JP5083535B2 - Film manufacturing method and manufacturing apparatus - Google Patents

Description

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

  A film having a honeycomb structure is considered to be useful as a substrate for cell culture. In addition, a honeycomb structure film having a specific pore size and pore size variation is expected to be used as a blood filtration membrane. This filtration membrane is used to remove leukocytes from whole blood for transfusion.

  By the way, in recent years, in order to treat various diseases, medical devices such as stents are placed in the body. For example, bile duct stents and ureteral stents are known as medical devices for dilating bile ducts and ureters that have been narrowed or closed with cancer or the like.

  When these stents are used, the biliary tract and ureter once dilated may be restenotic or closed due to the progression of cancer. In order to prevent this, an attempt has been proposed in which a coating layer is provided on the surface of a medical device such as a stent and the progression of cancer is suppressed by the presence of this coating layer. An attempt to use a film having a honeycomb structure as the coating layer has been proposed by the present applicant (Patent Document 1).

  Patent Document 2 below discloses a method and apparatus for manufacturing a film having a honeycomb structure. In the method described in this document, first, a polymer solution is cast on a substrate to form a solution film. Thereafter, water droplets made of condensed water are formed on the surface of the solution film. This water droplet is contained in the solution film, and then the solvent in the solution film and the water droplet are evaporated to produce a film having a honeycomb structure.

  However, in the conventional method and apparatus for producing a film having a honeycomb structure, humidified air is blown from the nozzle substantially perpendicularly to the surface of the solution film, so that the substrate holding the solution film is substantially the same as the nozzle blowing direction. It is moved vertically. For this reason, with respect to the solution film, the air blowing speed is constant from the time when condensation starts on the surface of the solution film to the time when condensation is formed on the entire surface, and condensed water having a uniform diameter is supplied to the entire surface of the solution film. However, it is difficult to form only one layer uniformly. It is difficult to produce a film having a periodic honeycomb structure in which pores having a uniform pore diameter are formed, even if too much or too little condensed water is generated on the entire surface of the solution film.

Further, in the conventional method and apparatus for producing a film having a honeycomb structure, the substrate on which the solution film is formed moves relative to the nozzle, and the air humidified on the surface of the solution film is substantially perpendicular to the nozzle. Since it is sprayed, it is difficult to maintain the parallelism of the surface of the solution film. For this reason, variations in the film thickness of the resulting film occur, and as a result, it is difficult to manufacture a film having a periodic honeycomb structure.
PCT / JP2006 / 308980 JP 2006-70254 A

  The present invention is made in view of such a situation, and provides a film manufacturing method and a manufacturing apparatus capable of efficiently manufacturing a film having a periodic honeycomb structure in which pores having a uniform hole diameter are formed. For the purpose.

In order to achieve the above object, a film production method according to the present invention comprises:
Forming a solution film of a predetermined thickness comprising a polymer solution on a substrate;
The humidified gas is sprayed from the nozzle onto the surface of the solution film so that the gas flow parallel to the surface exists, and is parallel to the surface of the solution film in a direction opposite to the gas blowing direction. Moving the nozzle in a direction to form water droplets due to condensation on the surface of the solution film;
Evaporating the solvent contained in the solution film;
Evaporating water droplets contained in the solution film,
Holes corresponding to the water droplets are formed inside or on the surface of the film.

The film production apparatus according to the present invention comprises:
A substrate holder for holding a substrate on which a solution film of a predetermined thickness is formed;
A chamber capable of maintaining the ambient atmosphere of the substrate holder at a constant temperature and humidity;
A nozzle that blows the humidified gas on the surface of the solution film so that there is a flow of the gas parallel to the surface;
Nozzle moving means capable of moving the nozzle in a direction parallel to the surface of the solution film in a direction opposite to the gas blowing direction;
Substrate temperature control means for controlling the temperature of the substrate.

  In the film manufacturing method and the manufacturing apparatus according to the present invention, since the nozzle is moved without moving the substrate, the parallelism of the solution film formed on the substrate is easily maintained. In addition, since the nozzle that blows out the gas is moved in a direction parallel to the surface of the solution film in the direction opposite to the direction of blowing the gas, the gas blowing speed decreases on the surface of the solution film as the nozzle moves away. Therefore, new condensed water is not generated on the surface of the solution film on which condensed water has already been formed, and inconveniences such as the formation of condensed water in two or more layers can be prevented.

  Furthermore, on the surface of the solution film, the boundary between the surface portion where the condensed water is generated and the surface portion where the condensed water is not yet formed gradually moves as the nozzle moves, and between water droplets or a cluster of water droplets. It is easy to release the compressive stress acting between them.

  As a result, the film manufacturing method and manufacturing apparatus according to the present invention can efficiently manufacture a film having a periodic honeycomb structure in which pores having a uniform hole diameter are formed. In addition, by controlling the blowing speed of the gas blown from the nozzle, the moving speed of the nozzle, the angle of the blowing outlet of the nozzle, and the like, the size of the holes and the periodic pattern in the honeycomb structure can be changed.

  Furthermore, in the method and apparatus for producing a film according to the present invention, there is no inconvenience such as collapse of the honeycomb structure because there is no step of winding the film into a roll after production of the film.

  Preferably, the polymer solution contains a solvent having a boiling point lower than that of water. This is because the solvent in the solution film is first evaporated, and then water droplets are evaporated to form pores corresponding to the water droplets in the film, thereby obtaining a honeycomb structure.

  The polymer solution may contain two or more solvents having a boiling point lower than that of water. By controlling the evaporation rate of the solvent, a film having a honeycomb structure with high periodicity can be obtained.

  Preferably, the nozzle moves from the first end to the second end on the surface of the solution film along the moving direction of the nozzle, and thereafter moves away from the surface of the solution film. On the surface of the solution film, the boundary between the surface portion where condensation water is generated and the surface portion where condensation water is not yet formed gradually moves as the nozzle moves, and condensation forms on the entire surface of the solution film. It is preferable that the nozzle is separated from the surface of the solution film after the water is formed. This is to prevent multiple layers of condensed water from being formed on the surface of the solution film.

  Preferably, after the temperature and humidity in the chamber are controlled to be constant, the gas is blown from the nozzle onto the surface of the solution film in the chamber. Preferably, the temperature of the substrate is controlled so that the temperature of the surface of the solution film is equal to or lower than the dew point of the gas blown from the nozzle, and then the gas is supplied from the nozzle to the solution film. Spray on the surface.

  Preferably, after forming water droplets due to condensation on the entire surface of the solution film, the temperature of the substrate is raised so that the temperature near the surface of the solution film is close to the dew point, and the state is maintained, and the solution is maintained. The solvent contained in the membrane is evaporated.

  Preferably, the outlet of the nozzle that blows out the gas faces a direction substantially parallel to the surface of the solution film. The outlet angle of the outlet may be controllable.

Hereinafter, the present invention will be described based on embodiments shown in the drawings.
1A is a cross-sectional view of a main part of a film having a honeycomb structure according to an embodiment of the present invention, and FIG. 1B is a cross-sectional view of a main part of a film having a honeycomb structure according to another embodiment of the present invention. 1 (C) is a cross-sectional view of a main part of a film having a honeycomb structure according to still another embodiment of the present invention,
FIG. 2 is a plan view of the honeycomb structure film shown in FIG.
FIG. 3 shows a film production apparatus according to an embodiment of the present invention.
4 is a perspective view showing the relationship between the nozzle and the substrate shown in FIG.
FIG. 5 is a schematic cross-sectional view showing the formation process of condensed water,
FIG. 6 is a graph showing the temperature change of the substrate over time.

  As shown in FIG. 1A, FIG. 1B, and FIG. 2, the film 2 formed by the film manufacturing method of the present embodiment, which will be described later, has holes 4 with a substantially uniform hole diameter regularly in the plane direction. It is a film having a honeycomb structure formed periodically. In the film 2 of the embodiment shown in FIG. 1 (A), the holes 4 are formed so as to be partially in contact with each other in the plane direction, and are opened only on one surface of the film 2. As shown in FIG. 1C, the contact portions of the adjacent holes 4 may communicate with each other.

  Depending on the manufacturing conditions of the film manufacturing method of this embodiment to be described later, not only the film 2 shown in FIG. 1 (A) and FIG. 1 (C) but also the film 2 shown in FIG. it can. In the film 2 shown in FIG. 1 (B), the holes 4 are formed without contacting each other in the plane direction, and are open on both sides of the film 2.

  In any film 2 shown in FIGS. 1A and 1B, the holes 4 are preferably formed in one layer along the planar direction of the film 2. The average pore diameter of the pores 4 is usually 0.05 to 100 μm, preferably 0.1 to 100 μm, more preferably 0.1 to 20 μm, and further preferably 0.5 to 10 μm. preferable. The honeycomb-structured film 2 having the pores 4 having such an average pore diameter is excellent in the cell growth inhibiting action. However, the use of the film 2 of this embodiment is not limited to medical use as a film provided on the surface of a stent, for example, and can be widely used for other uses.

  Here, the hole diameter refers to the diameter of the maximum inscribed circle with respect to the opening shape of the hole. For example, when the opening shape of the hole is substantially circular, it refers to the diameter of the circle, and is substantially elliptical. In this case, it refers to the minor axis of the ellipse.If it is substantially square, it refers to the length of the side of the square.If it is substantially rectangular, it refers to the length of the short side of the rectangle. is there. The pore size can be measured using a scanning electron microscope (SEM) or the like.

  In the film 2 of the present embodiment, the variation coefficient [= standard deviation ÷ average value × 100 (%)] of the pore diameter of the pores 4 is preferably 30% or less, and the variation coefficient of the pore diameter is 20% or less. Is more preferable. By forming such a porous structure (honeycomb structure) with a high uniformity of pore diameter, it is possible to obtain a film 2 having a more excellent cell growth inhibitory effect.

  It does not specifically limit as resin which comprises the film 2, Both non-biodegradable resin and biodegradable resin can be used. From the viewpoint of maintaining the cell growth inhibitory action in the living body for a long period of time, those formed from non-biodegradable resins that are not easily decomposed in the living body are preferable.

  Specific examples of the resin constituting the film 2 of the present invention include polybutadiene (1,2-polybutadiene, 1,4-polybutadiene), polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, acrylonitrile-butadiene. -Conjugated diene polymer such as styrene copolymer; Poly ε-caprolactone; Polyurethane; Cellulose polymer such as cellulose acetate, celluloid, cellulose nitrate, acetylcellulose, cellophane; Polyamide 6, Polyamide 66, Polyamide 610, Polyamide 612 Polyamide polymers such as polyamide 12, polyamide 46; fluorine polymers such as polytetrafluoroethylene, polytrifluoroethylene, perfluoroethylene-propylene copolymer; polystyrene, styrene-ethylene -Propylene copolymer, styrene-ethylene-butylene copolymer, chlorinated polyethylene-acrylonitrile-styrene copolymer, methacrylate-styrene copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer Styrene polymers such as polymers, acrylate-acrylonitrile-styrene copolymers; polyethylene, chlorinated polyethylene, ethylene-α-olefin copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl chloride copolymers, Olefin polymers such as ethylene-vinyl acetate copolymer, polypropylene, olefin-vinyl alcohol copolymer, polymethylpentene; formaldehyde polymers such as phenol resin, amino resin, urea resin, melamine resin, benzoguanamine resin; Polyester polymers such as ribylene terephthalate, polyethylene terephthalate, polyethylene naphthalate; epoxy resin; (meth) such as poly (meth) acrylate, poly-2-hydroxyethyl acrylate, methacrylate-vinyl acetate copolymer Examples thereof include acrylic polymers; norbornene resins; silicon resins; polymers of hydroxycarboxylic acids such as polylactic acid, polyhydroxybutyric acid, and polyglycolic acid. These can be used alone or in combination of two or more.

  Among these, in order to obtain a film having a cell growth inhibitory action, the use of a conjugated diene polymer, a styrene polymer or polyurethane is more preferred, and the use of 1,2-polybutadiene is particularly preferred.

  Further, an amphiphilic substance may be added to the resin constituting the film 2. The amphiphilic substance to be added is a polyethylene glycol-polypropylene glycol block copolymer; an amphiphilic resin having an acrylamide polymer as a main chain skeleton and a dodecyl group as a hydrophobic side chain and a lactose group or a carboxyl group as a hydrophilic side chain. An ion complex of an anionic polymer such as heparin, dextran sulfate, and nucleic acid (DNA or RNA) and a long-chain alkylammonium salt; an amphiphilic resin having a water-soluble protein such as gelatin, collagen or albumin as a hydrophilic group; And amphiphilic resins such as a polylactic acid-polyethylene glycol block copolymer, a polyε-caprolactone-polyethylene glycol block copolymer, and a polymalic acid-polymalic acid alkyl ester block copolymer.

  In the present embodiment, the thickness of the film 2 having such a honeycomb structure is not particularly limited, but is more preferably 0.05 to 100 μm, and further preferably 0.5 to 20 μm. The film 2 of this embodiment is manufactured by the film manufacturing apparatus 10 shown in FIG.

  The manufacturing apparatus 10 includes a chamber 12, and a substrate holding table 16 that holds the substrate 14 is fixed inside the chamber 12. A substrate temperature adjusting device 18 is attached to the lower part of the substrate holding table 16. A cooling element such as a Peltier element is mounted inside the substrate temperature control device 18, and the temperature of the substrate 14 is controlled by supplying power from the power operation panel 24 and the temperature controller 22.

  Inside the chamber 12 and above the substrate 14, a nozzle 30 having an outlet 30a is disposed so as to be movable in the X-axis direction. The nozzle 30 is connected to the moving unit 32 via a connecting tool 34, and the driving unit 38 is rotated together with the driving shaft nozzle 30 by rotating the drive shaft 38 around the axis by rotating the motor 35. It moves in the axial direction.

  The motor 35 has a step as a motor, for example, and can control the moving speed, stop position, and the like of the nozzle 30 in the X-axis direction by controlling the number of rotations thereof. In addition, the nozzle 30 is connected to the moving unit via the connecting tool 34, and the connecting tool 34 is constituted by a rotating hinge or the like, so that the main stream in the gas blown from the outlet 30a of the nozzle 30 with respect to the X-axis. The angle of the blowing direction 30b can be changed.

  For example, in the example shown in FIG. 3, the blowing direction 30b is almost parallel to the direction of the X axis, but may be tilted in the range of +15 degrees to −15 degrees with respect to the X axis. Further, the angle may be changed during the movement of the nozzle 30 in the X-axis direction.

  The gas blown out from the blowout port 30a of the nozzle 30 is humidified, and the relative humidity is preferably 60 to 95%, and a gas having a slightly higher humidity than the relative humidity inside the chamber 12 is blown out. The The gas blown out from the outlet 30a is generally air, but other gases may be used in some cases. Humidified air is introduced from the outside of the chamber 12 through a duct 36 connected to the top of the nozzle 30.

  The temperature, humidity and pressure inside the chamber 12 are detected by a temperature sensor, a humidity sensor, a pressure sensor, etc., and controlled to a constant temperature, humidity and pressure. The temperature inside the chamber 12 is, for example, 15 to 30 ° C., and the relative humidity inside the chamber 12 is, for example, 10 to 95%. A plenum chamber 12 a is mounted on the upper portion of the chamber 12, and air having a constant temperature and humidity introduced through the duct 12 b is uniformly supplied into the chamber 12 in a laminar flow state. In this example, the plenum chamber 12 a has a box shape in which a grid-like metal plate or the like is arranged at the boundary with the chamber 12.

  As shown in FIGS. 4 and 5, in this embodiment, an outer peripheral convex portion 15 is formed along the outer periphery of the rectangular substrate 14, and the film 2 and the film 2 are formed on the upper surface of the substrate 14 in a later step. A solution film 2a is formed. In a state where no external force other than gravity acts, the surface of the solution film 2a is parallel to the X axis and the Y axis and is perpendicular to the vertical Z axis. In this embodiment, the Y axis is parallel to the longitudinal direction of the substrate 14.

  The substrate 14 is preferably composed of an inorganic substrate such as a glass substrate, a metal substrate, or a silicon substrate, but may be an organic substrate made of a polymer such as polypropylene, polyethylene, or polyetherketone.

  As shown in FIG. 4, the width W1 of the outlet 30a in the nozzle 30 is preferably larger than the width W2 of the solution film 2a formed on the upper surface of the substrate 14, and more preferably the width of the substrate 14 in the Y-axis direction. Is preferably larger.

  As shown in FIG. 5, the nozzle 30 moves along the X axis in the opposite direction to the mainstream blowing direction 30b of the gas blown from the blowing port 30a. In that case, the gap h1 between the lower end of the outlet 30a of the nozzle 30 and the outer peripheral edge convex portion 15 of the substrate 14 is not particularly limited, but is larger than 0, preferably within 50 cm, more preferably within 30 cm, particularly Preferably it is within 15 cm. If the gap h1 is too far away, the gas from the blowing port 30a will not easily hit the surface of the solution film 2a when the blowing direction 30b is parallel to the surface of the solution film 2a.

  The moving speed of the nozzle 30 along the X-axis in the state shown in FIG. 5 is determined in relation to the speed of the gas blown from the blowing port 30a, and is preferably 0.1 cm / min to 100 cm / min. . The speed of the gas blown out from the blowout port 30a is not particularly limited, but is preferably 0.01 m / second to 5 m / second.

  Next, the manufacturing method of the film which concerns on one Embodiment of this invention is demonstrated. First, the temperature and humidity inside the chamber 12 shown in FIG. 3 are controlled to be constant. The temperature and humidity ranges inside the chamber 12 are as described above.

  Next, as shown in FIG. 5, a solution film 2 a is formed on the surface of the substrate 14 inside the chamber 12. The solution film 2 a is formed by applying or pouring a polymer solution onto the surface of the substrate 14. At that time, the substrate 14 is not cooled by the temperature control device 18 shown in FIG. 3, and the temperature of the substrate 14 is substantially the same as the internal temperature of the chamber 12. The initial film thickness t0 of the solution film 2a is about 2 to 10 mm, more preferably about 3 to 7 mm.

  The polymer solution for forming the solution film 2a contains a water-insoluble organic solvent.

  Examples of the organic solvent include halogenated hydrocarbon solvents such as chloroform and methylene chloride; saturated hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane Aromatic hydrocarbon solvents such as benzene, toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as diethyl ketone and methyl isobutyl ketone; carbon disulfide; These organic solvents can be used alone or as a mixed solvent composed of two or more of these.

  The concentration of the resin dissolved in the organic solvent is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight. If the resin concentration is lower than 0.01% by weight, the resulting film has insufficient mechanical strength, which is not desirable. If the resin concentration is 10% by weight or more, a desired porous structure (honeycomb structure) may not be obtained.

  It is preferable that an amphiphilic substance is added to the resin film in the solution film 2a. Among them, it is preferable to add an amphiphilic resin (hereinafter referred to as “Cap resin”) that has low solubility in water and is soluble in organic dissolution.

  By adding such an amphiphilic substance, fusion of water droplets is suppressed and stabilized, and thus a member having a porous structure with further improved pore diameter uniformity can be obtained. The amount of the amphiphilic substance added is preferably 99: 1 to 50:50 by weight ratio of resin: amphiphile.

  After forming the solution film 2a, the substrate 14 is cooled by the temperature control device 18 shown in FIG. The cooling temperature of the substrate 14 is determined so that the surface of the solution film 2 a is equal to or lower than the dew point of the gas blown out from the outlet 30 a of the nozzle 30.

  Immediately or simultaneously, the nozzle 30 is moved in the direction opposite to the blowing direction 30b of the blowing port 30a of the nozzle 30 from the vicinity of the position of the one outer peripheral convex portion 15 along the X-axis direction in the substrate 14 shown in FIG. It moves toward the other outer peripheral convex part 15 along the X-axis. At the same time, the blowing of the humidified gas from the outlet 30a is also started. The moving speed of the nozzle is as described above.

  As shown in FIG. 5, as the nozzle 30 moves, the humidified gas blown from the blower outlet 30a hits the surface of the solution film 2a, where it is cooled below the dew point, and water droplets 4a of condensed water are generated. And gradually formed on the surface of the solution film 2a. As the nozzle 30 moves in the direction opposite to the blowing direction 30b along the X-axis direction, as shown in FIG. 4, the region where the water droplets 4a of condensed water are formed on the surface of the solution film 2a expands. As a result, the boundary between the surface portion where the condensed water is generated and the surface portion where the condensed water is not formed gradually moves as the nozzle 30 moves, and the compression works between the water droplets or between the water droplet clusters. Easy to release stress.

  In FIG. 4, the region where the dew condensation water droplets 4a are formed is formed in a mountain shape because the blowing speed of the gas blown from the blowing port 30a is the Y-axis direction at the blowing port 30a. This is considered to be high at the center of the plate and low at both ends.

  As indicated by a two-dot chain line in FIG. 5, after the outlet 30 a of the nozzle 30 has moved to the outer peripheral convex portion 15 located at the other end in the X-axis direction on the substrate 14, the nozzle 30 further moves to X The nozzle 30 continues to move along the axis, and the nozzle 30 stops at a position away from the substrate 14 in the X-axis direction, as shown in FIG. However, after that, it is preferable to continue blowing the humidified gas from the outlet 30a.

  At the stage where one layer of the water droplet 4a made of condensed water is formed on the entire surface of the solution film 2a shown in FIG. 4, the nozzle 30 is located away from the substrate 14 in the X-axis direction, and the temperature control device shown in FIG. 18, the temperature of the substrate is raised to a temperature near the dew point. The internal temperature of the chamber 12 is maintained at a constant temperature and humidity.

  In this state, the solvent contained in the solution film 2a evaporates, and the water droplet 4a hardly evaporates. Therefore, the thickness t0 of the solution film 2a decreases, and the water droplet 4a is taken into the solution film 2a.

  At the stage where the thickness t0 of the solution film 2a becomes approximately the same as the outer diameter of the water droplet 4a, the temperature of the substrate 14 is raised by the temperature adjusting device 18 shown in FIG. 3 to evaporate the water droplet 4a. As a result, the portion corresponding to the water droplet 4a shown in FIG. 5 becomes the hole 4 shown in FIG. 1 (A) or FIG. 1 (B), and the timing for raising the temperature of the substrate is adjusted, so that FIG. Alternatively, it becomes possible to manufacture a film 2 having a honeycomb structure as shown in FIG. FIG. 6 is a graph showing an example of temperature control of the substrate 14, and it is preferable that the temperature of the substrate is increased stepwise after the water droplets 4a due to condensation are formed on the surface of the solution film 2a. The series of operations described above is preferably performed inside the chamber 12.

  For example, after manufacturing a film 2 having a honeycomb structure as shown in FIG. 1A or 1B on the surface of the substrate 14, the film 2 is taken out of the chamber 12 together with the substrate 14. Thereafter, the film 2 is removed from the substrate 14. Note that the film 2 may be removed from the substrate 14 inside the chamber 12.

  The film 2 may then be stretched. Or you may laminate | stack with another film. Further, when the substrate 14 is a resin substrate, it can be laminated integrally with the substrate 14 in the manufacturing process of the film 2.

  In the film manufacturing method and manufacturing apparatus according to this embodiment, the parallelism of the solution film 2 a formed on the substrate 14 is easily maintained because the nozzle 30 is moved without moving the substrate 14. Further, in order to move the nozzle 30 that blows out the gas in the X-axis direction parallel to the surface of the solution film 2a in the direction opposite to the gas blowing direction 30b, the gas 30 moves away from the surface of the solution film 2a as the nozzle 30 moves away. Spraying speed is reduced. Therefore, new condensed water is not generated on the surface of the solution film 2a on which condensed water has already been formed, and inconveniences such as the formation of condensed water in two or more layers can be prevented.

  Further, on the surface of the solution film 2a, the boundary between the surface portion where the condensed water is generated and the surface portion where the condensed water is not yet formed gradually moves as the nozzle moves, It is easy to release the compressive stress acting between the clusters.

  As a result, in the film manufacturing method and manufacturing apparatus according to the present embodiment, it is possible to efficiently manufacture the film 2 having a periodic honeycomb structure in which the pores 4 having a uniform hole diameter are formed. It is also possible to change the size and periodic pattern of the holes 4 in the honeycomb structure by controlling the blowing speed of the gas blown from the nozzle 30, the moving speed of the nozzle, the angle of the nozzle blowing port, and the like. is there.

  Furthermore, in the manufacturing method and manufacturing apparatus of the film 2 according to the present embodiment, there is no inconvenience that the honeycomb structure is crushed because there is no step of winding the film into a roll after the film 2 is manufactured.

  The present invention is not limited to the above-described embodiment, and can be variously modified within the scope of the present invention.

  For example, in the present invention, the temperature adjustment device 18 that adjusts the temperature of the substrate 14 is not limited to the above-described embodiment. Further, the mechanism for moving the nozzle 30 is not limited to the illustrated embodiment.

Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples.
Example 1

  The film 2 of this example was produced as follows. That is, 1,2-polybutadiene (trade name, manufactured by RB820 JSR) and Cap resin (weight average molecular weight: 62,000, number average molecular weight: 21,000) were mixed at a weight ratio of 20: 1, and then chloroform was mixed. And a resin solution (1) having a concentration of 5.0 mg / mL was prepared.

  The prepared resin solution (1) was cast on the substrate 14 shown in FIG. 5, and then the inside of the chamber 12 was placed in an atmosphere of 23 ° C. and a relative humidity of 60%, and high-humidity air with a relative humidity of 80% was added to the nozzle. The air was blown out from 30 air outlets 30a. At the same time, the nozzle 30 was moved in the direction opposite to the blowing direction 30b as shown in FIG.

  A film sample was manufactured by controlling the speed of the humidified air blown from the outlet of the nozzle 30 and the moving speed of the nozzle 30. It was confirmed that a film having a honeycomb structure with high periodicity was obtained.

1A is a cross-sectional view of a main part of a film having a honeycomb structure according to an embodiment of the present invention, and FIG. 1B is a cross-sectional view of a main part of a film having a honeycomb structure according to another embodiment of the present invention. 1 (C) is a cross-sectional view of a main part of a film having a honeycomb structure according to still another embodiment of the present invention. FIG. 2 is a plan view of the honeycomb structured film shown in FIG. FIG. 3 shows a film manufacturing apparatus according to an embodiment of the present invention. FIG. 4 is a perspective view showing the relationship between the nozzle and the substrate shown in FIG. FIG. 5 is a schematic cross-sectional view showing the process of forming condensed water. FIG. 6 is a graph showing the temperature change of the substrate over time.

Explanation of symbols

DESCRIPTION OF SYMBOLS 2 ... Film 2a ... Solution film 4 ... Hole 4a ... Water drop 10 ... Film manufacturing apparatus 12 ... Chamber 14 ... Substrate 16 ... Substrate holding stand 18 ... Substrate temperature control device 30 ... Nozzle 30a ... Outlet 30b ... Outlet direction 35 ... motor

Claims (9)

Forming a solution film of a predetermined thickness comprising a polymer solution on a substrate;
The humidified gas is sprayed from the nozzle onto the surface of the solution film so that the gas flow parallel to the surface exists, and is parallel to the surface of the solution film in a direction opposite to the gas blowing direction. Moving the nozzle in a direction to form water droplets due to condensation on the surface of the solution film;
Evaporating the solvent contained in the solution film;
Evaporating water droplets contained in the solution film,
A method for producing a film, wherein holes corresponding to the water droplets are formed in or on the surface of the film.   The method for producing a film according to claim 1, wherein the polymer solution contains a solvent having a boiling point lower than that of water.   The method for producing a film according to claim 1, wherein the polymer solution contains two or more solvents having a boiling point lower than that of water.   The nozzle moves from the first end to the second end on the surface of the solution film along the moving direction of the nozzle, and thereafter moves away from the surface of the solution film. The manufacturing method of the film of description.   The method for producing a film according to any one of claims 1 to 4, wherein after the temperature and humidity in the chamber are controlled to be constant, the gas is blown from the nozzle onto the surface of the solution film in the chamber.   The temperature of the substrate is controlled so that the temperature of the surface of the solution film is lower than the dew point of the gas blown from the nozzle, and then the gas is blown from the nozzle to the surface of the solution film. The manufacturing method of the film in any one of 1-5.   After forming water droplets due to condensation on the entire surface of the solution film, the temperature of the substrate is raised so that the temperature near the surface of the solution film is close to the dew point, and the state is maintained, and is included in the solution film. The method for producing a film according to claim 1, wherein the solvent to be evaporated is evaporated. A substrate holder for holding a substrate on which a solution film of a predetermined thickness is formed;
A chamber capable of maintaining the ambient atmosphere of the substrate holder at a constant temperature and humidity;
A nozzle that blows the humidified gas on the surface of the solution film so that there is a flow of the gas parallel to the surface;
Nozzle moving means capable of moving the nozzle in a direction parallel to the surface of the solution film in a direction opposite to the gas blowing direction;
A film manufacturing apparatus comprising substrate temperature control means for controlling the temperature of the substrate.   The film production apparatus according to claim 8, wherein a blowout port of the nozzle that blows out the gas faces a direction substantially parallel to the surface of the solution film.

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