WO2017038769A1 - Stratifié d'aérogel et matériau thermo-isolant - Google Patents

Stratifié d'aérogel et matériau thermo-isolant 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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PCT/JP2016/075206
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English (en)
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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Priority to JP2017538019A priority Critical patent/JP6834961B2/ja
Publication of WO2017038769A1 publication Critical patent/WO2017038769A1/fr

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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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Thermal Insulation (AREA)
  • Silicon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un stratifié d'aérogel, qui comporte un matériau de base, une couche de résine disposée sur le matériau de base, et une couche d'aérogel disposée sur la couche de résine, la couche de résine contenant une résine comportant de l'azote en tant qu'atome constitutif dans la structure moléculaire.
PCT/JP2016/075206 2015-09-02 2016-08-29 Stratifié d'aérogel et matériau thermo-isolant WO2017038769A1 (fr)

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WO2019171543A1 (fr) * 2018-03-08 2019-09-12 日立化成株式会社 Méthode de production d'aérogel, aérogel, bloc d'aérogel et composé polysiloxane
WO2022007797A1 (fr) * 2020-07-07 2022-01-13 巩义市泛锐熠辉复合材料有限公司 Panneau sandwich composite et son procédé de préparation
CN115124758A (zh) * 2022-08-17 2022-09-30 大连海洋大学 一种气凝胶复合材料的制备工艺

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US6068882A (en) * 1995-11-09 2000-05-30 Aspen Systems, Inc. Flexible aerogel superinsulation and its manufacture
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JP2010221605A (ja) * 2009-03-25 2010-10-07 Achilles Corp ナノ構造を有する多孔質体の微粉末を層状に配列させた複合体
WO2014132652A1 (fr) * 2013-02-28 2014-09-04 パナソニック株式会社 Structure d'isolation thermique utilisant un aérogel
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US6068882A (en) * 1995-11-09 2000-05-30 Aspen Systems, Inc. Flexible aerogel superinsulation and its manufacture
JP2006504543A (ja) * 2002-01-29 2006-02-09 キャボット　コーポレイション 耐熱性エーロゾル絶縁複合材料およびその製造方法、エーロゾルバインダー組成物およびその製造方法
JP2008156502A (ja) * 2006-12-25 2008-07-10 Hitachi Kasei Polymer Co Ltd 二液硬化型接着剤
JP2010221605A (ja) * 2009-03-25 2010-10-07 Achilles Corp ナノ構造を有する多孔質体の微粉末を層状に配列させた複合体
WO2014132652A1 (fr) * 2013-02-28 2014-09-04 パナソニック株式会社 Structure d'isolation thermique utilisant un aérogel
JP5761472B1 (ja) * 2013-09-18 2015-08-12 Dic株式会社 バリア性積層体及びこれを用いた包装材

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019171543A1 (fr) * 2018-03-08 2019-09-12 日立化成株式会社 Méthode de production d'aérogel, aérogel, bloc d'aérogel et composé polysiloxane
JPWO2019171543A1 (ja) * 2018-03-08 2021-02-25 昭和電工マテリアルズ株式会社 エアロゲルの製造方法、エアロゲル、エアロゲルブロック及びポリシロキサン化合物
JP7078104B2 (ja) 2018-03-08 2022-05-31 昭和電工マテリアルズ株式会社 エアロゲルの製造方法、エアロゲル、エアロゲルブロック及びポリシロキサン化合物
WO2022007797A1 (fr) * 2020-07-07 2022-01-13 巩义市泛锐熠辉复合材料有限公司 Panneau sandwich composite et son procédé de préparation
CN115124758A (zh) * 2022-08-17 2022-09-30 大连海洋大学 一种气凝胶复合材料的制备工艺

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TW201714747A (zh) 2017-05-01
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