WO2017010551A1 - エアロゲル複合材料 - Google Patents

エアロゲル複合材料 Download PDF

Info

Publication number
WO2017010551A1
WO2017010551A1 PCT/JP2016/070878 JP2016070878W WO2017010551A1 WO 2017010551 A1 WO2017010551 A1 WO 2017010551A1 JP 2016070878 W JP2016070878 W JP 2016070878W WO 2017010551 A1 WO2017010551 A1 WO 2017010551A1
Authority
WO
WIPO (PCT)
Prior art keywords
airgel
group
composite material
mass
parts
Prior art date
Application number
PCT/JP2016/070878
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
寛之 泉
正人 宮武
智彦 小竹
雄太 赤須
入野　哲朗
Original Assignee
日立化成株式会社
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 日立化成株式会社 filed Critical 日立化成株式会社
Priority to JP2017528726A priority Critical patent/JP6330974B2/ja
Priority to CN201680040843.1A priority patent/CN107849287A/zh
Publication of WO2017010551A1 publication Critical patent/WO2017010551A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/242—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using metal fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • the present invention relates to a novel airgel composite material, and more particularly to an airgel composite material suitably used as a heat insulating material for construction, for cryogenic containers, for high temperature containers and the like.
  • a vacuum heat insulating material having a core material using inorganic fibers and a phenol resin binder is known (for example, Patent Document 2 below).
  • Patent Document 2 a vacuum heat insulating material having a core material using inorganic fibers and a phenol resin binder.
  • airgel is known as a material having the lowest thermal conductivity at normal pressure (for example, Patent Document 3).
  • the airgel has a fine porous structure, so that the heat transfer is reduced by suppressing the movement of gas including air.
  • general aerogels are very fragile, difficult to handle, and have problems with productivity. For example, a mass of airgel may be damaged simply by trying to lift it by hand.
  • This invention is made
  • a silicon compound having a hydrolyzable functional group or a condensable functional group and a silicon compound having the hydrolyzable functional group
  • An airgel (aerogel obtained by drying a wet gel generated from the sol) that is a dried product of a wet gel that is a condensate of a sol containing at least one selected from the group consisting of hydrolysis products is porous.
  • the airgel composite material adhering to the base material having a structure has an excellent heat insulating property, and the airgel has flexibility, and is found to be a material with less aerogel falling off (powder falling), The present invention has been completed.
  • the present invention includes a base material having a porous structure and an airgel attached to the base material, wherein the airgel has a hydrolyzable functional group or a condensable functional group, and the hydrolysate.
  • an airgel composite material which is a dried product of a wet gel which is a condensate of a sol containing at least one selected from the group consisting of hydrolysis products of silicon compounds having degradable functional groups.
  • the airgel composite material of the present invention has excellent heat insulating properties as compared with conventional heat insulating materials. Moreover, according to the airgel composite material of this invention, since the airgel has a softness
  • the airgel composite material of the present invention can be bent according to the flexibility of the base material while suppressing the airgel from falling off because the airgel has flexibility.
  • the production cost may be high, or the production efficiency may not be sufficient due to batch production.
  • the airgel composite material of the present invention the airgel composite material can be obtained without using supercritical drying.
  • the sol may further contain silica particles. Thereby, the further outstanding heat insulation and softness
  • the average primary particle diameter of the silica particles can be 1 to 500 nm. Thereby, it becomes easy to improve heat insulation and a softness
  • the silicon compound may include a silicon compound having an alkoxy group as the hydrolyzable functional group.
  • the alkoxy group may have 1 to 6 carbon atoms.
  • the silicon compound may include a silicon compound having a hydroxyalkyl group as the condensable functional group.
  • the hydroxyalkyl group may have 1 to 6 carbon atoms.
  • the silicon compound may include a polysiloxane compound having a hydrolyzable functional group or a condensable functional group.
  • the polysiloxane compound may include a compound 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 .
  • the polysiloxane compound may include a compound having a structure represented by the following general formula (B).
  • R 1b represents an alkyl group or an alkoxy group
  • R 2b and R 3b each independently represents an alkoxy group
  • R 4b and R 5b each independently represent an alkyl group or an aryl group
  • m Represents an integer of 1 to 50.
  • the airgel may have a structure represented by the following general formula (1).
  • R 1 and R 2 each independently represent an alkyl group or an aryl group
  • R 3 and R 4 each independently represent an alkylene group.
  • the airgel may have a ladder structure including a support portion and a bridge portion, and the bridge portion may have a structure represented by the following general formula (2).
  • R 5 and R 6 each independently represents an alkyl group or an aryl group, and b represents an integer of 1 to 50. ]
  • the airgel may have a ladder structure represented by the following general formula (3).
  • R 5 , R 6 , R 7 and R 8 each independently represents an alkyl group or an aryl group, a and c each independently represent an integer of 1 to 3000, and b represents 1 to 50 Indicates an integer.
  • the pores in the porous structure may be communication holes, and the total volume of the pores may be 50 to 99% by volume of the total volume of the substrate. As a result, the heat insulating property is further improved.
  • the airgel composite material according to the present invention may be configured such that the airgel is filled in the communication hole. Thereby, the heat conduction by air is suppressed and heat insulation is further improved.
  • the substrate having the porous structure may be a sheet made of a fibrous material having a diameter of 0.1 to 1000 ⁇ m. Thereby, the heat conduction by the fibers can be suppressed, and a sufficient space is secured, so that the impregnation property of the sol into the sheet is improved.
  • the airgel composite material of the present invention can be in a form in which the airgel is attached to the fibrous substance. Thereby, since airgel exists in the intersection of the said fibrous substances, the heat conduction between fibrous substances can be suppressed and heat insulation is further improved.
  • an airgel composite material having excellent heat insulation properties and capable of suppressing airgel falling off.
  • FIG. 1 is a cross-sectional view showing an embodiment of an airgel composite material.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value of a numerical range in a certain step may be replaced with the upper limit value or the lower limit value of a numerical range in another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • “A or B” only needs to include either A or B, and may include both.
  • the materials exemplified in the present specification can be used singly or in combination of two or more unless otherwise specified.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. means.
  • the airgel composite material of this embodiment includes a base material having a porous structure (porous base material) and an airgel attached to the base material.
  • the airgel includes a silicon compound having a hydrolyzable functional group or a condensable functional group (silicon compound), and a hydrolysis product of the silicon compound having the hydrolyzable functional group (hydrolyzable functional group).
  • a dried product of a wet gel (wet gel derived from the sol) which is a condensate of a sol containing at least one selected from the group consisting of hydrolyzed silicon compounds.
  • the airgel 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.
  • the wet gel produced from the sol containing is dried.
  • the airgel is filled, for example, inside the substrate.
  • the airgel composite material of the present embodiment includes, for example, a porous base material and an airgel layer that covers at least a part of the porous base material.
  • Fig.1 (a) and FIG.1 (b) are sectional drawings which show embodiment of an airgel composite material.
  • An airgel composite material 100 shown in FIG. 1A and an airgel composite material 200 shown in FIG. 1B include a porous substrate 10 and an airgel layer 20.
  • FIG. 1 (a) the inside of the porous substrate 10 is filled with airgel, and the entire porous substrate 10 is covered with the airgel layer 20.
  • the airgel layer 20 is disposed on the surface of the porous substrate 10.
  • the airgel composite material of this embodiment is 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.
  • Airgel aerogel obtained by drying a wet gel generated from the sol
  • the conventional airgel is excellent in heat insulation, but is fragile and difficult to handle.
  • the use of the specific airgel improves flexibility, so that it is easy to handle. Can be improved.
  • the thickness of the airgel layer can be 200 ⁇ m or less, 100 ⁇ m or less, 80 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less. By setting the thickness of the airgel layer to 200 ⁇ m or less, powder falling is easily suppressed and the airgel layer is easy to handle.
  • the thickness of the airgel layer can be 1 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more.
  • the thickness of the airgel composite material of the present embodiment may be 100 mm or less, 10 mm or less, or 1 mm or less. By setting the thickness of the airgel composite material to 100 mm or less, the airgel composite material is easily cut and the workability is improved.
  • the airgel means “a gel composed of a microporous solid whose dispersed phase is a gas”, which is an aerogel in a broad sense, that is, “Gel compressed of a microporous solid in which the dispersed phase is a gas”. To do.
  • the inside of an 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 bonded. 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 in the present embodiment is a layer composed of airgel.
  • the airgel layer may be a layer containing an airgel having a structure derived from polysiloxane.
  • the airgel of the present embodiment is a group consisting of 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 is a dried product of a wet gel that is a condensate of a sol containing at least one selected from the above. That is, the airgel of this embodiment is obtained from 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).
  • 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 of 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 of this 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.
  • the airgel of this embodiment includes the following modes. By adopting these aspects, it becomes easy to obtain an airgel that is further excellent in heat insulation and flexibility. By employ
  • the airgel of 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 wet gel which is a condensate of a 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 product.
  • the airgel of this embodiment is a hydrolysis product of a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and 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.
  • 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 phenolic hydroxyl 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 specifically 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, and may be 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.
  • Examples of the polysiloxane compound having an alkoxy group include compounds having a structure represented by the following general formula (B).
  • R 1b represents an alkyl group, an alkoxy group or an aryl group
  • R 2b and R 3b each independently represent an alkoxy group
  • R 4b and R 5b each independently represent an alkyl group or an aryl group.
  • M 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 1b s may be the same or different
  • two R 2b s may be the same or different.
  • R 3b may be the same or different.
  • when m is an integer of 2 or more, two or more R 4b may be the same or different, and similarly, two or more R 5b may be the same. May be different.
  • examples of R 1b include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and specific examples include a methyl group, a methoxy group, and an ethoxy group. It is done.
  • R 2b and R 3b may each independently be an alkoxy group having 1 to 6 carbon atoms.
  • 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 can be 2 to 30, and may be 5 to 20.
  • the polysiloxane compound having the structure represented by the general formula (B) can be obtained by appropriately referring to the production methods reported in, for example, JP-A Nos. 2000-26609 and 2012-233110. Can do.
  • 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.
  • Each of the hydrolyzable functional group or the polysiloxane compound having a condensable functional group and the hydrolysis product of the polysiloxane compound having the hydrolyzable functional group may be used alone or in combination of two or more. May be used.
  • the content of the polysiloxane compound group contained in the sol (the content of the polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and the water
  • the total content of hydrolysis products of polysiloxane compounds having degradable functional groups) can be 1 part by mass or more with respect to 100 parts by mass of the total amount of sol. Alternatively, it may be 4 parts by mass or more, 5 parts by mass or more, or 7 parts by mass or more. Since it becomes easier to obtain good compatibility, the content of the polysiloxane compound group can be 50 parts by mass or less with respect to 100 parts by mass of the total amount of the sol, and may be 30 parts by mass or less.
  • the content of the polysiloxane compound group can be 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the sol, and may be 3 to 50 parts by mass, or 4 to 50 parts by mass. It may be 5 to 50 parts by mass, 7 to 30 parts by mass, or 7 to 15 parts by mass.
  • the silicon compound having a hydrolyzable functional group or a condensable functional group a silicon compound (silicon compound) other than the polysiloxane compound may be used. That is, the airgel of this embodiment includes a silicon compound (excluding a polysiloxane compound) having a hydrolyzable functional group or a condensable functional group (in the molecule), and silicon having the hydrolyzable functional group. It may be a dried product of a wet gel that is a condensate of sol containing at least one compound selected from the group consisting of hydrolysis products of compounds (hereinafter sometimes referred to as “silicon compound group”). The number of silicon atoms in the molecule of the silicon compound can be 1 or 2.
  • the silicon compound having a hydrolyzable functional group is not particularly limited, and examples thereof include alkyl silicon alkoxides.
  • the number of hydrolyzable functional groups may be 3 or less, or 2 to 3.
  • the alkyl silicon alkoxide include monoalkyltrialkoxysilane, monoalkyldialkoxysilane, dialkyldialkoxysilane, monoalkylmonoalkoxysilane, dialkylmonoalkoxysilane and trialkylmonoalkoxysilane.
  • Examples of the alkyl silicon alkoxide include methyltrimethoxysilane, methyldimethoxysilane, dimethyldimethoxysilane, and ethyltrimethoxysilane.
  • the number of hydrolyzable functional groups is 3 or less, and as a silicon compound having a reactive group, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, N-phenyl-3-amino Propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like can also be used.
  • bistrimethoxysilylmethane, bistrimethoxysilylethane, bistrimethoxysilylhexane, or the like can also be used as a silicon compound having three or less hydrolyzable functional groups at the molecular terminals.
  • Each of the hydrolyzable functional group or the silicon compound having a condensable functional group (excluding the polysiloxane compound) and the hydrolyzate of the silicon compound having the hydrolyzable functional group either alone or 2 You may mix and use a kind or more.
  • Content of silicon compounds contained in the sol (contents of silicon compounds having hydrolyzable functional groups or condensable functional groups (excluding polysiloxane compounds) contained in the sol because it becomes easier to obtain good reactivity.
  • the total content of hydrolysis products of the silicon compound having a hydrolyzable functional group can be 5 parts by mass or more with respect to 100 parts by mass of the total amount of the sol. It may be 12 mass parts or more, 15 mass parts or more, or 18 mass parts or more. Since it becomes easier to obtain good compatibility, the content of the silicon compound group can be 50 parts by mass or less with respect to 100 parts by mass of the total amount of the sol, and may be 30 parts by mass or less. It may be 25 parts by mass or less, or 20 parts by mass or less.
  • the content of the silicon compound group may be 5 to 50 parts by mass with respect to 100 parts by mass of the sol, may be 10 to 30 parts by mass, or 12 to 30 parts by mass. It may be 15 to 25 parts by mass, or 18 to 20 parts by mass.
  • the sum of the content of the polysiloxane compound group and the content of the silicon compound group can more easily obtain good reactivity, and therefore can be 5 parts by mass or more with respect to 100 parts by mass of the total amount of sol. It may be 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, or 22 parts by mass or more. Since it becomes easier to obtain good compatibility, the sum of the contents can be 50 parts by mass or less, or 30 parts by mass or less, and 25 parts by mass with respect to 100 parts by mass of the sol. Or less. That is, the total content may be 5 to 50 parts by mass with respect to 100 parts by mass of the sol, may be 10 to 30 parts by mass, and may be 15 to 30 parts by mass. 20 to 30 parts by mass, or 22 to 25 parts by mass.
  • the ratio of the content of the polysiloxane compound group to the content of the silicon compound group can be 1: 0.5 to 1: 4. It may be ⁇ 1: 2, may be 1: 2 to 1: 4, and may be 1: 3 to 1: 4.
  • By setting the ratio of the content of these compounds to 1: 0.5 or more it becomes easier to obtain good compatibility.
  • By setting the content ratio to 1: 4 or less it becomes easier to suppress the shrinkage of the gel.
  • the airgel of this embodiment can have a structure represented by the following general formula (1).
  • the airgel of this embodiment can have a structure represented by the following general formula (1a) as a structure including the structure represented by the 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 each independently represent an alkyl group or an aryl group
  • R 3 and R 4 each independently represent an alkylene group.
  • 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.
  • p represents an integer of 1 to 50.
  • two or more R 1 s may be the same or different, and similarly, two or more R 2 s may be the same or different.
  • two R 3 s may be the same or different, and similarly, two R 4 s may be the same or different.
  • 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 of the present embodiment may be an airgel having a ladder type structure including a support portion and a bridge portion, and the bridge portion may be an airgel having a structure represented by the following general formula (2). .
  • 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 has a structure derived from a conventional ladder-type silsesquioxane (that is, has a structure represented by the following general formula (X)). It becomes the airgel which has the outstanding softness
  • the structure of the bridge portion is —O—.
  • the structure of the hanging portion is a structure (polysiloxane structure) represented by the general formula (2).
  • R represents a hydroxy group, an alkyl group or an aryl group.
  • the structure to be the strut part and the chain length, and the interval between the structures to be the bridging part are not particularly limited, but from the viewpoint of further improving the heat resistance and mechanical strength, the ladder type structure has the following general formula ( It may have a ladder structure represented by 3).
  • R 5 , R 6 , R 7 and R 8 each independently represents an alkyl group or an aryl group
  • a and c each independently represents an integer of 1 to 3000
  • b is 1 to 50 Indicates an integer.
  • 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.
  • b is an integer of 2 or more
  • two or more R 5 s may be the same or different
  • similarly, two or more R 6 s may be the same. May be different.
  • formula (3) when a is an integer of 2 or more, two or more R 7 s may be the same or different.
  • when c is an integer of 2 or more, 2 or more R 8 may be the same or different from each other.
  • R 5 , R 6 , R 7 and R 8 are: Each may be independently an alkyl group having 1 to 6 carbon atoms or a phenyl group. The alkyl group may be a methyl group.
  • a and c can be independently 6 to 2000, and may be 10 to 1000.
  • b can be 2 to 30, and can be 5 to 20.
  • the airgel of this embodiment may contain silica particles.
  • the sol that gives the airgel may further contain silica particles. That is, the airgel of this 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. That is, the airgel layer may be composed of a layer obtained by drying a wet gel generated from a sol containing silica particles.
  • the airgel described so far is also 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). May be.
  • the silica particles can be used without particular limitation, and examples thereof include amorphous silica particles.
  • examples of the amorphous silica particles include fused silica particles, fumed silica particles, and colloidal silica particles.
  • colloidal silica particles have high monodispersity and are easy to suppress aggregation in the sol.
  • the shape of the silica particles is not particularly limited, and examples thereof include a spherical shape, an eyebrows type, 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 can easily be imparted with an appropriate strength to the airgel, and an airgel excellent in shrinkage resistance during drying can be easily obtained. It may be 10 nm or more.
  • the average primary particle diameter of the silica particles can be 500 nm or less, even if it is 300 nm or less. It may be 250 nm or less. That is, the average primary particle diameter of the silica particles can be 1 to 500 nm, can be 5 to 300 nm, and can be 10 to 250 nm.
  • the number of silanol groups per gram of silica particles can be 10 ⁇ 10 18 pieces / g or more, and may be 50 ⁇ 10 18 pieces / g or more. It may be 100 ⁇ 10 18 pieces / g or more. Since it becomes easy to obtain a homogeneous airgel, the number of silanol groups per gram of silica particles can be 1000 ⁇ 10 18 pieces / g or less, and may be 800 ⁇ 10 18 pieces / g or less, and 700 ⁇ 10 18 pieces / g or less may be sufficient.
  • the number of silanol groups per gram of silica particles can be 10 ⁇ 10 18 to 1000 ⁇ 10 18 pcs / g, or 50 ⁇ 10 18 to 800 ⁇ 10 18 pcs / g, or 100 ⁇ 10 10 It may be 18 to 700 ⁇ 10 18 pieces / g.
  • the content of the silica particles contained in the sol is 1 mass relative to 100 mass parts of the total amount of the sol. It may be 4 parts by mass or more. Since it becomes easy to suppress the solid heat conduction of the silica particles and it becomes easy to obtain an airgel excellent in heat insulation, the content of the silica particles contained in the sol can be 20 parts by mass or less, and 15 parts by mass or less. It may be 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 can be 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the sol, and may be 4 to 15 parts by mass or 4 to 12 parts by mass. It may be 4 to 10 parts by mass, or 4 to 8 parts by mass.
  • the airgel of this embodiment can have a structure represented by the following general formula (4).
  • the airgel of the present embodiment contains silica particles and can have a structure represented by the following general formula (4).
  • 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 of the present embodiment can have a structure represented by the following general formula (5).
  • the airgel of the present embodiment contains silica particles and can have a structure represented by the following general formula (5).
  • R 10 and R 11 each independently represent an alkyl group.
  • alkyl group examples include alkyl groups having 1 to 6 carbon atoms, and specific examples include a methyl group.
  • the airgel of this embodiment can have a structure represented by the following general formula (6).
  • the airgel of the present embodiment contains silica particles and can have a structure represented by the following general formula (6).
  • R 12 represents an alkylene group.
  • the alkylene group include an alkylene group having 1 to 10 carbon atoms, and specific examples include an ethylene group and a hexylene group.
  • the airgel of this embodiment may have a structure derived from polysiloxane.
  • Examples of the structure derived from polysiloxane include structures represented by the above general formula (1), (2), (3), (4), (5), or (6).
  • the airgel of this embodiment may have at least one of the structures represented by the general formulas (4), (5), and (6) without containing silica particles.
  • Porous substrate is a general term for materials containing a large number of pores (micropores), and is classified into microporous materials, mesoporous materials, and macroporous materials depending on the size of the pores. In form, it is referred to as a “porous substrate” regardless of the size of the pores.
  • the porous substrate include a substrate made of a fibrous material and a substrate that forms a three-dimensional complex skeleton.
  • examples of the porous substrate include a nonwoven fabric and a porous sheet having a porous structure. The pores in the porous structure (pores constituting the porous structure) may be communication holes.
  • the communication hole is a state in which the pores (voids) inside the porous substrate and the pores (voids) on the surface of the porous substrate are combined to form a two-dimensional or three-dimensional void network. Means the state.
  • the airgel may be filled in the communication hole.
  • the size of the hole indicates the maximum linear distance of the shape formed by the hole on the observation surface when observing the cross-sections of any 10 locations on the substrate along the surface direction of the substrate (direction orthogonal to the thickness direction). .
  • the pore size can be 0.1 to 1000 ⁇ m. If the size is 0.1 ⁇ m or more, the sol coating liquid can be easily impregnated. If the size is 1000 ⁇ m or less, it is possible to easily prevent the airgel from dropping out of the holes.
  • the total volume of the pores may be 50 to 99% by volume of the total volume of the substrate, may be 60 to 99% by volume, and 70 to 99% by volume. There may be. As a result, the heat insulating property is further improved.
  • the holes in the porous structure are communication holes, the total volume of the holes may satisfy the above range.
  • Examples of the material constituting the porous substrate include organic polymers such as vinyl polymer, polyester, polyacrylonitrile, polysulfone, phenol resin, polyurethane, polyamide, polyimide, and carbon; glass, metal (for example, nickel), metal oxide Examples thereof include inorganic porous materials such as (for example, alumina).
  • Examples of the vinyl polymer include polyolefins (for example, polyethylene and polypropylene), cellulose acetate, nitrocellulose, polytetrafluoroethylene, polycarbonate, polystyrene, polyvinyl alcohol, polyacrylic acid ester, and polyvinyl acetate.
  • glass, metal or metal oxide for example, alumina
  • glass, metal or metal oxide can be used because it is further excellent in heat resistance, and glass or alumina is used from the point of further reducing thermal conductivity. Can be used.
  • the airgel is present in a void portion of a base material made of a fibrous substance or a base material forming a three-dimensional complex skeleton.
  • a base material made of a fibrous substance or a base material forming a three-dimensional complex skeleton.
  • the porous substrate may be a sheet (nonwoven fabric, fiber sheet, etc.) made of a fibrous material.
  • a porous substrate for example, airgel is attached to a fibrous substance.
  • Fibrous materials include nylon, polyester, polypropylene, polyacrylonitrile, vinylon, polyolefin, polyurethane, rayon, carbon fiber and other organic fibers; glass, rock wool, ceramic and other inorganic fibers; copper, iron, stainless steel, gold, silver And metal fibers such as aluminum.
  • inorganic fibers can be used from the viewpoint of further excellent heat resistance
  • glass, rock wool, or ceramic can be used from the viewpoint of further reducing the thermal conductivity.
  • the diameter of the fibrous material may be 0.1 to 1000 ⁇ m, may be 0.1 to 100 ⁇ m, and may be 0.1 to 80 ⁇ m. Thereby, the heat conduction by the fibers can be easily suppressed, and the voids are sufficiently secured, so that the impregnation of the sol into the sheet is improved.
  • the diameter of the fibrous substance can be measured by observing with a microscope and measured as an average value of the diameters of 10 arbitrarily selected fibers.
  • the airgel composite material of the present embodiment is 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 can be obtained by drying a wet gel (wet gel produced from the sol) which is a condensate of sol containing at least one of the above.
  • the method for producing an airgel composite material of the present embodiment includes a drying step of drying the wet gel, and includes a hydrolyzable functional group or a silicon compound having a condensable functional group, and the hydrolyzable functional group. There may be further provided a gel generation step of obtaining the wet gel by reacting a sol containing at least one selected from the group consisting of hydrolysis products of silicon compounds.
  • the airgel composite material can be produced, for example, by the following method.
  • the airgel composite material of the present embodiment includes, for example, a sol generation step for producing a sol for forming an airgel, an impregnation step for impregnating a porous substrate with the sol obtained in the sol generation step, and a sol Gel generation step of gelling to obtain a wet gel, aging step of aging a porous substrate filled with voids with sol or wet gel, and cleaning and / or solvent replacement step of cleaning and / or solvent replacement of the aged composite material And a drying step of drying the washed and / or solvent-substituted composite material.
  • the “sol” is a state before the gelation reaction occurs, and in the present embodiment, the state in which the silicon compound (and if necessary, further silica particles) is dissolved or dispersed in the solvent. means.
  • the gel generation step may be performed after the impregnation step, or the impregnation step may be performed after the gel generation step.
  • an airgel composite material can be obtained by preparing a substance and making it into a non-woven fabric.
  • the bonding mode such as bonding by the chemical interaction between the functional group on the fiber surface and the functional group on the airgel surface, bonding by intermolecular interaction between the fiber surface and the airgel is limited. Not what you want. Airgel particles (particles constituting the airgel) may be attached to part or the whole of the fiber surface.
  • the sol generation step is, for example, a step of mixing a silicon compound (and if necessary, further silica particles) and a solvent, performing a hydrolysis reaction, and then performing a sol-gel reaction to obtain a semi-gelled sol coating liquid. is there.
  • 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 solvent is not particularly limited as long as a good impregnation property can be obtained in the impregnation step described later, and for example, water or a mixed solution of water and alcohol can be used.
  • the alcohol include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol and t-butanol.
  • water can be used because of its high surface tension and low volatility.
  • the acid catalyst examples include inorganic acids such as hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, bromic acid, chloric acid, chlorous acid, and hypochlorous acid; Acid phosphates such as aluminum phosphate, acid magnesium phosphate and acid zinc phosphate; organic such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid, azelaic acid Carboxylic acids are mentioned.
  • inorganic acids such as hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, bromic acid, chloric acid, chlorous acid, and hypochlorous acid
  • Acid phosphates such as aluminum phosphate, acid magnesium phosphate and acid zinc phosphate
  • organic such as for
  • organic carboxylic acids can be used, and specifically include acetic acid, formic acid, propionic acid, oxalic acid and malonic acid, Acetic acid may be used. You may use an acid catalyst individually or in mixture of 2 or more types.
  • the addition amount of the acid catalyst can be 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the silicon compound.
  • 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.
  • nonionic surfactant for example, a compound containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group, a compound containing a hydrophilic part such as polyoxypropylene, and the like can be used.
  • the compound containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether and the like.
  • the compound having a hydrophilic portion such as polyoxypropylene include polyoxypropylene alkyl ether, a block copolymer of polyoxyethylene and polyoxypropylene, and the like.
  • 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 and cetyltrimethylammonium chloride.
  • the anionic surfactant 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 have the effect of reducing the difference in chemical affinity between the solvent in the reaction system and the growing siloxane polymer and suppressing phase separation in the impregnation step described later. It is considered.
  • the amount of the surfactant added depends on the type of surfactant or the type and amount of the silicon compound. For example, it 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 is considered to generate a base catalyst by thermal hydrolysis, thereby making the reaction solution basic and promoting the sol-gel reaction. Accordingly, the thermohydrolyzable compound is not particularly limited as long as it can make the reaction solution basic after hydrolysis.
  • urea for example, urea; formamide, N-methylformamide, N, N-dimethylformamide, acetamide And acid amides such as N-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 added can be 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of silicon compound, and even if it is 2 to 150 parts by mass. Good. By making the addition amount 1 mass part or more, it becomes easier to obtain good reactivity. By making the addition amount 200 parts by mass or less, it becomes easy to suppress precipitation of crystals and a decrease in gel density.
  • the hydrolysis in the sol production step depends on the type and amount of silicon compound, silica particles, acid catalyst, surfactant, etc. in the mixed solution, but for example, in a temperature environment of 20 to 60 ° C. for 10 minutes to 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 can be 0 to 40 ° C., and may be 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, sec Aliphatic amines such as butylamine, propylamine, 3- (
  • ammonium hydroxide (ammonia water) has high volatility and is difficult to remain in the airgel layer after drying, and is excellent in terms of being hard to impair water resistance and economical. You may use said base catalyst individually or in mixture of 2 or more types.
  • 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 It can be performed in a shorter time.
  • ammonia is highly volatile and hardly remains in the airgel composite material. Therefore, an airgel composite material with better water resistance can be obtained by using ammonia as the base catalyst.
  • the addition amount of the base catalyst can be 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of silicon compounds (polysiloxane compound group and silicon compound group), and may be 1 to 4 parts by mass. .
  • the addition amount of the base catalyst 0.5 parts by mass or more, gelation can be performed in a shorter time.
  • the addition amount of the base catalyst 5 parts by mass or less it is possible to easily suppress a decrease in water resistance.
  • the impregnation step is, for example, a step of filling the sol coating liquid into a porous substrate or adhering it to a raw material fiber of a nonwoven fabric.
  • a dipping method in which the material of the porous base material is immersed in the sol coating liquid or a coating method in which the sol coating liquid is applied to the porous base material can be mentioned.
  • the impregnation 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 porous substrate.
  • the method of treating the sol coating liquid on the raw material fibers of the nonwoven fabric for example, a wet method in which the fibers are put into a container containing the sol coating liquid and the fibers are surface-treated by heating and stirring for a predetermined time, and the fibers are mixed with a stirrer
  • a dry method in which a sol coating solution is added while stirring at high speed to uniformly treat the fiber surface can be mentioned.
  • the method for treating the sol coating solution on the fiber is not particularly limited, but a wet method can be used because the sol coating solution is easy to uniformly treat the fiber surface.
  • a die coater, a comma coater, a bar coater, a kiss coater, a roll coater, etc. can be used, and it is appropriately used depending on the material or thickness of the porous substrate, the viscosity or the coating amount of the sol coating solution, etc. .
  • the heating / drying method heating, hot air blowing, or the like can be used.
  • the heating / drying conditions after applying the sol coating liquid to the porous substrate are, for example, heating / drying so that the moisture content of the airgel layer after heating / drying is 10% by mass or more (for example, 50% by mass or more). Let By setting the water content to 10% by mass or more, it becomes easy to obtain adhesiveness with the porous substrate.
  • the heating / drying temperature varies depending on the amount of water and / or the amount of organic solvent in the sol coating liquid, the boiling point of the organic solvent, etc., but can be, for example, 50 to 150 ° C., or even 60 to 120 ° C. Good. By setting the heating / drying temperature to 50 ° C. or higher, gelation can be performed in a shorter time. By setting the heating / drying temperature to 150 ° C. or lower, it becomes easy to obtain adhesion with the porous substrate.
  • the heating / drying time varies depending on the heating / drying temperature, but can be, for example, 0.2 to 10 minutes, or 0.5 to 8 minutes. By setting the heating / drying time to 0.2 minutes or more, the airgel layer is easily formed. By setting the heating / drying time to 10 minutes or less, it becomes easy to obtain adhesion with the porous substrate. As the heating / drying conditions, suitable heating / drying conditions can be appropriately set by simple experiments in advance.
  • a separator can be laminated on both sides of the porous substrate. By laminating the separator, it is possible to prevent transfer or contamination of the uncured sol in the conveyance of the porous substrate and other processes.
  • Examples of the method of laminating the separator in the impregnation step include a method of laminating after impregnating the sol coating liquid, and a method of laminating after heating and drying.
  • Examples of the separator include inorganic fibers such as glass nonwoven fabric and glass cloth; organic fibers such as polyimide, polyamideimide, and polyester; base film made of polyolefin, polyester, polycarbonate, polyimide, and the like; release paper; copper foil, aluminum foil, and the like Can be mentioned.
  • the separator may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
  • a base film made of polyolefin, polyester, polycarbonate, polyimide, or the like can be used from the viewpoint of keeping the water content of the airgel layer high.
  • inorganic fibers such as glass nonwoven fabric and glass cloth; organics such as polyimide, polyamideimide, and polyester, from the viewpoint that they do not need to be peeled off in the aging step and washing / solvent replacement step described later.
  • a fiber etc. can be used.
  • the gel generation step is a step of obtaining a wet gel by gelling the sol obtained in the sol generation step.
  • a base catalyst can be used to promote gelation. Since it is often difficult to determine the end point of gelation of the sol, gelation of the sol and subsequent aging may be performed in a series of operations.
  • the gelation of the sol in the gel generation step may be performed in a sealed container so that the solvent and the base catalyst do not volatilize.
  • the gelation temperature can be 30 to 90 ° C., but it may be 40 to 80 ° C. By setting the gelation temperature to 30 ° C. or higher, gelation can be performed in a shorter time, and a wet gel with high strength can be obtained. By setting the gelation temperature to 90 ° C. or less, it becomes easy to suppress the volatilization of the solvent (particularly alcohol), and thus gelation can be performed while suppressing volume shrinkage.
  • the aging step is a step of aging the composite material obtained by the impregnation step or the gel generation step by heating.
  • the airgel layer is preferably aged so that the water content is 10% by mass or more, and is 50% by mass or more. It is better to age.
  • the aging method is not particularly limited as long as the above range is satisfied.For example, a method of aging the composite material in a sealed atmosphere, and a constant temperature and humidity chamber that can suppress a decrease in moisture content due to heating, etc. A method of aging is mentioned.
  • the aging temperature can be, for example, 40 to 90 ° C., and may be 50 to 80 ° C. By setting the aging temperature to 40 ° C. or more, the aging time can be shortened. By setting the aging temperature to 90 ° C. or lower, it is possible to suppress a decrease in moisture content.
  • the aging time can be, for example, 1 to 48 hours, and may be 3 to 24 hours. By setting the aging time to 1 hour or longer, further excellent heat insulation can be obtained. By setting the aging time to 48 hours or less, high adhesion to the porous substrate can be obtained.
  • the washing / solvent replacement step is a step having a step of washing the composite material obtained by the aging step (washing step) and a step of substitution with a solvent suitable for the drying step described later (solvent substitution step).
  • the washing and solvent replacement technique is not particularly limited, and for example, continuous treatment can be performed using a plurality of washing tanks and / or solvent replacement tanks in a roll-to-roll manner.
  • the washing / solvent replacement step can be performed in a form in which only the solvent replacement step is performed without performing the step of cleaning the composite material, but it reduces impurities such as unreacted substances and by-products in the airgel layer, and more. From the viewpoint of enabling the production of a highly pure airgel composite material, the aged airgel layer may be washed.
  • the composite material 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 can 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.
  • the hydrophilic organic solvent used in the washing step can serve as a preliminary replacement for the solvent replacement step. Therefore, among the above organic solvents, hydrophilic organic solvents such as methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, and the like can be used. From the economical viewpoint, methanol, ethanol, or methyl ethyl ketone may be used. .
  • the amount of water or organic solvent used in the washing step can be a quantity that can sufficiently replace the solvent in the airgel layer and can be washed.
  • the amount of the solvent is 3 to 10 times the volume of the airgel layer. Can be used.
  • the washing can be repeated until the water content in the airgel layer after washing becomes 10% by mass or less.
  • the temperature in the washing step can be set to a temperature equal to or lower than the boiling point of the solvent used for washing.
  • the temperature can be about 30 to 60 ° C.
  • the solvent of the washed airgel layer can be replaced with a predetermined replacement solvent in order to suppress shrinkage of the airgel layer in the drying step described later.
  • the replacement efficiency can be improved by heating.
  • Specific examples of the solvent for substitution include a low surface tension solvent described later in the drying step when drying is performed under atmospheric pressure at a temperature lower than the critical point of the solvent used for drying.
  • the replacement solvent for example, ethanol, methanol, 2-propanol, dichlorodifluoromethane, or carbon dioxide may be used alone, or a mixture of two or more of these may be used. Also good.
  • Examples of the low surface tension solvent include a solvent having a surface tension at 20 ° C. of 30 mN / m or less. The surface tension may be 25 mN / m or less, or 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),
  • the parenthesis indicates the surface tension at 20 ° C., and the unit is [mN / m].
  • aliphatic hydrocarbons hexane, heptane, etc.
  • 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 at normal pressure of 100 ° C. or less may be used because it is easy to dry in the drying step described later. You may use said solvent individually or in mixture of 2 or more types.
  • the amount of the solvent used in the solvent replacement step can be an amount that can sufficiently replace the solvent in the airgel layer after washing, and the amount of the solvent is 3 to 10 times the volume of the airgel layer. be able to.
  • the temperature in the solvent replacement step can be a temperature not higher than the boiling point of the solvent used for the replacement, for example, about 30 to 60 ° C.
  • the solvent replacement step is not necessarily essential as described above.
  • the inferred mechanism is as follows.
  • the silica particles function as a support of a three-dimensional network airgel skeleton, whereby the skeleton is supported and gel shrinkage in the drying process is suppressed. Therefore, it is considered that the gel can be directly subjected to the drying step without replacing the solvent used for washing.
  • the washing / solvent replacement step to the drying step can be simplified.
  • the separator When separators are laminated in the impregnation step, from the viewpoint of improving the efficiency of washing the airgel layer and replacing the solvent, the separator can be extracted before the washing step and laminated again after the solvent substitution step.
  • the separator by treating with the composite material without removing it, it is possible to suppress a reduction in the efficiency of washing and solvent substitution of the airgel layer in the washing / solvent substitution step to the drying step, and drying in the drying step described later.
  • a glass nonwoven fabric, organic fiber, etc. can be used from a viewpoint which can suppress the fall of efficiency.
  • the drying method is not particularly limited, and known atmospheric drying, supercritical drying or freeze drying can be used.
  • atmospheric pressure drying or supercritical drying can be used from the viewpoint of easy production of a low-density airgel layer.
  • atmospheric drying can be used from the viewpoint of being able to produce at low cost.
  • the normal pressure means 0.1 MPa (atmospheric pressure).
  • the airgel composite material of this embodiment can be obtained by drying a washed and / or solvent-substituted composite material at a temperature below the critical point of the solvent used for drying under atmospheric pressure.
  • 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 porous substrate, but can be 60 to 180 ° C., and 90 to 150 It may be ° C.
  • the drying time varies depending on the volume of the airgel layer and the drying temperature, but can be 2 to 48 hours. In the present embodiment, drying can be accelerated by applying pressure within a range that does not impair productivity.
  • pre-drying may be performed before the drying step from the viewpoint of improving the drying efficiency in atmospheric drying.
  • the pre-drying method is not particularly limited.
  • the washing / solvent replacement step to the drying step can be performed continuously.
  • the pre-drying temperature can be 60 to 180 ° C., and may be 90 to 150 ° C.
  • the predrying time can be 1 to 30 minutes. Note that the composite material obtained by such pre-drying can be further dried in the drying step.
  • the separators When the separators are laminated in the washing / solvent replacement step, the separators can be extracted before pre-drying and laminated again after pre-drying from the viewpoint of drying efficiency and transport efficiency. In the case where the washing / solvent replacement step to the drying step are carried out continuously, the separator can be extracted before the washing step and laminated again after the pre-drying.
  • a separator laminated after pre-drying a glass nonwoven fabric, organic fiber, etc. can be used from a viewpoint which can suppress the fall of the drying efficiency in a drying process.
  • the airgel composite material of this embodiment can also be obtained by supercritical drying of a cleaned and / or solvent-substituted composite material.
  • Supercritical drying can be performed by a known method. Examples of 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. Is substituted with carbon dioxide having a lower critical point than that of the solvent, and then carbon dioxide alone or a mixture of carbon dioxide and the solvent is removed.
  • the airgel composite material of the present embodiment described as described above includes 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.
  • An airgel (aerogel obtained by drying a wet gel generated from the sol) that is a dried product of a wet gel that is a condensate of a sol containing at least one selected from the group, and a substrate having a porous structure It is possible to form an airgel sheet and board, which has been conventionally difficult to handle.
  • the airgel composite material of the present embodiment can be applied to a use as a heat insulating material in a cryogenic container, a space field, an architectural field, an automobile field, a home appliance field, a semiconductor field, an industrial facility, and the like. Further, the airgel composite material of the present embodiment can be used for water repellent, sound absorbing, static vibration, catalyst support, etc., in addition to the use as a heat insulating material.
  • the airgel sheet having the structure represented by the general formula (2) has a ladder structure including a support portion and a bridge portion, and the bridge portion is represented by the general formula (2).
  • the bridge portion is represented by the general formula (2).
  • Example 1 [Sol coating solution 1] 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 120.0 parts by mass, methanol 80.0 parts by mass and 0.10 parts by mass of acetic acid as an acid catalyst were mixed to obtain a mixture.
  • PL-2L manufactured by Fuso Chemical Industry Co., Ltd., product name, average primary particle size: 20 nm, solid content: 20% by mass
  • water is 120.0 parts by mass
  • the sol coating solution 1 is placed in a vat, and a glass nonwoven fabric (manufactured by Nippon Sheet Glass Co., Ltd., product name: MGP BMS-5, fiber diameter: 1.5 ⁇ m, void) (length) 300 mm ⁇ (width) 200 mm ⁇ (thickness) 3 mm
  • the sol coating solution 1 was impregnated with the sol coating solution 1.
  • the gel was gelled at 60 ° C. for 30 minutes to obtain an airgel sheet. Thereafter, the obtained airgel sheet (wet gel) was transferred to a sealed container and aged at 60 ° C. for 12 hours.
  • the aged airgel sheet 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 airgel sheet 1 having the structure represented by the above general formulas (4) and (5) was obtained by drying the washed and solvent-substituted airgel sheet at 120 ° C. for 6 hours under normal pressure.
  • Example 2 [Sol coating liquid 2] ST-OZL-35 (product name, average primary particle size: 100 nm, solid content: 35% by mass) 100.0 parts by mass and 100.0 parts by mass of water as a silica particle-containing raw material 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB (cetyltrimethylammonium bromide) as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound To obtain a mixture.
  • CTAB cetyltrimethylammonium bromide
  • Example 3 [Sol coating solution 3] 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 As a heat hydrolyzable compound, 120.0 parts by mass of urea was mixed to obtain a mixture.
  • polysiloxane compound a bifunctional alkoxy-modified polysiloxane compound having a structure represented by the above general formula (B) as a polysiloxane compound (hereinafter referred to as “polysiloxane compound”) 20.0 parts by mass of A)) 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.
  • 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. under reduced pressure of 1.3 kPa for 2 hours 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
  • Example 4 [Sol coating solution 4] 100.0 parts by mass of PL-2L as a raw material containing silica particles, 200.0 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 As a heat hydrolyzable compound, 120.0 parts by mass of urea was mixed to obtain a mixture.
  • polysiloxane compound a trifunctional alkoxy-modified polysiloxane compound having both ends as a polysiloxane compound having a structure represented by the above general formula (B) (hereinafter referred to as “polysiloxane compound”) 40.0 parts by mass of “B”) was added, and the mixture was 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 4.
  • the “polysiloxane compound B” was synthesized as follows. First, in a 1 L three-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser, 100.0 parts by mass of XC96-723, 202.6 parts by mass of tetramethoxysilane, and 0 of t-butylamine were added. 50 parts by mass were mixed and reacted at 30 ° C. for 5 hours. Thereafter, this reaction solution was heated at 140 ° C. under reduced pressure of 1.3 kPa for 2 hours to remove volatile components, thereby obtaining a trifunctional alkoxy-modified polysiloxane compound (polysiloxane compound B) at both ends.
  • Example 5 [Sol 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 As a heat hydrolyzable compound, 120.0 parts by mass of urea was mixed to obtain a mixture. To this mixture, 60.0 parts by mass of MTMS and 40.0 parts by mass of DMDMS were added as silicon compounds and reacted at 25 ° C. for 2 hours. Thereafter, a sol-gel reaction was performed at 60 ° C. for 1.0 hour to obtain a sol coating solution 5.
  • Example 6 [Sol coating liquid 6] 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 As a heat hydrolyzable compound, 120.0 parts by mass of urea was mixed to obtain a mixture. To this mixture, 60.0 parts by mass of MTMS as a silicon compound, 20.0 parts by mass of DMDMS, and 20.0 parts by mass of X-22-160AS as a polysiloxane compound were added and reacted at 25 ° C. for 2 hours. . Thereafter, a sol-gel reaction was performed at 60 ° C. for 1.0 hour to obtain a sol coating liquid 6.
  • Example 7 [Sol coating liquid 7] 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 As a heat hydrolyzable compound, 120.0 parts by mass of urea was mixed to obtain a mixture. To this mixture, 60.0 parts by mass of MTMS as a silicon compound and 20.0 parts by mass of DMDMS and 20.0 parts by mass of polysiloxane compound A as a polysiloxane compound were added and reacted at 25 ° C. for 2 hours. Thereafter, a sol-gel reaction was performed at 60 ° C. for 1.0 hour to obtain a sol coating liquid 7.
  • Example 2 Thereafter, the washing / solvent replacement step and the drying step are performed in the same manner as in Example 1, and the glass fiber to which the airgel having the structure represented by the general formulas (2), (3), (4) and (5) is attached is attached. was gotten.
  • a papermaking apparatus an apparatus comprising an upper papermaking tank (capacity 30L) and a lower water tank (capacity 10L) provided with a stirrer with a rotor blade, and a porous support is provided between the papermaking tank and the water tank. was used. First, the dispersion was stirred using a stirrer until air microbubbles were generated.
  • the glass fiber whose mass was adjusted so as to have a desired basis weight was put into a dispersion liquid in which fine air bubbles were dispersed, and stirred to obtain a slurry in which the glass fiber to which the airgel was adhered was dispersed.
  • the slurry was sucked from the water storage tank and dehydrated through a porous support to obtain a fiber paper product.
  • the papermaking product was dried with a hot air dryer at 150 ° C. for 2 hours to obtain an airgel sheet 8 having a basis weight of 100 g / m 2 and a porosity of 90% by volume.
  • Example 9 [Sol coating liquid 9] 143.0 parts by mass of ST-OZL-35 as a raw material containing silica particles, 57.0 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 120.0 mass parts of urea was mixed as a thermohydrolyzable compound, and the mixture was obtained. To this mixture, 60.0 parts by mass of MTMS as a silicon compound and 20.0 parts by mass of DMDMS and 20.0 parts by mass of polysiloxane compound A as a polysiloxane compound were added and reacted at 25 ° C. for 2 hours. Thereafter, a sol-gel reaction was performed at 60 ° C. for 2.0 hours to obtain a sol coating liquid 9.
  • Airgel board 9 While using the said sol coating liquid 9, it replaces with a glass nonwoven fabric, and it is a porous nickel sheet (The product made from Sumitomo Electric Industries, product name: Celmet, thickness: 1.4 mm, nickel basis weight: 420 g / m ⁇ 2 >, porosity: 97
  • the airgel board 9 having the structure represented by the general formulas (2), (3), (4) and (5) was obtained in the same manner as in Example 1 except that the volume%) was used.
  • Example 10 [Sol coating solution 10]
  • PL-20 manufactured by Fuso Chemical Industry Co., Ltd., product name, average primary particle size: 200 nm, solid content: 20% by mass
  • water is 100.0 parts by mass
  • acid A mixture was obtained by mixing 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.
  • Example 1 Example 1 except that the sol coating liquid 10 was used and a porous alumina sheet (manufactured by Aszac Co., Ltd., product name: AZP60, average thickness: 700 ⁇ m, porosity: 60 vol%) was used instead of the glass nonwoven fabric. Similarly, the airgel board 10 which has a structure represented by the said General Formula (2), (3), (4) and (5) was obtained.
  • Comparative Example 1 While using the sol coating liquid 1, a PET film (product name: G2 manufactured by Teijin DuPont Co., Ltd.) having no porous structure is used in place of the glass nonwoven fabric, and the sol coating liquid 1 is applied to the PET film by a bar coater.
  • the PET core airgel sheet having the structure represented by the above general formulas (4) and (5) was obtained in the same manner as in Example 1 except that the sol coating solution was coated to a thickness of 80 ⁇ m.
  • Example 2 In place of the glass nonwoven fabric, a thin glass having no porous structure (manufactured by Nippon Electric Glass Co., Ltd., product name: OA-10G, thickness: 150 ⁇ m) is used, and the sol coating solution 1 is applied to the thin glass with a bar coater.
  • a glass core airgel sheet having the structure represented by the general formulas (4) and (5) was obtained in the same manner as in Example 1 except that the sol coating solution was applied to a thickness of 50 ⁇ m.
  • the thickness of the airgel layer covering the substrate on the surface of the substrate was measured. Specifically, using a micrometer (manufactured by Mitutoyo Corporation, product name: CLM1-15QM) to measure the thickness of the airgel composite material with a measuring force of 0.5 N, the thickness of the porous substrate is reduced. Calculated with The results are shown in Table 1.
  • Thermal conductivity measurement The thermal conductivity was measured using a thermal conductivity measuring device (product name: HC-074) manufactured by Eihiro Seiki Co., Ltd. A 20 cm ⁇ 20 cm sample was used as a measurement sample, and the temperature of the upper and lower heat plates was set to 30 ° C. and 10 ° C., respectively, and the thermal conductivity was measured. The results are shown in Table 1.
  • the airgel composite material of the example has good thermal conductivity and a small amount of powder fall off. Therefore, the amount of dust generated during construction of the heat insulating material can be reduced, and the handleability during construction is good. On the other hand, in the comparative example, both the thermal conductivity and the amount of powder fall are inferior.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Thermal Insulation (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Silicon Compounds (AREA)
PCT/JP2016/070878 2015-07-15 2016-07-14 エアロゲル複合材料 WO2017010551A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2017528726A JP6330974B2 (ja) 2015-07-15 2016-07-14 エアロゲル複合材料
CN201680040843.1A CN107849287A (zh) 2015-07-15 2016-07-14 气凝胶复合材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-141448 2015-07-15
JP2015141448 2015-07-15

Publications (1)

Publication Number Publication Date
WO2017010551A1 true WO2017010551A1 (ja) 2017-01-19

Family

ID=57757934

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/070878 WO2017010551A1 (ja) 2015-07-15 2016-07-14 エアロゲル複合材料

Country Status (4)

Country Link
JP (2) JP6330974B2 (zh)
CN (1) CN107849287A (zh)
TW (1) TW201710086A (zh)
WO (1) WO2017010551A1 (zh)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107513863A (zh) * 2017-08-01 2017-12-26 上海工程技术大学 一种纳米复合多孔网状超疏水纺织品的制备方法
WO2018143363A1 (ja) * 2017-02-02 2018-08-09 日立化成株式会社 粒子処理用の処理剤、撥水性粒子及びその製造方法、撥水層並びに浸透防止構造体
WO2018142552A1 (ja) * 2017-02-02 2018-08-09 日立化成株式会社 繊維処理用の処理剤、繊維及びその製造方法並びに繊維シートの製造方法
WO2018142551A1 (ja) * 2017-02-02 2018-08-09 日立化成株式会社 撥水処理剤、撥水構造体及びその製造方法
JP2018145330A (ja) * 2017-03-07 2018-09-20 日立化成株式会社 ゾル塗液
WO2020084668A1 (ja) * 2018-10-22 2020-04-30 日立化成株式会社 エアロゲル複合材料
JP2020193316A (ja) * 2019-05-27 2020-12-03 ティエムファクトリ株式会社 エアロゲル複合体
JP2021172567A (ja) * 2020-04-28 2021-11-01 台湾気凝膠科技材料開発股▲分▼有限公司Taiwan Aerogel Technology Material Co., Ltd. 疎水性エアロゲル断熱材の作製方法とその使用

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102604538B1 (ko) * 2018-12-20 2023-11-22 주식회사 엘지화학 실리카 에어로겔 블랭킷의 제조방법
JP7322479B2 (ja) * 2019-04-10 2023-08-08 株式会社レゾナック 塗液、複合材料及び塗膜
JP2022541827A (ja) * 2019-09-03 2022-09-27 エルジー・ケム・リミテッド エアロゲルブランケット
TWI717257B (zh) * 2020-04-14 2021-01-21 台灣氣凝膠科技材料開發股份有限公司 耐高溫、隔熱、及防火之氣凝膠/無機纖維複合膠材的製備方法及其產物的應用
TWI760728B (zh) * 2020-04-20 2022-04-11 台灣氣凝膠科技材料開發股份有限公司 禦寒、隔熱之疏水性氣凝膠複合膠狀物的製備方法及其相關產物
KR20210151540A (ko) 2020-06-05 2021-12-14 주식회사 엘지화학 실리카 에어로겔 제조방법
US20220380222A1 (en) * 2020-06-19 2022-12-01 Lg Chem, Ltd. Hydrophobic silica aerogel blanket and method for preparing same
CN111893649B (zh) * 2020-07-17 2022-07-26 3M创新有限公司 保暖材料、制备保暖材料的方法、以保暖材料制备的制品
KR20220013190A (ko) 2020-07-24 2022-02-04 주식회사 엘지화학 실리카 에어로겔 제조방법
TWI741746B (zh) * 2020-08-20 2021-10-01 趙國昇 二氧化矽氣凝膠複合纖維毯之製造方法
CN114592353B (zh) * 2020-12-07 2024-02-02 财团法人纺织产业综合研究所 用于电子元件的无纺布膜材及其制备方法
CN117430922A (zh) * 2022-07-15 2024-01-23 凯传工业股份有限公司 含硅气凝胶聚酯母粒、其制备方法及含硅气凝胶聚酯纤维

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02248335A (ja) * 1989-02-10 1990-10-04 Enichem Spa エーロゲルモノリスの製法
JPH06191822A (ja) * 1992-12-22 1994-07-12 Matsushita Electric Works Ltd エアロゲル複合材料の製造方法
JPH08300567A (ja) * 1995-04-28 1996-11-19 Matsushita Electric Works Ltd エアロゲルパネルの製法
JPH09169515A (ja) * 1995-12-20 1997-06-30 Matsushita Electric Works Ltd 密度傾斜性エアロゲルの製法
US20020061396A1 (en) * 1997-11-17 2002-05-23 Susan M White Aerogel loaded tile composite material
JP2002275305A (ja) * 2001-03-16 2002-09-25 Matsushita Electric Ind Co Ltd 複合多孔体およびその製造方法
WO2005003476A2 (en) * 2003-06-24 2005-01-13 Aspen Aerogels, Inc. Methods to produce gel sheets
US20070222116A1 (en) * 2004-07-12 2007-09-27 Aspen Aerogels, Inc. High strength, nanoporous bodies reinforced with fibrous materials
US7635411B2 (en) * 2004-12-15 2009-12-22 Cabot Corporation Aerogel containing blanket
JP2011162756A (ja) * 2010-02-15 2011-08-25 Eiju Sangyo:Kk 多孔質シリカ−繊維複合体の製造方法、多孔質シリカ−繊維複合体およびそれを用いた真空断熱材
JP2011178925A (ja) * 2010-03-02 2011-09-15 Asahi Kagaku Kk エアロゲルシートの製造方法、エアロゲルシート、及び真空断熱材
WO2016047740A1 (ja) * 2014-09-25 2016-03-31 日立化成株式会社 エアロゲル複合体、エアロゲル複合体付き支持部材及び断熱材
WO2016121372A1 (ja) * 2014-01-30 2016-08-04 オゾンセーブ株式会社 断熱材及び断熱材の製造方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001162756A (ja) * 1999-12-14 2001-06-19 Kyodo Printing Co Ltd 断熱包材およびそれを用いた断熱容器
CA2551843A1 (en) * 2004-01-06 2005-10-20 Aspen Aerogels, Inc. Ormosil aerogels containing silicon bonded polymethacrylate
KR100836732B1 (ko) * 2005-12-01 2008-06-10 주식회사 엘지화학 중굴절 및 고굴절 실록산계 피복 조성물
GB0604583D0 (en) * 2006-03-08 2006-04-19 Dow Corning Impregnated flexible sheet material
FR2908406B1 (fr) * 2006-11-14 2012-08-24 Saint Gobain Couche poreuse, son procede de fabrication et ses applications.
TW200835648A (en) * 2007-02-26 2008-09-01 Ind Tech Res Inst Porous material and method for preparing the same
US8663742B2 (en) * 2008-06-30 2014-03-04 Stc.Unm Durable polymer-aerogel based superhydrophobic coatings, a composite material
CN101722604B (zh) * 2009-11-30 2013-08-21 浙江省普瑞科技有限公司 纤维基材与二氧化硅气凝胶复合保温隔热套筒的制备方法
CN101948297B (zh) * 2010-09-28 2013-02-20 航天特种材料及工艺技术研究所 一种自催化的气凝胶隔热复合材料及其制备方法
CN103059306B (zh) * 2011-10-18 2015-02-18 北京化工大学 一种高折射率透明有机硅树脂及其制备方法
CN202787531U (zh) * 2012-06-21 2013-03-13 蓝烟（北京）科技有限公司 一种疏水性二氧化硅气凝胶绝热保温毡
CN103334336B (zh) * 2013-06-20 2016-06-29 陕西盟创纳米新型材料股份有限公司 气凝胶纸、其制备方法及应用
CN103435320B (zh) * 2013-08-19 2016-05-04 航天特种材料及工艺技术研究所 一种高性能气凝胶复合材料及其制备方法和设备
JP2017223881A (ja) * 2016-06-17 2017-12-21 株式会社半導体エネルギー研究所 表示装置、表示モジュール、および電子機器

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02248335A (ja) * 1989-02-10 1990-10-04 Enichem Spa エーロゲルモノリスの製法
JPH06191822A (ja) * 1992-12-22 1994-07-12 Matsushita Electric Works Ltd エアロゲル複合材料の製造方法
JPH08300567A (ja) * 1995-04-28 1996-11-19 Matsushita Electric Works Ltd エアロゲルパネルの製法
JPH09169515A (ja) * 1995-12-20 1997-06-30 Matsushita Electric Works Ltd 密度傾斜性エアロゲルの製法
US20020061396A1 (en) * 1997-11-17 2002-05-23 Susan M White Aerogel loaded tile composite material
JP2002275305A (ja) * 2001-03-16 2002-09-25 Matsushita Electric Ind Co Ltd 複合多孔体およびその製造方法
WO2005003476A2 (en) * 2003-06-24 2005-01-13 Aspen Aerogels, Inc. Methods to produce gel sheets
US20070222116A1 (en) * 2004-07-12 2007-09-27 Aspen Aerogels, Inc. High strength, nanoporous bodies reinforced with fibrous materials
US7635411B2 (en) * 2004-12-15 2009-12-22 Cabot Corporation Aerogel containing blanket
JP2011162756A (ja) * 2010-02-15 2011-08-25 Eiju Sangyo:Kk 多孔質シリカ−繊維複合体の製造方法、多孔質シリカ−繊維複合体およびそれを用いた真空断熱材
JP2011178925A (ja) * 2010-03-02 2011-09-15 Asahi Kagaku Kk エアロゲルシートの製造方法、エアロゲルシート、及び真空断熱材
WO2016121372A1 (ja) * 2014-01-30 2016-08-04 オゾンセーブ株式会社 断熱材及び断熱材の製造方法
WO2016047740A1 (ja) * 2014-09-25 2016-03-31 日立化成株式会社 エアロゲル複合体、エアロゲル複合体付き支持部材及び断熱材

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3578712A4 (en) * 2017-02-02 2020-12-02 Hitachi Chemical Company, Ltd. TREATMENT AGENT FOR TREATING FIBERS, FIBERS AND ASSOCIATED PRODUCTION PROCESS, AND FIBER SHEET AND ASSOCIATED PRODUCTION PROCESS
WO2018142551A1 (ja) * 2017-02-02 2018-08-09 日立化成株式会社 撥水処理剤、撥水構造体及びその製造方法
JPWO2018143356A1 (ja) * 2017-02-02 2019-11-21 日立化成株式会社 撥水処理剤、撥水構造体及びその製造方法
US11905452B2 (en) 2017-02-02 2024-02-20 Resonac Corporation Treatment agent for treating fibers, fibers and production method therefor, and fiber sheet and production method therefor
WO2018143356A1 (ja) * 2017-02-02 2018-08-09 日立化成株式会社 撥水処理剤、撥水構造体及びその製造方法
WO2018142542A1 (ja) * 2017-02-02 2018-08-09 日立化成株式会社 粒子処理用の処理剤、撥水性粒子及びその製造方法、撥水層並びに浸透防止構造体
WO2018143364A1 (ja) * 2017-02-02 2018-08-09 日立化成株式会社 繊維処理用の処理剤、繊維及びその製造方法、並びに繊維シート及びその製造方法
KR102605764B1 (ko) * 2017-02-02 2023-11-27 가부시끼가이샤 레조낙 발수 처리제, 발수 구조체 및 그 제조 방법
CN110234725A (zh) * 2017-02-02 2019-09-13 日立化成株式会社 粒子处理用的处理剂、拒水性粒子及其制造方法、拒水层以及防渗透结构体
CN110234726A (zh) * 2017-02-02 2019-09-13 日立化成株式会社 拒水处理剂、拒水结构体及其制造方法
CN110249091A (zh) * 2017-02-02 2019-09-17 日立化成株式会社 纤维处理用的处理剂、纤维及其制造方法、以及纤维片及其制造方法
KR20190105605A (ko) * 2017-02-02 2019-09-17 히타치가세이가부시끼가이샤 섬유 처리용의 처리제, 섬유 및 그 제조 방법, 그리고 섬유 시트 및 그 제조 방법
KR20190113801A (ko) * 2017-02-02 2019-10-08 히타치가세이가부시끼가이샤 발수 처리제, 발수 구조체 및 그 제조 방법
KR20190113802A (ko) * 2017-02-02 2019-10-08 히타치가세이가부시끼가이샤 입자 처리용의 처리제, 발수성 입자 및 그 제조 방법, 발수층 그리고 침투 방지 구조체
JPWO2018143363A1 (ja) * 2017-02-02 2019-11-21 日立化成株式会社 粒子処理用の処理剤、撥水性粒子及びその製造方法、撥水層並びに浸透防止構造体
JPWO2018143364A1 (ja) * 2017-02-02 2019-11-21 日立化成株式会社 繊維処理用の処理剤、繊維及びその製造方法、並びに繊維シート及びその製造方法
WO2018142552A1 (ja) * 2017-02-02 2018-08-09 日立化成株式会社 繊維処理用の処理剤、繊維及びその製造方法並びに繊維シートの製造方法
KR102605765B1 (ko) * 2017-02-02 2023-11-27 가부시끼가이샤 레조낙 입자 처리용의 처리제, 발수성 입자 및 그 제조 방법, 발수층 그리고 침투 방지 구조체
WO2018143363A1 (ja) * 2017-02-02 2018-08-09 日立化成株式会社 粒子処理用の処理剤、撥水性粒子及びその製造方法、撥水層並びに浸透防止構造体
KR102549062B1 (ko) * 2017-02-02 2023-06-29 가부시끼가이샤 레조낙 섬유 처리용의 처리제, 섬유 및 그 제조 방법, 그리고 섬유 시트 및 그 제조 방법
TWI793102B (zh) * 2017-02-02 2023-02-21 日商昭和電工材料股份有限公司 撥水性粒子及其製造方法、撥水層及浸透防止結構體
EP3578620A4 (en) * 2017-02-02 2020-12-23 Hitachi Chemical Company, Ltd. TREATMENT PRODUCTS FOR THE TREATMENT OF PARTICLES, WATER-REPELLENT PARTICLES AND MANUFACTURING METHOD FOR THESE, WATER-REPELLENT LAYER AND PENETRATION-PREVENTING STRUCTURE
EP3578621A4 (en) * 2017-02-02 2020-12-23 Hitachi Chemical Company, Ltd. WATER-REPELLENT AGENT, WATER-REPELLENT STRUCTURE AND PROCESS FOR THE PRODUCTION OF SUCH STRUCTURE
JP7156038B2 (ja) 2017-02-02 2022-10-19 昭和電工マテリアルズ株式会社 粒子処理用の処理剤、撥水性粒子及びその製造方法、撥水層並びに浸透防止構造体
JP7156037B2 (ja) 2017-02-02 2022-10-19 昭和電工マテリアルズ株式会社 撥水処理剤、撥水構造体及びその製造方法
JP7107230B2 (ja) 2017-02-02 2022-07-27 昭和電工マテリアルズ株式会社 繊維処理用の処理剤、繊維及びその製造方法、並びに繊維シート及びその製造方法
TWI778015B (zh) * 2017-02-02 2022-09-21 日商昭和電工材料股份有限公司 撥水性纖維及撥水性纖維片
JP2018145330A (ja) * 2017-03-07 2018-09-20 日立化成株式会社 ゾル塗液
CN107513863A (zh) * 2017-08-01 2017-12-26 上海工程技术大学 一种纳米复合多孔网状超疏水纺织品的制备方法
JPWO2020084668A1 (ja) * 2018-10-22 2021-09-30 昭和電工マテリアルズ株式会社 エアロゲル複合材料
JP7163967B2 (ja) 2018-10-22 2022-11-01 昭和電工マテリアルズ株式会社 エアロゲル複合材料
WO2020084668A1 (ja) * 2018-10-22 2020-04-30 日立化成株式会社 エアロゲル複合材料
WO2020241620A1 (ja) * 2019-05-27 2020-12-03 ティエムファクトリ株式会社 エアロゲル複合体
JP2020193316A (ja) * 2019-05-27 2020-12-03 ティエムファクトリ株式会社 エアロゲル複合体
JP2021172567A (ja) * 2020-04-28 2021-11-01 台湾気凝膠科技材料開発股▲分▼有限公司Taiwan Aerogel Technology Material Co., Ltd. 疎水性エアロゲル断熱材の作製方法とその使用
JP7164853B2 (ja) 2020-04-28 2022-11-02 台湾気凝膠科技材料開発股▲分▼有限公司 疎水性エアロゲル断熱材の作製方法とその使用

Also Published As

Publication number Publication date
TW201710086A (zh) 2017-03-16
JP6330974B2 (ja) 2018-05-30
CN107849287A (zh) 2018-03-27
JPWO2017010551A1 (ja) 2018-02-22
JP2018111803A (ja) 2018-07-19

Similar Documents

Publication Publication Date Title
JP6330974B2 (ja) エアロゲル複合材料
JP6428783B2 (ja) エアロゲル複合体、エアロゲル複合体付き支持部材及び断熱材
WO2017038779A1 (ja) エアロゲル積層複合体及び断熱材
JP6927194B2 (ja) ゾル組成物、エアロゲル複合体、エアロゲル複合体付き支持部材及び断熱材
WO2017168847A1 (ja) エアロゲル層付き部材
JP6269903B2 (ja) エアロゲル複合体、エアロゲル複合体付き支持部材及び断熱材
JP2018118488A (ja) エアロゲル積層複合体及び断熱材
JPWO2019069495A1 (ja) 塗液、塗膜の製造方法及び塗膜
WO2020209131A1 (ja) 塗液、複合材料及び塗膜
JPWO2019069492A1 (ja) 塗液、塗膜の製造方法及び塗膜
JPWO2019069494A1 (ja) 塗液、塗膜の製造方法及び塗膜
JP2018118489A (ja) エアロゲル積層複合体及び断熱材
JP7163967B2 (ja) エアロゲル複合材料
WO2017170498A1 (ja) エアロゲル複合体、エアロゲル複合体付き支持部材及び断熱材
US20210115266A1 (en) Method for suppressing corrosion under heat-insulating material, and paste for suppressing corrosion under heat-insulating material
JP6750626B2 (ja) エアロゲル複合体
JP6699292B2 (ja) エアロゲル複合体の製造方法
JP6693221B2 (ja) エアロゲル複合体の製造方法
WO2017168845A1 (ja) エアロゲル層付き部材
JP6693222B2 (ja) エアロゲル複合体の製造方法、エアロゲル複合体、エアロゲル複合体付き支持部材及び断熱材
JPWO2019069493A1 (ja) 塗液、塗膜の製造方法及び塗膜

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: 16824531

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017528726

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16824531

Country of ref document: EP

Kind code of ref document: A1