WO2017038769A1 - Aerogel laminate and heat-insulating material - Google Patents

Aerogel laminate and heat-insulating material Download PDF

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Publication number
WO2017038769A1
WO2017038769A1 PCT/JP2016/075206 JP2016075206W WO2017038769A1 WO 2017038769 A1 WO2017038769 A1 WO 2017038769A1 JP 2016075206 W JP2016075206 W JP 2016075206W WO 2017038769 A1 WO2017038769 A1 WO 2017038769A1
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WIPO (PCT)
Prior art keywords
airgel
group
layer
resin
compound
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Application number
PCT/JP2016/075206
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French (fr)
Japanese (ja)
Inventor
慧 高安
智彦 小竹
知里 吉川
竜也 牧野
寛之 泉
雄太 赤須
正人 宮武
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日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to JP2017538019A priority Critical patent/JP6834961B2/en
Publication of WO2017038769A1 publication Critical patent/WO2017038769A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials

Definitions

  • the present invention relates to an airgel laminate and a heat insulating material.
  • Patent Document 1 proposes a plate-like foam containing at least one metal thin film on the surface and / or inside of a polypropylene resin foam. ing.
  • Patent Document 2 discloses a laminated heat insulating material in which a reflective film in which a metal layer is formed on one or both sides of a polyimide film and a net-like spacer made of plastic yarn are laminated. Has been.
  • Patent Document 3 discloses a laminated heat insulating material obtained by laminating a reflective plate in which a metal layer is formed on one or both sides or inside of a thermoplastic liquid crystal polymer film and a sheet-like spacer made of thermoplastic polymer fibers. Yes.
  • heat insulating material using a resin foam in order to obtain good heat insulating performance, it is necessary to increase the thickness of the foam, and it is difficult to reduce the thickness of the heat insulating layer. Further, heat insulating materials used in fields such as cryogenic technology and superconducting technology that require cryogenic substances are required to have further improved heat insulating performance after being reduced in thickness.
  • airgel is known as a material having low thermal conductivity and heat insulation properties. However, since airgel is difficult to handle, part of the airgel layer falls off when a thin airgel layer is formed on a substrate. Sometimes.
  • the present invention has been made in view of the above circumstances, and provides an airgel laminate that can be reduced in thickness and can be reduced in thickness, and a heat insulating material that includes the airgel laminate. .
  • the present invention includes a base material, a resin layer provided on the base material, and an airgel layer provided on the resin layer, and the resin layer includes a resin having nitrogen as a constituent atom. Provide the body.
  • the airgel laminate has a structure in which the airgel layer and the base material are laminated via a resin layer, so that the airgel layer can be prevented from falling off from the base material, and the thickness of the laminate can be reduced. It becomes.
  • the resin may have at least one bond selected from the group consisting of urethane bond, amide bond, urea bond, imide bond, sulfonamide bond, thiourethane bond, thioamide bond, thiourea bond and thioimide bond. Good. Thereby, the adhesiveness of a resin layer and an airgel layer improves, and the fall-off
  • the resin may have a urethane bond.
  • the urethane bond may be a bond formed by a reaction between a compound having a hydroxyl group and a compound having an isocyanate group.
  • the equivalent ratio of the isocyanate group to the hydroxyl group can be 0.1: 1 to 10: 1.
  • the compound having a hydroxyl group may be a polyol compound.
  • the compound having an isocyanate group may be a polyisocyanate compound.
  • the airgel layer may be a layer containing an airgel having a structure derived from polysiloxane. Thereby, the thickness of an airgel layer can be made thin and it becomes easy to make an airgel laminated body thin.
  • the airgel layer may be a layer in which silica particles are combined. Thereby, it becomes easy to provide the heat insulation property and the softness
  • the average primary particle diameter of the silica particles can be 1 to 500 nm. Thereby, it becomes easy to further improve the heat insulation and flexibility of the airgel layer.
  • the base material may have a heat ray reflection function or a heat ray absorption function.
  • This invention can also provide a heat insulating material provided with the airgel laminated body mentioned above.
  • a heat insulating material is excellent in handleability, and can exhibit excellent heat insulating performance after the thickness is reduced.
  • an airgel laminate in which the airgel layer is prevented from falling off from the base material and can be thinned.
  • a heat insulating material provided with such an airgel laminated body is excellent in handleability, and can express the outstanding heat insulation performance, after reducing thickness.
  • the substrate when a thin airgel layer is formed on a substrate, the substrate may be oxidized or corroded.
  • the airgel laminate of the present invention by providing a structure in which the airgel layer and the base material are laminated via the resin layer, it is possible to suppress oxidation, corrosion, and the like of the base material. At the same time, it becomes possible to improve the heat insulation of the laminate.
  • 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 laminate of the present embodiment has a structure in which a base material and an airgel layer are laminated via a layer containing a resin having a nitrogen atom.
  • the airgel layer is excellent in flexibility and can be formed into a sheet of airgel, which has been difficult to handle in the past, and can be integrated with the base material. Therefore, when the airgel laminate is used as a heat insulating material, The layer can be thinned.
  • the airgel layer is laminated on a non-thermally conductive base material to prevent the temperature from rising due to heat conduction. And a base material can be protected by providing a resin layer on a base material, and it is effective especially when a base material contains a metal.
  • FIG. 1 is a diagram schematically showing a cross section of the airgel laminate of the present embodiment.
  • the airgel laminated body has the structure where the base material 3 and the airgel layer 1 were laminated
  • the airgel laminate can be thinned and has excellent heat insulating properties and flexibility.
  • the airgel layer 1 may be laminated
  • FIG. 2 is a diagram schematically showing a cross section of a multilayer laminate in which a plurality of airgel laminates of the present embodiment are laminated.
  • the airgel laminate of the present embodiment can be a multilayer laminate in which a plurality of airgel layers 1 and base materials 3 provided with a resin layer 2 are alternately laminated. If the airgel laminate is laminated so that the substrates 3 or the resin layers 2 are not in direct contact with each other, the multilayer laminate may be 5 layers or more, 10 layers or more, 20 It may be a layer or more.
  • the airgel layer which concerns on this embodiment is a layer comprised by airgel.
  • dry gel obtained by using supercritical drying method for wet gel is aerogel
  • dry gel obtained by drying under atmospheric pressure is xerogel
  • dry gel obtained by freeze-drying is cryogel
  • the obtained low-density dried gel is referred to as an aerogel regardless of the drying method of the wet gel.
  • 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.
  • 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 according to the present embodiment may be a layer containing an airgel having a structure derived from polysiloxane.
  • the airgel according to the present embodiment includes a silicon compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a hydrolysis product of the silicon compound having the hydrolyzable functional group. It may be a dried product of a wet gel that is a condensate of a sol containing at least one selected from the group. That is, the airgel layer according to the present embodiment includes (in the molecule) a hydrolyzable functional group or a silicon compound having a condensable functional group, and a hydrolyzed product of the silicon compound having the hydrolyzable functional group.
  • the wet gel produced from the sol containing at least one selected from the group consisting of products can be obtained by drying.
  • 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 according to the present embodiment can contain polysiloxane having a main chain including a siloxane bond (Si—O—Si).
  • the airgel can have the following M unit, D unit, T unit or Q unit as a structural unit.
  • R represents an atom (hydrogen atom or the like) or an atomic group (alkyl group or the like) bonded to a silicon atom.
  • the M unit is a unit composed of a monovalent group in which a silicon atom is bonded to one oxygen atom.
  • the D unit is a unit composed of a divalent group in which a silicon atom is bonded to two oxygen atoms.
  • the T unit is a unit composed of a trivalent group in which a silicon atom is bonded to three oxygen atoms.
  • the Q unit is a unit composed of a tetravalent group in which a silicon atom is bonded to four oxygen atoms. Information on the content of these units can be obtained by Si-NMR.
  • the airgel 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.
  • Examples of the airgel according to the present embodiment include the following modes. By adopting these aspects, it becomes easy to obtain an airgel that is further excellent in heat insulation and flexibility and can be made thin. By adopting each aspect, an airgel having heat insulation and flexibility according to each aspect and capable of being thinned can be obtained.
  • the airgel according to the present embodiment includes a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule), and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group.
  • a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group.
  • Wet which is a condensate of sol containing at least one compound selected from the group consisting of (the hydrolyzable functional group hydrolyzed polysiloxane compound) (hereinafter sometimes referred to as “polysiloxane compound group”) It may be a dried gel.
  • the airgel according to the present embodiment includes a hydrolyzable polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a 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. In addition, each airgel mentioned later is also from the hydrolysis product of the polysiloxane compound which has a hydrolyzable functional group or a condensable functional group, and the polysiloxane compound which has the said hydrolyzable functional group in this way. It may be a wet gel dried product (obtained by drying a wet gel generated from the sol), which is a condensate of a sol containing at least one selected from the group.
  • the airgel layer is at least one selected from the group consisting of a hydrolyzable functional group or a polysiloxane compound having a condensable functional group, and a hydrolysis product of the polysiloxane compound having a hydrolyzable functional group. It may be a layer composed of a dried product of a wet gel that is a condensate of sol containing That is, the airgel layer is selected from the group consisting of a hydrolyzable functional group or a polysiloxane compound having a condensable functional group, and a hydrolysis product of the polysiloxane compound having a hydrolyzable functional group. You may be comprised by the layer formed by drying the wet gel produced
  • a polysiloxane compound having a hydrolyzable functional group or a condensable functional group is a reactive group different from the hydrolyzable functional group and the condensable functional group (hydrolyzable functional group and condensable functional group). May further have a functional group that does not fall under.
  • the reactive group is not particularly limited, and examples thereof include an epoxy group, a mercapto group, a glycidoxy group, a vinyl group, an acryloyl group, a methacryloyl group, and an amino group.
  • the epoxy group may be contained in an epoxy group-containing group such as a glycidoxy group. You may use the polysiloxane compound which has the said reactive group individually or in mixture of 2 or more types.
  • Examples of the functional group include an alkoxy group, a silanol group, a hydroxyalkyl group, and a polyether group from the viewpoint of improving the flexibility of the airgel.
  • Examples of the functional group include an alkoxy group and a hydroxyalkyl group from the viewpoint of improving the compatibility of the sol. From the viewpoint of improving the reactivity of the polysiloxane compound and reducing the thermal conductivity of the airgel, the number of carbon atoms of the alkoxy group and hydroxyalkyl group can be 1 to 6, and from the viewpoint of further improving the flexibility of the airgel. It may be ⁇ 4.
  • 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. It may be 5 parts by mass or more, or 10 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. 15 parts by mass or less.
  • the content of the polysiloxane compound and the hydrolysis product of the polysiloxane compound can be 5 to 50 parts by mass with respect to 100 parts by mass of the sol, and may be 10 to 30 parts by mass. It may be 10 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 according to the present embodiment has (in the molecule) a hydrolyzable functional group or a silicon compound having a condensable functional group (excluding a polysiloxane compound) and the hydrolyzable functional group. It may be a wet gel dried product which is a condensate of sol containing at least one compound selected from the group consisting of hydrolysis products of silicon 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 sol containing the polysiloxane compound group may further contain a silicon compound group.
  • 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 silicon compound having a condensable functional group is not particularly limited.
  • silane tetraol, methyl silane triol, dimethyl silane diol, phenyl silane triol, phenyl methyl silane diol, diphenyl silane diol, n-propyl silane triol examples include hexyl silane triol, octyl silane triol, decyl silane triol, and trifluoropropyl silane triol.
  • the number of hydrolyzable functional groups is 3 or less, and silicon compounds having reactive groups include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like can also be used.
  • vinylsilane triol 3-glycidoxypropylsilanetriol, 3-glycidoxypropylmethylsilanediol, 3-methacryloxypropylsilanetriol, 3-methacryloxypropylmethylsilanediol, 3-acryloxypropylsilanetriol, 3-mercaptopropylsilanetriol, 3-mercaptopropylmethylsilanediol, N-phenyl-3-aminopropylsilanetriol, N-2- (aminoethyl ) -3-Aminopropylmethylsilanediol and the like can also be used.
  • Bistrimethoxysilylmethane, bistrimethoxysilylethane, bistrimethoxysilylhexane, etc. can be used as the silicon compound having 3 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 15 parts by mass 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. That is, 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, and is 15 to 25 parts by mass. Also good.
  • 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 sol. It may be greater than or equal to part by mass, greater than or equal to 15 parts by mass, or greater than or equal to 20 parts by mass. 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 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 according to the present embodiment can have a structure represented by the following general formula (1).
  • the airgel which concerns on this embodiment can have a structure represented by the following general formula (1a) as a structure containing the structure represented by Formula (1).
  • the structures represented by the formulas (1) and (1a) can be introduced into the skeleton of the airgel.
  • R 1 and R 2 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 according to 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.
  • the “ladder structure” has two struts and bridges connecting the struts (having a so-called “ladder” form). It is.
  • 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—, but in the airgel of this embodiment, The structure of the bridge 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 ladder structure may be represented by the following general formula (3 It may have a ladder type structure represented by.
  • 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 according to the present embodiment may contain silica particles. That is, the sol that provides the airgel may further contain silica particles.
  • the airgel according to the present embodiment may be a wet gel dried product (condensate of sol containing silica particles) (obtained by drying a wet gel produced 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 layer is a layer in which silica particles are combined.
  • 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. Thereby, the further outstanding heat insulation and softness
  • the airgel containing silica particles according to this embodiment 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 containing silica particles according to the present embodiment 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 containing silica particles according to the present embodiment 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 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 monodispersibility 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, and may be 300 nm or less because it is easy to suppress the solid heat conduction of the silica particles and it is easy to obtain an airgel excellent in heat insulation. 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 average primary particle diameter of the silica particles can be obtained by directly observing the cross section of the airgel layer using a scanning electron microscope (hereinafter abbreviated as “SEM”).
  • SEM scanning electron microscope
  • the particle diameter of each silica particle can be obtained based on the diameter of the cross section.
  • the diameter here means the diameter when the cross section of the skeleton forming the three-dimensional network skeleton is regarded as a circle.
  • the diameter when the cross section is regarded as a circle is the diameter of the circle when the area of the cross section is replaced with a circle having the same area.
  • the average particle diameter the diameter of a circle is obtained for 100 particles, and the average is taken.
  • the biaxial average primary particle diameter is calculated as follows from the result of observing 20 arbitrary particles by SEM. That is, for example, colloidal silica particles having a solid content concentration of 5 to 40% by mass dispersed in water are taken as an example.
  • a chip with a 2 cm square wafer with a pattern wiring is immersed in a dispersion of colloidal silica particles for about 30 seconds. Thereafter, the chip is rinsed with pure water for about 30 seconds and blown with nitrogen.
  • the chip is placed on a sample stage for SEM observation, an acceleration voltage of 10 kV is applied, the silica particles are observed at a magnification of 100,000, and an image is taken.
  • 20 silica particles are arbitrarily selected from the obtained image, and the average of the particle diameters of these particles is defined as the average particle diameter.
  • a rectangle (circumscribed rectangle L) circumscribing the silica particles P and arranged so that the long side is the longest is led.
  • the long side of the circumscribed rectangle L is X
  • the short side is Y
  • the biaxial average primary particle diameter is calculated as (X + Y) / 2, and is defined as the particle diameter of the particle.
  • the 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. 100 ⁇ 10 18 pieces / g or more.
  • 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. It may be 700 ⁇ 10 18 pieces / g or less.
  • 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, It may be 10 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.
  • the content of silica particles contained in the sol can be 20 parts by mass or less, and 15 masses. Part or less, 12 parts by weight or less, 10 parts by weight or less, or 8 parts by weight 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 according to the present 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 which concerns on this embodiment may have at least 1 type among the structures represented by the said General formula (4), (5) and (6), without containing a silica particle. That is, the airgel layer according to the present embodiment may be composed of a layer containing an airgel having a polysiloxane-derived structure.
  • Examples of the structure derived from polysiloxane include structures represented by the above general formula (1), (2), (3), (4), (5), or (6). Therefore, the airgel according to the present embodiment may include at least one of the structures represented by the general formulas (4), (5), and (6) without containing silica particles. .
  • the thickness of the airgel layer can be 1 ⁇ m or more because it is easy to obtain good heat insulation, and can be 10 ⁇ m or more, or 30 ⁇ m or more.
  • the thickness of the airgel layer can be 200 ⁇ m or less, may be 100 ⁇ m or less, and may be 80 ⁇ m or less. That is, the thickness of the airgel layer may be 1 to 200 ⁇ m, may be 10 to 100 ⁇ m, and may be 30 to 80 ⁇ m.
  • density at 25 ° C. of the airgel layer may be a 0.05 g / cm 3 or more, may also be 0.1 g / cm 3 or more, 0.2 g / Cm 3 or more.
  • the density of the airgel layer at 25 ° C. can be set to 0.3 g / cm 3 or less, and may be 0.25 g / cm 3 or less. / Cm 3 or less. That is, the density of the airgel layer at 25 ° C. can be 0.05 to 0.3 g / cm 3 , or 0.1 to 0.25 g / cm 3 , or 0.1 to 0.2 g / cm 3. cm 3 may also be used.
  • the porosity of the airgel layer at 25 ° C. can be 85% or more, may be 87% or more, and from the viewpoint of obtaining better strength and flexibility. It can be 95% or less, and may be 93% or less. That is, the porosity of the airgel layer at 25 ° C. can be 85 to 95%, and may be 87 to 93%.
  • the density and porosity of the airgel layer can be measured by a mercury intrusion method according to DIN 66133.
  • a mercury intrusion method according to DIN 66133.
  • Autopore IV9520 manufactured by Shimadzu Corporation, product name
  • Shimadzu Corporation product name
  • the resin layer according to the present embodiment is a non-aerogel layer, and is a layer containing a resin having a nitrogen atom in the molecular structure.
  • a resin layer can improve adhesiveness with an airgel layer by containing resin which has nitrogen as a constituent atom.
  • the resin having a nitrogen atom for example, a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin such as an ultraviolet ray can be used.
  • the resin layer may be a single layer or multiple layers.
  • thermoplastic resin examples include polyamide resin, polyurethane resin, N-vinyl resin, and polyimide resin.
  • thermosetting resin a resin obtained by reacting a thermosetting compound having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, or an unsaturated hydrocarbon group with a curing agent can be used.
  • the curing agent include compounds having functional groups such as epoxy groups, hydroxyl groups, amino groups, amide groups, carboxyl groups, thiol groups, and isocyanate groups, acid anhydrides, metal chlorides, metal oxides, and peroxides. Can be used.
  • a catalyst may be added for the purpose of increasing the curing reaction rate of the thermosetting resin.
  • thermosetting resin examples include urea resin, melamine resin, epoxy resin, polyurethane resin, thiourethane resin, furan resin, polyimide resin, sulfoamide resin, aniline resin, cyanate resin, and isocyanate resin.
  • the active energy ray curable resin examples include resins having an acrylic resin, an epoxy resin, a polyester resin, a urethane resin, or the like as a base polymer and a radically polymerizable or cationically polymerizable functional group added thereto.
  • the radical polymerizable functional group examples include acryloyl group, methacryloyl group, vinyl group and allyl group.
  • a cation polymerizable functional group an epoxy group, a glycidyl ether group, a glycidylamino group etc. are mentioned, for example.
  • Specific examples of the active energy ray curable resin include an acrylic urethane resin.
  • the resin described above may have a functional group containing a nitrogen atom.
  • functional groups include amino groups, amide groups, imide groups, urethane groups, isocyanate groups, carbodiimide groups, allophanate groups, biuret groups, oxazolidone groups, sulfoamide groups, thiourethane groups, and isothiocyanate groups.
  • the resin having a nitrogen atom includes a urethane bond, an amide bond, a urea bond, an imide bond, a sulfonamide bond, a thiourethane bond, a thioamide bond, a thiourea bond, and a thioimide bond.
  • a resin having at least one bond selected from the group consisting of can be used.
  • the resin having a urethane bond for example, a resin synthesized from a compound having a hydroxyl group and a compound having an isocyanate group can be used.
  • Examples of the compound having a hydroxyl group include a monool compound having one hydroxyl group and a polyol compound having two or more hydroxyl groups. From the viewpoint of increasing the strength of the resin layer, a polyol compound can be used.
  • the compound having a hydroxyl group may be used alone or in combination of two or more.
  • the polyol compound examples include ethylene glycol, propylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, and fluorinated polyol.
  • the polyol compound may be an acrylic polyol, a polyester polyol, a polyether polyol, a polycarbonate polyol, a fluorinated polyol, or an acrylic polyol.
  • the acrylic polyol is not particularly limited and may be modified.
  • an acrylic polyol for example, the product name “Dianal LR-2586” (hydroxyl value 60 mg KOH / g, acid value 3 mg KOH / g, weight average molecular weight 30000, glass transition temperature 40 ° C.) manufactured by Mitsubishi Rayon Co., Ltd.
  • the product name “Acryset 2050-55”, the product name “Hitaroid 3371” of Hitachi Chemical Co., Ltd., etc. can be obtained commercially.
  • Examples of the compound having an isocyanate group include a monoisocyanate compound having one isocyanate group and a polyisocyanate compound having two or more isocyanate groups.
  • a polyisocyanate compound can be used because it reacts well with the polyol compound and the formed coating film has high strength.
  • the compound which has an isocyanate group may be used individually by 1 type, or may use 2 or more types together.
  • polyisocyanate compound examples include aliphatic diisocyanates such as hexamethylene diisocyanate, hydrogenated diphenyl diisocyanate, and isophorone diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m And aromatic diisocyanates such as -xylene diisocyanate and p-xylene diisocyanate.
  • aliphatic diisocyanates such as hexamethylene diisocyanate, hydrogenated diphenyl diisocyanate, and isophorone diisocyanate
  • 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate
  • 4,4′-diphenylmethane diisocyanate 4,4′-diphenylmethane diisocyanate
  • aromatic diisocyanates such as -xylene diisocyan
  • aliphatic diisocyanates examples include Asahi Kasei Corporation product name “Duranate 24A-90PX” (NCO: 23.6%), Sumitomo Bayer Urethane Co., Ltd. product name “Sumijour N-3200-90M”, Mitsui Takeda Chemical Co., Ltd. Company product name “Takenate D165N-90X”, Sumitomo Bayer Urethane Co., Ltd. product name “Sumijoule N-3300”, “Sumijoule N-3500”, Asahi Kasei Co., Ltd. product names “Duranate THA-100”, “TLA” ⁇ 100 ”,“ TSA-100 ”,“ TPA-100 ”, etc. are commercially available.
  • aromatic diisocyanate for example, product names “Bernock D-750”, “DN-950”, “DN-980” and the like of DIC Corporation can be obtained commercially.
  • the equivalent ratio (NCO / OH equivalent ratio) between the isocyanate group of the polyisocyanate compound and the hydroxyl group of the polyol compound when producing a resin having a urethane bond should be 0.1: 1 to 10: 1. Can be from 0.3: 1 to 10: 1 and from 0.5: 1 to 10: 1. When the equivalent ratio of isocyanate groups to hydroxyl groups is within the above range, the crosslinking reaction in the coating film tends to proceed, the strength of the resin layer increases, and the durability of the resin layer tends to increase.
  • the NCO / OH equivalent ratio indicates the molar ratio of the isocyanate group (NCO) in the polyisocyanate compound to the hydroxyl group (OH) in the polyol compound.
  • the resin layer according to this embodiment may further contain a resin component or various additives that do not contain nitrogen, as long as the effects of the present invention are not impaired.
  • the resin component not containing nitrogen may have a functional group containing at least one atom selected from the group consisting of an oxygen atom and a sulfur atom.
  • functional groups include hydroxyl groups, ether groups, epoxy groups, carboxyl groups, ester groups, mercapto groups, thioether groups, thioester groups, and sulfonyl groups.
  • Examples of the resin component not containing nitrogen contained in the resin layer include a thermoplastic resin, a thermosetting resin, and a photocurable resin.
  • Examples of the resin component include polyester resins such as polyethylene terephthalate, olefin resins such as polyethylene and polypropylene, chlorine-containing resins such as polyvinyl chloride and polyvinylidene chloride, fluorine-containing resins, polycarbonate resins, acrylic resins, ABS resins, and polystyrene.
  • Resin polyvinyl acetate resin, melamine resin, phenol resin, silicone resin, cellulose resin, styrene acrylic resin, vinyl ether resin, styrene-butadiene resin, polyvinyl alcohol resin, phenol resin, unsaturated polyester resin, allyl resin, epoxy ( Examples include meth) acrylate, epoxy-modified polybutadiene, epoxy-modified polyester, polybutadiene (meth) acrylate, and acryl-modified polyester.
  • additives contained in the resin layer include, for example, organic fine particles, inorganic fine particles, crosslinking agents, flame retardants, flame retardant aids, heat stabilizers, oxidation stabilizers, leveling agents, slip activators, antistatic agents, Examples include ultraviolet absorbers, light stabilizers, nucleating agents, dyes, fillers, dispersants, and coupling agents.
  • the thickness of the resin layer can be 1 nm or more from the viewpoint of obtaining good adhesion to the base material and the airgel layer, and may be 100 nm or more, or 500 nm or more.
  • the thickness of the resin layer can be 5 ⁇ m or less from the viewpoint of improving the heat insulation performance of the airgel laminate, and may be 3 ⁇ m or less, or 1 ⁇ m or less. That is, the thickness of the resin layer may be 1 nm to 5 ⁇ m, 100 nm to 3 ⁇ m, or 500 nm to 1 ⁇ m.
  • the base material which concerns on this embodiment is a non-aerogel layer, and it does not specifically limit as a structure of a base material, A single layer or a multilayer may be sufficient.
  • As a shape of a base material since lightness can be provided to an airgel laminated body, it can be set as a film form or foil shape.
  • the heat insulating property of the airgel laminate can be further improved.
  • a base material having a heat ray reflection function or a heat ray absorption function can function as a radiator and can play a role of blocking heat from the outside.
  • the heat ray reflection function refers to a function in which reflection of light in the near infrared or infrared region of about 800 to 3000 nm is larger than light absorption and light transmission.
  • the heat ray absorption function refers to a function in which light absorption in the near infrared or infrared region of, for example, about 800 to 3000 nm is larger than light reflection and light transmission.
  • light reflection includes light scattering.
  • the base material according to the present embodiment may be composed of at least one of a layer having a heat ray reflecting function and a layer having a heat ray absorbing function, and may be composed of only a layer having a heat ray reflecting function. It may consist of only the layers it has.
  • the base material may be a laminate of a layer having a heat ray reflecting function and a layer having a heat ray absorbing function.
  • the base material may be a laminate of a layer having a heat ray reflecting function or a heat ray absorbing function and a layer not having a heat ray reflecting function and a heat ray absorbing function.
  • the layer having the heat ray reflecting function or the heat ray absorbing function may be formed on one side or both sides of the layer not having the heat ray reflecting function and the heat ray absorbing function.
  • the layer having a heat ray reflective function can contain a heat ray reflective material.
  • the heat ray reflective material is not particularly limited as long as it is a material that reflects light in the near infrared or infrared region.
  • heat-reflective materials include aluminum compounds such as aluminum and aluminum oxide, zinc compounds such as zinc aluminate, magnesium compounds such as hydrotalcite, silver compounds such as silver, titanium, titanium oxide, and strontium titanate.
  • Examples include titanium compounds, copper compounds such as copper and bronze, microballoons such as stainless steel, nickel, tin, and shirasu balloons, ceramic balloons, and pearl mica. These may be used alone or in combination of two or more.
  • materials containing aluminum, magnesium, silver, or titanium can be used as the heat ray reflective material from the viewpoint of easily reducing thermal conductivity, being inexpensive and excellent in handleability.
  • the layer having a heat ray reflecting function may be composed of a metal foil such as an aluminum foil or a copper foil.
  • the layer having a heat ray reflecting function may be a resin film prepared by kneading an aluminum paste or titanium oxide with a resin such as polyolefin, polyester, polycarbonate, or polyimide.
  • the layer having a heat ray reflecting function may be a deposited film obtained by depositing aluminum, silver or the like on a resin film such as polyolefin, polyester, polycarbonate, polyimide, etc. by physical vapor deposition such as sputtering or vacuum vapor deposition or chemical vapor deposition.
  • the layer having a heat ray absorbing function can include a heat ray absorbing material.
  • the heat-absorbing material is not particularly limited as long as it is a substance that absorbs light in the near infrared or infrared region.
  • heat-absorbing materials include carbon graphite such as flaky graphite, earthy graphite, and artificial graphite, carbon powder such as carbon black; barium sulfate, strontium sulfate, calcium sulfate, mercalite (KHSO 4 ), halotristone, Metal sulfates such as alumite and iron alumite; antimony compounds such as antimony trioxide; metal oxides such as tin oxide, indium oxide, indium tin oxide, zinc oxide and anhydrous zinc antimonate; ammonium-based, urea-based, Imonium, aminium, cyanine, polymethine, anthraquinone, dithiol, copper ion, phenylened
  • the heat ray-absorbing material a material containing carbon graphite, carbon black, metal sulfate, or an antimony compound can be used from the viewpoint of easily reducing the thermal conductivity, and being inexpensive and easy to handle.
  • the layer having a heat ray absorbing function may be a resin film prepared by kneading carbon black, antimony oxide or barium sulfate.
  • the base material is a layer composed of a material containing at least one selected from the group consisting of carbon graphite, aluminum, magnesium, silver, titanium, carbon black, metal sulfate and antimony compounds.
  • the substrate may be an aluminum foil, an aluminum deposited film, a silver deposited film, or an antimony oxide-containing film.
  • the surface of the substrate on which the airgel layer is not provided may have a protective layer for the purpose of protecting the airgel layer when a plurality of airgel laminates are stacked.
  • a protective layer for the purpose of protecting the airgel layer when a plurality of airgel laminates are stacked.
  • the constituent material of the protective layer include a urethane resin, a polyester resin, an acrylic resin, a phenol resin, and the like, and may be the same material as the resin layer described above. These resin layers may be a single layer or multiple layers.
  • the surface of the base material on which the airgel layer is not laminated may be subjected to a release treatment.
  • the thickness of the substrate is not particularly limited, from the viewpoint of handling properties, it can be 3 ⁇ m or more, may be 5 ⁇ m or more, and may be 7 ⁇ m or more.
  • the thickness of the base material can be 100 ⁇ m or less, 80 ⁇ m or less, or 50 ⁇ m or less. That is, the thickness of the base material can be 3 to 100 ⁇ m, 5 to 80 ⁇ m, or 7 to 50 ⁇ m.
  • the manufacturing method of the airgel laminated body of this embodiment is not specifically limited, For example, it can manufacture with the following method.
  • the airgel laminate of the present embodiment includes a resin layer forming step for forming a resin layer containing a resin having nitrogen atoms on a base material, a sol generating step for producing a sol for forming an airgel, and a resin layer
  • the sol obtained in the sol generating step is applied to a base material provided with a coating step, and dried to form an airgel layer, the aging step to age the airgel layer obtained in the coating step, and the aged aerogel It can be produced by a production method mainly comprising a step of washing and solvent replacement of the layer and a drying step of drying the airgel layer after washing and solvent substitution (if necessary).
  • the “sol” is a state before the gelation reaction occurs, and in the present embodiment, the above-described silicon compound (if necessary, further silica particles) is dissolved or dispersed in a solvent. means.
  • a resin layer forming coating liquid obtained by mixing the above-described resin component having a nitrogen atom with an organic solvent is applied to a substrate and dried to cure the coating liquid. This is a step of forming a resin layer on the surface. However, it is desirable that this resin layer is in a state in which an adhesive force with the substrate is ensured.
  • the organic solvent is not particularly limited as long as it is a solvent capable of forming a good coating film on the substrate, and a solvent that does not react with the resin component contained in the resin layer forming coating solution can be used.
  • organic solvent examples include hydrocarbon compounds such as toluene, xylene and cyclohexane; ester compounds such as ethyl acetate, n-butyl acetate and isobutyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; diethylene glycol dimethyl ether and dipropylene And ether compounds such as glycol dimethyl ether.
  • hydrocarbon compounds such as toluene, xylene and cyclohexane
  • ester compounds such as ethyl acetate, n-butyl acetate and isobutyl acetate
  • ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • ether compounds such as glycol dimethyl ether.
  • a die coater, a comma coater, a bar coater, a kiss coater, a roll coater, or the like can be used, and it is appropriately used depending on the thickness of the resin layer.
  • the coating film composed of the coating solution for forming a resin layer after application can be dried by heating or the like.
  • the drying temperature varies depending on the amount of solvent in the resin layer-forming coating solution and the boiling point of the solvent, but can be, for example, 50 to 200 ° C. or 80 to 150 ° C.
  • the drying temperature can be, for example, 50 to 200 ° C. or 80 to 150 ° C.
  • the drying time varies depending on the drying temperature, but can be, for example, 0.2 to 10 minutes, or may be 0.5 to 5 minutes. By setting the drying time to 0.2 minutes or more, the resin layer can be easily formed, and by setting the drying time to 10 minutes or less, it becomes easy to obtain adhesion to the substrate.
  • the drying conditions can be set as appropriate by simple experiments in advance.
  • the sol generation step is a step of mixing the above-described silicon compound and a solvent containing silica particles in some cases, performing a hydrolysis reaction, and then performing a sol-gel reaction to obtain a semi-gelled sol coating liquid.
  • an acid catalyst may be further added to the solvent in order to promote the hydrolysis reaction.
  • a surfactant, a thermohydrolyzable compound, or the like can be added to the solvent.
  • a base catalyst may be added to promote the gelation reaction.
  • the solvent is not particularly limited as long as good coating properties can be obtained in the coating 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 acids such as acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid, azelaic acid Carboxylic acids are mentioned. Among these, organic carboxylic acids can be used as an acid catalyst that further improves the water resistance of the obtained airgel layer. Specific examples include acetic acid, formic acid, propionic acid, oxalic acid, and malonic acid. It may be. You may use these 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 and the polysiloxane compound.
  • a nonionic surfactant As the surfactant, a nonionic surfactant, an ionic surfactant, or the like can be used. You may use these 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 nonyl phenyl ether, polyoxyethylene octyl phenyl 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.
  • 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.
  • These surfactants act to reduce the difference in chemical affinity between the solvent in the reaction system and the growing siloxane polymer in the coating process described later, and to suppress phase separation. It is considered.
  • the amount of surfactant added depends on the type of surfactant or the type and amount of silicon compound (silicon compound group and polysiloxane compound group).
  • the total amount of silicon compound is 100 parts by mass.
  • the amount may be 1 to 100 parts by mass, and 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 compounds (silicon compound group and polysiloxane compound group). It may be 2 to 150 parts by mass.
  • Hydrolysis in the sol production step depends on the types and amounts of silicon compound, polysiloxane compound silica particles, acid catalyst, surfactant, etc. in the mixed solution, but for example, in a temperature environment of 20 to 60 ° C., The treatment may be performed for 10 minutes to 24 hours, or in a temperature environment of 50 to 60 ° C. for 5 minutes to 8 hours. Thereby, the hydrolyzable functional group in a silicon compound and a polysiloxane compound is fully hydrolyzed, and the hydrolysis product of a silicon compound and the hydrolysis product of a polysiloxane 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 of 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) is excellent in that it has high volatility and does not easily remain in the airgel layer after drying, so that it is difficult to impair water resistance, and further, it is 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 can be shortened. Can be done in time.
  • ammonia is highly volatile and hardly remains in the airgel layer. Therefore, by using ammonia as a base catalyst, an airgel layer with better water resistance can be obtained.
  • 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. .
  • gelation can be performed in a shorter time, and by setting it to 5 parts by mass or less, a decrease in water resistance can be further suppressed.
  • the sol-gel reaction in the sol production step requires that the sol be in a semi-gelled state for the purpose of obtaining good coating properties in the coating step described later.
  • This reaction is preferably performed in a sealed container so that the solvent and the base catalyst do not volatilize.
  • the gelation temperature depends on the type and amount of the silicon compound, polysiloxane compound, silica particles, acid catalyst, surfactant, base catalyst, etc. in the sol, but can be 30 to 90 ° C., It may be 40-80 ° C. By setting the gelation temperature to 30 ° C. or higher, gelation can be performed in a shorter time, and by setting the gelation temperature to 90 ° C. or lower, sudden gelation can be suppressed.
  • the sol-gel reaction time varies depending on the gelation temperature
  • the gelation time may be shortened as compared with a sol applied to a conventional aerogel. it can. This is because the silanol groups and / or reactive groups of the silicon compounds (polysiloxane compound group and silicon compound group) in the sol form hydrogen bonds and / or chemical bonds with the silanol groups of the silica particles. I guess.
  • the gelation time can be 10 to 360 minutes, and may be 20 to 180 minutes.
  • the gelation time By setting the gelation time to 10 minutes or more, the viscosity of the sol is improved, and it becomes easy to obtain good coating properties in the coating process described later, and by setting it to 360 minutes or less, the complete gelation of the sol is suppressed And it becomes easy to obtain adhesiveness with a resin layer.
  • the coating step is a step of forming the airgel layer on the resin layer by applying the semi-gelled sol coating solution obtained in the sol generating step to the base material provided with the resin layer.
  • the sol coating liquid is applied to a substrate provided with a resin layer and dried to gel the sol coating liquid to form an airgel layer on the surface of the resin layer.
  • this airgel layer is desirably in a state in which an adhesive force with the resin layer is ensured.
  • the airgel laminated body of this embodiment can be wound up and stored in a roll shape.
  • a die coater, a comma coater, a bar coater, a kiss coater, a roll coater or the like can be used, and is used as appropriate depending on the thickness of the airgel layer.
  • the coating film comprising the sol coating liquid after coating can be dried by heating or the like.
  • Drying after applying the sol coating liquid to the substrate provided with the resin layer can be performed, for example, under the condition that the moisture content of the airgel layer after drying is 10% by mass or more, and is 50% by mass or more. It may be performed under conditions. By making the water content of the airgel layer 10% by mass, it becomes easy to obtain adhesiveness with the resin layer.
  • the drying temperature varies depending on the amount of water and / or the amount of the organic solvent in the sol coating liquid and the boiling point of the organic solvent, but can be, for example, 50 to 150 ° C. or 60 to 120 ° C. By setting the drying temperature to 50 ° C. or higher, gelation can be performed in a shorter time, and by setting the drying temperature to 150 ° C. or lower, it becomes easy to obtain adhesiveness with the resin layer.
  • the drying time varies depending on the drying temperature, but can be, for example, 0.2 to 10 minutes, or 0.5 to 8 minutes. By setting the drying time to 0.2 minutes or more, an airgel layer can be easily formed, and by setting the drying time to 10 minutes or less, it becomes easy to obtain adhesiveness with the resin layer.
  • the drying conditions can be set as appropriate by simple experiments in advance.
  • a separator can be further laminated on the surface of the airgel layer opposite to the base material side. By laminating the separator, it is possible to prevent transfer of the airgel surface to the back surface of the base material when the airgel laminate is wound into a roll.
  • the separator when the separator is laminated, for example, the separator may be laminated after the sol coating liquid is applied, or may be laminated after the coating film made of the sol coating liquid is dried.
  • the separator include resin films made of resins such as polyolefin, polyester, polycarbonate, and polyimide, metal foils such as copper foil and aluminum foil, and release paper.
  • a resin film when laminating the separator after applying the sol coating liquid, a resin film can be used from the viewpoint of keeping the water content of the airgel layer high.
  • the separator may be subjected to a release treatment such as a mat treatment or a corona treatment.
  • the aging step is a step of aging the airgel layer formed by the coating step by heating.
  • the airgel layer is aged so that the water content is 10% by mass or more, and is aged so as to be 50% by mass or more.
  • the aging method is not particularly limited as long as the above range is satisfied.
  • the aging is performed using a method of aging the airgel laminate in a sealed atmosphere, a thermo-hygrostat that can suppress a decrease in moisture content due to heating, and the like. The method of doing 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, excellent heat insulating properties can be obtained, and by setting it to 48 hours or shorter, high adhesiveness with the resin layer can be obtained.
  • the washing and solvent replacement step is a step having a step of washing the airgel laminate 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 method is not particularly limited.
  • the cleaning and solvent replacement step can be carried out in a form in which only the solvent replacement step is performed without performing the step of cleaning the airgel laminate, but reduces impurities such as unreacted substances and by-products in the airgel layer, From the viewpoint of enabling the production of an airgel laminate with higher purity, the airgel layer after aging may be washed.
  • the airgel layer may be repeatedly washed with water or an organic solvent with respect to the airgel laminate obtained in the aging step.
  • 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 said organic solvent individually or in mixture of 2 or more types.
  • the organic solvent used in the washing step is preferably a hydrophilic organic solvent having high mutual solubility in both water and a low surface tension solvent.
  • 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, and methyl ethyl ketone can be used. Further, from the viewpoint of economy, methanol, ethanol, or methyl ethyl ketone can be used. Good.
  • 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, and 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 contained in the washed airgel layer is 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.
  • ethanol, methanol, 2-propanol, dichlorodifluoromethane, or carbon dioxide may be used alone as a substitution solvent, and a solvent in which two or more of these are mixed is 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 of 100 ° C. or less at normal pressure 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 substitution step can be set to a temperature not higher than the boiling point of the solvent used for substitution.
  • heptane when used, it can be 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 for 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 transferred to the drying step without replacing the solvent used for washing.
  • the washing and solvent replacement process to the drying process can be simplified.
  • the separator when laminating the separator in the coating process, from the viewpoint of improving the efficiency of washing the airgel layer and replacing the solvent, the separator may be extracted before the washing process and laminated again after the solvent replacing process. Good.
  • the drying method is not particularly limited, and known atmospheric pressure drying, supercritical drying, or freeze drying can be used. Among these, atmospheric drying or supercritical drying can be used from the viewpoint of easy production of a low-density airgel layer. Further, atmospheric drying can be used from the viewpoint of enabling production at low cost.
  • the normal pressure means 0.1 MPa (atmospheric pressure).
  • the airgel laminate of this embodiment can be obtained by drying an airgel layer that has been washed and (if necessary) solvent-substituted 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 substrate, but can be 60 to 180 ° C., and is 90 to 150 ° C. There may be.
  • 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.
  • the airgel laminate of the present embodiment may be pre-dried before the drying step from the viewpoint of improving the drying efficiency in atmospheric drying.
  • the pre-drying method is not particularly limited.
  • 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.
  • the airgel laminated body obtained by such predrying can be further dried in a drying process.
  • the separators When the separators are laminated in the washing and 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.
  • the separator When the washing and solvent replacement step to the drying step are performed continuously, the separator can be extracted before the washing step and laminated again after the pre-drying.
  • the airgel laminate of this embodiment can also be obtained by supercritical drying of an airgel laminate that has been washed and (if necessary) solvent-substituted.
  • 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. And carbon dioxide having a lower critical point than that of the solvent, and then removing carbon dioxide alone or a mixture of carbon dioxide and the solvent.
  • the heat insulating material of the present embodiment includes at least one of the airgel laminates described so far, and has high heat insulating properties and excellent flexibility.
  • the airgel laminated body obtained by the manufacturing method of the said airgel laminated body can be made into a heat insulating material as it is (processed into a predetermined shape as needed).
  • the heat insulating material may be a laminate in which a plurality of the airgel laminates are laminated.
  • the airgel laminate of this embodiment has at least one structure in which an airgel layer, a resin layer, and a base material are laminated in the thickness direction.
  • the airgel laminate of the present embodiment can be used as a heat insulating material having excellent heat insulating properties and flexibility because it is possible to reduce the thickness of the airgel, which has been difficult to handle in the past, and the heat insulating material is made thinner. Is possible.
  • the airgel laminate of the present embodiment is a heat insulating material in the cryogenic field (superconducting, cryogenic container, etc.), the space field, the building field, the automobile field, the home appliances, the semiconductor field, and industrial equipment. It can be applied to the use as.
  • the airgel laminated body of this embodiment can be utilized as a water-repellent sheet, a sound-absorbing sheet, a static vibration sheet, a catalyst carrying sheet, etc. besides the use as a heat insulating material.
  • Coating liquid 1 “Hitaroid 3204EB-1” (Hitachi Chemical Co., Ltd., hydroxyl value 30 KOH mg / g, viscosity 4030 mPa ⁇ s, weight average molecular weight 47000), and polyisocyanate compound “Duranate E405-80T” (Asahi Kasei Corporation) NCO content 7 mass%, viscosity 252 Pa ⁇ s) and toluene are mixed so that the NCO / OH equivalent ratio is 0.5: 1 and the solid content is 1.5 mass%, and stirred for 2 minutes. Thus, a coating liquid 1 was produced.
  • Coating liquid 2 A coating liquid 2 was prepared in the same manner as in the preparation of the coating liquid 1 except that the NCO / OH equivalent ratio was changed to 1: 1.
  • Coating liquid 3 A coating liquid 3 was prepared in the same manner as the coating liquid 1 except that the NCO / OH equivalent ratio was changed to 2: 1.
  • Coating solution 4 A coating solution 4 was prepared in the same manner as the coating solution 1 except that the NCO / OH equivalent ratio was changed to 3: 1.
  • Coating fluid 5 A coating solution 5 was prepared in the same manner as the coating solution 1 except that the NCO / OH equivalent ratio was changed to 9: 1.
  • Coating liquid 6 A coating liquid 6 was prepared in the same manner as in the preparation of the coating liquid 1 except that the NCO / OH equivalent ratio was changed to 10: 1.
  • Coating fluid 7 Epoxy resin “jER-811” (manufactured by Mitsubishi Chemical Corporation), curing agent “triethylenetetramine” (manufactured by Wako Pure Chemical Industries, Ltd.), and toluene have an epoxy group / amino group equivalent ratio. The mixture was blended so as to have a solid content of 1.5% by mass and stirred for 2 minutes to prepare a coating liquid 7.
  • Coating fluid 8 The epoxy resin “jER-811”, the polyisocyanate compound “Duranate E405-80T”, and toluene have an epoxy group / isocyanate group equivalent ratio of 1: 1 and a solid content of 1.5 mass%. Then, the mixture was stirred for 2 minutes to prepare a coating liquid 8.
  • Coating fluid 9 A polyisocyanate compound “Duranate E405-80T” and toluene were blended so that the solid content was 1.5% by mass, and stirred for 2 minutes to prepare a coating solution 9.
  • Coating solution 10 A polyol compound “Hitaroid 3204EB-1”, an isocyanate-based silane coupling agent “3-isocyanatopropyltriethoxysilane” KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.), and toluene are combined with a hydroxyl group / isocyanate group. The mixture was blended so that the equivalent ratio was 1: 1 and the solid content was 1.5% by mass, and stirred for 2 minutes to prepare a coating solution 10.
  • Coating solution 11 A polyol compound “Hitaroid 3204EB-1” and toluene were blended so that the solid content was 1.5 mass%, and stirred for 2 minutes to prepare a coating solution 11.
  • Coating fluid 12 Epoxy resin “jER-811”, polyol compound “Hitaroid 3204EB-1”, and toluene so that the epoxy group / hydroxyl group equivalent ratio is 1: 1 and the solid content is 1.5 mass%. The mixture was mixed and stirred for 2 minutes to prepare a coating solution 12.
  • Coating fluid 13 A polyol compound “Hitaroid 3204EB-1”, an epoxy silane coupling agent 3-glycidoxypropyltrimethoxysilane “KBM-403” (manufactured by Shin-Etsu Chemical Co., Ltd.)) and toluene / Epoxy group equivalent ratio was 1: 1 and the solid content was 1.5 mass%, and the mixture was stirred for 2 minutes to prepare a coating solution 13.
  • 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 100.0 parts by mass, acid catalyst 0.10 parts by mass of acetic acid, 20.0 parts by mass of hexadecyltrimethylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “CTAB”) as an ionic surfactant, and urea as a thermohydrolyzable compound 120.0 parts by mass, 60.0 parts by mass of methylcitrimethoxylane (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “MTMS”) and dimethoxydimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a silicon compound.
  • CTAB hexadecyltrimethylammonium bromide
  • DDMS dissiloxane compound A
  • 20.0 parts by mass of polysiloxane compound A as a polysiloxane compound It was allowed to react for 1 hour at 25 ° C.. Thereafter, a sol-gel reaction was performed at 80 ° C. for 15 minutes to obtain a sol coating solution.
  • Example 1 The coating liquid 1 is dried on a double-sided aluminum vapor-deposited PET film (product name: VM-PET, manufactured by Hitachi AIC Co., Ltd.) having a base of (length) 1500 mm ⁇ (width) 1000 mm ⁇ (thickness) 12 ⁇ m.
  • the film was applied using a film applicator (product name: PI-1210, manufactured by Tester Sangyo Co., Ltd.) so as to have a thickness of 1 ⁇ m, and dried at 120 ° C. for 1 minute to form a resin layer on the substrate.
  • a film applicator product name: PI-1210, manufactured by Tester Sangyo Co., Ltd.
  • the sol coating solution is applied onto the resin layer of the base material using a film applicator (product name: PI-1210, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after gelation is 40 ⁇ m. It dried at 1.5 degreeC for 1.5 minute (s), and the airgel laminated body which has a gel-like airgel layer was obtained. Thereafter, the obtained airgel laminate was transferred to a sealed container and aged at 60 ° C. for 3 hours.
  • a film applicator product name: PI-1210, manufactured by Tester Sangyo Co., Ltd.
  • the aged airgel laminate was washed with 2000 mL of water for 2 minutes and then immersed in 2000 mL of methanol for 2 minutes for cleaning. This washing operation is performed twice while exchanging with new methanol, and the washed and solvent-substituted airgel laminate is dried at 120 ° C. for 1 hour, and is represented by the above general formulas (6) and (7).
  • the airgel laminated body 1 which has a structure was obtained.
  • Example 2 The airgel laminated body 2 was obtained like Example 1 except having formed the resin layer using the coating liquid 2.
  • FIG. 1 is a diagrammatic representation of Example 2
  • Example 3 The airgel laminated body 3 was obtained like Example 1 except having formed the resin layer using the coating liquid 3.
  • FIG. 3
  • Example 4 The airgel laminated body 4 was obtained like Example 1 except having formed the resin layer using the coating liquid 4.
  • FIG. 4 is a diagrammatic representation of Example 4
  • Example 5 The airgel laminated body 5 was obtained like Example 1 except having formed the resin layer using the coating liquid 5.
  • FIG. 5 The airgel laminated body 5 was obtained like Example 1 except having formed the resin layer using the coating liquid 5.
  • Example 6 The airgel laminated body 6 was obtained like Example 1 except having formed the resin layer using the coating liquid 6.
  • FIG. 6 The airgel laminated body 6 was obtained like Example 1 except having formed the resin layer using the coating liquid 6.
  • Example 7 The airgel laminated body 7 was obtained like Example 1 except having formed the resin layer using the coating liquid 7.
  • FIG. 7
  • Example 8 The airgel laminated body 8 was obtained like Example 1 except having formed the resin layer using the coating liquid 8.
  • FIG. 8 The airgel laminated body 8 was obtained like Example 1 except having formed the resin layer using the coating liquid 8.
  • Example 9 The airgel laminated body 9 was obtained like Example 1 except having formed the resin layer using the coating liquid 9.
  • FIG. 9 is a diagrammatic representation of Example 9
  • Example 10 The airgel laminated body 10 was obtained like Example 1 except having formed the resin layer using the coating liquid 10.
  • FIG. 10 The airgel laminated body 10 was obtained like Example 1 except having formed the resin layer using the coating liquid 10.
  • Example 1 The sol coating solution was directly applied to a double-sided aluminum vapor-deposited PET film (vertical) 1500 mm ⁇ (horizontal) 1000 mm ⁇ (thickness) 12 ⁇ m, which was the base material, in the same manner as in Example 1 except that an airgel layer was formed.
  • the airgel laminated body 11 was obtained.
  • Double-sided aluminum vapor-deposited PET film (product name: VM-PET, manufactured by Hitachi AIC Co., Ltd.) of 1500 mm ⁇ (width) 1000 mm ⁇ (thickness) 12 ⁇ m, which is a base material, and 1500 mm ⁇ (length), which becomes a heat insulating layer
  • Laminate insulation 1 was obtained by laminating E glass cloth (manufactured by Nitto Boseki Co., Ltd.) of 1000 mm ⁇ (thickness) 42 ⁇ m (IPC spec: 1078).
  • each example and comparative example was the same as each example and comparative example except that the base material was changed to a single-sided aluminum vapor-deposited PET film (manufactured by Hitachi AIC Co., Ltd., product name: VM-PET).
  • the airgel laminated body corresponding to each was produced.
  • the resin layer and the airgel layer were formed on the aluminum layer side (in the case of the conditions corresponding to Comparative Example 1, the airgel layer was directly formed on the aluminum layer).
  • a test piece obtained by cutting each obtained airgel laminate into 50 mm ⁇ 50 mm was impregnated with an aqueous urea solution adjusted to pH 9 contained in a sealed container, and the container was heated at 60 ° C. for 1 hour. I took it out. And in the test piece after impregnation with urea aqueous solution, the presence or absence of whitening or dissolution of the aluminum layer on the airgel layer side of the PET film was visually confirmed from the PET film side. If the aluminum layer on the airgel layer side is whitened or dissolved in any of the confirmed test pieces, the corrosion of the airgel laminate is “present” (no corrosion resistance), and the aluminum layer on the airgel layer side is whitened.
  • the airgel laminate when there was no dissolution, the airgel laminate was “no corrosion” (has corrosion resistance).
  • the PET film since the PET film is transparent, it is visually confirmed from the PET film side, but the airgel layer may be removed to visually confirm the surface of the substrate on the airgel layer side.
  • the airgel laminate and the laminated heat insulating material are (vertical) 606 mm ⁇ (horizontal) 343 mm sheet A, (vertical) 612 mm ⁇ (horizontal) 362 mm sheet B, (vertical ) 618 mm ⁇ (width) 380 mm sheet C, (diameter) 105 mm sheet D, (diameter) 112 mm sheet E, (diameter) 118 mm sheet F.
  • a sheet D10 obtained by laminating 10 layers of sheet D, a sheet E10 obtained by laminating 10 layers of sheet E, and a sheet F10 obtained by laminating 10 layers of sheet F were produced.
  • a liquid nitrogen container having a height of 600 mm and a diameter of 100 mm was prepared, a sheet A10 was disposed on the side surface, sheets D10 were disposed above and below the liquid nitrogen container, and the liquid nitrogen container was wound around the liquid nitrogen container.
  • the sheet B10 is disposed on the sheet A10
  • the sheet E10 is disposed on the sheet D10
  • the sheet C10 is disposed on the sheet B10
  • the sheet F10 is disposed on the sheet D10.
  • a liquid nitrogen container for heat insulation evaluation in which 30 layers of airgel laminate or laminated heat insulating material were laminated was obtained.
  • seat of a side surface and the upper and lower sheets was affixed with the aluminum tape.
  • FIG. 4 is a cross-sectional view schematically showing the structure of a liquid nitrogen container for heat insulation evaluation in which the heat insulating material 10 is wound around the liquid nitrogen container 12.
  • a heat insulating material 10 made of a 30-layer airgel laminate or a laminated heat insulating material is laminated on a liquid nitrogen container 12 having an inlet 11 so as to cover the outer periphery.
  • the total thickness D 30 (mm) of the heat insulating material 10 provided on the outer periphery of the liquid nitrogen container 12 was calculated from the following equation.
  • D 30 D c /2 ⁇ 50.0
  • D c (mm) indicates the diameter of the liquid nitrogen container after 30 layers of the airgel laminated sheet or the laminated heat insulating material are wound.
  • Thermal insulation performance Thermal insulation performance was measured using a liquid nitrogen container for thermal insulation evaluation.
  • FIG. 5 the schematic of a heat insulation performance test apparatus is shown. First, the liquid nitrogen container 12 around which the heat insulating material 10 was wound was placed in a thermostatic chamber 14 set to 283K and installed in the vacuum container 16. Next, evacuation in the vacuum vessel 16 was performed with the turbo molecular pump 20, and the vacuum pressure inside the vacuum vessel 16 was measured with the Pirani vacuum gauge 22 and the ion vacuum gauge 24.
  • the vacuum pressure was measured with the ion vacuum gauge 24 and the pressure in the vacuum vessel 16 was 1 Vacuum evacuation was performed for 7 days until the pressure reached 10 ⁇ 2 Pa or less. After that, after injecting liquid nitrogen into the liquid nitrogen container 12 installed in the vacuum container 16, the temperature of the neck pipe 18 and the flow rate of the evaporated nitrogen gas are substantially constant values, and it is confirmed that they are in a steady state. The heat flux q passing through the heat insulating material 10 was calculated.
  • the evaporative gas mass flow rate m (kg / s) of liquid nitrogen was obtained from the following formula (I).
  • ⁇ g T represents a room temperature gas density (kg / m 3 )
  • V g T represents a room temperature gas flow rate (m 3 / s)
  • the output of the wet flow meter 26 and the wet flow meter 26 is a value measured by the internal temperature.
  • the efficiency ⁇ was obtained from the following formula (IV).
  • C p (J / (kg ⁇ K)) represents specific heat.
  • the value of the A s, a 0.243 ⁇ 10 -4 (m 2) the value of the L is 199000 (J / kg).
  • the heat flux q (W / m 2 ) passing through the airgel laminate and the laminated heat insulating material was obtained from the following formula (V).
  • the heat flux was measured three times, and the average value was used as the heat flux of this evaluation.
  • a r (m 2 ) represents the surface area of the liquid nitrogen container, and the value is 0.2041 (m 2 ).
  • Table 1 shows the layer structure of the airgel laminate or laminated heat insulating material obtained in each Example and Comparative Example, the amount of airgel layer falling off, the evaluation results of corrosion resistance and heat insulation.
  • the airgel laminated body produced in the Example has the airgel layer and the base material integrated through the resin layer, it is possible to reduce the dropping of the airgel layer from the base material, and It can be confirmed that the thickness can be reduced. It can be confirmed from Table 1 that by providing the resin layer on the base material, corrosion of the base material can be suppressed and dropping of the airgel layer from the base material can be reduced. Moreover, it can confirm that it has high heat insulation performance also in the airgel laminated body which provided the resin layer.
  • SYMBOLS 1 Airgel layer, 2 ... Resin layer, 3 ... Base material, 10 ... Heat insulating material, 11 ... Inlet, 12 ... Liquid nitrogen container, 14 ... Constant temperature bath, 16 ... Vacuum vessel, 17 ... Flange, 18 ... Neck piping, 20 ... turbo molecular pump, 22 ... Pirani vacuum gauge, 24 ... ion vacuum gauge, 26 ... wet flow meter, L ... circumscribed rectangle, P ... silica particles.

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Abstract

The invention pertains to an aerogel laminate provided with a base material, a resin layer provided on the base material, and an aerogel layer provided on the resin layer, in which the resin layer contains a resin having nitrogen as a constituent atom in the molecular structure.

Description

エアロゲル積層体及び断熱材Airgel laminate and heat insulating material
　本発明は、エアロゲル積層体及び断熱材に関する。 The present invention relates to an airgel laminate and a heat insulating material.
　近年、居住空間の快適性及び省エネルギー化の要求が高まっていることから、断熱性が要求される対象物の形状は複雑となり、断熱材の設置空間も狭小となる傾向にある。そのため、断熱性能を向上するだけでなく、薄型化した断熱材が求められている。 In recent years, the demand for comfort and energy saving in living spaces has increased, so the shape of objects requiring heat insulation has become complex, and the space for installing heat insulation tends to be narrow. Therefore, there is a demand for a heat insulating material that is not only improved in heat insulating performance but also made thinner.
　発泡樹脂を用いた断熱材の断熱性能向上の試みとして、例えば、特許文献１では、ポリプロピレン系樹脂発泡体の表面及び／又は内部に少なくとも１層の金属薄膜を含有する板状発泡体が提案されている。 As an attempt to improve the heat insulation performance of a heat insulating material using a foam resin, for example, Patent Document 1 proposes a plate-like foam containing at least one metal thin film on the surface and / or inside of a polypropylene resin foam. ing.
　また、液体窒素、液体ヘリウム等の極低温物質は、内容器と外容器とからなる二重壁構造を有する容器に保管されており、内容器と外容器との間は真空になっており、断熱材が充填されている。真空空間に充填する断熱材として、例えば、特許文献２には、ポリイミドフィルムの片面又は両面に金属層を形成した反射膜と、プラスチックヤーンからなるネット状のスペーサーとを積層した積層断熱材が開示されている。また、特許文献３には、熱可塑性液晶ポリマーフィルムの片面もしくは両面又は内部に金属層を形成した反射板と、熱可塑性ポリマー繊維からなるシート状のスペーサーとを積層した積層断熱材が開示されている。 In addition, cryogenic substances such as liquid nitrogen and liquid helium are stored in a container having a double wall structure consisting of an inner container and an outer container, and a vacuum is formed between the inner container and the outer container. Insulation is filled. As a heat insulating material for filling the vacuum space, for example, Patent Document 2 discloses a laminated heat insulating material in which a reflective film in which a metal layer is formed on one or both sides of a polyimide film and a net-like spacer made of plastic yarn are laminated. Has been. Patent Document 3 discloses a laminated heat insulating material obtained by laminating a reflective plate in which a metal layer is formed on one or both sides or inside of a thermoplastic liquid crystal polymer film and a sheet-like spacer made of thermoplastic polymer fibers. Yes.
特開２００１－１７９８６６号公報JP 2001-179866 A 特開平９－１０９３２３号公報JP-A-9-109323 特開２０００－２６６２８２号公報JP 2000-266282 A
　しかしながら、樹脂発泡体を用いた断熱材の場合、良好な断熱性能を得るためには、発泡体を厚くする必要があり、断熱層の薄型化は難しい。また、極低温物質を必要とする極低温技術、超電導技術等の分野において用いられる断熱材には、厚みを薄くした上で、断熱性能の更なる向上が求められている。一方、熱伝導率が小さく断熱性を有する材料としてエアロゲルが知られているが、エアロゲルは取扱い難いため、基材上に薄膜のエアロゲル層を形成した場合にエアロゲル層の一部が脱落してしまうことがある。 However, in the case of a heat insulating material using a resin foam, in order to obtain good heat insulating performance, it is necessary to increase the thickness of the foam, and it is difficult to reduce the thickness of the heat insulating layer. Further, heat insulating materials used in fields such as cryogenic technology and superconducting technology that require cryogenic substances are required to have further improved heat insulating performance after being reduced in thickness. On the other hand, airgel is known as a material having low thermal conductivity and heat insulation properties. However, since airgel is difficult to handle, part of the airgel layer falls off when a thin airgel layer is formed on a substrate. Sometimes.
　本発明は上記事情に鑑みてなされたものであり、エアロゲル層の基材からの脱落が低減され、かつ、薄型化が可能なエアロゲル積層体、及び、該エアロゲル積層体を備える断熱材を提供する。 The present invention has been made in view of the above circumstances, and provides an airgel laminate that can be reduced in thickness and can be reduced in thickness, and a heat insulating material that includes the airgel laminate. .
　本発明は、基材と、該基材上に設けられた樹脂層と、該樹脂層上に設けられたエアロゲル層とを備え、樹脂層が、構成原子として窒素を有する樹脂を含む、エアロゲル積層体を提供する。 The present invention includes a base material, a resin layer provided on the base material, and an airgel layer provided on the resin layer, and the resin layer includes a resin having nitrogen as a constituent atom. Provide the body.
　上記エアロゲル積層体は、樹脂層を介してエアロゲル層と基材とが積層された構造を備えることで、エアロゲル層の基材からの脱落を低減することができると共に、積層体の薄型化が可能となる。 The airgel laminate has a structure in which the airgel layer and the base material are laminated via a resin layer, so that the airgel layer can be prevented from falling off from the base material, and the thickness of the laminate can be reduced. It becomes.
　上記樹脂は、ウレタン結合、アミド結合、ウレア結合、イミド結合、スルホンアミド結合、チオウレタン結合、チオアミド結合、チオウレア結合及びチオイミド結合からなる群より選択される少なくとも１種の結合を有していてもよい。これにより、樹脂層とエアロゲル層との接着性が向上し、エアロゲル層の基材からの脱落を更に低減することができる。 The resin may have at least one bond selected from the group consisting of urethane bond, amide bond, urea bond, imide bond, sulfonamide bond, thiourethane bond, thioamide bond, thiourea bond and thioimide bond. Good. Thereby, the adhesiveness of a resin layer and an airgel layer improves, and the fall-off | omission from the base material of an airgel layer can further be reduced.
　樹脂層とエアロゲル層との接着性をより向上する観点から、上記樹脂は、ウレタン結合を有していてもよい。ウレタン結合は、水酸基を有する化合物とイソシアネート基を有する化合物とが反応してなる結合であってもよい。また、上記イソシアネート基と上記水酸基との当量比は、０．１：１～１０：１とすることができる。 From the viewpoint of further improving the adhesion between the resin layer and the airgel layer, the resin may have a urethane bond. The urethane bond may be a bond formed by a reaction between a compound having a hydroxyl group and a compound having an isocyanate group. The equivalent ratio of the isocyanate group to the hydroxyl group can be 0.1: 1 to 10: 1.
　上記水酸基を有する化合物はポリオール化合物であってもよい。また、上記イソシアネート基を有する化合物はポリイソシアネート化合物であってもよい。 The compound having a hydroxyl group may be a polyol compound. The compound having an isocyanate group may be a polyisocyanate compound.
　上記エアロゲル層は、ポリシロキサン由来の構造を有するエアロゲルを含有する層であってもよい。これにより、エアロゲル層の厚みを薄くでき、エアロゲル積層体を薄型化し易くなる。 The airgel layer may be a layer containing an airgel having a structure derived from polysiloxane. Thereby, the thickness of an airgel layer can be made thin and it becomes easy to make an airgel laminated body thin.
　さらに、上記エアロゲル層は、シリカ粒子が複合化された層であってもよい。これにより、エアロゲル層に優れた断熱性及び柔軟性を付与し易くなる。 Furthermore, the airgel layer may be a layer in which silica particles are combined. Thereby, it becomes easy to provide the heat insulation property and the softness | flexibility which were excellent in the airgel layer.
　上記シリカ粒子の平均一次粒子径は、１～５００ｎｍとすることができる。これにより、エアロゲル層の断熱性と柔軟性とを更に向上し易くなる。 The average primary particle diameter of the silica particles can be 1 to 500 nm. Thereby, it becomes easy to further improve the heat insulation and flexibility of the airgel layer.
　エアロゲル積層体の断熱性を向上する観点から、上記基材は、熱線反射機能又は熱線吸収機能を有していてもよい。 From the viewpoint of improving the heat insulation properties of the airgel laminate, the base material may have a heat ray reflection function or a heat ray absorption function.
　本発明はまた、上述したエアロゲル積層体を備える断熱材を提供することができる。これのような断熱材は、取り扱い性に優れ、厚みを薄くした上で、優れた断熱性能を発現することができる。 This invention can also provide a heat insulating material provided with the airgel laminated body mentioned above. Such a heat insulating material is excellent in handleability, and can exhibit excellent heat insulating performance after the thickness is reduced.
　本発明によれば、エアロゲル層の基材からの脱落が低減され、かつ、薄型化が可能なエアロゲル積層体を提供することができる。そして、このようなエアロゲル積層体を備える断熱材は、取扱い性に優れ、厚みを薄くした上で、優れた断熱性能を発現することができる。 According to the present invention, it is possible to provide an airgel laminate in which the airgel layer is prevented from falling off from the base material and can be thinned. And a heat insulating material provided with such an airgel laminated body is excellent in handleability, and can express the outstanding heat insulation performance, after reducing thickness.
　また、基材上に薄膜のエアロゲル層を形成する場合、基材に酸化、腐食等が起こることがある。これに対して、上記本発明のエアロゲル積層体によれば、樹脂層を介してエアロゲル層と基材とが積層された構造を備えることで、基材の酸化、腐食等を抑制することができると共に、積層体の断熱性を向上することが可能となる。 Also, when a thin airgel layer is formed on a substrate, the substrate may be oxidized or corroded. On the other hand, according to the airgel laminate of the present invention, by providing a structure in which the airgel layer and the base material are laminated via the resin layer, it is possible to suppress oxidation, corrosion, and the like of the base material. At the same time, it becomes possible to improve the heat insulation of the laminate.
本実施形態のエアロゲル積層体の模式断面図である。It is a schematic cross section of the airgel laminated body of this embodiment. 本実施形態のエアロゲル積層体が積層された多層積層体の模式断面図である。It is a schematic cross section of the multilayer laminated body on which the airgel laminated body of this embodiment was laminated | stacked. 粒子の二軸平均一次粒子径の算出方法を示す図である。It is a figure which shows the calculation method of the biaxial average primary particle diameter of particle | grains. 断熱性評価用の液体窒素容器の模式断面図である。It is a schematic cross section of the liquid nitrogen container for heat insulation evaluation. 断熱性能試験装置の概略図である。It is the schematic of a heat insulation performance test apparatus.
　以下、場合により図面を参照しつつ本発明の実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings depending on cases. However, the present invention is not limited to the following embodiments.
＜定義＞
　本明細書において、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。本明細書に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。「Ａ又はＢ」とは、Ａ及びＢのどちらか一方を含んでいればよく、両方とも含んでいてもよい。本明細書に例示する材料は、特に断らない限り、１種を単独で又は２種以上を組み合わせて用いることができる。本明細書において、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する複数の物質の合計量を意味する。 <Definition>
In this specification, 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. In the numerical ranges described stepwise in this specification, 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. In the numerical range described in this specification, 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. In the present specification, 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.
［エアロゲル積層体］
　本実施形態のエアロゲル積層体は、基材とエアロゲル層とが、窒素原子を有する樹脂を含む層を介して積層された構造を備える。エアロゲル層を基材に積層させることにより、優れた断熱性を発現することができる。該エアロゲル層は、可とう性に優れており、従来、取扱い性が困難であったエアロゲルのシート化が可能となり、基材と一体化できるため、エアロゲル積層体を断熱材として用いた場合、断熱層を薄型化することができる。また、エアロゲル層は、非熱伝導性の基材に積層することで、熱伝導によって温度が上昇することを防いでいる。そして、樹脂層を基材上に設けることで、基材を保護することができ、特に、基材が金属を含む場合に有効である。 [Airgel laminate]
The airgel laminate of the present embodiment has a structure in which a base material and an airgel layer are laminated via a layer containing a resin having a nitrogen atom. By laminating the airgel layer on the base material, excellent heat insulation can be expressed. The airgel layer is excellent in flexibility and can be formed into a sheet of airgel, which has been difficult to handle in the past, and can be integrated with the base material. Therefore, when the airgel laminate is used as a heat insulating material, The layer can be thinned. In addition, the airgel layer is laminated on a non-thermally conductive base material to prevent the temperature from rising due to heat conduction. And a base material can be protected by providing a resin layer on a base material, and it is effective especially when a base material contains a metal.
　図１は、本実施形態のエアロゲル積層体の断面を模式的に示す図である。図１に示すように、エアロゲル積層体は、基材３とエアロゲル層１とが、窒素原子を含有する樹脂層２を介して積層された構造を有している。このような構造を１つ以上有することで、薄型化可能となり、優れた断熱性及び柔軟性を有するエアロゲル積層体となる。なお、エアロゲル層１は、樹脂層２を介して基材３の両面に積層されていてもよい。 FIG. 1 is a diagram schematically showing a cross section of the airgel laminate of the present embodiment. As shown in FIG. 1, the airgel laminated body has the structure where the base material 3 and the airgel layer 1 were laminated | stacked through the resin layer 2 containing a nitrogen atom. By having one or more such structures, the airgel laminate can be thinned and has excellent heat insulating properties and flexibility. In addition, the airgel layer 1 may be laminated | stacked on both surfaces of the base material 3 through the resin layer 2. As shown in FIG.
　図２は、本実施形態のエアロゲル積層体が複数積層された多層積層体の断面を模式的に示す図である。本実施形態のエアロゲル積層体は、図２に示すように、エアロゲル層１と樹脂層２を設けた基材３とが、交互に複数積層された多層積層体とすることができる。基材３同士、あるいは樹脂層２同士が直接接触しないようにエアロゲル積層体が積層されていれば、多層積層体は、５層以上であってもよく、１０層以上であってもよく、２０層以上であってもよい。 FIG. 2 is a diagram schematically showing a cross section of a multilayer laminate in which a plurality of airgel laminates of the present embodiment are laminated. As shown in FIG. 2, the airgel laminate of the present embodiment can be a multilayer laminate in which a plurality of airgel layers 1 and base materials 3 provided with a resin layer 2 are alternately laminated. If the airgel laminate is laminated so that the substrates 3 or the resin layers 2 are not in direct contact with each other, the multilayer laminate may be 5 layers or more, 10 layers or more, 20 It may be a layer or more.
　エアロゲル層１と基材３とが樹脂層２を介して積層された構造を複数層設けることにより、１層のエアロゲル積層体では得られない優れた断熱性能を発現することができる。 By providing a plurality of layers in which the airgel layer 1 and the base material 3 are laminated with the resin layer 2 interposed therebetween, excellent heat insulation performance that cannot be obtained with a single airgel laminate can be expressed.
＜エアロゲル層＞
　本実施形態に係るエアロゲル層は、エアロゲルにより構成される層である。狭義には、湿潤ゲルに対して超臨界乾燥法を用いて得られた乾燥ゲルをエアロゲル、大気圧下での乾燥により得られた乾燥ゲルをキセロゲル、凍結乾燥により得られた乾燥ゲルをクライオゲルと称するが、本実施形態においては、湿潤ゲルのこれらの乾燥手法によらず、得られた低密度の乾燥ゲルをエアロゲルと称する。すなわち、本実施形態においてエアロゲルとは、広義のエアロゲルである「Ｇｅｌ　ｃｏｍｐｒｉｓｅｄ　ｏｆ　ａ　ｍｉｃｒｏｐｏｒｏｕｓ　ｓｏｌｉｄ　ｉｎ　ｗｈｉｃｈ　ｔｈｅ　ｄｉｓｐｅｒｓｅｄ　ｐｈａｓｅ　ｉｓ　ａ　ｇａｓ（分散相が気体である微多孔性固体から構成されるゲル）」を意味するものである。一般的にエアロゲルの内部は網目状の微細構造となっており、２～２０ｎｍ程度のエアロゲル粒子（エアロゲルを構成する粒子）が結合したクラスター構造を有している。このクラスターにより形成される骨格間には、１００ｎｍに満たない細孔がある。これにより、エアロゲルは、三次元的に微細な多孔性の構造をしている。なお、本実施形態におけるエアロゲルは、シリカを主成分とするシリカエアロゲルである。シリカエアロゲルとしては、例えば、有機基（メチル基等）又は有機鎖を導入した、いわゆる有機－無機ハイブリッド化されたシリカエアロゲルが挙げられる。本実施形態に係るエアロゲル層は、ポリシロキサン由来の構造を有するエアロゲルを含有する層であってもよい。 <Airgel layer>
The airgel layer which concerns on this embodiment is a layer comprised by airgel. In a narrow sense, dry gel obtained by using supercritical drying method for wet gel is aerogel, dry gel obtained by drying under atmospheric pressure is xerogel, dry gel obtained by freeze-drying is cryogel and However, in the present embodiment, the obtained low-density dried gel is referred to as an aerogel regardless of the drying method of the wet gel. In other words, in the present embodiment, 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. In general, 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. In addition, the airgel in this embodiment is a silica airgel which has a silica as a main component. Examples of 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 according to the present embodiment may be a layer containing an airgel having a structure derived from polysiloxane.
　本実施形態に係るエアロゲルは、（分子内に）加水分解性の官能基又は縮合性の官能基を有するケイ素化合物、及び、前記加水分解性の官能基を有するケイ素化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルの縮合物である湿潤ゲルの乾燥物であってもよい。すなわち、本実施形態に係るエアロゲル層は、（分子内に）加水分解性の官能基又は縮合性の官能基を有するケイ素化合物、及び、前記加水分解性の官能基を有するケイ素化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルから生成された湿潤ゲルを乾燥して得ることができる。これらの態様を採用することにより、エアロゲル層の断熱性と柔軟性とがより向上する。前記縮合物は、加水分解性の官能基を有するケイ素化合物の加水分解により得られた加水分解生成物の縮合反応により得られてもよく、加水分解により得られた官能基ではない縮合性の官能基を有するケイ素化合物の縮合反応により得られてもよい。前記ケイ素化合物は、加水分解性の官能基及び縮合性の官能基の少なくとも一方を有していればよく、加水分解性の官能基及び縮合性の官能基の双方を有していてもよい。なお、後述する各エアロゲルは、このように、加水分解性の官能基又は縮合性の官能基を有するケイ素化合物、及び、前記加水分解性の官能基を有するケイ素化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルの縮合物である湿潤ゲルの乾燥物（前記ゾルから生成された湿潤ゲルを乾燥することで得られるもの）であってもよい。 The airgel according to the present embodiment includes a silicon compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a hydrolysis product of the silicon compound having the hydrolyzable functional group. It may be a dried product of a wet gel that is a condensate of a sol containing at least one selected from the group. That is, the airgel layer according to the present embodiment includes (in the molecule) a hydrolyzable functional group or a silicon compound having a condensable functional group, and a hydrolyzed product of the silicon compound having the hydrolyzable functional group. The wet gel produced from the sol containing at least one selected from the group consisting of products can be obtained by drying. By adopting these aspects, the heat insulating property and flexibility of the airgel layer are further improved. 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. In addition, 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).
　エアロゲル層は、加水分解性の官能基又は縮合性の官能基を有するケイ素化合物、及び、前記加水分解性の官能基を有するケイ素化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルの縮合物である湿潤ゲルの乾燥物から構成される層であってもよい。すなわち、エアロゲル層は、加水分解性の官能基又は縮合性の官能基を有するケイ素化合物、及び、前記加水分解性の官能基を有するケイ素化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルから生成された湿潤ゲルを乾燥してなる層で構成されていてもよい。 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.
　本実施形態に係るエアロゲルは、シロキサン結合（Ｓｉ－Ｏ－Ｓｉ）を含む主鎖を有するポリシロキサンを含有することができる。エアロゲルは、構造単位として、下記Ｍ単位、Ｄ単位、Ｔ単位又はＱ単位を有することができる。 The airgel according to the present embodiment can contain polysiloxane having a main chain including a siloxane bond (Si—O—Si). The airgel can have the following M unit, D unit, T unit or Q unit as a structural unit.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　上記式中、Ｒは、ケイ素原子に結合している原子（水素原子等）又は原子団（アルキル基等）を示す。Ｍ単位は、ケイ素原子が１個の酸素原子と結合した一価の基からなる単位である。Ｄ単位は、ケイ素原子が２個の酸素原子と結合した二価の基からなる単位である。Ｔ単位は、ケイ素原子が３個の酸素原子と結合した三価の基からなる単位である。Ｑ単位は、ケイ素原子が４個の酸素原子と結合した四価の基からなる単位である。これらの単位の含有量に関する情報は、Ｓｉ－ＮＭＲにより得ることができる。 In the above formula, 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.
　本実施形態のエアロゲルは、シルセスキオキサンを含有していてもよい。シルセスキオキサンは、構造単位として上記Ｔ単位を有するポリシロキサンであり、組成式：（ＲＳｉＯ１．５）ｎを有する。シルセスキオキサンは、カゴ型、ラダー型、ランダム型等の種々の骨格構造を有することができる。 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.
　加水分解性の官能基としては、例えば、アルコキシ基が挙げられる。縮合性の官能基（加水分解性の官能基に該当する官能基を除く）としては、例えば、水酸基、シラノール基、カルボキシル基及びフェノール性水酸基が挙げられる。水酸基は、ヒドロキシアルキル基等の水酸基含有基に含まれていてもよい。加水分解性の官能基及び縮合性の官能基のそれぞれは、単独で又は２種類以上を混合して用いてもよい。 Examples of the hydrolyzable functional group include an alkoxy group. Examples of the condensable functional group (excluding the functional group corresponding to the hydrolyzable 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.
　ケイ素化合物は、加水分解性の官能基としてアルコキシ基を有するケイ素化合物を含むことが可能であり、また、縮合性の官能基としてヒドロキシアルキル基を有するケイ素化合物を含むことができる。ケイ素化合物は、エアロゲルの柔軟性が更に向上する観点から、アルコキシ基、シラノール基、ヒドロキシアルキル基及びポリエーテル基からなる群より選ばれる少なくとも１種を有することができる。ケイ素化合物は、ゾルの相溶性が向上する観点から、アルコキシ基及びヒドロキシアルキル基からなる群より選ばれる少なくとも１種を有することができる。 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.
　ケイ素化合物の反応性の向上とエアロゲルの熱伝導率の低減の観点から、アルコキシ基及びヒドロキシアルキル基のそれぞれの炭素数は、１～６とすることができ、エアロゲルの柔軟性が更に向上する観点から２～４であってもよい。アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。ヒドロキシアルキル基としては、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基等が挙げられる。 From the viewpoint of improving the reactivity of the silicon compound and reducing the thermal conductivity of the airgel, 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. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
　本実施形態に係るエアロゲルとしては、以下の態様が挙げられる。これらの態様を採用することにより、断熱性と柔軟性とに更に優れ、薄膜化が可能なエアロゲルを得ることが容易となる。各々の態様を採用することで、各々の態様に応じた断熱性及び柔軟性を有し、薄膜化が可能なエアロゲルを得ることができる。 Examples of the airgel according to the present embodiment include the following modes. By adopting these aspects, it becomes easy to obtain an airgel that is further excellent in heat insulation and flexibility and can be made thin. By adopting each aspect, an airgel having heat insulation and flexibility according to each aspect and capable of being thinned can be obtained.
（第一の態様）
　本実施形態に係るエアロゲルは、（分子内に）加水分解性の官能基又は縮合性の官能基を有するポリシロキサン化合物、及び、前記加水分解性の官能基を有するポリシロキサン化合物の加水分解生成物（前記加水分解性の官能基が加水分解したポリシロキサン化合物）からなる群より選択される少なくとも一種の化合物（以下、場合により「ポリシロキサン化合物群」という）を含有するゾルの縮合物である湿潤ゲルの乾燥物であってもよい。すなわち、本実施形態に係るエアロゲルは、（分子内に）加水分解性の官能基又は縮合性の官能基を有するポリシロキサン化合物、及び、前記加水分解性の官能基を有するポリシロキサン化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルから生成された湿潤ゲルを乾燥して得られるものであってもよい。なお、後述する各エアロゲルも、このように、加水分解性の官能基又は縮合性の官能基を有するポリシロキサン化合物、及び、前記加水分解性の官能基を有するポリシロキサン化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルの縮合物である湿潤ゲルの乾燥物（前記ゾルから生成された湿潤ゲルを乾燥することで得られるもの）であってもよい。 (First aspect)
The airgel according to the present embodiment includes a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule), and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group. Wet which is a condensate of sol containing at least one compound selected from the group consisting of (the hydrolyzable functional group hydrolyzed polysiloxane compound) (hereinafter sometimes referred to as “polysiloxane compound group”) It may be a dried gel. That is, the airgel according to the present embodiment includes a hydrolyzable polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a 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. In addition, 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.
　エアロゲル層は、加水分解性の官能基又は縮合性の官能基を有するポリシロキサン化合物、及び、前記加水分解性の官能基を有するポリシロキサン化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルの縮合物である湿潤ゲルの乾燥物から構成される層であってもよい。すなわち、エアロゲル層は、加水分解性の官能基又は縮合性の官能基を有するポリシロキサン化合物、及び、前記加水分解性の官能基を有するポリシロキサン化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルから生成された湿潤ゲルを乾燥してなる層で構成されていてもよい。このようにして得られたエアロゲル積層体は、断熱性と柔軟性とのバランスに優れるものとなる。 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 | generated from the sol containing at least 1 type. Thus, the obtained airgel laminated body becomes a thing excellent in the balance of heat insulation and a softness | flexibility.
　加水分解性の官能基又は縮合性の官能基を有するポリシロキサン化合物は、加水分解性の官能基及び縮合性の官能基とは異なる反応性基（加水分解性の官能基及び縮合性の官能基に該当しない官能基）を更に有していてもよい。反応性基としては、特に限定されないが、例えば、エポキシ基、メルカプト基、グリシドキシ基、ビニル基、アクリロイル基、メタクリロイル基及びアミノ基が挙げられる。エポキシ基は、グリシドキシ基等のエポキシ基含有基に含まれていてもよい。前記反応性基を有するポリシロキサン化合物は、単独で又は２種類以上を混合して用いてもよい。 A polysiloxane compound having a hydrolyzable functional group or a condensable functional group is a reactive group different from the hydrolyzable functional group and the condensable functional group (hydrolyzable functional group and condensable functional group). May further have a functional group that does not fall under. The reactive group is not particularly limited, and examples thereof include an epoxy group, a mercapto group, a glycidoxy group, a vinyl group, an acryloyl group, a methacryloyl group, and an amino group. The epoxy group may be contained in an epoxy group-containing group such as a glycidoxy group. You may use the polysiloxane compound which has the said reactive group individually or in mixture of 2 or more types.
　官能基として、エアロゲルの柔軟性を向上する観点から、例えば、アルコキシ基、シラノール基、ヒドロキシアルキル基及びポリエーテル基が挙げられる。官能基として、ゾルの相溶性を向上する観点から、例えば、アルコキシ基及びヒドロキシアルキル基が挙げられる。ポリシロキサン化合物の反応性の向上とエアロゲルの熱伝導率の低減の観点から、アルコキシ基及びヒドロキシアルキル基の炭素数は１～６とすることができ、エアロゲルの柔軟性をより向上する観点から２～４であってもよい。 Examples of the functional group include an alkoxy group, a silanol group, a hydroxyalkyl group, and a polyether group from the viewpoint of improving the flexibility of the airgel. Examples of the functional group include an alkoxy group and a hydroxyalkyl group from the viewpoint of improving the compatibility of the sol. From the viewpoint of improving the reactivity of the polysiloxane compound and reducing the thermal conductivity of the airgel, the number of carbon atoms of the alkoxy group and hydroxyalkyl group can be 1 to 6, and from the viewpoint of further improving the flexibility of the airgel. It may be ~ 4.
　ヒドロキシアルキル基を有するポリシロキサン化合物としては、例えば、下記一般式（Ａ）で表される構造を有する化合物が挙げられる。 Examples of the polysiloxane compound having a hydroxyalkyl group include compounds having a structure represented by the following general formula (A).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式（Ａ）中、Ｒ１ａはヒドロキシアルキル基を示し、Ｒ２ａはアルキレン基を示し、Ｒ３ａ及びＲ４ａはそれぞれ独立にアルキル基又はアリール基を示し、ｎは１～５０の整数を示す。ここで、アリール基としては、例えばフェニル基及び置換フェニル基が挙げられる。置換フェニル基の置換基としては、例えばアルキル基、ビニル基、メルカプト基、アミノ基、ニトロ基及びシアノ基が挙げられる。式（Ａ）中、２個のＲ１ａは各々同一であっても異なっていてもよく、同様に、２個のＲ２ａは各々同一であっても異なっていてもよい。式（Ａ）中、２個以上のＲ３ａは各々同一であっても異なっていてもよく、同様に、２個以上のＲ４ａは各々同一であっても異なっていてもよい。 In 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, and n represents an integer of 1 to 50. Here, 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. In formula (A), two R 1a s may be the same or different, and similarly, two R 2a s may be the same or different. In formula (A), 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.
　上記構造のポリシロキサン化合物を含有するゾルの縮合物である湿潤ゲル（前記ゾルから生成された湿潤ゲル）を用いることにより、低熱伝導率かつ柔軟なエアロゲルを更に得易くなる。同様の観点から、以下に示す特徴を満たしてもよい。式（Ａ）中、Ｒ１ａとしては、例えば炭素数が１～６のヒドロキシアルキル基が挙げられ、具体的には、ヒドロキシエチル基及びヒドロキシプロピル基が挙げられる。式（Ａ）中、Ｒ２ａとしては、例えば炭素数が１～６のアルキレン基が挙げられ、具体的には、エチレン基及びプロピレン基が挙げられる。式（Ａ）中、Ｒ３ａ及びＲ４ａはそれぞれ独立に炭素数が１～６のアルキル基又はフェニル基であってもよい。該アルキル基は、メチル基であってもよい。式（Ａ）中、ｎは２～３０とすることができ、５～２０であってもよい。 By using a wet gel that is a condensate of a sol containing the polysiloxane compound having the above structure (a wet gel generated from the sol), it becomes easier to obtain a flexible airgel having low thermal conductivity. From the same viewpoint, the following features may be satisfied. In the formula (A), examples of R 1a include a hydroxyalkyl group having 1 to 6 carbon atoms, and specifically include a hydroxyethyl group and a hydroxypropyl group. In the formula (A), 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. In the formula (A), 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. In the formula (A), n may be 2 to 30, and may be 5 to 20.
　上記一般式（Ａ）で表される構造を有するポリシロキサン化合物としては、市販品を用いることができ、例えば、Ｘ－２２－１６０ＡＳ、ＫＦ－６００１、ＫＦ－６００２、ＫＦ－６００３等の化合物（いずれも、信越化学工業株式会社製）、及び、ＸＦ４２－Ｂ０９７０、Ｆｌｕｉｄ　ＯＦＯＨ　７０２－４％等の化合物（いずれも、モメンティブ社製）が挙げられる。 As the polysiloxane compound having the structure represented by the general formula (A), commercially available products can be used. For example, 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.) and compounds such as XF42-B0970, Fluid OFOH 702-4% (all manufactured by Momentive).
　アルコキシ基を有するポリシロキサン化合物としては、例えば、下記一般式（Ｂ）で表される構造を有する化合物が挙げられる。 Examples of the polysiloxane compound having an alkoxy group include compounds having a structure represented by the following general formula (B).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（Ｂ）中、Ｒ１ｂはアルキル基、アルコキシ基又はアリール基を示し、Ｒ２ｂ及びＲ３ｂはそれぞれ独立にアルコキシ基を示し、Ｒ４ｂ及びＲ５ｂはそれぞれ独立にアルキル基又はアリール基を示し、ｍは１～５０の整数を示す。ここで、アリール基としては、例えば、フェニル基及び置換フェニル基が挙げられる。置換フェニル基の置換基としては、例えば、アルキル基、ビニル基、メルカプト基、アミノ基、ニトロ基及びシアノ基が挙げられる。なお、式（Ｂ）中、２個のＲ１ｂは各々同一であっても異なっていてもよく、２個のＲ２ｂは各々同一であっても異なっていてもよく、同様に、２個のＲ３ｂは各々同一であっても異なっていてもよい。式（Ｂ）中、ｍが２以上の整数の場合、２個以上のＲ４ｂは各々同一であっても異なっていてもよく、同様に、２個以上のＲ５ｂは各々同一であっても異なっていてもよい。 In 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, and R 4b and R 5b each independently represent an alkyl group or an aryl group. , M represents an integer of 1 to 50. Here, 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. In the formula (B), two R 1b s may be the same or different, and two R 2b s may be the same or different. Similarly, R 3b may be the same or different. In the formula (B), 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.
　上記構造のポリシロキサン化合物又はその加水分解生成物を含有するゾルの縮合物である湿潤ゲル（前記ゾルから生成された湿潤ゲル）を用いることにより、低熱伝導率かつ柔軟なエアロゲルを更に得易くなる。同様の観点から、以下に示す特徴を満たしてもよい。式（Ｂ）中、Ｒ１ｂとしては、例えば炭素数が１～６のアルキル基及び炭素数が１～６のアルコキシ基が挙げられ、具体的には、メチル基、メトキシ基及びエトキシ基が挙げられる。式（Ｂ）中、Ｒ２ｂ及びＲ３ｂは、それぞれ独立に炭素数が１～６のアルコキシ基であってもよい。該アルコキシ基としては、例えばメトキシ基及びエトキシ基が挙げられる。式（Ｂ）中、Ｒ４ｂ及びＲ５ｂは、それぞれ独立に炭素数が１～６のアルキル基又はフェニル基であってもよい。該アルキル基は、メチル基であってもよい。式（Ｂ）中、ｍは２～３０とすることができ、５～２０であってもよい。 By using a wet gel (wet gel generated from the sol) that is a condensate of a sol containing the polysiloxane compound having the above structure or a hydrolysis product thereof, it becomes easier to obtain a flexible airgel having low thermal conductivity. . From the same viewpoint, the following features may be satisfied. In the formula (B), 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. In the formula (B), R 2b and R 3b may each independently be an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group include a methoxy group and an ethoxy group. In the formula (B), 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. In the formula (B), m can be 2 to 30, and may be 5 to 20.
　上記一般式（Ｂ）で表される構造を有するポリシロキサン化合物は、例えば、特開２０００－２６６０９号公報、特開２０１２－２３３１１０号公報等にて報告される製造方法を適宜参照して得ることができる。 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.
　なお、アルコキシ基は加水分解するため、アルコキシ基を有するポリシロキサン化合物はゾル中にて加水分解生成物として存在する可能性があり、アルコキシ基を有するポリシロキサン化合物と、その加水分解生成物とは混在していてもよい。また、アルコキシ基を有するポリシロキサン化合物において、分子中のアルコキシ基の全てが加水分解されていてもよいし、部分的に加水分解されていてもよい。 In addition, since the alkoxy group is hydrolyzed, 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. In the polysiloxane compound having an alkoxy group, all of the alkoxy groups in the molecule may be hydrolyzed or partially hydrolyzed.
　加水分解性の官能基又は縮合性の官能基を有するポリシロキサン化合物、及び、前記加水分解性の官能基を有するポリシロキサン化合物の加水分解生成物のそれぞれは、単独で又は２種類以上を混合して用いてもよい。 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.
　良好な反応性を更に得易くなることから、上記ゾルに含まれるポリシロキサン化合物群の含有量（加水分解性の官能基又は縮合性の官能基を有するポリシロキサン化合物の含有量、及び、前記加水分解性の官能基を有するポリシロキサン化合物の加水分解生成物の含有量の総和）は、ゾルの総量１００質量部に対し、１質量部以上とすることができ、３質量部以上であってもよく、５質量部以上であってもよく、１０質量部以上であってもよい。良好な相溶性を更に得易くなることから、ポリシロキサン化合物群の前記含有量は、ゾルの総量１００質量部に対し、５０質量部以下とすることができ、３０質量部以下であってもよく、１５質量部以下であってもよい。すなわち、ポリシロキサン化合物及び該ポリシロキサン化合物の加水分解生成物の含有量は、ゾルの総量１００質量部に対し、５～５０質量部とすることができ、１０～３０質量部であってもよく、１０～１５質量部であってもよい。 Since it becomes easier to obtain good reactivity, 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. It may be 5 parts by mass or more, or 10 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. 15 parts by mass or less. That is, the content of the polysiloxane compound and the hydrolysis product of the polysiloxane compound can be 5 to 50 parts by mass with respect to 100 parts by mass of the sol, and may be 10 to 30 parts by mass. It may be 10 to 15 parts by mass.
［第二の態様］
　加水分解性の官能基又は縮合性の官能基を有するケイ素化合物としては、ポリシロキサン化合物以外のケイ素化合物（シリコン化合物）を用いてもよい。すなわち、本実施形態に係るエアロゲルは、（分子内に）加水分解性の官能基又は縮合性の官能基を有するケイ素化合物（ポリシロキサン化合物を除く）、及び、前記加水分解性の官能基を有するケイ素化合物の加水分解生成物からなる群より選択される少なくとも一種の化合物（以下、場合により「ケイ素化合物群」という）を含有するゾルの縮合物である湿潤ゲルの乾燥物であってもよい。ケイ素化合物における分子内のケイ素数は、１又は２とすることができる。 [Second embodiment]
As 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 according to the present embodiment has (in the molecule) a hydrolyzable functional group or a silicon compound having a condensable functional group (excluding a polysiloxane compound) and the hydrolyzable functional group. It may be a wet gel dried product which is a condensate of sol containing at least one compound selected from the group consisting of hydrolysis products of silicon 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.
　本実施形態に係るエアロゲルを作製するにあたり、上記のポリシロキサン化合物群を含有するゾルは、ケイ素化合物群を更に含有することができる。 In preparing the airgel according to the present embodiment, the sol containing the polysiloxane compound group may further contain a silicon compound group.
　加水分解性の官能基を有するケイ素化合物としては、特に限定されないが、例えば、アルキルケイ素アルコキシドが挙げられる。アルキルケイ素アルコキシドにおいて、耐水性が向上する観点から、加水分解性の官能基の数は、３個以下であってもよく、２～３個であってもよい。アルキルケイ素アルコキシドとしては、例えば、モノアルキルトリアルコキシシラン、モノアルキルジアルコキシシラン、ジアルキルジアルコキシシラン、モノアルキルモノアルコキシシラン、ジアルキルモノアルコキシシラン及びトリアルキルモノアルコキシシランが挙げられる。アルキルケイ素アルコキシドとしては、例えば、メチルトリメトキシシラン、メチルジメトキシシラン、ジメチルジメトキシシラン及びエチルトリメトキシシランが挙げられる。 The silicon compound having a hydrolyzable functional group is not particularly limited, and examples thereof include alkyl silicon alkoxides. In the alkyl silicon alkoxide, from the viewpoint of improving water resistance, the number of hydrolyzable functional groups may be 3 or less, or 2 to 3. Examples of the alkyl silicon alkoxide include monoalkyltrialkoxysilane, monoalkyldialkoxysilane, dialkyldialkoxysilane, monoalkylmonoalkoxysilane, dialkylmonoalkoxysilane and trialkylmonoalkoxysilane. Examples of the alkyl silicon alkoxide include methyltrimethoxysilane, methyldimethoxysilane, dimethyldimethoxysilane, and ethyltrimethoxysilane.
　縮合性の官能基を有するケイ素化合物としては、特に限定されないが、例えば、シランテトラオール、メチルシラントリオール、ジメチルシランジオール、フェニルシラントリオール、フェニルメチルシランジオール、ジフェニルシランジオール、ｎ－プロピルシラントリオール、ヘキシルシラントリオール、オクチルシラントリオール、デシルシラントリオール及びトリフルオロプロピルシラントリオールが挙げられる。 The silicon compound having a condensable functional group is not particularly limited. For example, silane tetraol, methyl silane triol, dimethyl silane diol, phenyl silane triol, phenyl methyl silane diol, diphenyl silane diol, n-propyl silane triol, Examples include hexyl silane triol, octyl silane triol, decyl silane triol, and trifluoropropyl silane triol.
　加水分解性の官能基の数が３個以下であり、反応性基を有するケイ素化合物として、ビニルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－アクリロキシプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン等も用いることができる。 The number of hydrolyzable functional groups is 3 or less, and silicon compounds having reactive groups include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like can also be used.
　縮合性の官能基を有し、前述の反応性基を有するケイ素化合物として、ビニルシラントリオール、３－グリシドキシプロピルシラントリオール、３－グリシドキシプロピルメチルシランジオール、３－メタクリロキシプロピルシラントリオール、３－メタクリロキシプロピルメチルシランジオール、３－アクリロキシプロピルシラントリオール、３－メルカプトプロピルシラントリオール、３－メルカプトプロピルメチルシランジオール、Ｎ－フェニル－３－アミノプロピルシラントリオール、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルシランジオール等も用いることができる。 As a silicon compound having a condensable functional group and having the above-mentioned reactive group, vinylsilane triol, 3-glycidoxypropylsilanetriol, 3-glycidoxypropylmethylsilanediol, 3-methacryloxypropylsilanetriol, 3-methacryloxypropylmethylsilanediol, 3-acryloxypropylsilanetriol, 3-mercaptopropylsilanetriol, 3-mercaptopropylmethylsilanediol, N-phenyl-3-aminopropylsilanetriol, N-2- (aminoethyl ) -3-Aminopropylmethylsilanediol and the like can also be used.
　分子末端の加水分解性の官能基が３個以下のケイ素化合物として、ビストリメトキシシリルメタン、ビストリメトキシシリルエタン、ビストリメトキシシリルヘキサン等も用いることができる。 Bistrimethoxysilylmethane, bistrimethoxysilylethane, bistrimethoxysilylhexane, etc. can be used as the silicon compound having 3 or less hydrolyzable functional groups at the molecular terminals.
　加水分解性の官能基又は縮合性の官能基を有するケイ素化合物（ポリシロキサン化合物を除く）、及び、前記加水分解性の官能基を有するケイ素化合物の加水分解生成物のそれぞれは、単独で又は２種類以上を混合して用いてもよい。 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.
　良好な反応性を更に得易くなることから、上記ゾルに含まれるケイ素化合物群の含有量（加水分解性の官能基又は縮合性の官能基を有するケイ素化合物（ポリシロキサン化合物を除く）の含有量、及び、前記加水分解性の官能基を有するケイ素化合物の加水分解生成物の含有量の総和）は、ゾルの総量１００質量部に対し、５質量部以上とすることができ、１０質量部以上であってもよく、１５質量部以上であってもよい。良好な相溶性を更に得易くなることから、ケイ素化合物群の前記含有量は、ゾルの総量１００質量部に対し、５０質量部以下とすることができ、３０質量部以下であってもよく、２５質量部以下であってもよい。すなわち、ケイ素化合物群の前記含有量は、ゾルの総量１００質量部に対し、５～５０質量部とすることができ、１０～３０質量部であってもよく、１５～２５質量部であってもよい。 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. , And 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 15 parts by mass 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. That is, 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, and is 15 to 25 parts by mass. Also good.
　ポリシロキサン化合物群の含有量及びケイ素化合物群の含有量の総和は、良好な反応性を更に得易くなることから、ゾルの総量１００質量部に対し、５質量部以上とすることができ、１０質量部以上であってもよく、１５質量部以上であってもよく、２０質量部以上であってもよい。良好な相溶性を更に得易くなることから、前記含有量の総和は、ゾルの総量１００質量部に対し、５０質量部以下とすることができ、３０質量部以下であってもよく、２５質量部以下であってもよい。すなわち、前記含有量の総和は、ゾルの総量１００質量部に対し、５～５０質量部とすることができ、１０～３０質量部であってもよく、１５～３０質量部であってもよく、２０～２５質量部であってもよい。 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 sol. It may be greater than or equal to part by mass, greater than or equal to 15 parts by mass, or greater than or equal to 20 parts by mass. 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 25 parts by mass.
　前記ポリシロキサン化合物群の含有量と、前記ケイ素化合物群の含有量との比（ポリシロキサン化合物群：ケイ素化合物群）は、１：０．５～１：４とすることができ、１：１～１：２であってもよく、１：２～１：４であってもよく、１：３～１：４であってもよい。これらの化合物の含有量の比を１：０．５以上とすることにより、良好な相溶性を更に得易くなる。上記含有量の比を１：４以下とすることにより、ゲルの収縮を更に抑制し易くなる。 The ratio of the content of the polysiloxane compound group to the content of the silicon compound group (polysiloxane compound group: 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.
（第三の態様）
　本実施形態に係るエアロゲルは、下記一般式（１）で表される構造を有することができる。本実施形態に係るエアロゲルは、式（１）で表される構造を含む構造として、下記一般式（１ａ）で表される構造を有することができる。上記一般式（Ａ）で表される構造を有するポリシロキサン化合物を使用することにより、式（１）及び式（１ａ）で表される構造をエアロゲルの骨格中に導入することができる。 (Third embodiment)
The airgel according to the present embodiment can have a structure represented by the following general formula (1). The airgel which concerns on this embodiment can have a structure represented by the following general formula (1a) as a structure containing the structure represented by Formula (1). By using the polysiloxane compound having the structure represented by the general formula (A), the structures represented by the formulas (1) and (1a) can be introduced into the skeleton of the airgel.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（１）及び式（１ａ）中、Ｒ１及びＲ２はそれぞれ独立にアルキル基又はアリール基を示し、Ｒ３及びＲ４はそれぞれ独立にアルキレン基を示す。ここで、アリール基としては、例えば、フェニル基及び置換フェニル基が挙げられる。置換フェニル基の置換基としては、例えば、アルキル基、ビニル基、メルカプト基、アミノ基、ニトロ基及びシアノ基が挙げられる。ｐは１～５０の整数を示す。式（１ａ）中、２個以上のＲ１は各々同一であっても異なっていてもよく、同様に、２個以上のＲ２は各々同一であっても異なっていてもよい。式（１ａ）中、２個のＲ３は各々同一であっても異なっていてもよく、同様に、２個のＲ４は各々同一であっても異なっていてもよい。 In formula (1) and formula (1a), R 1 and R 2 each independently represent an alkyl group or an aryl group, and R 3 and R 4 each independently represent an alkylene group. Here, 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. p represents an integer of 1 to 50. In formula (1a), 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. In formula (1a), two R 3 s may be the same or different, and similarly, two R 4 s may be the same or different.
　上記式（１）又は式（１ａ）で表される構造をエアロゲルの骨格中に導入することにより、低熱伝導率かつ柔軟なエアロゲルを容易に得ることができる。同様の観点から、以下に示す特徴を満たしてもよい。式（１）及び式（１ａ）中、Ｒ１及びＲ２は、それぞれ独立に炭素数が１～６のアルキル基又はフェニル基であってもよい。該アルキル基は、メチル基であってもよい。式（１）及び式（１ａ）中、Ｒ３及びＲ４は、それぞれ独立に炭素数が１～６のアルキレン基であってもよい。該アルキレン基は、エチレン基又はプロピレン基であってもよい。式（１ａ）中、ｐは２～３０とすることができ、５～２０であってもよい。 By introducing the structure represented by the above formula (1) or formula (1a) into the skeleton of the airgel, a flexible airgel having low thermal conductivity can be easily obtained. From the same viewpoint, the following features may be satisfied. In formula (1) and formula (1a), 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. In formula (1) and formula (1a), 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. In the formula (1a), p can be 2 to 30, and can be 5 to 20.
（第四の態様）
　本実施形態に係るエアロゲルは、支柱部及び橋かけ部を備えるラダー型構造を有するエアロゲルであり、かつ、橋かけ部が下記一般式（２）で表される構造を有するエアロゲルであってもよい。エアロゲルの骨格中にこのようなラダー型構造を導入することにより、耐熱性及び機械的強度を向上させることができる。上記一般式（Ｂ）で表される構造を有するポリシロキサン化合物を使用することにより、一般式（２）で表される構造を有する橋かけ部を含むラダー型構造をエアロゲルの骨格中に導入することができる。なお、本実施形態において「ラダー型構造」とは、２本の支柱部（ｓｔｒｕｔｓ）と支柱部同士を連結する橋かけ部（ｂｒｉｄｇｅｓ）とを有するもの（いわゆる「梯子」の形態を有するもの）である。本態様において、エアロゲル骨格がラダー型構造からなっていてもよいが、エアロゲルが部分的にラダー型構造を有していてもよい。 (Fourth aspect)
The airgel according to 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). . By introducing such a ladder structure into the airgel skeleton, heat resistance and mechanical strength can be improved. By using the polysiloxane compound having the structure represented by the general formula (B), a ladder structure including a bridge portion having the structure represented by the general formula (2) is introduced into the skeleton of the airgel. be able to. In this embodiment, the “ladder structure” has two struts and bridges connecting the struts (having a so-called “ladder” form). It is. In this embodiment, the airgel skeleton may have a ladder structure, but the airgel may partially have a ladder structure.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（２）中、Ｒ５及びＲ６はそれぞれ独立にアルキル基又はアリール基を示し、ｂは１～５０の整数を示す。ここで、アリール基としては、例えば、フェニル基及び置換フェニル基が挙げられる。置換フェニル基の置換基としては、例えば、アルキル基、ビニル基、メルカプト基、アミノ基、ニトロ基及びシアノ基が挙げられる。なお、式（２）中、ｂが２以上の整数の場合、２個以上のＲ５は各々同一であっても異なっていてもよく、同様に、２個以上のＲ６は各々同一であっても異なっていてもよい。 In 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. Here, 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. In formula (2), when 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.
　上記の構造をエアロゲルの骨格中に導入することにより、例えば、従来のラダー型シルセスキオキサンに由来する構造を有する（すなわち、下記一般式（Ｘ）で表される構造を有する）エアロゲルよりも優れた柔軟性を有するエアロゲルとなる。なお、下記一般式（Ｘ）にて示すように、従来のラダー型シルセスキオキサンに由来する構造を有するエアロゲルでは、橋かけ部の構造が－Ｏ－であるが、本態様のエアロゲルでは、橋かけ部の構造が上記一般式（２）で表される構造（ポリシロキサン構造）である。
Figure JPOXMLDOC01-appb-C000007
 By introducing the above structure into the skeleton of the airgel, for example, 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 | flexibility. As shown by the following general formula (X), in the airgel having a structure derived from a conventional ladder-type silsesquioxane, the structure of the bridge portion is —O—, but in the airgel of this embodiment, The structure of the bridge portion is a structure (polysiloxane structure) represented by the general formula (2).
Figure JPOXMLDOC01-appb-C000007
　式（Ｘ）中、Ｒはヒドロキシ基、アルキル基又はアリール基を示す。 In the formula (X), R represents a hydroxy group, an alkyl group or an aryl group.
　支柱部となる構造及びその鎖長、並びに橋かけ部となる構造の間隔は特に限定されないが、耐熱性と機械的強度とをより向上させる観点から、ラダー型構造としては、下記一般式（３）で表されるラダー型構造を有していてもよい。
Figure JPOXMLDOC01-appb-C000008
 There are no particular restrictions on the structure that serves as the strut part and its chain length, and the spacing between the structures that serve as the bridging parts. However, from the viewpoint of further improving the heat resistance and mechanical strength, the ladder structure may be represented by the following general formula (3 It may have a ladder type structure represented by.
Figure JPOXMLDOC01-appb-C000008
　式（３）中、Ｒ５、Ｒ６、Ｒ７及びＲ８はそれぞれ独立にアルキル基又はアリール基を示し、ａ及びｃはそれぞれ独立に１～３０００の整数を示し、ｂは１～５０の整数を示す。ここで、アリール基としては、例えば、フェニル基及び置換フェニル基が挙げられる。置換フェニル基の置換基としては、例えば、アルキル基、ビニル基、メルカプト基、アミノ基、ニトロ基及びシアノ基が挙げられる。式（３）中、ｂが２以上の整数の場合、２個以上のＲ５は各々同一であっても異なっていてもよく、同様に、２個以上のＲ６は各々同一であっても異なっていてもよい。式（３）中、ａが２以上の整数の場合、２個以上のＲ７は各々同一であっても異なっていてもよく、同様に、ｃが２以上の整数の場合、２個以上のＲ８は各々同一であっても異なっていてもよい。 In the 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 represents an integer of 1 to 3000, and b is 1 to 50 Indicates an integer. Here, 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. In Formula (3), when 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 may be the same. May be different. In formula (3), when a is an integer of 2 or more, two or more R 7 s may be the same or different. Similarly, when c is an integer of 2 or more, 2 or more R 8 may be the same or different from each other.
　より優れた柔軟性を得る観点から、式（２）及び式（３）中、Ｒ５、Ｒ６、Ｒ７及びＲ８（ただし、Ｒ７及びＲ８は式（３）中のみ）は、それぞれ独立に炭素数が１～６のアルキル基又はフェニル基であってもよい。該アルキル基は、メチル基であってもよい。式（３）中、ａ及びｃは、それぞれ独立に６～２０００とすることができ、１０～１０００であってもよい。式（２）及び式（３）中、ｂは、２～３０とすることができ、５～２０であってもよい。 From the viewpoint of obtaining better flexibility, in formula (2) and formula (3), R 5 , R 6 , R 7 and R 8 (however, R 7 and R 8 are only in formula (3)) 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. In the formula (3), a and c can be independently 6 to 2000, and may be 10 to 1000. In the formulas (2) and (3), b can be 2 to 30, and can be 5 to 20.
［第五の態様］
　本実施形態に係るエアロゲルは、シリカ粒子を含有していてもよい。すなわち、エアロゲルを与えるゾルは、シリカ粒子を更に含有していてもよい。本実施形態に係るエアロゲルは、シリカ粒子を含有するゾルの縮合物である湿潤ゲルの乾燥物（前記ゾルから生成された湿潤ゲルを乾燥して得られるもの）であってもよい。エアロゲル層は、シリカ粒子を含有するゾルの縮合物である湿潤ゲルの乾燥物から構成される層であってもよい。すなわち、エアロゲル層は、シリカ粒子を含有するゾルから生成された湿潤ゲルを乾燥してなる層で構成されていてもよい。該エアロゲル層は、シリカ粒子が複合化された層である。なお、これまで述べてきたエアロゲルも、このように、シリカ粒子を含有するゾルの縮合物である湿潤ゲルの乾燥物（前記ゾルから生成された湿潤ゲルを乾燥することで得られるもの）であってもよい。これにより、更に優れた断熱性及び柔軟性を達成することができる。 [Fifth aspect]
The airgel according to the present embodiment may contain silica particles. That is, the sol that provides the airgel may further contain silica particles. The airgel according to the present embodiment may be a wet gel dried product (condensate of sol containing silica particles) (obtained by drying a wet gel produced 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 layer is a layer in which silica particles are combined. In addition, 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. Thereby, the further outstanding heat insulation and softness | flexibility can be achieved.
　本実施形態に係るシリカ粒子を含有するエアロゲルは、下記一般式（４）で表される構造を有することができる。
Figure JPOXMLDOC01-appb-C000009
 The airgel containing silica particles according to this embodiment can have a structure represented by the following general formula (4).
Figure JPOXMLDOC01-appb-C000009
　式（４）中、Ｒ９はアルキル基を示す。アルキル基としては、例えば、炭素数が１～６のアルキル基が挙げられ、具体的には、メチル基が挙げられる。 In formula (4), R 9 represents an alkyl group. Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms, and specific examples include a methyl group.
　本実施形態に係るシリカ粒子を含有するエアロゲルは、下記一般式（５）で表される構造を有することができる。
Figure JPOXMLDOC01-appb-C000010
 The airgel containing silica particles according to the present embodiment can have a structure represented by the following general formula (5).
Figure JPOXMLDOC01-appb-C000010
　式（５）中、Ｒ１０及びＲ１１はそれぞれ独立にアルキル基を示す。アルキル基としては、例えば、炭素数が１～６のアルキル基が挙げられ、具体的には、メチル基が挙げられる。 In formula (5), R 10 and R 11 each independently represent an alkyl group. Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms, and specific examples include a methyl group.
　本実施形態に係るシリカ粒子を含有するエアロゲルは、下記一般式（６）で表される構造を有することができる。
Figure JPOXMLDOC01-appb-C000011
 The airgel containing silica particles according to the present embodiment can have a structure represented by the following general formula (6).
Figure JPOXMLDOC01-appb-C000011
　式（６）中、Ｒ１２はアルキレン基を示す。アルキレン基としては、例えば、炭素数が１～１０のアルキレン基が挙げられ、具体的には、エチレン基及びヘキシレン基が挙げられる。 In the formula (6), R 12 represents an alkylene group. Examples of the alkylene group include an alkylene group having 1 to 10 carbon atoms, and specific examples include an ethylene group and a hexylene group.
　シリカ粒子としては特に制限なく用いることができ、例えば、非晶質シリカ粒子が挙げられる。非晶質シリカ粒子としては、例えば、溶融シリカ粒子、ヒュームドシリカ粒子及びコロイダルシリカ粒子が挙げられる。これらのうち、コロイダルシリカ粒子は単分散性が高く、ゾル中での凝集を抑制し易い。 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. Among these, colloidal silica particles have high monodispersibility and are easy to suppress aggregation in the sol.
　シリカ粒子の形状としては、特に制限されず、球状、まゆ型、会合型等が挙げられる。これらのうち、シリカ粒子として球状の粒子を用いることにより、ゾル中での凝集を抑制し易くなる。シリカ粒子の平均一次粒子径は、適度な強度をエアロゲルに付与し易くなり、乾燥時の耐収縮性に優れるエアロゲルが得易くなることから、１ｎｍ以上とすることができ、５ｎｍ以上であってもよく、１０ｎｍ以上であってもよい。一方、シリカ粒子の固体熱伝導を抑制し易くなり、断熱性に優れるエアロゲルが得易くなることから、シリカ粒子の平均一次粒子径は、５００ｎｍ以下とすることができ、３００ｎｍ以下であってもよく、２５０ｎｍ以下であってもよい。すなわち、シリカ粒子の平均一次粒子径は、１～５００ｎｍとすることができ、５～３００ｎｍであってもよく、１０～２５０ｎｍであってもよい。 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. On the other hand, the average primary particle diameter of the silica particles can be 500 nm or less, and may be 300 nm or less because it is easy to suppress the solid heat conduction of the silica particles and it is easy to obtain an airgel excellent in heat insulation. 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.
　本実施形態において、シリカ粒子の平均一次粒子径は、走査型電子顕微鏡（以下「ＳＥＭ」と略記する。）を用いてエアロゲル層の断面を直接観察することにより得ることができる。例えば、三次元網目骨格からは、その断面の直径に基づきシリカ粒子個々の粒子径を得ることができる。ここでいう直径とは、三次元網目骨格を形成する骨格の断面を円とみなした場合の直径を意味する。また、断面を円とみなした場合の直径とは、断面の面積を同じ面積の円に置き換えたときの当該円の直径のことである。なお、平均粒子径の算出に当たっては、１００個の粒子について円の直径を求め、その平均を取るものとする。 In this embodiment, the average primary particle diameter of the silica particles can be obtained by directly observing the cross section of the airgel layer using a scanning electron microscope (hereinafter abbreviated as “SEM”). For example, from the three-dimensional network skeleton, the particle diameter of each silica particle can be obtained based on the diameter of the cross section. The diameter here means the diameter when the cross section of the skeleton forming the three-dimensional network skeleton is regarded as a circle. The diameter when the cross section is regarded as a circle is the diameter of the circle when the area of the cross section is replaced with a circle having the same area. In calculating the average particle diameter, the diameter of a circle is obtained for 100 particles, and the average is taken.
　また、エアロゲル層を形成する前に原料のシリカ粒子から平均粒子径を測定することが可能である。例えば、二軸平均一次粒子径は、任意の粒子２０個をＳＥＭにより観察した結果から、次のようにして算出される。すなわち、通常水に分散している固形分濃度５～４０質量％のコロイダルシリカ粒子を例にすると、コロイダルシリカ粒子の分散液にパターン配線付きウエハを２ｃｍ角に切ったチップを約３０秒間浸した後、当該チップを純水にて約３０秒間すすぎ、窒素ブロー乾燥する。その後、チップをＳＥＭ観察用の試料台に載せ、加速電圧１０ｋＶを掛け、１０万倍の倍率にてシリカ粒子を観察し、画像を撮影する。得られた画像から２０個のシリカ粒子を任意に選択し、それらの粒子の粒子径の平均を平均粒子径とする。この際、選択したシリカ粒子が図３に示すような形状であった場合、シリカ粒子Ｐに外接し、その長辺が最も長くなるように配置した長方形（外接長方形Ｌ）を導く。そして、その外接長方形Ｌの長辺をＸ、短辺をＹとして、（Ｘ＋Ｙ）／２として二軸平均一次粒子径を算出し、その粒子の粒子径とする。 Also, it is possible to measure the average particle diameter from the raw silica particles before forming the airgel layer. For example, the biaxial average primary particle diameter is calculated as follows from the result of observing 20 arbitrary particles by SEM. That is, for example, colloidal silica particles having a solid content concentration of 5 to 40% by mass dispersed in water are taken as an example. A chip with a 2 cm square wafer with a pattern wiring is immersed in a dispersion of colloidal silica particles for about 30 seconds. Thereafter, the chip is rinsed with pure water for about 30 seconds and blown with nitrogen. Thereafter, the chip is placed on a sample stage for SEM observation, an acceleration voltage of 10 kV is applied, the silica particles are observed at a magnification of 100,000, and an image is taken. 20 silica particles are arbitrarily selected from the obtained image, and the average of the particle diameters of these particles is defined as the average particle diameter. At this time, when the selected silica particles have a shape as shown in FIG. 3, a rectangle (circumscribed rectangle L) circumscribing the silica particles P and arranged so that the long side is the longest is led. And the long side of the circumscribed rectangle L is X, the short side is Y, and the biaxial average primary particle diameter is calculated as (X + Y) / 2, and is defined as the particle diameter of the particle.
　耐収縮性に優れるエアロゲルを得易くなることから、シリカ粒子の１ｇ当りのシラノール基数は、１０×１０１８個／ｇ以上とすることができ、５０×１０１８個／ｇ以上であってもよく、１００×１０１８個／ｇ以上であってもよい。一方、均質なエアロゲルが得易くなることから、シリカ粒子の１ｇ当りのシラノール基数は、１０００×１０１８個／ｇ以下とすることができ、８００×１０１８個／ｇ以下であってもよく、７００×１０１８個／ｇ以下であってもよい。すなわち、シリカ粒子の１ｇ当りのシラノール基数は、１０×１０１８～１０００×１０１８個／ｇとすることができ、５０×１０１８～８００×１０１８個／ｇであってもよく、１００×１０１８～７００×１０１８個／ｇであってもよい。 Since it becomes easy to obtain an airgel excellent in shrinkage resistance, 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. 100 × 10 18 pieces / g or more. On the other hand, 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. It may be 700 × 10 18 pieces / g or less. That is, 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, It may be 10 18 to 700 × 10 18 pieces / g.
　適度な強度をエアロゲルに付与し易くなり、乾燥時の耐収縮性に優れるエアロゲルが得易くなることから、上記ゾルに含まれるシリカ粒子の含有量は、ゾルの総量１００質量部に対し、１質量部以上とすることができ、４質量部以上であってもよい。一方、シリカ粒子の固体熱伝導を抑制し易くなり、断熱性に優れるエアロゲルが得易くなることから、上記ゾルに含まれるシリカ粒子の含有量は、２０質量部以下とすることができ、１５質量部以下であってもよく、１２質量部以下であってもよく、１０質量部以下であってもよく、８質量部以下であってもよい。すなわち、シリカ粒子の含有量は、ゾルの総量１００質量部に対し、１～２０質量部とすることができ、４～１５質量部であってもよく、４～１２質量部であってもよく、４～１０質量部であってもよく、４～８質量部であってもよい。 Since it becomes easy to impart an appropriate strength to the airgel and it becomes easy to obtain an airgel excellent in shrinkage resistance at the time of drying, 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. On the other hand, since it becomes easy to suppress the solid heat conduction of silica particles and it becomes easy to obtain an airgel excellent in heat insulating properties, the content of silica particles contained in the sol can be 20 parts by mass or less, and 15 masses. Part or less, 12 parts by weight or less, 10 parts by weight or less, or 8 parts by weight or less. That is, 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.
（その他の態様）
　本実施形態に係るエアロゲルは、ポリシロキサン由来の構造を有していてもよい。ポリシロキサン由来の構造としては、例えば、上記一般式（１）、（２）、（３）、（４）、（５）又は（６）で表される構造が挙げられる。本実施形態に係るエアロゲルは、シリカ粒子を含有せずに、上記一般式（４）、（５）及び（６）で表される構造のうち、少なくとも一種を有するものであってもよい。すなわち、本実施形態に係るエアロゲル層は、ポリシロキサン由来の構造を有するエアロゲルを含有する層で構成されていてもよい。ポリシロキサン由来の構造としては、例えば、上記一般式（１）、（２）、（３）、（４）、（５）又は（６）で表される構造が挙げられる。よって、本実施形態に係るエアロゲルは、シリカ粒子を含有せずに、上記一般式（４）、（５）及び（６）で表される構造のうち、少なくとも一種を有するものであってもよい。 (Other aspects)
The airgel according to the present 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 which concerns on this embodiment may have at least 1 type among the structures represented by the said General formula (4), (5) and (6), without containing a silica particle. That is, the airgel layer according to the present embodiment may be composed of a layer containing an airgel having a polysiloxane-derived structure. Examples of the structure derived from polysiloxane include structures represented by the above general formula (1), (2), (3), (4), (5), or (6). Therefore, the airgel according to the present embodiment may include at least one of the structures represented by the general formulas (4), (5), and (6) without containing silica particles. .
　エアロゲル層の厚みは、良好な断熱性を得易くなることから、１μｍ以上とすることができ、１０μｍ以上であってもよく、３０μｍ以上であってもよい。一方、薄型化の観点から、エアロゲル層の厚みは２００μｍ以下とすることができ、１００μｍ以下であってもよく、８０μｍ以下であってもよい。すなわち、エアロゲル層の厚みは、１～２００μｍとすることができ、１０～１００μｍであってもよく、３０～８０μｍであってもよい。 The thickness of the airgel layer can be 1 μm or more because it is easy to obtain good heat insulation, and can be 10 μm or more, or 30 μm or more. On the other hand, from the viewpoint of thinning, the thickness of the airgel layer can be 200 μm or less, may be 100 μm or less, and may be 80 μm or less. That is, the thickness of the airgel layer may be 1 to 200 μm, may be 10 to 100 μm, and may be 30 to 80 μm.
　より優れた強度及び柔軟性を得る観点から、エアロゲル層の２５℃における密度は、０．０５ｇ／ｃｍ３以上とすることができ、０．１ｇ／ｃｍ３以上であってもよく、０．２ｇ／ｃｍ３以上であってもよい。一方、より優れた断熱性を得る観点から、エアロゲル層の２５℃における密度は、０．３ｇ／ｃｍ３以下とすることができ、０．２５ｇ／ｃｍ３以下であってもよく、０．２ｇ／ｃｍ３以下であってもよい。すなわち、エアロゲル層の２５℃における密度は０．０５～０．３ｇ／ｃｍ３とすることができ、０．１～０．２５ｇ／ｃｍ３であってもよく、０．１～０．２ｇ／ｃｍ３であってもよい。 From the viewpoint of obtaining more excellent strength and flexibility, density at 25 ° C. of the airgel layer may be a 0.05 g / cm 3 or more, may also be 0.1 g / cm 3 or more, 0.2 g / Cm 3 or more. On the other hand, from the viewpoint of obtaining better heat insulation, the density of the airgel layer at 25 ° C. can be set to 0.3 g / cm 3 or less, and may be 0.25 g / cm 3 or less. / Cm 3 or less. That is, the density of the airgel layer at 25 ° C. can be 0.05 to 0.3 g / cm 3 , or 0.1 to 0.25 g / cm 3 , or 0.1 to 0.2 g / cm 3. cm 3 may also be used.
　より優れた断熱性を得る観点から、エアロゲル層の２５℃における気孔率は、８５％以上とすることができ、８７％以上であってもよく、より優れた強度及び柔軟性を得る観点から、９５％以下とすることができ、９３％以下であってもよい。すなわち、エアロゲル層の２５℃における気孔率は、８５～９５％とすることができ、８７～９３％であってもよい。 From the viewpoint of obtaining better heat insulation, the porosity of the airgel layer at 25 ° C. can be 85% or more, may be 87% or more, and from the viewpoint of obtaining better strength and flexibility. It can be 95% or less, and may be 93% or less. That is, the porosity of the airgel layer at 25 ° C. can be 85 to 95%, and may be 87 to 93%.
　エアロゲル層の密度及び気孔率は、ＤＩＮ６６１３３に準じて水銀圧入法により測定することができる。測定装置としては、例えば、オートポアＩＶ９５２０（株式会社島津製作所製、製品名）を用いることができる。 The density and porosity of the airgel layer can be measured by a mercury intrusion method according to DIN 66133. As a measuring device, for example, Autopore IV9520 (manufactured by Shimadzu Corporation, product name) can be used.
＜樹脂層＞
　本実施形態に係る樹脂層は、非エアロゲル層であり、分子構造中に窒素原子を有する樹脂を含有する層である。樹脂層は、構成原子として窒素を有する樹脂を含有することで、エアロゲル層との接着性を向上することができる。窒素原子を有する樹脂としては、例えば、熱可塑性樹脂、熱硬化性樹脂、及び、紫外線等の活性エネルギー線硬化性樹脂を用いることできる。樹脂層は、単層であっても複層であってもよい。 <Resin layer>
The resin layer according to the present embodiment is a non-aerogel layer, and is a layer containing a resin having a nitrogen atom in the molecular structure. A resin layer can improve adhesiveness with an airgel layer by containing resin which has nitrogen as a constituent atom. As the resin having a nitrogen atom, for example, a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin such as an ultraviolet ray can be used. The resin layer may be a single layer or multiple layers.
　熱可塑性樹脂としては、例えば、ポリアミド樹脂、ポリウレタン樹脂、Ｎ－ビニル樹脂及びポリイミド樹脂が挙げられる。 Examples of the thermoplastic resin include polyamide resin, polyurethane resin, N-vinyl resin, and polyimide resin.
　熱硬化性樹脂としては、カルボキシル基、水酸基、エポキシ基、アミノ基、不飽和炭化水素基等の官能基を有する熱硬化性の化合物と、硬化剤とを反応させた樹脂を用いることができる。硬化剤として、例えば、エポキシ基、水酸基、アミノ基、アミド基、カルボキシル基、チオール基、イソシアネート基等の官能基を有する化合物、酸無水物、金属塩化物、金属酸化物、過酸化物等を用いることができる。熱硬化性樹脂の硬化反応速度を増加する目的で、触媒を添加してもよい。熱硬化性樹脂として、例えば、ユリア樹脂、メラミン樹脂、エポキシ樹脂、ポリウレタン樹脂、チオウレタン樹脂、フラン樹脂、ポリイミド樹脂、スルホアミド樹脂、アニリン樹脂、シアネート樹脂及びイソシアネート樹脂が挙げられる。 As the thermosetting resin, a resin obtained by reacting a thermosetting compound having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, or an unsaturated hydrocarbon group with a curing agent can be used. Examples of the curing agent include compounds having functional groups such as epoxy groups, hydroxyl groups, amino groups, amide groups, carboxyl groups, thiol groups, and isocyanate groups, acid anhydrides, metal chlorides, metal oxides, and peroxides. Can be used. A catalyst may be added for the purpose of increasing the curing reaction rate of the thermosetting resin. Examples of the thermosetting resin include urea resin, melamine resin, epoxy resin, polyurethane resin, thiourethane resin, furan resin, polyimide resin, sulfoamide resin, aniline resin, cyanate resin, and isocyanate resin.
　活性エネルギー線硬化性樹脂としては、例えば、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂、ウレタン樹脂等をベースポリマーとし、ラジカル重合性又はカチオン重合性官能基を付与させた樹脂が挙げられる。ラジカル重合性官能基としては、例えば、アクリロイル基、メタクリロイル基、ビニル基、アリル基等が挙げられる。また、カチオン重合性官能基としては、例えば、エポキシ基、グリシジルエーテル基、グリシジルアミノ基等が挙げられる。具体的な活性エネルギー線硬化性樹脂としては、例えば、アクリルウレタン樹脂等が挙げられる。 Examples of the active energy ray curable resin include resins having an acrylic resin, an epoxy resin, a polyester resin, a urethane resin, or the like as a base polymer and a radically polymerizable or cationically polymerizable functional group added thereto. Examples of the radical polymerizable functional group include acryloyl group, methacryloyl group, vinyl group and allyl group. Moreover, as a cation polymerizable functional group, an epoxy group, a glycidyl ether group, a glycidylamino group etc. are mentioned, for example. Specific examples of the active energy ray curable resin include an acrylic urethane resin.
　上述した樹脂は、窒素原子を含む官能基を有していてもよい。このような官能基としては、例えば、アミノ基、アミド基、イミド基、ウレタン基、イソシアネート基、カルボジイミド基、アロファネート基、ビウレット基、オキサゾリドン基、スルホアミド基、チオウレタン基及びイソチオシアネート基が挙げられる。 The resin described above may have a functional group containing a nitrogen atom. Examples of such functional groups include amino groups, amide groups, imide groups, urethane groups, isocyanate groups, carbodiimide groups, allophanate groups, biuret groups, oxazolidone groups, sulfoamide groups, thiourethane groups, and isothiocyanate groups. .
　樹脂層とエアロゲル層との接着性を向上する観点から、窒素原子を有する樹脂として、ウレタン結合、アミド結合、ウレア結合、イミド結合、スルホンアミド結合、チオウレタン結合、チオアミド結合、チオウレア結合及びチオイミド結合からなる群より選択される少なくとも１種の結合を有する樹脂を用いることができる。窒素原子を有する樹脂が、ウレタン結合を有する樹脂を含有すると、樹脂層とエアロゲル層との接着性により優れるものとなる。 From the viewpoint of improving the adhesion between the resin layer and the airgel layer, the resin having a nitrogen atom includes a urethane bond, an amide bond, a urea bond, an imide bond, a sulfonamide bond, a thiourethane bond, a thioamide bond, a thiourea bond, and a thioimide bond. A resin having at least one bond selected from the group consisting of can be used. When the resin having a nitrogen atom contains a resin having a urethane bond, the adhesiveness between the resin layer and the airgel layer is improved.
　ウレタン結合を有する樹脂としては、例えば、水酸基を有する化合物とイソシアネート基を有する化合物とから合成される樹脂を用いることができる。 As the resin having a urethane bond, for example, a resin synthesized from a compound having a hydroxyl group and a compound having an isocyanate group can be used.
　水酸基を有する化合物としては、例えば、水酸基を１つ有するモノオール化合物及び水酸基を２つ以上有するポリオール化合物が挙げられる。樹脂層の強度を高くする観点から、ポリオール化合物を用いることができる。水酸基を有する化合物は、１種を単独で用いても、２種以上を併用してもよい。 Examples of the compound having a hydroxyl group include a monool compound having one hydroxyl group and a polyol compound having two or more hydroxyl groups. From the viewpoint of increasing the strength of the resin layer, a polyol compound can be used. The compound having a hydroxyl group may be used alone or in combination of two or more.
　ポリオール化合物としては、例えば、エチレングリコール、プロピレングリコール、アクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール及びフッ素化ポリオールが挙げられる。樹脂層の柔軟性を向上する観点から、ポリオール化合物は、アクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール又はフッ素化ポリオールであってもよく、アクリルポリオールであってもよい。 Examples of the polyol compound include ethylene glycol, propylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, and fluorinated polyol. From the viewpoint of improving the flexibility of the resin layer, the polyol compound may be an acrylic polyol, a polyester polyol, a polyether polyol, a polycarbonate polyol, a fluorinated polyol, or an acrylic polyol.
　アクリルポリオールとしては、特に限定されず、変性されたものであってもよい。アクリルポリオールとして、例えば、三菱レイヨン株式会社の製品名「ダイヤナールＬＲ－２５８６」（水酸基価６０ｍｇＫＯＨ／ｇ、酸価３ｍｇＫＯＨ／ｇ、重量平均分子量３００００、ガラス転移温度４０℃）、株式会社日本触媒の製品名「アクリセット２０５０－５５」、日立化成株式会社の製品名「ヒタロイド３３７１」等を商業的に入手することができる。 The acrylic polyol is not particularly limited and may be modified. As an acrylic polyol, for example, the product name “Dianal LR-2586” (hydroxyl value 60 mg KOH / g, acid value 3 mg KOH / g, weight average molecular weight 30000, glass transition temperature 40 ° C.) manufactured by Mitsubishi Rayon Co., Ltd. The product name “Acryset 2050-55”, the product name “Hitaroid 3371” of Hitachi Chemical Co., Ltd., etc. can be obtained commercially.
　イソシアネート基を有する化合物としては、例えば、イソシアネート基を１つ有するモノイソシアネート化合物及びイソシアネート基を２つ以上有するポリイソシアネート化合物が挙げられる。ポリオール化合物と良好に反応し、形成される塗膜が高い強度を有することから、ポリイソシアネート化合物を用いることができる。イソシアネート基を有する化合物は、１種を単独で用いても、２種以上を併用してもよい。 Examples of the compound having an isocyanate group include a monoisocyanate compound having one isocyanate group and a polyisocyanate compound having two or more isocyanate groups. A polyisocyanate compound can be used because it reacts well with the polyol compound and the formed coating film has high strength. The compound which has an isocyanate group may be used individually by 1 type, or may use 2 or more types together.
　ポリイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート、水素添加ジフェニルジイソシアネート、イソホロンジイソシアネート等の脂肪族ジイソシアネート；２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、ｍ－キシレンジイソシアネート、ｐ－キシレンジイソシアネート等の芳香族ジイソシアネートが挙げられる。 Examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate, hydrogenated diphenyl diisocyanate, and isophorone diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m And aromatic diisocyanates such as -xylene diisocyanate and p-xylene diisocyanate.
　脂肪族ジイソシアネートとして、例えば、旭化成株式会社の製品名「デュラネート２４Ａ－９０ＰＸ」（ＮＣＯ：２３．６％）、住友バイエルウレタン株式会社の製品名「スミジュールＮ－３２００－９０Ｍ」、三井武田ケミカル株式会社の製品名「タケネートＤ１６５Ｎ－９０Ｘ」、住友バイエルウレタン株式会社の製品名「スミジュールＮ－３３００」、「スミジュールＮ－３５００」、旭化成株式会社の製品名「デュラネートＴＨＡ－１００」、「ＴＬＡ－１００」、「ＴＳＡ－１００」、「ＴＰＡ－１００」等を商業的に入手することができる。芳香族ジイソシアネートとしては、例えば、ＤＩＣ株式会社の製品名「バーノックＤ－７５０」、「ＤＮ－９５０」、「ＤＮ－９８０」等を商業的に入手することができる。 Examples of aliphatic diisocyanates include Asahi Kasei Corporation product name “Duranate 24A-90PX” (NCO: 23.6%), Sumitomo Bayer Urethane Co., Ltd. product name “Sumijour N-3200-90M”, Mitsui Takeda Chemical Co., Ltd. Company product name “Takenate D165N-90X”, Sumitomo Bayer Urethane Co., Ltd. product name “Sumijoule N-3300”, “Sumijoule N-3500”, Asahi Kasei Co., Ltd. product names “Duranate THA-100”, “TLA” −100 ”,“ TSA-100 ”,“ TPA-100 ”, etc. are commercially available. As the aromatic diisocyanate, for example, product names “Bernock D-750”, “DN-950”, “DN-980” and the like of DIC Corporation can be obtained commercially.
　ウレタン結合を有する樹脂を作製する際のポリイソシアネート化合物が有するイソシアネート基と、ポリオール化合物が有する水酸基との当量比（ＮＣＯ／ＯＨ当量比）は、０．１：１～１０：１とすることができ、０．３：１～１０：１であってよく、０．５：１～１０：１であってよい。イソシアネート基と水酸基との当量比が上記範囲内にあると、塗膜中の架橋反応が進行し易くなり、樹脂層の強度が高くなり、樹脂層の耐久性も高くなる傾向にある。ＮＣＯ／ＯＨ当量比は、ポリオール化合物中の水酸基（ＯＨ）に対するポリイソシアネート化合物中のイソシアネート基（ＮＣＯ）のモル比を示す。 The equivalent ratio (NCO / OH equivalent ratio) between the isocyanate group of the polyisocyanate compound and the hydroxyl group of the polyol compound when producing a resin having a urethane bond should be 0.1: 1 to 10: 1. Can be from 0.3: 1 to 10: 1 and from 0.5: 1 to 10: 1. When the equivalent ratio of isocyanate groups to hydroxyl groups is within the above range, the crosslinking reaction in the coating film tends to proceed, the strength of the resin layer increases, and the durability of the resin layer tends to increase. The NCO / OH equivalent ratio indicates the molar ratio of the isocyanate group (NCO) in the polyisocyanate compound to the hydroxyl group (OH) in the polyol compound.
　本実施形態に係る樹脂層には、本発明の効果を阻害しない範囲内で、窒素を含まない樹脂成分又は各種添加剤を更に含んでいてもよい。 The resin layer according to this embodiment may further contain a resin component or various additives that do not contain nitrogen, as long as the effects of the present invention are not impaired.
　窒素を含まない樹脂成分は、酸素原子及び硫黄原子からなる群から選択される少なくとも１種以上の原子を含む官能基を有していてもよい。このような官能基としては、例えば、水酸基、エーテル基、エポキシ基、カルボキシル基、エステル基、メルカプト基、チオエーテル基、チオエステル基及びスルホニル基が挙げられる。 The resin component not containing nitrogen may have a functional group containing at least one atom selected from the group consisting of an oxygen atom and a sulfur atom. Examples of such functional groups include hydroxyl groups, ether groups, epoxy groups, carboxyl groups, ester groups, mercapto groups, thioether groups, thioester groups, and sulfonyl groups.
　樹脂層に含まれる窒素を含まない樹脂成分としては、熱可塑性樹脂、熱硬化性樹脂、光硬化性樹脂等が挙げられる。当該樹脂成分としては、例えば、ポリエチレンテレフタレート等のポリエステル樹脂、ポリエチレン、ポリプロピレン等のオレフィン樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン等の含塩素樹脂、含フッ素樹脂、ポリカーボネート樹脂、アクリル樹脂、ＡＢＳ樹脂、ポリスチレン樹脂、ポリ酢酸ビニル樹脂、メラミン系樹脂、フェノール系樹脂、シリコーン樹脂、セルロース樹脂、スチレンアクリル樹脂、ビニルエーテル樹脂、スチレン－ブタジエン樹脂、ポリビニルアルコール樹脂、フェノール樹脂、不飽和ポリエステル樹脂、アリル樹脂、エポキシ（メタ）アクリレート、エポキシ変性ポリブタジエン、エポキシ変性ポリエステル、ポリブタジエン（メタ）アクリレート及びアクリル変性ポリエステル等が挙げられる。 Examples of the resin component not containing nitrogen contained in the resin layer include a thermoplastic resin, a thermosetting resin, and a photocurable resin. Examples of the resin component include polyester resins such as polyethylene terephthalate, olefin resins such as polyethylene and polypropylene, chlorine-containing resins such as polyvinyl chloride and polyvinylidene chloride, fluorine-containing resins, polycarbonate resins, acrylic resins, ABS resins, and polystyrene. Resin, polyvinyl acetate resin, melamine resin, phenol resin, silicone resin, cellulose resin, styrene acrylic resin, vinyl ether resin, styrene-butadiene resin, polyvinyl alcohol resin, phenol resin, unsaturated polyester resin, allyl resin, epoxy ( Examples include meth) acrylate, epoxy-modified polybutadiene, epoxy-modified polyester, polybutadiene (meth) acrylate, and acryl-modified polyester.
　樹脂層に含まれる各種添加剤としては、例えば、有機微粒子、無機微粒子、架橋剤、難燃剤、難燃助剤、耐熱安定剤、耐酸化安定剤、レベリング剤、滑り賦活剤、帯電防止剤、紫外線吸収剤、光安定化剤、核剤、染料、充填剤、分散剤及びカップリング剤が挙げられる。 Various additives contained in the resin layer include, for example, organic fine particles, inorganic fine particles, crosslinking agents, flame retardants, flame retardant aids, heat stabilizers, oxidation stabilizers, leveling agents, slip activators, antistatic agents, Examples include ultraviolet absorbers, light stabilizers, nucleating agents, dyes, fillers, dispersants, and coupling agents.
　樹脂層の厚さは、基材及びエアロゲル層と良好な接着性を得る観点から、１ｎｍ以上とすることができ、１００ｎｍ以上であってもよく、５００ｎｍ以上であってもよい。また、樹脂層の厚さは、エアロゲル積層体の断熱性能を向上する観点から、５μｍ以下とするができ、３μｍ以下であってもよく、１μｍ以下であってもよい。すなわち、樹脂層の厚さは、１ｎｍ～５μｍであってもよく、１００ｎｍ～３μｍであってもよく、５００ｎｍ～１μｍであってもよい。 The thickness of the resin layer can be 1 nm or more from the viewpoint of obtaining good adhesion to the base material and the airgel layer, and may be 100 nm or more, or 500 nm or more. In addition, the thickness of the resin layer can be 5 μm or less from the viewpoint of improving the heat insulation performance of the airgel laminate, and may be 3 μm or less, or 1 μm or less. That is, the thickness of the resin layer may be 1 nm to 5 μm, 100 nm to 3 μm, or 500 nm to 1 μm.
＜基材＞
　本実施形態に係る基材は、非エアロゲル層であり、基材の構成としては、特に限定されず、単層でも複層でも構わない。基材の形状としては、エアロゲル積層体に軽量性を付与できることから、フィルム状又は箔状とすることができる。 <Base material>
The base material which concerns on this embodiment is a non-aerogel layer, and it does not specifically limit as a structure of a base material, A single layer or a multilayer may be sufficient. As a shape of a base material, since lightness can be provided to an airgel laminated body, it can be set as a film form or foil shape.
　基材は、熱線反射機能又は熱線吸収機能を有する層を少なくとも１層有すると、エアロゲル積層体の断熱性をより向上することができる。熱線反射機能又は熱線吸収機能を有する基材は、輻射体として働き、外部からの熱を遮断する役割を果たすことができる。 When the base material has at least one layer having a heat ray reflecting function or a heat ray absorbing function, the heat insulating property of the airgel laminate can be further improved. A base material having a heat ray reflection function or a heat ray absorption function can function as a radiator and can play a role of blocking heat from the outside.
　熱線反射機能とは、例えば、８００～３０００ｎｍ程度の近赤外又は赤外領域における光の反射が、光の吸収及び光の透過よりも大きい機能をいう。これに対して、熱線吸収機能とは、例えば、８００～３０００ｎｍ程度の近赤外又は赤外領域における光の吸収が、光の反射及び光の透過よりも大きい機能をいう。ここで、光の反射には光の散乱が含まれる。 The heat ray reflection function refers to a function in which reflection of light in the near infrared or infrared region of about 800 to 3000 nm is larger than light absorption and light transmission. On the other hand, the heat ray absorption function refers to a function in which light absorption in the near infrared or infrared region of, for example, about 800 to 3000 nm is larger than light reflection and light transmission. Here, light reflection includes light scattering.
　本実施形態に係る基材は、熱線反射機能を有する層及び熱線吸収機能を有する層のうち少なくとも一方から構成されていてもよく、熱線反射機能を有する層のみからなるものでも、熱線吸収機能を有する層のみからなるものでもよい。また、基材は、熱線反射機能を有する層と熱線吸収機能を有する層とが積層されたものであってもよい。さらに、基材は、熱線反射機能又は熱線吸収機能を有する層と熱線反射機能及び熱線吸収機能を有しない層とが積層されたものでもよい。この場合、熱線反射機能又は熱線吸収機能を有する層は、熱線反射機能及び熱線吸収機能を有しない層の片面又は両面に形成されていてもよい。 The base material according to the present embodiment may be composed of at least one of a layer having a heat ray reflecting function and a layer having a heat ray absorbing function, and may be composed of only a layer having a heat ray reflecting function. It may consist of only the layers it has. The base material may be a laminate of a layer having a heat ray reflecting function and a layer having a heat ray absorbing function. Furthermore, the base material may be a laminate of a layer having a heat ray reflecting function or a heat ray absorbing function and a layer not having a heat ray reflecting function and a heat ray absorbing function. In this case, the layer having the heat ray reflecting function or the heat ray absorbing function may be formed on one side or both sides of the layer not having the heat ray reflecting function and the heat ray absorbing function.
　熱線反射機能を有する層は、熱線反射性の材料を含むことができる。熱線反射性の材料としては、近赤外又は赤外領域の光を反射する材料であれば、特に限定されない。熱線反射性の材料として、例えば、アルミニウム、酸化アルミニウム等のアルミニウム化合物、アルミン酸亜鉛等の亜鉛化合物、ハイドロタルサイト等のマグネシウム化合物、銀等の銀化合物、チタン、酸化チタン、チタン酸ストロンチウム等のチタン化合物、銅、青銅等の銅化合物、ステンレス、ニッケル、錫、シラスバルーン等のマイクロバルーン、セラミックバルーン及びパールマイカが挙げられる。これらは、単独で用いてもよいし、２種類以上を併用してもよい。 The layer having a heat ray reflective function can contain a heat ray reflective material. The heat ray reflective material is not particularly limited as long as it is a material that reflects light in the near infrared or infrared region. Examples of heat-reflective materials include aluminum compounds such as aluminum and aluminum oxide, zinc compounds such as zinc aluminate, magnesium compounds such as hydrotalcite, silver compounds such as silver, titanium, titanium oxide, and strontium titanate. Examples include titanium compounds, copper compounds such as copper and bronze, microballoons such as stainless steel, nickel, tin, and shirasu balloons, ceramic balloons, and pearl mica. These may be used alone or in combination of two or more.
　これらの中でも、熱伝導率を低減し易く、廉価性及び取り扱い性に優れる観点から、熱線反射性の材料として、アルミニウム、マグネシウム、銀又はチタンを含む材料を用いることができる。 Among these, materials containing aluminum, magnesium, silver, or titanium can be used as the heat ray reflective material from the viewpoint of easily reducing thermal conductivity, being inexpensive and excellent in handleability.
　熱線反射機能を有する層は、アルミニウム箔、銅箔等の金属箔から構成されていてもよい。また、熱線反射機能を有する層は、アルミニウムペースト又は酸化チタンをポリオレフィン、ポリエステル、ポリカーボネート、ポリイミド等の樹脂に混練して作製される樹脂フィルムであってもよい。さらに、熱線反射機能を有する層は、アルミニウム、銀等をスパッタリング、真空蒸着等の物理蒸着又は化学蒸着により、ポリオレフィン、ポリエステル、ポリカーボネート、ポリイミド等の樹脂フィルムへ蒸着した蒸着フィルムであってもよい。 The layer having a heat ray reflecting function may be composed of a metal foil such as an aluminum foil or a copper foil. The layer having a heat ray reflecting function may be a resin film prepared by kneading an aluminum paste or titanium oxide with a resin such as polyolefin, polyester, polycarbonate, or polyimide. Furthermore, the layer having a heat ray reflecting function may be a deposited film obtained by depositing aluminum, silver or the like on a resin film such as polyolefin, polyester, polycarbonate, polyimide, etc. by physical vapor deposition such as sputtering or vacuum vapor deposition or chemical vapor deposition.
　熱線吸収機能を有する層は、熱線吸収性の材料を含むことができる。熱線吸収性の材料としては、近赤外又は赤外領域の光を吸収する物質であれば、特に限定されない。熱線吸収性の材料として、例えば、鱗片状黒鉛、土状黒鉛、人造黒鉛等のカーボングラファイト、カーボンブラックなどの炭素粉末；硫酸バリウム、硫酸ストロンチウム、硫酸カルシウム、メルカライト（ＫＨＳＯ４）、ハロトリ石、ミョウバン石、鉄ミョウバン石等の金属硫酸塩；三酸化アンチモン等のアンチモン化合物；酸化錫、酸化インジウム、酸化インジウムスズ、酸化亜鉛、無水酸化アンチモン酸亜鉛等の金属酸化物；アンモニウム系、尿素系、イモニウム系、アミニウム系、シアニン系、ポリメチン系、アントラキノン系、ジチオール系、銅イオン系、フェニレンジアミン系、フタロシアニン系、ベンゾトリアゾール系、ベンゾフェノン系、シュウ酸アニリド系、シアノアクリレート系又はベンゾトリアゾール系の染料又は顔料を挙げることができる。 The layer having a heat ray absorbing function can include a heat ray absorbing material. The heat-absorbing material is not particularly limited as long as it is a substance that absorbs light in the near infrared or infrared region. Examples of heat-absorbing materials include carbon graphite such as flaky graphite, earthy graphite, and artificial graphite, carbon powder such as carbon black; barium sulfate, strontium sulfate, calcium sulfate, mercalite (KHSO 4 ), halotristone, Metal sulfates such as alumite and iron alumite; antimony compounds such as antimony trioxide; metal oxides such as tin oxide, indium oxide, indium tin oxide, zinc oxide and anhydrous zinc antimonate; ammonium-based, urea-based, Imonium, aminium, cyanine, polymethine, anthraquinone, dithiol, copper ion, phenylenediamine, phthalocyanine, benzotriazole, benzophenone, oxalic anilide, cyanoacrylate, or benzotriazole dyes Or face It can be mentioned.
　これらの中でも、熱線吸収性の材料としては、熱伝導率を低減し易く、廉価性及び取扱い性に優れる観点から、カーボングラファイト、カーボンブラック、金属硫酸塩又はアンチモン化合物を含む材料を用いることができる。熱伝導率をより一層低減する観点から、熱線吸収機能を有する層は、カーボンブラック、酸化アンチモン又は硫酸バリウムを混練して作製される樹脂フィルムであってもよい。 Among these, as the heat ray-absorbing material, a material containing carbon graphite, carbon black, metal sulfate, or an antimony compound can be used from the viewpoint of easily reducing the thermal conductivity, and being inexpensive and easy to handle. . From the viewpoint of further reducing the thermal conductivity, the layer having a heat ray absorbing function may be a resin film prepared by kneading carbon black, antimony oxide or barium sulfate.
　断熱性をより向上する観点から、基材は、カーボングラファイト、アルミニウム、マグネシウム、銀、チタン、カーボンブラック、金属硫酸塩及びアンチモン化合物からなる群より選ばれる少なくとも一種を含む材料から構成される層を有することができる。取扱い性に優れると共に、断熱性を向上する観点から、基材は、アルミニウム箔、アルミニウム蒸着フィルム、銀蒸着フィルム又は酸化アンチモン含有フィルムであってもよい。 From the viewpoint of further improving heat insulation, the base material is a layer composed of a material containing at least one selected from the group consisting of carbon graphite, aluminum, magnesium, silver, titanium, carbon black, metal sulfate and antimony compounds. Can have. From the viewpoint of improving handleability and improving heat insulation properties, the substrate may be an aluminum foil, an aluminum deposited film, a silver deposited film, or an antimony oxide-containing film.
　基材のエアロゲル層が設けられていない側の面には、エアロゲル積層体を複数層重ねた際にエアロゲル層を保護する目的で保護層を有していてもよい。保護層の構成材料としては、例えば、ウレタン樹脂、ポリエステル樹脂、アクリル樹脂、フェノール樹脂等が挙げられ、上述した樹脂層と同じ材料であってもよい。これらの樹脂層は、単層であっても複層であってもよい。 The surface of the substrate on which the airgel layer is not provided may have a protective layer for the purpose of protecting the airgel layer when a plurality of airgel laminates are stacked. Examples of the constituent material of the protective layer include a urethane resin, a polyester resin, an acrylic resin, a phenol resin, and the like, and may be the same material as the resin layer described above. These resin layers may be a single layer or multiple layers.
　基材のエアロゲル層が積層されていない側の面には、離型処理を施してもよい。 The surface of the base material on which the airgel layer is not laminated may be subjected to a release treatment.
　基材の厚みは特に限定されないが、ハンドリング性の観点から、３μｍ以上とすることができ、５μｍ以上であってもよく、７μｍ以上であってもよい。一方、断熱性を向上する観点から、基材の厚みは、１００μｍ以下とすることができ、８０μｍ以下であってもよく、５０μｍ以下であってもよい。すなわち、基材の厚みは３～１００μｍとすることができ、５～８０μｍであってもよく、７～５０μｍであってもよい。 Although the thickness of the substrate is not particularly limited, from the viewpoint of handling properties, it can be 3 μm or more, may be 5 μm or more, and may be 7 μm or more. On the other hand, from the viewpoint of improving heat insulation, the thickness of the base material can be 100 μm or less, 80 μm or less, or 50 μm or less. That is, the thickness of the base material can be 3 to 100 μm, 5 to 80 μm, or 7 to 50 μm.
＜エアロゲル積層体の製造方法＞
　本実施形態のエアロゲル積層体の製造方法は、特に限定されないが、例えば以下の方法により製造することができる。 <Method for producing airgel laminate>
Although the manufacturing method of the airgel laminated body of this embodiment is not specifically limited, For example, it can manufacture with the following method.
　すなわち、本実施形態のエアロゲル積層体は、基材に窒素原子を有する樹脂を含有する樹脂層を形成する樹脂層形成工程と、エアロゲルを形成するためのゾルを作製するゾル生成工程と、樹脂層を設けた基材にゾル生成工程で得られたゾルを塗布し、乾燥してエアロゲル層を形成する塗工工程と、塗工工程で得られたエアロゲル層を熟成する熟成工程と、熟成したエアロゲル層を洗浄及び溶媒置換する工程と、洗浄及び（必要に応じ）溶媒置換したエアロゲル層を乾燥する乾燥工程を主に備える製造方法により製造することができる。なお、「ゾル」とは、ゲル化反応が生じる前の状態であって、本実施形態においては上記ケイ素化合物（必要に応じて、更にシリカ粒子）が溶媒中に溶解又は分散している状態を意味する。 That is, the airgel laminate of the present embodiment includes a resin layer forming step for forming a resin layer containing a resin having nitrogen atoms on a base material, a sol generating step for producing a sol for forming an airgel, and a resin layer The sol obtained in the sol generating step is applied to a base material provided with a coating step, and dried to form an airgel layer, the aging step to age the airgel layer obtained in the coating step, and the aged aerogel It can be produced by a production method mainly comprising a step of washing and solvent replacement of the layer and a drying step of drying the airgel layer after washing and solvent substitution (if necessary). The “sol” is a state before the gelation reaction occurs, and in the present embodiment, the above-described silicon compound (if necessary, further silica particles) is dissolved or dispersed in a solvent. means.
　以下、本実施形態のエアロゲル積層体の製造方法の各工程について説明する。 Hereinafter, each process of the manufacturing method of the airgel laminated body of this embodiment is demonstrated.
（樹脂層形成工程）
　樹脂層形成工程は、上述の窒素原子を有する樹脂成分を有機溶媒と混合して得られる樹脂層形成用塗液を、基材に塗布し、乾燥することにより塗液を硬化させて基材の表面に樹脂層を形成する工程である。ただし、この樹脂層は、基材との接着力が確保される状態であることが望ましい。 (Resin layer forming process)
In the resin layer forming step, a resin layer forming coating liquid obtained by mixing the above-described resin component having a nitrogen atom with an organic solvent is applied to a substrate and dried to cure the coating liquid. This is a step of forming a resin layer on the surface. However, it is desirable that this resin layer is in a state in which an adhesive force with the substrate is ensured.
　有機溶媒としては、基材上に良好な塗膜が形成される溶媒であれば特に限定されないが、樹脂層形成用塗液に含まれる樹脂成分と反応しない溶媒を用いることができる。 The organic solvent is not particularly limited as long as it is a solvent capable of forming a good coating film on the substrate, and a solvent that does not react with the resin component contained in the resin layer forming coating solution can be used.
　有機溶媒としては、例えば、トルエン、キシレン、シクロヘキサン等の炭化水素化合物；酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル等のエステル化合物；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン化合物；ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル等のエーテル化合物が挙げられる。 Examples of the organic solvent include hydrocarbon compounds such as toluene, xylene and cyclohexane; ester compounds such as ethyl acetate, n-butyl acetate and isobutyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; diethylene glycol dimethyl ether and dipropylene And ether compounds such as glycol dimethyl ether.
　塗布装置としては、ダイコータ、コンマコータ、バーコータ、キスコータ、ロールコータ等を利用でき、樹脂層の厚みによって適宜使用される。塗布後の樹脂層形成用塗液からなる塗膜は、加熱等により乾燥することができる。 As the coating device, a die coater, a comma coater, a bar coater, a kiss coater, a roll coater, or the like can be used, and it is appropriately used depending on the thickness of the resin layer. The coating film composed of the coating solution for forming a resin layer after application can be dried by heating or the like.
　乾燥温度は、樹脂層形成用塗液中の溶媒量、溶媒の沸点によっても異なるが、例えば、５０～２００℃とすることができ、８０～１５０℃であってもよい。乾燥温度を５０℃以上とすることにより、短時間で樹脂層の乾燥を行うことができ、２００℃以下とすることにより、基材との接着性を得易くなる。 The drying temperature varies depending on the amount of solvent in the resin layer-forming coating solution and the boiling point of the solvent, but can be, for example, 50 to 200 ° C. or 80 to 150 ° C. By setting the drying temperature to 50 ° C. or higher, the resin layer can be dried in a short time, and by setting the drying temperature to 200 ° C. or lower, it becomes easy to obtain adhesion to the substrate.
　乾燥時間は、乾燥温度によって異なるが、例えば、０．２～１０分とすることができ、０．５～５分であってもよい。乾燥時間を０．２分以上とすることにより、樹脂層が形成し易くなり、１０分以下とすることにより、基材との接着性を得易くなる。上記乾燥条件は、予め簡単な実験により適宜設定することができる。 The drying time varies depending on the drying temperature, but can be, for example, 0.2 to 10 minutes, or may be 0.5 to 5 minutes. By setting the drying time to 0.2 minutes or more, the resin layer can be easily formed, and by setting the drying time to 10 minutes or less, it becomes easy to obtain adhesion to the substrate. The drying conditions can be set as appropriate by simple experiments in advance.
（ゾル生成工程）
　ゾル生成工程は、上述のケイ素化合物と、場合によりシリカ粒子を含む溶媒とを混合し、加水分解反応を行った後、ゾルゲル反応を行い、半ゲル化のゾル塗液を得る工程である。本工程においては、加水分解反応を促進させるため、溶媒中にさらに酸触媒を添加してもよい。また、特許第５２５０９００号公報に示されるように、溶媒中に界面活性剤、熱加水分解性化合物等を添加することもできる。さらに、ゲル化反応を促進させるため、塩基触媒を添加してもよい。なお、本工程、後述する塗工工程及び熟成工程における工程時間を短縮し、加熱及び乾燥温度を低温化する観点から、ゾル中にシリカ粒子を含有するとよい。 (Sol generation process)
The sol generation step is a step of mixing the above-described silicon compound and a solvent containing silica particles in some cases, performing a hydrolysis reaction, and then performing a sol-gel reaction to obtain a semi-gelled sol coating liquid. In this step, an acid catalyst may be further added to the solvent in order to promote the hydrolysis reaction. Further, as disclosed in Japanese Patent No. 5250900, a surfactant, a thermohydrolyzable compound, or the like can be added to the solvent. Furthermore, a base catalyst may be added to promote the gelation reaction. In addition, it is good to contain a silica particle in a sol from a viewpoint of shortening the process time in this process, the coating process mentioned later, and a maturing process, and making temperature of heating and drying low.
　溶媒としては、後述する塗工工程において、良好な塗膜性が得られれば特に限定されず、例えば、水、又は、水及びアルコールの混合液を用いることができる。アルコールとしては、例えば、メタノール、エタノール、ｎ－プロパノール、２－プロパノール、ｎ－ブタノール、２－ブタノール及びｔ－ブタノールが挙げられる。これらの中でも、表面張力が高く、揮発性が低い点から、水を用いることができる。 The solvent is not particularly limited as long as good coating properties can be obtained in the coating step described later, and for example, water or a mixed solution of water and alcohol can be used. Examples of the alcohol include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol and t-butanol. Among these, water can be used because of its high surface tension and low volatility.
　酸触媒としては、例えば、フッ酸、塩酸、硝酸、硫酸、亜硫酸、リン酸、亜リン酸、次亜リン酸、臭素酸、塩素酸、亜塩素酸、次亜塩素酸等の無機酸類；酸性リン酸アルミニウム、酸性リン酸マグネシウム、酸性リン酸亜鉛等の酸性リン酸塩類；酢酸、ギ酸、プロピオン酸、シュウ酸、マロン酸、コハク酸、クエン酸、リンゴ酸、アジピン酸、アゼライン酸等の有機カルボン酸類が挙げられる。これらの中でも、得られるエアロゲル層の耐水性をより向上する酸触媒として、有機カルボン酸類を用いることができ、具体的には、酢酸、ギ酸、プロピオン酸、シュウ酸又はマロン酸が挙げられ、酢酸であってもよい。これらは単独で又は２種類以上を混合して用いてもよい。 Examples of the acid catalyst 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 acids such as acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid, azelaic acid Carboxylic acids are mentioned. Among these, organic carboxylic acids can be used as an acid catalyst that further improves the water resistance of the obtained airgel layer. Specific examples include acetic acid, formic acid, propionic acid, oxalic acid, and malonic acid. It may be. You may use these individually or in mixture of 2 or more types.
　酸触媒を用いることで、ケイ素化合物及びポリシロキサン化合物の加水分解反応を促進させて、より短時間でゾルを得ることができる。 By using an acid catalyst, the hydrolysis reaction of the silicon compound and the polysiloxane compound is promoted, and a sol can be obtained in a shorter time.
　酸触媒の添加量は、ケイ素化合物及びポリシロキサン化合物の総量１００質量部に対し、０．００１～０．１質量部とすることができる。 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 and the polysiloxane compound.
　界面活性剤としては、非イオン性界面活性剤、イオン性界面活性剤等を用いることができる。これらは単独で又は２種類以上を混合して用いてもよい。 As the surfactant, a nonionic surfactant, an ionic surfactant, or the like can be used. You may use these individually or in mixture of 2 or more types.
　非イオン性界面活性剤としては、例えば、ポリオキシエチレン等の親水部と主にアルキル基からなる疎水部とを含む化合物、ポリオキシプロピレン等の親水部を含む化合物などを使用できる。ポリオキシエチレン等の親水部と主にアルキル基からなる疎水部とを含む化合物としては、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンアルキルエーテル等が挙げられる。ポリオキシプロピレン等の親水部を含む化合物としては、ポリオキシプロピレンアルキルエーテル、ポリオキシエチレンとポリオキシプロピレンのブロック共重合体等が挙げられる。 As the 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. Examples of the compound containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether and the like. Examples of the compound having a hydrophilic portion such as polyoxypropylene include polyoxypropylene alkyl ether, a block copolymer of polyoxyethylene and polyoxypropylene, and the like.
　イオン性界面活性剤としては、カチオン性界面活性剤、アニオン性界面活性剤、両イオン性界面活性剤等を用いることができる。カチオン性界面活性剤としては、例えば、臭化セチルトリメチルアンモニウム及び塩化セチルトリメチルアンモニウムが挙げられる。アニオン性界面活性剤としては、例えば、ドデシルスルホン酸ナトリウムが挙げられる。両イオン性界面活性剤としては、例えば、アミノ酸系界面活性剤、ベタイン系界面活性剤及びアミンオキシド系界面活性剤が挙げられる。アミノ酸系界面活性剤としては、例えば、アシルグルタミン酸が挙げられる。ベタイン系界面活性剤としては、例えば、ラウリルジメチルアミノ酢酸ベタイン及びステアリルジメチルアミノ酢酸ベタインが挙げられる。アミンオキシド系界面活性剤としては、例えば、ラウリルジメチルアミンオキシドが挙げられる。 As the ionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, or the like can be used. Examples of the cationic surfactant include cetyltrimethylammonium bromide and cetyltrimethylammonium chloride. Examples of the anionic surfactant include sodium dodecyl sulfonate. Examples of amphoteric surfactants include amino acid surfactants, betaine surfactants, and amine oxide surfactants. Examples of amino acid surfactants include acyl glutamic acid. Examples of betaine surfactants include lauryldimethylaminoacetic acid betaine and stearyldimethylaminoacetic acid betaine. Examples of the amine oxide surfactant include lauryl dimethylamine oxide.
　これらの界面活性剤は、後述する塗工工程において、反応系中の溶媒と、成長していくシロキサン重合体との間の化学的親和性の差異を小さくし、相分離を抑制する作用をすると考えられている。 These surfactants act to reduce the difference in chemical affinity between the solvent in the reaction system and the growing siloxane polymer in the coating process described later, and to suppress phase separation. It is considered.
　界面活性剤の添加量は、界面活性剤の種類、又は、ケイ素化合物（ケイ素化合物群及びポリシロキサン化合物群）の種類並びに量にも左右されるが、例えば、ケイ素化合物の総量１００質量部に対し、１～１００質量部とすることができ、５～６０質量部であってもよい。 The amount of surfactant added depends on the type of surfactant or the type and amount of silicon compound (silicon compound group and polysiloxane compound group). For example, the total amount of silicon compound is 100 parts by mass. The amount may be 1 to 100 parts by mass, and may be 5 to 60 parts by mass.
　熱加水分解性化合物は、熱加水分解により塩基触媒を発生して、反応溶液を塩基性とし、ゾルゲル反応を促進すると考えられている。よって、この熱加水分解性化合物としては、加水分解後に反応溶液を塩基性にできる化合物であれば、特に限定されず、例えば、尿素；ホルムアミド、Ｎ－メチルホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド、アセトアミド、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド等の酸アミド；ヘキサメチレンテトラミン等の環状窒素化合物を挙げることができる。これらの中でも、特に尿素は上記促進効果を得られ易い。 The 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. 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. Among these, urea is particularly easy to obtain the above-mentioned promoting effect.
　熱加水分解性化合物の添加量は、ゾルゲル反応を十分に促進することができる量であれば、特に限定されない。例えば、熱加水分解性化合物として尿素を用いた場合、その添加量は、ケイ素化合物（ケイ素化合物群及びポリシロキサン化合物群）の総量１００質量部に対して、１～２００質量部とすることができ、２～１５０質量部であってもよい。添加量を１質量部以上とすることにより、良好な反応性を更に得易くなり、また、２００質量部以下とすることにより、結晶の析出及びゲル密度の低下を更に抑制し易くなる。 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. For example, when urea is used as the thermally hydrolyzable compound, the amount added can be 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of silicon compounds (silicon compound group and polysiloxane compound group). It may be 2 to 150 parts by mass. By making the addition amount 1 mass part or more, it becomes easier to obtain good reactivity, and by making it 200 mass parts or less, it becomes easier to further suppress the precipitation of crystals and the decrease in gel density.
　ゾル生成工程の加水分解は、混合液中のケイ素化合物、ポリシロキサン化合物シリカ粒子、酸触媒、界面活性剤等の種類及び量にも左右されるが、例えば２０～６０℃の温度環境下で、１０分～２４時間行ってもよく、５０～６０℃の温度環境下で５分～８時間行ってもよい。これにより、ケイ素化合物及びポリシロキサン化合物中の加水分解性官能基が十分に加水分解され、ケイ素化合物の加水分解生成物及びポリシロキサン化合物の加水分解生成物をより確実に得ることができる。 Hydrolysis in the sol production step depends on the types and amounts of silicon compound, polysiloxane compound silica particles, acid catalyst, surfactant, etc. in the mixed solution, but for example, in a temperature environment of 20 to 60 ° C., The treatment may be performed for 10 minutes to 24 hours, or in a temperature environment of 50 to 60 ° C. for 5 minutes to 8 hours. Thereby, the hydrolyzable functional group in a silicon compound and a polysiloxane compound is fully hydrolyzed, and the hydrolysis product of a silicon compound and the hydrolysis product of a polysiloxane compound can be obtained more reliably.
　溶媒中に熱加水分解性化合物を添加する場合は、ゾル生成工程の温度環境を、熱加水分解性化合物の加水分解を抑制してゾルのゲル化を抑制する温度に調節してもよい。この時の温度は、熱加水分解性化合物の加水分解を抑制できる温度であれば、いずれの温度であってもよい。例えば、熱加水分解性化合物として尿素を用いた場合は、ゾル生成工程の温度環境は０～４０℃とすることができ、１０～３０℃であってもよい。 When adding a thermohydrolyzable compound in the solvent, 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. For example, when urea is used as the thermally hydrolyzable compound, the temperature environment of the sol production step can be 0 to 40 ° C., and may be 10 to 30 ° C.
　塩基触媒としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウム等のアルカリ金属水酸化物；水酸化アンモニウム、フッ化アンモニウム、塩化アンモニウム、臭化アンモニウム等のアンモニウム化合物；メタ燐酸ナトリウム、ピロ燐酸ナトリウム、ポリ燐酸ナトリウム等の塩基性燐酸ナトリウム塩；アリルアミン、ジアリルアミン、トリアリルアミン、イソプロピルアミン、ジイソプロピルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、２－エチルヘキシルアミン、３－エトキシプロピルアミン、ジイソブチルアミン、３－（ジエチルアミノ）プロピルアミン、ジ－２－エチルヘキシルアミン、３－（ジブチルアミノ）プロピルアミン、テトラメチルエチレンジアミン、ｔ－ブチルアミン、ｓｅｃ－ブチルアミン、プロピルアミン、３－（メチルアミノ）プロピルアミン、３－（ジメチルアミノ）プロピルアミン、３－メトキシアミン、ジメチルエタノールアミン、メチルジエタノールアミン、ジエタノールアミン、トリエタノールアミン等の脂肪族アミン類；モルホリン、Ｎ－メチルモルホリン、２－メチルモルホリン、ピペラジン及びその誘導体、ピペリジン及びその誘導体、イミダゾール及びその誘導体等の含窒素複素環状化合物類などが挙げられる。これらの中でも、水酸化アンモニウム（アンモニア水）は、揮発性が高く、乾燥後のエアロゲル層に残存し難いため耐水性を損ないづらいという点、更には経済性の点で優れている。上記の塩基触媒は、単独で又は２種類以上を混合して用いてもよい。 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- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxyamine, dimethylethanolamine, methyldiethanolamine, diethanolamine, triethanolamine; morpholine, N -Nitrogen-containing heterocyclic compounds such as methylmorpholine, 2-methylmorpholine, piperazine and derivatives thereof, piperidine and derivatives thereof, imidazole and derivatives thereof, and the like. Among these, ammonium hydroxide (ammonia water) is excellent in that it has high volatility and does not easily remain in the airgel layer after drying, so that it is difficult to impair water resistance, and further, it is economical. You may use said base catalyst individually or in mixture of 2 or more types.
　塩基触媒を用いることで、ゾル中のケイ素化合物（ポリシロキサン化合物群及びケイ素化合物群）及びシリカ粒子の脱水縮合反応及び／又は脱アルコール縮合反応を促進することができ、ゾルのゲル化をより短時間で行うことができる。特に、アンモニアは揮発性が高く、エアロゲル層に残留し難いので、塩基触媒としてアンモニアを用いることで、より耐水性の優れたエアロゲル層を得ることができる。 By using a base catalyst, 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 can be shortened. Can be done in time. In particular, ammonia is highly volatile and hardly remains in the airgel layer. Therefore, by using ammonia as a base catalyst, an airgel layer with better water resistance can be obtained.
　塩基触媒の添加量は、ケイ素化合物（ポリシロキサン化合物群及びケイ素化合物群）の総量１００質量部に対し、０．５～５質量部とすることができ、１～４質量部であってもよい。塩基触媒の添加量を０．５質量部以上とすることにより、ゲル化をより短時間で行うことができ、５質量部以下とすることにより、耐水性の低下をより抑制することができる。 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. . By setting the addition amount of the base catalyst to 0.5 parts by mass or more, gelation can be performed in a shorter time, and by setting it to 5 parts by mass or less, a decrease in water resistance can be further suppressed.
　ゾル生成工程におけるゾルゲル反応は、後述する塗工工程において、良好な塗膜性を得る目的から、ゾルを半ゲル化状態にすることが必要である。この反応は、溶媒及び塩基触媒が揮発しないように密閉容器内で行うことが好ましい。ゲル化温度は、ゾル中のケイ素化合物、ポリシロキサン化合物、シリカ粒子、酸触媒、界面活性剤、塩基触媒等の種類及び量にも左右されるが、３０～９０℃とすることができるが、４０～８０℃であってもよい。ゲル化温度を３０℃以上とすることにより、ゲル化をより短時間に行うことができ、ゲル化温度を９０℃以下にすることにより、急なゲル化を抑制することができる。 The sol-gel reaction in the sol production step requires that the sol be in a semi-gelled state for the purpose of obtaining good coating properties in the coating step described later. This reaction is preferably performed in a sealed container so that the solvent and the base catalyst do not volatilize. The gelation temperature depends on the type and amount of the silicon compound, polysiloxane compound, silica particles, acid catalyst, surfactant, base catalyst, etc. in the sol, but can be 30 to 90 ° C., It may be 40-80 ° C. By setting the gelation temperature to 30 ° C. or higher, gelation can be performed in a shorter time, and by setting the gelation temperature to 90 ° C. or lower, sudden gelation can be suppressed.
　ゾルゲル反応の時間は、ゲル化温度により異なるが、本実施形態においてはゾル中にシリカ粒子を含有する場合は、従来のエアロゲルに適用されるゾルと比較して、ゲル化時間を短縮することができる。この理由は、ゾル中のケイ素化合物（ポリシロキサン化合物群及びケイ素化合物群）が有するシラノール基及び／又は反応性基が、シリカ粒子のシラノール基と水素結合及び／又は化学結合を形成するためであると推察する。なお、ゲル化時間は、１０～３６０分とすることができ、２０～１８０分であってもよい。ゲル化時間を１０分以上とすることにより、ゾルの粘度が向上し、後述する塗工工程において良好な塗工性を得易くなり、３６０分以下とすることにより、ゾルの完全ゲル化を抑制し、樹脂層との接着性を得易くなる。 Although the sol-gel reaction time varies depending on the gelation temperature, in the present embodiment, when silica particles are contained in the sol, the gelation time may be shortened as compared with a sol applied to a conventional aerogel. it can. This is because the silanol groups and / or reactive groups of the silicon compounds (polysiloxane compound group and silicon compound group) in the sol form hydrogen bonds and / or chemical bonds with the silanol groups of the silica particles. I guess. The gelation time can be 10 to 360 minutes, and may be 20 to 180 minutes. By setting the gelation time to 10 minutes or more, the viscosity of the sol is improved, and it becomes easy to obtain good coating properties in the coating process described later, and by setting it to 360 minutes or less, the complete gelation of the sol is suppressed And it becomes easy to obtain adhesiveness with a resin layer.
（塗工工程）
　塗工工程は、上記ゾル生成工程で得られた半ゲル化状態のゾル塗液を、樹脂層が設けられた基材に塗工し、樹脂層上にエアロゲル層を形成する工程である。具体的には、上記ゾル塗液を、樹脂層が設けられた基材に塗布し、乾燥することによりゾル塗液をゲル化させてエアロゲル層を樹脂層の表面に形成する。ただし、このエアロゲル層は、樹脂層との接着力が確保される状態であることが望ましい。本実施形態のエアロゲル積層体は、ロール状に巻き取って貯蔵することができる。 (Coating process)
The coating step is a step of forming the airgel layer on the resin layer by applying the semi-gelled sol coating solution obtained in the sol generating step to the base material provided with the resin layer. Specifically, the sol coating liquid is applied to a substrate provided with a resin layer and dried to gel the sol coating liquid to form an airgel layer on the surface of the resin layer. However, this airgel layer is desirably in a state in which an adhesive force with the resin layer is ensured. The airgel laminated body of this embodiment can be wound up and stored in a roll shape.
　塗工装置としては、ダイコータ、コンマコータ、バーコータ、キスコータ、ロールコータ等が利用でき、エアロゲル層の厚みによって適宜使用される。塗工後のゾル塗液からなる塗膜は、加熱等により乾燥することができる。 As the coating apparatus, a die coater, a comma coater, a bar coater, a kiss coater, a roll coater or the like can be used, and is used as appropriate depending on the thickness of the airgel layer. The coating film comprising the sol coating liquid after coating can be dried by heating or the like.
　ゾル塗液を樹脂層が設けられた基材に塗布した後の乾燥は、例えば、乾燥後のエアロゲル層の含水率が１０質量％以上となる条件で行うことができ、５０質量％以上となる条件で行ってもよい。エアロゲル層の含水量を１０質量％とすることにより、樹脂層との接着性を得易くなる。 Drying after applying the sol coating liquid to the substrate provided with the resin layer can be performed, for example, under the condition that the moisture content of the airgel layer after drying is 10% by mass or more, and is 50% by mass or more. It may be performed under conditions. By making the water content of the airgel layer 10% by mass, it becomes easy to obtain adhesiveness with the resin layer.
　乾燥温度は、ゾル塗液中の水分量及び／又は有機溶媒量、有機溶媒の沸点によっても異なるが、例えば、５０～１５０℃とすることができ、６０～１２０℃であってもよい。乾燥温度を５０℃以上とすることにより、ゲル化をより短時間で行うことができ、１５０℃以下とすることにより、樹脂層との接着性を得易くなる。 The drying temperature varies depending on the amount of water and / or the amount of the organic solvent in the sol coating liquid and the boiling point of the organic solvent, but can be, for example, 50 to 150 ° C. or 60 to 120 ° C. By setting the drying temperature to 50 ° C. or higher, gelation can be performed in a shorter time, and by setting the drying temperature to 150 ° C. or lower, it becomes easy to obtain adhesiveness with the resin layer.
　乾燥時間は、乾燥温度によって異なるが、例えば、０．２～１０分とすることができ、０．５～８分であってもよい。乾燥時間を０．２分以上とすることにより、エアロゲル層が形成し易くなり、１０分以下とすることにより、樹脂層との接着性を得易くなる。上記乾燥条件は、予め簡単な実験により適宜設定することができる。 The drying time varies depending on the drying temperature, but can be, for example, 0.2 to 10 minutes, or 0.5 to 8 minutes. By setting the drying time to 0.2 minutes or more, an airgel layer can be easily formed, and by setting the drying time to 10 minutes or less, it becomes easy to obtain adhesiveness with the resin layer. The drying conditions can be set as appropriate by simple experiments in advance.
　また、エアロゲル層の基材側と反対の面には、セパレーターを更に積層することができる。セパレーターを積層することにより、エアロゲル積層体をロール状に巻き取った際の、上記エアロゲル面の基材の裏面への転写を防止することができる。塗工工程において、セパレーターを積層する場合、例えば、ゾル塗液を塗布した後に積層してもよく、ゾル塗液からなる塗膜を乾燥した後に積層してもよい。セパレーターとしては、例えば、ポリオレフィン、ポリエステル、ポリカーボネート、ポリイミド等の樹脂からなる樹脂フィルム、銅箔、アルミニウム箔等の金属箔及び離型紙を挙げることができる。これらの中でも、ゾル塗液を塗布した後にセパレーターを積層する場合は、エアロゲル層の含水率を高く保てる観点から、樹脂フィルムを用いることができる。なお、セパレーターには、マット処理、コロナ処理等の離型処理を施してもよい。 Further, a separator can be further laminated on the surface of the airgel layer opposite to the base material side. By laminating the separator, it is possible to prevent transfer of the airgel surface to the back surface of the base material when the airgel laminate is wound into a roll. In the coating step, when the separator is laminated, for example, the separator may be laminated after the sol coating liquid is applied, or may be laminated after the coating film made of the sol coating liquid is dried. Examples of the separator include resin films made of resins such as polyolefin, polyester, polycarbonate, and polyimide, metal foils such as copper foil and aluminum foil, and release paper. Among these, when laminating the separator after applying the sol coating liquid, a resin film can be used from the viewpoint of keeping the water content of the airgel layer high. The separator may be subjected to a release treatment such as a mat treatment or a corona treatment.
（熟成工程）
　熟成工程は、上記塗工工程により形成されたエアロゲル層を、加熱にて熟成させる工程である。本工程において、エアロゲル層の樹脂層に対する接着性の低下を抑制する観点から、エアロゲル層の含水率が１０質量％以上となるように熟成させるとよく、５０質量％以上となるように熟成させるとよりよい。熟成方法としては、上記範囲を満足すれば特に制限されないが、例えば、エアロゲル積層体を、密閉雰囲気で熟成する方法、及び、加熱による含水率の低下を抑制できる恒湿恒温槽等を用いて熟成する方法が挙げられる。 (Aging process)
The aging step is a step of aging the airgel layer formed by the coating step by heating. In this step, from the viewpoint of suppressing a decrease in the adhesion of the airgel layer to the resin layer, it is preferable that the airgel layer is aged so that the water content is 10% by mass or more, and is aged so as to be 50% by mass or more. Better. The aging method is not particularly limited as long as the above range is satisfied. For example, the aging is performed using a method of aging the airgel laminate in a sealed atmosphere, a thermo-hygrostat that can suppress a decrease in moisture content due to heating, and the like. The method of doing is mentioned.
　熟成温度は、例えば、４０～９０℃とすることができ、５０～８０℃であってもよい。熟成温度を４０℃以上とすることにより、熟成時間を短縮できる。熟成温度を９０℃以下とすることにより、含水率の低下を抑制できる。 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.
　熟成時間は、例えば、１～４８時間とすることができ、３～２４時間であってもよい。熟成時間を１時間以上とすることにより、優れた断熱性を得ることができ、４８時間以下にすることにより、樹脂層との高い接着性を得ることができる。 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, excellent heat insulating properties can be obtained, and by setting it to 48 hours or shorter, high adhesiveness with the resin layer can be obtained.
（洗浄及び溶媒置換工程）
　洗浄及び溶媒置換工程は、上記熟成工程により得られたエアロゲル積層体を洗浄する工程（洗浄工程）と、後述する乾燥工程に適した溶媒に置換する工程（溶媒置換工程）を有する工程である。洗浄及び溶媒置換手法は特に制限はされない。洗浄及び溶媒置換工程は、エアロゲル積層体を洗浄する工程を行わず、溶媒置換工程のみを行う形態でも実施可能であるが、エアロゲル層中の未反応物、副生成物等の不純物を低減し、より純度の高いエアロゲル積層体の製造を可能にする観点からは、熟成後のエアロゲル層を洗浄してもよい。 (Washing and solvent replacement process)
The washing and solvent replacement step is a step having a step of washing the airgel laminate 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 method is not particularly limited. The cleaning and solvent replacement step can be carried out in a form in which only the solvent replacement step is performed without performing the step of cleaning the airgel laminate, but reduces impurities such as unreacted substances and by-products in the airgel layer, From the viewpoint of enabling the production of an airgel laminate with higher purity, the airgel layer after aging may be washed.
　洗浄工程では、上記熟成工程で得られたエアロゲル積層体に対し、水又は有機溶媒を用いて、エアロゲル層を繰り返し洗浄してもよい。 In the washing step, the airgel layer may be repeatedly washed with water or an organic solvent with respect to the airgel laminate obtained in the aging step.
　有機溶媒としては、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、アセトン、メチルエチルケトン、１，２－ジメトキシエタン、アセトニトリル、ヘキサン、トルエン、ジエチルエーテル、クロロホルム、酢酸エチル、テトラヒドロフラン、塩化メチレン、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、酢酸、ギ酸等の各種の有機溶媒を使用することができる。上記の有機溶媒は単独で又は２種類以上を混合して用いてもよい。 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 said organic solvent individually or in mixture of 2 or more types.
　後述する溶媒置換工程では、乾燥によるエアロゲル層の収縮を抑制するため、低表面張力の溶媒を用いることができる。しかし、低表面張力の溶媒は、一般的に水との相互溶解度が極めて低い。そのため、溶媒置換工程において低表面張力の溶媒を用いる場合、洗浄工程で用いる有機溶媒は、水及び低表面張力の溶媒の双方に対して高い相互溶解性を有する親水性有機溶媒であることが好ましい。なお、洗浄工程において用いられる親水性有機溶媒は、溶媒置換工程のための予備置換の役割を果たすことができる。このことから、上記の有機溶媒の中でも、メタノール、エタノール、２－プロパノール、アセトン、メチルエチルケトン等の親水性有機溶媒を用いることができ、さらに経済性の点から、メタノール、エタノール又はメチルエチルケトンを用いてもよい。 In the solvent replacement step described later, a low surface tension solvent can be used to suppress shrinkage of the airgel layer due to drying. However, low surface tension solvents generally have very low mutual solubility with water. Therefore, when using a low surface tension solvent in the solvent replacement step, the organic solvent used in the washing step is preferably a hydrophilic organic solvent having high mutual solubility in both water and a low surface tension solvent. . Note that 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, and methyl ethyl ketone can be used. Further, from the viewpoint of economy, methanol, ethanol, or methyl ethyl ketone can be used. Good.
　洗浄工程に使用される水又は有機溶媒の量としては、エアロゲル層中の溶媒を十分に置換し、洗浄できる量とすることができ、エアロゲル層の容量に対して３～１０倍の量の溶媒を用いることができる。洗浄は、洗浄後のエアロゲル層中の含水率が１０質量％以下となるまで繰り返すことができる。 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, and 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.
　洗浄工程における温度は、洗浄に用いる溶媒の沸点以下の温度とすることができ、例えば、メタノールを用いる場合は、３０～６０℃程度とすることができる。 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. For example, when methanol is used, the temperature can be about 30 to 60 ° C.
　溶媒置換工程では、後述する乾燥工程におけるエアロゲル層の収縮を抑制するため、洗浄したエアロゲル層に含まれる溶媒を所定の置換用溶媒に置き換える。この際、加温することにより置換効率を向上させることができる。置換用溶媒としては、具体的には、乾燥工程において、乾燥に用いられる溶媒の臨界点未満の温度にて、大気圧下で乾燥する場合は、後述の低表面張力の溶媒が挙げられる。一方、超臨界乾燥をする場合は、置換用溶媒として、例えば、エタノール、メタノール、２－プロパノール、ジクロロジフルオロメタン又は二酸化炭素を単独で用いてもよく、これらを２種類以上混合した溶媒を用いてもよい。 In the solvent replacement step, the solvent contained in the washed airgel layer is replaced with a predetermined replacement solvent in order to suppress shrinkage of the airgel layer in the drying step described later. At this time, 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. On the other hand, when performing supercritical drying, for example, ethanol, methanol, 2-propanol, dichlorodifluoromethane, or carbon dioxide may be used alone as a substitution solvent, and a solvent in which two or more of these are mixed is used. Also good.
　低表面張力の溶媒としては、例えば、２０℃における表面張力が３０ｍＮ／ｍ以下の溶媒が挙げられる。当該表面張力は、２５ｍＮ／ｍ以下であってもよく、２０ｍＮ／ｍ以下であってもよい。低表面張力の溶媒としては、例えば、ペンタン（１５．５）、ヘキサン（１８．４）、ヘプタン（２０．２）、オクタン（２１．７）、２－メチルペンタン（１７．４）、３－メチルペンタン（１８．１）、２－メチルヘキサン（１９．３）、シクロペンタン（２２．６）、シクロヘキサン（２５．２）、１－ペンテン（１６．０）等の脂肪族炭化水素類；ベンゼン（２８．９）、トルエン（２８．５）、ｍ－キシレン（２８．７）、ｐ－キシレン（２８．３）等の芳香族炭化水素類；ジクロロメタン（２７．９）、クロロホルム（２７．２）、四塩化炭素（２６．９）、１－クロロプロパン（２１．８）、２－クロロプロパン（１８．１）等のハロゲン化炭化水素類；エチルエーテル（１７．１）、プロピルエーテル（２０．５）、イソプロピルエーテル（１７．７）、ブチルエチルエーテル（２０．８）、１，２－ジメトキシエタン（２４．６）等のエーテル類；アセトン（２３．３）、メチルエチルケトン（２４．６）、メチルプロピルケトン（２５．１）、ジエチルケトン（２５．３）等のケトン類；酢酸メチル（２４．８）、酢酸エチル（２３．８）、酢酸プロピル（２４．３）、酢酸イソプロピル（２１．２）、酢酸イソブチル（２３．７）、エチルブチレート（２４．６）等のエステル類が挙げられる。かっこ内は２０℃での表面張力を示し、単位は［ｍＮ／ｍ］である。これらの中で、脂肪族炭化水素類（ヘキサン、ヘプタン等）は低表面張力でありかつ作業環境性に優れている。また、これらの中でも、アセトン、メチルエチルケトン、１，２－ジメトキシエタン等の親水性有機溶媒を用いることで、上記洗浄工程の有機溶媒と兼用することができる。なお、これらの中でも、さらに後述する乾燥工程における乾燥が容易な点で、常圧での沸点が１００℃以下の溶媒を用いてもよい。上記の溶媒は単独で又は２種類以上を混合して用いてもよい。 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), 2-chloropropane (18.1) and other halogenated hydrocarbons; ethyl ether (17.1), propyl ether (20.5) ), Isop Ethers such as pyrether (17.7), butyl ethyl ether (20.8), 1,2-dimethoxyethane (24.6); acetone (23.3), methyl ethyl ketone (24.6), methyl propyl ketone (25.1), ketones such as diethyl ketone (25.3); methyl acetate (24.8), ethyl acetate (23.8), propyl acetate (24.3), isopropyl acetate (21.2), Examples include esters such as isobutyl acetate (23.7) and ethyl butyrate (24.6). The parenthesis indicates the surface tension at 20 ° C., and the unit is [mN / m]. Among these, aliphatic hydrocarbons (hexane, heptane, etc.) have a low surface tension and an excellent working environment. Among these, by using 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. Among these, a solvent having a boiling point of 100 ° C. or less at normal pressure 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.
　溶媒置換工程に使用される溶媒の量としては、洗浄後のエアロゲル層中の溶媒を十分に置換できる量とすることができ、エアロゲル層の容量に対して３～１０倍の量の溶媒を用いることができる。 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.
　溶媒置換工程における温度は、置換に用いる溶媒の沸点以下の温度とすることができ、例えば、ヘプタンを用いる場合は、３０～６０℃程度とすることができる。 The temperature in the solvent substitution step can be set to a temperature not higher than the boiling point of the solvent used for substitution. For example, when heptane is used, it can be about 30 to 60 ° C.
　なお、本実施形態においては、ゾルがシリカ粒子を含有している場合は、上述のとおり溶媒置換工程は必ずしも必須ではない。推察されるメカニズムとしては次のとおりである。本実施形態においてはシリカ粒子が三次元網目状のエアロゲル骨格の支持体として機能することにより、当該骨格が支持され、乾燥工程におけるゲルの収縮が抑制される。そのため、洗浄に用いた溶媒を置換せずに、ゲルをそのまま乾燥工程に移すことができると考えられる。このように、本実施形態において、ゾルがシリカ粒子を含有している場合は、洗浄及び溶媒置換工程～乾燥工程の簡略化が可能である。 In the present embodiment, when the sol contains silica particles, the solvent replacement step is not necessarily essential as described above. The inferred mechanism is as follows. In the present embodiment, the silica particles function as a support for 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 transferred to the drying step without replacing the solvent used for washing. Thus, in the present embodiment, when the sol contains silica particles, the washing and solvent replacement process to the drying process can be simplified.
　また、塗工工程にてセパレーターを積層している場合は、エアロゲル層の洗浄及び溶媒置換の効率を向上させる観点から、洗浄工程前にセパレーターを抜き取り、溶媒置換工程後に再度セパレーターを積層してもよい。 Moreover, when laminating the separator in the coating process, from the viewpoint of improving the efficiency of washing the airgel layer and replacing the solvent, the separator may be extracted before the washing process and laminated again after the solvent replacing process. Good.
（乾燥工程）
　乾燥工程では、上記のとおり洗浄及び（必要に応じ）溶媒置換したエアロゲル層を乾燥させる。これにより、最終的なエアロゲル積層体を得ることができる。 (Drying process)
In the drying step, the airgel layer that has been washed and solvent-substituted (if necessary) is dried as described above. Thereby, the final airgel laminated body can be obtained.
　乾燥の手法としては特に制限されず、公知の常圧乾燥、超臨界乾燥又は凍結乾燥を用いることができる。これらの中で、低密度のエアロゲル層を製造し易い観点から、常圧乾燥又は超臨界乾燥を用いることができる。また、低コストで生産可能な観点からは常圧乾燥を用いることができる。なお、本実施形態において、常圧とは０．１ＭＰａ（大気圧）を意味する。 The drying method is not particularly limited, and known atmospheric pressure drying, supercritical drying, or freeze drying can be used. Among these, atmospheric drying or supercritical drying can be used from the viewpoint of easy production of a low-density airgel layer. Further, atmospheric drying can be used from the viewpoint of enabling production at low cost. In the present embodiment, the normal pressure means 0.1 MPa (atmospheric pressure).
　本実施形態のエアロゲル積層体は、洗浄及び（必要に応じ）溶媒置換したエアロゲル層を、乾燥に用いられる溶媒の臨界点未満の温度にて、大気圧下で乾燥することにより得ることができる。乾燥温度は、置換された溶媒（溶媒置換を行わない場合は洗浄に用いられた溶媒）の種類又は基材の耐熱性により異なるが、６０～１８０℃とすることができ、９０～１５０℃であってもよい。乾燥時間は、エアロゲル層の容量及び乾燥温度により異なるが、２～４８時間とすることができる。なお、本実施形態において、生産性を阻害しない範囲内において圧力をかけて乾燥を早めることもできる。 The airgel laminate of this embodiment can be obtained by drying an airgel layer that has been washed and (if necessary) solvent-substituted 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 substrate, but can be 60 to 180 ° C., and is 90 to 150 ° C. There may be. 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.
　また、本実施形態のエアロゲル積層体は、常圧乾燥における乾燥効率を向上させる観点から、乾燥工程の前にプレ乾燥を行ってもよい。プレ乾燥方法としては特に制限されない。プレ乾燥温度は、６０～１８０℃とすることができ、９０～１５０℃であってもよい。また、プレ乾燥時間は、１～３０分とすることができる。なお、このようなプレ乾燥により得られたエアロゲル積層体は、更に乾燥工程にて乾燥することができる。 In addition, the airgel laminate of the present embodiment may be pre-dried before the drying step from the viewpoint of improving the drying efficiency in atmospheric drying. The pre-drying method is not particularly limited. 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. In addition, the airgel laminated body obtained by such predrying can be further dried in a drying process.
　洗浄及び溶媒置換工程にてセパレーターを積層している場合は、乾燥効率と搬送効率の観点から、プレ乾燥前に抜き取り、プレ乾燥後に再度セパレーターを積層することができる。また、洗浄及び溶媒置換工程～乾燥工程まで連続で行う場合は、洗浄工程前にセパレーターを抜き取り、プレ乾燥後に再度セパレーターを積層することができる。 When the separators are laminated in the washing and 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. When the washing and solvent replacement step to the drying step are performed continuously, the separator can be extracted before the washing step and laminated again after the pre-drying.
　本実施形態のエアロゲル積層体は、また、洗浄及び（必要に応じ）溶媒置換したエアロゲル積層体を、超臨界乾燥することによっても得ることができる。超臨界乾燥は、公知の手法にて行うことができる。超臨界乾燥する方法としては、例えば、エアロゲル層に含まれる溶媒の臨界点以上の温度及び圧力にて溶媒を除去する方法が挙げられる。あるいは、超臨界乾燥する方法としては、エアロゲル層を、液化二酸化炭素中に、例えば、２０～２５℃、５～２０ＭＰａ程度の条件で浸漬することで、エアロゲル層に含まれる溶媒の全部又は一部を当該溶媒より臨界点の低い二酸化炭素に置換した後、二酸化炭素を単独で、又は二酸化炭素及び溶媒の混合物を除去する方法が挙げられる。 The airgel laminate of this embodiment can also be obtained by supercritical drying of an airgel laminate that has been washed and (if necessary) solvent-substituted. 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. Alternatively, as a method of supercritical drying, the airgel layer is immersed in liquefied carbon dioxide under conditions of, for example, about 20 to 25 ° C. and about 5 to 20 MPa, so that all or part of the solvent contained in the airgel layer is used. And carbon dioxide having a lower critical point than that of the solvent, and then removing carbon dioxide alone or a mixture of carbon dioxide and the solvent.
［断熱材］
　本実施形態の断熱材は、これまで説明したエアロゲル積層体の少なくとも一つを備えるものであり、高断熱性と優れた柔軟性とを有している。なお、上記エアロゲル積層体の製造方法により得られるエアロゲル積層体をそのまま（必要に応じ所定の形状に加工し）断熱材とすることができる。断熱材は、該エアロゲル積層体が複数層積層されたものであってもよい。 [Insulation]
The heat insulating material of the present embodiment includes at least one of the airgel laminates described so far, and has high heat insulating properties and excellent flexibility. In addition, the airgel laminated body obtained by the manufacturing method of the said airgel laminated body can be made into a heat insulating material as it is (processed into a predetermined shape as needed). The heat insulating material may be a laminate in which a plurality of the airgel laminates are laminated.
　本実施形態のエアロゲル積層体は、厚み方向にエアロゲル層と、樹脂層と、基材とが積層されてなる構造を、少なくとも一つ有するものである。従来では取扱い性が困難であったエアロゲルの薄膜化が可能であるため、本実施形態のエアロゲル積層体は、優れた断熱性と柔軟性を有する断熱材として用いることができ、断熱材の薄型化が可能である。 The airgel laminate of this embodiment has at least one structure in which an airgel layer, a resin layer, and a base material are laminated in the thickness direction. The airgel laminate of the present embodiment can be used as a heat insulating material having excellent heat insulating properties and flexibility because it is possible to reduce the thickness of the airgel, which has been difficult to handle in the past, and the heat insulating material is made thinner. Is possible.
　このような利点から、本実施形態のエアロゲル積層体は、極低温分野（超伝導、極低温容器等）、宇宙分野、建築分野、自動車分野、家電製品、半導体分野、産業用設備等における断熱材としての用途等に適用できる。また、本実施形態のエアロゲル積層体は、断熱材としての用途の他に、撥水シート、吸音シート、静振シート、触媒担持シート等として利用することができる。 Because of such advantages, the airgel laminate of the present embodiment is a heat insulating material in the cryogenic field (superconducting, cryogenic container, etc.), the space field, the building field, the automobile field, the home appliances, the semiconductor field, and industrial equipment. It can be applied to the use as. Moreover, the airgel laminated body of this embodiment can be utilized as a water-repellent sheet, a sound-absorbing sheet, a static vibration sheet, a catalyst carrying sheet, etc. besides the use as a heat insulating material.
　次に、下記の実施例により本発明を更に詳しく説明するが、これらの実施例はいかなる意味においても制限するものではない。 Next, the present invention will be described in more detail with reference to the following examples, but these examples are not intended to limit the present invention in any way.
［樹脂層形成用塗液の作製］
（塗液１）
　ポリオール化合物である「ヒタロイド３２０４ＥＢ－１」（日立化成株式会社製、水酸基価３０ＫＯＨｍｇ／ｇ、粘度４０３０ｍＰａ・ｓ、重量平均分子量４７０００）と、ポリイソシアネート化合物である「デュラネートＥ４０５－８０Ｔ」（旭化成株式会社製、ＮＣＯ含有率７質量％、粘度２５２Ｐａ・ｓ）と、トルエンとを、ＮＣＯ／ＯＨ当量比が０．５：１、固形分が１．５質量％になるように配合し、２分間攪拌して塗液１を作製した。 [Preparation of coating solution for resin layer formation]
(Coating liquid 1)
“Hitaroid 3204EB-1” (Hitachi Chemical Co., Ltd., hydroxyl value 30 KOH mg / g, viscosity 4030 mPa · s, weight average molecular weight 47000), and polyisocyanate compound “Duranate E405-80T” (Asahi Kasei Corporation) NCO content 7 mass%, viscosity 252 Pa · s) and toluene are mixed so that the NCO / OH equivalent ratio is 0.5: 1 and the solid content is 1.5 mass%, and stirred for 2 minutes. Thus, a coating liquid 1 was produced.
（塗液２）
　ＮＣＯ／ＯＨ当量比を１：１に変更した以外は、塗液１の作製と同様にして塗液２を作製した。 (Coating liquid 2)
A coating liquid 2 was prepared in the same manner as in the preparation of the coating liquid 1 except that the NCO / OH equivalent ratio was changed to 1: 1.
（塗液３）
　ＮＣＯ／ＯＨ当量比を２：１に変更した以外は、塗液１の作製と同様にして塗液３を作製した。 (Coating liquid 3)
A coating liquid 3 was prepared in the same manner as the coating liquid 1 except that the NCO / OH equivalent ratio was changed to 2: 1.
（塗液４）
　ＮＣＯ／ＯＨ当量比を３：１に変更した以外は、塗液１の作製と同様にして塗液４を作製した。 (Coating solution 4)
A coating solution 4 was prepared in the same manner as the coating solution 1 except that the NCO / OH equivalent ratio was changed to 3: 1.
（塗液５）
　ＮＣＯ／ＯＨ当量比を９：１に変更した以外は、塗液１の作製と同様にして塗液５を作製した。 (Coating fluid 5)
A coating solution 5 was prepared in the same manner as the coating solution 1 except that the NCO / OH equivalent ratio was changed to 9: 1.
（塗液６）
　ＮＣＯ／ＯＨ当量比を１０：１に変更した以外は、塗液１の作製と同様にして塗液６を作製した。 (Coating liquid 6)
A coating liquid 6 was prepared in the same manner as in the preparation of the coating liquid 1 except that the NCO / OH equivalent ratio was changed to 10: 1.
（塗液７）
　エポキシ樹脂である「ｊＥＲ－８１１」（三菱化学株式会社製）と、硬化剤である「トリエチレンテトラミン」（和光純薬工業株式会社製）と、トルエンとを、エポキシ基／アミノ基当量比が１：１、固形分が１．５質量％になるように配合し、２分間攪拌して塗液７を作製した。 (Coating fluid 7)
Epoxy resin “jER-811” (manufactured by Mitsubishi Chemical Corporation), curing agent “triethylenetetramine” (manufactured by Wako Pure Chemical Industries, Ltd.), and toluene have an epoxy group / amino group equivalent ratio. The mixture was blended so as to have a solid content of 1.5% by mass and stirred for 2 minutes to prepare a coating liquid 7.
（塗液８）
　エポキシ樹脂である「ｊＥＲ－８１１」と、ポリイソシアネート化合物である「デュラネートＥ４０５－８０Ｔ」と、トルエンとを、エポキシ基／イソシアネート基が当量比１：１、固形分が１．５質量％になるように配合し、２分間攪拌して塗液８を作製した。 (Coating fluid 8)
The epoxy resin “jER-811”, the polyisocyanate compound “Duranate E405-80T”, and toluene have an epoxy group / isocyanate group equivalent ratio of 1: 1 and a solid content of 1.5 mass%. Then, the mixture was stirred for 2 minutes to prepare a coating liquid 8.
（塗液９）
　ポリイソシアネート化合物である「デュラネートＥ４０５－８０Ｔ」と、トルエンとを、固形分が１．５質量％になるように配合し、２分間攪拌して塗液９を作製した。 (Coating fluid 9)
A polyisocyanate compound “Duranate E405-80T” and toluene were blended so that the solid content was 1.5% by mass, and stirred for 2 minutes to prepare a coating solution 9.
（塗液１０）
　ポリオール化合物である「ヒタロイド３２０４ＥＢ－１」と、イソシアネート系シランカップリング剤である３－イソシアネートプロピルトリエトキシシラン「ＫＢＥ－９００７」（信越化学工業株式会社製）と、トルエンとを、水酸基／イソシアネート基当量比が１：１、固形分が１．５質量％になるように配合し、２分間攪拌して塗液１０を作製した。 (Coating solution 10)
A polyol compound “Hitaroid 3204EB-1”, an isocyanate-based silane coupling agent “3-isocyanatopropyltriethoxysilane” KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.), and toluene are combined with a hydroxyl group / isocyanate group. The mixture was blended so that the equivalent ratio was 1: 1 and the solid content was 1.5% by mass, and stirred for 2 minutes to prepare a coating solution 10.
（塗液１１）
　ポリオール化合物である「ヒタロイド３２０４ＥＢ－１」と、トルエンとを、固形分が１．５質量％になるように配合し、２分間攪拌して塗液１１を作製した。 (Coating solution 11)
A polyol compound “Hitaroid 3204EB-1” and toluene were blended so that the solid content was 1.5 mass%, and stirred for 2 minutes to prepare a coating solution 11.
（塗液１２）
　エポキシ樹脂である「ｊＥＲ－８１１」と、ポリオール化合物である「ヒタロイド３２０４ＥＢ－１」と、トルエンとを、エポキシ基／水酸基当量比が１：１、固形分が１．５質量％になるように配合し、２分間攪拌して塗液１２を作製した。 (Coating fluid 12)
Epoxy resin “jER-811”, polyol compound “Hitaroid 3204EB-1”, and toluene so that the epoxy group / hydroxyl group equivalent ratio is 1: 1 and the solid content is 1.5 mass%. The mixture was mixed and stirred for 2 minutes to prepare a coating solution 12.
（塗液１３）
　ポリオール化合物である「ヒタロイド３２０４ＥＢ－１」と、エポキシ系シランカップリング剤である３－グリシドキシプロピルトリメトキシシラン「ＫＢＭ－４０３」（信越化学工業株式会社製））と、トルエンとを、水酸基／エポキシ基当量比が１：１、固形分が１．５質量％になるように配合し、２分間攪拌して塗液１３を作製した。 (Coating fluid 13)
A polyol compound “Hitaroid 3204EB-1”, an epoxy silane coupling agent 3-glycidoxypropyltrimethoxysilane “KBM-403” (manufactured by Shin-Etsu Chemical Co., Ltd.)) and toluene / Epoxy group equivalent ratio was 1: 1 and the solid content was 1.5 mass%, and the mixture was stirred for 2 minutes to prepare a coating solution 13.
［エアロゲル層形成用ゾル塗液の作製］
（ポリシロキサン化合物Ａの合成）
　撹拌機、温度計及びジムロート冷却管を備えた１Ｌの３つ口フラスコにて、ヒドロキシ末端ジメチルポリシロキサン「ＸＣ９６－７２３」（モメンティブ社製、製品名）を１００．０質量部、メチルトリメトキシシランを１８１．３質量部及びｔ－ブチルアミンを０．５０質量部混合し、３０℃で５時間反応させた。その後、この反応液を、１．３ｋＰａの減圧下、１４０℃で２時間加熱し、揮発分を除去することで、上記一般式（Ｂ）で表される両末端２官能アルコキシ変性ポリシロキサン化合物（ポリシロキサン化合物Ａ）を得た。 [Preparation of sol coating solution for airgel layer formation]
(Synthesis of polysiloxane compound A)
In a 1 L three-necked flask equipped with a stirrer, thermometer and Dimroth condenser, 100.0 parts by mass of hydroxy-terminated dimethylpolysiloxane “XC96-723” (product name), methyltrimethoxysilane Was mixed with 181.3 parts by mass and 0.50 part by mass of t-butylamine and reacted at 30 ° C. for 5 hours. Thereafter, the reaction solution was heated at 140 ° C. for 2 hours under a reduced pressure of 1.3 kPa to remove volatile components, whereby a bifunctional alkoxy-modified polysiloxane compound represented by the above general formula (B) ( Polysiloxane compound A) was obtained.
（ゾル塗液）
　シリカ粒子含有原料としてＰＬ－２Ｌ（扶桑化学工業株式会社製、製品名、平均一次粒子径：２０ｎｍ、固形分：２０質量％）を１００．０質量部、水を１００．０質量部、酸触媒として酢酸を０．１０質量部、イオン性界面活性剤としてヘキサデシルトリメチルアンモニウムブロミド（和光純薬工業株式会社製、以下「ＣＴＡＢ」と略記）を２０．０質量部及び熱加水分解性化合物として尿素を１２０．０質量部混合し、これにシリコン化合物としてメチルシトリメトキシラン（信越化学工業株式会社製、以下「ＭＴＭＳ」と略記）を６０．０質量部及びジメトキシジメチルシラン（東京化成工業株式会社製、以下「ＤＭＤＭＳ」と略記）を２０．０質量部、並びにポリシロキサン化合物としてポリシロキサン化合物Ａを２０．０質量部加え、２５℃で１時間反応させた。その後、８０℃で１５分間ゾルゲル反応させてゾル塗液を得た。 (Sol coating liquid)
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 100.0 parts by mass, acid catalyst 0.10 parts by mass of acetic acid, 20.0 parts by mass of hexadecyltrimethylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “CTAB”) as an ionic surfactant, and urea as a thermohydrolyzable compound 120.0 parts by mass, 60.0 parts by mass of methylcitrimethoxylane (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “MTMS”) and dimethoxydimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a silicon compound. Hereinafter abbreviated as “DMDMS”) and 20.0 parts by mass of polysiloxane compound A as a polysiloxane compound. It was allowed to react for 1 hour at 25 ° C.. Thereafter, a sol-gel reaction was performed at 80 ° C. for 15 minutes to obtain a sol coating solution.
（実施例１）
　塗液１を、基材である（縦）１５００ｍｍ×（横）１０００ｍｍ×（厚）１２μｍの両面アルミニウム蒸着ＰＥＴフィルム（日立ＡＩＣ株式会社製、製品名：ＶＭ－ＰＥＴ）に、乾燥後の厚みが１μｍとなるようにフィルムアプリケーター（テスター産業株式会社製、製品名：ＰＩ－１２１０）を用いて塗布し、１２０℃で１分乾燥して、基材上に樹脂層を形成した。 Example 1
The coating liquid 1 is dried on a double-sided aluminum vapor-deposited PET film (product name: VM-PET, manufactured by Hitachi AIC Co., Ltd.) having a base of (length) 1500 mm × (width) 1000 mm × (thickness) 12 μm. The film was applied using a film applicator (product name: PI-1210, manufactured by Tester Sangyo Co., Ltd.) so as to have a thickness of 1 μm, and dried at 120 ° C. for 1 minute to form a resin layer on the substrate.
　次いで、上記ゾル塗液を、上記基材の樹脂層上にゲル化後の厚みが４０μｍとなるようにフィルムアプリケーター（テスター産業株式会社製、製品名：ＰＩ－１２１０）を用いて塗布し、９０℃で１．５分間乾燥して、ゲル状のエアロゲル層を有するエアロゲル積層体を得た。その後、得られたエアロゲル積層体を密閉容器に移し、６０℃で３時間熟成した。 Next, the sol coating solution is applied onto the resin layer of the base material using a film applicator (product name: PI-1210, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after gelation is 40 μm. It dried at 1.5 degreeC for 1.5 minute (s), and the airgel laminated body which has a gel-like airgel layer was obtained. Thereafter, the obtained airgel laminate was transferred to a sealed container and aged at 60 ° C. for 3 hours.
　次いで、熟成したエアロゲル積層体を水２０００ｍＬで２分間洗浄した後、メタノール２０００ｍＬに２分間浸漬して洗浄を行った。この洗浄操作を、新しいメタノールに交換しながら２回行って、洗浄及び溶媒置換されたエアロゲル積層体を１２０℃で１時間乾燥することで、上記一般式（６）及び（７）で表される構造を有するエアロゲル積層体１を得た。 Next, the aged airgel laminate was washed with 2000 mL of water for 2 minutes and then immersed in 2000 mL of methanol for 2 minutes for cleaning. This washing operation is performed twice while exchanging with new methanol, and the washed and solvent-substituted airgel laminate is dried at 120 ° C. for 1 hour, and is represented by the above general formulas (6) and (7). The airgel laminated body 1 which has a structure was obtained.
（実施例２）
　塗液２を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体２を得た。 (Example 2)
The airgel laminated body 2 was obtained like Example 1 except having formed the resin layer using the coating liquid 2. FIG.
（実施例３）
　塗液３を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体３を得た。 (Example 3)
The airgel laminated body 3 was obtained like Example 1 except having formed the resin layer using the coating liquid 3. FIG.
（実施例４）
　塗液４を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体４を得た。 Example 4
The airgel laminated body 4 was obtained like Example 1 except having formed the resin layer using the coating liquid 4. FIG.
（実施例５）
　塗液５を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体５を得た。 (Example 5)
The airgel laminated body 5 was obtained like Example 1 except having formed the resin layer using the coating liquid 5. FIG.
（実施例６）
　塗液６を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体６を得た。 (Example 6)
The airgel laminated body 6 was obtained like Example 1 except having formed the resin layer using the coating liquid 6. FIG.
（実施例７）
　塗液７を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体７を得た。 (Example 7)
The airgel laminated body 7 was obtained like Example 1 except having formed the resin layer using the coating liquid 7. FIG.
（実施例８）
　塗液８を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体８を得た。 (Example 8)
The airgel laminated body 8 was obtained like Example 1 except having formed the resin layer using the coating liquid 8. FIG.
（実施例９）
　塗液９を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体９を得た。 Example 9
The airgel laminated body 9 was obtained like Example 1 except having formed the resin layer using the coating liquid 9. FIG.
（実施例１０）
　塗液１０を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体１０を得た。 (Example 10)
The airgel laminated body 10 was obtained like Example 1 except having formed the resin layer using the coating liquid 10. FIG.
（比較例１）
　上記ゾル塗液を、基材である（縦）１５００ｍｍ×（横）１０００ｍｍ×（厚）１２μｍの両面アルミニウム蒸着ＰＥＴフィルムに直接塗布してエアロゲル層を形成した以外は、実施例１と同様にして、エアロゲル積層体１１を得た。 (Comparative Example 1)
The sol coating solution was directly applied to a double-sided aluminum vapor-deposited PET film (vertical) 1500 mm × (horizontal) 1000 mm × (thickness) 12 μm, which was the base material, in the same manner as in Example 1 except that an airgel layer was formed. The airgel laminated body 11 was obtained.
（比較例２）
　基材である（縦）１５００ｍｍ×（横）１０００ｍｍ×（厚）１２μｍの両面アルミニウム蒸着ＰＥＴフィルム（日立ＡＩＣ株式会社製、製品名：ＶＭ－ＰＥＴ）と、断熱層となる（縦）１５００ｍｍ×（横）１０００ｍｍ×（厚）４２μｍ（ＩＰＣスペック：１０７８）のＥガラスクロス（日東紡績株式会社製）とを積層することで、積層断熱材１を得た。 (Comparative Example 2)
Double-sided aluminum vapor-deposited PET film (product name: VM-PET, manufactured by Hitachi AIC Co., Ltd.) of 1500 mm × (width) 1000 mm × (thickness) 12 μm, which is a base material, and 1500 mm × (length), which becomes a heat insulating layer Laminate insulation 1 was obtained by laminating E glass cloth (manufactured by Nitto Boseki Co., Ltd.) of 1000 mm × (thickness) 42 μm (IPC spec: 1078).
（比較例３）
　塗液１１を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体１２を得た。 (Comparative Example 3)
The airgel laminated body 12 was obtained like Example 1 except having formed the resin layer using the coating liquid 11. FIG.
（比較例４）
　塗液１２を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体１３を得た。 (Comparative Example 4)
The airgel laminated body 13 was obtained like Example 1 except having formed the resin layer using the coating liquid 12. FIG.
（比較例５）
　塗液１３を用いて樹脂層を形成した以外は、実施例１と同様にして、エアロゲル積層体１４を得た。 (Comparative Example 5)
The airgel laminated body 14 was obtained like Example 1 except having formed the resin layer using the coating liquid 13. FIG.
［接着性の評価］
　樹脂層又は基材への接着性の評価は、テープ剥離試験により行った。具体的には、エアロゲル積層体のエアロゲル層に、セロハンテープ（積水化学工業株式会社製、製品名：セキスイセロテープＣ４０ＳＨ０２）を指で上から押し付けるようにして密着させた後、引き剥がし速度１０ｍｍ／秒でセロハンテープを９０度方向に引き剥がした。次いで、テープ剥離試験前後の質量減少量を算出し、接触面積で除することで単位面積当たりの脱落量を求めた。 [Evaluation of adhesion]
Evaluation of adhesiveness to the resin layer or the substrate was performed by a tape peeling test. Specifically, the cellophane tape (manufactured by Sekisui Chemical Co., Ltd., product name: Sekisei Cello Tape C40SH02) was brought into close contact with the airgel layer of the airgel laminate by pressing with a finger from above, and then the peeling speed was 10 mm / second. Then, the cellophane tape was peeled off at 90 degrees. Next, the amount of mass decrease before and after the tape peel test was calculated, and the amount of dropout per unit area was determined by dividing by the contact area.
［剥がれの評価］
　樹脂層又は基材からのエアロゲル層の剥がれの評価は、上述の熟成工程にてエアロゲル積層体を１０ｃｍ×１０ｃｍに切り出し、上述した水及びメタノールによる洗浄操作を行い、洗浄及び溶媒置換されたエアロゲル積層体を得た後に、目視にて確認した。エアロゲル層に、剥がれがある場合は「有り」、剥がれが無い場合は「無し」とした。 [Evaluation of peeling]
Evaluation of peeling of the airgel layer from the resin layer or the base material is performed by cutting the airgel laminate into 10 cm × 10 cm in the above-described aging step, performing the above-described washing operation with water and methanol, and washing and solvent-substituted airgel lamination After obtaining the body, it was confirmed visually. When the airgel layer peeled off, it was judged as “Yes”, and when there was no peeling, it was judged as “No”.
［耐腐食性の評価］
　エアロゲル積層体の耐腐食性は、以下の試験にて評価を行った。
　まず、評価用に、基材を片面アルミニウム蒸着ＰＥＴフィルム（日立ＡＩＣ株式会社製、製品名：ＶＭ－ＰＥＴ）に変更した以外は各実施例及び比較例と同様にして、各実施例及び比較例に相当するエアロゲル積層体をそれぞれ作製した。なお、樹脂層及びエアロゲル層はアルミニウム層側に形成した（比較例１相当の条件の場合は、エアロゲル層をアルミニウム層上に直接形成）。次いで、得られたそれぞれのエアロゲル積層体を５０ｍｍ×５０ｍｍに裁断した試験片を、密閉容器に入ったｐＨ９に調整した尿素水溶液に含浸し、容器を６０℃で１時間加熱した後、試験片を取り出した。そして、尿素水溶液に含浸後の試験片において、ＰＥＴフィルムのエアロゲル層側のアルミニウム層の白化又は溶解の有無を、ＰＥＴフィルム側から目視にて確認した。確認した試験片において、一部でもエアロゲル層側のアルミニウム層が白化又は溶解している場合は、エアロゲル積層体の腐食「有り」（耐腐食性が無い）とし、エアロゲル層側のアルミニウム層の白化又は溶解が無い場合には、エアロゲル積層体の腐食「無し」（耐腐食性が有る）とした。
　なお、ＰＥＴフィルムが透明であるため、ＰＥＴフィルム側からの目視で確認しているが、エアロゲル層を取り除いて基材のエアロゲル層側の表面を目視で確認してもよい。 [Evaluation of corrosion resistance]
The corrosion resistance of the airgel laminate was evaluated by the following test.
First, for evaluation, each example and comparative example was the same as each example and comparative example except that the base material was changed to a single-sided aluminum vapor-deposited PET film (manufactured by Hitachi AIC Co., Ltd., product name: VM-PET). The airgel laminated body corresponding to each was produced. The resin layer and the airgel layer were formed on the aluminum layer side (in the case of the conditions corresponding to Comparative Example 1, the airgel layer was directly formed on the aluminum layer). Next, a test piece obtained by cutting each obtained airgel laminate into 50 mm × 50 mm was impregnated with an aqueous urea solution adjusted to pH 9 contained in a sealed container, and the container was heated at 60 ° C. for 1 hour. I took it out. And in the test piece after impregnation with urea aqueous solution, the presence or absence of whitening or dissolution of the aluminum layer on the airgel layer side of the PET film was visually confirmed from the PET film side. If the aluminum layer on the airgel layer side is whitened or dissolved in any of the confirmed test pieces, the corrosion of the airgel laminate is “present” (no corrosion resistance), and the aluminum layer on the airgel layer side is whitened. Alternatively, when there was no dissolution, the airgel laminate was “no corrosion” (has corrosion resistance).
In addition, since the PET film is transparent, it is visually confirmed from the PET film side, but the airgel layer may be removed to visually confirm the surface of the substrate on the airgel layer side.
［断熱性性能の評価］
　実施例及び比較例で得られたエアロゲル積層体並びに比較例で得られた積層断熱材について、以下の条件に従い、測定又は評価をした。 [Evaluation of thermal insulation performance]
About the airgel laminated body obtained by the Example and the comparative example, and the laminated heat insulating material obtained by the comparative example, it measured or evaluated according to the following conditions.
（１）断熱性評価用の液体窒素容器の準備
　エアロゲル積層体及び積層断熱材を、（縦）６０６ｍｍ×（横）３４３ｍｍのシートＡ、（縦）６１２ｍｍ×（横）３６２ｍｍのシートＢ、（縦）６１８ｍｍ×（横）３８０ｍｍのシートＣ、（直径）１０５ｍｍのシートＤ、（直径）１１２ｍｍのシートＥ、（直径）１１８ｍｍのシートＦのサイズにそれぞれ加工した。 (1) Preparation of Liquid Nitrogen Container for Thermal Insulation Evaluation The airgel laminate and the laminated heat insulating material are (vertical) 606 mm × (horizontal) 343 mm sheet A, (vertical) 612 mm × (horizontal) 362 mm sheet B, (vertical ) 618 mm × (width) 380 mm sheet C, (diameter) 105 mm sheet D, (diameter) 112 mm sheet E, (diameter) 118 mm sheet F.
　次に、液体窒素容器外周用シートとして、エアロゲル層又は断熱層を介して隣接する基材同士が直接接触しないようにシートＡを１０層積層したシートＡ１０、シートＢを１０層積層したシートＢ１０、シートＣを１０層積層したシートＣ１０をそれぞれ作製した。同様にして、液体窒素容器上下用シートとして、シートＤを１０層積層したシートＤ１０、シートＥを１０層積層したシートＥ１０及びシートＦを１０層積層したシートＦ１０をそれぞれ作製した。 Next, as a liquid nitrogen container outer peripheral sheet, a sheet A10 in which 10 layers of sheet A are laminated so that adjacent substrates do not directly contact each other via an airgel layer or a heat insulating layer, a sheet B10 in which 10 layers of sheet B are laminated, Each of the sheets C10 obtained by laminating 10 layers of the sheets C was prepared. Similarly, as a liquid nitrogen container upper and lower sheet, a sheet D10 obtained by laminating 10 layers of sheet D, a sheet E10 obtained by laminating 10 layers of sheet E, and a sheet F10 obtained by laminating 10 layers of sheet F were produced.
　高さ６００ｍｍ、直径１００ｍｍの液体窒素容器を準備し、その側面にシートＡ１０を配置し、液体窒素容器の上下にシートＤ１０をそれぞれ配置し、液体窒素容器に巻きつけた。次に、シートＡ１０の上にシートＢ１０を配置し、シートＤ１０の上にシートＥ１０を配置し、さらに、シートＢ１０の上にシートＣ１０を配置し、シートＤ１０の上にシートＦ１０を配置することで、エアロゲル積層体又は積層断熱材が３０層積層された断熱性評価用の液体窒素容器を得た。なお、側面のシートと上下のシートの合わせ部は、アルミニウムテープで貼り付けた。 A liquid nitrogen container having a height of 600 mm and a diameter of 100 mm was prepared, a sheet A10 was disposed on the side surface, sheets D10 were disposed above and below the liquid nitrogen container, and the liquid nitrogen container was wound around the liquid nitrogen container. Next, the sheet B10 is disposed on the sheet A10, the sheet E10 is disposed on the sheet D10, the sheet C10 is disposed on the sheet B10, and the sheet F10 is disposed on the sheet D10. Thus, a liquid nitrogen container for heat insulation evaluation in which 30 layers of airgel laminate or laminated heat insulating material were laminated was obtained. In addition, the joining part of the sheet | seat of a side surface and the upper and lower sheets was affixed with the aluminum tape.
　図４は、断熱材１０を液体窒素容器１２に巻き付けた断熱性評価用の液体窒素容器の構造を模式的に表した断面図である。３０層のエアロゲル積層体又は積層断熱材からなる断熱材１０は、注入口１１を有する液体窒素容器１２に外周を覆うように積層されている。 FIG. 4 is a cross-sectional view schematically showing the structure of a liquid nitrogen container for heat insulation evaluation in which the heat insulating material 10 is wound around the liquid nitrogen container 12. A heat insulating material 10 made of a 30-layer airgel laminate or a laminated heat insulating material is laminated on a liquid nitrogen container 12 having an inlet 11 so as to cover the outer periphery.
（２）断熱材の厚みの測定
　液体窒素容器１２の外周に設けられた断熱材１０の総厚みＤ３０（ｍｍ）を、次式より算出した。
　　Ｄ３０＝Ｄｃ／２―５０．０
式中、Ｄｃ（ｍｍ）は、エアロゲル積層シート又は積層断熱材を３０層巻き付けた後の液体窒素容器の直径を示す。 (2) Measurement of thickness of heat insulating material The total thickness D 30 (mm) of the heat insulating material 10 provided on the outer periphery of the liquid nitrogen container 12 was calculated from the following equation.
D 30 = D c /2−50.0
In the formula, D c (mm) indicates the diameter of the liquid nitrogen container after 30 layers of the airgel laminated sheet or the laminated heat insulating material are wound.
（３）断熱性能（熱流束）
　断熱性評価用の液体窒素容器を用いて、断熱性能を測定した。図５に、断熱性能試験装置の概略図を示す。まず、断熱材１０が巻き付けられた液体窒素容器１２を２８３Ｋに設定した恒温槽１４に入れ、真空容器１６内に設置した。次に、真空容器１６内の真空排気をターボ分子ポンプ２０で行い、真空容器１６内部の真空圧力をピラニー真空計２２及びイオン真空計２４で計測した。ターボ分子ポンプ２０を運転して、ピラニー真空計２２が４×１０－１Ｐａ以下の真空圧力を示したのを確認後、イオン真空計２４で真空圧力を計測し、真空容器１６の圧力が１×１０－２Ｐａ以下になるまで、７日間真空排気を行った。その後、真空容器１６内に設置された液体窒素容器１２に液体窒素を注液後、首配管１８の温度と蒸発した窒素ガス流量がほぼ一定値であり、定常状態であることを確認したときの、断熱材１０を通過する熱流束ｑを算出した。 (3) Thermal insulation performance (heat flux)
Thermal insulation performance was measured using a liquid nitrogen container for thermal insulation evaluation. In FIG. 5, the schematic of a heat insulation performance test apparatus is shown. First, the liquid nitrogen container 12 around which the heat insulating material 10 was wound was placed in a thermostatic chamber 14 set to 283K and installed in the vacuum container 16. Next, evacuation in the vacuum vessel 16 was performed with the turbo molecular pump 20, and the vacuum pressure inside the vacuum vessel 16 was measured with the Pirani vacuum gauge 22 and the ion vacuum gauge 24. After operating the turbo molecular pump 20 and confirming that the Pirani vacuum gauge 22 showed a vacuum pressure of 4 × 10 −1 Pa or less, the vacuum pressure was measured with the ion vacuum gauge 24 and the pressure in the vacuum vessel 16 was 1 Vacuum evacuation was performed for 7 days until the pressure reached 10 −2 Pa or less. After that, after injecting liquid nitrogen into the liquid nitrogen container 12 installed in the vacuum container 16, the temperature of the neck pipe 18 and the flow rate of the evaporated nitrogen gas are substantially constant values, and it is confirmed that they are in a steady state. The heat flux q passing through the heat insulating material 10 was calculated.
　液体窒素の蒸発ガス質量流量ｍ（ｋｇ／ｓ）は、次式（Ｉ）より求めた。
Figure JPOXMLDOC01-appb-M000012
 式（Ｉ）中、ρｇ，Ｔは室温のガス密度（ｋｇ／ｍ３）、Ｖｇ，Ｔは室温のガス流量（ｍ３／ｓ）を示し、湿式流量計２６の出力と湿式流量計２６内部の温度により計測される値である。 The evaporative gas mass flow rate m (kg / s) of liquid nitrogen was obtained from the following formula (I).
Figure JPOXMLDOC01-appb-M000012
 In the formula (I), ρ g, T represents a room temperature gas density (kg / m 3 ), V g, T represents a room temperature gas flow rate (m 3 / s), and the output of the wet flow meter 26 and the wet flow meter 26 is a value measured by the internal temperature.
　次に、断熱材１０を通して入る放射熱量Ｑｒ（Ｗ）、及び、フランジ１７と液体窒素容器１２を接続している首配管１８からの伝導熱Ｑｃ（Ｗ）の和は、次式（ＩＩ）より求めた。
Figure JPOXMLDOC01-appb-M000013
 式（ＩＩ）中、Ｌは液体窒素の蒸発潜熱（Ｊ／ｋｇ）、ρｇ，Ｓは大気圧飽和温度における窒素ガス密度（ｋｇ／ｍ３）、ρｌ，Ｓは液体窒素密度（ｋｇ／ｍ３）を示す。 Next, the sum of the amount of radiant heat Q r (W) entering through the heat insulating material 10 and the conduction heat Q c (W) from the neck pipe 18 connecting the flange 17 and the liquid nitrogen container 12 is expressed by the following formula (II) )
Figure JPOXMLDOC01-appb-M000013
 In the formula (II), L is the latent heat of vaporization of liquid nitrogen (J / kg), ρg , S is the nitrogen gas density (kg / m 3 ) at the atmospheric pressure saturation temperature, ρl , S is the liquid nitrogen density (kg / m 3 ).
　また、Ｑｃは、次式（ＩＩＩ）より求めた。
Figure JPOXMLDOC01-appb-M000014
 式（ＩＩＩ）中、（　）内は首配管１８の伝導熱を示し、Ａｓ（ｍ２）は、首配管１８の断面積、Ｌｃ（ｍ）は、首配管１８の長さを示し、Ｔｈ（Ｋ）は、高温温度、Ｔｌ（Ｋ）は、低温温度を示し、λｓｕｓ（Ｗ／（ｍ・Ｋ））は、ステンレスの熱伝導率を示す。首配管１８の伝導熱は、蒸発ガスの熱伝達によって首配管１８の表面から熱を奪うので効率φの係数が関わる。 Moreover, Qc was calculated | required from following Formula (III).
Figure JPOXMLDOC01-appb-M000014
 In the formula (III), () indicates the conduction heat of the neck pipe 18, A s (m 2 ) indicates the cross-sectional area of the neck pipe 18, and L c (m) indicates the length of the neck pipe 18, T h (K) represents a high temperature, T l (K) represents a low temperature, and λ sus (W / (m · K)) represents the thermal conductivity of stainless steel. Since the conduction heat of the neck pipe 18 takes heat from the surface of the neck pipe 18 by the heat transfer of the evaporating gas, the coefficient of efficiency φ is involved.
　効率φは、次式（ＩＶ）より求めた。
Figure JPOXMLDOC01-appb-M000015
 式（ＩＶ）中、Ｃｐ（Ｊ／（ｋｇ・Ｋ））は、比熱を示す。なお、本評価において、上記Ａｓの値は、０．２４３×１０－４（ｍ２）であり、上記Ｌの値は、１９９０００（Ｊ／ｋｇ）である。 The efficiency φ was obtained from the following formula (IV).
Figure JPOXMLDOC01-appb-M000015
 In formula (IV), C p (J / (kg · K)) represents specific heat. In the present evaluation, the value of the A s, a 0.243 × 10 -4 (m 2) , the value of the L is 199000 (J / kg).
　エアロゲル積層体及び積層断熱材を通過する熱流束ｑ（Ｗ／ｍ２）は、次式（Ｖ）より求めた。熱流束の測定は、３回行い、その平均値を本評価の熱流束とした。
Figure JPOXMLDOC01-appb-M000016
 式（Ｖ）中、Ａｒ（ｍ２）は、液体窒素容器の表面積を示し、その値は、０．２０４１（ｍ２）である。 The heat flux q (W / m 2 ) passing through the airgel laminate and the laminated heat insulating material was obtained from the following formula (V). The heat flux was measured three times, and the average value was used as the heat flux of this evaluation.
Figure JPOXMLDOC01-appb-M000016
 In formula (V), A r (m 2 ) represents the surface area of the liquid nitrogen container, and the value is 0.2041 (m 2 ).
　各実施例及び比較例で得られたエアロゲル積層体又は積層断熱材の層構成、エアロゲル層の脱落量、耐腐食性及び断熱性の評価結果を表１に示す。 Table 1 shows the layer structure of the airgel laminate or laminated heat insulating material obtained in each Example and Comparative Example, the amount of airgel layer falling off, the evaluation results of corrosion resistance and heat insulation.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
　表１から、実施例で作製したエアロゲル積層体は、エアロゲル層と基材とが樹脂層を介して一体化されているため、エアロゲル層の基材からの脱落を低減でき、かつ、断熱材の薄型化が可能となることが確認できる。表１から基材に樹脂層を設けることで、基材の腐食を抑制でき、かつ、エアロゲル層の基材からの脱落を低減できることを確認できる。また、樹脂層を設けたエアロゲル積層体においても、高い断熱性能を有することを確認できる。 From Table 1, since the airgel laminated body produced in the Example has the airgel layer and the base material integrated through the resin layer, it is possible to reduce the dropping of the airgel layer from the base material, and It can be confirmed that the thickness can be reduced. It can be confirmed from Table 1 that by providing the resin layer on the base material, corrosion of the base material can be suppressed and dropping of the airgel layer from the base material can be reduced. Moreover, it can confirm that it has high heat insulation performance also in the airgel laminated body which provided the resin layer.
　１…エアロゲル層、２…樹脂層、３…基材、１０…断熱材、１１…注入口、１２…液体窒素容器、１４…恒温槽、１６…真空容器、１７…フランジ、１８…首配管、２０…ターボ分子ポンプ、２２…ピラニー真空計、２４…イオン真空計、２６…湿式流量計、Ｌ…外接長方形、Ｐ…シリカ粒子。 DESCRIPTION OF SYMBOLS 1 ... Airgel layer, 2 ... Resin layer, 3 ... Base material, 10 ... Heat insulating material, 11 ... Inlet, 12 ... Liquid nitrogen container, 14 ... Constant temperature bath, 16 ... Vacuum vessel, 17 ... Flange, 18 ... Neck piping, 20 ... turbo molecular pump, 22 ... Pirani vacuum gauge, 24 ... ion vacuum gauge, 26 ... wet flow meter, L ... circumscribed rectangle, P ... silica particles.

Claims (12)

  1. 　基材と、該基材上に設けられた樹脂層と、該樹脂層上に設けられたエアロゲル層と、を備え、
    　前記樹脂層が、構成原子として窒素を有する樹脂を含有する、エアロゲル積層体。     A base material, a resin layer provided on the base material, and an airgel layer provided on the resin layer,
    The airgel laminated body in which the said resin layer contains resin which has nitrogen as a constituent atom.
  2. 　前記樹脂が、ウレタン結合、アミド結合、ウレア結合、イミド結合、スルホンアミド結合、チオウレタン結合、チオアミド結合、チオウレア結合及びチオイミド結合からなる群より選択される少なくとも１種の結合を有する、請求項１に記載のエアロゲル積層体。 The resin has at least one bond selected from the group consisting of a urethane bond, an amide bond, a urea bond, an imide bond, a sulfonamide bond, a thiourethane bond, a thioamide bond, a thiourea bond, and a thioimide bond. The airgel laminate according to 1.
  3. 　前記樹脂が、ウレタン結合を有する、請求項１又は２に記載のエアロゲル積層体。 The airgel laminate according to claim 1 or 2, wherein the resin has a urethane bond.
  4. 　前記ウレタン結合を有する樹脂が、水酸基を有する化合物とイソシアネート基を有する化合物とから合成される樹脂である、請求項２又は３に記載のエアロゲル積層体。 The airgel laminate according to claim 2 or 3, wherein the resin having a urethane bond is a resin synthesized from a compound having a hydroxyl group and a compound having an isocyanate group.
  5. 　前記イソシアネート基と前記水酸基との当量比が０．１：１～１０：１である、請求項４に記載のエアロゲル積層体。 The airgel laminate according to claim 4, wherein the equivalent ratio of the isocyanate group to the hydroxyl group is 0.1: 1 to 10: 1.
  6. 　前記水酸基を有する化合物がポリオール化合物である、請求項４又は５に記載のエアロゲル積層体。 The airgel laminate according to claim 4 or 5, wherein the compound having a hydroxyl group is a polyol compound.
  7. 　前記イソシアネート基を有する化合物がポリイソシアネート化合物である、請求項４～６のいずれか一項に記載のエアロゲル積層体。 The airgel laminate according to any one of claims 4 to 6, wherein the compound having an isocyanate group is a polyisocyanate compound.
  8. 　前記エアロゲル層が、ポリシロキサン由来の構造を有するエアロゲルを含有する層である、請求項１～７のいずれか一項に記載のエアロゲル積層体。 The airgel laminate according to any one of claims 1 to 7, wherein the airgel layer is a layer containing an airgel having a structure derived from polysiloxane.
  9. 　前記エアロゲル層が、シリカ粒子が複合化された層である、請求項１～８のいずれか一項に記載のエアロゲル積層体。 The airgel laminate according to any one of claims 1 to 8, wherein the airgel layer is a layer in which silica particles are combined.
  10. 　前記シリカ粒子の平均一次粒子径が、１～５００ｎｍである、請求項９に記載のエアロゲル積層体。 The airgel laminate according to claim 9, wherein the silica particles have an average primary particle diameter of 1 to 500 nm.
  11. 　前記基材が、熱線反射機能又は熱線吸収機能を有する、請求項１～１０のいずれか一項に記載のエアロゲル積層体。 The airgel laminate according to any one of claims 1 to 10, wherein the base material has a heat ray reflection function or a heat ray absorption function.
  12. 　請求項１～１１のいずれか一項に記載のエアロゲル積層体を備える、断熱材。 A heat insulating material comprising the airgel laminate according to any one of claims 1 to 11.
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