JP5405374B2 - Manufacturing method of honeycomb structure film - Google Patents

Description

  The present invention relates to a method for manufacturing a honeycomb structure film.

  In order to meet the demand for higher integration, higher information density, and higher definition of image information in the optical and electronic fields, the honeycomb structure film with finely formed pores has been studied for its manufacturing method. It is being advanced. Honeycomb structure films are also being used in the medical field, such as for use in medical materials such as anti-adhesion materials that prevent adhesion between tissues during surgery and as a cell culture substrate. Expectation.

  As a typical method for producing a honeycomb structure film, there is a dew condensation method. The dew condensation method is a method in which humidified air is applied to a liquid film made of a polymer compound solution to form water droplets, and the liquid components in the liquid film and the formed water droplets are evaporated (for example, Patent Document 1). In this dew condensation method, water droplets sink into the liquid film, and the honeycomb structure is formed using the water droplets as a mold.

  The number of holes forming the honeycomb structure depends on the number of water droplets. Further, when the formation density of water droplets on the exposed surface of the liquid film is small, that is, the number of water droplets per unit area of the exposed surface is too small and the water droplets are separated from each other, a honeycomb structure cannot be obtained. Therefore, in order to form many water droplets densely, a method has been proposed in which a surfactant is included in the solution to be cast (for example, Patent Document 1). In addition, since the size of the holes in the honeycomb structure depends on the size of the water droplets, the generated water droplets must be grown to form holes having a large diameter. The method of Patent Document 1 using a solution containing a surfactant also has an effect of growing water droplets.

  However, in the dew condensation method, it is difficult to control the conditions of the atmosphere because moisture in the atmosphere is condensed. Therefore, a method has been proposed in which condensation is performed by dissolving a polymer compound in a mixture of a hydrophobic solvent and a hydrophilic solvent and forming a liquid film from this solution so that the condensation is reliably performed. (For example, refer to Patent Document 2). According to the method of Patent Document 2, water droplets can be formed densely.

JP 2007-175962 A JP 2008-179749 A

  However, according to the method of Patent Document 1, the number of generated water droplets is limited, and the formation density of water droplets is also limited. Therefore, a porous film can be manufactured regardless of the size of the pores and the uniformity of the arrangement, but the honeycomb structure film having a uniform pore size is limited to a range of pore diameters even if it can be manufactured. Specifically, when a liquid film is dried while a water droplet is small in order to form a honeycomb structure with a small hole diameter, only a film in which the holes and holes are greatly separated can be obtained without forming the honeycomb structure. Further, when water droplets are grown so as to form a honeycomb structure having a large pore diameter, the water droplets are combined while the water droplets are growing. For this reason, even if the hole diameter is large, the obtained film has variations in the size and shape of the holes, and the arrangement of the holes is irregular.

  Moreover, although the method of patent document 2 has the merit on production efficiency of making a water droplet generate | occur | produce earlier and making it grow faster compared with the method of patent document 1, promotion of generation | occurrence | production and growth of a water droplet is obtained. If a moderate amount of hydrophilic solvent is used, the size and shape of the water droplets will be non-uniform, and the arrangement will tend to be disturbed. For this reason, although the film obtained by the method of Patent Document 2 can be said to be a porous film, it is not uniform enough to be called a honeycomb structure.

  In view of the above problems, the present invention provides a method for manufacturing a film having a honeycomb structure in which holes having a hole diameter in a range of 0.05 μm to 50 μm and holes having a uniform size are formed in a regular arrangement. With the goal.

  In the method for manufacturing a honeycomb structure film of the present invention, moisture in the atmosphere is added to a solution containing a hydrophobic liquid, a surfactant, and a hydrophobic polymer compound, and not containing a hydrophilic liquid. A water droplet forming step for generating water droplets by condensation and growing the water droplets to a predetermined size; and an evaporation step for evaporating the liquid components of the solution and the water droplets that have entered the solution. The liquid is characterized in that the solubility in water having the same temperature as the solution in the water droplet forming step is 0.5 (g / 100 g water) or less.

  The surfactant is included in the solution in an amount that does not exceed the critical micelle concentration in the solution. And in the manufacturing method of this invention, it is preferable to determine a hydrophobic liquid based on the said solubility according to the magnitude | size of the water droplet which should be formed.

  When the hydrophobic liquid is a poor solvent for the polymer compound, the solution preferably contains a good solvent for the polymer compound.

  According to the present invention, a honeycomb structure film having a small hole diameter of about 0.05 μm to a large hole diameter of about 50 μm can be manufactured, and a honeycomb structure film having a uniform hole size and a regular arrangement can be obtained.

1 is a plan view of a honeycomb structured film manufactured according to the present invention. FIG. It is sectional drawing which follows the II-II line of FIG. It is sectional drawing which follows the III-III line of FIG. It is sectional drawing of another honeycomb structure film manufactured by this invention. It is the schematic of a film manufacturing equipment. It is explanatory drawing which shows the state of surfactant in a solution. It is explanatory drawing which shows the state of surfactant in a solution. It is explanatory drawing of the solubility of the strong hydrophobic liquid with respect to water. It is a graph which shows the relationship between the magnitude | size of the water droplet formed and the solubility of the strong hydrophobic liquid with respect to water.

[the film]
1 to 4 are schematic views of a honeycomb structure film manufactured according to the present invention. 1 is a plan view of a honeycomb structure film (hereinafter simply referred to as “film”) 10, FIG. 2 is a cross-sectional view taken along line II-II in FIG. 1, and FIG. 3 is a cross-sectional view taken along line III-III in FIG. It is. FIG. 4 is a cross-sectional view of another embodiment of the film 20, but the plan view of the film 20 is the same as FIG.

  The films 10 and 20 have a honeycomb shape, so-called honeycomb structure, as shown in FIGS. That is, in the films 10 and 20, a plurality of holes 11 and 21 are densely formed along the film surfaces 10 a and 20 a, the plurality of holes 11 in the film 10 are formed by the partition walls 14, and the plurality of holes 21 in the film 20 are formed. Are independent of each other by the partition walls 24. The holes 11 and 21 have a substantially constant shape and size, and are formed so as to be regularly arranged along the film surfaces 10a and 20a. Therefore, the regularity of the arrangement of the holes 11 and 21 can be said to be a two-dimensional regularity along the film surface. And when the film 10 is seen from the normal line direction of one film surface 10a, it is located so that the circumference | surroundings of one hole 11 may surround the hole 11 (for example, six according to FIG. 6). In the film 10 of FIG. 1, the number of the holes 11 formed around one hole 11 is 6, but the number is 3 to 5 or 7 or more depending on manufacturing conditions.

  The holes 11 of the film 10 are so-called through holes formed so as to penetrate the film 10 in the thickness direction from one film surface 10a to the other film surface 10b, as shown in FIGS. On the other hand, the hole 21 of the film 20 of FIG. 4 is a depression formed only on one film surface 20a, that is, a concave shape. Whether it is formed as a through-hole or a depression depends on the depth of entry of water droplets into the liquid film in the manufacturing process described later.

  In the present invention, the thickness T of the film 10 is 0.05 μm or more and 100 μm or less, the diameter D1 of the hole 11 is 0.05 μm or more and 100 μm or less, and the center distance L between adjacent holes 11 is 0.05 μm or more and 120 μm or less. This is effective when manufacturing such a porous structure, and is particularly effective when manufacturing a porous structure having a pore diameter D1 in the range of 0.05 μm or more and 50 μm or less.

  In addition, said films 10 and 20 may be formed so that it may overlap on a support body. In the case of a composite material in which the support and the film 10 or the film 20 are overlapped, the films 10 and 20 may be used together with the support, or may be peeled off from the support and used. Good.

  Since the manufacturing method of the film 10 and the film 20 is basically the same, the following manufacturing method is described as manufacturing the film 10. As shown in FIG. 5, the film manufacturing facility 30 for carrying out the present invention includes a delivery device 34 that sends out a support 31 that supports the film 10, and a film forming device 35 that forms the film 10 on a long support 31. And a cutting device 36 for cutting the film 10 into a predetermined shape together with the support 31.

  A plurality of rollers 37 that support the support 31 on its peripheral surface are provided in the conveyance path of the support 31 from the delivery device 34 to the cutting device 36. Among these rollers 37, there is a driving roller that rotates in the circumferential direction, and the support 31 is conveyed by the rotation of the driving roller. In addition, a plurality of temperature control plates (not shown) for adjusting the temperature of the support 31 are provided below the support 31 in the transport path along the transport direction of the support 31 indicated by the arrow X. . The temperature of the support 31 is adjusted by the temperature control plate, and the temperature of the liquid film 40 formed on the support 31 becomes a predetermined value at a predetermined timing.

  The delivery device 34 pulls out the support 31 from the support roll 38 in which the long support 31 is rolled, and continuously sends it to the film forming device 35.

  The film forming apparatus 35 includes a first chamber 41, a second chamber 42, and a third chamber 43 arranged in order from the upstream side in the transport direction X of the support 31. The film forming device 35 includes the first chamber 41, the first chamber 41, and the first chamber 41. While transporting the two chambers 42 and the third chamber 43, a liquid film 40 made of the solution 46 is formed on the support 31, and the liquid film 40 is dried, whereby the film 10 is placed on the support 31. Form.

  The first chamber 41 is provided with a casting die 47 through which the solution 46 flows out. By continuously flowing out from the casting die 47 arranged so that the outlet from which the solution 46 flows out is opposed to the support 31 onto the support 31 being transported, the solution 46 of the support 31 is removed. The liquid film 40 is formed by casting on the top. As described above, the liquid film forming step of casting the solution 46 to form the liquid film 40 is performed in the first chamber 41.

  The thickness of the liquid film 40 is adjusted by the viscosity and flow rate of the solution 46, the clearance at the outlet of the casting die 47, and the conveyance speed of the support 31. The thickness of the liquid film 40 immediately after formation is in the range of 10 μm or more and 2000 μm or less.

  Above the transport path of the support 31 in the second chamber 42, there is provided a blower suction unit 50 that supplies air above the liquid film 40 and sucks the gas, that is, the atmosphere above the liquid film 40. In FIG. 5, two air suction units 50 are provided side by side in the conveyance direction X of the support.

  The blower suction unit 50 includes a duct having a blower port 51 that discharges air toward the exposed surface of the liquid film 40 and an intake port 52 that sucks gas above the liquid film 40, and a blower unit 53. The blower unit 53 controls the temperature, dew point, and air volume of the air discharged from the blower port 51, and controls the dew point of the solvent gas by removing the solvent from the sucked gas and the suction air amount when sucked at the intake port 52. .

  In the second chamber 42, humidified air is supplied from the air blowing port 51 to cause moisture in the atmosphere to condense on the exposed surface of the liquid film 40 to generate water droplets. The generated water droplets have a predetermined size. A water droplet formation process is performed for growth until it becomes. The water droplets generated by the supply of humidified air are aligned by capillary force or the like and grow by continuing contact with the humidified air. In other words, the final water droplet size mainly depends on the dew point TD of the atmosphere and the contact time between the water vapor contained in the atmosphere. Therefore, in order to grow water droplets larger, it is preferable to increase the dew point TD of the atmosphere and to increase the residence time of the liquid film 40 in the second chamber 42. The dew point TD of the atmosphere can be adjusted by controlling the dew point of the air from the air outlet 51.

  Further, from the liquid film 40, the solvent evaporates slightly. Accompanying this evaporation, the water droplets gradually sink into the liquid film 40 while growing. That is, the depth of penetration of water droplets into the liquid film 40 depends on the evaporation rate and evaporation amount of the solvent until the liquid film 40 reaches a predetermined viscosity. Therefore, the film 10 and the film 20 can be separated by controlling the evaporation rate and the evaporation amount of the solvent.

  The progress of water droplet generation and the progress of growth can be controlled by supplying air humidified by the blower suction unit 50 and adjusting the temperature of the exposed surface of the liquid film 40. Specifically, the temperature TS is set such that a parameter ΔTw (= TD−TS) obtained by subtracting the temperature TS of the exposed surface of the liquid film 40 from the dew point TD in the atmosphere of the liquid film 40 is in a range of 1 ° C. or more and 30 ° C. or less. And adjust the humidity and temperature of the supplied air. Furthermore, by controlling the dew point of the solvent gas above the liquid film 40, the generation of water droplets and the progress of the growth can be more reliably controlled. The dew point of the solvent gas above the liquid film 40 can be controlled by adjusting the suction air volume from the intake port 52.

  In the third chamber 43, a plurality of blower suction units 56 are provided side by side along the transport direction X of the support 31. The blower suction unit 56 has the same configuration as the blower suction unit 50 of the second chamber 42, and includes a duct having a blower port 57 and an intake port 58, and a blower unit 59.

  In the third chamber 43, a drying process is performed in which the solvent and water droplets are evaporated from the liquid film 40 to obtain the film 10. Therefore, the dried air is flowed out from the blower opening of the blower suction unit 56, and the liquid film 40 is dried. Although both the solvent and the water droplet may be evaporated, it is more preferable to evaporate the solvent earlier than the water droplet.

  The film 10 is guided to the cutting device 36 in a state of being overlapped with the support 31, and is cut into a predetermined size together with the support 31 into a sheet-like product. In addition, in this embodiment, although the film 10 was cut | disconnected by the cutting apparatus 36 in the sheet form, it is good also as a roll-shaped product by winding up with the elongate. Moreover, after peeling off from the support body 31, you may make a sheet-like or roll-shaped product.

  In the present embodiment, the solution 46 is cast on the traveling support 31 to form the liquid film 40, and the films 10 and 20 are produced by dew condensation on the liquid film 40. Is not limited. For example, the films 10 and 20 can also be manufactured by a method in which the solution 46 is put in a container and the liquid surface of the solution 46 is condensed to form water droplets. Thus, the method of performing dew condensation on the solution 46 in the container is particularly effective when manufacturing the film 20 in which the hole 21 that is a depression is formed instead of the through hole.

  The films 10 and 20 are both composed of a hydrophobic polymer compound 61 and manufactured from the solution 46 as described above. That is, the hydrophobic polymer compound 61 is dissolved in the solution 46. In addition to the polymer compound 61, the solution 46 includes a surfactant 62 and a hydrophobic liquid 63 having a water solubility of 0.5 (g / 100 g water) or less. This solubility is an extremely strong hydrophobic level, even though it is generally said to be hydrophobic. In the following description, this liquid is referred to as “strongly hydrophobic liquid”. When the strong hydrophobic liquid 63 is a good solvent for the polymer compound 61, the strong hydrophobic liquid 63 can be used as the solvent component of the solution, so that it is not necessary to use another liquid as the solvent component. However, when the strongly hydrophobic liquid 63 is a poor solvent for the polymer compound 61, a good solvent 64 is further used. The solution 46 does not contain any hydrophilic substance other than the surfactant 62. Therefore, no hydrophilic liquid is used in the present invention.

(1) Polymer Compound The hydrophobic polymer compound is selected according to the use of the films 10 and 20. For example, poly-ε-caprolactone, poly-3-hydroxybutyrate, agarose, poly-2-hydroxyethyl acrylate, polysulfone, vinyl polymer (eg, polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, polyacrylamide, poly Methacrylamide, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyhexafluoropropene, polyvinyl ether, polyvinyl carbazole, polyvinyl acetate, polytetrafluoroethylene, etc., polyester (eg, polyethylene terephthalate, polyethylene naphthalate, polyethylene succin) , Polybutylene succinate, polylactic acid, etc.), polylactone (eg, polycaprolactone), polyamide (eg, , Nylon), containing a polyimide (polyamic acid), polyurethanes, polyureas, polycarbonates, polyaromatics, polyethersulfone, polysiloxane derivatives.

  From the viewpoint of solubility, optical properties, electrical properties, strength, elasticity, etc., the polymer compound may be each homopolymer listed above, or may be a copolymer, polymer blend, or polymer alloy. When the films 10 and 20 are used as a film-shaped adhesion preventing material, biodegradability is required, and therefore polylactic acid and poly-ε-caprolactone are particularly preferable. Moreover, these may be mixed and used in arbitrary ratios, or the copolymer which synthesize | combined the copolymer which has each of these repeating units may be used.

(2) Surfactant As is well known, a surfactant is an amphiphilic compound having in its structure a hydrophobic part exhibiting hydrophobicity and a hydrophilic part exhibiting hydrophilicity. The surfactant may be a monomer such as many commercially available surfactants, or may be an oligomer such as a dimer or trimer. When the films 10 and 20 are used as the film-shaped adhesion preventing material, it is preferable to use phospholipid because it has biodegradability.

  When the surfactant is contained in water, the hydrophobic part surrounded by water alone is unstable, so it appears that it is adsorbed at the interface between the outside air and water. It is located on the water surface that is the interface between water and outside air so that it is on the water side. Then, as the amount of the surfactant is increased, the surfactant aggregates and changes to a more stable form, and eventually stabilizes in water. The so-called micelles arranged or arranged in this way are so-called micelles, and the surfactant floats in water by forming spherical micelles having a spherical shape with the hydrophobic portion on the inside and the hydrophilic portion on the outside. The concentration of the surfactant that forms spherical micelles in this way is the critical micelle concentration (cmc).

  On the other hand, when a surfactant is contained in a hydrophobic liquid like the solution used in the present invention, as shown in FIG. 6, the surfactant 62 is hydrophilic at a concentration smaller than cmc. At the liquid surface 46a so that the portion 62a is on the outside air side and the hydrophobic portion 62b is on the solution 46 side, at a concentration of cmc or higher, as shown in FIG. The reverse micelle 71 is formed and drifts into the solution.

  It is more preferable to use the surfactant 62 in such an amount that the concentration is less than cmc in the solution 46. By suppressing the amount of the surfactant 62 used to a concentration lower than cmc, most of the surfactant 62 is located not on the inside of the solution 46 but on the liquid surface 46a. Therefore, when the liquid film 40 is formed, the liquid film 40 is positioned not on the liquid film 40 but on the liquid surface, that is, the exposed surface. Since the surfactant exists on the liquid surface in such a posture that the hydrophilic portion 62a is on the outside air side of the liquid surface 46a, each hydrophilic portion 62a serves as a scaffold for the generation of water droplets due to condensation. Therefore, almost all of the surfactant 62 in the solution 46 contributes to the generation of water droplets. This effect is similarly obtained even when the concentration of the surfactant 62 in the solution 46 is cmc. Accordingly, the surfactant 62 may be used in such an amount that does not exceed the cmc in the solution 46, that is, the cmc or less.

  In addition, if the concentration of the surfactant 62 in the solution 46 is higher than cmc, the reverse micelles 71 existing in the liquid film 40 may cause voids in the films 10 and 20. By suppressing the amount of the surfactant 62 used in the concentration, the generation of this void can be prevented. Even if the concentration is lower than cmc, the reverse micelles 71 are very slightly present in the liquid film 40. However, if the concentration is not more than cmc, there is a certain effect in suppressing the generation of voids. In order to obtain this effect more reliably, the concentration of the surfactant in the solution 46 is preferably set to 1/2 or less of cmc, and more preferably 1/10 or less. However, from the viewpoint of reliably generating many water droplets, the concentration of the surfactant 62 in the solution 46 is preferably at least 0.0001% by mass or more.

  Furthermore, although the surfactant 62 may remain in the films 10 and 20, even if it remains, the content of the surfactant 62 is extremely small, and therefore there is a possibility that the influence on the use environment such as a living body is further suppressed. Therefore, the possibility of utilization as a medical material such as an adhesion preventing material is increased.

  The surface tension of the solution 46 containing the surfactant 62 decreases as the concentration of the surfactant 62 increases. The relationship between the surface tension and the surfactant concentration is determined, and the concentration at which the surface tension does not change even when the surfactant concentration is increased is defined as the critical micelle concentration cmc. The surface tension of the solution 46 can be measured with a DropMaster series manufactured by Kyowa Interface Science Co., Ltd.

  The cmc of the surfactant 62 varies depending on the temperature of the solution 46, the presence or absence of the electrolyte in the solution 46, and the amount of the electrolyte. Specifically, the lower the temperature of the solution 46 and the greater the amount of electrolyte, the lower the cmc of the surfactant 62. Therefore, the solution 46 for obtaining cmc should be the same temperature as the temperature of the liquid film 40 during the water droplet formation step, and the same solution 46 as that in which all the formulations except the surfactant 62 are cast. preferable.

(3) Strongly Hydrophobic Liquid The strongly hydrophobic liquid 63 is for stably growing each of the water droplets generated in each hydrophilic portion 62 a of the surfactant 62. Stable growth means that, among the many water droplets that have occurred, some of the water droplets are joined together and the final size and arrangement of the water droplets are not uniform, and the individual water droplets remain the same while maintaining their shape. It means growing to size. Growing to the same size results in a uniform water droplet arrangement. The above effect of using the strong hydrophobic liquid 63 may be a case where the size of the water droplets to be formed is very small from 0.05 μm to 10 μm. It is more noticeable when 20 is made.

  Generally, the solubility referred to as hydrophilic is a region larger than 30 (g / 100 g) indicated by the symbol R1 in FIG. 8, and the solubility referred to as hydrophobic is within a range of 30 (g / 100 g) or less indicated by the symbol R2. . As the strongly hydrophobic liquid 63, a liquid having a solubility in the range of 0 to 0.5 (g / 100 g water) indicated by the symbol R3 is used. The greater the hydrophobicity of the strongly hydrophobic liquid 63, the better. That is, the solubility of the strongly hydrophobic liquid 63 in water is preferably as small as possible within the range indicated by the symbol R3, more preferably in the range of 0 to 0.1 (g / 100 g water), and more preferably 0 to 0.05 (g / 100 g). Water) is more preferably in the following range. Thus, as shown in FIG. 8, the solubility of the strongly hydrophobic liquid 63 is very low in the hydrophobic region R2, and the region R3 is a very small range in the region R2. The solubility in water in the present specification is the solubility in water at the same temperature as the liquid film 40 in the water droplet formation step, and the formation of water droplets in the solution 46 contained in the container without forming the liquid film 40. When the process is carried out, the solubility in water at the same temperature as the solution 46 at this time.

  The strong hydrophobic liquid 63 includes n (normal) -hexane (solubility ≦ 0.001 (g / 100 g water)), cyclohexane (solubility = 0.008 (g / 100 g water)), and other liquid n- at room temperature. Hydrocarbon compounds such as pentane, n-octane and heptane can be used. In addition, a fluorine-based solvent such as Asahi Clin (AK-225) (solubility = 0.033 (g / 100 g water)) manufactured by Asahi Glass Co., Ltd. can be used.

  The strongly hydrophobic liquid 64 used by mixing with the good solvent 64 preferably has a boiling point of 100 ° C. or lower. When a hydrophobic liquid is used in addition to the strong hydrophobic liquid 64, for example, when the good solvent 64 is a hydrophobic liquid, the boiling point of the hydrophobic liquid is Tr, and the boiling point of the strong hydrophobic liquid 64 is Tk. In this case, it is desirable to use a strongly hydrophobic liquid 64 and a hydrophobic liquid that satisfy Tk−Tr ≦ 10 ° C. When the boiling point of the strongly hydrophobic liquid 64 is significantly higher than the boiling points of the other liquids used in combination, the ratio of the other liquids increases in the vicinity of the surface of the mixed liquid of the strongly hydrophobic liquid 64 and the other liquids. There may be cases where the effect does not appear. More preferably, the strong hydrophobic liquid 64 and the hydrophobic liquid that satisfy Tk−Tr ≦ 5 ° C. are used in combination.

  Hydrophobic liquids have also been used in conventional manufacturing methods, but this has been selected from the viewpoints of solubility for dissolving the hydrophobic polymer compound 61 and ease of drying in the drying process. On the other hand, in the present invention, when selecting a liquid to be used as the strongly hydrophobic liquid 63, the solubility in water is used as a reference, not the viewpoint of dissolving the polymer compound 61 or the ease of drying. This is because the droplet formed by condensation is a water droplet, and the hydrophilic portion 62a of the surfactant 62 is used as a scaffold for the generation of the water droplet. The solubility of the water droplets and the hydrophilic portion 62a is included in the region R1, and the difference between the solubility of the water droplets and the solubility of the region R3 is extremely large. Therefore, each water droplet generated on the exposed surface is removed from each hydrophilic portion of the surfactant 62. This is because the effect of growing while maintaining a large contact angle while remaining on 62a is extremely strong. The solubility of the hydrophobic portion 62b of the surfactant and the good solvent 64 is in the region R4 between the region R3 and the region R1, and with this solubility, there is almost no effect of growing each water droplet while remaining in the hydrophilic portion 62a. Absent.

  Low solubility in water means strong hydrophobicity. Since the strong hydrophobic liquid 63 stably grows water droplets due to this hydrophobic strength, as shown in FIG. 9, by using the strong hydrophobic liquid 63 having a different hydrophobic strength, water droplets to be formed are used. The size of can be changed. The vertical axis of FIG. 9 is the size of water droplets that can be formed, meaning that the diameter of the water droplets increases toward the upper side, and the horizontal axis indicates the solubility (unit: g / g) of the strongly hydrophobic liquid 63 in water. 100 g water). In this graph, the ratio of the mass of the strongly hydrophobic liquid 63 to the mass of the surfactant 62 in the solution 46 is constant. According to FIG. 9, it can be seen that the smaller the solubility of the strong hydrophobic liquid 63, the larger the water droplets can grow. Therefore, a liquid to be used as the strong hydrophobic liquid 63 may be selected based on the solubility in water according to the size of the water droplet to be formed.

  When the size of the water droplets to be formed is very small, 0.05 μm or more and 10 μm or less, the strongly hydrophobic liquid 63 is a so-called poor solvent that does not dissolve rather than the polymer compound 61 having excellent solubility. Is preferred. This is because by using a poor solvent for the polymer compound 61 as the strong hydrophobic liquid 63, the liquid film 40 can be hardened more quickly, so that the growth of water droplets can be stopped at an early timing. Here, the poor solvent means that the solubility of the polymer compound 61 is less than 1%.

  In the case of stopping the growth of water droplets while having a very small diameter of 0.05 μm or more and 10 μm or less, the mass X of the strong hydrophobic liquid 63 as the poor solvent is at most 50% with respect to the mass Y of the solution 46. It is preferable to do. More preferably, the mass ratio of the strongly hydrophobic liquid 63 obtained by X / Y × 100 is 1% or more and 30% or less, and further preferably 5% or more and 30% or less. When the strong hydrophobic liquid 63 is a poor solvent for the polymer compound 61, a good solvent 64 is used.

(4) Good solvent The good solvent 64 is used to dissolve the polymer compound 61. Examples of the good solvent 64 include chloroform, dichloromethane, carbon tetrachloride, cyclohexane, and methyl acetate, and a plurality of these may be used in combination. Since the polymer compound 61 is hydrophobic, most of the liquids that can be used as the good solvent 64 are hydrophobic. However, when the good solvent 64 is selected, the hydrophobicity, that is, the solubility in water, is determined. There is no need to consider.

  As described above, according to the present invention, it is possible to manufacture a honeycomb structure film having a uniform pore diameter and a regular arrangement from a small hole of 0.05 μm to a large hole of 50 μm. Among them, the present invention has a particularly remarkable effect compared with the prior art when manufacturing a honeycomb structure film having a small pore size of 0.05 μm or more and 10 μm or less, and further a very small honeycomb structure film of 0.05 μm or more and 3 μm or less. Indicates.

  A solution 46 having the following composition was prepared. The solution 46 was filtered to remove foreign matters, and then supplied to the casting die 47. Polylactic acid was used as the hydrophobic polymer compound 61, polyacrylamide as an amphiphilic polymer as the surfactant 62, normal hexane as the strong hydrophobic liquid 63, and trichloromethane (chloroform) as the good solvent 64, respectively. The concentration of the polymer compound 61 in the solution 46 was 1.0% by mass. As described below, the mass ratio represented by (strong hydrophobic liquid 63) :( good solvent 64) was 30:70. In addition, cmc in the solution 46 of the surfactant 62 is 1.0%. In Table 1, each “solubility in water” is a value for water having the same temperature as the solution 46 in the water droplet formation step.

  In the first chamber 41, the solution 46, which is maintained at a substantially constant temperature in the range of 10 ° C. or more and 30 ° C. or less, is discharged from the casting die 47 to the support 31. A liquid film 40 was formed. Thus, the liquid film formation process was performed. The thickness of the liquid film 40 was 500 μm.

  In the second chamber 42, the humid air from the blower suction unit 50 was adjusted so that ΔTw was substantially constant within a range of 5.0 ° C. or more and 6.0 ° C. or less. And the wet air was applied to the liquid film 40 from the ventilation suction unit 50, and the water droplet formation process was performed. The wind speed of the wet air sent out from the blower suction unit 50 was 0.5 m / sec.

  In the third chamber 43, the dry air from the blower suction unit 56 was adjusted so that ΔTw became substantially constant within a range of −6.0 ° C. or more and −5.0 ° C. or less. And the drying process was performed by applying dry air to the liquid film 40 from the ventilation suction unit 56. The wind speed of the dry air sent out from the ventilation suction unit 56 was 5.0 m / sec.

  The average value of the diameters D1 of the holes 21 of the obtained film 20 and the coefficient of variation of the diameters D1 (hereinafter referred to as the hole diameter coefficient of variation) are obtained by the following method. The degree of sequence regularity was evaluated according to the following criteria. The evaluation results are shown in Table 2.

<Average value of diameter D1 and coefficient of variation in pore diameter>
The surface of the film 20 was observed at a magnification such that the number of holes in one screen was 50 or more in an SEM (Scanning Electron Microscope) photograph or an optical microscope photograph. Based on the observed micrograph, image analysis is performed on the holes existing in one screen, the diameter D1 of each hole 21 is measured, the average value DAV of the diameters D1 of the holes 21, and the standard deviation σD of the hole diameters, The pore diameter variation coefficient X was calculated. The pore diameter variation coefficient X (unit:%) is obtained by (σD / DAV) × 100.

<Evaluation criteria for degree of regularity of array>
A: When the coefficient of variation is less than 5% B: When the coefficient of variation is 5% or more and less than 10% C: When the coefficient of variation is 10% or more and less than 15% D: When the coefficient of variation is 15% or more

  (Strongly hydrophobic liquid 63): The same operation as in Example 1 was performed except that the mass ratio represented by (good solvent 64) was 1:99.

  The obtained film 20 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  As strong hydrophobic liquid 63, Asahi Clin AK-225 of Asahi Glass Co., Ltd. was used instead of n-hexane. The mass ratio represented by (strongly hydrophobic liquid 63) :( good solvent 64) was 10:90. Except for these, the same procedure as in Example 1 was performed.

  The obtained film 20 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  As the strong hydrophobic liquid 63, cyclohexane was used instead of n-hexane. Instead of trichloromethane, dichloromethane was used as a good solvent 64. The mass ratio represented by (strongly hydrophobic liquid 63) :( good solvent 64) was 10:90. Except for these, the same procedure as in Example 1 was performed.

  The obtained film 20 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  The mass ratio of the surfactant 62 in the solution 46 was set to 2%, which is larger than 1.0% which is cmc. Except this, the same procedure as in Example 1 was performed.

  The obtained film 20 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Comparative Example 1]
A solution to be cast was prepared without using the strong hydrophobic liquid 63. The liquid components of the solution are dimethyl sulfoxide (DMSO) and trichloromethane as the good solvent 64. The solubility of DMSO in water is 100 (g / 100 g water) or more. The mass ratio represented by DMSO: (good solvent 64) was 30:70.

  The obtained film was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

10,20 film 11,21 hole 14 partition 40 liquid film 46 solution 70 surfactant

Claims (4)

On a solution containing a hydrophobic liquid, a surfactant, and a hydrophobic polymer, and not containing a hydrophilic liquid, moisture in the atmosphere is condensed to generate water droplets. A water droplet formation process for growing the product to a predetermined size;
Evaporating the liquid component of the solution and the water droplets that have entered the solution; and
The method for producing a honeycomb structure film, wherein the hydrophobic liquid has a solubility in water having the same temperature as that of the solution in the water droplet formation step of 0.5 (g / 100 g water) or less.   The method for manufacturing a honeycomb structure film according to claim 1, wherein the surfactant is contained in the solution in an amount that does not exceed a critical micelle concentration in the solution.   The method for manufacturing a honeycomb structure film according to claim 1 or 2, wherein the hydrophobic liquid is determined based on the solubility according to the size of the water droplet to be formed.   The honeycomb structure film according to any one of claims 1 to 3, wherein when the hydrophobic liquid is a poor solvent for the polymer compound, the solution contains a good solvent for the polymer compound. Method.

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