG. First, in the state shown in FIG. 7A, the dispersed phase supply flow path 27 and the through hole 26 of the fine flow path / through hole substrate 22 are filled with the continuous phase 6, and the fine flow path / through hole substrate holding holder. It is assumed that the first dispersed phase supply slit 24 is filled with the first dispersed phase, and the second dispersed phase supply slit 25 is filled with the second dispersed phase.

  From this state, when the pressure acting on the first dispersed phase and the second dispersed phase is increased, the dispersed phase supply channel 27 of the fine channel / through-hole substrate 22 is transferred to the dispersed channel supply channel 27 as shown in FIG. As shown in (c), the first dispersed phase and the second dispersed phase enter the through hole 26 to form a two-phase parallel flow. When this two-phase parallel flow is pushed into the continuous phase 6 as shown in FIG. 7 (d), the dichroic microdroplet 10 is separated from the two-phase parallel flow as shown in FIG. 7 (e). Is obtained.

  FIG. 8 is a top view showing another example of the fine channel / through-hole substrate. The fine flow path 27 of the fine flow path / through hole substrate 22 may be connected across the plurality of through holes 26 arranged in a row.

  In the present invention, the supply flow paths for the first and second dispersed phases may be directly connected to the through-hole to form a two-phase parallel flow at the through-hole inlet or inside, or before reaching the through-hole. A structure in which the two-phase parallel flow formed in advance is supplied to the through-hole by combining the supply flow paths of the first and second dispersed phases within the substrate surface.

  In the present invention, the cross-sectional sizes of the first dispersed phase supply channel and the second dispersed phase supply channel can be determined according to the purpose, but the through holes and / or the first and second dispersed phase supply channels can be determined. By setting the cross-sectional area of the flow path in the section from the final branch point to the through-hole to be smaller than the cross-sectional size of the upstream section, the flow rate variation of the first and second dispersed phases supplied to the through-hole It is desirable to keep the value small.

  The shape of the through-hole can be arbitrarily determined within the range where processing is possible, but it causes a non-uniform shearing force to act on the interface between the first and second dispersed phases extruded into the continuous phase and the dichroic microdroplet. A non-circular shape is desirable for facilitating droplet generation by allowing a continuous phase to partially flow into the through hole during the generation process. In addition, the through-holes may have the same cross-sectional shape or different cross-sectional shapes on the dispersed phase inflow side and the opening side filled with the continuous phase. On the other hand, the size of the through hole can be determined according to the size of the target dichroic microdroplet. For example, in the case of a square opening, one side is usually 0.1 to 500 μm, preferably 1 to The depth is selected from about 50 μm, and the depth is usually selected from 1 to 5000 μm, preferably from about 10 to 500 μm.

With the above configuration, the number of through-holes per minute channel / through-hole substrate is greatly increased (for example, 500 / cm ² or more), and mass production of dichroic microdroplets is performed. Is possible.

  The material of the fine groove / through hole substrate and the cover substrate forming the fine flow path / through hole chip may be, for example, plastic, ceramic, metal, or the like. For example, in order to produce water-in-oil type emulsion droplets, it is preferable to use a material having a hydrophilic surface for the micro-groove / through-hole substrate, such as quartz glass, borosilicate glass (for example, “Pyrex” (trademark) )) Etc. can be used. On the other hand, in order to generate oil-in-water type emulsion droplets, a fine groove / through-hole substrate having a hydrophobic surface is preferable, and for example, an acrylic resin, a silicone resin, or the like is preferable. It is also possible to modify the surface wettability inherent in the material using various surface treatment techniques such as application of a surface modifier or plasma irradiation. The shape and size of the material forming the fine flow path and the through-hole can be appropriately selected depending on the intended use and the like, and examples thereof include a plate state of several centimeters square.

  In addition, the dichroic microdroplet of the present invention is formed so as to have, for example, achromatic white, black, or any two hues selected from chromatic red, blue, green, purple and yellow. , Preferably, the two hemispheres of the microdroplet are colored differently. Since the micro-droplet of the present invention has two phases, the micro-droplet can be adjusted to two polarities either in a chargeable manner or magnetically in advance, and can easily be charged or magnetically charged in two polar droplets. Can be formed.

  In the present invention, the liquid forming the continuous phase is an organic compound or water, while the liquid forming the dispersed phase is a curable liquid containing a polymerizable resin component. As the organic compound, the organic phase is not particularly limited, but is preferably alkanes such as decane and octane, halogenated hydrocarbons such as chloroform, aromatic hydrocarbons such as toluene, and fatty acids such as oleic acid. Etc.

  The curable liquid is not particularly limited as long as it is a liquid that can be cured by heat or light. For example, known polymerizable monomers, oligomers or polymers can be mentioned, and (meth) acrylate monomers, styrene monomers, etc., which will be described later, are preferable. As will be described later, the first dispersed phase and the second dispersed phase contain different colorants, and the curable liquids constituting these dispersed phases may be the same or different.

  The combination of the dispersed phase and the continuous phase can be generally O / W, O / O type, and W / O type. Near the inlet of the fine through-hole, the two dispersed phases merge to form a laminar parallel flow, and into the continuous phase near the outlet of the fine through-hole, it is gradually transformed into spherical microdroplets. At the same time or time difference, the fine droplets are cured to form two-color fine particles.

  The flow rates of the dispersed phase and the continuous phase are usually selected from about 10 mL to 10 L / hour, though depending on the size of the fine flow path and the type of liquid.

  In the dispersed phase in the present invention, different colorants that separate the hue into two colors are added, and an additive for imparting charging or magnetic field responsiveness is used as necessary. Examples of the colorant include two-phase hues selected from achromatic white and black, or chromatic red, blue, green, purple, yellow, and the like. The dye / pigment for forming such a hue is not particularly limited, and various dyes such as oil solubility or various inorganic / organic pigments can be used. These dyes and pigments can be appropriately selected and used in accordance with the dispersibility in the curable component and the color tone desired in the intended use of the resulting dichroic fine particles. The colorant can also be used in only one dispersed phase.

  The addition amount of the dye / pigment as the colorant is not particularly limited, but it is usually appropriately used within a range of about 0.1 to 10 parts by mass per 100 parts by mass of the curing component.

  In the present invention, the curable components that have been phase-separated into these two colors can be formed with components that are positively and negatively charged using different charge imparting agents. Alternatively, as the polymerizable monomer, depending on the type of the functional group or substituent, the chargeability in the present invention described above may be a monomer species that tends to exhibit (−) chargeability and (+) chargeability, respectively. it can. For example, (-) chargeable polymerizable monomers include (meth) acrylic acid aryl esters such as phenyl (meth) acrylate, epoxy group-containing polymerizable compounds such as glycidyl (meth) acrylate, ( Examples thereof include hydroxy group-containing polymerizable compounds such as (meth) acrylic acid-2-hydroxyethyl, and styrene monomers such as methylstyrene. On the other hand, examples of the polymerizable monomer having a (+) chargeability tendency include amide group-containing vinyl monomers such as methacrylamide.

  In the present invention, by dispersing the magnetic powder, the fine liquid droplets that have been separated into two hues can have different magnetic field responsiveness.

The dichroic microdroplet obtained by the method of the present invention can be cured by heat, light such as UV, etc. to obtain dichroic fine particles.
In the present invention, a photopolymerization initiator such as acetophenones can be used when polymerized and cured by UV irradiation, and a thermal decomposition type polymerization start such as organic peroxides when polymerized and cured under heating. Agents can also be used.

  The dichroic fine particles obtained by the method of the present invention can be used in a display device such as a PLD, for example, in chargeability or magnetic field responsiveness excellent in reversal display of colored spherical particles in an electric field display cell or in a magnetic field display cell. It is useful as an excellent dichroic fine particle.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
(Specific example 1)
A microchannel / through-hole chip as shown in FIG. 1 was fabricated by deep reactive ion etching (DRIE) on a silicon substrate and bonding of a glass substrate to a processed substrate. On a 4 inch silicon wafer with a thickness of 525 μm, the flow paths for supplying two colors of liquid to the through holes were processed in parallel in 50 rows with a depth of 100 μm and a width of 250 μm. In addition, 100 rows of through-holes with a rectangular cross section of 150 μm x 50 μm arranged at a pitch of 200 μm in the short side direction so as to be connected to the processed supply channel are arranged in 50 rows at a pitch of 400 μm in the long side direction. , A total of 5000 pieces were processed and cut into a size of 30 mm x 30 mm. Two through-holes (Φ1.0 mm) for supplying two colors of liquid to the flow path are provided in the cut silicon chip, and then a glass substrate of the same area is anodically bonded to the surface on which the flow path is processed As a result, a fine channel / through-hole chip was formed. This was set in a stainless steel (SUS304) part manufactured by machining and connected to a liquid feed and drain tube (inner diameter 1.0 mm, outer diameter 2.0 mm). 1,6-hexanediol diacrylate (Shin Nakamura Chemical Co., Ltd.) as the first dispersed phase, oil-soluble dye (Oil Red O, Sigma-Aldrich) in the above 1,6-hexanediol diacrylate as the second dispersed phase, continuous As a phase, a 2% aqueous solution of polyvinyl alcohol (GL-03 manufactured by Nippon Synthetic Chemical) was used. For delivery, one syringe pump (KD Scientific, KDS200) was used for each of the first dispersed phase, the second dispersed phase, and the continuous phase. The first dispersed phase, the second dispersed phase, and the continuous phase are fed, and dichroic microdroplets of uniform size as shown in FIG. 3 (d) are generated at the exits of the through holes of the chip. I was able to observe

  According to the present invention, a dichroic micro-droplet, and a micro-droplet manufacturing apparatus using a micro-channel using a micro-channel capable of producing a micro-droplet at low cost, efficiently and mass-produced, and A method for producing dichroic fine particles obtained therefrom can be provided. Since the obtained two colored spherical particles are preferably divided into two hues, they can be adjusted to two polarities in a chargeable or magnetic manner in advance, and can easily be charged or charged in two polarities. Two colored spherical polymer particles can be formed.

DESCRIPTION OF SYMBOLS 1 Fine flow path and through-hole chip 2 Cover substrate 3 Fine groove and through-hole board 4 1st disperse phase 5 2nd disperse phase 6 Continuous phase 7 1st disperse phase distribution flow path 8 2nd disperse phase distribution flow path 9 2 colors Through-holes for generating conductive microdroplets 10 Dichroic microdroplets 11 First dispersed phase chip inlet 12 Second dispersed phase chip inlet 13 Tip holder with window 14 Microchannel / through-hole chip holder 15 Transparent Plate 16 Holding with Window 17 First Dispersed Phase Holder Introducing Tube 18 Second Dispersed Phase Holder Introducing Tube 19 Continuous Phase Holder Introducing Tube 20 Chamber 21 Holder Discharge Tube 22 Fine Channel / Through Hole Substrate 23 Fine Channel / Through Hole Substrate Holding Holder 24 First Dispersed Phase Supply Slit 25 Second Dispersed Phase Supply Slit 26 Through Hole 27 Dispersed Phase Supply Channel

Claims (11)

A method for producing microdroplets with a microdroplet manufacturing device using microchannels and through-holes,
The apparatus comprises a fine channel / through-hole substrate;
A fine flow path / through-hole substrate includes a plurality of through-holes formed in the thickness direction of the substrate and a fine flow formed in the surface direction of the substrate for supplying the first and second dispersed phases to these through-holes. Has a road;
The first dispersed phase and the second dispersed phase are merged in the through-hole portion or the fine flow channel before the through-hole portion, and then the merged first dispersed phase and the second dispersed phase are filled with the continuous phase. A method for producing microdroplets by extrusion into a chamber filled with a continuous phase on the opening side of a pore;
The dichroic microdroplet is characterized in that the first dispersed phase and the second dispersed phase have different hues, and the produced droplet is composed of the first dispersed phase and the second dispersed phase. Production method.   The method for producing dichroic microdroplets according to claim 1, wherein the first dispersed phase and the second dispersed phase are oily or aqueous fluid media containing a polymerizable resin component.   The method for producing dichroic microdroplets according to claim 2, wherein the polymerizable resin component is heat or photocurable.   The method for producing dichroic microdroplets according to any one of claims 1 to 3, wherein the first dispersed phase and the second dispersed phase are different in chargeability or band magnetism.   A method for producing dichroic microparticles, wherein the dichroic microdroplets according to any one of claims 1 to 4 are cured to obtain microparticles. In an apparatus for producing a microdroplet using a microchannel and a through-hole, in which a biphasic microdroplet composed of first and second dispersed phases is formed in a continuous phase,
The apparatus comprises a fine channel / through-hole substrate,
A fine flow path / through-hole substrate is formed with a plurality of through-holes formed in the thickness direction of the substrate, and branched fines formed in the surface direction of the substrate for supplying the first and second dispersed phases to these through-holes. A flow path, an inlet for supplying the first and second dispersed phases to the branched fine flow path, and a through hole provided downstream, for extruding the first and second dispersed phases from the opening side of the through hole With a chamber of
The first dispersed phase and the second dispersed phase are merged in the through-hole portion or the fine flow channel before the through-hole portion, and then the merged first and second dispersed phases are drawn from the through-hole filled with the continuous phase. An apparatus for producing biphasic microdroplets for producing biphasic microdroplets composed of first and second dispersed phases, configured to be extruded into a chamber filled with a continuous phase. In an apparatus for producing a microdroplet using a microchannel and a through-hole, in which a biphasic microdroplet composed of first and second dispersed phases is formed in a continuous phase,
The apparatus comprises a fine channel / through hole substrate and a holder for holding the fine channel / through hole substrate,
The microchannel / through-hole substrate has a plurality of through-holes in the thickness direction of the substrate formed in a row, and a row of micro-channels that supply the first and second dispersed phases to the through-holes,
The microchannel / through-hole substrate holding holder is formed with a slit portion corresponding to the row of microchannels for supplying the first and second dispersed phases, and a biphasic microdroplet is produced. apparatus.   The cross-sectional area of the microchannel in the through hole and / or the section from the final branching point of the supply channel of the first and second dispersed phases to the through hole is the supply flow of the first and second dispersed phases further upstream The apparatus for producing biphasic microdroplets according to claim 6 or 7, wherein the apparatus is set to be smaller than a cross-sectional area of the path.   The biphasic microfluid according to any one of claims 6 to 8, wherein the shape of the through hole is a non-circular shape that causes a non-uniform shearing force to act on the interface of the dispersed phase extruded into the continuous phase. Drop production equipment.   10. The biphasic microdroplet according to claim 6, wherein the through holes have different cross-sectional shapes on the side of the opening filled with the continuous phase and on the side of the dispersed phase supply. Manufacturing equipment. 11. The apparatus for producing biphasic microdroplets according to claim 6, wherein the number of through holes is 500 / cm ² or more.