WO2021010216A1 - Procédé de fabrication de gel et appareil de fabrication de gel - Google Patents

Procédé de fabrication de gel et appareil de fabrication de gel Download PDF

Info

Publication number
WO2021010216A1
WO2021010216A1 PCT/JP2020/026457 JP2020026457W WO2021010216A1 WO 2021010216 A1 WO2021010216 A1 WO 2021010216A1 JP 2020026457 W JP2020026457 W JP 2020026457W WO 2021010216 A1 WO2021010216 A1 WO 2021010216A1
Authority
WO
WIPO (PCT)
Prior art keywords
raw material
liquid layer
material liquid
layer
press member
Prior art date
Application number
PCT/JP2020/026457
Other languages
English (en)
Japanese (ja)
Inventor
室伏　英伸
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Publication of WO2021010216A1 publication Critical patent/WO2021010216A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons

Definitions

  • the present disclosure relates to a gel manufacturing method and a gel manufacturing apparatus.
  • Patent Document 1 discloses a method for producing a gel. According to this method, in a container composed of a bottom plate and a side plate extending upward from the peripheral edge of the bottom plate, a second liquid material containing a gel raw material is placed on a first liquid layer made of the first liquid material. The second liquid layer is gelled in the presence of the second liquid layer composed of.
  • the raw material liquid of the gel When the raw material liquid of the gel is supplied onto the base liquid layer B having a higher density than the raw material liquid, the raw material liquid layer A is formed on the base liquid layer B. If the base liquid layer B is sufficiently wider than the raw material liquid layer A, the thickness of the raw material liquid layer A naturally tends to be constant. The thickness is also called the equilibrium thickness.
  • the equilibrium thickness HA0 is obtained from the following equation (1).
  • the equilibrium thickness HA0 is determined by the combination of the raw material liquid which is the material of the raw material liquid layer A and the base liquid which is the material of the base liquid layer B.
  • One aspect of the present disclosure provides a technique capable of forming a raw material liquid layer thinner than the equilibrium thickness on a high-density base liquid layer, and thus forming a gel layer thinner than the equilibrium thickness.
  • the raw material liquid layer formed of the raw material liquid of the gel is surrounded by a mold of a base liquid layer having a higher density than the raw material liquid layer.
  • the raw material liquid layer is pressed against the surface by a press member arranged on the raw material liquid layer, the raw material liquid layer is thinned to a thickness less than the equilibrium thickness, and the raw material liquid layer is pressed against the liquid surface of the base liquid layer by the press member. Is gelled on the liquid surface of the base liquid layer.
  • the gel manufacturing apparatus supplies a mold that surrounds the outer periphery of the liquid surface of the base liquid layer having a higher density than the raw material liquid of the gel, and the raw material liquid inside the mold. Then, the raw material liquid supply unit that forms the raw material liquid layer on the liquid surface of the base liquid layer and the raw material liquid layer are pressed against the liquid surface of the base liquid layer from above the raw material liquid layer, and the raw material liquid layer is pressed. Promotion of gelation by gelling the press member for thinning to a thickness less than the equilibrium thickness and the raw material liquid layer pressed against the liquid surface of the base liquid layer by the press member on the liquid surface of the base liquid layer. It has a part and.
  • the press member includes a flexible sheet in contact with the upper surface of the raw material liquid layer and a rigid plate that holds the flexible sheet flat from above. Including.
  • the support plate has a plurality of through holes penetrating the front and back surfaces of the support plate at intervals in the main surface direction of the support plate.
  • a raw material liquid layer thinner than the equilibrium thickness can be formed on the high-density base liquid layer, and thus a gel layer thinner than the equilibrium thickness can be formed.
  • FIG. 1A is a cross-sectional view showing a gel manufacturing apparatus according to an embodiment, and is a cross-sectional view showing a state before thinning of the raw material liquid layer.
  • FIG. 1B is a cross-sectional view showing a state after thinning of the raw material liquid layer shown in FIG. 1A.
  • FIG. 2A is a cross-sectional view showing an example of a base liquid supply unit and a recovery unit, and is a cross-sectional view showing a state of the base liquid layer before the liquid level rises.
  • FIG. 2B is a cross-sectional view showing a state of the base liquid layer shown in FIG. 2A after the liquid level rises.
  • FIG. 3 is a flowchart showing a method for producing a gel according to an embodiment.
  • FIG. 3 is a flowchart showing a method for producing a gel according to an embodiment.
  • FIG. 4A is a cross-sectional view showing an example of force balance when the raw material liquid layer is separated from the entire inner circumference of the mold.
  • FIG. 4B is a cross-sectional view showing an example of force balance when the raw material liquid layer is in contact with the entire inner circumference of the mold.
  • FIG. 4C is a cross-sectional view showing an example of an operation of peeling the flexible sheet from the raw material liquid layer.
  • FIG. 4D is a cross-sectional view showing an example of the balance of the forces of the raw material liquid layer after the press member is removed.
  • FIG. 5 is a cross-sectional view showing an example of unevenness formed on the side surface of the mold.
  • FIG. 6 is a cross section showing another example of the force balance of the raw material liquid layer in the state where the press member is placed.
  • FIG. 7 is a flowchart showing a method for producing a gel according to a modified example.
  • FIG. 8A is a cross-sectional view showing an example of mounting (S2) of the press member shown in FIG. 7.
  • FIG. 8B is a cross-sectional view showing an example of the formation (S1) of the raw material liquid layer shown in FIG. 7.
  • FIG. 9 is a flowchart showing an example of a method for producing xerogel, following FIG. 3 or FIG.
  • FIG. 10 is a cross-sectional view showing an example of taking out the gel from the mold.
  • FIG. 11 is a cross-sectional view showing another example of removing the gel from the mold.
  • Gel includes both “wet gel” and “xerogel”.
  • Weight gel means a gel in which the three-dimensional network is swollen by a swelling agent. It includes hydrogels in which the swelling agent is water, alcohol gels in which the swelling agent is alcohol, and organogels in which the swelling agent is an organic solvent.
  • Xerogel is a technical term for the structure and process of sol, gel, mesh, and inorganic-organic composite materials of the "International Union of Pure and Applied Chemistry (IUPAC) Inorganic Chemistry Subcommittee and Polymer Subcommittee, Polymer Terminology Subcommittee”. According to the definition (IUPAC Recommendation 2007), it means "a gel consisting of an open network formed by removing a swelling agent from a gel.” There is also a classification method in which the swelling agent is removed by supercritical drying is referred to as airgel, the swelling agent is removed by normal evaporation drying as xerogel, and the swelling agent is removed by freeze-drying as cryogel. In the scope of claims, these are collectively referred to as xerogel.
  • “Surface tension” is the force acting on the boundary between a liquid or solid and a gas (for example, air).
  • the X-axis direction, Y-axis direction, and Z-axis direction are perpendicular to each other.
  • the X-axis direction and the Y-axis direction are horizontal directions, and the Z-axis direction is a vertical direction.
  • the raw material liquid layer A is thinned and subsequently gelled on the liquid surface of the base liquid layer B having a higher density than the raw material liquid layer A, and becomes a gel layer C. Become.
  • the manufacturing apparatus 1 has an accommodating portion 2 accommodating the base liquid layer B.
  • the accommodating portion 2 includes, for example, a mold 21 and a bottom lid 22 that closes the opening of the mold 21 from below.
  • the formwork 21 projects upward from the entire peripheral edge of the bottom lid 22.
  • the bottom lid 22 supports the base liquid layer B from below and is in contact with the lower surface of the base liquid layer B.
  • the mold 21 surrounds the outer periphery of the liquid surface of the base liquid layer B.
  • the raw material liquid layer A is formed on the liquid surface.
  • the raw material liquid layer A is thinned and then gelled to become a gel layer C. Therefore, the shape and size of the opening of the mold 21 are appropriately determined according to the shape and size of the gel layer C which is a product.
  • Examples of the shape of the opening of the mold 21 include a rectangle, a circle, and an ellipse in a plan view. Rectangle includes not only those with right angles but also those with rounded corners. Rectangle includes square.
  • the height of the mold 21 is determined to be higher than the upper surface of the raw material liquid layer A before thinning shown in FIG. 1A. Since the raw material liquid layer A before thinning it is formed on a part of the liquid surface of the base liquid layer B, thickness H A raw material liquid layer A before thinning is equilibrium thickness H A0.
  • the material of the mold 21 is not particularly limited as long as it does not deteriorate or swell due to the raw material liquid and the base liquid and does not react with the raw material liquid layer A and the base liquid layer B, and is not particularly limited to metal, resin, rubber, glass, and the like. And ceramic or the like.
  • a metal such as stainless steel is suitable from the viewpoint of load bearing capacity.
  • the side surface of the metal mold 21 may be coated with a resin.
  • the material of the mold 21 may be any material that can withstand the heating temperature of the raw material liquid layer A.
  • the material of the bottom lid 22 may be the same as that of the mold 21.
  • the manufacturing apparatus 1 has a raw material liquid supply unit 3 that supplies the raw material liquid of the gel onto the liquid surface of the base liquid layer B.
  • the total feed volume V A of the raw material liquid for example, obtained from the volume V C of the gel layer C is a product, a volumetric shrinkage r from the raw material liquid layer A to the gel layer C.
  • Volumetric shrinkage r is the difference between the volume V A before shrinkage and the volume V C after shrinking (V A -V C), divided by the volume V A before shrinkage value ((V A -V C) / VA ), which is obtained in advance by experiments and the like.
  • the total feed weight W A raw material liquid may be, for example, the total supply volume V A raw material liquid is determined as the product of the density [rho A raw material liquid.
  • the density ⁇ A of the raw material liquid is determined in advance by an experiment or the like.
  • the raw material liquid supply unit 3 forms the raw material liquid layer A on a part of the liquid surface of the base liquid layer B. If the raw material liquid layer A is formed on a part of the liquid surface of the base liquid layer B, the raw material liquid layer A can be expanded and the raw material liquid layer A can be thinned as shown in FIG. 1B. Since the base liquid layer B has a higher density than the raw material liquid layer A, the raw material liquid layer A can be stably formed on the base liquid layer B.
  • the liquid level of the base liquid layer B is naturally adjusted horizontally by gravity, a flat and uniform raw material liquid layer A can be easily obtained by using the horizontal liquid level. Further, since the liquid surface of the base liquid layer B flows according to the expansion and contraction of the raw material liquid layer A during gelation and the removal of the gel layer C, the stress applied to the gel layer C is small and the gel layer C is defective. Less is. Further, since the entire lower surface of the gel layer C is supported horizontally, the area of the gel layer C can be increased.
  • the gel layer C obtained on the liquid surface of the base liquid layer B is a wet gel containing a solvent as a swelling agent.
  • the thickness of the wet gel is, for example, 0.1 mm to 20 mm, preferably 0.5 mm to 10 mm.
  • the wet gel is dried to a xerogel.
  • the thickness of the xerogel is, for example, 0.1 mm to 20 mm, preferably 0.5 mm to 10 mm.
  • the xerogel may be a porous monolith having transparency and heat insulating properties. Xerogel having transparency and heat insulating property is used as a transparent heat insulating material in, for example, window glass for automobiles and window glass for buildings.
  • the transmittance of xerogel at a wavelength of 500 nm is preferably 70% or more, preferably 80% or more, and preferably 90% or more in terms of thickness of 1 mm.
  • the transmittance is measured in accordance with the Japanese Industrial Standards (JIS R 3106: 1998).
  • xerogel examples include filters, adsorbents, sound absorbing materials, moisture absorbing materials, oil absorbing materials, and separation membranes, in addition to heat insulating materials.
  • Xerogel may not be transparent or may be opaque depending on the application.
  • xerogel The type of xerogel is (1) polysiloxane xerogel in the present embodiment, but may be (2) polymer xerogel or (3) polysaccharide xerogel such as cellulose xerogel.
  • the raw material liquid contains, for example, a gel raw material (hereinafter, also referred to as "gel raw material") and a solvent for dissolving the gel raw material.
  • the gel raw material is appropriately selected according to the type of xerogel finally obtained.
  • the solvent is, for example, water or an organic solvent.
  • organic solvent examples include alcohols (methanol, ethanol, isopropyl alcohol, tert-butyl alcohol, benzyl alcohol, etc.), aprotic polar organic solvents (N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, etc.), Examples thereof include ketones (cyclopentanone, cyclohexanone, methylethylketone, methylisobutylketone, acetone, etc.), hydrocarbons (n-hexane, heptane, etc.) and the like.
  • alcohols methanol, ethanol, isopropyl alcohol, tert-butyl alcohol, benzyl alcohol, etc.
  • aprotic polar organic solvents N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, etc.
  • ketones cyclopentanone, cyclohexanone, methylethylketone,
  • examples of the gel raw material include those containing (1A) a silane compound and (1B) a catalyst. (1B) The catalyst is for uniformly promoting gelation.
  • the gel raw material may further contain (1C) a surfactant.
  • silane compound examples include alkoxysilane, a 6-membered ring-containing silane compound having a 6-membered ring-containing skeleton and a hydrolyzable silyl group, and a silyl group-containing polymer having an organic polymer skeleton and a hydrolyzable silyl group. Can be mentioned.
  • alkoxysilane examples include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), monoalkyltrialkoxysilane (methyltrimethoxysilane, methyltriethoxysilane, etc.), and dialkyldialkoxysilane (dimethyldimethoxysilane, dimethyldiethoxysilane, etc.).
  • trimethoxyphenylsilane compounds having alkoxysilyl groups at both ends of the alkylene group (1,6-bis (trimethoxysilyl) hexane, 1,6-bis (methyldimethoxysilyl) hexane, 1,6-bis (Methyldiethoxysilyl) hexane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (methyldimethoxysilyl) ethane, 1,2-bis (methyldiethoxysilyl) ethane, etc.), perfluoropolyether Alkoxysilane having a group (perfluoropolyether triethoxysilane, perfluoropolyether methyldiethoxysilane, etc.), alkoxysilane having a perfluoroalkyl group (perfluoroethyltriethoxysilane, etc.), pentafluorophenylethoxydimethylsi
  • the 6-membered ring-containing skeleton in the 6-membered ring-containing silane compound is an organic skeleton having at least one 6-membered ring selected from the group consisting of an isocyanul ring, a triazine ring and a benzene ring.
  • the organic polymer skeleton in the silyl group-containing polymer is an organic skeleton having at least one chain selected from the group consisting of polyethylene chains, polyether chains, polyester chains and polycarbonate chains.
  • Examples of the (1B) catalyst include a base catalyst and an acid catalyst, and an aqueous solution thereof may be used.
  • the base catalyst include amines (triethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc.), urea, ammonia, sodium hydroxide, potassium hydroxide and the like.
  • the acid catalyst include inorganic acids (nitric acid, sulfuric acid, hydrochloric acid, etc.) and organic acids (girate, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, trifluoroacetic acid, etc.).
  • (1C) surfactant examples include hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, Pluronic F127 (trade name of BASF), EH-208 (trade name of NOF Corporation) and the like.
  • the gel raw material includes a thermoplastic resin, a curable resin, and the like.
  • thermoplastic resin examples include those capable of dissolving in a solvent when heated and forming a monolith (porous body) when cooled, and specific examples thereof include polymethylmethacrylate and polystyrene.
  • Examples of the curable resin include a photocurable resin and a thermosetting resin.
  • Examples of the photocurable resin include those containing either one or both of acrylate and methacrylate and a photopolymerization initiator.
  • Examples of the thermosetting resin include those containing one or both of acrylate and methacrylate and a thermal polymerization initiator, an addition condensate of resorcinol and formaldehyde, and an addition condensate of melamine and formaldehyde. Be done.
  • examples of the gel raw material include those containing (3A) polysaccharide nanofibers and (3B) acid.
  • examples of polysaccharides include chitin, chitosan, and gellan gum in addition to cellulose.
  • Examples of the (3A) polysaccharide nanofiber include 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) oxidized cellulose nanofiber.
  • Examples of the (3A) polysaccharide nanofiber include chitin nanofiber and chitosan nanofiber in addition to cellulose nanofiber.
  • Examples of the (3B) acid include the inorganic acid and the organic acid. Bases can be used instead of acids.
  • the base liquid layer B preferably has a large density difference from the raw material liquid layer A so that the raw material liquid layer A can stably exist on the base liquid layer B.
  • the density difference is preferably 0.1 g / cm 3 or more, and more preferably 0.5 g / cm 3 or more. From the viewpoint of weight reduction, the density difference is preferably 3.0 g / cm 3 or less, and more preferably 2.0 g / cm 3 or less.
  • the base liquid layer B preferably has low compatibility with the raw material liquid layer A so that the raw material liquid layer A can stably exist on the base liquid layer B.
  • the compatibility between the base liquid layer B and the raw material liquid layer A can be estimated by the upper limit amount of the raw material liquid dissolved in 100 g of the liquid of the base liquid layer B.
  • the upper limit is preferably 100 g or less, more preferably 10 g or less, and even more preferably 1 g or less.
  • the upper limit amount is 100 g or less, the separated state of the base liquid layer B and the raw material liquid layer A can be maintained for a long time.
  • the lower the upper limit is, the better, and it may be 0 g.
  • the base liquid layer B preferably contains substantially no gel raw material.
  • the fact that the gel raw material is substantially not contained means that the gel raw material other than the gel raw material transferred from the raw material liquid layer A is not contained.
  • the base liquid is appropriately selected according to the solvent of the raw material liquid.
  • the base liquid include a liquid compound having a fluorine atom, a liquid compound having a chlorine atom, a liquid compound having a silicon atom, water, mercury, etc., and if there is a density difference from the raw material liquid, fluorine, chlorine, bromine, etc. Alternatively, it does not need to contain a halogen atom such as iodine or a silicon atom.
  • the water may contain water-soluble salts to adjust the density of the base liquid layer B. Examples of the water-soluble salt include sodium chloride and the like.
  • the liquid compound having a fluorine atom is excellent in that it has high density, high boiling point, high heat-resistant decomposition property, and nonflammability.
  • Examples of the liquid compound having a fluorine atom include a fluorine-based solvent and a fluorine-based oil.
  • Fluorine-based solvents include hydrofluoroalkanes, chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluoromonoethers, perfluoromonoethers, perfluoroalkanes, perfluoropolyethers, perfluoroamines, fluorine atom-containing alkenes, fluorine atom-containing aromatic compounds, and fluorine. Examples thereof include atom-containing ketones and fluorine atom-containing esters.
  • fluorine-based oils examples include Solvay's brand name Fomblin and Daikin Industries' brand name Demnum and Daikin Industries.
  • liquid compound having a chlorine atom examples include chlorine-based solvents and chlorine-based oils.
  • chlorine-based solvent examples include carbon tetrachloride, chloroform, methylene chloride and the like.
  • Examples of the liquid compound having a silicon atom include silicone oil and the like.
  • Examples of the silicone oil include dimethyl silicone oil and methyl phenyl silicone oil.
  • Examples of commercially available silicone oil products include KF-96, which is a trade name of Shin-Etsu Chemical Co., Ltd.
  • the thickness of the base liquid layer B may be, for example, 10 mm or more so that the raw material liquid does not break through the base liquid layer B and reach the bottom lid 22 when the raw material liquid is supplied. This is because when the raw material liquid reaches the bottom lid 22, it adheres to the bottom lid 22 due to the wetting effect and remains submerged. If the thickness of the base liquid layer B is thick, the supply speed of the raw material liquid can be increased.
  • the raw material liquid supply unit 3 includes, for example, a storage tank 31 for temporarily storing the raw material liquid.
  • the storage tank 31 may be, for example, a mixing tank that mixes the (1A) silane compound and the (1B) catalyst.
  • the mixing tank may include a cooling device for cooling the raw material liquid in order to suppress the progress of gelation.
  • the temperature of the mixing tank is preferably lower from the viewpoint of suppressing the progress of gelation, but may be set higher than the freezing point of the raw material liquid from the viewpoint of preventing freezing, for example, 0 ° C. to 20 ° C.
  • the mixing tank may include a stirrer for stirring the raw material liquid.
  • the silane compound and the catalyst can be mixed in a short time, and the raw material liquid can be homogenized in a short time.
  • the mixing tank is connected to the silane compound supply source via the first pipe, and is connected to the catalyst supply source via the second pipe.
  • the first pipe is provided with a first flow rate controller that controls the flow rate of the silane compound
  • the second pipe is provided with a second flow rate controller that controls the flow rate of the catalyst. Since the flow rate of the silane compound and the flow rate of the catalyst can be controlled, the residence time in the mixing tank can be shortened.
  • the flow rate of the silane compound and the flow rate of the catalyst are appropriately determined according to the flow rate of the raw material liquid supplied on the base liquid layer B.
  • the raw material liquid supply unit 3 includes a discharge nozzle 32 that supplies the raw material liquid supplied from the storage tank 31 to the inside of the mold 21.
  • the discharge nozzle 32 supplies the raw material liquid onto the liquid surface of the base liquid layer B.
  • the discharge nozzle 32 may be arranged at a position close to the liquid surface of the base liquid layer B and may be arranged inside the mold 21 so that the raw material liquid does not break through the base liquid layer B when the raw material liquid is supplied. ..
  • the discharge nozzle 32 is arranged inside the mold 21 as shown in FIG. 1A, and when the raw material liquid is supplied, the discharge nozzle 32 is configured to be movable between a position where the raw material liquid is supplied and a position outside the mold 21. May be done.
  • the discharge nozzle 32 can be retracted to the outside of the mold 21 and interference between the discharge nozzle 32 and the press member 4 can be prevented.
  • the gel layer C is taken out from the mold 21 after the raw material liquid layer A is gelled, the discharge nozzle 32 can be retracted to the outside of the mold 21 and interference between the discharge nozzle 32 and the gel layer C can be prevented. ..
  • the raw material liquid supply unit 3 includes a supply pump 34 that sends the raw material liquid in the middle of the supply line 33 that connects the storage tank 31 and the discharge nozzle 32.
  • the supply pump 34 When the supply pump 34 is operated, the discharge nozzle 32 discharges the raw material liquid.
  • the discharge nozzle 32 stops the discharge of the raw material liquid.
  • the raw material liquid supply unit 3 may include a flow meter for measuring the flow rate of the raw material liquid in the middle of the supply line 33.
  • the flow rate may be either a volume flow rate or a mass flow rate.
  • the raw material liquid supply unit 3 may include a mass meter for measuring the mass change of the storage tank 31. Since the mass reduction amount of the storage tank 31 is equal to the total supply mass of the raw material liquid, it is possible to check whether or not the total supply mass of the raw material liquid has reached the target value. When the total supply mass of the raw material liquid reaches the target value, the supply of the raw material liquid is stopped.
  • the manufacturing apparatus 1 has a press member 4 that presses the raw material liquid layer A against the liquid surface of the base liquid layer B from above the raw material liquid layer A.
  • the press member 4 is placed on the raw material liquid layer A and presses the raw material liquid layer A against the liquid surface of the base liquid layer B.
  • the raw material liquid layer A is expanded by the weight of the press member 4. Since the lower surface of the press member 4 comes into contact with the raw material liquid layer A, it may be a flat surface.
  • the laminate of the press member 4 and the raw material liquid layer A is floated on the base liquid layer B.
  • the lower surface of the press member 4 becomes horizontal, so that a flat and uniform raw material liquid layer A can be obtained.
  • the press member 4 may be pushed evenly from above, but may not be pushed. This is because if the lower surface of the press member 4 is tilted by pushing the press member 4 from above, at least the upper surface of the raw material liquid layer A is tilted, and the thickness of the raw material liquid layer A becomes non-uniform. ..
  • the density of the press member 4 may be lower or higher than the density of the base liquid layer B as long as the laminate of the press member 4 and the raw material liquid layer A floats on the base liquid layer B, but it is preferably small. If the density of the press member 4 is smaller than the density of the base liquid layer B, the laminate of the press member 4 and the raw material liquid layer A can be reliably floated on the base liquid layer B.
  • the density of the press member 4 may be smaller or higher than the density of the raw material liquid layer A, but is preferably smaller. If the density of the press member 4 is smaller than the density of the raw material liquid layer A, it is possible to prevent the raw material liquid of the raw material liquid layer A from wrapping around above the press member 4.
  • the inside of the press member may be porous so that the density of the press member 4 becomes small. However, since the lower surface of the press member 4 comes into contact with the raw material liquid layer A, it may be dense so that the raw material liquid does not infiltrate. That is, the press member 4 may have a porous inside and a dense surface. Specific examples include foamed resins such as Styrofoam.
  • the material of the press member 4 is not particularly limited as long as it does not deteriorate or swell due to the raw material liquid and the base liquid and does not react with the raw material liquid layer A and the base liquid layer B, similarly to the material of the mold 21. , Metal, resin, rubber, glass, ceramic and the like.
  • the press member 4 is opaque in this embodiment, but may be transparent. If the press member 4 is transparent, the state below the press member 4 can be confirmed from above the press member 4.
  • the adsorption force between the press member 4 and the raw material liquid layer A depends on the surface tension of the raw material liquid layer A in addition to the surface tension of the lower surface of the press member 4, and the contact angle of the raw material liquid with respect to the lower surface of the press member 4 The larger the value, the smaller the adsorption force.
  • the press member 4 is removed from the raw material liquid layer A before the raw material liquid layer A is gelled, but after the raw material liquid layer A is gelled, the press member 4 is removed from the gel layer C. May be good. Also in the latter case, the smaller the surface tension of the lower surface of the press member 4, the smaller the adsorption force between the lower surface of the press member 4 and the raw material liquid layer A. Therefore, from the gel layer C obtained by gelling the raw material liquid layer A. The press member 4 can be easily removed.
  • the material of the lower surface of the press member 4 may be, for example, fluororesin in order to reduce the surface tension thereof.
  • the press member 4 may be entirely made of fluororesin, or may be a base material such as metal coated with fluororesin.
  • As the coating agent in addition to the fluororesin, a water-repellent coating agent or an oil-repellent coating agent can also be used.
  • the press member 4 may have a single-layer structure, but in the present embodiment, it has a multi-layer structure. As shown in FIGS. 1A and 1B, the press member 4 includes a flexible sheet 41 in contact with the upper surface of the raw material liquid layer A and a rigid plate 42 that holds the flexible sheet 41 flat from above. The rigid plate 42 and the flexible sheet 41 may be adhered by an adhesive, an anchor effect, hydrogen bonds, surface tension, static electricity, or the like. Further, after the flexible sheet 41 is floated on the raw material liquid layer A by a density difference or surface tension, the rigid plate 42 may be placed on the flexible sheet 41.
  • the flexible sheet 41 is not particularly limited as long as it has flexibility, but since it is in contact with the upper surface of the raw material liquid layer A, it may be, for example, a fluororesin sheet in order to reduce its surface tension.
  • the rigid plate 42 is not particularly limited as long as it does not deform so as to hold the flexible sheet 41 flat from above. Further, another member may be arranged between the rigid plate 42 and the flexible sheet 41.
  • the rigid plate 42 holds the flexible sheet 41 flat from above, so that the press member 4 uses the raw material.
  • the liquid layer A can be pressed flat.
  • the rigid plate 42 is first lifted and removed from the flexible sheet 41.
  • the flexible sheet 41 is bent, and the flexible sheet 41 is gradually peeled off from one end to the other end of the upper surface of the raw material liquid layer A. Since the flexible sheet 41 is gradually peeled off, the stress applied to the raw material liquid layer A can be reduced, and the shape of the raw material liquid layer A can be suppressed from collapsing.
  • the rigid plate 42 can be removed from the flexible sheet 41, and then the flexible sheet 41 can be bent.
  • the flexible sheet 41 may be gradually peeled off from one end to the other end of the upper surface of the gel layer C. The stress related to the gel layer C can be reduced, and the shape collapse of the gel layer C can be suppressed.
  • the press member 4 When the press member 4 has a single-layer structure and includes only the rigid plate 42, the press member 4 is pressed so that the lower surface of the press member 4 is inclined instead of lifting the press member 4 while the lower surface of the press member 4 remains horizontal. The member 4 may be lifted. In the latter case, the stress applied to the raw material liquid layer A can be reduced and the shape collapse of the raw material liquid layer A can be suppressed as compared with the former case.
  • a through hole may be formed on the side surface of the mold 21, and the transparent member 23 may be fitted into the through hole.
  • the transparent member 23 is provided on the side of the raw material liquid layer A.
  • the raw material liquid layer A can be confirmed from the side through the transparent member 23.
  • the confirmation may be performed by the human eye or by a camera.
  • the transparent member 23 is arranged so as to project below the interface between the raw material liquid layer A and the base liquid layer B and protrude above the upper surface of the raw material liquid layer A, for example. The height of the liquid level of the base liquid layer B and the thickness of the raw material liquid layer A can be confirmed. The transparent member 23 may be arranged so as to project further upward than the press member 4 placed on the raw material liquid layer A. It can be confirmed whether or not the movement of the press member 4 is normal.
  • the material of the transparent member 23 is not particularly limited as long as it does not deteriorate or swell due to the raw material liquid and the base liquid and does not react with the raw material liquid layer A and the base liquid layer B, similarly to the material of the mold 21. , Resin, glass, etc. may be used.
  • the mold 21 may be transparent, in which case the transparent member 23 is unnecessary.
  • the transparent member 23 is provided when the mold 21 is opaque.
  • a gap S may exist between the outer circumference of the press member 4 and the inner circumference of the mold 21 as shown in FIG. 4B.
  • the gap S exists, the frictional resistance from the mold 21 can be reduced when the press member 4 moves up and down, and the press member 4 can move up and down smoothly. Further, if the gap S is present, air is likely to escape when the press member 4 moves up and down. Even if the gap S exists, the raw material liquid layer A can be brought into contact with the entire inner circumference of the mold 21 due to the surface tension of the raw material liquid layer A.
  • a handle for transporting or the like may be provided on the upper surface of the press member 4. It is easy to push the press member 4 from the outside of the mold 21 into the inside and to pull out the press member 4 from the inside of the mold 21 to the outside. These tasks may be performed by humans or by machines.
  • the manufacturing apparatus 1 may have a transport unit 5 for transporting the press member 4.
  • the transport unit 5 is, for example, a transport robot that pushes the press member 4 from the outside of the mold 21 into the inside and pulls out the press member 4 from the inside of the mold 21 to the outside. These operations can be performed automatically.
  • the manufacturing apparatus 1 includes a gelation promoting unit 6 that gels the diluted raw material liquid layer A on the liquid surface of the base liquid layer B.
  • the gel raw material contains (1A) a silane compound and (1B) a catalyst
  • gelation of the raw material liquid layer A is performed by heating.
  • the silane compound is hydrolyzed by an acid catalyst or the like to form a sol having a silanol group (Si—OH).
  • the sol is heated, the silanol groups undergo a dehydration condensation reaction between the molecules to form a Si—O—Si bond, and the raw material liquid layer A is gelled.
  • the gelation promoting unit 6 has, for example, a heater 61 for heating the raw material liquid layer A.
  • the heater 61 may be arranged outside the accommodating portion 2, may be arranged inside, or may be arranged both outside and inside.
  • the heater 61 When the heater 61 is arranged inside the accommodating portion 2, for example, it is arranged inside the base liquid layer B, and by heating the base liquid layer B, the raw material liquid layer A is heated from below.
  • the heater 61 When the heater 61 is arranged outside the accommodating portion 2, the heater 61 may be arranged at at least one of the upper, lateral, and lower parts of the raw material liquid layer A.
  • the heater 61 is preferably arranged so as to heat the raw material liquid layer A from both the upper and lower sides. Further, it is preferable that the heater 61 is arranged so as to heat the entire outer circumference of the raw material liquid layer A from the side.
  • the heating method of the heater 61 is not particularly limited, but is appropriately selected from, for example, a resistance heating type, an infrared heating type, an arc heating type, and the like according to the installation location of the heater 61.
  • the means for gelling the raw material liquid layer A is not limited to the heater, and is appropriately selected according to the type of the gel raw material.
  • the means for gelling the raw material liquid layer A is a cooler.
  • the cooler cools the raw material liquid layer A on the base liquid layer B and gels the raw material liquid layer A.
  • the cooler may be arranged and controlled in the same manner as the heater. Natural cooling may be performed instead of forced cooling by the cooler.
  • the means for gelling the raw material liquid layer A is a light source.
  • the light source irradiates the raw material liquid layer A existing on the base liquid layer B with light such as ultraviolet rays to cure the photocurable monomer and gel the raw material liquid layer A.
  • the light source may be arranged and controlled in the same manner as the heater.
  • the press member 4 or the like may be made of a transparent material so that the light reaches the raw material liquid layer A.
  • the means for gelling the raw material liquid layer A is a heater.
  • the gel raw material is a polysaccharide nanofiber
  • the polysaccharide nanofiber gels in a short time when it comes into contact with an acid catalyst or a base catalyst. Therefore, the raw material liquid may contain polysaccharide nanofibers and may not contain an acid catalyst or a base catalyst.
  • the acid catalyst or the base catalyst may be supplied in a shower shape from above to the raw material liquid layer A formed on the base liquid layer B.
  • the means for gelling the raw material liquid layer A is a feeder that supplies an acid catalyst or a base catalyst to the raw material liquid layer A from above. In this case, it is preferable to supply the acid catalyst or the base catalyst after removing the press member 4 from the raw material liquid layer A.
  • the outer periphery of the gel layer C may be peeled from the mold 21 by the curing shrinkage. Since the size of the gel layer C is smaller than the size of the opening of the mold 21, it is easy to take out the gel layer C from the mold 21.
  • the raw material liquid layer A may be cured and shrunk, and the solvent may be extruded from the inside of the gel layer C.
  • the solvent itself is easy to evaporate, but the catalyst or surfactant dissolved in the solvent suppresses the evaporation of the solvent.
  • the solvent extruded from the inside of the gel layer C accumulates on the liquid surface of the base liquid layer B even after the gel layer C is taken out from the liquid surface of the base liquid layer B, and the solvent is accumulated on the liquid surface of the raw material liquid layer A from the next time onward. Can inhibit formation or gelation.
  • the manufacturing apparatus 1 takes out the gel layer C from above the liquid surface of the base liquid layer B, and then removes the solvent of the raw material liquid that accumulates on the liquid surface, as shown in FIGS. 2A and 2B.
  • the base liquid may be supplied to the inside of the accommodating portion 2. Since the thickness of the base liquid layer B increases from the thickness shown in FIG. 2A to the thickness shown in FIG. 2B due to the supply of the base liquid, the liquid accumulated on the liquid surface of the base liquid layer B overflows from the upper end of the accommodating portion 2. , Will be removed. This operation may be performed on a regular basis.
  • the manufacturing apparatus 1 has a base liquid supply unit 7 that supplies the base liquid inside the accommodating unit 2.
  • the base liquid supply unit 7 includes, for example, a storage tank 71 for temporarily storing the base liquid and a supply nozzle 72 for supplying the base liquid supplied from the storage tank 71 to the inside of the storage unit 2.
  • the supply nozzle 72 applies the base liquid below the liquid level of the base liquid layer B in order to prevent the solvent of the raw material liquid that collects on the liquid surface of the base liquid layer B from being mixed with the newly supplied base liquid. Discharge.
  • the base liquid supply unit 7 includes a supply pump 74 that sends the base liquid in the middle of the supply line 73 that connects the storage tank 71 and the supply nozzle 72.
  • a supply pump 74 that sends the base liquid in the middle of the supply line 73 that connects the storage tank 71 and the supply nozzle 72.
  • the supply pump 74 When the supply pump 74 is operated, the supply nozzle 72 discharges the base liquid.
  • the supply nozzle 72 stops the discharge of the base liquid.
  • the base liquid supply unit 7 supplies the base liquid to the inside of the storage unit 2 until, for example, the liquid level of the base liquid layer B is equal to or higher than the lowest portion of the upper end of the storage unit 2.
  • the height of a part of the upper end of the accommodating portion 2 is lower than the height of the rest so that the liquid overflows from a specific portion. That is, a notch N is formed in a part of the upper end of the accommodating portion 2, and the liquid overflows from the notch N.
  • the manufacturing apparatus 1 may have a recovery unit 8 for collecting the liquid overflowing from the upper end of the storage unit 2 in order to keep the periphery of the storage unit 2 clean.
  • the collecting unit 8 collects the liquid that has overflowed from a specific portion of the upper end of the accommodating unit 2. Since the recovered liquid contains a plurality of components, it may be discarded, or it may be purified and then recycled.
  • the manufacturing apparatus 1 has a drainage line 75 for discharging the base liquid from the base liquid layer B and an on-off valve 76 provided in the middle of the drainage line 75 in order to return the thickness of the base liquid layer B to the original thickness. You can do it.
  • the on-off valve 76 When the on-off valve 76 is opened, the base liquid is discharged from the base liquid layer B, and the thickness of the base liquid layer B returns to the original thickness. The discharged base liquid may be discarded or may be recycled.
  • the supply nozzle 72 can discharge the base liquid from the base liquid layer B and send it back to the storage tank 71. In this case, the drainage line 75 and the on-off valve 76 are unnecessary.
  • the base liquid supply unit 7, the recovery unit 8, and the like may not be necessary, and may be installed according to the type of gel.
  • the gel production method includes, for example, formation of the raw material liquid layer A (S1), placement of the press member 4 (S2), removal of the press member 4 (S3), and raw material liquid layer. It has gelation of A (S4).
  • the order of the processes shown in FIG. 3 is not particularly limited.
  • the press member 4 may be removed (S3) after the raw material liquid layer A is gelled (S4).
  • the raw material liquid layer A is formed on a part of the liquid surface of the base liquid layer B.
  • the raw material liquid layer A is separated from the entire inner circumference of the mold 21 in FIG. 4A, it may be formed on a part of the liquid surface of the base liquid layer B and is in contact with only a part of the inner circumference of the mold 21. You may.
  • the thickness HA of the raw material liquid layer A becomes the equilibrium thickness HA 0 .
  • the first inward force F1 and the first outward force F2 are balanced over the entire outer circumference of the raw material liquid layer A.
  • the first inward force F1 is caused by the surface tension of the material liquid layer A, reduced the material liquid layer A inwardly, increasing the thickness H A raw material liquid layer A.
  • the first outward force F2 is caused by gravity, spread the material liquid layer A outwardly, reducing the thickness H A raw material liquid layer A.
  • the first outward force F2 because caused by gravity, dependent on the thickness H A raw material liquid layer A. The thicker the thickness HA , the larger the first outward force F2.
  • the thickness HA of the raw material liquid layer A becomes the equilibrium thickness HA 0 .
  • the press member 4 (S2), for example, as shown in FIG. 4B, the press member 4 is placed on the raw material liquid layer A, the raw material liquid layer A is spread by the press member 4, and the thickness is equal to HA0. Dilute.
  • the thickness HA of the raw material liquid layer A before thinning is equal to or greater than the equilibrium thickness HA 0 as shown in FIG. 4A. Further, the entire outer circumference of the raw material liquid layer A is in contact with the mold 21.
  • the press member 4 when the press member 4 is placed on the raw material liquid layer A, the raw material liquid layer A is expanded by the weight of the press member 4, so that the second outer circumference of the raw material liquid layer A is entirely covered.
  • the directional force F3 acts. Since the second outward force F3 is generated by the weight W of the press member 4, it depends on the weight W of the press member 4. The heavier the weight W of the press member 4, the larger the second outward force F3.
  • the mold 21 is the raw material liquid.
  • the layer A is pushed back, and the pushing back produces a second inward force F5.
  • the second inward force F5 may be zero because it is generated to keep the forces in balance, in other words, to adjust the balance.
  • the press member 4 In the removal of the press member 4 (S3), for example, as shown in FIG. 4C, the press member 4 is removed from the raw material liquid layer A.
  • the press member 4 is lifted and removed from the raw material liquid layer A, for example, the rigid plate 42 is first lifted and removed from the flexible sheet 41.
  • the flexible sheet 41 is bent, and the flexible sheet 41 is gradually peeled off from one end to the other end of the upper surface of the raw material liquid layer A. Since the flexible sheet 41 is gradually peeled off, the stress applied to the raw material liquid layer A can be reduced, and the shape of the raw material liquid layer A can be suppressed from collapsing.
  • the second but outward force F3 disappears, can be maintained so that it remains third outward force F4 is generated, the thickness H A raw material liquid layer A thin state than the equilibrium thickness H A0 ..
  • the entire outer circumference of the raw material liquid layer A is in contact with the entire inner circumference of the mold 21 so that the third outward force F4 acts on the entire outer circumference of the raw material liquid layer A.
  • the raw material liquid layer A does not have to be completely in contact with the entire inner circumference of the mold 21, and the raw material liquid layer A is inside the mold 21 to the extent that the raw material liquid layer A is not torn when the press member 4 is removed. It suffices to substantially touch the entire circumference. In other words, the entire outer circumference of the raw material liquid layer A may be substantially in contact with the mold 21 so that the raw material liquid layer A is not torn when the press member 4 is removed. If there are some small bubbles at the interface between the raw material liquid layer A and the mold 21, the raw material liquid layer A will not be torn when the press member 4 is removed. In addition, a gap that can be immediately filled with fluctuations in the system is allowed.
  • the third outward force F4 decreases.
  • the thickness HA of the raw material liquid layer A is set so that the resultant force of the first outward force F2 and the third outward force F4 is equal to or greater than the first inward force F1. This is because if the resultant force becomes smaller than the first inward force F1, the balance of the forces is lost and the raw material liquid layer A is broken.
  • the third outward force F4 depends on the surface tension of the raw material liquid layer A in addition to the surface tension of the mold 21, and the smaller the contact angle of the raw material liquid with respect to the mold 21, the better the wettability.
  • the directional force F4 increases.
  • the contact angle is preferably less than 90 °.
  • unevenness 211 may be formed on at least a portion of the side surface of the mold 21 that comes into contact with the raw material liquid layer A.
  • the shape of the unevenness 211 is triangular wavy in FIG. 5, but may be rectangular wavy or sinusoidal, and is not particularly limited. Since the contact area between the mold 21 and the raw material liquid layer A can be increased by the unevenness 211 and the third outward force F4 generated by adsorption can be increased, the thickness HA can be further reduced.
  • the shape of the upper surface of the bottom lid 22 is not transferred to the lower surface of the gel layer C. Therefore, the roughness of the upper surface of the bottom lid 22 does not matter, and special processing for smoothing the upper surface of the bottom lid 22 surrounded by the mold 21 is unnecessary.
  • the raw material liquid layer A is gelled on the liquid surface of the base liquid layer B with the press member 4 removed.
  • the gelling means is appropriately selected according to the type of gel raw material.
  • the press member 4 is removed (S3) before the raw material liquid layer A is gelled (S4), the upper surface of the raw material liquid layer A is naturally horizontal, and is flat and thick. A uniform gel layer C is obtained. Further, it is possible to prevent the surface shape of the lower surface of the press member 4 from being transferred to the gel layer C.
  • the press member 4 is removed (S3) before the raw material liquid layer A is gelled (S4), so that the entire outer circumference of the raw material liquid layer A is in contact with the mold 21. , The press member 4 spreads the raw material liquid layer A. Even it disappears second outward force F3 by removal of the pressing member 4, and the third outward force F4 remains, can maintain a thickness H A raw material liquid layer A thin state than the equilibrium thickness H A0.
  • the press member 4 is removed (S3) before the raw material liquid layer A is gelled (S4), but as described above, the raw material liquid layer is removed before the press member 4 is removed (S3). Gelation of A (S4) may be performed.
  • the raw material liquid layer A is gelled on the liquid surface of the base liquid layer B with the press member 4 placed therein. Since remains remained second outward force F3 during gelling, the second outward force F3 can utilize both third outward force F4, the thickness H A raw material liquid layer A may thinner.
  • the entire outer circumference of the raw material liquid layer A is formed from the mold 21 as shown in FIG. It may be separated.
  • the thickness H A raw material liquid layer A than the equilibrium thickness H A Can also be diluted.
  • the raw material liquid layer A is gelled and solidified before the press member 4 is removed. Since the gel layer C is harder than the raw material liquid layer A, it is possible to suppress the shape collapse of the press member 4 when it is removed.
  • the manufacturing method shown in FIG. 7 is different from the manufacturing method shown in FIG. 3, and the raw material liquid layer A is formed (S1) after the press member 4 is placed (S2).
  • the press member 4 In the placement of the press member 4 (S2), the press member 4 is floated on the base liquid layer B as shown in FIG. 8A. The press member 4 is in contact with the base liquid layer B, and the raw material liquid layer A does not exist between the press member 4 and the base liquid layer B.
  • the raw material liquid is supplied to the inside of the base liquid layer B in which the press member 4 is floated. Since the density of the raw material liquid is lower than the density of the base liquid, the raw material liquid floats from the inside of the base liquid layer B to the liquid surface of the base liquid layer B, and the raw material liquid is placed between the base liquid layer B and the press member 4. Layer A is formed.
  • the discharge nozzle 32 of the raw material liquid supply unit 3 may be inserted into a through hole that horizontally penetrates the mold 21, or may be inserted into a through hole that vertically penetrates the bottom lid 22. Good. In any case, the discharge nozzle 32 discharges the raw material liquid from below the liquid level of the base liquid layer B.
  • the transparent member 23 When the transparent member 23 is fitted into the through hole on the side surface of the mold 21, the transparent member 23 protrudes above the liquid level of the base liquid layer B and below the discharge port 321 of the discharge nozzle 32. May be placed in. It can be confirmed through the transparent member 23 that the raw material liquid is discharged from the discharge port 321 and then floats up to the liquid surface of the base liquid layer B.
  • the press member 4 When the raw material liquid layer A is formed between the base liquid layer B and the press member 4, the press member 4 is lifted upward. There is no air layer between the press member 4 and the raw material liquid layer A, and the press member 4 is placed on the raw material liquid layer A. The raw material liquid layer A is pressed against the liquid surface of the base liquid layer B by the press member 4 placed on the raw material liquid layer A. Therefore, the thickness H A raw material liquid layer A can be made thinner than the equilibrium thickness H A0.
  • the raw material liquid layer A is gelled (S4). As described in the explanation of FIG. 3, the raw material liquid layer A is gelled (S4). After S4), the press member 4 may be removed (S3).
  • a method for producing a gel includes, for example, removal of the gel layer C (S5), solvent substitution of the gel layer C (S6), and drying of the gel layer C (S7).
  • the method for producing the gel does not have to include all the treatments shown in FIG. 9.
  • the solvent of the raw material liquid is suitable for drying (S7)
  • the solvent substitution (S6) may not be carried out. ..
  • the method for producing a gel may include a treatment different from the treatment shown in FIG.
  • the gel layer C is lifted from the base liquid layer B and taken out from the mold 21. If the magnitude of the curing shrinkage of the raw material liquid layer A is large at the final stage of gelation (S4), the outer circumference of the gel layer C is peeled off from the mold 21, so the accommodating portion 2 is tilted as shown in FIG. Is unnecessary, and the gel layer C can be easily taken out.
  • the accommodating portion 2 includes a container 24 for accommodating the form 21, a support plate 25 installed under the form 21, and a support for supporting the support plate 25. It may have a rod 26 and the like.
  • the support plate 25 is used in place of the bottom lid 22 shown in FIGS. 1A and 1B, and the mold 21 is separably placed on the support plate 25.
  • the container 24 includes a bottom plate 241 and a side plate 242 extending upward from the entire peripheral edge of the bottom plate 241.
  • a base liquid layer B is formed inside the container 24, and a mold 21 surrounds a part of the liquid surface of the base liquid layer B.
  • the formwork 21 is arranged away from the side plate 242 of the container 24.
  • the raw material liquid layer A is formed inside the mold 21 and is not formed outside the mold 21.
  • the mold 21 projects downward from the interface between the raw material liquid layer A and the base liquid layer B, and protrudes upward from the upper surface of the raw material liquid layer A.
  • the support plate 25 is installed below the interface between the base liquid layer B and the raw material liquid layer A before forming the raw material liquid layer A on the liquid surface of the base liquid layer B.
  • the support plate 25 supports the gel layer C from below when the gel layer C is lifted from the base liquid layer B. Since the support plate 25 supports the gel layer C from below, it is possible to prevent the gel layer C from cracking due to gravity.
  • the support plate 25 may have a plurality of through holes H penetrating the front and back surfaces of the support plate 25 at intervals in the main surface direction of the support plate 25.
  • punching metal or wire mesh is used as the support plate 25.
  • the mold 21 is decomposed into a plurality of parts and the gel layer is formed. It can be removed from C. This is because the mold 21 is arranged away from the side plate 242 of the container 24, so that a work space for disassembling the mold 21 into a plurality of parts can be secured between the side plate 242 and the mold 21.
  • the mold 21 is decomposed into a plurality of parts.
  • the mold 21 can be removed from the gel layer C without disassembling.
  • the gel layer C can be supported by the support plate 25.
  • the support plate 25 and the gel layer C may be immersed in a solvent stored in a container different from the container 24 to carry out solvent substitution (S6).
  • the solvent can be replaced from the front and back sides of the gel layer C.
  • the solvent substitution (S6) can also be carried out inside the container 24.
  • the inside of the container 24 is temporarily emptied, and the solvent to be replaced with the solvent contained in the gel layer C is stored inside the container 24.
  • the solvent contained inside the gel layer C is water
  • the solvent replaced with water usually has a lower density than that of water, so that the gel layer C sinks in the solvent replaced with water, and the solvent replacement is efficient. Is done.
  • the support plate 25 has the through hole H, the solvent can be replaced from the front and back sides of the gel layer C.
  • solvent substitution the solvent contained inside the gel layer C is replaced with another solvent.
  • the gel layer C is a fine porous body and contains a solvent inside.
  • the solvent substitution (S6) is carried out before the drying (S7) for the purpose of suppressing the shrinkage of the gel layer C due to the surface tension of the solvent during drying and suppressing the fine structure of the gel layer C from being damaged. Will be implemented.
  • the solvent contained inside the gel layer C is replaced with a solvent suitable for gelation (that is, a solvent for the raw material solution) with a solvent suitable for drying.
  • a solvent suitable for gelation that is, a solvent for the raw material solution
  • a solvent suitable for drying that is, a solvent for the raw material solution
  • the solvent after the replacement is appropriately selected depending on the drying method.
  • the drying method supercritical drying, freeze drying, or atmospheric drying is used.
  • the solvent contained inside the gel layer C is replaced with a supercritical fluid.
  • a solvent suitable for supercritical drying for example, methanol, ethanol, isopropyl alcohol and the like are used.
  • the supercritical fluid carbon dioxide gas in a supercritical state is generally used. Supercritical drying is carried out inside a closed high-pressure container.
  • freeze-drying the solvent contained inside the gel layer C is frozen and then evaporated in a vacuum. This is usually called sublimation.
  • a solvent suitable for freeze-drying water, tert-butyl alcohol, cyclohexane, 1,4-dioxane, a fluorine-based solvent and the like are used. Freeze-drying is carried out inside a closed vacuum vessel.
  • the solvent contained inside the gel layer C is evaporated under normal pressure. Since it is important to reduce the shrinkage force of the fine skeleton of the gel layer C due to the capillary force accompanying solvent evaporation, a solvent having a small surface tension, for example, a low molecular weight fat such as hexane or heptane, is a solvent suitable for atmospheric drying. A group hydrocarbon solvent or a fluorine solvent is used. Since normal pressure drying is performed at normal pressure, a closed container is not required.
  • Solvent substitution is carried out at a temperature below the boiling point of the solvent in order to prevent the fine structure of the gel layer C from being damaged by boiling of the solvent.
  • the solvent may be heated at a temperature below the boiling point.
  • the heating temperature is, for example, 40 ° C to 100 ° C.
  • the number of times the solvent is replaced is once in this embodiment, but it may be a plurality of times. That is, the solvent contained inside the gel layer C is replaced from the solvent of the raw material liquid with a first solvent having a composition different from that of the solvent of the raw material liquid, and further, a solvent having a composition different from that of the solvent of the raw material liquid and the first solvent. It may be replaced with two solvents.
  • the compatibility between the solvent of the raw material solution and the second solvent is low, the substitution efficiency will be poor. Therefore, by temporarily introducing substitution with the first solvent during that time, the solvent of the raw material solution can be changed to the second solvent. The time required for replacement can be shortened.
  • the first solvent a solvent having high compatibility with both the solvent of the raw material liquid and the second solvent is used.
  • solvent replacement is not necessary.
  • drying the solvent contained inside the gel layer C is removed.
  • supercritical drying, freeze drying, or atmospheric drying is used as a method for drying the gel layer C.
  • atmospheric drying is excellent in that a closed container is not required.
  • Atmospheric pressure drying is carried out at a temperature below the boiling point of the solvent in order to prevent the fine structure of the gel layer C from being damaged by boiling of the solvent.
  • the gel layer C may be heated at a temperature below the boiling point.
  • the drying temperature of the gel layer C is, for example, room temperature to 100 ° C.
  • the gel layer C obtained after drying is a xerogel, which is a porous monolith.
  • Drying may be carried out with the gel layer C supported by the support plate 25.
  • the support plate 25 has a through hole H, the solvent can be removed from the front and back sides of the gel layer C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Colloid Chemistry (AREA)

Abstract

Un procédé de fabrication de gel comprend les étapes suivantes : au moyen d'un élément de pression disposé sur une couche de liquide de matière première formée d'un liquide de matière première de gel pour presser la couche de liquide de matière première contre une surface liquide d'une couche de liquide de base présentant une densité supérieure à celle de la couche de liquide de matière première, la surface liquide étant entourée sur la périphérie externe par un moule ; l'amincissement de la couche de liquide de matière première jusqu'à une épaisseur inférieure à une épaisseur d'équilibre ; et la gélification de la couche de liquide de matière première pressée contre la surface liquide de la couche de liquide de base par l'élément de pression sur la surface liquide de la couche de liquide de base.
PCT/JP2020/026457 2019-07-18 2020-07-06 Procédé de fabrication de gel et appareil de fabrication de gel WO2021010216A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-132668 2019-07-18
JP2019132668A JP2022126894A (ja) 2019-07-18 2019-07-18 ゲルの製造方法、及びゲルの製造装置

Publications (1)

Publication Number Publication Date
WO2021010216A1 true WO2021010216A1 (fr) 2021-01-21

Family

ID=74210508

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/026457 WO2021010216A1 (fr) 2019-07-18 2020-07-06 Procédé de fabrication de gel et appareil de fabrication de gel

Country Status (2)

Country Link
JP (1) JP2022126894A (fr)
WO (1) WO2021010216A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6097044A (ja) * 1979-03-26 1985-05-30 コ−ニング　グラス　ワ−クス 無機ゲルおよびその製造方法
JP2007296491A (ja) * 2006-05-02 2007-11-15 National Institute For Materials Science 保型容器およびそれを用いたコロイド結晶ゲルの製造方法
JP2012055847A (ja) * 2010-09-10 2012-03-22 Seiko Epson Corp ゲル製造装置及びゲル製造方法
WO2019044669A1 (fr) * 2017-09-01 2019-03-07 Ａｇｃ株式会社 Procédés de production de gel humide et de xérogel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6097044A (ja) * 1979-03-26 1985-05-30 コ−ニング　グラス　ワ−クス 無機ゲルおよびその製造方法
JP2007296491A (ja) * 2006-05-02 2007-11-15 National Institute For Materials Science 保型容器およびそれを用いたコロイド結晶ゲルの製造方法
JP2012055847A (ja) * 2010-09-10 2012-03-22 Seiko Epson Corp ゲル製造装置及びゲル製造方法
WO2019044669A1 (fr) * 2017-09-01 2019-03-07 Ａｇｃ株式会社 Procédés de production de gel humide et de xérogel

Also Published As

Publication number Publication date
JP2022126894A (ja) 2022-08-31

Similar Documents

Publication Publication Date Title
JP7001098B2 (ja) キセロゲル、断熱材及び合わせガラスの製造方法
JP6909875B2 (ja) シリカエアロゲルブランケットの製造方法及びその製造装置
JPWO2012161315A1 (ja) 微細凹凸構造を表面に有する物品の製造方法
TWI613511B (zh) 防塵薄膜組件
JP2013508144A (ja) 傾斜ナノボイド含有物品の製法
TW201521989A (zh) 脫模膜、及半導體封裝件之製造方法
JP2013531808A (ja) 基板のハイスループット、ミクロンスケールエッチングのためのステンシルならびにその製造方法および使用方法
WO2021010216A1 (fr) Procédé de fabrication de gel et appareil de fabrication de gel
CN105073856B (zh) 包含具有低摩擦系数表面的聚合物的制品和其制造方法
KR20200019850A (ko) 스테레오리소그래피 시스템에 사용하기 위한 용기
JP5549943B2 (ja) モールドの製造方法および微細凹凸構造を表面に有する物品の製造方法
WO2020261901A1 (fr) Procédé de production de gel et appareil de production de gel
WO2021010215A1 (fr) Procédé de production de gel et dispositif de production de gel
WO2021010214A1 (fr) Procédé et dispositif de production de gel
CN110256724B (zh) 一种用于光固化连续面成型3d打印的防粘附薄膜制备方法
US20200190276A1 (en) Durable superhydrophobic surfaces
WO2020261900A1 (fr) Procédé de production de gel et dispositif de production de gel
WO2020261899A1 (fr) Procédé de production de gel et dispositif de production de gel
JP6954292B2 (ja) 含フッ素重合体、その製造方法、および含フッ素重合体の硬化物を備える物品
JP2004000833A (ja) 塗布物の製造法
Nakagawa et al. Investigation of nonreactive fluoroalkyl-containing surfactants for reducing release energy of ultraviolet-cured acrylate resins
JP2023000851A (ja) 透明シート、合わせガラス、合わせガラスの製造方法、及びガラス積層板
JP3209296B2 (ja) ガラス容器の強化方法
Bartali et al. Graphene as Barrier to Prevent Volume Increment of Air Bubbles over Silicone Polymer in Aqueous Environment
JP2005215133A (ja) 無端ベルト、定着ベルトおよびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20841384

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20841384

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP