JP2016160355A - Method for producing protrusion structural body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a protrusion structural body easily producing a film-shaped protrusion structural body uniform over the large area from a film having a honeycomb structure.SOLUTION: Provided is a honeycomb structural body 20 formed of a hydrophobic polymer, and in which the first film face 20a has a honeycomb structure where a plurality of pores are arranged. The honeycomb structural body 20 is charged to the liquid tank 65 of an ultraviolet treatment device 60. The liquid tank 65 is charged with water 63. The honeycomb structural body 20 is irradiated with ultraviolet vibration via the water 63 by the ultraviolet treatment device 60, and the side of the first film face 20a is eliminated from the honeycomb structural body 20. In the honeycomb structural body 20, a part of a bulkhead between the pores is left as projections to obtain a projection structural body in which a plurality of the projections are arranged at either film face.SELECTED DRAWING: Figure 6

Description

  The present invention relates to a method for manufacturing a protruding structure.

  There is a film structure as a protrusion structure in which a large number of minute columnar protrusions are formed. Such a film structure is called a pillar film or a pillar structure film. This pillar film is expected to be used for various purposes including cell culture due to its fine uneven structure on the surface on which the protrusions are formed.

  The pillar film can be manufactured from a film having a honeycomb structure by arranging a plurality of minute holes along the film surface (hereinafter referred to as a honeycomb film). As a method of manufacturing a pillar film from a honeycomb film, a hole is formed by sticking an adhesive film having an adhesive on the surface of one of the honeycomb film holes and pulling the adhesive film. There is a method of peeling off the above-mentioned one film surface side portion from the other film surface side portion, and the other film surface side portion becomes a pillar film (see, for example, Patent Document 1). A method of manufacturing a pillar film by irradiating a honeycomb film with ultrasonic waves has also been proposed (see, for example, Patent Document 2). According to these methods, a pillar film can be easily produced from a honeycomb film.

  Moreover, the honeycomb film used as the material of the pillar film can be manufactured by a dew condensation method (also referred to as a Breath Figure method) (see, for example, Patent Document 1). In the dew condensation method, a solution made from a hydrophobic polymer for forming a honeycomb film is cast to form a cast film, and the film is condensed to form water droplets, and the solvent and water droplets are evaporated. This is a method for manufacturing a honeycomb film (see, for example, Patent Document 1). According to this dew condensation method, it is possible to obtain a honeycomb film in which a plurality of extremely small and uniform holes are regularly arranged using water droplets as a mold of holes, so that the protrusions are uniform and regular. It is preferable as a material for producing a pillar film arranged in a row.

  Furthermore, the honeycomb film can be formed on a curved surface. For example, as a method of forming a honeycomb film on the outer peripheral surface and inner peripheral surface of a cylinder, a wet gas is supplied to the outer periphery and the hollow portion of the cylinder after the cylinder is immersed in the above solution using a hydrophobic polymer as a raw material. Then, there is a method of supplying a dry gas (see, for example, Patent Document 3).

JP 2009-293019 A International Publication No. 2004/048064 Pamphlet JP 2010-229373 A

  However, the method for manufacturing a pillar film using an adhesive tape as in Patent Document 1 requires uniform application of the adhesive tape to the honeycomb film and uniform stripping of the one film surface side using the adhesive tape. It is. For this reason, there exists a problem that enlargement of the area of the pillar film to manufacture is difficult. Further, in the manufacturing method by ultrasonic irradiation described in Patent Document 2, as the area of the pillar film to be manufactured is increased, the honeycomb structure on the honeycomb film partially remains or protrusions having irregular sizes and shapes are formed. It becomes a non-uniform pillar film.

  An object of the present invention is to provide a method for manufacturing a protruding structure capable of easily manufacturing a uniform and film-like protruding structure from a honeycomb film in a large area.

  In order to solve the above-mentioned problems, the present invention provides a method for manufacturing a protrusion structure including a plurality of protrusions and formed from a hydrophobic polymer, and a honeycomb structure formed from a hydrophobic polymer and having a plurality of pores arranged on the surface. An ultrasonic treatment step in which part of the surface side is detached from the honeycomb structure by applying ultrasonic vibration in the liquid to the honeycomb structure having the structure, and a part of the partition walls between the holes is left as protrusions; And a wettability improving step for improving the wettability of the structure with respect to the liquid.

  The liquid is water, and the wettability improving process is to improve the wettability of the honeycomb structure by bringing alcohol into contact with the honeycomb structure before the ultrasonic treatment process, or the liquid is alcohol and improving the wettability. In the step, it is preferable to improve the wettability of the honeycomb structure by bringing alcohol into contact with the honeycomb structure in the ultrasonic treatment step.

  Adjacent holes are connected internally in the direction along the surface, and the protrusions are preferably columnar.

  The honeycomb structure is preferably a film, and the surface is preferably one film surface. It is more preferable to apply ultrasonic vibration in a state where the honeycomb structure is supported by the support from the other film surface.

  It is preferable to apply ultrasonic vibration in a state where the honeycomb structure is hardened by the curing treatment.

  The honeycomb structure includes a polymerizable compound that is polymerized by light irradiation, and the curing process is a light curing process that polymerizes the polymerizable compound by irradiating the honeycomb structure with light, and ultrasonic vibration is performed after the curing process. The honeycomb structure is preferably provided.

  The curing process is a cooling process in which the honeycomb structure is cooled below the glass transition point of the hydrophobic polymer, and ultrasonic vibration is preferably applied to the honeycomb structure during the curing process.

  According to the present invention, a uniform and film-like protruding structure can be easily produced from a honeycomb film in a large area.

It is sectional drawing of the protrusion structure which implemented this invention. 1 is a plan view of a honeycomb structure embodying the present invention. It is sectional drawing which follows the III-III line of FIG. It is sectional drawing which follows the IV-IV line of FIG. It is explanatory drawing which shows the manufacturing process of a protrusion structure. It is explanatory drawing which shows the outline of an ultrasonic processing apparatus. It is the electron micrograph which looked at the honeycomb structure from the perpendicular direction of one surface. It is the electron micrograph which looked at the protrusion structure from the direction which cross | intersected one film surface and the perpendicular | vertical direction of the film surface. It is explanatory drawing which shows another manufacturing process of a protrusion structure. It is sectional drawing of the protrusion structure which implemented this invention. It is a perspective view which shows the protrusion structure provided with a protrusion structure part and a honeycomb structure part. It is a perspective view which shows a mask board. It is the optical microscope photograph which looked at the projection structure provided with a projection structure part and a honeycomb structure part from the perpendicular direction of one surface.

[First Embodiment]
As shown in FIG. 1, a protrusion structure 10 embodying the present invention is a film, that is, formed into a film shape, and has a plurality of protrusions on one film surface (hereinafter referred to as a first film surface) 10a. 11 is provided. On the other film surface (hereinafter referred to as the second film surface) 10 b, a film surface opening 10 c is formed between the protrusion 11 and the protrusion 11. The thickness T10 of the protruding structure 10 is 3 μm in this example, but is not limited to this, and is in the range of 0.1 μm to 100 μm.

  The plurality of protrusions 11 have substantially the same shape and size, and are regularly arranged on the first film surface 10a. The protrusion 11 is columnar and has a so-called tapered shape with a diameter that decreases toward the tip. The protrusion structure 10 is manufactured from a honeycomb structure 20 (see FIGS. 2 to 4) described later, and the tip of the protrusion 11 has a rounded shape in this example, but the partition wall 22 in the honeycomb structure 20. The shape changes according to the thickness (see FIGS. 3 and 4). Further, the thickness of the protrusion 11 also varies depending on the thickness of the partition wall 22. For example, the smaller the thickness of the partition wall 22, the sharper the tip of the protrusion 11 and the thinner the protrusion 11 becomes. In FIG. 1, the thickness of the protrusion 11 is greatly exaggerated with respect to the thickness T <b> 10 of the protrusion structure 10.

  The height of the protrusion 11 (hereinafter referred to as the protrusion height) is approximately 3 μm in this example, but is not limited to this and is in the range of 0.1 μm to 50 μm. The height of the protrusion can be changed depending on the thickness T20 of the honeycomb structure 20 described later, the mode of the partition walls 22, and the conditions of the ultrasonic treatment described later. The distance between adjacent protrusions 11 (hereinafter referred to as the distance between protrusions) is approximately 8 μm in this example, but is not limited to this, and is generally constant within a range of 0.5 μm to 50 μm. . From the viewpoint of expressing the water repellency in the protrusion structure 10, it is more preferable that the protrusion height is in the range of 1 μm to 50 μm and the distance between the protrusions is in the range of 0.5 μm to 50 μm. The inter-projection distance is the distance between the tips of the projections 11 and 11. The distance between the protrusions varies depending on the size of the hole 21 of the honeycomb structure 20. For example, the smaller the hole 21, the smaller the distance between the protrusions. Although the protruding structure 10 of this example is a rectangle of 20 cm × 30 cm, the size and shape are not limited thereto. For example, when it is circular, indefinite, or continuously manufactured as described later, it can be made into a web-like body.

  The protruding structure 10 is formed from a hydrophobic polymer 42 (see FIG. 5). Examples of the hydrophobic polymer 42 include polylactic acid, polycaprolactone, polyglycolic acid, polydioxanone, polyhydroxybutyrate, polybutadiene, polyurethane, polystyrene (PS), polymethyl methacrylate, polycarbonate, and a copolymer containing these repeating units. A polymer or the like is preferable, and polystyrene is used in this embodiment. The protruding structure 10 may contain, for example, an amphiphilic compound in addition to the hydrophobic polymer 42, and the amphiphilic compound may be any of a polymer, an oligomer, and a monomer. When the amphiphilic compound is included, the mass of the amphiphilic compound is preferably 10 or less with respect to the mass 100 of the protruding structure 10.

  The protrusion structure 10 has a water contact angle on the first film surface 10a in the range of approximately 140 ° to 160 °, and a water contact angle (approximately 100 on the first film surface 20a of the honeycomb structure 20 described later). It is larger than within the range of not less than 110 ° and not more than 110 °. Moreover, the protrusion structure 10 has a contact angle of air (bubbles) on the first film surface 10a in the range of 150 ° to 170 ° in water.

  The protrusion structure 10 is used as, for example, a culture carrier for culturing cells. When culturing cells, cells to be cultured are placed on the first film surface 10a on the side where the protrusions 11 are formed.

  The honeycomb structure as a material of the protruding structure 10 has a honeycomb structure in which a plurality of holes are arranged on the surface. The honeycomb structure, that is, the honeycomb structure, is not limited to the one having a strict hexagonal opening formed by the partition walls. Therefore, first, the honeycomb structure in the present embodiment will be described with reference to FIG. 2 to FIG. 4, and then the honeycomb structure and the honeycomb structure as other aspects will be described.

  As shown in FIG. 2 to FIG. 4, the honeycomb structure 20 that is a material of the protruding structure 10 is a film, one surface (hereinafter referred to as a first film surface) 20 a and the other surface (hereinafter referred to as a first film surface). 2) (referred to as “film surface”) 20b. 3 and 4, the honeycomb structure 20 is drawn with an exaggerated thickness of the partition wall 22 between the adjacent holes 21 with respect to the thickness T20 of the honeycomb structure 20.

  The plurality of holes 21 are regularly arranged along the first film surface 20a, more specifically, in a matrix. The holes 21 penetrate the honeycomb structure 20 in the thickness direction, and open to the first film surface 20a and the second film surface 20b, respectively, to form a surface opening 21a. Moreover, as FIG. 3 and FIG. 4 show, the partition 22 between the adjacent hole 21 and the hole 21 goes to the center in the thickness direction from each of the 1st film surface 20a and the 2nd film surface 20b. According to this, the thickness gradually decreases. In this example, the partition wall 22 has a partition wall opening 22a formed substantially at the center in the thickness direction, whereby the adjacent holes 21 are formed in the direction along the first film surface 20a inside the honeycomb structure 20. It is connected to. However, the partition wall 22 may not be formed with the partition opening 22a, and in this case, the holes 21 are individually independent. In the honeycomb structure 20, the structure in which the partition wall opening 22 a is formed in the partition wall 22 is preferable from the viewpoint of reliably forming the columnar protrusions 11 as compared with the structure in which the partition wall opening 22 a is not formed. In the case where the partition wall opening 22a is not formed in the partition wall 22, the thickness of the partition wall 22 is preferably smaller from the viewpoint of reliably forming the columnar protrusions 11. The size and shape of each hole 21 are constant, and the size and shape of the surface opening 21a are also constant. In such a honeycomb structure 20, when viewed from a direction perpendicular to the first film surface 20a, the surrounding six holes 21 are arranged at each apex of the hexagon centered on any one hole 21. In this state, the holes 21 are densely arranged. Thereby, the honeycomb structure 20 has a honeycomb structure having a honeycomb shape.

  In the honeycomb structure, the shape of the surface opening 21a and the shape of the cross section of the hole 21 parallel to the first film surface 20a may be hexagonal, but it is not necessary to be hexagonal. In this example, the shape of the surface opening 21a is circular. Depending on the density of the holes 21 per unit area of the first film surface 20a, the distance between adjacent holes 21, the shape of the holes 21 in the cross section parallel to the surface opening 21a and the first film surface 20a is rounded, for example. In some cases, it has a substantially hexagonal shape or a substantially octagonal shape, and the honeycomb structure includes such an aspect. In addition to the structure in which the holes 21 are independent from each other, the honeycomb structure includes a structure in which adjacent holes 21 are connected to each other inside the honeycomb structure 20 as in this example. Furthermore, the arrangement of the holes 21 is not limited to the above. Three to five or seven or more holes 21 may be arranged around any one hole 21, and the holes 21 may be arranged in a square.

  The honeycomb structure 20 is formed from a hydrophobic polymer 42 (see FIG. 5), and may contain an amphiphilic compound, for example, in addition to the hydrophobic polymer 42. The amphiphilic compound may be a polymer, an oligomer, or a monomer. A preferable example of the hydrophobic polymer 42 and a preferable mass of the amphiphilic compound when including the amphiphilic compound are the same as the above-described example and mass in the protruding structure 10.

  The thickness T20 of the honeycomb structure 20 is preferably in the range of 0.5 μm to 100 μm. When the thickness T20 of the honeycomb structure 20 is 0.5 μm or more, it is more preferable because the strength as the honeycomb structure 20 is higher than when it is less than 0.5 μm. When the thickness T20 is 100 μm or less, it is more than 100 μm. Compared to the above, it is more preferable from the viewpoint of easy manufacture of the honeycomb structure 20.

  The diameter φ21 of the surface opening 21a and the distance D21 between the holes 21 may be determined according to the target interprotrusion distance of the protrusion structure 10 to be manufactured. When the distance between protrusions in the protrusion structure 10 is in the range of 0.5 μm or more and 50 μm or less, the diameter φ21 of the surface opening 21a is in the range of 0.3 μm or more and 70 μm or less, and the distance D21 between the holes 21 is It is preferably in the range of 0.5 μm or more and 50 μm or less.

  In this example, the honeycomb structure 20 in which each hole 21 penetrates in the thickness direction is used, but a honeycomb structure having a structure in which each hole 21 does not penetrate in the thickness direction may be used. In the structure in which the holes 21 do not penetrate in the thickness direction, the holes 21 open only on the first film surface of the honeycomb structure, and the second film surface is a flat surface without the surface opening 21a. Thus, when using the honeycomb structure in which the holes 21 are opened only on the first film surface, the obtained protrusion structure has the film surface opening 10c not formed on the second film surface, that is, the second The film surface is flat.

  The honeycomb structure 20 is manufactured, for example, by a protruding structure manufacturing process 30 shown in FIG. The protruding structure manufacturing process 30 includes a solution preparation process 31, a casting process 32, a dew condensation process 33, an evaporation process 34, an alcohol contact process 35, an ultrasonic treatment process 36, and a peeling process 37.

  The solution preparation step 31 is a step of preparing a solution 41 for forming the honeycomb structure 20. In this example, the hydrophobic polymer 42 described above is dissolved in a solvent 43 to form a solution 41. The casting step 32 is a step of forming the casting film 44 by spreading and spreading the solution 41 on the support 68 (see FIG. 6). It is preferable that the temperature of the support 68 is adjusted in advance, and the temperature is also adjusted while the casting film 44 is formed. As the support 68, in the present embodiment, a sheet-like polyethylene terephthalate (PET) is used. However, the material of the support 68 is not limited to PET as long as it does not dissolve in the solvent 43, and may be, for example, glass or aluminum. The form of the support 68 may adopt various forms such as a sheet form and a plate form. Further, the casting film 44 is formed by making the supporting body 68 into a long film shape, causing the long supporting body 68 to travel in the longitudinal direction, and continuously flowing down the solution 41 on the traveling supporting body 68. May be formed long. In the traveling in the longitudinal direction, for example, a plurality of rollers (not shown) are arranged in the traveling path of the support 68, the support 68 is supported by the peripheral surface of each roller, and the rollers are rotated in the circumferential direction. It can be done by the technique to make.

  The dew condensation process 33 is a process of forming water droplets by dew condensation on the film surface of the casting film 44. The water droplets are formed, for example, by cooling the casting film 44 through the support 68 so that the temperature is lower than the temperature of the surrounding atmosphere. However, from the viewpoint of aligning the timing of occurrence of a plurality of water droplets or evenly aligning the size of the formed water droplets, while adjusting the temperature of the support 68 so that the support 68 is maintained at a predetermined temperature, It is preferable to supply a humidified gas (for example, air) onto the casting film 44.

  The evaporation step 34 is a step of evaporating the water droplets formed in the dew condensation step 33 and the solvent 43. In the evaporation step 34, for example, a dry gas (for example, air) is supplied to evaporate the solvent 43 faster than the water droplets. Thereby, a water droplet is submerged in the casting film 44, and the hole 21 is formed using the submerged water droplet as a mold. For this reason, it is preferable to use the solvent 43 having a higher evaporation rate than water, and chloroform is used in this embodiment. However, the timing at which the water droplets start to evaporate may not be after all of the solvent 43 has been evaporated. Further, as long as the formed holes 21 are maintained, some solvent 43 may remain in the casting film 44 even after the evaporation of water droplets is completed. In this case, the remaining solvent 43 Evaporate after the evaporation of the water droplets is complete. In addition, during the condensation process 33, water droplets may start to sink into the casting film 44. The honeycomb structure 20 is obtained on the support 68 by the evaporation step 34. In this example, the surface in contact with the support 68 of the honeycomb structure 20 is the second film surface 20b described above, and the exposed surface is the first film surface 20a described above. The dew condensation step 33 and the evaporation step 34 are steps of a dew condensation method that is well known as a method for manufacturing the honeycomb structure 20. Further, the dew condensation process 33 and the evaporation process 34 in the case where the casting film 44 is formed in a long length conveys the support 68 on which the casting film 44 is formed in the longitudinal direction, and the humidified gas is supplied. The humidification zone and the drying zone to which the dried gas is supplied can be sequentially passed, whereby a long film as a honeycomb structure can be obtained. In this example, the honeycomb structure 20 is manufactured by the dew condensation method. However, the present invention is not limited to this method. For example, a honeycomb structure having a honeycomb structure on the surface may be manufactured by a known nanoimprint method. .

  The alcohol contact step 35 is a wettability improving step for improving the wettability of the honeycomb structure 20 with respect to water. In the ultrasonic treatment process 36 of the present embodiment, ultrasonic vibration is applied to the honeycomb structure 20 in water, and the first film surface 20a of the honeycomb structure 20 is formed of the type of the hydrophobic polymer 42 and the surface opening 26a. Depending on the diameter φ 26, the distance D 26 between the holes 26, etc., the wettability with respect to water may be low and water may not easily enter the hole 21. In the alcohol contact step 35, alcohol is brought into contact with the honeycomb structure 20 to improve wettability with water. Thereby, in the ultrasonic treatment process 36, water enters the hole 21 more reliably. As a result, the later-described detachment from the honeycomb structure 20 becomes more reliable, and in addition, the detachment is performed evenly. In addition, the ultrasonic treatment time can be further shortened. The honeycomb structure 20 after contact with the alcohol is preferably subjected to the ultrasonic treatment step 36 while the alcohol does not completely evaporate, that is, while the alcohol remains, and more preferably while the alcohol is wet. . Note that increasing the wettability with water means increasing the contact angle of water.

  As described above, the alcohol contact is for improving the wettability of the honeycomb structure 20 with respect to water when water is used in the ultrasonic treatment step 36. Therefore, when alcohol is used instead of water in the ultrasonic treatment step 36, the alcohol contact step 35 is in the ultrasonic treatment step 36. In the alcohol contact process 35 in this case, the alcohol used in the ultrasonic treatment has both functions of improving wettability of the honeycomb structure 20 and transmitting ultrasonic vibration.

  The alcohol used in the alcohol contact step 35 may be selected according to the type of the hydrophobic polymer 42 and is not particularly limited. However, it is preferable that the hydrophobic polymer 42 is not dissolved as much as possible, and alcohol having a solubility of the hydrophobic polymer 42 of about 0.1 g / 100 g or less is preferable. The unit of solubility “g / 100 g” means a mass at which the hydrophobic polymer 42 is dissolved in 100 g of alcohol. Moreover, this solubility is under the temperature of the alcohol made to contact, and is set to room temperature (within a range of 15 ° C. or higher and 30 ° C. or lower) in this embodiment. When the hydrophobic polymer 42 is polystyrene, ethanol, 1-propanol, 2-propanol and the like are preferable as the alcohol, and these may be used alone or in admixture of two or more. The polylactic acid, polycaprolactone, polyglycolic acid, polydioxanone, polyhydroxybutyrate, polybutadiene, polyurethane, polymethyl methacrylate, polycarbonate, and a copolymer containing these repeating units are used as the hydrophobic polymer 42. In the same manner, ethanol, 1-propanol, 2-propanol and the like are preferable as the alcohol, and these may be used alone or in admixture of two or more. In the present embodiment, polystyrene is used as the hydrophobic polymer 42 as described above, and ethanol is used as the alcohol.

  In the present embodiment, the alcohol contact is a technique in which the honeycomb structure 20 is immersed in alcohol accommodated in a container (not shown) in a state where the honeycomb structure 20 is superimposed on the support 68, but is not limited thereto. For example, instead of or in addition to dipping, a method of applying alcohol to the first film surface 20a of the honeycomb structure 20 or a method of spraying in the form of droplets or mist may be used. When the long film honeycomb structure 20 is subjected to the alcohol contact step 35, the support 68 on which the honeycomb structure 20 is formed is conveyed in the longitudinal direction and passed through the alcohol in the container. The alcohol may be contacted by dipping or applying or spraying alcohol onto the first film surface 20a of the honeycomb structure 20 being conveyed.

  The ultrasonic treatment process 36 is a process for applying the ultrasonic vibration to the honeycomb structure 20 to form the protruding structure 10. In the ultrasonic processing step 36, for example, an ultrasonic processing device 60 (see FIG. 6) described later is used.

  The peeling process 37 is a process of peeling the protruding structure 10 from the support body 68. Note that the peeling step 37 may not be provided depending on how the protruding structure 10 is stored or used. For example, when a culture carrier for culturing cells is used, there is no peeling step 37, and the protruding structure 10 is stored in a state where it overlaps the support 68 and is used.

  The ultrasonic processing apparatus 60 is for the ultrasonic processing step 36, and includes an apparatus main body 61 and a holding unit 62 as shown in FIG. The apparatus main body 61 includes a liquid tank 65 for storing a liquid, an ultrasonic vibrator (not shown), an ultrasonic oscillator (not shown), and the like. In the present embodiment, water 63 is used as the liquid stored in the liquid tank 65. In this embodiment, the ultrasonic vibrator is composed of a plurality of ultrasonic vibration elements (not shown) provided on the side and bottom of the liquid tank 65, but is not limited to this. For example, in the liquid tank Alternatively, a so-called throwing vibrator that is submerged and a vibrator that is attached to a hole in the bottom when a liquid tank having a hole in the bottom is used may be used. The ultrasonic vibration element generates a sound wave by converting high-frequency electrical energy generated by the ultrasonic oscillator into mechanical vibration energy. Such an apparatus main body 61 may be commercially available as an ultrasonic cleaning machine. In this embodiment, AU-308CB manufactured by Aiwa Medical Industry Co., Ltd. is used.

  The holding unit 62 includes a clip 66, a moving mechanism 67, and the like. The clip 66 is for holding the honeycomb structure 20, and in this embodiment, the honeycomb structure 20 that overlaps the support body 68 is sandwiched together with the support body 68. The clip 66 includes a sandwiching member 66a that sandwiches the honeycomb structure 20 and the support body 68, and a clip main body 66b that controls sandwiching by the sandwiching member 66a and release thereof. The clip main body 66b is connected to a moving mechanism 67, and the moving mechanism 67 displaces the clip main body 66b in the vertical direction, that is, moves up and down. Thereby, the honeycomb structure 20 and the support body 68 sandwiched by the sandwiching member 66a are displaced in the vertical direction. As long as the honeycomb structure 20 is held, the clip 66 is not limited, and a frame-like holding member that holds the periphery of the honeycomb structure 20 may be used.

  The liquid stored in the liquid tank 65 is not limited to water, and any liquid that does not dissolve the hydrophobic polymer 42 (see FIG. 5) as much as possible or does not swell the honeycomb structure 20 can be used. The thing which does not melt | dissolve as much as possible has preferable the alcohol whose solubility of the hydrophobic polymer 42 is about 0.1 g / 100g or less. The unit of solubility “g / 100 g” means the mass at which the hydrophobic polymer 42 is dissolved in 100 g of the liquid contained in the liquid tank 65. This solubility is at a temperature during ultrasonic treatment, and is set to room temperature (within a range of 15 ° C. to 30 ° C.) in the present embodiment. Preferred examples of liquids other than water include ethanol, 1-propanol, butanol, and the like when the hydrophobic polymer 42 is polystyrene. These may be used alone or in combination of two or more. Also good. When the hydrophobic polymer 42 is polybutadiene, ethanol, 1-propanol, acetone or the like is preferable, and these may be used alone or in admixture of two or more.

  In this embodiment, the processing time for applying the ultrasonic vibration to the honeycomb structure 20 is 10 minutes. However, the processing time is set according to the thickness of the partition wall 22, the presence or absence of the partition opening 22 a, the type of the hydrophobic polymer 42, etc., and is not limited to the above 10 minutes, for example, in the range of 10 seconds to 60 minutes. Is preferably within the range of 1 minute to 30 minutes, and more preferably within the range of 1 minute to 10 minutes. Further, the larger the oscillation output, the shorter the processing can be performed. The smaller the oscillation output, the longer the processing time should be set. Note that the higher the specific gravity of the liquid stored in the liquid tank 65 is, the more difficult it is to transmit ultrasonic vibration, so that the processing time is longer and the oscillation output is preferably set larger.

  The operation of the ultrasonic processing apparatus 60 is as follows. The honeycomb structure 20 is sandwiched by the sandwiching member 66a in a state where the honeycomb structure 20 overlaps the support body 68. The clip 66 is lowered by the moving mechanism 67 in a state where the honeycomb structure 20 and the support body 68 are held by the holding member 66a, and thereby the honeycomb structure 20 is moved to a processing position below the water surface. The electric energy from the ultrasonic oscillator is converted into mechanical vibration energy by the ultrasonic vibrator, and this vibration energy is applied to the honeycomb structure 20 through the water in the liquid tank 65. In this way, the honeycomb structure 20 is subjected to ultrasonic vibration in the water 63.

  By applying ultrasonic vibration in the water 63, the honeycomb structure 20 has a brittle portion, that is, a thickness that is the smallest in the thickness direction of the honeycomb structure 20 and the partition wall 22 having the partition wall opening 22a is formed from approximately the center. A part of the one film surface 20 a side is crushed and detached from the honeycomb structure 20. Since the entire surface of the honeycomb structure 20 on the second film surface 20b side is in close contact with the support 68, the form is reliably maintained even when ultrasonic vibration is applied. Thereby, a part of the partition wall 22 on the second film surface 20b side remains as the protrusion 11, and the honeycomb structure 20 shown in FIGS. 2 to 4 becomes the protrusion structure 10 shown in FIG. Further, since the wettability of the first film surface 20a of the honeycomb structure 20 with respect to water is enhanced by the alcohol contact step 35 described above, since the water 63 surely enters all the holes 21, the ultrasonic vibration Is more reliably and evenly applied to all the partitions 22. As a result, a uniform protruding structure 10 is obtained.

  When the long film honeycomb structure 20 is subjected to the ultrasonic treatment step 36, the support 68 on which the honeycomb structure 20 is formed is conveyed in the longitudinal direction, and the water contained in the liquid tank 65 is transferred. It is good to give ultrasonic vibration by passing through the inside and soaking. In addition, when alcohol is accommodated in the liquid tank 65, the alcohol contact and the ultrasonic treatment are performed in parallel in the liquid tank 65.

  In this example, ultrasonic vibration is applied to the honeycomb structure 20 while being supported by the support body 68. However, when the second film surface 20b side of the honeycomb structure 20 has strength to withstand the stress of ultrasonic vibration. May apply ultrasonic vibration to the honeycomb structure 20 in a state of being peeled from the support 68.

  After the first film surface 20a side is detached, the clip 66 is raised by the moving mechanism 67 to move the protruding structure 10 to the retracted position on the water surface. The holding of the protruding structure 10 and the support 68 by the holding member 66 a is released, and the protruding structure 10 is dried while being supported by the support 68. For drying, a known drying method such as spraying a dry gas (for example, air) or the like can be used. In this example, the protruding structure 10 is dried after the clamping by the clamping member 66a is released. However, the protruding structure 10 may be dried in the clamped state. Further, the protrusion structure 10 may be peeled off from the support 68 in the peeling step 37 and then dried. However, drying in a state supported by the support 68 suppresses deformation of the protrusion structure 10. More preferred.

  In the present embodiment, the support 68 in the ultrasonic treatment step 36 is used in the casting step 32, but is not limited thereto. For example, after the evaporation step 34, the honeycomb structure 20 is peeled from the support used in the casting step 32, and the honeycomb structure 20 is attached to another support with an adhesive or an adhesive tape before the alcohol contact step 35. In addition, the honeycomb structure 20 may be provided to the alcohol contact step 35 and the ultrasonic treatment step 36 in the attached state. As the support in this case, a support formed from a material that does not dissolve as much as possible in the alcohol used in the alcohol contact step 35 and the liquid used in the ultrasonic treatment step 36 is used.

  According to the above method, the protrusion structure 10 having a larger size can be easily manufactured as compared with the conventional peeling method using an adhesive tape. Further, when the support 68 and the honeycomb structure 20 have flexibility, they may be immersed in the water 63 of the liquid tank 65 in a state of being wound in a cylindrical shape or in a bent state, for example, thereby The structure 10 is manufactured in a larger area. Further, the protruding structure 10 is reliably manufactured even when the first film surface 20a is a curved surface as in the case of the honeycomb structure 20 in a bent state. Therefore, for example, a film-like honeycomb structure 20 is formed on the inner wall or the outer wall of the glass tube, and the glass tube on which the honeycomb structure 20 is formed is immersed in the water 63 of the liquid tank 65, thereby providing a protruding structure. 10 is formed on the inner wall and the outer wall of the glass tube. Also in this case, it is more preferable to perform the alcohol contact treatment before the ultrasonic treatment because the wettability of water on the first film surface 20a of the honeycomb structure 20 formed on the inner wall or the outer wall is improved. . For the alcohol contact step 35, for example, even when the honeycomb structure 20 is formed on the inner wall of a very thin tube having an outer diameter of 1 mm and an inner diameter of 0.7 mm, the tube is immersed in alcohol to wet the tube with water. Thus, the protrusion structure 10 is uniformly and easily formed on the inner wall of the tube.

[Second Embodiment]
In the ultrasonic treatment, the lower the elastic modulus of the honeycomb structure 20 is, that is, the softer the above-described detachment action becomes. In such a case, it is preferable to perform a hardening process for making the honeycomb structure 20 harder and to use the ultrasonic process in a hardened state. The elastic modulus of the honeycomb structure 20 can be measured in accordance with Japanese Industrial Standard JIS K7127 (name: plastic—test method for tensile properties—part 3: test conditions for film and sheet). The elastic modulus of the honeycomb structure 20 is preferably set to 1 GPa or more by the curing process. In the present embodiment, a cooling process for cooling the honeycomb structure 20 is performed as the curing process. In the case of performing the cooling process, for example, water and ice are put into the liquid tank 65, and the honeycomb structure 20 is immersed in the liquid tank 65 to perform ultrasonic treatment. As a result, the honeycomb structure 20 is subjected to ultrasonic vibration in a state where the temperature is lowered and the substrate becomes harder, that is, in a state where the elastic modulus is higher, so that the first film surface 20a side is more reliably detached. What is put in the liquid tank 65 in the cooling process is not limited to water and ice, but may be liquid nitrogen, for example.

  The cooling treatment is preferably performed on the honeycomb structure 20 in the ultrasonic treatment step 36. The cooling treatment is particularly effective when, for example, polybutadiene, polylactic acid, or the like is used as the hydrophobic polymer 42. In this embodiment, polybutadiene, which is a material softer than polystyrene used in the first embodiment, is used. When the hydrophobic polymer 42 forming the honeycomb structure 20 has a glass transition point, it is more preferable that the honeycomb structure 20 is cooled below the glass transition point in the cooling treatment.

[Third Embodiment]
Another example of the curing process is a photocuring process. The photocuring treatment is effective when a so-called photopolymerizable compound that is polymerized by irradiating light is used instead of or in addition to the hydrophobic polymer 42. The photopolymerizable compound may be a polymer, an oligomer, or a mixture of a polymer and an oligomer. Moreover, the above-mentioned polymerization includes crosslinking.

  In the present embodiment as an example for performing photocuring treatment, as shown in FIG. 9, the honeycomb structure 20 is subjected to a photocuring step 71, an alcohol contact step 35, an ultrasonic treatment step 36, and a peeling step 37 in this order. Provide. However, as described above, the alcohol contact step 35 and the peeling step 37 may not be present, and the alcohol contact step 35 may be present in the ultrasonic treatment step 36. As described above, the photocuring step 71 may be provided before the ultrasonic treatment step 36. The photocuring step 71 is a step of performing the above-described photocuring treatment, and irradiates the honeycomb structure 20 containing the photopolymerizable compound with light that causes the photopolymerizable compound to polymerize, thereby polymerizing the photopolymerizable compound. The honeycomb structure 20 is made harder. In this embodiment, polybutadiene (manufactured by JSR Co., Ltd., syndiotactic 1,2-polybutadiene, RB820) that is crosslinked by irradiation with ultraviolet rays is used as the hydrophobic polymer 42, and the honeycomb structure 20 is made of this hydrophobic polymer 42. It is composed of

  In the photocuring treatment of the present embodiment, the honeycomb structure 20 is irradiated with ultraviolet rays by a light source (not shown) that emits ultraviolet rays. The light source is disposed on the first film surface 20a side of the honeycomb structure 20, and irradiates ultraviolet rays toward the first film surface 20a. However, the light source may be arranged on the second film surface 20b side instead of or in addition to the first film surface 20a side, depending on the presence and degree of light transmission of the material constituting the honeycomb structure 20. . The time for irradiating ultraviolet rays is 10 minutes in the present embodiment, but is not limited to this, and is preferably within a range of approximately 1 minute to 60 minutes.

  The hydrophobic polymer 42 in this example is cross-linked by irradiation with ultraviolet rays, and the honeycomb structure 20 becomes hard. The honeycomb structure 20 that has undergone the photocuring step 71 is subjected to the above-described alcohol contact step 35 and then subjected to the ultrasonic treatment step 36. Since the honeycomb structure 20 is harder in the photocuring step 71, the first film surface 20a side of the honeycomb structure 20 is more reliably detached than in the case where the photocuring process is not performed, and the honeycomb structure 20 has a more uniform structure. The protruding structure 10 is obtained. In this embodiment as well, the ultrasonic treatment time is 10 minutes as in the first embodiment.

  The manufactured protrusion structure is not limited to a structure in which a plurality of columnar protrusions as shown in FIG. 1 are individually independent. In FIG. 10, a film-like protrusion structure 80 includes protrusions 81 that are continuous with one first film surface 80a. A plurality of holes 82 are formed in the first film surface 80a, and the protrusions 81 form partition walls that make the plurality of holes 82 individually independent. As described above, the protrusion structure is not limited to a so-called pillar structure in which a plurality of columnar protrusions are individually independent, and a so-called dimple (in which a plurality of holes are individually independent by this protrusion, and the protrusions are continuously formed. dimple) structure. In the protrusion structure 80, a film surface opening 80c is formed on the other second film surface 80b at approximately the center of the hole 82 when the second film surface 80b is viewed from the vertical direction.

  The protruding structure 80 is manufactured from a honeycomb structure in which the partition wall opening is not formed in the partition wall. However, even if the partition wall opening is formed in the partition wall, the partition structure opening is very small with respect to the partition wall. Thus, the protruding structure 80 can be manufactured. In addition, when the other second film surface 80b of the protruding structure 80 is formed flat, that is, when the film surface opening 80c is not formed on the second film surface 80b, the honeycomb structure as a material has a hole having a thickness. It is non-penetrating in the direction.

  The protrusion structure to be manufactured is not limited to the film-like structure as described above. For example, a block-like structure having a thickness much larger than the protruding structures 10 and 80 may be used. By using a honeycomb structure having a honeycomb structure on the surface in a block shape, a block-shaped concavo-convex structure is manufactured. As an example, the solution 41 is put into a desired mold, and the solution 41 in the mold is subjected to the above-described dew condensation process 33 and evaporation process 34, thereby forming a honeycomb structure using water droplets generated on the liquid surface of the solution 41 as a mold. A block-like honeycomb structure (not shown) formed on a part of the surface of the block can be obtained. By subjecting this honeycomb structure to the ultrasonic treatment step 36, a block-like projection structure (not shown) is obtained. Also in this case, the above-described alcohol contact treatment and curing treatment may be performed.

[Fourth Embodiment]
As shown in FIG. 11, the protruding structure 90 of the fourth embodiment is formed in a film shape and includes a protruding structure 92 and a honeycomb structure 93. In addition, except being demonstrated below, it is the same as that of the protrusion structure 10 or the honeycomb structure 20, and the same code | symbol is attached | subjected to the substantially same member, and the detailed description is abbreviate | omitted.

  The protrusion structure portion 92 is configured in the same manner as the film 10, and is formed in a form in which a plurality of protrusions 11 are regularly arranged on the first film surface 90a which is one surface. The honeycomb structure portion 93 is configured in the same manner as the honeycomb structure 20, and a plurality of holes 21 penetrating in the thickness direction from the first film surface 90a to the second film surface 90b which is the other surface are regularly arranged. Formed in the above manner. In the protrusion structure 90 in this example, the protrusion 11 is formed over the entire surface of the protrusion structure portion 92 and the hole 21 is formed over the entire surface of the honeycomb structure portion 93 on the first film surface 90a. 11 and FIG. 12, only a part thereof is exaggerated.

  The protrusion structure portion 92 is formed in an island shape surrounded by the honeycomb structure portion 93. For example, the protrusion structure portion is formed so as to surround the honeycomb structure portion by forming the honeycomb structure portion in an island shape. Also good. Further, the protrusion structure portion 92 in this example has a mirror image shape of the numeral “2” when viewed from a direction perpendicular to the first film surface 90a, but is not limited to this shape. For example, the protrusion structure portion may have various shapes such as a circle, a rectangle, and an indeterminate shape when viewed from a direction perpendicular to the first film surface 90a. It may be formed independently. The height of the first film surface 90 a is lower in the protrusion structure portion 92 than in the honeycomb structure portion 93.

  In this example, the second film surface 90b opposite to the illustrated first film surface 90a is formed with a film surface opening 10c (see FIG. 1) in the protrusion structure portion 92, and has a honeycomb structure. In the portion 93, a surface opening 21a (see FIGS. 3 and 4) is formed. However, in FIG. 11, the film surface opening 10c and the surface opening 21a in the second film surface 90b are not shown.

  According to the above configuration, the first film surface 90a has a different water contact angle and a different air (bubble) contact angle between the protrusion structure portion 92 and the honeycomb structure portion 93. For this reason, a use spreads by patterning and forming the area | region from which wettability differs in one surface. For example, it is possible to form a microchannel without partition walls, and in addition, when used as a culture carrier for culturing cells, the protrusion structure part is less likely to adhere to the cells than the honeycomb structure part, It becomes possible to control the place where the cell adheres and the place where the cell does not adhere.

  When manufacturing the protrusion structure 90, as shown in FIG. 12, ultrasonic treatment is performed with the mask plate 94 overlaid on the first film surface 20a of the honeycomb structure 20 (see FIGS. 2 to 4). Do. The alcohol contact step 35 does not necessarily have to be overlaid on the mask plate 94, but more preferably, the alcohol contact step 35 is sequentially supplied to the alcohol contact step 35 and the ultrasonic treatment step 36 with the mask plate 94 overlaid. In this example, polybutadiene is used as the hydrophobic polymer 42 (see FIG. 5). For this reason, the honeycomb structure 20 is subjected to the photocuring step 71 in the state where the mask plates 94 are overlapped, and then subjected to the alcohol contact step 35 and the ultrasonic treatment step 36 in this order.

  The mask plate 94 is, for example, a plate-like member having the same size as the honeycomb structure 20 or larger than the honeycomb structure 20, and an opening 94 a is formed in a portion corresponding to the protruding structure portion 92. The mask plate 94 is made of a metal that does not transmit ultraviolet rays, so that the region covered with the mask plate 94 of the honeycomb structure 20 is not irradiated with ultraviolet rays. By changing the size, shape, position, number, etc. of the openings 94a in the mask plate 94, the honeycomb structure portions and the protrusion structure portions are formed in various patterns having different sizes, shapes, positions, numbers, etc. of the protrusion structure portions 92. be able to. From the viewpoint of clarifying the boundary between the protrusion structure portion 92 and the honeycomb structure portion 93, the honeycomb structure 20 and the mask plate 94 are preferably overlapped in close contact.

  By irradiating the honeycomb structure 20 with ultraviolet rays in a state where the mask plate 94 is overlapped, the hydrophobic polymer 42 of the honeycomb structure 20 exposed from the openings 94 a is cross-linked and hardened, and is covered with the mask plate 94. The hydrophobic polymer 42 in the region does not crosslink. Moreover, after this photocuring process 71, the mask board 94 is removed from the honeycomb structure 20, and alcohol contact is performed continuously. Thereby, the 1st film surface 20a improves the wettability with respect to water.

  Next, ultrasonic vibration is applied to the honeycomb structure 20. As a result, in the region exposed from the opening 94a during the ultraviolet irradiation, a part of the first film surface 20a side from the approximate center of the partition wall 22 is crushed and detached from the honeycomb structure 20 to form a protruding structure 92. Is done. Since ultrasonic vibration is applied in a state where the wettability to water is enhanced by the contact of alcohol, a uniform protrusion structure portion 92 having the same size and shape of the protrusion 11 is formed. On the other hand, the region covered with the mask plate 94 during the ultraviolet irradiation maintains the shape of the honeycomb structure 20 and becomes the honeycomb structure portion 93. In the obtained honeycomb structure 20, as shown in FIG. 13, the boundary between the protruding structure portion 92 and the honeycomb structure portion 93 is recognized.

10, 80, 90 Protrusion structure 11, 81 Protrusion 20 Honeycomb structure 21 Hole 22 Partition 60 Ultrasonic treatment device 63 Water 68 Support

Claims (9)

In a method for producing a protrusion structure comprising a plurality of protrusions and formed from a hydrophobic polymer,
A part of the surface side is detached from the honeycomb structure by applying ultrasonic vibration in a liquid to the honeycomb structure having a honeycomb structure formed of the hydrophobic polymer and having a plurality of pores arranged on the surface. An ultrasonic treatment step of leaving a part of the partition wall between the holes as the protrusion,
And a wettability improving step for increasing the wettability of the honeycomb structure with respect to the liquid. The liquid is water;
The method for manufacturing a protruding structure according to claim 1, wherein the wettability improving step improves the wettability of the honeycomb structure by bringing alcohol into contact with the honeycomb structure before the ultrasonic treatment step. The liquid is alcohol;
The method for manufacturing a protruding structure according to claim 1, wherein the wettability improving step improves the wettability of the honeycomb structure by bringing the alcohol into contact with the honeycomb structure during the ultrasonic treatment step. The adjacent holes are connected internally in the direction along the surface,
The method for manufacturing a protruding structure according to claim 1, wherein the protrusion has a columnar shape.   The method for manufacturing a protruding structure according to any one of claims 1 to 4, wherein the honeycomb structure is a film, and the surface is one film surface.   The method for manufacturing a protruding structure according to claim 5, wherein the ultrasonic vibration is applied in a state where the honeycomb structure is supported by a support from the other film surface.   The method for manufacturing a protruding structure according to any one of claims 1 to 6, wherein the ultrasonic vibration is applied in a state where the honeycomb structure is hardened by a curing process. The honeycomb structure includes a polymerizable compound that is polymerized by light irradiation,
The curing treatment is a photocuring treatment for polymerizing the polymerizable compound by irradiating the honeycomb structure with the light.
The method for manufacturing a protruding structure according to claim 7, wherein the ultrasonic vibration is applied to the honeycomb structure after the curing treatment. The curing treatment is a cooling treatment for cooling the honeycomb structure to a glass transition point or less of the hydrophobic polymer,
The method for manufacturing a protruding structure according to claim 7, wherein the ultrasonic vibration is applied to the honeycomb structure during the curing process.