JP2011246334A - Laminated porous glass membrane and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem that a device for obtaining a fine particle in a membrane emulsification method has a limitation in high pressure, and a porus glass membrane for membrane emulsification is required so as to easily obtain the fine particle under low pressure.SOLUTION: The porus glass membrane having uniform micropores formed by a phase separation method is characterized by that a laminated porus glass membrane is integrated by tightly laminating two or more porus glass membranes by thermal fusion without peeling. The laminated porus glass membrane includes different micropore diameters. The laminated porus glass membrane includes a same micropore diameter. The laminated porus glass membrane includes a skin layer of a thin porus glass membrane having a micropore diameter, and a support layer of a thick porus glass membrane having a pore diameter larger than the micropore diameter. The three-layered laminated porus glass membrane formed of different micropore diameters includes the skin layer of the thin porus glass membrane having the micropore diameter, and the support layer of the thick porus glass membrane having a larger pore diameter than the micropore diameter, and is formed by tightly laminating the support layers on both sides so as to sandwich the skin layer.

Description

  The present invention is particularly necessary for producing fine particles because the film thickness becomes the permeation pressure film resistance as it is in the liquid-liquid mixed film emulsification method consisting of a dispersed phase liquid and a continuous phase liquid or the gas-liquid mixed film bubbling method. Without reducing the thickness of the porous glass membrane plate having a fine pore size, and by laminating closely with the porous glass membrane plate having a larger pore diameter than the thin porous glass membrane plate having the fine pore diameter, By using an integral porous glass membrane, the permeation pressure can be reduced, and the present invention relates to a laminated porous glass membrane having different micropore diameters that can generate fine particles at a low pressure. Similarly, the thickness formed by one porous glass membrane micropore and the other porous glass membrane skeleton at the interface between the porous glass membrane plates by laminating several porous glass membrane plates in the same manner without peeling. Pole without Can be miniaturized permeate through fine gaps, to a laminated porous glass membrane reducing the transmission pressure is possible.

  Conventionally, in the preparation of emulsions, when a coarse mixed liquid of a dispersed phase liquid and a continuous phase liquid is made into fine particles by a membrane permeation method in a fine pore porous glass membrane, a high membrane permeation pressure such as several MPa is required, and further emulsification It is necessary to make the device have a high breakdown voltage specification.

  For example, as in Patent Document 1, nitrogen gas pressurization of 3.00 MPa is required to pass a pre-emulsified oil / fat composition through a cylindrical shirasu porous glass membrane of 0.94 μm, and the obtained average particles The diameter is 0.92 μm. Further, in order to reduce the magnitude of the membrane resistance of the porous glass film, as in Patent Document 2 or Non-Patent Document 1, in the porous glass film formed by the phase separation method, the composition has a different phase separation speed. Asymmetric porous glass membrane can be obtained by welding different basic glasses as skin layer and support layer, respectively, and phase-separating them by heat treatment, and it is possible to demonstrate high fractionation accuracy and permeation performance of porous glass membrane There is a porous glass film having a two-layer structure. In addition, as in Patent Document 3, in order to generate fine particles of W / O / W, it is destroyed when directly permeated through a porous film having a fine pore diameter, so that the pore diameter of the support layer is about 1 to 20 μm. Using a porous film composed of a support layer and a fine-grained layer with ultrafine alumina particles of 0.004 to 0.5 μm immobilized on the surface, the support is primary from the support layer side to the fine-grained layer side. (Preliminary) Permeation of the emulsion W / O / W emulsion allows fine particles to be produced without breaking the emulsion.

Patent No. 3884242 Japanese Patent Application 2000-355570 Japanese Patent Application No. 2003-194777

“Development of SPG Asymmetric Membranes”, 1998 Regional Industry-Academia-Government Joint Research Project Research Report, Application of SPG Technology to Medical Engineering and Creation of New Industries, Part 3, January 2000, Miyazaki Prefectural Industrial Technology Center, p. 1-6

  However, in the membrane emulsification method, in Patent Document 1, it is considered that there is a limit to the high pressure even in these apparatuses for obtaining fine particles, and a porous glass membrane for membrane emulsification that can easily obtain fine particles at a low pressure is required. Is done. Therefore, in Patent Document 2 or Non-Patent Document 1, raw materials having different glass compositions are required at the time of basic glass molding in order to obtain an asymmetric porous glass film such as a reduction in permeation pressure. There is also a problem in quality because there is a description that partition walls that are thought to be formed by mutual phase separation occur at the weld interface between compositions with different phase separation speeds, and that continuous pores do not penetrate. Laminated basic glass molding is very troublesome for a small variety of products. In Patent Document 3, a ceramic film obtained by a sintering method used as a porous film cannot be expected to have a uniform pore diameter as much as a laminated porous glass film obtained by a phase separation method in the present invention.

  Therefore, as a result of intensive studies in view of the above-described conventional problems, the laminated porous glass film of the present invention is a porous glass film having uniform micropores formed by a phase separation method, and has two or more porous layers. It is a laminated porous glass film that is integrally laminated by thermal fusion without peeling off the porous glass film and without crushing the pores, and it is a uniform fine film formed by the phase separation method. It is a laminated porous glass film having different fine pore diameters that have pores and are integrally laminated by heat fusion without peeling porous glass films having different fine pore diameters. The porous glass film is a laminated porous glass film having the same fine pore diameter which is integrally laminated by heat fusion without peeling off the porous glass film having a pore diameter. Further, the present invention provides a thin porous glass membrane having a fine pore diameter as a skin layer, and heat fusion without peeling off the porous glass membrane having a pore diameter larger than that of the fine pore diameter porous glass membrane as a support layer. It is a laminated porous glass film having different micropore diameters integrated by close lamination, and a porous glass film having a thin micropore diameter is used as a skin layer, and the pore diameter is larger than that of the porous glass film having the micropore diameter. Triple laminated porous glass consisting of different fine pore diameters with a large-thick porous glass membrane as a supporting layer, which are closely laminated by heat fusion without peeling to both sides so as to sandwich the skin layer. It is a film.

  The present invention pays attention to the point that an ultra-high permeation pressure such as several MPa was required to produce fine particles in the membrane permeation method that produces fine particles using a porous glass membrane. Not only is the pressure-resistant membrane permeation device unnecessary, but it can be expected that the membrane can permeate at a low pressure and the amount of permeation can be further increased.

  Further, if fine particles of, for example, submicron can be generated at low pressure, a dispersed phase or a continuous phase or a mixture in which a dispersed phase and a continuous phase are mixed in advance between two chambers partitioned by a porous glass membrane disk. It is possible to easily generate submicron fine particles with a handy type pumping type membrane emulsifying device that can be gradually and uniformly dispersed by reciprocating alternately in the palm using a syringe.

  DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below based on examples shown in the drawings. Needless to say, the present invention is not limited to the contents of the following examples and descriptions.

  FIG. 1 is a cross-sectional view schematically showing a laminated porous glass membrane plate having different fine pore diameters according to the present invention, and FIG. 1 (a) shows a skin of a thin porous glass membrane plate having a fine pore diameter. As a layer, a thick porous glass membrane plate having a larger pore diameter is closely adhered and laminated as a support layer. In particular, in FIG. 1 (b), a thin porous glass membrane plate having a fine pore diameter is used as a skin layer, and the skin layer is sandwiched from both sides using a thick porous glass membrane plate having a larger pore diameter as a support layer. FIG. 1 (c) shows a porous glass membrane plate having a pore diameter which is between the skin layer and the support layer of (b) and which is between the fine pore diameter of the skin layer and the pore diameter of the support layer. Is a three-layer laminated porous glass membrane with a FIG. 2 is a cross-sectional view schematically showing a laminated porous glass membrane plate having the same fine pore diameter. FIG. 2 (a) is a two-sheet laminated type, and FIG. 2 (b) is a four-sheet laminated type. It is a porous glass membrane. 2 (c) is an enlarged view of the interface A where the porous glass membrane plates in FIG. 2 (a) are in close contact with each other, and is formed from the micropores of one porous glass membrane and the other porous glass membrane skeleton. It is sectional drawing which shows typically the very fine space | gap without thickness. FIG. 2D is a cross-sectional view schematically showing ultrafine gaps at the interface where the porous glass membrane plates of FIG. FIG. 3 is a pumping type membrane emulsification using a handy type device 8, and the use of an apparatus capable of uniformly dispersing fine emulsion particles gradually by reciprocating alternately in the palm by using a syringe. It is the schematic diagram which showed the example. FIG. 4 is a comparison of the emulsified particle diameter of the pumping membrane between the conventional porous glass membrane and the laminated porous glass membrane according to the present invention. FIG. 5 is a particle size distribution of the emulsified particle size of the pumping membrane according to the conventional porous glass membrane shown in FIG. FIG. 6 shows the particle size distribution of the emulsified particle diameter of the pumping membrane by the laminated porous glass membrane according to the present invention shown in FIG. 4, and FIG. 7 shows the conventional porous glass membrane and the laminated porous glass membrane according to the present invention. A comparison of pumping membrane emulsified particle sizes is shown.

Table 1 shows experimental examples of the laminated porous glass membrane according to the present invention. The thickness of the porous glass membrane plate of each layer is about 0.5 mm for the support layer portion and about 0.2 mm for the skin layer portion. Here, Experimental Example 1 is the laminated porous glass film of FIG. 1A, and Experimental Examples 2 to 3 are the laminated porous glass film of FIG. These are each made by closely laminating the porous glass films themselves produced by the phase separation method, and they are stuck together with an adhesive, which is a binder that fills the pores, or simply stacked so that each layer can be easily peeled off. Instead, the lamination of the porous glass membrane plate according to the present invention is firmly adhered by heating at 300 to 800 ° C. so that the pores are not crushed and a heat fusion press under heating time conditions.

Table 2 shows experimental examples of the laminated porous glass membrane according to the present invention. The thickness of the porous glass membrane plate of each layer is about 0.3 mm.

  Experimental examples together with comparative examples of permeation pressure and permeation speed with conventional porous glass membranes and particle diameters produced by membrane emulsification using the laminated porous glass membranes of Tables 1 and 2 according to the present invention As shown. Incidentally, the thickness of the conventional porous glass membrane is about 0.6 to 0.8 mm. In addition, the emulsified mixed liquid used in the following experimental examples is an oil-in-water emulsion (o / w emulsion), soybean oil is used as the dispersed phase liquid, and 0.5% HCO-60 (polyoxyethylene hydrogenated castor oil 60: Nikko Chemicals) aqueous solution was used.

(Experimental example 5)
FIG. 4 shows a laminated porous glass membrane (skin layer: pore diameter 1.1 μm, support layer: pore diameter 19.8 μm) of Experimental Example 1 according to the present invention, and a conventional porous glass membrane pore diameter 3 μm as a comparative example. And 5 μm, pumping membrane emulsification was carried out with the device 8 shown in FIG. In the emulsification of the pumping membrane with these three kinds of porous glass membranes, the emulsion particle diameter when the membrane permeation is once permeated (n1), 5 times permeated (n5), 20 times permeated (n20), 40 times permeated (n40) The change state is shown in FIG. (Invention laminated porous glass membrane FIG. 4 title “pc1 + 20”, conventional porous glass membrane 3 μm FIG. 4 title “pc3”, conventional porous glass membrane 5 μm FIG. 4 title “pc5”)

  Here, the emulsification of the pumping membrane has a limit, but the particle diameter tends to decrease as the number of membrane permeation is repeated. Incidentally, the pore diameter of the porous glass membrane that can be emulsified in the palm of the pumping membrane is limited to about 3 μm because of the small permeation pressure, and the emulsion particle size produced by this is finally 1 after 40 permeation as shown in FIG. Although the particle size becomes 148 μm, the emulsified particle size of the pumping membrane by the laminated porous glass membrane according to the present invention in Experimental Example 1 can already generate 0.933 μm particles once per membrane passage (n1). In addition, 0.405 μm particles could be generated after 5 membrane passages (n5). The particle size distributions obtained by emulsification of these three pumping membranes are shown in FIGS. 5 and 6, respectively. (Conventional porous glass membrane 3 μm FIG. 5 distribution No. 1 “pc3 = n20” and No. 2 “pc3 = n40”, Conventional porous glass membrane 5 μm FIG. 5 distribution No. 3 “pc5 = n20” and No. 4 “ pc5 = n40 ”, the present invention laminated porous glass membrane FIG. 6 distribution No.1“ pc1 + 20 = n1 ”and No.2“ pc1 + 20 = n5 ”)

(Experimental example 6)
FIG. 7 shows FIG. 3 as in Experimental Example 5, using the laminated porous glass membrane of Experimental Example 2 according to the present invention (skin layer: pore diameter 1.8 μm, both-side support layer: pore diameter 19.8 μm). The particle diameter distribution which implemented the pumping membrane emulsification by the device 8 is shown. Also in this experimental example, a particle mode diameter of 0.499 μm can be generated by membrane permeation 5 times (FIG. 7 distribution No. 1 “pc20 + 1.8 + 20 = n5”), and further, membrane permeation 20 times (FIG. 7 distribution). No. 2 “pc20 + 1.8 + 20 = n20”) and a particle mode diameter of 0.329 μm could be produced by palm-pumping membrane emulsification.

(Experimental example 7)
Next, the laminated porous glass membrane of Example 3 according to the present invention (skin layer: pore size 1.1 μm, both-side support layer: pore size 4.9 μm) and conventional porous glass membrane (pore size 1.1 μm) As a comparison, using the permeable membrane emulsifying apparatus shown in FIG. 8, the permeation pressure and permeation speed are shown in FIG. 9, and the emulsion particle size distribution generated at this time is shown in FIG. Each porous glass membrane is mounted on the membrane emulsification device 19 in FIG. Here, with respect to the permeable membrane emulsifying apparatus of FIG. 8, water to be permeated through the porous glass membrane or a mixed liquid of the dispersed phase liquid and the continuous phase liquid is previously put in the tank 15, and the porous glass membrane is mounted. With the membrane emulsification device 19 connected, the gas pressure 13 is applied to recover the liquid that has passed through the membrane in the beaker 20. At this time, by holding the beaker 20 on the electronic balance 21, the permeation amount at the permeation pressure can be measured over time. Furthermore, in order to obtain a crude mixed solution 16 of a dispersed phase liquid and a continuous phase liquid before permeation into the tank, a stirrer 18 is provided under the tank 15 and the inside of the tank is permeated through the rotor 17 with stirring. Separation due to the difference in specific gravity between the dispersed phase liquid and the continuous phase liquid can be prevented, and the distribution ratio between the dispersed phase liquid and the continuous phase liquid in the membrane permeate can be kept constant.

  As shown in FIG. 9, when water was permeated through the porous glass membrane of Experimental Example 3 (skin layer: pore diameter 1.1 μm, both side support layers: pore diameter 4.9 μm) at a gas pressure of 0.4 MPa, When 99.82 cc / min / cm 2 (“pc5 + 1 + 5 water” in FIG. 9) passes water through the conventional porous glass membrane (pore diameter 1.1 μm) of the comparative example at a gas pressure of 0.4 MPa, 40.95 cc / Min / cm 2 (“P1 water” in FIG. 9), and the laminated porous glass membrane of Experimental Example 3 according to the present invention has a permeation amount nearly 2.4 times that of the conventional porous glass membrane. As a result. Further, when the mixture of the dispersed phase liquid and the continuous phase liquid is permeated as the membrane permeation liquid, the gas pressure of 0.6 MPa is 23.43 cc / min / in the case of the laminated porous glass membrane of Experimental Example 3. In the case of the conventional porous glass film of the comparative example, a result of 3.27 cc / min / cm 2 (“P1ow” in FIG. 9) was obtained at cm2 (“pc5 + 1 + 5ow” in FIG. 9). The difference between the transmission rate of about 2.4 times when passing through water and the transmission rate of about 7.2 times when passing through the coarsely mixed o / w emulsion is that the porous glass membrane is hydrophilic and fine It is suggested that the effect of the laminated porous glass film of the present invention having a thin skin layer appears more prominently as the liquid that permeates through the pores is, for example, a hard-to-permeate liquid such as an emulsion.

  FIG. 10 shows the particle size distribution obtained by passing through the coarsely mixed o / w emulsion. Here, the laminated porous glass permeable membrane emulsification distribution no. 1 “pc5 + 1 + 5 = p060”, the conventional porous glass permeable membrane emulsification distribution No. 1 2 Fine particles having an average particle diameter of “P1 = p060” of approximately 1.057 μm and 0.917 μm were obtained.

(Experimental example 8)
Pumping membrane emulsification was performed with the device 8 shown in FIG. 3 using the laminated porous glass membrane of Experimental Example 4, and the resulting emulsion particle size distribution is shown in FIG. Here, as shown in FIGS. 4 to 5, for example, if the conventional porous glass membrane has a pore diameter of 5 μm, the particle diameter is 1.742 μm even when the number of emulsification permeation of the pumping membrane in FIG. According to this experimental example, as shown in the emulsion particle diameter of FIG. 11 or Table 3, fine particles of 1.155 μm could be obtained by one membrane permeation. Further, when the membrane permeated 20 times, the fine particle diameter was 0.435 μm. From the above, the porous glass film formed by the phase separation method has a uniform pore diameter and also has a uniform skeleton. It is considered that a uniform and extremely fine gap is formed at the interface where both are in close contact, and fine particles are considered to be generated in the process of passing through the extremely fine gap. In addition, the ultrafine gap is formed on the interface and does not have a constant thickness unlike a microporous film. In other words, the thickness of the film becomes a permeation resistance in the permeation of the film. As in the experimental example, ultrafine particles in the sub-micron region could be obtained in the palm only with the thickness permeation resistance of the conventional porous glass membrane pore diameter of about 5 μm and the laminated thickness.

  Conventionally, when producing an emulsified preparation of fine particles such as submicron, it is considered that a high-pressure homogenizer or the like requires a large amount of generally expensive chemical raw material, and wasteful residual medicine is generated. Such a machine is very cumbersome for custom-made and frequent preparations. In addition, in order to produce ultrafine particles such as submicron, it is generally produced by using a high-pressure homogenizer, and in a severe atmosphere such as high temperature, it is very safe in terms of high-pressure and high-temperature conditions. I have anxiety. Therefore, the present invention can be prepared as a sterile disposable device, for example, in the form of the device 8, for example, to prepare an emulsion aseptically, especially for preparing a small amount of a submicron fine particle emulsion. It can be produced very easily in the palm. When an emulsion preparation having a large number of compositions is produced in a small amount, it is very easy to handle and can be produced in a short time. In addition, when the emulsion composition of desired fine particles is a high-viscosity product and it is necessary to carry out film emulsification under severe conditions such as ultra-high pressure conditions in a high temperature atmosphere such as 300 ° C., for example, the film emulsification device 19 can By using the type porous glass membrane, fine particles can be generated more safely at a low pressure even in a high-temperature atmosphere, and the amount of emulsification treatment per unit time can be increased. That is, the production cost can be reduced, and profits can be ensured or the sales unit price can be reduced.

It is sectional drawing of the porous glass membrane board which shows typically the lamination pattern which consists of a different fine pore diameter which concerns on this invention. It is sectional drawing of the porous glass film board which shows typically the lamination pattern which consists of the same micropore diameter concerning this invention. It is a handy type pumping type membrane emulsification device equipped with a porous glass membrane. It is a comparison of the emulsified particle size of the pumping membrane between the conventional porous glass membrane and the laminated porous glass membrane according to the present invention. It is a particle size distribution of the emulsification particle diameter of the pumping membrane by the conventional porous glass membrane shown in FIG. FIG. 5 is a particle size distribution of the emulsified particle diameter of the pumping membrane by the laminated porous glass membrane according to the present invention shown in FIG. It is a comparison of the emulsified particle diameter of the pumping membrane by the laminated porous glass membrane according to the present invention. It is the schematic of the porous glass permeable membrane emulsification experiment apparatus which concerns on this invention. 9 is a comparison of permeation pressure and permeation rate between a conventional porous glass membrane using the apparatus of FIG. 8 and a laminated porous glass membrane according to the present invention. 10 is a comparison of emulsion particle size distribution according to FIG. 9. It is a particle size distribution of the emulsification particle diameter of the pumping membrane by the laminated porous glass membrane according to the present invention.

DESCRIPTION OF SYMBOLS 1 Porous glass membrane 2 having a fine pore diameter 2 Porous glass membrane 3 having a fine pore diameter larger than 1 Porous glass membrane 4 having a pore diameter worth between the pore diameters of 1 and 2 Porous glass pore 5 Fine Gap 6 Porous glass skeleton 7 Porous glass membrane 8 Pumping type membrane emulsifying device 9 Syringe 10 Continuous phase liquid 11 Dispersed phase liquid 12 Fine particles 13 Gas pressure 14 Pressure gauge 15 Mixed liquid tank 16 Rough mixing of dispersed phase and continuous phase Liquid 17 Rotor 18 Stirrer 19 Membrane emulsification device 20 Beaker 21 Electronic balance

Claims (5)

In a porous glass film having uniform fine pores formed by a phase separation method, two or more porous glass films are adhered and laminated by heat fusion without peeling, and integrated laminated porous glass film Production method. The laminated glass film according to claim 1, wherein the porous glass film has uniform fine pores formed by phase separation method and has different fine pore diameters integrated by closely laminating porous glass films having different fine pore diameters without peeling. Type porous glass membrane. The laminated glass film according to claim 1, comprising a porous glass film having uniform fine pores formed by a phase separation method, wherein the porous glass films having the same fine pore diameter are integrally laminated without being peeled and integrated. Type porous glass membrane. A thin porous glass membrane having a fine pore diameter is used as a skin layer, and the porous glass membrane having a larger pore diameter than the porous glass membrane having a fine pore diameter is used as a support layer, and the layers are closely stacked without being peeled to form an integrated micro-fine film. The laminated porous glass membrane according to claim 1 or 2, comprising a pore size. A thin porous glass membrane having a fine pore diameter is used as a skin layer, a porous glass membrane having a larger pore diameter than the porous glass membrane having a fine pore diameter is used as a support layer, and the support layer is disposed on both sides so as to sandwich the skin layer. The laminated porous glass film according to claim 1 or 2, comprising different fine pore diameters that are integrally laminated without being separated from each other.

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