WO2018142530A1 - Procédé de production de structure - Google Patents

Procédé de production de structure Download PDF

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Publication number
WO2018142530A1
WO2018142530A1 PCT/JP2017/003739 JP2017003739W WO2018142530A1 WO 2018142530 A1 WO2018142530 A1 WO 2018142530A1 JP 2017003739 W JP2017003739 W JP 2017003739W WO 2018142530 A1 WO2018142530 A1 WO 2018142530A1
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WO
WIPO (PCT)
Prior art keywords
airgel
layer
group
sol
mass
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PCT/JP2017/003739
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English (en)
Japanese (ja)
Inventor
寛之 泉
竜也 牧野
智彦 小竹
雄太 赤須
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日立化成株式会社
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Priority to PCT/JP2017/003739 priority Critical patent/WO2018142530A1/fr
Priority to JP2018565157A priority patent/JP6911874B2/ja
Publication of WO2018142530A1 publication Critical patent/WO2018142530A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material

Definitions

  • silica airgel As an airgel, for example, silica airgel is known (for example, see Patent Document 1). Silica airgel is generally produced by a method using a supercritical drying method.
  • the problem of workability can be easily solved and the heat insulation can be improved.
  • the flexibility is improved, so that the aerogel is further prevented from falling off, and the structure including such an airgel layer has the flexibility of the main body. It becomes easy to bend according to.
  • the diameter of the sol droplet may be 0.1 to 1000 ⁇ m. According to such a sol, a thick airgel layer can be formed more easily, and cracks in the airgel layer are further suppressed.
  • the coating layer may contain a filler. Thereby, peeling and dropping of the airgel layer at the time of high temperature use are further suppressed.
  • FIG. 1 is a cross-sectional view schematically showing a structure obtained by the structure manufacturing method according to the present embodiment.
  • the structure (aerogel composite, airgel composite structure) 100 has an airgel layer 5 formed on an object 10 (hereinafter also referred to as “object”) that is an object for forming an airgel layer.
  • object an object for forming an airgel layer.
  • the structure 100 may have, for example, a structure in which the airgel layer 5 is integrally formed on the object 10. That is, the structure 100 may include the target object 10 and the airgel layer 5 integrally bonded to the target object 10.
  • the object 10 and the airgel layer 5 may be integrally fixed.
  • the airgel layer 5 is an airgel layer formed from a mist-like (mist-like) sol.
  • the object 10 is a support part that supports the airgel layer 5, for example.
  • the structure 100 according to the present embodiment is excellent in heat insulation and water repellency, is excellent in unique optical characteristics and electrical characteristics, and is suppressed from falling off the airgel.
  • the structure 100 is a structure including an airgel layer 5 disposed on at least a part (a part or the whole) of the surface 10a of the object 10, for example.
  • Such a structure 100 is considered to exhibit excellent heat insulating properties, water repellency, unique optical characteristics and electrical characteristics, and to prevent the airgel from falling off.
  • the surface 10a on which the airgel layer 5 is disposed may be a flat surface, a composite plane (combination of inclined surfaces), or a curved surface.
  • the object 10 may include a main body 3 and a covering layer 4 that covers at least part of the surface of the main body 3.
  • the airgel layer 5 is formed on at least the coating layer 4 so that the coating layer 4 becomes an intermediate layer.
  • FIG. 2 is a cross-sectional view schematically showing a structure obtained by the structure manufacturing method according to the present embodiment.
  • the structure (aerogel composite, airgel composite structure) 200 includes a main body 3 and a coating layer 4 that covers at least a part of the surface of the main body 3 so that the coating layer 4 is an intermediate layer. At least the airgel layer 5 is formed on the coating layer 4. That is, the object 10 may include the main body 3 and the coating layer 4 that covers at least a part of the surface of the main body 3.
  • the structure 200 may include the main body 3 and the airgel layer 5 that is integrally joined to the main body 3 via the coating layer 4 that is an intermediate layer.
  • the airgel layer 5 may be integrally joined to the main body part 3 via the coating layer 4 serving as an intermediate layer.
  • the main body 3, the coating layer 4, and the airgel layer 5 may be integrated.
  • the main body 3 is, for example, a support that supports the airgel layer 5.
  • the structure 200 according to the present embodiment is excellent in adhesiveness and adhesion between the main body 3 and the airgel layer 5, and can further suppress the peeling and dropping of the airgel layer 5.
  • the structure 200 is also excellent in the protection performance of the main body 3.
  • the structure 200 according to the present embodiment includes, for example, a coating layer (also referred to as “intermediate layer”) 4 disposed on at least a part (a part or the whole) of the surface 3a of the main body 3, and the main body of the coating layer 4
  • the structure includes an airgel layer 5 disposed on at least a part (a part or the whole) of the surface 4a opposite to the part 3.
  • the main body 3 and the airgel layer 5 are integrally fixed via a covering layer 4 serving as an intermediate layer.
  • the surface 3a on which the coating layer 4 is disposed may be a flat surface, a composite plane (a combination of inclined surfaces), or a curved surface.
  • the covering layer is not necessarily essential. That is, the target object that forms the airgel layer may be the main body.
  • the structure is a structure including an airgel layer disposed on at least a part (a part or the whole) of the surface of the main body, and the main body and the airgel layer are directly It has a contact structure.
  • the surface of the main body portion on which the airgel layer is disposed may be a flat surface, a composite plane (combination of inclined surfaces), or a curved surface.
  • the airgel layer 5 includes a hydrolyzable functional group or a silicon compound having a condensable functional group (silicon compound) and a hydrolysis product (hydrolyzable functional group) of the silicon compound having the hydrolyzable functional group.
  • a silicon compound (silicon) having a hydrolyzable functional group or a condensable functional group which may be formed from a sol containing at least one selected from the group consisting of hydrolyzed silicon compounds) Compound), and condensation of sol containing at least one selected from the group consisting of hydrolysis products of silicon compounds having hydrolyzable functional groups (silicon compounds in which hydrolyzable functional groups are hydrolyzed) It may be a layer composed of a dried product of a wet gel (a wet gel derived from the sol).
  • the sol comprises at least one selected from the group consisting of a hydrolyzable functional group or a silicon compound having a condensable functional group, and a hydrolysis product of the silicon compound having the hydrolyzable functional group. You may contain.
  • the airgel layer is such, both heat insulation and flexibility can be achieved at a high level, and the airgel can be prevented from dropping off.
  • the material constituting the main body examples include metal, ceramic, glass, resin, and composite materials thereof.
  • the main body may include at least one selected from the group consisting of metal, ceramic, glass, and resin.
  • a block shape, a sheet shape, a spherical shape, a fiber shape, or the like can be adopted depending on the purpose or material to be used.
  • the metal is not particularly limited, and examples include a single metal, a metal alloy, and a metal on which an oxide film is formed.
  • the metal include iron, copper, nickel, aluminum, zinc, titanium, chromium, cobalt, tin, gold, and silver.
  • simple metals such as titanium, gold and silver; iron and aluminum on which an oxide film is formed can be used as the metal.
  • the ceramic examples include oxides such as alumina, titania, zirconia, and magnesia; nitrides such as silicon nitride and aluminum nitride; carbides such as silicon carbide and boron carbide; and mixtures thereof.
  • Examples of the glass include quartz glass, soda glass, and borosilicate glass.
  • the resin examples include polyvinyl chloride, polyvinyl alcohol, polystyrene, polyethylene, polypropylene, polyacetal, polymethyl methacrylate, polycarbonate, polyamide, and polyurethane.
  • the main body there is no particular limitation on the shape of the main body, and it may have either a flat surface or a curved surface.
  • Examples of the shape of the main body include a plate shape, a cylindrical shape, a spherical shape, and a rod shape.
  • Examples of the cylindrical main body include piping.
  • the surface roughness of the main body may be 100 nm or more, or 500 nm or more from the viewpoint of obtaining a good anchor effect and further improving the adhesion of the airgel layer.
  • the object may include a coating layer.
  • the material constituting the coating layer include organic materials, inorganic materials, and organic-inorganic hybrid materials.
  • the organic material examples include urethane resin, polyester resin, acrylic resin, phenol resin, epoxy resin, polyimide, polyamideimide, polybenzimidazole, polyetheretherketone, silicone, and composite materials thereof.
  • the organic material includes, for example, at least one selected from the group consisting of urethane resin, polyester resin, acrylic resin, phenol resin, epoxy resin, polyimide, polyamideimide, polybenzimidazole, polyetheretherketone, and silicone. It may be.
  • the organic material is, for example, from a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a mercapto group, a cyano group, an ester bond, a urethane bond, and an amide bond.
  • the inorganic material examples include glass, a single metal, a metal alloy, a metal on which an oxide film is formed, ceramic, silicon carbide, silicon nitride, and sodium silicate.
  • the inorganic material includes, for example, at least one selected from the group consisting of glass, simple metal, metal alloy, metal with an oxide film, ceramic, silicon carbide, silicon nitride, and sodium silicate. There may be.
  • Examples of the metal include titanium, chromium, aluminum, copper, and platinum.
  • Examples of the ceramic include alumina and zirconia.
  • the inorganic material may further contain a binder.
  • the binder include metal alkoxide and water glass.
  • organic-inorganic hybrid material examples include a composite material of the organic material and the inorganic material, an epoxy-silica hybrid material, and an acrylic-silica hybrid material.
  • the material constituting the coating layer may be an inorganic material or an organic-inorganic hybrid material from the viewpoint of further improving the heat resistance, and the difference in thermal expansion between the main body and the coating layer when used in a high temperature environment.
  • an organic-inorganic hybrid material may be used.
  • a material having a low elastic modulus can also be used as a material constituting the coating layer.
  • the coating layer may be, for example, a layer composed of ceramic (ceramic layer) and / or a layer composed of metal (metal layer).
  • the coating layer may contain a filler from the viewpoint of further improving the heat resistance, further suppressing cracks, and further suppressing separation and dropping of the airgel layer during high temperature use.
  • a filler from the viewpoint of further improving the heat resistance, further suppressing cracks, and further suppressing separation and dropping of the airgel layer during high temperature use.
  • the reason why the airgel layer is further prevented from peeling and falling off by containing the filler is, for example, that the thermal expansion coefficient of the coating layer is adjusted by containing the filler, and the main body, the coating layer, and the airgel at high temperatures. It is assumed that this is because the difference in thermal expansion coefficient generated between the layers is reduced.
  • the filler examples include inorganic fillers and organic fillers.
  • the filler may be an inorganic filler from the viewpoint of improving the heat resistance of the coating layer and further suppressing peeling and dropping under high temperature conditions, and a thermal cycle when repeatedly used in a high temperature environment. From the viewpoint of improving reliability, an organic filler may be used.
  • an inorganic filler from the viewpoint of improving the heat resistance of the coating layer and further suppressing peeling and dropping under high temperature conditions, and a thermal cycle when repeatedly used in a high temperature environment.
  • an organic filler may be used.
  • limiting in particular in the shape of a filler For example, a short fiber form, fine powder form, and a hollow form may be sufficient.
  • the material constituting the inorganic filler examples include silica, mica, talc, glass, calcium carbonate, quartz, metal hydrate, metal hydroxide, and composite materials thereof.
  • the inorganic filler may include at least one selected from the group consisting of silica, mica, talc, glass, calcium carbonate, quartz, metal hydrate, and metal hydroxide.
  • Examples of the metal hydrate include potassium aluminum sulfate 12 hydrate, magnesium nitrate hexahydrate, and magnesium sulfate heptahydrate.
  • Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.
  • the aluminum hydroxide may be boehmite type aluminum hydroxide.
  • the inorganic filler may contain silica, glass, or metal hydroxide, and the glass may be glass short fiber or hollow glass.
  • the metal hydroxide may be magnesium hydroxide or boehmite type aluminum hydroxide.
  • the material constituting the organic filler examples include phosphate ester, polyester, polystyrene, pulp, elastomer, and composite materials thereof.
  • the organic filler may include at least one selected from the group consisting of phosphate ester, polyester, polystyrene, pulp, and elastomer.
  • the pulp may be in the form of pulp floc.
  • the organic filler may contain an elastomer because the thermal expansion difference between the main body and the coating layer is relieved of stress and cracks are easily suppressed.
  • the elastomer examples include styrene elastomers, olefin elastomers, urethane elastomers, polybutadiene elastomers, fluorine elastomers, and silicone elastomers.
  • styrene elastomers examples include styrene elastomers, olefin elastomers, urethane elastomers, polybutadiene elastomers, fluorine elastomers, and silicone elastomers.
  • a fluorine-based elastomer or a silicone-based elastomer can be used as the elastomer.
  • the content of the filler contained in the coating layer may be 0.1% by volume or more based on the total volume of the coating layer from the viewpoint of further improving the heat resistance.
  • the content of the filler contained in the coating layer is based on the total volume of the coating layer from the viewpoint of improving workability when forming the coating layer and improving the adhesion between the main body and the airgel layer. 70 volume% or less, 50 volume% or less, 40 volume% or less, or 30 volume% or less. From these viewpoints, the content of the filler contained in the coating layer may be 0.1 to 70% by volume or 0.1 to 50% by volume with respect to the total volume of the coating layer. 0.1 to 40% by volume, or 0.1 to 30% by volume.
  • the coating layer may contain, for example, an adhesion improver, a flame retardant, and an antioxidant.
  • adhesion improver examples include urea compounds such as urea silane; and silane coupling agents.
  • Examples of the flame retardant include melamine cyanurate and bis (pentabromophenyl) ethane.
  • antioxidants examples include an antioxidant made of ceramic powder such as alumina and zirconia and an inorganic binder.
  • the thermal decomposition temperature of the coating layer may be 300 ° C. or higher from the viewpoint of further improving the heat resistance.
  • the thermal decomposition temperature of 300 ° C. or higher means that the material is heated at a rate of 10 ° C./temperature in a nitrogen atmosphere using a high-temperature differential thermothermal gravimetric measuring device TG / DTA7300 manufactured by SII Nanotechnology. When measured under the condition of minutes, it means that the temperature when the weight is reduced by 5% is 300 ° C. or higher.
  • the thickness of the coating layer is 0.01 ⁇ m or more from the viewpoint of reducing damage due to impact and the like, and improving the protection performance of the main body, and further improving the adhesion between the main body and the airgel layer. It may be 0.1 ⁇ m or more, or 1 ⁇ m or more. From the viewpoint of suppressing cracks during formation of the coating layer, the thickness of the coating layer may be 1000 ⁇ m or less, may be less than 1000 ⁇ m, or may be 500 ⁇ m or less. The thickness of the coating layer may be 100 ⁇ m or less from the viewpoint of suppressing cracks due to a difference in thermal expansion between the main body portion and the coating layer and improving the thermal cycle stability. From these viewpoints, the thickness of the coating layer may be 0.01 to 1000 ⁇ m, 0.01 to 500 ⁇ m, or 0.01 to 100 ⁇ m.
  • the coating layer having a low water absorption rate By using a coating layer having a low water absorption rate, it is possible to further reduce the chemical influence of water-soluble acidic or basic substances and inorganic salts on the main body. Specifically, for example, the chemical change (corrosion, modification, etc.) of the main body due to the influence of a sol coating solution described later can be further reduced. That is, it is difficult to be influenced by the conditions for forming the airgel layer and the composition of the sol coating solution, and the structure can be easily manufactured. From these viewpoints, the water absorption rate of the coating layer may be less than 5%, less than 4%, or less than 3%.
  • the water absorption rate of the coating layer is a change in mass when a test piece obtained by molding the constituent material of the coating layer into a size of 20 mm ⁇ 20 mm ⁇ 0.5 mm is left in a constant temperature and humidity chamber at 60 ° C. and 90% RH for 6 hours. Means rate.
  • the surface roughness (Ra) of the coating layer may be 200 nm or more, or 300 nm or more from the viewpoint of obtaining a good anchor effect between the coating layer and the airgel layer and further improving the adhesion of the airgel layer. It may be 500 nm or more.
  • the surface roughness of the coating layer can be adjusted by, for example, forming a coating layer on the main body and then subjecting the coating layer to polishing (polishing) or roughening (roughening).
  • the polishing process or the roughening process may be a mechanical process or a chemical process. Examples of processing methods include mechanical processing with abrasive grains such as slurry or abrasive; wet etching with acid or base, oxidizing agent or reducing agent; and dry etching with sulfur hexafluoride or carbon tetrafluoride. It is done.
  • the coating layer may be a single layer or a plurality of layers.
  • the airgel layer according to the present embodiment is made of airgel and is formed from a mist-like sol.
  • dry gel obtained by using supercritical drying method for wet gel is aerogel
  • dry gel obtained by drying under atmospheric pressure is xerogel
  • dry gel obtained by freeze-drying is cryogel and
  • the obtained low-density dried gel is referred to as “aerogel” regardless of the drying method of the wet gel.
  • “aerogel” is a gel in a broad sense, “Gel composed of a microporous solid in which the dispersed phase is a gas” (a gel composed of a microporous solid in which the dispersed phase is a gas).
  • the inside of the airgel has a network-like fine structure, and has a cluster structure in which airgel particles of about 2 to 20 nm (particles constituting the airgel) are combined. There are pores less than 100 nm between the skeletons formed by these clusters. Thereby, the airgel has a three-dimensionally fine porous structure.
  • the airgel in this embodiment is a silica airgel which has a silica as a main component, for example.
  • the silica airgel include so-called organic-inorganic hybrid silica airgel into which an organic group (such as a methyl group) or an organic chain is introduced.
  • the airgel layer may be a layer containing an airgel having a structure derived from polysiloxane.
  • the aerogel according to the present embodiment may have, for example, pores smaller than the mean free path of gas from the viewpoint of excellent heat insulation and a unique electrical characteristic.
  • the primary particle diameter of the airgel according to the present embodiment may be, for example, about several nm from the viewpoint of exhibiting unique optical characteristics.
  • the airgel according to the present embodiment includes a silicon compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a hydrolysis product of the silicon compound having the hydrolyzable functional group. It may be a dried product of a wet gel that is a condensate of a sol containing at least one selected from the group. That is, the airgel according to the present embodiment includes a hydrolyzable functional group or a silicon compound having a condensable functional group (in the molecule) and a hydrolysis product of the silicon compound having the hydrolyzable functional group.
  • the condensate may be obtained by a condensation reaction of a hydrolysis product obtained by hydrolysis of a silicon compound having a hydrolyzable functional group, and is not a functional group obtained by hydrolysis. It may be obtained by a condensation reaction of a silicon compound having a group.
  • the silicon compound may have at least one of a hydrolyzable functional group and a condensable functional group, and may have both a hydrolyzable functional group and a condensable functional group.
  • each airgel mentioned later is a group which consists of a hydrolysis product of the silicon compound which has a hydrolyzable functional group or a condensable functional group, and the said hydrolyzable functional group in this way. It may be a dried product of a wet gel that is a condensate of a sol containing at least one selected from the above (obtained by drying a wet gel produced from the sol).
  • such an airgel is considered to have excellent heat insulation and a very low refractive index. Therefore, for example, it is considered that it can be used for a heat insulating material, a light reflecting material, and the like.
  • Airgel according to the present embodiment (at least selected from the group consisting of hydrolyzable functional groups or silicon compounds having a condensable functional group, and hydrolysis products of silicon compounds having the hydrolyzable functional group) It is considered that an airgel formed from a sol containing one kind is unlikely to deteriorate in function due to water absorption.
  • the airgel layer contains at least one selected from the group consisting of a hydrolyzable functional group or a silicon compound having a condensable functional group, and a hydrolysis product of the silicon compound having the hydrolyzable functional group. It may be a layer composed of a dried product of a wet gel that is a condensate of the sol. That is, the airgel layer is at least one selected from the group consisting of a hydrolyzable functional group or a silicon compound having a condensable functional group, and a hydrolysis product of the silicon compound having the hydrolyzable functional group. It may be composed of a layer formed by drying a wet gel produced from a sol containing.
  • the airgel according to the present embodiment can contain polysiloxane having a main chain including a siloxane bond (Si—O—Si).
  • the airgel can have the following M unit, D unit, T unit or Q unit as a structural unit.
  • R represents an atom (hydrogen atom or the like) or an atomic group (alkyl group or the like) bonded to a silicon atom.
  • the M unit is a unit composed of a monovalent group in which a silicon atom is bonded to one oxygen atom.
  • the D unit is a unit composed of a divalent group in which a silicon atom is bonded to two oxygen atoms.
  • the T unit is a unit composed of a trivalent group in which a silicon atom is bonded to three oxygen atoms.
  • the Q unit is a unit composed of a tetravalent group in which a silicon atom is bonded to four oxygen atoms. Information on the content of these units can be obtained by Si-NMR.
  • the airgel according to the present embodiment may contain silsesquioxane.
  • Silsesquioxane is a polysiloxane having the above T unit as a structural unit, and has a composition formula: (RSiO 1.5 ) n .
  • Silsesquioxane can have various skeletal structures such as a cage type, a ladder type, and a random type.
  • Examples of the hydrolyzable functional group include an alkoxy group.
  • Examples of the condensable functional group include a hydroxyl group, a silanol group, a carboxyl group, and a phenolic hydroxyl group.
  • the hydroxyl group may be contained in a hydroxyl group-containing group such as a hydroxyalkyl group.
  • Each of the hydrolyzable functional group and the condensable functional group may be used alone or in admixture of two or more.
  • the silicon compound can include a silicon compound having an alkoxy group as a hydrolyzable functional group, and can also include a silicon compound having a hydroxyalkyl group as a condensable functional group.
  • the silicon compound can have at least one selected from the group consisting of an alkoxy group, a silanol group, a hydroxyalkyl group and a polyether group from the viewpoint of further improving the flexibility of the airgel.
  • the silicon compound can have at least one selected from the group consisting of an alkoxy group and a hydroxyalkyl group from the viewpoint of improving the compatibility of the sol.
  • the number of carbon atoms of the alkoxy group and the hydroxyalkyl group can be 1 to 6, and the viewpoint of further improving the flexibility of the airgel 2 to 4.
  • the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.
  • the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
  • Examples of the airgel according to the present embodiment include the following modes. By adopting these aspects, it becomes easy to obtain an airgel excellent in water repellency and flexibility. By employing each aspect, an airgel having water repellency and flexibility according to each aspect can be obtained.
  • the airgel according to the present embodiment includes a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule), and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group.
  • a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group.
  • Wet which is a condensate of sol containing at least one compound selected from the group consisting of (the hydrolyzable functional group hydrolyzed polysiloxane compound) (hereinafter sometimes referred to as “polysiloxane compound group”) It may be a dried gel.
  • the airgel according to the present embodiment includes a hydrolyzable functional group or a polysiloxane compound having a condensable functional group (in the molecule) and hydrolysis of the polysiloxane compound having the hydrolyzable functional group. It may be obtained by drying a wet gel produced from a sol containing at least one selected from the group consisting of products. That is, the airgel layer is composed of a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group. It may be formed from a sol containing at least one selected from the group.
  • each airgel mentioned later is also from the hydrolysis product of the polysiloxane compound which has a hydrolyzable functional group or a condensable functional group, and the polysiloxane compound which has the said hydrolyzable functional group in this way.
  • It may be a wet gel dried product (obtained by drying a wet gel generated from the sol), which is a condensate of a sol containing at least one selected from the group.
  • the airgel layer is at least one selected from the group consisting of a hydrolyzable functional group or a polysiloxane compound having a condensable functional group, and a hydrolysis product of the polysiloxane compound having a hydrolyzable functional group. It may be a layer composed of a dried product of a wet gel that is a condensate of sol containing That is, the airgel layer is selected from the group consisting of a hydrolyzable functional group or a polysiloxane compound having a condensable functional group, and a hydrolysis product of the polysiloxane compound having a hydrolyzable functional group. You may be comprised by the layer formed by drying the wet gel produced
  • a polysiloxane compound having a hydrolyzable functional group or a condensable functional group is a reactive group different from the hydrolyzable functional group and the condensable functional group (hydrolyzable functional group and condensable functional group). May further have a functional group that does not fall under.
  • the reactive group is not particularly limited, and examples thereof include an epoxy group, a mercapto group, a glycidoxy group, a vinyl group, an acryloyl group, a methacryloyl group, and an amino group.
  • the epoxy group may be contained in an epoxy group-containing group such as a glycidoxy group. You may use the polysiloxane compound which has the said reactive group individually or in mixture of 2 or more types.
  • Examples of the polysiloxane compound having a hydroxyalkyl group include compounds having a structure represented by the following general formula (A).
  • R 1a represents a hydroxyalkyl group
  • R 2a represents an alkylene group
  • R 3a and R 4a each independently represents an alkyl group or an aryl group
  • n represents an integer of 1 to 50.
  • examples of the aryl group include a phenyl group and a substituted phenyl group.
  • the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
  • two R 1a s may be the same or different, and similarly, two R 2a s may be the same or different.
  • two or more R 3a s may be the same or different, and similarly, two or more R 4a s may be the same or different.
  • examples of R 1a include a hydroxyalkyl group having 1 to 6 carbon atoms, and specific examples include a hydroxyethyl group and a hydroxypropyl group.
  • examples of R 2a include an alkylene group having 1 to 6 carbon atoms, and specific examples include an ethylene group and a propylene group.
  • R 3a and R 4a may each independently be an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • the alkyl group may be a methyl group.
  • n may be 2 to 30, or 5 to 20.
  • polysiloxane compound having the structure represented by the general formula (A) commercially available products can be used.
  • compounds such as X-22-160AS, KF-6001, KF-6002, KF-6003 and the like All of which are manufactured by Shin-Etsu Chemical Co., Ltd.
  • compounds such as XF42-B0970, Fluid OFOH 702-4% all manufactured by Momentive.
  • alkoxy group examples include a methoxy group and an ethoxy group.
  • R 4b and R 5b may each independently be an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • the alkyl group may be a methyl group.
  • m may be 2 to 30, or 5 to 20.
  • the polysiloxane compound having an alkoxy group may exist as a hydrolysis product in the sol.
  • the polysiloxane compound having an alkoxy group and the hydrolysis product are It may be mixed.
  • all of the alkoxy groups in the molecule may be hydrolyzed or partially hydrolyzed.
  • the total content of the decomposition products may be 1 part by mass or 3 parts by mass or more with respect to 100 parts by mass of the total amount of sol, from the viewpoint of further easily obtaining good reactivity. Alternatively, it may be 4 parts by mass or more, 5 parts by mass or more, 7 parts by mass or more, or 10 parts by mass or more.
  • the content of the polysiloxane compound group may be 50 parts by mass or less, or 30 parts by mass or less with respect to 100 parts by mass of the total amount of sol, from the viewpoint of further easily obtaining good compatibility. 15 parts by mass or less. From these viewpoints, the content of the polysiloxane compound group may be 1 to 50 parts by mass, 3 to 50 parts by mass, or 4 to 50 parts by mass based on 100 parts by mass of the sol. Part, 5 to 50 parts by weight, 7 to 30 parts by weight, 10 to 30 parts by weight, or 10 to 15 parts by weight. .
  • bistrimethoxysilylmethane, bistrimethoxysilylethane, bistrimethoxysilylhexane, bistrimethoxysilyloctane or the like which is a silicon compound having more than three hydrolyzable functional groups at the molecular terminals may be used. it can.
  • the ratio of the content of the polysiloxane compound group to the content of the silicon compound group may be 1: 0.5 to 1: 5. It may be 1: 0.5 to 1: 4, may be 1: 1 to 1: 2, may be 1: 2 to 1: 4, and may be 1: 3 to 1: 4. It may be.
  • the airgel according to the present embodiment can have a structure represented by the following general formula (1).
  • the airgel which concerns on this embodiment can have a structure represented by the following general formula (1a) as a structure containing the structure represented by Formula (1).
  • the structures represented by the formulas (1) and (1a) can be introduced into the skeleton of the airgel.
  • R 1 and R 2 may each independently be an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • the alkyl group may be a methyl group.
  • R 3 and R 4 may each independently be an alkylene group having 1 to 6 carbon atoms.
  • the alkylene group may be an ethylene group or a propylene group.
  • p can be 2 to 30, and can be 5 to 20.
  • the airgel which concerns on this embodiment is an airgel which has a ladder type structure provided with a support
  • a ladder structure By introducing such a ladder structure into the airgel skeleton, heat resistance and mechanical strength can be easily improved.
  • the polysiloxane compound having the structure represented by the general formula (B) a ladder structure including a bridge portion having the structure represented by the general formula (2) is introduced into the skeleton of the airgel. be able to.
  • the “ladder structure” is a structure having two struts and bridges connecting the struts (a structure having a so-called “ladder” form). ).
  • the airgel skeleton may have a ladder structure, but the airgel may partially have a ladder structure.
  • R 5 and R 6 each independently represents an alkyl group or an aryl group, and b represents an integer of 1 to 50.
  • examples of the aryl group include a phenyl group and a substituted phenyl group.
  • examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
  • b is an integer of 2 or more
  • two or more R 5 s may be the same or different, and similarly, two or more R 6 s are the same. Or different.
  • the airgel according to the present embodiment may contain silica particles from the viewpoint of further toughening the airgel layer and further achieving excellent heat insulation and flexibility.
  • the sol that gives the airgel may further contain silica particles. That is, the airgel according to the present embodiment may be a dried product of a wet gel that is a condensate of a sol containing silica particles (obtained by drying a wet gel generated from the sol).
  • the airgel layer may be a layer composed of a dried product of a wet gel that is a condensate of a sol containing silica particles.
  • the airgel layer may be composed of a layer obtained by drying a wet gel generated from a sol containing silica particles.
  • the shape of the silica particles is not particularly limited, and examples thereof include a spherical shape, a cage shape, and an association type. Among these, by using spherical particles as silica particles, it becomes easy to suppress aggregation in the sol.
  • the average primary particle diameter of the silica particles may be 1 nm or more, or 5 nm or more, from the viewpoint that it is easy to impart an appropriate strength and flexibility to the airgel, and an airgel excellent in shrinkage resistance during drying is easily obtained. It may be 10 nm or more, or 20 nm or more.
  • the average particle diameter of the silica particles can be measured from the raw material.
  • the biaxial average primary particle diameter is calculated as follows from the result of observing 20 arbitrary particles by SEM. That is, when colloidal silica particles having a solid content concentration of 5 to 40% by mass, which are usually dispersed in water, are taken as an example, a chip obtained by cutting a wafer with a patterned wiring into 2 cm squares is dispersed in a colloidal silica particle dispersion. After soaking for 30 seconds, the chip is rinsed with pure water for about 30 seconds and blown with nitrogen.
  • the chip is placed on a sample stage for SEM observation, an acceleration voltage of 10 kV is applied, the silica particles are observed at a magnification of 100,000, and an image is taken.
  • 20 silica particles are arbitrarily selected from the obtained image, and the average of the particle diameters of these particles is defined as the average particle diameter.
  • a rectangle (circumscribed rectangle L) circumscribing the silica particles P and arranged so that the long side is the longest is led.
  • the long side of the circumscribed rectangle L is X
  • the short side is Y
  • the biaxial average primary particle diameter is calculated as (X + Y) / 2, and is defined as the particle diameter of the particle.
  • the content of the silica particles contained in the sol is 1 mass with respect to 100 mass parts of the total amount of the sol from the viewpoint of easily imparting an appropriate strength to the airgel and easily obtaining an airgel excellent in shrinkage resistance during drying. Or 4 parts by mass or more.
  • the content of the silica particles contained in the sol is 20 parts by mass or less with respect to 100 parts by mass of the total amount of the sol, from the viewpoint of easily suppressing the solid heat conduction of the silica particles and easily obtaining an airgel excellent in heat insulation. It may be 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, or 8 parts by mass or less.
  • the content of the silica particles contained in the sol may be 1 to 20 parts by mass, 4 to 15 parts by mass, or 4 to 4 parts by mass with respect to 100 parts by mass of the total amount of the sol. It may be 12 parts by mass, 4 to 10 parts by mass, or 4 to 8 parts by mass.
  • R 9 represents an alkyl group.
  • alkyl group examples include alkyl groups having 1 to 6 carbon atoms, and specific examples include a methyl group.
  • the airgel according to the present embodiment can have a structure represented by the following general formula (5).
  • the airgel which concerns on this embodiment can have a structure represented by following General formula (5) while containing a silica particle.
  • the airgel according to the present embodiment can have a structure represented by the following general formula (6).
  • the airgel which concerns on this embodiment can have a structure represented by following General formula (6) while containing a silica particle.
  • the airgel layer forming step may be, for example, a step of forming the airgel layer from the sol layer after forming the sol layer from the mist in the form of mist.
  • a coating layer formation process is a process of making the composition for coating layer formation contact the base material used as a main-body part, for example, and forming a coating layer on a main-body part. Specifically, for example, the composition for forming a coating layer is brought into contact with the substrate, and if necessary, the coating layer is formed on the surface of the substrate by heating and drying.
  • the composition for forming a coating layer may be a liquid composition such as a primer solution or a sheet-like composition such as an adhesive sheet.
  • the contact method is appropriately selected depending on the type of the coating layer forming composition, the thickness of the coating layer, or the shape of the substrate.
  • the composition for forming a coating layer is a sheet-like composition
  • a method of laminating on a substrate can be used
  • the composition for forming a coating layer is a liquid composition, for example, dip coating Spray coating, spin coating, roll coating, etc. can be used.
  • heat treatment may be performed from the viewpoint of drying and fixing the composition for forming the coating layer, and washing and / or drying from the viewpoint of removing impurities and improving the adhesion of the coating layer. May be performed. Further, for the purpose of adjusting the surface roughness of the coating layer, the surface of the coating layer may be subjected to polishing treatment and / or roughening treatment.
  • a silicon compound (if necessary, further silica particles) and a solvent are mixed and a hydrolysis reaction is performed, and then a sol-gel reaction is performed to obtain a semi-gelled sol coating liquid.
  • an acid catalyst may be further added to the solvent in order to promote the hydrolysis reaction.
  • a surfactant, a thermohydrolyzable compound, or the like can be added to the solvent.
  • a base catalyst may be added to promote the gelation reaction.
  • the boiling point of the solvent may be less than 200 ° C., 170 ° C. or less, or 150 ° C. or less from the viewpoint of obtaining good coatability in the contact step. That is, the sol may contain a solvent having a boiling point of less than 200 ° C., may contain a solvent having a boiling point of 170 ° C. or less, and may contain a solvent having a boiling point of 150 ° C. or less. According to the sol containing such a solvent, a thick airgel layer can be formed more easily, and cracks in the airgel layer are further suppressed.
  • the solvent may have a high surface tension from the viewpoint of improving the coating film formability and easy control of the film thickness.
  • the solvent may have a low volatility from the viewpoint of suppressing changes in the sol viscosity and resin content and improving storage stability.
  • Examples of the solvent that satisfies these characteristics include water or a mixed solution of water and alcohol.
  • Examples of the alcohol include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol and t-butanol. Among these, water may be used because it has a high surface tension and low volatility.
  • the acid catalyst examples include hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, bromic acid, chloric acid, chlorous acid, hypochlorous acid, and other inorganic acids; Acid phosphates such as aluminum phosphate, acid magnesium phosphate, acid zinc phosphate; organics such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid, azelaic acid Carboxylic acid is mentioned.
  • an organic carboxylic acid can be used from the viewpoint of further improving the water resistance of the resulting structure.
  • acetic acid, formic acid, propionic acid, oxalic acid and malonic acid are used. May be acetic acid. You may use an acid catalyst individually or in mixture of 2 or more types.
  • a nonionic surfactant As the surfactant, a nonionic surfactant, an ionic surfactant, or the like can be used. You may use surfactant individually or in mixture of 2 or more types.
  • a cationic surfactant As the ionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant or the like can be used, and a cationic surfactant or an anionic surfactant may be used.
  • the cationic surfactant include cetyltrimethylammonium bromide (CTAB) and cetyltrimethylammonium chloride.
  • CTAB cetyltrimethylammonium bromide
  • anionic surfactant examples include sodium dodecyl sulfonate.
  • amphoteric surfactants include amino acid surfactants, betaine surfactants, and amine oxide surfactants.
  • amino acid surfactants include acyl glutamic acid.
  • betaine surfactants include lauryldimethylaminoacetic acid betaine and stearyldimethylaminoacetic acid betaine.
  • the amine oxide surfactant include lauryl dimethylamine oxide.
  • surfactants are thought to have the effect of reducing phase separation by reducing the difference in chemical affinity between the solvent in the reaction system and the growing siloxane polymer in the contacting step. .
  • the addition amount of the surfactant depends on the type of the surfactant or the type and amount of the silicon compound.
  • the amount of the surfactant may be 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the silicon compound. It may be 5 to 60 parts by mass.
  • thermohydrolyzable compound generates a base catalyst by thermal hydrolysis to make the reaction solution basic and promote the sol-gel reaction.
  • the thermohydrolyzable compound is not particularly limited as long as it can make the reaction solution basic after hydrolysis.
  • urea include acid amides such as methylacetamide and N, N-dimethylacetamide; and cyclic nitrogen compounds such as hexamethylenetetramine.
  • urea is particularly easy to obtain the above-mentioned promoting effect.
  • the amount of the thermally hydrolyzable compound added is not particularly limited as long as it is an amount that can sufficiently promote the sol-gel reaction.
  • the amount of the thermally hydrolyzable compound (urea or the like) added may be 1 to 200 parts by mass or 2 to 150 parts by mass with respect to 100 parts by mass of the total amount of the silicon compound.
  • the addition amount of the thermohydrolyzable compound (urea or the like) is 1 part by mass or more, good reactivity can be further easily obtained, and when it is 200 parts by mass or less, the precipitation of crystals and the gel density are reduced. It becomes easy to suppress the decrease.
  • the hydrolysis in the sol production step depends on the types and amounts of silicon compound, silica particles, acid catalyst, surfactant, etc. in the mixed solution, but for example, 10 minutes to 20-60 ° C. in a temperature environment.
  • the reaction may be performed for 24 hours, or in a temperature environment of 50 to 60 ° C. for 5 minutes to 8 hours.
  • the hydrolyzable functional group in a silicon compound is fully hydrolyzed, and the hydrolysis product of a silicon compound can be obtained more reliably.
  • the temperature environment of the sol generation step may be adjusted to a temperature that suppresses hydrolysis of the thermohydrolyzable compound and suppresses gelation of the sol.
  • the temperature at this time may be any temperature as long as the hydrolysis of the thermally hydrolyzable compound can be suppressed.
  • the temperature environment in the sol production step (for example, the temperature environment when urea is used as the thermohydrolyzable compound) may be 0 to 40 ° C. or 10 to 30 ° C.
  • Base catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; ammonium compounds such as ammonium hydroxide, ammonium fluoride, ammonium chloride, and ammonium bromide; sodium metaphosphate Basic sodium phosphates such as sodium pyrophosphate and sodium polyphosphate; allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, tetramethylethylenediamine, t-butylamine aliphatic amines such as sec-butylamine, propylamine, 3- (methyl
  • ammonium hydroxide (ammonia water) can be used from the viewpoint of high volatility and hardly remaining in the airgel layer after drying, and from the viewpoint of not impairing water resistance and economical efficiency.
  • the dehydration condensation reaction and / or dealcoholization condensation reaction of the silicon compound (polysiloxane compound group and silicon compound group) and silica particles in the sol can be promoted, and the gelation of the sol Furthermore, it can be performed in a short time.
  • ammonia is highly volatile and hardly remains in the structure. Therefore, by using ammonia as the base catalyst, a structure having further excellent water resistance can be obtained.
  • the addition amount of the base catalyst may be 0.5 to 5 parts by mass or 1 to 4 parts by mass with respect to 100 parts by mass of the total amount of silicon compounds (polysiloxane compound group and silicon compound group). .
  • the addition amount of the base catalyst is 0.5 parts by mass or more, gelation can be performed in a shorter time, and when it is 5 parts by mass or less, the water repellency is improved.
  • the sol-gel reaction in the sol production step can obtain a sol in a semi-gelled state for the purpose of obtaining good coating properties in the contact step.
  • This reaction can be performed in an airtight container so that a solvent and a base catalyst may not volatilize.
  • the gelation temperature depends on the type and amount of the silicon compound, silica particles, acid catalyst, surfactant, base catalyst and the like in the sol, but may be 30 to 90 ° C. or 40 to 80 ° C. There may be. When the gelation temperature is 30 ° C. or higher, gelation can be performed in a shorter time. When the gelation temperature is 90 ° C. or less, rapid gelation can be suppressed.
  • the sol-gel reaction time varies depending on the gelation temperature
  • the gelation time may be shortened as compared with a sol applied to a conventional aerogel. it can.
  • the reason for this is presumed that the hydrolyzable functional group or the condensable functional group of the silicon compound in the sol forms hydrogen bonds and / or chemical bonds with the silanol groups of the silica particles.
  • the gelation time may be 10 to 360 minutes or 20 to 180 minutes. When the gelation time is 10 minutes or longer, the viscosity of the sol is improved, and good coating properties are easily obtained in the contact process. It becomes easy to obtain adhesiveness with a part or a coating layer.
  • the sol coating liquid (semi-gelled sol coating liquid or the like) obtained in the sol generation step is brought into contact with the main body or the coating layer in the form of a mist to produce a structure (coating). Construction process).
  • the sol coating liquid is brought into contact with the main body part or the coating layer in the form of a mist, and the sol coating liquid is gelled by heating and drying as necessary to form the airgel layer of the main body part or the coating layer. Form on the surface.
  • the airgel layer is desirably in a state in which an adhesive force with the main body portion or the coating layer is ensured.
  • the contact method is not particularly limited as long as the sol can be contacted (applied) to the main body or the layer in a mist form, and examples thereof include spray coating. According to this method, since the mist generated by spraying only needs to reach the surface to be coated, for example, an airgel layer can be formed also on the inner surface of a cylindrical main body such as a pipe. .
  • sprays used for spray coating include air spray that mists are applied by applying compressed gas, and airless sprays that apply mist by applying pressure to the sol and spray mist from the spray gun.
  • a liquid electrostatic spray that efficiently attaches a mist to an adherend by applying a static voltage can be used.
  • the coating method is not limited, and a suitable method can be selected according to physical properties such as the size, shape, and elastic modulus of the main body or the coating layer.
  • the pressure of the gas used can be adjusted according to the specifications of the air gun and air brush used, for example.
  • the pressure is not particularly limited, but may be, for example, less than 0.5 MPa.
  • the thickness of the airgel layer formed in the contacting step can be adjusted by, for example, the pressure of the gas used for spraying, the coating amount of the sol, the viscosity of the sol, the distance between the spray and the main body, and the coating time.
  • the thickness of the airgel layer may be adjusted by the coating time from the viewpoint of workability. In this case, for example, a calibration curve indicating the relationship between the coating time and the thickness of the semi-cured gel or the thickness of the airgel layer may be created, and thereby the thickness may be controlled.
  • the diameter of the mist droplets of the sol may be 0.1 ⁇ m or more, from the viewpoint of easily forming a thick airgel layer and further suppressing cracking of the airgel layer, and may be 0.3 ⁇ m or more. It may be 0.5 ⁇ m or more. From the same viewpoint, the diameter of the sol droplet may be 1000 ⁇ m or less, 800 ⁇ m or less, or 500 ⁇ m or less. From these viewpoints, the diameter of the sol droplet may be 0.1 to 1000 ⁇ m, 0.3 to 800 ⁇ m, or 0.5 to 500 ⁇ m. When the diameter of the droplet is in such a range, it is easy to form a thick airgel layer and the crack of the airgel layer can be further suppressed. For example, a droplet having such a size has a sufficient surface area. Since it is large, it is assumed that the solvent in the sol evaporates in a short time after adhering to the main body or the coating layer, and the sol contracts accordingly.
  • the non-coating part is masked with a tape or the like, and then the sol is applied to the coating part. May be contacted.
  • the mask When masking is applied, from the viewpoint of reducing airgel loss and peeling at the boundary between the coated and non-coated areas, for example, after spray coating, the mask is removed at a semi-cured gel-like timing. May be.
  • these conditions are such that the moisture content of the airgel layer after heating and drying is, for example, 10% by mass from the viewpoint of easily obtaining adhesion between the airgel layer and the main body portion or the coating layer.
  • the conditions may be as described above, or the conditions may be 50% by mass or more.
  • the heating and drying temperature varies depending on conditions such as the amount of water in the sol coating liquid, the amount of the organic solvent, the boiling point of the organic solvent, etc., from the viewpoint of shortening the gelation time, for example, may be 50 ° C. It may be 60 ° C. or higher.
  • the heating and drying temperature may be, for example, 150 ° C. or less or 120 ° C. or less from the viewpoint of easily obtaining adhesion between the airgel layer and the main body portion or the coating layer. From these viewpoints, the heating and drying temperature may be, for example, 50 to 150 ° C. or 60 to 120 ° C.
  • the heating and drying time varies depending on the heating and drying temperature, but may be, for example, 0.2 minutes or more, or 0.5 minutes or more from the viewpoint of ease of forming the airgel layer.
  • the heating and drying time may be, for example, 10 minutes or less or 8 minutes or less from the viewpoint of easily obtaining the adhesion between the airgel layer and the main body portion or the coating layer. From these viewpoints, the heating and drying time may be, for example, 0.2 to 10 minutes or 0.5 to 8 minutes.
  • suitable conditions can be appropriately set by conducting a simple experiment in advance.
  • coating and drying may be repeated a plurality of times. By repeating the coating and drying, it is easy to adjust the moisture content of the airgel layer after heating and drying, and the film can be easily thickened.
  • the aging step is a step of aging the structure obtained by the contact step by heating.
  • the moisture content of the airgel layer after aging may be 10% by mass or more, or 50% by mass or more from the viewpoint of suppressing a decrease in adhesiveness between the airgel layer and the main body portion or the coating layer. May be.
  • the aging method is not particularly limited, and examples thereof include a method of aging the structure in a sealed atmosphere, and a method of aging using a constant temperature and humidity bath that can suppress a decrease in moisture content due to heating.
  • the aging temperature may be, for example, 40 to 90 ° C. or 50 to 80 ° C.
  • the aging temperature is 40 ° C. or higher, the aging time can be shortened, and when it is 90 ° C. or lower, a decrease in water content can be suppressed.
  • the aging time may be, for example, 1 to 48 hours, or 3 to 24 hours.
  • the aging time is 1 hour or longer, excellent heat insulating properties can be easily obtained, and when it is 48 hours or shorter, high adhesion between the airgel layer and the main body portion or the coating layer can be obtained.
  • the washing and solvent substitution step is a step having a step of washing the structure obtained by the aging step (washing step) and a step of substitution with a solvent suitable for the drying step (solvent substitution step).
  • the cleaning and solvent replacement method is not particularly limited, and for example, continuous processing can be performed using a plurality of cleaning tanks and / or solvent replacement tanks by conveyor conveyance.
  • the cleaning and solvent replacement step can be carried out in a form in which only the solvent replacement step is performed without performing the step of cleaning the structure, but it is possible to reduce impurities such as unreacted substances and by-products in the airgel layer.
  • the airgel layer can be washed from the viewpoint of enabling production of a highly pure structure.
  • the structure obtained in the aging step can be repeatedly washed with water or an organic solvent.
  • Organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, acetonitrile, hexane, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran, methylene chloride , N, N-dimethylformamide, dimethyl sulfoxide, acetic acid, formic acid, and other various organic solvents can be used. You may use an organic solvent individually or in mixture of 2 or more types.
  • a low surface tension solvent may be used to suppress shrinkage of the airgel layer due to drying.
  • low surface tension solvents generally have very low mutual solubility with water. Therefore, when a low surface tension solvent is used in the solvent replacement step, a hydrophilic organic solvent having high mutual solubility in both water and a low surface tension solvent is used as the organic solvent used in the washing step. it can. Note that the hydrophilic organic solvent used in the washing step can serve as a preliminary replacement for the solvent replacement step.
  • methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone can be used from the viewpoint of being a hydrophilic organic solvent among the above organic solvents, and methanol, ethanol can be used from the viewpoint of excellent economy.
  • methyl ethyl ketone can be used.
  • the amount of water or organic solvent used in the washing step can be an amount that can sufficiently wash the solvent in the airgel layer and can be washed, and is 3 to 10 times the volume of the airgel layer. These solvents can be used.
  • the washing can be repeated until the water content in the airgel layer after washing becomes 10% by mass or less.
  • a temperature below the boiling point of the solvent used for washing can be used.
  • a temperature of about 30 to 60 ° C. can be used.
  • the solvent in the washed airgel layer can be replaced with a predetermined replacement solvent in order to suppress the shrinkage of the airgel layer in the drying step.
  • the replacement efficiency can be improved by heating.
  • a solvent having a low surface tension which will be described later, can be used in the drying step when drying under atmospheric pressure at a temperature lower than the critical point of the solvent used for drying.
  • a solvent such as ethanol, methanol, 2-propanol, dichlorodifluoromethane, carbon dioxide, or the like can be used alone, or a solvent in which two or more of these are mixed can be used.
  • the low surface tension solvent may be a solvent having a surface tension at 20 ° C. of 30 mN / m or less, a solvent of 25 mN / m or less, or a solvent of 20 mN / m or less.
  • Examples of the low surface tension solvent include pentane (15.5), hexane (18.4), heptane (20.2), octane (21.7), 2-methylpentane (17.4), 3- Aliphatic hydrocarbons such as methylpentane (18.1), 2-methylhexane (19.3), cyclopentane (22.6), cyclohexane (25.2), 1-pentene (16.0); Aromatic hydrocarbons such as (28.9), toluene (28.5), m-xylene (28.7), p-xylene (28.3); dichloromethane (27.9), chloroform (27.2) ), Carbon tetrachloride (26.9), 1-chloropropane (21.8), 2-chloropropane (18.1) and other halogenated hydrocarbons; ethyl ether (17.1), propyl ether (20.5) ), Isop Ethers such as pyrether (17.7), butyl ethy
  • aliphatic hydrocarbons may be used, and hexane or heptane may be used.
  • a hydrophilic organic solvent such as acetone, methyl ethyl ketone, 1,2-dimethoxyethane, it can be used as the organic solvent in the washing step.
  • a solvent having a boiling point of 100 ° C. or less at normal pressure may be used from the viewpoint of easy drying in the drying step.
  • Low surface tension solvents may be used alone or in combination of two or more.
  • an amount capable of sufficiently replacing the solvent in the airgel layer after washing can be used, and the amount of the solvent is 3 to 10 times the volume of the airgel layer. Can be used.
  • a temperature below the boiling point of the solvent used for the replacement can be used.
  • a temperature of about 30 to 60 ° C. can be used.
  • the solvent replacement step is not necessarily essential.
  • the inferred mechanism is as follows.
  • the silica particles function as a three-dimensional network airgel skeleton support, whereby the skeleton is supported and gel shrinkage in the drying process is suppressed. Therefore, it is considered that the gel can be directly transferred to the drying step without replacing the solvent used for washing.
  • the drying method is not particularly limited, and known atmospheric pressure drying, supercritical drying, or freeze drying can be used.
  • atmospheric drying or supercritical drying can be used from the viewpoint of easy production of a low-density airgel layer. From the viewpoint of being able to produce at low cost, atmospheric drying can be used.
  • “normal pressure” means 0.1 MPa (atmospheric pressure).
  • the structure according to the present embodiment can be obtained, for example, by drying a structure after washing and solvent substitution (if necessary) at a temperature below the critical point of the solvent used for drying under atmospheric pressure. It can.
  • the drying temperature varies depending on the type of the substituted solvent (the solvent used for washing when solvent substitution is not performed) or the heat resistance of the main body, but may be 60 to 500 ° C., or 90 to 150 ° C. There may be.
  • the drying time varies depending on the capacity of the airgel layer and the drying temperature, but may be 2 to 48 hours. In the present embodiment, drying can be accelerated by applying pressure within a range that does not impair productivity.
  • the structure according to the present embodiment may be pre-dried before the drying step from the viewpoint of improving the drying efficiency in atmospheric drying.
  • the predrying temperature may be 60 to 180 ° C, or 90 to 150 ° C.
  • the pre-drying time varies depending on the volume of the airgel layer and the drying temperature, but may be 1 to 30 minutes.
  • supercritical drying can also be used as a drying method.
  • Supercritical drying can be performed by a known method.
  • the supercritical drying method include a method of removing the solvent at a temperature and pressure higher than the critical point of the solvent contained in the airgel layer.
  • the airgel layer is immersed in liquefied carbon dioxide under conditions of, for example, about 20 to 25 ° C. and about 5 to 20 MPa, so that all or part of the solvent contained in the airgel layer is used. And carbon dioxide having a lower critical point than that of the solvent, and then removing carbon dioxide alone or a mixture of carbon dioxide and the solvent.
  • the manufacturing method of a structure is not limited to this embodiment.
  • the airgel layer which concerns on this embodiment is applicable to water-repellent uses, such as an architecture field, a clothing field, a motor vehicle field, a household appliance field, a semiconductor field, an industrial facility, for example.
  • the airgel layer can be used for a heat insulating application, a sound absorbing application, a static vibration application, a catalyst supporting application and the like in addition to the application as a water repellent material.
  • the following glass plate, aluminum plate, SUS piping and PET film were prepared as the main body.
  • Glass plate Tempax (manufactured by Toshin Rikou Co., Ltd., dimensions: 100 mm x 100 mm x 2 mm)
  • Aluminum plate A1035P (manufactured by Takeuchi Metal Foil Powder Industry Co., Ltd., dimensions: 100 mm x 100 mm x 0.5 mm)
  • SUS piping SUS316TPD (manufactured by Mori Kogyo Co., Ltd., outer diameter 115 mm ⁇ thickness 2 mm ⁇ length 50 mm)
  • PET film Tetoron G2 (Teijin Limited, dimensions: 100 mm x 100 mm x 0.1 mm)
  • intermediate layer (Formation of coating layer (hereinafter also referred to as “intermediate layer”)) An intermediate layer 1 and an intermediate layer 2 were formed on the prepared various main body portions in the combinations shown in Table 1 as follows.
  • Sol coating liquid [Sol coating solution 1] ST-OXS (manufactured by Nissan Chemical Industries, Ltd., product name, average primary particle size: 5 nm, solid content: 10% by mass) as silica particle-containing raw material 100.0 parts by mass, water 50.0 parts by mass, acid catalyst As a mixture, 0.10 parts by mass of acetic acid, 20.0 parts by mass of CTAB as a cationic surfactant and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed to obtain a mixed solution.
  • methyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., product name: LS-530, hereinafter abbreviated as “MTMS”
  • MTMS methyltrimethoxysilane
  • DDMS dimethyldimethoxysilane
  • Solid coating liquid 2 As a silica particle-containing raw material, 100.0 parts by mass of ST-OXS, 100.0 parts by mass of water, and 100.0 parts by mass of methanol were mixed to obtain a mixed solution. To this mixed solution, 80.0 parts by mass of MTMS as a silicon compound and 60.0 parts by mass of KBE-22 (dimethyldiethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product name) are added and reacted at 25 ° C. for 2 hours. It was. A sol coating solution 2 was obtained by adding 50.0 parts by mass of 5% aqueous ammonia as a base catalyst.
  • KBM-3063 hexyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product name
  • KBM-3086 (1,8-bis (trimethoxysilyl) octane, 80.0 parts by mass of Shin-Etsu Chemical Co., Ltd., product name) was added and reacted at 25 ° C. for 2 hours. Thereafter, a sol-gel reaction was performed at 60 ° C. for 2 hours to obtain a sol coating solution 3.
  • Solid coating solution 4 As a silica particle-containing raw material, PL-2L (manufactured by Fuso Chemical Industry Co., Ltd., product name, average primary particle size: 20 nm, solid content: 20% by mass) is 100.0 parts by mass, water is 50.0 parts by mass, acid 0.10 parts by mass of acetic acid as a catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed to obtain a mixed solution.
  • PL-2L manufactured by Fuso Chemical Industry Co., Ltd., product name, average primary particle size: 20 nm, solid content: 20% by mass
  • Solid coating solution 5 100.0 parts by mass of PL-2L as a raw material containing silica particles, 100.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and hot water addition
  • 120.0 parts by mass of urea was mixed to obtain a mixed solution.
  • the “polysiloxane compound A” was synthesized as follows. First, 100.0 mass of dimethylpolysiloxane (product name: XC96-723, manufactured by Momentive) having silanol groups at both ends in a 1 L three-necked flask equipped with a stirrer, a thermometer, and a Dimroth condenser. Parts, 181.3 parts by mass of methyltrimethoxysilane and 0.50 parts by mass of t-butylamine were mixed and reacted at 30 ° C. for 5 hours. Thereafter, this reaction solution was heated at 140 ° C. for 2 hours under reduced pressure of 1.3 kPa to remove volatile components, thereby obtaining a bifunctional alkoxy-modified polysiloxane compound (polysiloxane compound A) at both ends.
  • dimethylpolysiloxane product name: XC96-723, manufactured by Momentive
  • silica particle-containing raw material 100.0 parts by mass
  • water 100.0 parts by mass
  • 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed to obtain a mixed solution.
  • polysiloxane compound B a bifunctional alkoxy-modified polysiloxane compound having a structure represented by the above general formula (B) as a polysiloxane compound 40.0 parts by mass
  • the “polysiloxane compound B” was synthesized as follows. First, 100.0 parts by mass of XC96-723, 202.6 parts by mass of tetramethoxysilane and 0.50 of t-butylamine in a 1 L three-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser. Mass parts were mixed and reacted at 30 ° C. for 5 hours. Thereafter, this reaction solution was heated at 140 ° C. for 2 hours under a reduced pressure of 1.3 kPa to remove volatile components, thereby obtaining a trifunctional alkoxy-modified polysiloxane compound (polysiloxane compound B) at both ends.
  • KBM-3063 hexyltrimethoxysilane
  • airgel composite structure (Production of structure (hereinafter also referred to as “airgel composite structure”))
  • the airgel layers 1 to 7 are formed on the main body or the intermediate layer in the combinations shown in Table 1 as follows, and the airgel layer is integrally joined to the main body directly or via the intermediate layer.
  • An airgel composite structure comprising:
  • the aged structure was immersed in 2000 mL of water and washed for 30 minutes. Next, it was immersed in 2000 mL of methanol and washed at 60 ° C. for 30 minutes. Washing with methanol was performed twice more while exchanging with fresh methanol. Next, it was immersed in 2000 mL of methyl ethyl ketone, and solvent substitution was performed at 60 ° C. for 30 minutes. Washing with methyl ethyl ketone was performed twice more while exchanging with new methyl ethyl ketone.
  • the washed and solvent-substituted structure is dried at 120 ° C. for 6 hours under normal pressure, so that the airgel layer 1 including the airgel having the structure represented by the general formulas (4) and (5) (main body)
  • An airgel composite structure provided with an airgel layer integrally bonded directly to the part or via an intermediate layer was obtained.
  • the sol coating liquid 2 is applied in a mist form on the main body or intermediate layer using a spray gun so that the thickness after gelation is 500 ⁇ m, and the structure is gelled at 60 ° C. for 30 minutes. Obtained. Thereafter, the obtained structure was transferred to a sealed container and aged at 60 ° C. for 12 hours.
  • the washing and solvent replacement step and the drying step are performed in the same manner as the method described in “Airgel layer 1”, and the airgel layer 2 includes the airgel having the structure represented by the general formulas (4) and (5).
  • An airgel composite structure provided with an airgel layer integrally bonded to the main body directly or via an intermediate layer was obtained.
  • a foamed urethane foam structure was obtained by applying a foamed urethane foam (manufactured by Henkel Japan Co., Ltd., product name: Sista M5230) to a glass plate as the main body so as to have a thickness of 100 ⁇ m.
  • a foamed urethane foam manufactured by Henkel Japan Co., Ltd., product name: Sista M5230

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Silicon Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne un procédé de production d'une structure sur laquelle une couche d'aérogel est formée, le procédé de production d'une structure comprenant une étape consistant à former une couche d'aérogel à partir d'un sol sous forme de brume.
PCT/JP2017/003739 2017-02-02 2017-02-02 Procédé de production de structure WO2018142530A1 (fr)

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JP2018565157A JP6911874B2 (ja) 2017-02-02 2017-02-02 構造体の製造方法

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006227596A (ja) * 2005-01-21 2006-08-31 Pentax Corp 反射防止膜を有する光学素子及びその製造方法
JP2007193051A (ja) * 2006-01-18 2007-08-02 Pentax Corp 光学膜の形成方法及び光学膜を有する光学物品
JP2009258711A (ja) * 2008-03-25 2009-11-05 Hoya Corp 反射防止膜の形成方法及び光学素子
WO2016121757A1 (fr) * 2015-01-27 2016-08-04 日立化成株式会社 Stratifié aérogel et matière d'isolation thermique
WO2017038648A1 (fr) * 2015-08-28 2017-03-09 日立化成株式会社 Procédé de fabrication de corps thermiquement isolé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006227596A (ja) * 2005-01-21 2006-08-31 Pentax Corp 反射防止膜を有する光学素子及びその製造方法
JP2007193051A (ja) * 2006-01-18 2007-08-02 Pentax Corp 光学膜の形成方法及び光学膜を有する光学物品
JP2009258711A (ja) * 2008-03-25 2009-11-05 Hoya Corp 反射防止膜の形成方法及び光学素子
WO2016121757A1 (fr) * 2015-01-27 2016-08-04 日立化成株式会社 Stratifié aérogel et matière d'isolation thermique
WO2017038648A1 (fr) * 2015-08-28 2017-03-09 日立化成株式会社 Procédé de fabrication de corps thermiquement isolé

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