JP5648782B2 - Film manufacturing apparatus and manufacturing method - Google Patents

Description

  The present invention relates to a manufacturing apparatus and a manufacturing method for 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. The applicant has proposed an attempt to manufacture a film having a periodic honeycomb structure as the covering layer (Patent Document 1).

  However, in the conventional method and apparatus for producing a film having a honeycomb structure, in the step of forming water droplets of condensed water, the gas blowing speed is not necessarily uniform in the width direction of the blowing port, but is uniform along the width direction. It is difficult to make water droplets of condensed water. Therefore, it is difficult to manufacture a film having a uniform honeycomb structure along the width direction.

JP 2009-108163 A

  The present invention has been made in view of such a situation, and an object thereof is to provide a film manufacturing apparatus and a manufacturing method capable of manufacturing a film having a uniform honeycomb structure over a wider region.

In order to achieve the above object, a 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 device having an outlet for blowing the humidified gas on the surface of the solution film against 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,
The nozzle device is
An inlet for introducing the gas into the nozzle device;
A casing in which the inlet and the outlet are formed;
Fixed in which the first end is fixed to the inner wall surface of the casing along the gas blowing direction, and is alternately displaced in different directions along the gas blowing direction in the casing. And a plurality of rectifying plates whose free ends form a flow gap between the second end opposite to the first end and the inner wall surface of the casing.

  In the present invention, by arranging the plurality of rectifying plates inside the nozzle device so as to be displaced alternately, it is possible to ensure a large flow path length of the humidified gas flowing inside the casing. Further, the humidified gas introduced into the casing is rectified in the width direction of the casing while flowing through the flow path, and the humidified gas is blown out from the blowout outlet with a uniform air volume in the width direction of the casing. The humidified gas is blown with a uniform air volume in the width direction of the casing so that a gas flow parallel to the surface of the solution film exists. Therefore, it is possible to produce a film having a uniform property over a wider area. Therefore, the yield of products can be improved.

  Preferably, the plurality of rectifying plates are arranged in parallel to each other. Thereby, the rectification | straightening effect | action of the width direction of a casing improves.

  Preferably, the width of the flow path gap is 30 to 80% of the arrangement interval between the adjacent flow straightening plates. By setting the width of the flow passage gap to a predetermined range, the rectifying action in the width direction of the casing is improved.

  Preferably, the current plate is arranged in 3 to 10 sheets in the casing. Preferably, the plurality of rectifying plates are arranged at a predetermined interval. Arranging such a predetermined number of sheets at a predetermined interval improves the rectifying action in the width direction of the casing.

  Preferably, the introduction port is located in an upper part of the nozzle device. Thereby, introduction of gas is easy and it becomes possible to secure the length of the flow path to the maximum.

  Preferably, the introduction port is disposed above the fixed end of the current plate on the uppermost layer. Since the introduced humidified gas hits the vicinity of the fixed end of the uppermost rectifying plate and flows toward the free end of the rectifying plate, the rectifying action in the width direction of the casing is improved.

  A plate-shaped flap that can change the flow of the gas may be further disposed at the outlet. This makes it possible to freely finely adjust the wind direction with respect to the surface of the solution film.

  A triangular pyramid-shaped protrusion may be arranged at the air outlet. As a result, the humidified gas is blown out from the air outlet with a more uniform air volume in the width direction of the casing.

  The method for producing a film according to the present invention includes a step of forming the solution film of a polymer solution having a predetermined thickness on the substrate, and the humidified gas from the nozzle device to the surface of the solution film. The gas flow is parallel to the surface of the solution film, and the nozzle is moved in a direction parallel to the surface of the solution film in a direction opposite to the gas blowing direction. A step of forming water droplets, a step of evaporating a solvent contained in the solution film, and a step of evaporating water droplets contained in the solution film, wherein pores corresponding to the water droplets are formed inside or on the surface of the film. It is characterized by forming in.

FIG. 1 is a film manufacturing apparatus according to an embodiment of the present invention. FIG. 2 is a perspective view of the nozzle device shown in FIG. 3 is a cross-sectional view taken along the line III-III in FIG. FIG. 4 is an explanatory view showing a state in which the humidified gas is blown out from the outlet of the nozzle device shown in FIG. FIG. 5 is a schematic cross-sectional view showing a process of forming condensed water. 6A 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. 6B is a cross-sectional view of a main part of a film having a honeycomb structure according to another embodiment of the present invention. FIG. 6C 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. 7 is a plan view of the honeycomb structured film shown in FIG. FIG. 8 is a perspective view of a nozzle device according to another embodiment of the present invention. FIG. 9 is a perspective view of a nozzle device according to another embodiment of the present invention. FIGS. 10A to 10C are explanatory views showing a process of using the manufactured film for a break test. FIG. 11 is a schematic diagram for explaining a film tensile test. FIG. 12 is a graph showing the relationship between the film thickness and the breaking load in the breaking load test. FIG. 13 is a graph showing the relationship between film thickness and breaking elongation in a breaking load test. FIG. 14A is an explanatory view showing the dried state of the film in the example, and FIG. 14B is an explanatory view showing the dried state of the film in the comparative example.

  The film 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.

  A nozzle device 30 is disposed inside the chamber 12 and above the substrate 14 so as to be movable in the X-axis direction. The nozzle device 30 is connected to the moving unit 42 via a connector 44, and the moving unit 42 is rotated together with the drive shaft nozzle device 30 by rotating the motor 45 to rotate the drive shaft 48 around the axis. , Move in the X-axis direction.

  The motor 45 is, for example, a step motor, and can control the moving speed, stop position, and the like of the nozzle device 30 in the X-axis direction by controlling the number of rotations thereof. Further, the nozzle device 30 is connected to the moving unit via the connecting tool 44, and the connecting tool 44 is constituted by a rotating hinge or the like, so that the gas blown out from the outlet 34 of the nozzle device 30 with respect to the X axis is used. The angle of the mainstream blowing direction 30b can be changed.

  For example, in the example shown in FIG. 1, 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 device 30 in the X-axis direction.

  The gas blown out from the air outlet 34 of the nozzle device 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. Is done. The gas blown out from the blowout port 34 is generally air, but may be other gas depending on circumstances. The humidified air is introduced from the outside of the chamber 12 through a duct 46 connected to the upper part of the nozzle device 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 FIG. 2, in this embodiment, an outer peripheral convex portion 15 is formed along the outer periphery of the rectangular substrate 14, and the solution film that becomes the film 2 in a later step on the upper surface of the substrate 14. 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. 2, the width W1 of the air outlet 34 in the nozzle device 30 is preferably equal to or greater 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. Equivalent or better than is preferable.

  As shown in FIG. 3, the nozzle device 30 includes an inlet 32 for introducing gas into the nozzle device 30 and a casing 31 in which the inlet 32 and the outlet 34 are formed.

  The length 30c in the Z-axis direction of the casing 31 is preferably 500 to 1000 mm, and the length 30d in the X-axis direction is preferably 100 to 400 mm. Moreover, as for the width W1 (shown in FIG. 2) of the blower outlet 34 mentioned above, W1 = 300-700 mm is preferable.

  A plurality of rectifying plates 36 are arranged in the casing 31 so as to be alternately displaced along the gas blowing direction 30b. Each rectifying plate 36 has a first end that is fixed to the inner wall surface 31a of the casing 31 along the gas blowing direction 30b, and a second end opposite to the first end. It is the free end 36b which forms the flow-path gap 38 between the wall surfaces 31a.

  The rectifying plates 36 are arranged at a predetermined interval 30e, and between the adjacent rectifying plates 36, the fixed ends 36a (free ends 36b) are opposite to each other. The predetermined interval 30e is preferably 20 to 100 mm. The rectifying plates 36 are arranged in parallel to each other along the Z-axis direction. It is preferable that 3 to 10 rectifying plates 36 are arranged in the casing 31. The length 30f of the rectifying plate 36 in the X-axis direction is preferably 40 to 370 mm. The width 30g of the flow path gap 38 is preferably 30 to 80% of the interval 30e between the adjacent rectifying plates 36.

  The introduction port 32 located at the upper part of the nozzle device 30 is preferably cylindrical, and its inner diameter is preferably 80 to 400% of the width 30 g of the flow path gap 38. As shown in FIG. 2, the introduction port 32 is formed in the upper part of the nozzle device 30. Further, as shown in FIG. 3, the introduction port 32 is preferably disposed above the fixed end 36 a of the uppermost rectifying plate 36.

  The height 30h in the Z-axis direction of the air outlet 34 is preferably 20 to 150 mm. As shown in FIG. 4, the humidified gas introduced from the inlet 32 is blown out from the outlet 34 with a uniform air volume in the width direction of the casing 30 (W1 shown in FIG. 2).

  As shown in FIG. 5, the nozzle device 30 moves along the X axis in the opposite direction to the main flow blowing direction 30 b of the gas blown from the blower outlet 34. In that case, the gap h1 between the lower end of the air outlet 34 of the nozzle device 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 device 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 blowout port 34, and preferably 0.1 cm / min to 100 cm / min. is there. Although the speed of the gas blown out from the blower outlet 34 is not particularly limited, it is preferably 0.01 m / second to 5 m / second.

  As shown in FIGS. 6 (A), 6 (B), and 7, the film 2 formed by the film manufacturing method of the present embodiment, which will be described later, has pores 4 with substantially uniform pore sizes 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. 6 (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. In addition, as shown in FIG.6 (C), the contact part of the adjacent void | hole 4 may be connected mutually.

  Depending on the manufacturing conditions of the film manufacturing method of this embodiment to be described later, not only the film 2 shown in FIGS. 6A and 6C but also the film 2 shown in FIG. 6B, for example, may be manufactured. it can. In the film 2 shown in FIG. 6B, 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. 6 (A) and 6 (B), the holes 4 are preferably formed in one layer along the plane 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.

  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. 1 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. 1, 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 device 30 is opposite to the blowing direction 30b of the outlet 34 of the nozzle device 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 periphery convex part 15 along the X-axis of a direction. At the same time, the blowing of the humidified gas from the outlet 34 is also started. The moving speed of the nozzle device 30 is as described above.

  As shown in FIG. 5, as the nozzle device 30 moves, the humidified gas blown from the blower outlet 34 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 device 30 moves in the direction opposite to the blowing direction 30b along the X-axis direction, the region where the water droplets 4a of condensed water are formed on the surface of the solution film 2a is expanded as shown in FIG. 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.

  As shown by the two-dot chain line in FIG. 5, after the outlet 34 of the nozzle device 30 has moved to the outer peripheral convex portion 15 located at the other end portion in the X-axis direction on the substrate 14, the nozzle device 30 is Further, the nozzle device 30 continues to move along the X axis, and the nozzle device 30 stops at a position away from the substrate 14 in the X axis direction, as shown in FIG. However, it is preferable to continue blowing the humidified gas from the outlet 34 after that.

  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. 2, the nozzle device 30 is located away from the substrate 14 in the X-axis direction, and the temperature control shown in FIG. The apparatus 18 raises the temperature of the substrate 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. 1 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. 6 (A) or FIG. 6 (B). By adjusting the timing for raising the temperature of the substrate, etc., FIG. Alternatively, it becomes possible to manufacture a film 2 having a honeycomb structure as shown in FIG. In addition, after the water droplet 4a by dew condensation is formed on the surface of the solution film 2a, it is preferable to raise the temperature of the substrate stepwise. The series of operations described above is preferably performed inside the chamber 12.

  For example, after the film 2 having a honeycomb structure as shown in FIG. 6A or 6B is manufactured on the surface of the substrate 14, the film 2 is taken out from 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 present embodiment, by arranging the plurality of rectifying plates 36 in the nozzle device 30 so as to be alternately displaced, the flow path length of the humidified gas flowing inside the casing 31 can be ensured to be large. The humidified gas introduced into the casing 31 is uniformly rectified in the width direction of the casing 31 while flowing through the flow path, and from the outlet 34, the air velocity is uniform in the width W1 direction of the outlet 34 of the casing 31. The humidified gas is blown out. The humidified gas is blown at a uniform wind speed in the width direction of the casing 31 so that a gas flow parallel to the surface of the solution film 2a exists. Therefore, it becomes possible to manufacture the film 2 having a uniform honeycomb structure over a wider area. In addition, the yield of products can be improved.

  Further, since the plurality of rectifying plates are arranged in parallel to each other, a stable flow path with a width of 30 i can be secured from the inlet to the outlet, and the humidified gas can be efficiently blown out. Become.

  Furthermore, by setting the width 30g of the flow passage gap to a predetermined range, the flow passage resistance is reduced and the rectifying action is improved.

  Further, by arranging the predetermined number of rectifying plates 36 at predetermined intervals, it is possible to improve the rectifying action while preventing condensation from occurring inside the casing 31.

  Moreover, the introduction of the introduction port 32 at the upper part of the nozzle device 30 facilitates the introduction of gas and ensures the maximum length of the flow path.

  The introduction port 32 is disposed above the fixed end 36 a of the uppermost rectifying plate 36. Since the introduced humidified gas hits the vicinity of the fixed end 36a of the uppermost rectifying plate 36 and flows toward the free end 36b of the rectifying plate 36, the rectifying action is improved.

  Further, as shown in FIG. 8, a plate-like flap 33 that can change the flow of gas may be further arranged at the outlet 34. This makes it possible to freely finely adjust the wind direction with respect to the surface of the solution film 2a.

  Further, as shown in FIG. 9, a triangular pyramid-shaped protrusion 35 may be disposed at the air outlet 34. As a result, the humidified gas is blown out from the air outlet 34 with a more uniform air volume in the width W1 direction of the air outlet 31 of the casing 31.

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

  The length 30c in the Z-axis direction of the casing 31 was 750 mm, the length 30d in the X-axis direction was 200 mm, and the width W1 of the air outlet 34 was 500 mm. The predetermined interval 30e between the rectifying plates 36 was set to 50 mm, and six sheets were arranged in the casing 31. The length 30f of the rectifying plate 36 in the X-axis direction is 170 mm, the height 30h of the outlet 34 in the Z-axis direction is 90 mm, the diameter of the inlet 32 is 70 mm, the flow gap 30g is 30 mm, The nozzle device 30 was manufactured by setting the width 30i in the Z-axis direction to 410 mm.

  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 having a concentration of 2.0 mg / mL was prepared.

  The prepared resin solution is cast on the substrate 14 shown in FIG. 5, and then, the inside of the chamber 12 is placed in an atmosphere of 25 ° C. and a relative humidity of 50%, and high-humidity air with a relative humidity of 65% is applied to the nozzle device 30. From the air outlet 34. At the same time, the nozzle device 30 was moved in the direction opposite to the blowing direction 30b as shown in FIG.

  The film sample 20 shown in FIG. 10A was manufactured by controlling the speed of the humidified air blown from the outlet 34 of the nozzle device 30 and the moving speed of the nozzle device 30. The film sample 20 had a length in the X-axis direction of 430 mm and a width in the Y-axis direction of 295 mm. From the film sample 20, test samples 21 to 24 were cut out from the positions shown in FIG.

  For each of the test samples 21 to 24, the film thickness was measured as shown in FIG. In the test sample 24 shown in FIG. 10B, the film thickness of the film sample was measured at six film thickness measurement locations 24n. The film thickness was measured using a 3D laser microscope (manufactured by Keyence Corporation: VK8710). For the test samples 21 to 23, the film thickness was measured in the same manner. The results are shown in Table 1.

  Next, a tensile test was performed using the film membrane test samples 21 to 24. Tensile sample 24a (shown in FIG. 10C) used for the tensile test was obtained by cutting test sample 24 shown in FIG. 10B with the dimensions shown in FIG. 10C and sampling five of them. And used for evaluation. The tensile samples 21a to 23a were sampled in the same manner. The tensile sample 24a had a length of 50 mm and a width of 20 mm.

  A rheometer was used for the tensile test. With respect to the test sample 24, as shown in FIG. 11, the tensile sample was sandwiched between silicon packings 50 and set in a rheometer with a distance between chucks of 10 mm. The sample was pulled in the arrow direction shown in FIG. 11 at a speed of 20 mm / min until the tensile sample broke. The breaking load was measured when the tensile sample reached breaking. The results are shown in FIG. In addition, the elongation at break when the tensile sample was broken was measured. The results are shown in FIG.

Comparative Example A film sample shown in FIG. 10A was manufactured under the same conditions as in Example 1 except that the rectifying plate 36 was not arranged in the nozzle device 30 shown in FIG. The film thickness was measured in the same manner as in Example 1 for the test samples 21 ′ to 24 ′ prepared from the film samples. The results are shown in Table 1. Similarly, a tensile test was performed to measure the breaking load. The results are shown in FIG. In addition, the elongation at break was measured. The results are shown in FIG.

  From these results, it can be confirmed that in Example 1, a film sample having a thick film thickness can be obtained, and a film having a uniform thickness over the entire surface can be obtained with small variations in film thickness (standard deviation). It was. Further, in Example 1, it was found that the film was not easily broken, and the breaking load was achieved at a reference value of 25 gf or more in all samples. Moreover, in Example 1, compared with the comparative example 1, it turned out that the elongation at break is high and it exceeds the reference value 500% in all the samples.

  Furthermore, the dry state of the film sample 20 was observed by visual observation. Compared to Comparative Example 1 shown in FIG. 14 (B), as shown in FIG. 14 (A), in Example 1, the state in which the dry state is distributed almost evenly along the width direction (Y-axis direction) is shown. I was able to confirm.

2a ... Solution film 12 ... Chamber 14 ... Substrate 16 ... Substrate holding base 30 ... Nozzle device 31 ... Casing 32 ... Inlet 33 ... Flaps 35 ... Projections 34 ... Air outlet 36 ... Current plate 36a ... Fixed end 36b ... Free end 38 ... channel gap

Claims (10)

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 device having an outlet for blowing the humidified gas on the surface of the solution film against the surface;
Nozzle moving means capable of moving the nozzle device 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,
The nozzle device is
An inlet for introducing the gas into the nozzle device;
A casing in which the inlet and the outlet are formed;
Fixed in which the first end is fixed to the inner wall surface of the casing along the gas blowing direction, and is alternately displaced in different directions along the gas blowing direction. And a plurality of rectifying plates that are free ends that form a flow gap between the second end opposite to the first end and the inner wall surface of the casing. apparatus.   The apparatus for producing a film according to claim 1, wherein the plurality of rectifying plates are arranged at a predetermined interval.   The apparatus for producing a film according to claim 1, wherein the plurality of rectifying plates are arranged in parallel to each other.   The width | variety of the said flow-path gap | interval is 30 to 80% of the arrangement | positioning space | interval of the said adjacent baffle plate, The film manufacturing apparatus in any one of Claims 1-3 characterized by the above-mentioned.   The said baffle plate is arrange | positioned by 3-10 sheets in the said casing, The manufacturing apparatus of the film in any one of Claims 1-4 characterized by the above-mentioned.   The film manufacturing apparatus according to claim 1, wherein the introduction port is located in an upper part of the nozzle device.   The said inlet is arrange | positioned above the said fixed end of the said baffle plate of the uppermost layer, The manufacturing apparatus of the film in any one of Claims 1-6 characterized by the above-mentioned.   The apparatus for producing a film according to claim 1, wherein a plate-like flap capable of changing the flow of the gas is further disposed at the outlet.   The apparatus for producing a film according to claim 1, wherein a triangular pyramid-shaped protrusion is disposed at the air outlet. Using the film production apparatus according to claim 1,
Forming the solution film of a predetermined thickness comprising a polymer solution on the substrate;
The humidified gas is sprayed from the nozzle device onto the surface of the solution film so that the gas flow parallel to the surface exists, and the surface of the solution film is opposite to the gas blowing direction. Moving the nozzle in a direction parallel to the surface, forming water droplets due to condensation on the surface of the solution film; and
Evaporating the solvent contained in the solution film;
Evaporating water droplets contained in the solution film,
A method for producing a film, wherein pores corresponding to the water droplets are formed in or on the film.

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