TW201938379A - Method for producing aerogel composite, aerogel composite and insulated body including a coating liquid infiltration step and a solvent removing step - Google Patents

Abstract

The present invention relates to a method for producing an aerogel composite, comprising: a step of infiltrating a coating liquid containing a coating material and a solvent into the aerogel; and a step of removing the solvent from the infiltrated coating liquid. The coating material includes a thermosetting resin that can form a good coating, and the aerogel composite has excellent toughness.

Description

氣凝膠複合體的製造方法、氣凝膠複合體及被絕熱體Method for producing aerogel composite, aerogel composite and thermal insulator

本發明是有關於一種氣凝膠複合體的製造方法、氣凝膠複合體及被絕熱體。The present invention relates to a method for producing an aerogel composite, an aerogel composite, and a thermal insulator.

作為低導熱性的材料，已知有氣凝膠。氣凝膠藉由具有微細多孔質的結構，於內部抑制以空氣為代表的氣體的移動，從而達成低導熱。作為有效利用氣凝膠的此種特性的絕熱構件，正在開發一種具備片狀的氣凝膠的絕熱片（例如，下述專利文獻1）。 [現有技術文獻] [專利文獻]As a material with low thermal conductivity, aerogel is known. The aerogel has a microporous structure, which suppresses the movement of gas represented by air inside, thereby achieving low thermal conductivity. As a heat-insulating member that effectively utilizes such characteristics of an aerogel, a heat-insulating sheet having a sheet-shaped aerogel is being developed (for example, the following Patent Document 1). [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2010-167685號公報[Patent Document 1] Japanese Patent Laid-Open No. 2010-167685

[發明所欲解決之課題] 且說，氣凝膠亦可謂奈米尺寸的微粒子的集合體，於使用時存在因自氣凝膠表面脫離的微粒子而揚塵的問題（掉粉）。另外，存在氣凝膠的骨架自身容易變脆、欠缺充分的耐久力的問題。該些問題結果導致作為絕熱構件的功能的下降。一般而言，絕熱構件需要長期將對象物絕熱，因此現狀為氣凝膠作為絕熱構件而難以長期發揮充分的性能。[Problems to be Solved by the Invention] In addition, an aerogel can also be referred to as an aggregate of nano-sized fine particles, and there is a problem (dusting off) of dust due to fine particles detached from the aerogel surface during use. In addition, there are problems that the aerogel skeleton itself becomes brittle and lacks sufficient durability. As a result of these problems, the function as a heat insulating member is reduced. Generally, a heat-insulating member needs to insulate an object for a long period of time. Therefore, it is difficult for an aerogel to perform sufficient performance for a long time as a heat-insulating member.

於專利文獻1中，主要為了應對揚塵的問題，利用經樹脂塗佈的玻璃纖維製棉布等夾入氣凝膠片並製成積層體來供於絕熱用途。In Patent Document 1, in order to cope with the problem of flying dust, an aerogel sheet is sandwiched with a resin-coated glass fiber cotton cloth or the like to form a laminated body for thermal insulation.

然而，於專利文獻1的技術中，即便可抑制自氣凝膠表面朝外部的揚塵，亦無法抑制揚塵自身。另外，氣凝膠片自身的脆性未得到改善，因此有氣凝膠的骨架自身因來自外部的衝擊而遭到破壞之虞。如此，於現有技術中會容易失去氣凝膠的優異的低導熱性，因此要求氣凝膠的強韌化。However, in the technique of Patent Document 1, even if the dust from the aerogel surface to the outside can be suppressed, the dust itself cannot be suppressed. In addition, since the brittleness of the aerogel sheet itself has not been improved, the skeleton of the aerogel itself may be damaged due to an impact from the outside. In this way, the aerogel's excellent low thermal conductivity is easily lost in the prior art, and thus the aerogel is required to be toughened.

本發明是鑒於所述情況而成者，其目的在於提供一種具有優異的韌性的氣凝膠複合體的製造方法、氣凝膠複合體及被絕熱體。 [解決課題之手段]The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing an aerogel composite having excellent toughness, an aerogel composite, and a heat-insulated body. [Means for solving problems]

本發明提供一種氣凝膠複合體的製造方法，其具備：使包含塗佈材料及溶媒的塗佈液滲透至氣凝膠中的步驟；以及自滲透的塗佈液中去除溶媒的步驟。利用此種方法而獲得的氣凝膠複合體具有優異的韌性。The present invention provides a method for producing an aerogel composite, comprising: a step of permeating a coating liquid containing a coating material and a solvent into the aerogel; and a step of removing the solvent from the permeated coating liquid. The aerogel composite obtained by this method has excellent toughness.

本發明中，塗佈液的25℃下的黏度可為35 mPa·s以下。藉此，可形成良好的塗層。In the present invention, the viscosity at 25 ° C of the coating liquid may be 35 mPa · s or less. Thereby, a good coating can be formed.

本發明中，塗佈材料可包含熱硬化性樹脂。藉此，可形成良好的塗層。In the present invention, the coating material may include a thermosetting resin. Thereby, a good coating can be formed.

本發明中，氣凝膠可為作為如下溶膠的縮合物的濕潤凝膠的乾燥物，所述溶膠含有選自由具有水解性官能基或縮合性官能基的矽化合物、及具有水解性官能基的矽化合物的水解產物所組成的群組中的至少一種。此種氣凝膠具有絕熱性及柔軟性，並且施工性亦優異。In the present invention, the aerogel may be a dried product of a wet gel as a condensate of a sol containing a silicon compound selected from the group consisting of a silicon compound having a hydrolyzable functional group or a condensable functional group, and a hydrolysable functional group. At least one of the group consisting of a hydrolyzate of a silicon compound. This aerogel has thermal insulation and flexibility, and is excellent in workability.

另外，本發明提供一種氣凝膠複合體，其具有：氣凝膠；以及塗層，被覆形成氣凝膠內部的空隙的氣凝膠粒子的表面的至少一部分。此種氣凝膠複合體具有優異的韌性。In addition, the present invention provides an aerogel composite including: an aerogel; and a coating layer that coats at least a part of a surface of an aerogel particle that forms a void inside the aerogel. This aerogel composite has excellent toughness.

本發明中，氣凝膠複合體的密度可設為0.30 g/cm³ ～1.15 g/cm³ 。藉此，氣凝膠複合體的韌性及絕熱性進一步提高。In the present invention, the density of the aerogel composite may be 0.30 g / cm ³ to 1.15 g / cm ³ . This improves the toughness and thermal insulation of the aerogel composite.

本發明中，氣凝膠複合體的相對於波長700 nm的光的透過率可為15%以下。藉此，氣凝膠複合體的絕熱性進一步提高。In the present invention, the aerogel composite may have a transmittance with respect to light having a wavelength of 700 nm of 15% or less. Thereby, the thermal insulation property of the aerogel composite is further improved.

進而，本發明提供一種被絕熱體，其於絕熱對象物具備所述氣凝膠複合體。由於為使用韌性優異的氣凝膠複合體的被絕熱體，因此難以容易地失去優異的低導熱性。 [發明的效果]Furthermore, this invention provides the to-be-insulated body provided with the said aerogel composite in a heat insulation object. Since it is a thermal insulation body using an aerogel composite excellent in toughness, it is difficult to easily lose excellent low thermal conductivity. [Effect of the invention]

根據本發明，可提供一種具有優異的韌性的氣凝膠複合體的製造方法、氣凝膠複合體及被絕熱體。According to the present invention, a method for producing an aerogel composite having excellent toughness, an aerogel composite, and a heat-insulated body can be provided.

以下，視情況，參照圖式對本揭示的較佳實施形態進行詳細說明。其中，本揭示並不限定於以下的實施形態。Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the drawings as appropriate. However, the present disclosure is not limited to the following embodiments.

＜定義＞ 本說明書中，使用「～」來表示的數值範圍表示包含「～」的前後所記載的數值分別作為最小值及最大值的範圍。本說明書中階段性地記載的數值範圍中，某階段的數值範圍的上限值或下限值亦可置換為其他階段的數值範圍的上限值或下限值。本說明書中記載的數值範圍中，該數值範圍的上限值或下限值亦可置換為實施例中所示的值。所謂「A或B」，只要包含A及B的其中任一者即可，亦可同時包含兩者。本說明書中例示的材料只要無特別說明，則可單獨使用一種或將兩種以上組合使用。本說明書中，於組成物中存在多種相當於各成分的物質的情況下，只要無特別說明，則組成物中的各成分的含量是指組成物中所存在的多種物質的合計量。<Definition> In this specification, a numerical range expressed using "~" means a range including numerical values described before and after "~" as the minimum and maximum values, respectively. Among the numerical ranges described stepwise in this specification, an upper limit value or a lower limit value of a numerical range at a certain stage may be replaced with an upper limit value or a lower limit value of a numerical range at another stage. In the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. The term "A or B" may include any one of A and B, or both. Unless otherwise specified, the materials exemplified in this specification may be used alone or in combination of two or more. In the present specification, when there are a plurality of substances corresponding to the respective components in the composition, the content of each component in the composition refers to the total amount of the plurality of substances present in the composition unless otherwise specified.

＜被絕熱體＞ 本實施形態的被絕熱體中，於絕熱對象物形成氣凝膠複合體。圖1是示意性地表示本實施形態的被絕熱體的剖面圖。如圖1所示，於被絕熱體10中，於絕熱對象物1形成氣凝膠複合體2作為絕熱層。氣凝膠複合體2具有：氣凝膠2a；以及塗層2b，被覆形成氣凝膠2a內部的空隙的氣凝膠粒子的表面的至少一部分。氣凝膠2a具有由氣凝膠粒子構成的三維的微細的網眼狀骨架，於該骨架中存在大量的空隙。即，於氣凝膠複合體2中，於保持該三維網眼狀骨架的狀態下，骨架（由氣凝膠粒子形成的氣凝膠2a）的表面的至少一部分由塗層2b被覆。<Insulated body> In the insulated body of this embodiment, an aerogel composite is formed on an object to be insulated. FIG. 1 is a cross-sectional view schematically showing a thermal insulation body according to this embodiment. As shown in FIG. 1, in the thermal insulation body 10, an aerogel composite 2 is formed on the insulation target 1 as a thermal insulation layer. The aerogel composite 2 includes: an aerogel 2a; and a coating layer 2b that coats at least a part of the surface of the aerogel particles forming a void in the aerogel 2a. The aerogel 2a has a three-dimensional fine mesh-like skeleton composed of aerogel particles, and there are a large number of voids in the skeleton. That is, in the aerogel composite 2, at least a part of the surface of the skeleton (aerogel 2 a formed of aerogel particles) is covered with the coating layer 2 b while the three-dimensional mesh-like skeleton is maintained.

氣凝膠複合體2可設於絕熱對象物1的至少一部分（一部分或整體）。被絕熱體10中絕熱對象物1與氣凝膠複合體2可直接一體地接合，絕熱對象物1與氣凝膠複合體2亦可經由底塗層等其他層進行接合。The aerogel composite 2 may be provided on at least a part (a part or the whole) of the thermal insulation object 1. The thermal insulation object 1 and the aerogel composite 2 in the to-be-insulated body 10 may be directly and integrally bonded, and the thermal insulation object 1 and the aerogel composite 2 may be bonded via other layers such as a primer layer.

被絕熱體10亦可於氣凝膠複合體2上進而具備阻障層（未圖示）。The thermal insulation body 10 may further include a barrier layer (not shown) on the aerogel composite 2.

（絕熱對象物） 作為構成絕熱對象物的材料，可列舉：金屬、陶瓷、玻璃、樹脂、該些的複合材料等。即，絕熱對象物可包含選自由金屬、陶瓷、玻璃及樹脂所組成的群組中的至少一種。作為絕熱對象物的形態，可根據使用的目的或材料而採用塊（block）狀、片狀、粉末狀、球狀、纖維狀等。(Insulation Object) Examples of the material constituting the insulation object include metals, ceramics, glass, resin, and composite materials thereof. That is, the object to be insulated may include at least one selected from the group consisting of metal, ceramic, glass, and resin. As the form of the object to be insulated, a block shape, a sheet shape, a powder shape, a spherical shape, a fibrous shape, or the like can be adopted depending on the purpose or material used.

作為所述金屬，可列舉：金屬的單體、金屬的合金、形成有氧化被膜的金屬等。作為金屬元素，可列舉：鐵、銅、鎳、鋁、鋅、鈦、鉻、鈷、錫、金、銀等。就對後述的溶膠生成步驟中使用的材料的耐腐蝕性優異的觀點而言，作為金屬，可使用鈦、金、銀等單體、形成有氧化被膜的鐵及鋁等。Examples of the metal include a single metal, an alloy of a metal, and a metal on which an oxide film is formed. Examples of the metal element include iron, copper, nickel, aluminum, zinc, titanium, chromium, cobalt, tin, gold, and silver. From the viewpoint of excellent corrosion resistance of a material used in the sol generation step described later, as the metal, a monomer such as titanium, gold, or silver, iron, aluminum having an oxide film formed, or the like can be used.

作為所述陶瓷，可列舉：氧化鋁、二氧化鈦、氧化鋯、氧化鎂等氧化物，氮化矽、氮化鋁等氮化物，碳化矽、碳化硼等碳化物，該些的混合物等。Examples of the ceramics include oxides such as alumina, titania, zirconia, and magnesium oxide, nitrides such as silicon nitride and aluminum nitride, carbides such as silicon carbide and boron carbide, and mixtures thereof.

作為所述玻璃，可列舉：石英玻璃、鈉玻璃、硼矽酸玻璃等。Examples of the glass include quartz glass, soda glass, and borosilicate glass.

作為所述樹脂，可列舉：聚氯乙烯、聚乙烯醇、聚苯乙烯、聚乙烯、聚丙烯、聚縮醛、聚甲基丙烯酸甲酯、聚碳酸酯、聚醯胺、聚胺基甲酸酯等。Examples of the resin include polyvinyl chloride, polyvinyl alcohol, polystyrene, polyethylene, polypropylene, polyacetal, polymethyl methacrylate, polycarbonate, polyamide, and polyurethane. Esters, etc.

藉由使用表面粗糙度大的絕熱對象物、或多孔質結構的絕熱對象物，可獲得良好的錨定效果，因此可進一步提高與氣凝膠複合體的密接性。就此種觀點而言，絕熱對象物1的表面粗糙度Ra可為100 nm以上，亦可為500 nm以上。於絕熱對象物為多孔質結構的情況下，就進一步提高絕熱性的觀點而言，可採用多孔質結構所具有的孔為連通孔的態樣、進而該孔的體積的合計於絕熱對象物的總體積中為50體積%～99體積%的態樣。再者，表面粗糙度Ra可以如下方式進行測定。即，可依據JIS B0601，並使用光學式表面粗糙度計（維易科精密儀器（Veeco Metrogy Group）製造，維克（Wyko）NT9100），對表面的算術平均粗糙度進行測定。By using a heat-insulating object having a large surface roughness or a heat-insulating object having a porous structure, a good anchoring effect can be obtained, and thus the adhesion with the aerogel composite can be further improved. From such a viewpoint, the surface roughness Ra of the insulation object 1 may be 100 nm or more, and may be 500 nm or more. In the case where the insulation object has a porous structure, from the viewpoint of further improving the insulation property, a state in which the pores of the porous structure are connected pores may be adopted, and the total volume of the pores is added to the insulation object. The total volume is in a state of 50% to 99% by volume. The surface roughness Ra can be measured as follows. That is, the arithmetic average roughness of the surface can be measured using an optical surface roughness meter (manufactured by Veeco Metrogy Group, Wyko NT9100) in accordance with JIS B0601.

（氣凝膠複合體） ·氣凝膠的定義 狹義而言，將對濕潤凝膠使用超臨界乾燥法而獲得的乾燥凝膠稱為氣凝膠，將藉由大氣壓下的乾燥而獲得的乾燥凝膠稱為乾凝膠（xerogel），將藉由冷凍乾燥而獲得的乾燥凝膠稱為凍凝膠（cryogel），但本實施形態中，不論濕潤凝膠的該些乾燥方法如何，均將所獲得的低密度的乾燥凝膠稱為「氣凝膠」。即，本實施形態中，所謂「氣凝膠」是指廣義的氣凝膠「由分散相為氣體的微多孔性固體所構成的凝膠（Gel comprised of a microporous solid in which the dispersed phase is a gas）」。一般而言，氣凝膠2a於其內部具有網眼狀的微細結構，且具有2 nm～20 nm左右的氣凝膠粒子（構成氣凝膠的粒子）結合而成的簇結構。於由該簇所形成的骨架間存在小於100 nm的細孔（空隙）。藉此，氣凝膠2a中形成有三維性微細的多孔性的結構。再者，本實施形態中的氣凝膠2a例如是以二氧化矽作為主成分的二氧化矽氣凝膠。作為二氧化矽氣凝膠，可列舉導入有例如有機基（甲基等）或有機鏈的所謂經有機-無機混合化的二氧化矽氣凝膠。(Aerogel complex) · Definition of aerogel In a narrow sense, a dry gel obtained by using a supercritical drying method on a wet gel is referred to as an aerogel, and a dry obtained by drying under atmospheric pressure is referred to as aerogel. The gel is called xerogel, and the dried gel obtained by freeze-drying is called cryogel. However, in this embodiment, regardless of the drying method of the wet gel, The obtained low-density dry gel is called "aerogel". That is, in the present embodiment, the "aerogel" refers to an aerogel in the broad sense "a gel consisting of a microporous solid in which the dispersed phase is a gas). " In general, the aerogel 2a has a mesh-like fine structure inside, and has a cluster structure in which aerogel particles (particles constituting the aerogel) of about 2 nm to 20 nm are combined. There are pores (voids) smaller than 100 nm between the skeletons formed by the clusters. Thereby, the aerogel 2a is formed with a three-dimensionally fine porous structure. The aerogel 2a in this embodiment is, for example, a silica aerogel containing silica as a main component. Examples of the silica aerogel include a so-called organic-inorganic hybrid silica aerogel into which, for example, an organic group (such as a methyl group) or an organic chain is introduced.

·氣凝膠的原料 氣凝膠可將各種矽化合物作為原料而獲得。具體而言，作為氣凝膠，可列舉作為如下溶膠的縮合物的濕潤凝膠的乾燥物，所述溶膠含有選自由具有水解性官能基或縮合性官能基的矽化合物、及具有水解性官能基的矽化合物的水解產物所組成的群組中的至少一種（將自溶膠生成的濕潤凝膠乾燥而獲得者）。再者，所述縮合物可利用藉由具有水解性官能基的矽化合物的水解而獲得的水解產物的縮合反應來獲得，亦可利用具有不為藉由水解而獲得的官能基的縮合性官能基的矽化合物的縮合反應來獲得。矽化合物只要具有水解性官能基及縮合性官能基的至少一者即可，亦可具有水解性官能基及縮合性官能基的兩者。· Aerogel raw materials Aerogels can be obtained from various silicon compounds as raw materials. Specifically, as the aerogel, a dried product of a wet gel as a condensate of a sol containing a silicon compound selected from the group consisting of a hydrolyzable functional group or a condensable functional group and a hydrolyzable function may be mentioned. At least one of the group consisting of a hydrolysate of a basic silicon compound (obtained by drying a wet gel produced from a sol). The condensate may be obtained by a condensation reaction of a hydrolysate obtained by hydrolysis of a silicon compound having a hydrolyzable functional group, or may be used by a condensation function having a functional group not obtained by hydrolysis. Is obtained by a condensation reaction of a silicon compound. The silicon compound may have at least one of a hydrolyzable functional group and a condensable functional group, and may also have both a hydrolyzable functional group and a condensable functional group.

矽化合物可包含具有水解性官能基或縮合性官能基的聚矽氧烷化合物。即，含有所述矽化合物的溶膠可含有選自由具有水解性官能基或縮合性官能基的聚矽氧烷化合物、以及具有水解性官能基的聚矽氧烷化合物的水解產物所組成的群組中的至少一種（以下，視情況稱為「聚矽氧烷化合物群組」）。The silicon compound may include a polysiloxane compound having a hydrolyzable functional group or a condensable functional group. That is, the sol containing the silicon compound may contain a group selected from the group consisting of a polysiloxane compound having a hydrolyzable functional group or a condensable functional group and a hydrolysate of a polysiloxane compound having a hydrolyzable functional group. At least one of them (hereinafter, referred to as the "polysiloxane group" as appropriate).

作為水解性官能基，例如可列舉烷氧基。作為縮合性官能基（與水解性官能基相當的官能基除外），可列舉：羥基、矽烷醇基、羧基、酚性羥基等。羥基亦可包含於羥基烷基等含羥基的基中。再者，具有水解性官能基或縮合性官能基的聚矽氧烷化合物亦可進而具有與水解性官能基及縮合性官能基不同的反應性基（與水解性官能基及縮合性官能基不相當的官能基）。作為反應性基，可列舉：環氧基、巰基、縮水甘油氧基、乙烯基、丙烯醯基、甲基丙烯醯基、胺基等。環氧基亦可包含於縮水甘油氧基等含環氧基的基中。具有該些官能基及反應性基的聚矽氧烷化合物可單獨使用或將兩種以上混合使用。該些官能基及反應性基中，例如，作為提高氣凝膠的柔軟性的基，可列舉：烷氧基、矽烷醇基、羥基烷基等，該些基中，烷氧基及羥基烷基可進一步提高溶膠的相容性。另外，就提高聚矽氧烷化合物的反應性及降低氣凝膠的導熱率的觀點而言，烷氧基及羥基烷基的碳數可設為1～6，就進一步提高氣凝膠的柔軟性的觀點而言，亦可為2～4。Examples of the hydrolyzable functional group include an alkoxy group. Examples of the condensable functional group (excluding a functional group equivalent to a hydrolyzable functional group) include a hydroxyl group, a silanol group, a carboxyl group, and a phenolic hydroxyl group. The hydroxyl group may be contained in a hydroxyl group-containing group such as a hydroxyalkyl group. Furthermore, the polysiloxane compound having a hydrolyzable functional group or a condensable functional group may further have a reactive group different from the hydrolyzable functional group and the condensable functional group. Equivalent functional group). Examples of the reactive group include an epoxy group, a mercapto group, a glycidyloxy group, a vinyl group, an acrylfluorenyl group, a methacrylfluorenyl group, and an amino group. The epoxy group may be contained in an epoxy group-containing group such as a glycidyl group. The polysiloxane compounds having these functional groups and reactive groups can be used alone or in combination of two or more. Among these functional groups and reactive groups, for example, examples of the group that improves the flexibility of the aerogel include alkoxy, silanol, and hydroxyalkyl groups. Among these groups, alkoxy and hydroxyalkyl groups Group can further improve the compatibility of the sol. In addition, from the viewpoint of improving the reactivity of the polysiloxane compound and lowering the thermal conductivity of the aerogel, the carbon number of the alkoxy group and the hydroxyalkyl group can be set to 1 to 6, which can further improve the flexibility of the aerogel. From the viewpoint of sex, it may be 2 to 4.

作為具有羥基烷基的聚矽氧烷化合物，例如可列舉具有下述通式（A）所表示的結構者。 [化1] Examples of the polysiloxane compound having a hydroxyalkyl group include a structure represented by the following general formula (A). [Chemical 1]

通式（A）中，R^1a 表示羥基烷基，R^2a 表示伸烷基，R^3a 及R^4a 分別獨立地表示烷基或芳基，n表示1～50的整數。此處，作為芳基，可列舉苯基、經取代的苯基等。另外，作為經取代的苯基的取代基，可列舉：烷基、乙烯基、巰基、胺基、硝基、氰基等。再者，通式（A）中，兩個R^1a 分別可相同亦可不同，同樣地，兩個R^2a 分別可相同亦可不同。另外，通式（A）中，兩個以上的R^3a 分別可相同亦可不同，同樣地，兩個以上的R^4a 分別可相同亦可不同。In the general formula (A), R ^1a represents a hydroxyalkyl group, R ^2a represents an alkylene group, R ^3a and R ^4a each independently represent an alkyl group or an aryl group, and n represents an integer of 1 to 50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. Furthermore, in the general formula (A), two R ^1a may be the same or different, and similarly, two R ^2a may be the same or different. In the general formula (A), two or more R ^3a may be the same or different, and similarly, two or more R ^4a may be the same or different.

藉由使用作為含有所述結構的聚矽氧烷化合物的溶膠的縮合物的濕潤凝膠，更容易獲得低導熱率且柔軟的氣凝膠。就此種觀點而言，通式（A）中，R^1a 可列舉碳數為1～6的羥基烷基等，作為該羥基烷基，可列舉羥基乙基、羥基丙基等。另外，通式（A）中，R^2a 可列舉碳數為1～6的伸烷基等，作為該伸烷基，可列舉伸乙基、伸丙基等。另外，通式（A）中，R^3a 及R^4a 分別獨立地可列舉碳數為1～6的烷基、苯基等，作為該烷基，可列舉甲基等。另外，通式（A）中，n可設為2～30，亦可為5～20。By using a moist gel as a condensate of a sol containing a polysiloxane compound having the above-mentioned structure, it is easier to obtain a soft aerogel having a low thermal conductivity. From such a viewpoint, in the general formula (A), R ^1a includes a hydroxyalkyl group having 1 to 6 carbon atoms, and examples of the hydroxyalkyl group include a hydroxyethyl group and a hydroxypropyl group. In the general formula (A), R ^2a includes an alkylene group having 1 to 6 carbon atoms, and examples of the alkylene group include an ethylene group and a propyl group. In the general formula (A), R ^3a and R ^4a each independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like, and examples of the alkyl group include a methyl group and the like. In the general formula (A), n may be 2 to 30, or 5 to 20 may be used.

作為具有所述通式（A）所表示的結構的聚矽氧烷化合物，可使用市售品，可列舉：X-22-160AS、KF-6001、KF-6002、KF-6003等化合物（均為信越化學工業股份有限公司製造），XF42-B0970、Fluid OFOH 702-4%等化合物（均為邁圖（Momentive）公司製造）等。As the polysiloxane compound having a structure represented by the general formula (A), a commercially available product can be used, and examples include compounds such as X-22-160AS, KF-6001, KF-6002, and KF-6003 (all (Made by Shin-Etsu Chemical Industry Co., Ltd.), XF42-B0970, Fluid OFOH 702-4% and other compounds (all manufactured by Momentive).

作為具有烷氧基的聚矽氧烷化合物，例如可列舉具有下述通式（B）所表示的結構者。 [化2] Examples of the polysiloxane compound having an alkoxy group include a structure represented by the following general formula (B). [Chemical 2]

通式（B）中，R^1b 表示烷基、烷氧基或芳基，R^2b 及R^3b 分別獨立地表示烷氧基，R^4b 及R^5b 分別獨立地表示烷基或芳基，m表示1～50的整數。此處，作為芳基，可列舉苯基、經取代的苯基等。另外，作為經取代的苯基的取代基，可列舉：烷基、乙烯基、巰基、胺基、硝基、氰基等。再者，通式（B）中，兩個R^1b 分別可相同亦可不同，兩個R^2b 分別可相同亦可不同，同樣地，兩個R^3b 分別可相同亦可不同。另外，通式（B）中，於m為2以上的整數的情況下，兩個以上的R^4b 分別可相同亦可不同，同樣地，兩個以上的R^5b 亦分別可相同亦可不同。In the 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, and m represents An integer from 1 to 50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. Moreover, in the general formula (B), two R ^1b may be the same or different, two R ^2b may be the same or different, and similarly, two R ^3b may be the same or different. In the general formula (B), when m is an integer of 2 or more, two or more R ^4b may be the same or different, and similarly, two or more R ^5b may be the same or different.

藉由使用作為含有所述結構的聚矽氧烷化合物或其水解產物的溶膠的縮合物的濕潤凝膠，更容易獲得低導熱率且柔軟的氣凝膠。就此種觀點而言，通式（B）中，R^1b 可列舉碳數為1～6的烷基、碳數為1～6的烷氧基等，作為該烷基或烷氧基，可列舉：甲基、甲氧基、乙氧基等。另外，通式（B）中，R^2b 及R^3b 分別獨立地可列舉碳數為1～6的烷氧基等，作為該烷氧基，可列舉甲氧基、乙氧基等。另外，通式（B）中，R^4b 及R^5b 分別獨立地可列舉碳數為1～6的烷基、苯基等，作為該烷基，可列舉甲基等。另外，通式（B）中，m可設為2～30，亦可為5～20。By using a moist gel that is a condensate of a sol containing a polysiloxane compound or a hydrolyzed product of the structure, it is easier to obtain a soft aerogel having a low thermal conductivity. From such a viewpoint, in the general formula (B), R ^1b includes an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group or alkoxy group include : Methyl, methoxy, ethoxy, etc. In the general formula (B), R ^2b and R ^3b each independently include an alkoxy group having 1 to 6 carbon atoms, and examples of the alkoxy group include a methoxy group and an ethoxy group. In the general formula (B), each of R ^4b and R ^5b independently includes an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like, and examples of the alkyl group include a methyl group and the like. In the general formula (B), m may be 2 to 30 or 5 to 20.

具有所述通式（B）所表示的結構的聚矽氧烷化合物例如可適宜參照日本專利特開2000-26609號公報、日本專利特開2012-233110號公報等中報告的製造方法而獲得。The polysiloxane compound having the structure represented by the general formula (B) can be obtained by appropriately referring to, for example, the production methods reported in Japanese Patent Laid-Open No. 2000-26609, Japanese Patent Laid-Open No. 2012-233110, and the like.

再者，烷氧基會水解，故具有烷氧基的聚矽氧烷化合物具有於溶膠中作為水解產物而存在的可能性，具有烷氧基的聚矽氧烷化合物與其水解產物亦可混在一起。另外，具有烷氧基的聚矽氧烷化合物中，分子中的烷氧基可全部水解，亦可部分性地水解。In addition, alkoxy groups are hydrolyzed, so a polysiloxane compound having an alkoxy group may exist as a hydrolysate in a sol, and a polysiloxane compound having an alkoxy group and its hydrolysate may also be mixed together. . In addition, in the polysiloxane compound having an alkoxy group, the alkoxy group in the molecule may be entirely hydrolyzed or partially hydrolyzed.

該些具有水解性官能基或縮合性官能基的聚矽氧烷化合物、以及具有水解性官能基的聚矽氧烷化合物的水解產物可單獨使用或將兩種以上混合使用。These polysiloxane compounds having a hydrolyzable functional group or a condensable functional group and the hydrolysates of the polysiloxane compounds having a hydrolyzable functional group may be used alone or as a mixture of two or more.

矽化合物亦可包含聚矽氧烷化合物以外的矽化合物。即，本實施形態的溶膠可含有選自由具有水解性官能基或縮合性官能基的矽化合物（聚矽氧烷化合物除外）、以及具有水解性官能基的矽化合物的水解產物所組成的群組中的至少一種（以下，視情況稱為「矽化合物群組」）。矽化合物中的分子內的矽數可設為1或2。The silicon compound may include a silicon compound other than a polysiloxane compound. That is, the sol according to the present embodiment may contain a group selected from the group consisting of a silicon compound (excluding a polysiloxane compound) having a hydrolyzable functional group or a condensable functional group, and a hydrolysate of a silicon compound having a hydrolyzable functional group. At least one of the following (hereinafter, referred to as the "silicon compound group" as appropriate). The number of silicon in the molecule in the silicon compound can be set to 1 or 2.

具有水解性官能基的矽化合物並無特別限定，例如可列舉烷氧化烷基矽。烷氧化烷基矽中，水解性官能基的數量為3個以下者可進一步提高耐水性。作為此種的烷氧化烷基矽，可列舉：單烷基三烷氧基矽烷、單烷基二烷氧基矽烷、二烷基二烷氧基矽烷、單烷基單烷氧基矽烷、二烷基單烷氧基矽烷、三烷基單烷氧基矽烷等，具體可列舉：甲基三甲氧基矽烷、甲基二甲氧基矽烷、二甲基二甲氧基矽烷、乙基三甲氧基矽烷等。The silicon compound having a hydrolyzable functional group is not particularly limited, and examples thereof include alkyl silicon alkoxides. In the alkoxyalkyl silicon, the number of hydrolyzable functional groups of 3 or less can further improve water resistance. Examples of such alkoxyalkyl silicon include monoalkyltrialkoxysilane, monoalkyldialkoxysilane, dialkyldialkoxysilane, monoalkylmonoalkoxysilane, and Alkyl monoalkoxysilanes, trialkyl monoalkoxysilanes, and the like, specifically, methyltrimethoxysilane, methyldimethoxysilane, dimethyldimethoxysilane, and ethyltrimethoxy Silane and so on.

具有縮合性官能基的矽化合物並無特別限定，例如可列舉：矽烷四醇、甲基矽烷三醇、二甲基矽烷二醇、苯基矽烷三醇、苯基甲基矽烷二醇、二苯基矽烷二醇、正丙基矽烷三醇、己基矽烷三醇、辛基矽烷三醇、癸基矽烷三醇、三氟丙基矽烷三醇等。The silicon compound having a condensable functional group is not particularly limited, and examples thereof include silanol tetraol, methylsilyltriol, dimethylsilanediol, phenylsilanetriol, phenylmethylsilanediol, and dibenzene. Silyl diol, n-propyl silyl triol, hexyl silyl triol, octyl silyl triol, decyl silyl triol, trifluoropropyl silyl triol, and the like.

具有水解性官能基或縮合性官能基的矽化合物亦可進而具有與水解性官能基及縮合性官能基不同的所述反應性基。The silicon compound having a hydrolyzable functional group or a condensable functional group may further have the reactive group different from the hydrolyzable functional group and the condensable functional group.

作為水解性官能基的數量為3個以下且具有反應性基的矽化合物，亦可使用：乙烯基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷等。As the silicon compound having three or less hydrolyzable functional groups and having a reactive group, vinyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidyloxy can also be used. Propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyl Trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropylmethyldimethoxysilane and the like.

另外，作為具有縮合性官能基且具有反應性基的矽化合物，亦可使用：乙烯基矽烷三醇、3-縮水甘油氧基丙基矽烷三醇、3-縮水甘油氧基丙基甲基矽烷二醇、3-甲基丙烯醯氧基丙基矽烷三醇、3-甲基丙烯醯氧基丙基甲基矽烷二醇、3-丙烯醯氧基丙基矽烷三醇、3-巰基丙基矽烷三醇、3-巰基丙基甲基矽烷二醇、N-苯基-3-胺基丙基矽烷三醇、N-2-(胺基乙基)-3-胺基丙基甲基矽烷二醇等。In addition, as the silicon compound having a condensable functional group and a reactive group, vinyl silanetriol, 3-glycidoxypropylsilyltriol, 3-glycidoxypropylmethylsilane can also be used. Diol, 3-methacryloxypropylsilyltriol, 3-methacryloxypropylmethylsilanediol, 3-propenyloxypropylsilyltriol, 3-mercaptopropyl Silanetriol, 3-mercaptopropylmethylsilanediol, N-phenyl-3-aminopropylsilanetriol, N-2- (aminoethyl) -3-aminopropylmethylsilane Diols, etc.

另外，亦可使用分子末端的水解性官能基的數量為3個以下的矽化合物即雙三甲氧基矽烷基甲烷、雙三甲氧基矽烷基乙烷、雙三甲氧基矽烷基己烷、乙基三甲氧基矽烷、乙烯基三甲氧基矽烷等。In addition, a silicon compound having a number of hydrolyzable functional groups at the molecular terminal of 3 or less, that is, ditrimethoxysilylmethane, ditrimethoxysilylethane, ditrimethoxysilylhexane, ethyl can also be used. Trimethoxysilane, vinyltrimethoxysilane, etc.

該些具有水解性官能基或縮合性官能基的矽化合物、以及具有水解性官能基的矽化合物的水解產物可單獨使用或將兩種以上混合使用。These silicon compounds having a hydrolyzable functional group or a condensable functional group, and hydrolysis products of the silicon compound having a hydrolyzable functional group may be used alone or as a mixture of two or more.

相對於溶膠的總量100質量份，聚矽氧烷化合物群組及矽化合物群組的含量的總和可設為5質量份以上，亦可為10質量份以上。相對於溶膠的總量100質量份，該含量的總和可設為50質量份以下，亦可為30質量份以下。即，相對於溶膠的總量100質量份，聚矽氧烷化合物群組及矽化合物群組的含量的總和可設為5質量份～50質量份，進而亦可設為10質量份～30質量份。藉由設為5質量份以上，更容易獲得良好的反應性，另外，藉由設為50質量份以下，更容易獲得良好的相容性。The total of the content of the polysiloxane compound group and the silicon compound group may be 5 parts by mass or more, or 10 parts by mass or more with respect to 100 parts by mass of the total amount of the sol. With respect to 100 parts by mass of the total amount of the sol, the sum of the contents may be 50 parts by mass or less, or 30 parts by mass or less. That is, the total of the content of the polysiloxane compound group and the silicon compound group may be set to 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of the sol, and may also be set to 10 to 30 parts by mass Serving. When it is 5 parts by mass or more, good reactivity is more easily obtained, and when it is 50 parts by mass or less, good compatibility is more easily obtained.

本實施形態的氣凝膠亦可含有二氧化矽粒子。即，形成氣凝膠的溶膠亦可進而含有二氧化矽粒子，本實施形態的氣凝膠亦可為作為含有二氧化矽粒子的溶膠的縮合物的濕潤凝膠的乾燥物。The aerogel of this embodiment may contain silica particles. That is, the aerogel-forming sol may further contain silicon dioxide particles, and the aerogel of the present embodiment may be a dried product of a wet gel that is a condensate of a sol containing silicon dioxide particles.

作為二氧化矽粒子，可無特別限制地使用，例如可列舉非晶質二氧化矽粒子。作為非晶質二氧化矽粒子，例如可列舉：熔融二氧化矽粒子、燻製二氧化矽粒子及膠體二氧化矽粒子。該些中，膠體二氧化矽粒子的單分散性高，且容易抑制於溶膠中的凝聚。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, smoked silica particles, and colloidal silica particles. Among these, the colloidal silica particles have high monodispersity, and it is easy to suppress aggregation in the sol.

二氧化矽粒子的形狀並無特別限制，可列舉球狀、繭型、締合型等。該些形狀中，藉由使用球狀的粒子作為二氧化矽粒子，容易抑制於溶膠中的凝聚。就容易對氣凝膠賦予適度的強度，容易獲得乾燥時的耐收縮性優異的氣凝膠的方面而言，二氧化矽粒子的平均一次粒徑可設為1 nm以上，可為5 nm以上，亦可為10 nm以上。另一方面，就容易抑制二氧化矽粒子的固體導熱，容易獲得絕熱性優異的氣凝膠的方面而言，二氧化矽粒子的平均一次粒徑可設為500 nm以下，可為300 nm以下，亦可為250 nm以下。即，二氧化矽粒子的平均一次粒徑可設為1 nm～500 nm，可為5 nm～300 nm，亦可為10 nm～250 nm。再者，二氧化矽粒子的平均一次粒徑可藉由使用掃描式電子顯微鏡（以下略記為「SEM」）的觀察來測定。The shape of the silica particles is not particularly limited, and examples thereof include a spherical shape, a cocoon shape, and an association type. In these shapes, by using spherical particles as the silica particles, it is easy to suppress aggregation in the sol. The average primary particle diameter of the silicon dioxide particles can be set to 1 nm or more and 5 nm or more in terms of easily providing a moderate strength to the aerogel and easily obtaining an aerogel having excellent shrinkage resistance during drying. It can also be more than 10 nm. On the other hand, the average primary particle diameter of the silicon dioxide particles can be 500 nm or less and 300 nm or less in terms of easily suppressing the solid heat conduction of the silicon dioxide particles and easily obtaining an aerogel having excellent thermal insulation properties. It can also be less than 250 nm. That is, the average primary particle diameter of the silicon dioxide particles may be 1 nm to 500 nm, 5 nm to 300 nm, or 10 nm to 250 nm. The average primary particle diameter of the silicon dioxide particles can be measured by observation using a scanning electron microscope (hereinafter abbreviated as "SEM").

就容易對氣凝膠賦予適度的強度，容易獲得乾燥時的耐收縮性優異的氣凝膠的方面而言，相對於溶膠的總量100質量份，所述溶膠中所含的二氧化矽粒子的含量可設為1質量份以上，亦可為4質量份以上。就容易抑制二氧化矽粒子的固體導熱，容易獲得絕熱性優異的氣凝膠的方面而言，所述溶膠中所含的二氧化矽粒子的含量可設為20質量份以下，可為15質量份以下，亦可為12質量份以下，亦可為10質量份以下，亦可為8質量份以下。即，相對於溶膠的總量100質量份，二氧化矽粒子的含量可設為1質量份～20質量份，可為4質量份～15質量份，亦可為4質量份～12質量份，亦可為4質量份～10質量份，亦可為4質量份～8質量份。From the viewpoint that it is easy to impart a moderate strength to the aerogel and to easily obtain an aerogel having excellent shrinkage resistance during drying, the silica particles contained in the sol are 100 parts by mass of the total amount of the sol. The content may be 1 part by mass or more, or 4 parts by mass or more. The content of the silicon dioxide particles contained in the sol may be 20 parts by mass or less, and may be 15 parts in terms of easily suppressing the solid heat conduction of the silicon dioxide particles and easily obtaining an aerogel having excellent thermal insulation properties. It may be 12 parts by mass or less, 10 parts by mass or less, or 8 parts by mass or less. That is, the content of the silicon dioxide particles may be 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the sol, 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.

·氣凝膠的結構 本實施形態的氣凝膠可含有具有包含矽氧烷鍵（Si-O-Si）的主鏈的聚矽氧烷。氣凝膠可具有下述M單元、D單元、T單元或Q單元作為結構單元。 [化3] · Structure of Aerogel The aerogel of this embodiment may contain a polysiloxane having a main chain including a siloxane bond (Si-O-Si). The aerogel may have the following M units, D units, T units, or Q units as structural units. [Chemical 3]

所述式中，R表示鍵結於矽原子上的原子（氫原子等）或原子團（烷基等）。M單元為包含矽原子與1個氧原子鍵結而成的一價基的單元。D單元為包含矽原子與2個氧原子鍵結而成的二價基的單元。T單元為包含矽原子與3個氧原子鍵結而成的三價基的單元。Q單元為包含矽原子與4個氧原子鍵結而成的四價基的單元。與該些單元的含量有關的資訊可藉由Si-核磁共振（Nuclear Magnetic Resonance，NMR）而獲得。In the formula, R represents an atom (such as a hydrogen atom) or an atom group (such as an alkyl group) bonded to a silicon atom. The M unit is a unit containing a monovalent group in which a silicon atom and an oxygen atom are bonded. The D unit is a unit containing a divalent group in which a silicon atom and two oxygen atoms are bonded. The T unit is a unit containing a trivalent group in which a silicon atom and three oxygen atoms are bonded. The Q unit is a unit containing a tetravalent group in which a silicon atom and four oxygen atoms are bonded. Information related to the content of these units can be obtained by Si-nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR).

作為本實施形態的氣凝膠，可列舉具有以下所示的結構等者。藉由氣凝膠具有該些結構，而容易表現出優異的導熱率及壓縮彈性係數。再者，本實施形態中，氣凝膠可具有以下所示的結構的任一種。Examples of the aerogel of the present embodiment include the following structures. With these structures, an aerogel easily exhibits excellent thermal conductivity and compressive elastic coefficient. In this embodiment, the aerogel may have any of the following structures.

本實施形態的氣凝膠可具有下述通式（1）所表示的結構。本實施形態的氣凝膠可具有下述通式（1a）所表示的結構作為包含通式（1）所表示的結構的結構。藉由使用具有所述通式（A）所表示的結構的聚矽氧烷化合物，可將通式（1）及通式（1a）所表示的結構導入至氣凝膠的骨架中。 [化4][化5] The aerogel of this embodiment may have a structure represented by the following general formula (1). The aerogel of this embodiment may have a structure represented by the following general formula (1a) as a structure including a structure represented by the general formula (1). By using a polysiloxane compound having a structure represented by the general formula (A), the structures represented by the general formula (1) and the general formula (1a) can be introduced into the aerogel skeleton. [Chemical 4] [Chemical 5]

通式（1）及通式（1a）中，R¹ 及R² 分別獨立地表示烷基或芳基，R³ 及R⁴ 分別獨立地表示伸烷基。此處，作為芳基，可列舉苯基、經取代的苯基等。再者，作為經取代的苯基的取代基，可列舉：烷基、乙烯基、巰基、胺基、硝基、氰基等。p表示1～50的整數。通式（1a）中，兩個以上的R¹ 分別可相同亦可不同，同樣地，兩個以上的R² 分別可相同亦可不同。通式（1a）中，兩個R³ 分別可相同亦可不同，同樣地，兩個R⁴ 分別可相同亦可不同。In the general formula (1) and the general formula (1a), R ¹ and R ² each independently represent an alkyl group or an aryl group, and R ³ and R ⁴ each independently represent an alkylene group. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. p represents an integer of 1 to 50. In the general formula (1a), two or more R ¹ may be the same or different, and similarly, two or more R ² may be the same or different. In the general formula (1a), two R ³ may be the same or different, and similarly, two R ⁴ may be the same or different.

藉由將所述通式（1）或通式（1a）所表示的結構導入至氣凝膠的骨架中，成為低導熱率且柔軟的氣凝膠。就此種觀點而言，通式（1）及通式（1a）中，R¹ 及R² 分別獨立地可列舉碳數為1～6的烷基、苯基等，作為該烷基，可列舉甲基等。另外，通式（1）及通式（1a）中，R³ 及R⁴ 分別獨立地可列舉碳數為1～6的伸烷基等，作為該伸烷基，可列舉伸乙基、伸丙基等。通式（1a）中，p可設為2～30，亦可為5～20。By introducing the structure represented by the general formula (1) or the general formula (1a) into the aerogel skeleton, a low-thermal-conductivity and flexible aerogel is obtained. From such a viewpoint, in the general formula (1) and the general formula (1a), R ¹ and R ² each independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like, and examples of the alkyl group include Methyl, etc. In the general formula (1) and the general formula (1a), R ³ and R ⁴ each independently include an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include an alkylene group and an alkylene group. Propyl and so on. In the general formula (1a), p may be 2 to 30, or 5 to 20 may be used.

本實施形態的氣凝膠為具有具備支柱部及橋聯部的階梯型結構的氣凝膠，且亦可為橋聯部由下述通式（2）所表示的氣凝膠。藉由於氣凝膠的骨架中導入此種階梯型結構，可提高耐熱性與機械強度。藉由使用具有所述通式（B）所表示的結構的聚矽氧烷化合物，可將具有通式（2）所表示的橋聯部的階梯型結構導入至氣凝膠的骨架中。再者，本實施形態中所謂「階梯型結構」是具有2根支柱部（struts）以及將支柱部彼此連結的橋聯部（bridges）者（具有所謂「梯子」的形態者）。本態樣中，氣凝膠骨架可包含階梯型結構，但氣凝膠亦可部分性地具有階梯型結構。 [化6] The aerogel of this embodiment is an aerogel having a stepped structure including a pillar portion and a bridge portion, and may be an aerogel having a bridge portion represented by the following general formula (2). By introducing such a stepped structure into the aerogel's skeleton, heat resistance and mechanical strength can be improved. By using a polysiloxane compound having a structure represented by the general formula (B), a stepped structure having a bridge portion represented by the general formula (2) can be introduced into the aerogel skeleton. The "stepped structure" in this embodiment is a person having two struts and bridges that connect the struts to each other (a person having a so-called "ladder"). In this aspect, the aerogel skeleton may include a stepped structure, but the aerogel may partially have a stepped structure. [Chemical 6]

通式（2）中，R⁵ 及R⁶ 分別獨立地表示烷基或芳基，b表示1～50的整數。此處，作為芳基，可列舉苯基、經取代的苯基等。另外，作為經取代的苯基的取代基，可列舉：烷基、乙烯基、巰基、胺基、硝基、氰基等。再者，通式（2）中，於b為2以上的整數的情況下，兩個以上的R⁵ 分別可相同亦可不同，同樣地，兩個以上的R⁶ 亦分別可相同亦可不同。In the general formula (2), R ⁵ and R ⁶ each independently represent an alkyl group or an aryl group, and b represents an integer of 1 to 50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. Furthermore, in the general formula (2), when b is an integer of 2 or more, two or more R ⁵ may be the same or different, and similarly, two or more R ⁶ may be the same or different. .

藉由將所述結構導入至氣凝膠的骨架中，例如成為較具有源於現有的階梯型倍半矽氧烷的結構（即，具有下述通式（X）所表示的結構）的氣凝膠而言，具有更優異的柔軟性的氣凝膠。倍半矽氧烷為具有組成式：(RSiO_1.5 )_n 的聚矽氧烷，可具有籠型、階梯型、無規型等多種骨架結構。如下述通式（X）所示，具有源於現有的階梯型倍半矽氧烷的結構的氣凝膠中，橋聯部的結構為-O-（具有所述T單元作為結構單元），但本態樣的氣凝膠中，橋聯部的結構為所述通式（2）所表示的結構（聚矽氧烷結構）。其中，本實施形態的氣凝膠除具有通式（1）～通式（3）所表示的結構以外，亦可進而具有源於倍半矽氧烷的結構。 [化7] By introducing the structure into the aerogel skeleton, for example, it becomes a gas having a structure derived from the existing stepped silsesquioxane (that is, having a structure represented by the following general formula (X)). As for the gel, an aerogel having more excellent flexibility. Silsesquioxane is a polysiloxane with a composition formula: (RSiO _1.5 ) _n , and can have a variety of skeleton structures such as cage, step, and random. As shown in the following general formula (X), in an aerogel having a structure derived from a conventional stepped silsesquioxane, the structure of the bridge portion is -O- (having the T unit as a structural unit), However, in the aerogel of this aspect, the structure of the bridging portion is a structure (polysiloxane structure) represented by the general formula (2). Among them, the aerogel of this embodiment may have a structure derived from a silsesquioxane in addition to the structure represented by the general formulae (1) to (3). [Chemical 7]

通式（X）中，R表示羥基、烷基或芳基。In the general formula (X), R represents a hydroxyl group, an alkyl group, or an aryl group.

成為支柱部的結構及其鏈長、以及成為橋聯部的結構的間隔並無特別限定，就進一步提高耐熱性與機械強度的觀點而言，階梯型結構可列舉下述通式（3）所表示的階梯型結構。 [化8] The structure serving as the pillar portion and its chain length, and the interval between the structures serving as the bridging portion are not particularly limited. From the viewpoint of further improving heat resistance and mechanical strength, the stepped structure may be represented by the following general formula (3) Represents a stepped structure. [Chemical 8]

通式（3）中，R⁵ 、R⁶ 、R⁷ 及R⁸ 分別獨立地表示烷基或芳基，a及c分別獨立地表示1～3000的整數，b表示1～50的整數。此處，作為芳基，可列舉苯基、經取代的苯基等。另外，作為經取代的苯基的取代基，可列舉：烷基、乙烯基、巰基、胺基、硝基、氰基等。再者，通式（3）中，於b為2以上的整數的情況下，兩個以上的R⁵ 分別可相同亦可不同，同樣地，兩個以上的R⁶ 亦分別可相同亦可不同。另外，通式（3）中，於a為2以上的整數的情況下，兩個以上的R⁷ 分別可相同亦可不同，同樣地，於c為2以上的整數的情況下，兩個以上的R⁸ 分別可相同亦可不同。In the general formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group or an aryl group, a and c each independently represent an integer of 1 to 3000, and b represents an integer of 1 to 50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. Furthermore, in the general formula (3), when b is an integer of 2 or more, two or more R ⁵ may be the same or different, and similarly, two or more R ⁶ may be the same or different. . In addition, in the general formula (3), when a is an integer of 2 or more, two or more R ⁷ may be the same or different, and similarly, when c is an integer of 2 or more, two or more R ⁷ may be the same. R ⁸ may be the same or different.

再者，就獲得更優異的柔軟性的觀點而言，通式（2）及通式（3）中，R⁵ 、R⁶ 、R⁷ 及R⁸ （其中，R⁷ 及R⁸ 僅於通式（3）中）分別獨立地可列舉碳數為1～6的烷基、苯基等，作為該烷基，可列舉甲基等。另外，通式（3）中，a及c可分別獨立地設為6～2000，進而亦可設為10～1000。另外，通式（2）及通式（3）中，b可設為2～30，進而亦可設為5～20。Furthermore, from the viewpoint of obtaining more excellent flexibility, in the general formulae (2) and (3), R ⁵ , R ⁶ , R ^7, and R ⁸ (wherein R ⁷ and R ⁸ are only In the formula (3)), an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like are each independently exemplified, and examples of the alkyl group include a methyl group and the like. In the general formula (3), a and c may be independently set to 6 to 2000, and may also be set to 10 to 1,000. In the general formula (2) and the general formula (3), b may be set to 2 to 30, and may also be set to 5 to 20.

本實施形態的氣凝膠可具有下述通式（4）所表示的結構。本實施形態的氣凝膠可含有二氧化矽粒子，並且具有下述通式（4）所表示的結構。 [化9] The aerogel of this embodiment may have a structure represented by the following general formula (4). The aerogel of this embodiment may contain silica particles and have a structure represented by the following general formula (4). [Chemical 9]

通式（4）中，R⁹ 表示烷基。此處，作為烷基，可列舉碳數為1～6的烷基等，作為該烷基，可列舉甲基等。In the general formula (4), R ⁹ represents an alkyl group. Here, examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group include a methyl group.

本實施形態的氣凝膠可具有下述通式（5）所表示的結構。本實施形態的氣凝膠可含有二氧化矽粒子，並且具有下述通式（5）所表示的結構。 [化10] The aerogel of this embodiment may have a structure represented by the following general formula (5). The aerogel of this embodiment may contain silica particles and have a structure represented by the following general formula (5). [Chemical 10]

通式（5）中，R¹⁰ 及R¹¹ 分別獨立地表示烷基。此處，作為烷基，可列舉碳數為1～6的烷基等，作為該烷基，可列舉甲基等。In the general formula (5), R ¹⁰ and R ¹¹ each independently represent an alkyl group. Here, examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group include a methyl group.

本實施形態的氣凝膠可具有下述通式（6）所表示的結構。本實施形態的氣凝膠可含有二氧化矽粒子，並且具有下述通式（6）所表示的結構。 [化11] The aerogel of this embodiment may have a structure represented by the following general formula (6). The aerogel of this embodiment may contain silica particles and have a structure represented by the following general formula (6). [Chemical 11]

通式（6）中，R¹² 表示伸烷基。此處，作為伸烷基，可列舉碳數為1～10的伸烷基等，作為該伸烷基，可列舉伸乙基、伸己基等。In the general formula (6), R ¹² represents an alkylene group. Here, examples of the alkylene group include an alkylene group having 1 to 10 carbon atoms, and examples of the alkylene group include an ethylene group and a hexyl group.

·塗層 作為形成塗層的材料（塗佈材料），可列舉熱硬化性樹脂。作為熱硬化性樹脂，可列舉：矽酮樹脂、酚樹脂、脲樹脂、三聚氰胺樹脂、不飽和聚酯樹脂、環氧樹脂、聚胺基甲酸酯樹脂等。該些中，就耐熱性與高強度的觀點而言，作為塗佈材料，可使用矽酮樹脂、環氧樹脂、酚樹脂等。Coating layer Examples of a material (coating material) for forming a coating layer include a thermosetting resin. Examples of the thermosetting resin include a silicone resin, a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, an epoxy resin, and a polyurethane resin. Among these, from the viewpoint of heat resistance and high strength, as the coating material, a silicone resin, an epoxy resin, a phenol resin, or the like can be used.

矽酮樹脂並無特別限定，可列舉：油系矽酮、彈性體系矽酮、樹脂系矽酮、矽烷系矽酮等各種矽酮樹脂。具體可列舉：胺基改質矽氧烷、環氧改質矽氧烷、苯酚改質矽氧烷、甲基丙烯酸酯改質矽氧烷、烷氧基改質矽氧烷、甲醇改質矽氧烷、乙烯改質矽氧烷、硫醇改質矽氧烷等。製品名則可列舉：RSN-0409、RSN-0431、RSN-0804、RSN-0805、RSN-0806、RSN-0808、RSN-0840等（東麗道康寧（Toray Dow-corning）公司製造）、KF-8010、X-22-161A、KF-105、X-22-163A、X-22-169AS、KF-6001、KF-2200、X-22-164A、X-22-162C、X-22-167C、X-22-173BX等（信越化學工業股份有限公司製造）。再者，亦可使用以適當的比例將種類、分子量、官能基等不同的兩種以上的矽酮樹脂混合而成的矽酮樹脂。The silicone resin is not particularly limited, and examples thereof include various silicone resins such as oil-based silicone, elastic silicone, resin-based silicone, and silane-based silicone. Specific examples: amine-modified silicone, epoxy-modified silicone, phenol-modified silicone, methacrylate-modified silicone, alkoxy-modified silicone, or methanol-modified silicone Oxane, ethylene modified siloxane, mercaptan modified siloxane and so on. Product names include RSN-0409, RSN-0431, RSN-0804, RSN-0805, RSN-0806, RSN-0808, RSN-0840, etc. (manufactured by Toray Dow-corning), KF- 8010, X-22-161A, KF-105, X-22-163A, X-22-169AS, KF-6001, KF-2200, X-22-164A, X-22-162C, X-22-167C, X-22-173BX, etc. (made by Shin-Etsu Chemical Industry Co., Ltd.). Furthermore, a silicone resin obtained by mixing two or more silicone resins having different kinds, molecular weights, functional groups, and the like at an appropriate ratio may be used.

作為矽酮樹脂的硬化劑，可列舉：酸、鹼、金屬觸媒等。具體而言，例如可列舉：鹽酸、硫酸、硝酸、磷酸、乙酸、丙酸等酸，氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、氨、二甲基胺、苯胺、胺改質矽氧烷等鹼，環烷酸鋅、辛酸鋅、環烷酸錳、環烷酸鈷、辛酸鈷等金屬觸媒等。該些可單獨使用，亦可併用兩種以上。Examples of the silicone resin hardener include acids, alkalis, and metal catalysts. Specific examples include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and propionic acid; sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, dimethylamine, aniline, and amine modification Bases such as siloxane, metal catalysts such as zinc naphthenate, zinc octoate, manganese naphthenate, cobalt naphthenate, and cobalt octoate. These may be used alone or in combination of two or more.

作為環氧樹脂，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、苯酚芳烷基型環氧樹脂、聯苯型環氧樹脂、三苯基甲烷型環氧樹脂、二環戊二烯型環氧樹脂等多官能環氧樹脂。該些可單獨使用，亦可併用兩種以上。Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and phenol aromatic resin. Polyfunctional epoxy resins such as alkyl epoxy resin, biphenyl epoxy resin, triphenylmethane epoxy resin, and dicyclopentadiene epoxy resin. These may be used alone or in combination of two or more.

作為環氧樹脂的硬化劑，可列舉：酚樹脂、酸酐、胺類、咪唑類、膦類等。該些可單獨使用，亦可併用兩種以上。Examples of the curing agent for epoxy resins include phenol resins, acid anhydrides, amines, imidazoles, and phosphines. These may be used alone or in combination of two or more.

作為酚樹脂，可列舉：苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、苯酚芳烷基樹脂、甲酚萘酚甲醛縮聚物、三苯基甲烷型多官能酚樹脂等。Examples of the phenol resin include a phenol novolak resin, a cresol novolac resin, a phenol aralkyl resin, a cresol naphthol formaldehyde polycondensate, and a triphenylmethane-type polyfunctional phenol resin.

作為酸酐，可列舉：甲基環己烷四羧酸二酐、偏苯三甲酸酐、均苯四甲酸酐、二苯甲酮四羧酸二酐、乙二醇雙脫水偏苯三酸酯等。Examples of the acid anhydride include methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and ethylene glycol dehydrated trimellitate.

作為胺類，例如可列舉：二氰二胺、脂環式多胺、脂肪族多胺、苯胺甲醛縮合物等。Examples of the amines include dicyandiamine, alicyclic polyamine, aliphatic polyamine, and aniline formaldehyde condensate.

作為咪唑類，可列舉：2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑偏苯三酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-十一烷基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、環氧樹脂與咪唑類的加成物等。Examples of imidazoles include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-cyano Ethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2 -Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamine -6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazole -(1 ')]-ethyl-mesytriazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-mesytriazine isomelamine Acid adduct, 2-phenylimidazole isotricyanic acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole , Adducts of epoxy resins and imidazoles, etc.

作為膦類，可列舉：三苯基膦、四苯基鏻四苯基硼酸鹽、四苯基鏻四(4-甲基苯基)硼酸鹽、四苯基鏻(4-氟苯基)硼酸鹽等。Examples of the phosphines include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate, and tetraphenylphosphonium (4-fluorophenyl) boronic acid. Salt, etc.

作為酚樹脂，可使用作為環氧樹脂的硬化劑而列舉者。即，可列舉：苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、苯酚芳烷基樹脂、甲酚萘酚甲醛縮聚物、三苯基甲烷型多官能酚樹脂等。As a phenol resin, the hardening | curing agent of an epoxy resin is mentioned. That is, a phenol novolak resin, a cresol novolak resin, a phenol aralkyl resin, a cresol naphthol formaldehyde polycondensate, a triphenylmethane type polyfunctional phenol resin, etc. are mentioned.

另外，作為塗佈材料，可列舉聚矽氮烷。聚矽氮烷的結構可由下述通式（P）表示。 [化12] Examples of the coating material include polysilazane. The structure of the polysilazane can be represented by the following general formula (P). [Chemical 12]

通式（P）中，R_x 、R_y 、R_z 分別獨立地表示氫或可具有取代基的烷基、芳基、烯基、環烷基、烷氧基等。n可設為2～1000。In the general formula _{(P), R x, R} y, R z each independently represent hydrogen or an optionally substituted alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, an alkoxy group and the like. n can be set to 2 to 1000.

可藉由使聚矽氮烷與水反應來獲得氧化矽。根據聚矽氮烷與水的反應的程度，可於將聚矽氮烷作為原料而獲得的氧化矽中含有Si-O所表示的鍵、Si-N所表示的鍵、Si-H所表示的鍵及N-H所表示的鍵等。作為聚矽氮烷，可列舉使全氫化聚矽氮烷（perhydro-polysilazane）、甲基氫化聚矽氮烷等有機聚矽氮烷、矽烷氧化物反應而獲得的加成矽烷氧化物的聚矽氮烷等。就獲得耐熱性、獲取容易性、緻密的塗層等觀點而言，可使用全氫化聚矽氮烷作為聚矽氮烷。聚矽氮烷的平均分子量可設為100 g/mol～50000 g/mol左右。Silicon oxide can be obtained by reacting polysilazane with water. Depending on the degree of reaction between polysilazane and water, the silicon oxide obtained using polysilazane as a raw material contains a bond represented by Si-O, a bond represented by Si-N, and a bond represented by Si-H. Bond, NH, etc. Examples of the polysilazane include polysilazane obtained by reacting an organic polysilazane such as perhydro-polysilazane, methylhydrogen polysilazane, or the like with a silane oxide, and a silanol oxide. Azane and so on. From the viewpoints of obtaining heat resistance, ease of obtaining, dense coating, etc., perhydropolysilazane can be used as the polysilazane. The average molecular weight of the polysilazane can be set to about 100 g / mol to 50000 g / mol.

·氣凝膠複合體的物性 就兼顧強韌化與絕熱特性的觀點而言，氣凝膠複合體的密度可設為0.30 g/cm³ 以上，可為0.50 g/cm³ 以上，亦可為0.70 g/cm³ 以上，或者可設為1.15 g/cm³ 以下，可為1.10 g/cm³ 以下，亦可為1.00 g/cm³ 以下。即，氣凝膠複合體的密度可設為0.30 g/cm³ ～1.15 g/cm³ ，可為0.50 g/cm³ ～1.10 g/cm³ ，亦可為0.70 g/cm³ ～1.00 g/cm³ 。密度例如可利用比重計，或者藉由進行樣品測長及重量測定來測定。· Physical properties of aerogel composites From the viewpoint of both toughening and adiabatic properties, the density of the aerogel composites can be 0.30 g / cm ³ or more, 0.50 g / cm ³ or more, or 0.70 g / cm ³ or more, or 1.15 g / cm ³ or less, 1.10 g / cm ³ or less, or 1.00 g / cm ³ or less. That is, the density of the aerogel composite may be 0.30 g / cm ³ to 1.15 g / cm ³ , may be 0.50 g / cm ³ to 1.10 g / cm ³ , or may be 0.70 g / cm ³ to 1.00 g / cm ³ . cm ³ . The density can be measured using, for example, a hydrometer or by measuring the length and weight of a sample.

就兼顧強韌化與絕熱特性的觀點而言，氣凝膠複合體的相對於波長700 nm的光的透過率可設為15%以下，可為10%以下，亦可為5%以下，抑或可為3%以下。該透過率的下限並無特別限定，可設為0。透過率可利用分光光度計、霧度計等來測定。From the viewpoint of both toughening and adiabatic properties, the transmittance of the aerogel composite with respect to light having a wavelength of 700 nm can be set to 15% or less, 10% or less, or 5% or less, or Can be less than 3%. The lower limit of the transmittance is not particularly limited, and may be set to zero. The transmittance can be measured with a spectrophotometer, a haze meter, or the like.

就表現出較佳的絕熱性的觀點而言，氣凝膠複合體中的氣凝膠的含量可設為30質量%以上，可為40質量%以上，或者可設為90質量%以下，可為80質量%以下。即，氣凝膠的含量可設為30質量%～90質量%，亦可為40質量%～80質量%。另外，就抑制絕熱性的下降的觀點而言，氣凝膠複合體中的塗層的含量可設為1質量%以上，可為5質量%以上，或者可設為60質量%以下，可為50質量%以下。即，塗層的含量可設為1質量%～60質量%，亦可為5質量%～50質量%。From the viewpoint of exhibiting better thermal insulation properties, the aerogel content in the aerogel composite may be 30% by mass or more, 40% by mass or more, or 90% by mass or less. It is 80% by mass or less. That is, the content of the aerogel may be 30 to 90% by mass, or 40 to 80% by mass. In addition, from the viewpoint of suppressing a decrease in thermal insulation property, the content of the coating layer in the aerogel composite may be 1% by mass or more, may be 5% by mass or more, or may be 60% by mass or less, and may be 50% by mass or less. That is, the content of the coating layer may be 1 to 60% by mass, or 5 to 50% by mass.

就容易獲得良好的絕熱性的方面而言，氣凝膠複合體的厚度可為1 μm以上，亦可為10 μm以上，抑或可為30 μm以上。就可縮短後述的清洗及溶媒置換步驟以及乾燥步驟的觀點而言，氣凝膠複合體的厚度可為1000 μm以下，亦可為200 μm以下，抑或可為100 μm以下。就該些觀點而言，氣凝膠複合體的厚度可為1 μm～1000 μm，亦可為10 μm～200 μm，抑或可為30 μm～100 μm。The thickness of the aerogel composite may be 1 μm or more, may be 10 μm or more, or may be 30 μm or more in terms of easily obtaining good thermal insulation properties. The thickness of the aerogel composite may be 1,000 μm or less, 200 μm or less, or 100 μm or less from the viewpoint of shortening the washing, solvent replacement step, and drying step described later. From these viewpoints, the thickness of the aerogel composite may be 1 μm to 1000 μm, may be 10 μm to 200 μm, or may be 30 μm to 100 μm.

（阻障層） 阻障層是以改善氣凝膠複合體的脆性、提高耐油性等為目的而形成。作為形成阻障層的材料（阻障層形成材料），可列舉聚矽氮烷與水的反應物、矽氧烷系化合物等。(Barrier layer) The barrier layer is formed for the purpose of improving the brittleness of the aerogel composite and improving the oil resistance. Examples of the material for forming the barrier layer (barrier layer-forming material) include a reactant of polysilazane and water, a siloxane-based compound, and the like.

作為聚矽氮烷，可使用所述的聚矽氮烷。As the polysilazane, the aforementioned polysilazane can be used.

矽氧烷系化合物為具有矽氧烷鍵（Si-O-Si鍵）的化合物。作為矽氧烷系化合物，例如可列舉具有矽氧烷鍵（Si-O-Si鍵）的聚合物或寡聚物。矽氧烷系化合物的具體例包含矽酮（矽樹脂）、具有水解性官能基的有機矽化合物的縮合物、及經矽酮改質的聚合物。作為具有水解性官能基的有機矽化合物，例如可列舉：甲基三甲氧基矽烷、二甲基二甲氧基矽烷及三甲基甲氧基矽烷。就與氣凝膠層的接著性、耐熱性等觀點而言，矽氧烷系化合物例如亦可為矽酮或甲基三甲氧基矽烷的縮合物。The siloxane-based compound is a compound having a siloxane bond (Si-O-Si bond). Examples of the siloxane compound include a polymer or an oligomer having a siloxane bond (Si-O-Si bond). Specific examples of the silicone compound include silicone (silicone resin), a condensate of an organic silicon compound having a hydrolyzable functional group, and a polymer modified with silicone. Examples of the organosilicon compound having a hydrolyzable functional group include methyltrimethoxysilane, dimethyldimethoxysilane, and trimethylmethoxysilane. From the viewpoints of adhesion to the aerogel layer, heat resistance, and the like, the siloxane compound may be, for example, a condensate of silicone or methyltrimethoxysilane.

所述阻障層例如亦可進而包含填充材。作為構成填充材的材料，可列舉金屬、陶瓷等。作為所述金屬，例如可列舉：金屬的單體；金屬的合金；形成有氧化被膜的金屬等。作為所述金屬，可列舉：鐵、銅、鎳、鋁、鋅、鈦、鉻、鈷、錫、金、銀等。作為所述陶瓷，可列舉：氧化鋁、二氧化鈦、氧化鋯、氧化鎂等氧化物；氮化矽、氮化鋁等氮化物；碳化矽、碳化硼等碳化物；該些的混合物等。構成填充材的材料例如可為熔融二氧化矽、燻製二氧化矽、膠體二氧化矽、中空狀二氧化矽、玻璃、及鱗片狀二氧化矽。作為所述玻璃，可列舉：石英玻璃、鈉玻璃、硼矽酸玻璃等。The barrier layer may further include, for example, a filler. Examples of the material constituting the filler include metals, ceramics, and the like. Examples of the metal include a single metal, an alloy of a metal, and a metal on which an oxide film is formed. Examples of the metal include iron, copper, nickel, aluminum, zinc, titanium, chromium, cobalt, tin, gold, and silver. Examples of the ceramics include oxides such as alumina, titania, zirconia, and magnesium oxide; nitrides such as silicon nitride and aluminum nitride; carbides such as silicon carbide and boron carbide; and mixtures thereof. The material constituting the filler may be, for example, fused silica, smoked silica, colloidal silica, hollow silica, glass, and scaly silica. Examples of the glass include quartz glass, soda glass, and borosilicate glass.

就容易獲得緻密的阻障層的觀點而言，相對於阻障層的總體積，阻障層中的阻障層形成材料的含量例如可為20體積%以上，亦可為30體積%以上，抑或可為40體積%以上。就用以形成阻障層的作業性提高的觀點而言，相對於阻障層的總體積，阻障層形成材料的含量例如可為80體積%以下，亦可為70體積%以下，抑或可為60體積%以下。於阻障層含有填充材的情況下，就抑制阻障層組成物於氣凝膠複合體中的滲透及提高耐熱性的觀點而言，相對於阻障層的總體積，阻障層中的填充材的含量例如可為0.1體積%以上，亦可為1體積%以上，抑或可為5體積%以上。From the viewpoint of easily obtaining a dense barrier layer, the content of the barrier layer-forming material in the barrier layer may be, for example, 20% by volume or more, and 30% by volume or more relative to the total volume of the barrier layer. Or it may be 40% by volume or more. From the viewpoint of improving the workability for forming the barrier layer, the content of the barrier layer-forming material may be, for example, 80% by volume or less, or 70% by volume or less, with respect to the total volume of the barrier layer. It is 60% by volume or less. When the barrier layer contains a filler, from the viewpoint of suppressing the penetration of the barrier layer composition into the aerogel composite and improving the heat resistance, the amount in the barrier layer is relative to the total volume of the barrier layer. The content of the filler may be, for example, 0.1% by volume or more, 1% by volume or more, or 5% by volume or more.

就脆性改善、耐油性提高等觀點而言，阻障層的厚度例如可為1 μm以上，亦可為5 μm以上，抑或可為10 μm以上。就阻障層形成後的操作性提高的觀點而言，阻障層的厚度例如可為1000 μm以下，亦可為200 μm以下，抑或可為100 μm以下。就獲得更良好的絕熱性及耐油性的觀點而言，氣凝膠複合體與阻障層的合計厚度例如可為2 μm以上，亦可為15 μm以上，抑或可為40 μm以上。就製造步驟時間的縮短、操作性提高等觀點而言，氣凝膠複合體與阻障層的合計厚度例如可為2000 μm以下，亦可為400 μm以下，抑或可為200 μm以下。From the viewpoints of improvement in brittleness and improvement in oil resistance, the thickness of the barrier layer may be, for example, 1 μm or more, 5 μm or more, or 10 μm or more. From the viewpoint of improving the operability after the barrier layer is formed, the thickness of the barrier layer may be, for example, 1,000 μm or less, 200 μm or less, or 100 μm or less. From the viewpoint of obtaining better thermal insulation and oil resistance, the total thickness of the aerogel composite and the barrier layer may be, for example, 2 μm or more, 15 μm or more, or 40 μm or more. The total thickness of the aerogel composite and the barrier layer may be, for example, 2000 μm or less, 400 μm or less, or 200 μm or less from the viewpoints of shortening the manufacturing process time and improving the operability.

＜被絕熱體的製造方法＞ 其次，對被絕熱體的製造方法進行說明。被絕熱體例如可利用如下方法來製造，所述方法具備：於絕熱對象物形成氣凝膠的步驟（A：氣凝膠形成步驟）；以及使塗佈液滲透至氣凝膠後去除溶媒的步驟（B：塗層步驟）。再者，於被絕熱體具備阻障層的情況下，可進而實施於藉由該些步驟而獲得的氣凝膠複合體上形成阻障層的步驟（C：阻障層形成步驟）。<The manufacturing method of a to-be-insulated body> Next, the manufacturing method of a to-be-insulated body is demonstrated. The to-be-insulated body can be produced by, for example, a method including a step (A: aerogel forming step) of forming an aerogel on an object to be insulated, and a method of removing the solvent after the coating liquid is penetrated into the aerogel. Step (B: Coating step). In addition, when the heat-insulated body has a barrier layer, a step of forming a barrier layer on the aerogel composite obtained by these steps (C: barrier layer forming step) may be further performed.

A：氣凝膠形成步驟 氣凝膠形成步驟例如可主要具備：溶膠生成步驟，生成用以形成氣凝膠的溶膠；溶膠塗膜形成步驟，將所獲得的溶膠塗敷於絕熱對象物而形成溶膠塗膜；濕潤凝膠生成步驟，自溶膠塗膜生成濕潤凝膠；對濕潤凝膠進行清洗（及視需要進行溶媒置換）的步驟；以及乾燥步驟，將經清洗的濕潤凝膠加以乾燥。再者，所謂「溶膠」，為產生凝膠化反應前的狀態，於本實施形態中，是指矽化合物（視需要，進而為二氧化矽粒子）溶解或分散於溶媒中的狀態。另外，所謂「濕潤凝膠」，是指雖然包含液體介質，但不具有流動性的濕潤狀態的凝膠固形物。A: Aerogel formation step The aerogel formation step may mainly include, for example, a sol generation step to generate a sol for forming an aerogel, and a sol coating film formation step to apply the obtained sol to an object to be insulated and formed. A sol coating film; a wet gel generation step, generating a wet gel from the sol coating film; a step of washing the wet gel (and performing solvent replacement if necessary); and a drying step of drying the washed wet gel. The term “sol” refers to a state before a gelation reaction occurs. In this embodiment, the state refers to a state in which a silicon compound (and, if necessary, silica particles) is dissolved or dispersed in a solvent. The "wet gel" refers to a gel solid in a wet state that does not have fluidity although it contains a liquid medium.

（溶膠生成步驟） 溶膠生成步驟是例如將矽化合物（視需要，進而為二氧化矽粒子）與溶媒混合，進行水解反應而生成溶膠的步驟。本步驟中，為了促進水解反應，亦可進而添加酸觸媒。另外，亦可如日本專利第5250900號公報所示，添加界面活性劑、熱水解性化合物等。進而，以抑制熱射線輻射等為目的，亦可添加碳石墨、鋁化合物、鎂化合物、銀化合物、鈦化合物等成分。(Sol-forming step) The sol-forming step is a step of, for example, mixing a silicon compound (and further, silicon dioxide particles, if necessary) with a solvent, and performing a hydrolysis reaction to generate a sol. In this step, in order to promote the hydrolysis reaction, an acid catalyst may be further added. In addition, as shown in Japanese Patent No. 5250900, a surfactant, a thermally hydrolyzable compound, and the like may be added. Further, for the purpose of suppressing heat ray radiation and the like, components such as carbon graphite, aluminum compounds, magnesium compounds, silver compounds, and titanium compounds may be added.

作為溶媒，例如可使用水、或者水及醇類的混合液。作為醇類，可列舉：甲醇、乙醇、正丙醇、2-丙醇、正丁醇、2-丁醇、第三丁醇等。該些中，就降低與凝膠壁的界面張力的方面而言，作為表面張力低且沸點低的醇，可列舉：甲醇、乙醇、2-丙醇等。該些可單獨使用或將兩種以上混合使用。As the solvent, for example, water or a mixed solution of water and alcohols can be used. Examples of the alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, and third butanol. Among these, in terms of reducing the interfacial tension with the gel wall, examples of the alcohol having a low surface tension and a low boiling point include methanol, ethanol, and 2-propanol. These can be used alone or in combination of two or more.

例如於使用醇類作為溶媒的情況下，相對於矽化合物的總量1莫耳，醇類的量例如可為4莫耳～8莫耳，亦可為4～6.5，抑或可為4.5莫耳～6莫耳。藉由將醇類的量設為4莫耳以上，更容易獲得良好的相容性，另外，藉由設為8莫耳以下，更容易抑制凝膠的收縮。For example, when using alcohols as a solvent, the amount of alcohols may be, for example, 4 to 8 mols, or 4 to 6.5, or 4.5 mols, relative to 1 mol of the total silicon compound. ~ 6 moles. By setting the amount of alcohol to 4 mol or more, it is easier to obtain good compatibility, and by setting it to 8 mol or less, it is easier to suppress gel shrinkage.

作為酸觸媒，可列舉：氫氟酸、鹽酸、硝酸、硫酸、亞硫酸、磷酸、亞磷酸、次磷酸、溴酸、氯酸、亞氯酸、次亞氯酸等無機酸類；酸性磷酸鋁、酸性磷酸鎂、酸性磷酸鋅等酸性磷酸鹽類；乙酸、甲酸、丙酸、乙二酸、丙二酸、丁二酸、檸檬酸、蘋果酸、己二酸、壬二酸等有機羧酸類等。該些中，作為進一步提高所獲得的氣凝膠的耐水性的酸觸媒，可列舉有機羧酸類。作為該有機羧酸類，可列舉乙酸，亦可為甲酸、丙酸、乙二酸、丙二酸等。該些可單獨使用或將兩種以上混合使用。Examples of the acid catalyst include inorganic acids such as hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, bromic acid, chloric acid, chlorous acid, and hypochlorous acid; acidic aluminum phosphate , Acid magnesium phosphate, acid zinc phosphate and other acidic phosphates; acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid, azelaic acid and other organic carboxylic acids Wait. Among these, as an acid catalyst which further improves the water resistance of the obtained aerogel, an organic carboxylic acid is mentioned. Examples of the organic carboxylic acid include acetic acid, and formic acid, propionic acid, oxalic acid, and malonic acid may be used. These can be used alone or in combination of two or more.

藉由使用酸觸媒，可促進矽化合物的水解反應，可以更短的時間獲得溶膠。By using an acid catalyst, a hydrolysis reaction of a silicon compound can be promoted, and a sol can be obtained in a shorter time.

相對於矽化合物的總量100質量份，酸觸媒的添加量例如可設為0.001質量份～0.1質量份。The addition amount of the acid catalyst may be, for example, 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the silicon compound.

作為界面活性劑，可使用非離子性界面活性劑、離子性界面活性劑等。該些可單獨使用或將兩種以上混合使用。As the surfactant, a nonionic surfactant, an ionic surfactant, or the like can be used. These can be used alone or in combination of two or more.

作為非離子性界面活性劑，例如可使用：含有聚氧乙烯等親水部及主要包含烷基的疏水部的化合物、包含聚氧丙烯等親水部的化合物等。作為含有聚氧乙烯等親水部及主要包含烷基的疏水部的化合物，可列舉：聚氧乙烯壬基苯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯烷基醚等。作為包含聚氧丙烯等親水部的化合物，可列舉：聚氧丙烯烷基醚、聚氧乙烯與聚氧丙烯的嵌段共聚物等。As the nonionic surfactant, for example, a compound containing a hydrophilic portion such as polyoxyethylene and a hydrophobic portion mainly containing an alkyl group, a compound containing a hydrophilic portion such as polyoxypropylene, and the like can be used. Examples of the compound containing a hydrophilic portion such as polyoxyethylene and a hydrophobic portion mainly containing an alkyl group include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene alkyl ether. Examples of the compound containing a hydrophilic portion such as polyoxypropylene include a polyoxypropylene alkyl ether, a block copolymer of polyoxyethylene and polyoxypropylene, and the like.

作為離子性界面活性劑，可列舉：陽離子性界面活性劑、陰離子性界面活性劑、兩離子性界面活性劑等。作為陽離子性界面活性劑，可列舉溴化鯨蠟基三甲基銨、氯化鯨蠟基三甲基銨等，作為陰離子性界面活性劑，可列舉十二烷基磺酸鈉等。另外，作為兩離子性界面活性劑，可列舉：胺基酸系界面活性劑、甜菜鹼系界面活性劑、胺氧化物系界面活性劑等。作為胺基酸系界面活性劑，可列舉醯基麩胺酸等。作為甜菜鹼系界面活性劑，可列舉月桂基二甲基胺基乙酸甜菜鹼、硬脂基二甲基胺基乙酸甜菜鹼等。作為胺氧化物系界面活性劑，例如可列舉月桂基二甲基胺氧化物等。Examples of the ionic surfactant include a cationic surfactant, an anionic surfactant, and a diionic surfactant. Examples of the cationic surfactant include cetyltrimethylammonium bromide and cetyltrimethylammonium chloride. Examples of the anionic surfactant include sodium dodecylsulfonate. Examples of the diionic surfactant include amino acid-based surfactants, betaine-based surfactants, and amine oxide-based surfactants. Examples of the amino acid-based surfactants include amidinoglutamic acid and the like. Examples of the betaine-based surfactant include lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, and the like. Examples of the amine oxide-based surfactant include lauryldimethylamine oxide.

認為該些界面活性劑於濕潤凝膠生成步驟中發揮如下作用：減小反應系統中的溶媒、與成長而來的矽氧烷聚合體之間的化學親和性的差異，抑制相分離。These surfactants are considered to play a role in the wet gel formation step by reducing the difference in chemical affinity between the solvent in the reaction system and the grown siloxane polymer, and suppressing phase separation.

界面活性劑的添加量亦受到界面活性劑的種類或矽化合物的種類以及量的影響，例如相對於矽化合物的總量100質量份，可為1質量份～100質量份，亦可為5質量份～60質量份。The amount of the surfactant added is also affected by the type of the surfactant or the type and amount of the silicon compound. For example, it may be 1 to 100 parts by mass, or 5 parts by mass, relative to 100 parts by mass of the total amount of the silicon compound. Parts to 60 parts by mass.

認為，熱水解性化合物藉由熱水解而產生鹼觸媒，使反應溶液成為鹼性，來促進濕潤凝膠生成步驟中的溶膠凝膠反應。因此，該熱水解性化合物只要為可於水解後使反應溶液成為鹼性的化合物，則並無特別限定，可列舉：脲；甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺等酸醯胺；六亞甲基四胺等環狀氮化合物等。該些中，特別是脲容易獲得所述促進效果。It is considered that a thermally hydrolyzable compound generates an alkali catalyst by thermal hydrolysis, makes the reaction solution alkaline, and promotes the sol-gel reaction in the wet gel generation step. Therefore, the thermally hydrolyzable compound is not particularly limited as long as it can make the reaction solution basic after hydrolysis, and examples thereof include urea; formamidine, N-methylformamide, and N, N- Acid amines such as dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and cyclic nitrogen compounds such as hexamethylenetetramine. Among these, urea is easy to obtain the said promotion effect.

熱水解性化合物的添加量只要為可充分促進濕潤凝膠生成步驟中的溶膠凝膠反應的量，則並無特別限定。例如，於使用脲作為熱水解性化合物的情況下，相對於矽化合物的總量100質量份，其添加量例如可為1質量份～200質量份，亦可為2質量份～150質量份。藉由將添加量設為1質量份以上，更容易獲得良好的反應性，另外，藉由設為200質量份以下，更容易抑制結晶的析出及凝膠密度的下降。The addition amount of the thermally hydrolyzable compound is not particularly limited as long as it is an amount that can sufficiently promote the sol-gel reaction in the wet gel generation step. For example, when urea is used as the thermally hydrolyzable compound, the addition amount may be, for example, 1 to 200 parts by mass, or 2 to 150 parts by mass, relative to 100 parts by mass of the total amount of the silicon compound. . By setting the addition amount to 1 part by mass or more, it is easier to obtain good reactivity, and by setting the amount to 200 parts by mass or less, it is easier to suppress the precipitation of crystals and the decrease in gel density.

溶膠生成步驟的水解亦受到混合液中的矽化合物、二氧化矽粒子、酸觸媒、界面活性劑等的種類及量的影響，例如可於20℃～60℃的溫度環境下進行10分鐘～24小時，亦可於50℃～60℃的溫度環境下進行5分鐘～8小時。藉此，矽化合物中的水解性官能基充分地水解，而可更確實地獲得矽化合物的水解產物。The hydrolysis in the sol-generating step is also affected by the types and amounts of silicon compounds, silicon dioxide particles, acid catalysts, and surfactants in the mixed solution. 24 hours, or 5 minutes to 8 hours in a temperature environment of 50 ° C to 60 ° C. Thereby, the hydrolyzable functional group in a silicon compound is fully hydrolyzed, and the hydrolyzate of a silicon compound can be obtained more reliably.

其中，於在溶媒中添加熱水解性化合物的情況下，亦可將溶膠生成步驟的溫度環境調節為抑制熱水解性化合物的水解而抑制溶膠的凝膠化的溫度。此時的溫度只要為可抑制熱水解性化合物的水解的溫度，則可為任意的溫度。例如，於使用脲作為熱水解性化合物的情況下，溶膠生成步驟的溫度環境可為0℃～40℃，亦可為10℃～30℃。Among them, when a thermally hydrolyzable compound is added to the solvent, the temperature environment of the sol generation step may be adjusted to a temperature that suppresses hydrolysis of the thermally hydrolyzable compound and suppresses gelation of the sol. The temperature at this time may be any temperature as long as it can suppress the hydrolysis of the thermally hydrolyzable compound. For example, in the case where urea is used as the thermally hydrolyzable compound, the temperature environment of the sol generation step may be 0 ° C to 40 ° C, or 10 ° C to 30 ° C.

（溶膠塗膜形成步驟） 溶膠塗膜形成步驟為將包含所述溶膠的溶膠塗液塗敷於絕熱對象物而形成溶膠塗膜的步驟。所述溶膠塗液亦可為包含所述溶膠的態樣。另外，所述溶膠塗液亦可為使所述溶膠以具有流動性的程度進行凝膠化（半凝膠化）而成者。例如為了促進凝膠化，溶膠塗液亦可包含鹼觸媒。(Sol Coating Film Forming Step) The sol coating film forming step is a step of applying a sol coating liquid containing the sol to an object to be insulated to form a sol coating film. The sol coating liquid may be in a state including the sol. The sol coating liquid may be one obtained by gelling (semi-gelling) the sol to such a degree that it has fluidity. For example, in order to promote gelation, the sol coating liquid may contain an alkali catalyst.

作為鹼觸媒，可列舉：氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銫等鹼金屬氫氧化物；氫氧化銨、氟化銨、氯化銨、溴化銨等銨化合物；偏磷酸鈉、焦磷酸鈉、多磷酸鈉等鹼性磷酸鈉鹽；烯丙基胺、二烯丙基胺、三烯丙基胺、異丙基胺、二異丙基胺、乙基胺、二乙基胺、三乙基胺、2-乙基己基胺、3-乙氧基丙基胺、二異丁基胺、3-(二乙基胺基)丙基胺、二-2-乙基己基胺、3-(二丁基胺基)丙基胺、四甲基乙二胺、第三丁基胺、第二丁基胺、丙基胺、3-(甲基胺基)丙基胺、3-(二甲基胺基)丙基胺、3-甲氧基胺、二甲基乙醇胺、甲基二乙醇胺、二乙醇胺、三乙醇胺等脂肪族胺類；嗎啉、N-甲基嗎啉、2-甲基嗎啉、哌嗪及其衍生物、哌啶及其衍生物、咪唑及其衍生物等含氮雜環狀化合物類等。該些中，氫氧化銨（氨水）於以下方面優異：由於揮發性高，難以殘存於乾燥後的氣凝膠中而不會損及耐水性的方面；以及經濟性的方面。所述鹼觸媒可單獨使用或將兩種以上混合使用。Examples of the alkali catalyst 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; Basic sodium phosphates such as sodium phosphate, sodium pyrophosphate, and sodium polyphosphate; allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, ethylamine, diamine Ethylamine, triethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethyl Hexylamine, 3- (dibutylamino) propylamine, tetramethylethylenediamine, third butylamine, second butylamine, propylamine, 3- (methylamino) propylamine , 3- (dimethylamino) propylamine, 3-methoxyamine, dimethylethanolamine, methyldiethanolamine, diethanolamine, triethanolamine and other aliphatic amines; morpholine, N-methyl? Nitrogen-containing heterocyclic compounds such as phthaloline, 2-methylmorpholine, piperazine and its derivatives, piperidine and its derivatives, imidazole and its derivatives, and the like. Among them, ammonium hydroxide (aqueous ammonia) is excellent in terms of high volatility and difficulty in remaining in the dried aerogel without impairing water resistance, and economical aspects. The alkali catalyst may be used alone or in combination of two or more.

藉由使用鹼觸媒，可促進溶膠中的矽化合物及二氧化矽粒子的脫水縮合反應、脫醇縮合反應、或所述兩種反應，且可以更短的時間進行溶膠的凝膠化。另外，藉此可獲得強度（剛性）更高的濕潤凝膠。特別是氨的揮發性高，難以殘留於氣凝膠中，因此藉由使用氨作為鹼觸媒，可獲得耐水性更優異的氣凝膠。By using an alkali catalyst, the dehydration condensation reaction, dealcoholization condensation reaction, or both of the silicon compound and silicon dioxide particles in the sol can be promoted, and gelation of the sol can be performed in a shorter time. In addition, a wet gel with higher strength (rigidity) can be obtained by this. In particular, ammonia has high volatility and is difficult to remain in aerogels. Therefore, by using ammonia as an alkali catalyst, an aerogel having more excellent water resistance can be obtained.

相對於矽化合物的總量100質量份，鹼觸媒的添加量例如可為0.5質量份～5質量份，亦可為1質量份～4質量份。藉由將所述添加量設為0.5質量份以上，可以更短的時間進行凝膠化，藉由設為5質量份以下，可進一步抑制耐水性的下降。The addition amount of the alkali catalyst may be, for example, 0.5 to 5 parts by mass, or 1 to 4 parts by mass with respect to 100 parts by mass of the total amount of the silicon compound. By setting the amount of addition to 0.5 parts by mass or more, gelation can be performed in a shorter period of time, and by setting to 5 parts by mass or less, a decrease in water resistance can be further suppressed.

於使所述溶膠進行半凝膠化的情況下，凝膠化可以溶媒及鹼觸媒不揮發的方式於密閉容器內進行。該情況下的凝膠化溫度例如可為30℃～90℃，亦可為40℃～80℃。藉由將凝膠化溫度設為30℃以上，可以更短的時間進行凝膠化。另外，藉由將凝膠化溫度設為90℃以下，容易抑制溶媒（特別是醇類）的揮發，因此可一面抑制體積收縮一面進行凝膠化。When the sol is semi-gelatinized, the gelation can be performed in a closed container in such a manner that the solvent and the alkali catalyst do not volatilize. The gelation temperature in this case may be, for example, 30 ° C to 90 ° C, or 40 ° C to 80 ° C. By setting the gelation temperature to 30 ° C or higher, gelation can be performed in a shorter time. In addition, by setting the gelation temperature to 90 ° C. or lower, volatilization of a solvent (especially alcohols) is easily suppressed, and thus gelation can be performed while suppressing volume shrinkage.

使所述溶膠進行半凝膠化時的凝膠化時間根據凝膠化溫度而不同，但於溶膠中含有二氧化矽粒子的情況下，與現有的氣凝膠中應用的溶膠相比較，可縮短凝膠化時間。推測其原因在於：溶膠中的矽化合物所具有的反應性基或矽烷醇基與二氧化矽粒子的矽烷醇基形成氫鍵或化學鍵。再者，凝膠化時間例如可為10分鐘～360分鐘，亦可為20分鐘～180分鐘。藉由凝膠化時間為10分鐘以上，溶膠的黏度適度地提高，於絕熱對象物的塗敷性提高，藉由為360分鐘以下，容易抑制溶膠完全地凝膠化，且容易獲得與絕熱對象物的良好的接著性。The gelation time when the sol is semi-gelatinized varies depending on the gelation temperature. However, when the sol contains silica particles, it can be compared with a sol applied to an existing aerogel. Reduce gelation time. It is speculated that the reason is that the reactive group or silanol group of the silicon compound in the sol forms a hydrogen bond or a chemical bond with the silanol group of the silicon dioxide particle. The gelation time may be, for example, 10 minutes to 360 minutes, or 20 minutes to 180 minutes. When the gelation time is 10 minutes or more, the viscosity of the sol is moderately increased, and the applicability to the heat-insulated object is improved. When the gelation time is 360 minutes or less, it is easy to suppress the complete gelation of the sol, and it is easy to obtain the heat-insulated object. Good adhesion of materials.

將溶膠塗液塗敷於絕熱對象物的方法並無特別限制，例如可列舉：浸漬塗佈、噴霧塗佈、旋轉塗佈、輥塗佈等。The method for applying the sol coating liquid to the object to be insulated is not particularly limited, and examples thereof include dip coating, spray coating, spin coating, and roll coating.

（濕潤凝膠生成步驟） 濕潤凝膠生成步驟例如為自所述溶膠塗膜生成濕潤凝膠的步驟。濕潤凝膠生成步驟中，例如藉由對所述溶膠塗膜進行加熱而使溶膠塗膜進行凝膠化後，藉由視需要使所獲得的凝膠熟化而生成濕潤凝膠。濕潤凝膠生成步驟亦可以溶媒及鹼觸媒不揮發的方式於密閉容器內進行。若於濕潤凝膠生成步驟中使凝膠熟化，則構成濕潤凝膠的成分的結合變強，結果為，容易獲得對於抑制乾燥時的收縮而言充分的強度（剛性）高的濕潤凝膠。濕潤凝膠生成步驟中的加熱溫度及熟化溫度例如可為30℃～90℃，亦可為40℃～80℃。藉由將加熱溫度或熟化溫度設為30℃以上，可獲得強度（剛性）更高的濕潤凝膠，藉由將加熱溫度或熟化溫度設為90℃以下，容易抑制溶媒（特別是醇類）的揮發，因此可一面抑制體積收縮一面進行凝膠化。(Wet Gel Generation Step) The wet gel generation step is, for example, a step of generating a wet gel from the sol coating film. In the wet gel generation step, for example, the sol coating film is gelled by heating the sol coating film, and then the obtained gel is matured as necessary to generate a wet gel. The wet gel formation step can also be performed in a closed container in a manner that the solvent and the alkali catalyst are not volatile. When the gel is matured in the wet gel generation step, the binding of the components constituting the wet gel is strengthened, and as a result, a wet gel having high strength (rigidity) sufficient to suppress shrinkage during drying is easily obtained. The heating temperature and the aging temperature in the wet gel generation step may be, for example, 30 ° C to 90 ° C, or 40 ° C to 80 ° C. By setting the heating temperature or curing temperature to 30 ° C or higher, a wet gel with higher strength (rigidity) can be obtained. By setting the heating temperature or curing temperature to 90 ° C or lower, the solvent (especially alcohols) is easily suppressed. As a result, the gelation can be performed while suppressing the volume shrinkage.

（清洗及溶媒置換步驟） 清洗及溶媒置換步驟為具有以下步驟的步驟：對藉由所述濕潤凝膠生成步驟而獲得的濕潤凝膠進行清洗的步驟（清洗步驟）；以及將濕潤凝膠中的清洗液置換為適合於乾燥條件（後述的乾燥步驟）的溶媒的步驟（溶媒置換步驟）。清洗及溶媒置換步驟亦可以不進行對濕潤凝膠進行清洗的步驟，而僅進行溶媒置換步驟的形態來實施，但就減少濕潤凝膠中的未反應物、副產物等雜質，可製造純度更高的氣凝膠的觀點而言，亦可對濕潤凝膠進行清洗。再者，於在凝膠中包含二氧化矽粒子的情況下，如後所述，溶媒置換步驟並非必需。(Washing and Solvent Replacement Step) The washing and solvent replacement step is a step having a step of washing the wet gel obtained by the wet gel generation step (washing step); and A step (solvent replacement step) of replacing the cleaning solution with a solvent suitable for drying conditions (the drying step described later). The cleaning and solvent replacement steps may be performed without the step of cleaning the wet gel, and only the solvent replacement step may be performed. However, impurities such as unreacted substances and by-products in the wet gel can be reduced, and the purity can be improved. From the viewpoint of a high aerogel, the wet gel can also be cleaned. When silica particles are contained in the gel, as described later, the solvent replacement step is not necessary.

清洗步驟中，對所述濕潤凝膠生成步驟中獲得的濕潤凝膠進行清洗。該清洗可使用例如水或有機溶媒來反覆進行。此時，可藉由加溫來提高清洗效率。In the washing step, the wet gel obtained in the wet gel generation step is washed. This washing can be performed repeatedly using, for example, water or an organic solvent. In this case, the cleaning efficiency can be improved by heating.

作為有機溶媒，例如可使用：甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、丙酮、甲基乙基酮、1,2-二甲氧基乙烷、乙腈、己烷、甲苯、二***、氯仿、乙酸乙酯、四氫呋喃、二氯甲烷、N、N-二甲基甲醯胺、二甲基亞碸、乙酸、甲酸等各種有機溶媒。所述有機溶媒可單獨使用或將兩種以上混合使用。As the organic solvent, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, acetonitrile, and hexane can be used. , Toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran, dichloromethane, N, N-dimethylformamide, dimethylmethane, acetic acid, formic acid and other organic solvents. The organic solvents may be used alone or as a mixture of two or more.

於後述的溶媒置換步驟中，為了抑制由乾燥引起的凝膠的收縮，可使用低表面張力的溶媒。其中，低表面張力的溶媒一般與水的相互溶解度極低。因此，於溶媒置換步驟中使用低表面張力的溶媒的情況下，作為清洗步驟中使用的有機溶媒，可列舉對水及低表面張力的溶媒的兩者具有高的相互溶解性的親水性有機溶媒。再者，清洗步驟中使用的親水性有機溶媒可發揮用以進行溶媒置換步驟的預置換的作用。所述有機溶媒中，作為親水性有機溶媒，可列舉：甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮等。再者，甲醇、乙醇、甲基乙基酮等於經濟性的方面優異。In the solvent replacement step described later, in order to suppress shrinkage of the gel caused by drying, a solvent having a low surface tension can be used. Among them, the low surface tension solvent generally has extremely low mutual solubility with water. Therefore, when a low surface tension solvent is used in the solvent replacement step, examples of the organic solvent used in the cleaning step include hydrophilic organic solvents that have high mutual solubility with respect to both water and low surface tension solvent. . Furthermore, the hydrophilic organic solvent used in the washing step can perform a pre-replacement function for performing the solvent replacement step. Among the organic solvents, examples of the hydrophilic organic solvent include methanol, ethanol, 2-propanol, acetone, and methyl ethyl ketone. Furthermore, methanol, ethanol, and methyl ethyl ketone are excellent in terms of economic efficiency.

清洗步驟中使用的水或有機溶媒的量可設為可將濕潤凝膠中的溶媒充分置換、清洗的量。相對於濕潤凝膠的容量，該量例如可設為3倍～10倍的量。可反覆進行清洗，直至例如清洗後的濕潤凝膠中的含水率相對於二氧化矽質量而成為10質量%以下。The amount of water or organic solvent used in the washing step may be an amount sufficient to replace and clean the solvent in the wet gel. This amount can be, for example, an amount of 3 to 10 times the capacity of the wet gel. It can be repeatedly washed until, for example, the moisture content in the wet gel after washing becomes 10% by mass or less with respect to the mass of silicon dioxide.

清洗步驟中的溫度環境可設為清洗中使用的溶媒的沸點以下的溫度。例如於使用甲醇的情況下，亦可為30℃～60℃左右的溫度。The temperature environment in the washing step can be set to a temperature below the boiling point of the solvent used in the washing. For example, when using methanol, the temperature may be about 30 ° C to 60 ° C.

於溶媒置換步驟中，為了抑制後述的乾燥步驟中的收縮，將經清洗的濕潤凝膠的溶媒置換為規定的置換用溶媒。此時，可藉由加溫來提高置換效率。作為置換用溶媒，具體而言，乾燥步驟中於在未滿乾燥中所使用的溶媒的臨界點的溫度下，在大氣壓下進行乾燥的情況下，可列舉後述的低表面張力的溶媒。另一方面，於進行超臨界乾燥的情況下，作為置換用溶媒，例如可列舉：乙醇、甲醇、2-丙醇、二氯二氟甲烷、二氧化碳等、或者將該些溶媒混合兩種以上而成的溶媒。In the solvent replacement step, in order to suppress shrinkage in the drying step described later, the solvent of the washed wet gel is replaced with a predetermined replacement solvent. In this case, the replacement efficiency can be improved by heating. As the replacement solvent, specifically, when the drying step is performed at a temperature lower than the critical point of the solvent used in the drying under atmospheric pressure, a low surface tension solvent described later may be mentioned. On the other hand, in the case of performing supercritical drying, examples of the replacement solvent include ethanol, methanol, 2-propanol, dichlorodifluoromethane, and carbon dioxide, or by mixing two or more of these solvents and Into a solvent.

作為低表面張力的溶媒，可列舉20℃下的表面張力為30 mN/m以下者。再者，該表面張力可為25 mN/m以下，或者亦可為20 mN/m以下。作為低表面張力的溶媒，例如可列舉：戊烷（15.5）、己烷（18.4）、庚烷（20.2）、辛烷（21.7）、2-甲基戊烷（17.4）、3-甲基戊烷（18.1）、2-甲基己烷（19.3）、環戊烷（22.6）、環己烷（25.2）、1-戊烯（16.0）等脂肪族烴類；苯（28.9）、甲苯（28.5）、間二甲苯（28.7）、對二甲苯（28.3）等芳香族烴類；二氯甲烷（27.9）、氯仿（27.2）、四氯化碳（26.9）、1-氯丙烷（21.8）、2-氯丙烷（18.1）等鹵化烴類；***（17.1）、丙醚（20.5）、異丙醚（17.7）、丁基***（20.8）、1,2-二甲氧基乙烷（24.6）等醚類；丙酮（23.3）、甲基乙基酮（24.6）、甲基丙基酮（25.1）、二乙基酮（25.3）等酮類；乙酸甲酯（24.8）、乙酸乙酯（23.8）、乙酸丙酯（24.3）、乙酸異丙酯（21.2）、乙酸異丁酯（23.7）、丁酸乙酯（24.6）等酯類等（括弧內表示20℃下的表面張力，單位為[mN/m]）。該些溶媒中，脂肪族烴類（己烷、庚烷等）為低表面張力且作業環境性優異。另外，該些溶媒中，藉由使用丙酮、甲基乙基酮、1,2-二甲氧基乙烷等親水性有機溶媒，可兼用作所述清洗步驟的有機溶媒。再者，該些溶媒中，就後述的乾燥步驟中的乾燥更容易的方面而言，亦可使用常壓下的沸點為100℃以下的溶媒。所述溶媒可單獨使用或將兩種以上混合使用。Examples of the low surface tension solvent include those having a surface tension of 20 mN / m or less at 20 ° C. 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), and 3-methylpentane. Aliphatic hydrocarbons such as alkane (18.1), 2-methylhexane (19.3), cyclopentane (22.6), cyclohexane (25.2), 1-pentene (16.0); benzene (28.9), toluene (28.5 ), M-xylene (28.7), para-xylene (28.3) and other aromatic hydrocarbons; dichloromethane (27.9), chloroform (27.2), carbon tetrachloride (26.9), 1-chloropropane (21.8), 2 -Halogenated hydrocarbons such as chloropropane (18.1); diethyl ether (17.1), propyl ether (20.5), isopropyl ether (17.7), butyl ether (20.8), 1,2-dimethoxyethane (24.6), etc. Ethers; ketones such as acetone (23.3), methyl ethyl ketone (24.6), methylpropyl ketone (25.1), diethyl ketone (25.3); methyl acetate (24.8), ethyl acetate (23.8) , Propyl acetate (24.3), isopropyl acetate (21.2), isobutyl acetate (23.7), ethyl butyrate (24.6) and other esters (the brackets indicate the surface tension at 20 ° C, the unit is [mN / m]). Among these solvents, aliphatic hydrocarbons (such as hexane and heptane) have a low surface tension and are excellent in working environment. Among these solvents, by using a hydrophilic organic solvent such as acetone, methyl ethyl ketone, or 1,2-dimethoxyethane, the solvent can also be used as the organic solvent in the cleaning step. Among these solvents, a solvent having a boiling point of 100 ° C. or lower at normal pressure may be used in terms of easier drying in a drying step described later. The solvents may be used alone or in combination of two or more.

溶媒置換步驟中使用的溶媒的量可設為可將清洗後的濕潤凝膠中的溶媒充分置換的量。相對於濕潤凝膠的容量，該量例如可設為3倍～10倍的量。The amount of the solvent used in the solvent replacement step may be an amount sufficient to replace the solvent in the wet gel after washing. This amount can be, for example, an amount of 3 to 10 times the capacity of the wet gel.

溶媒置換步驟中的溫度環境可設為置換中使用的溶媒的沸點以下的溫度。例如於使用庚烷的情況下，亦可為30℃～60℃左右的溫度。The temperature environment in the solvent replacement step may be a temperature below the boiling point of the solvent used in the replacement. For example, when using heptane, the temperature may be about 30 ° C to 60 ° C.

再者，如所述般，於在凝膠中包含二氧化矽粒子的情況下，溶媒置換步驟並非必需。所推測的機制如下所述。於不包含二氧化矽粒子的情況下，為了抑制乾燥步驟中的收縮，較佳為將濕潤凝膠的溶媒置換為規定的置換用溶媒（低表面張力的溶媒）。另一方面，於包含二氧化矽粒子的情況下，藉由二氧化矽粒子作為三維網眼狀的骨架的支撐體而發揮功能，該骨架被支撐，乾燥步驟中的凝膠的收縮得到抑制。因而，認為可不置換用於清洗的溶媒，而將凝膠直接賦予至乾燥步驟。再者，如此，可實現自清洗及溶媒置換步驟至乾燥步驟的簡化，但絲毫不排除進行溶媒置換步驟。Furthermore, as described above, when silica particles are included in the gel, the solvent replacement step is not necessary. The speculated mechanism is as follows. When the silica particles are not contained, in order to suppress shrinkage in the drying step, it is preferable to replace the solvent of the wet gel with a predetermined replacement solvent (low surface tension solvent). On the other hand, when the silica particles are contained, the silica particles function as a support for a three-dimensional mesh-like skeleton, the skeleton is supported, and the shrinkage of the gel in the drying step is suppressed. Therefore, it is considered that the gel can be directly supplied to the drying step without replacing the solvent used for washing. In addition, in this way, the simplification from the cleaning and solvent replacement steps to the drying step can be achieved, but the solvent replacement step is not excluded at all.

（乾燥步驟） 乾燥步驟中，使如上所述經清洗（及視需要經溶媒置換）的濕潤凝膠進行乾燥。(Drying step) In the drying step, the wet gel that has been washed (and optionally replaced with a solvent) as described above is dried.

乾燥的方法並無特別限制，可使用公知的常壓乾燥、超臨界乾燥或者冷凍乾燥。該些方法中，就容易製造低密度的氣凝膠的觀點而言，可使用常壓乾燥或超臨界乾燥。另外，就可以低成本來生產的觀點而言，可使用常壓乾燥。再者，本實施形態中，所謂常壓是指0.1 MPa（大氣壓）。The method of drying is not particularly limited, and known atmospheric pressure drying, supercritical drying, or freeze drying can be used. Among these methods, normal-pressure drying or supercritical drying can be used from the viewpoint of easily producing a low-density aerogel. In addition, from the viewpoint that production can be performed at low cost, atmospheric pressure drying can be used. In this embodiment, the normal pressure means 0.1 MPa (atmospheric pressure).

本實施形態的氣凝膠例如可藉由將經清洗及（視需要）溶媒置換的濕潤凝膠，於未滿乾燥中所使用的溶媒的臨界點的溫度下且於大氣壓下進行乾燥而獲得。乾燥溫度根據所置換的溶媒（於未進行溶媒置換的情況下為清洗中所使用的溶媒）的種類而不同，但鑒於存在特別是高溫下的乾燥加快溶媒的蒸發速度而使凝膠產生大的龜裂的情況的方面，例如可為20℃～150℃，亦可為60℃～120℃。另外，乾燥時間根據濕潤凝膠的容量及乾燥溫度而不同，例如可設為4小時～120小時。再者，本實施形態中，於不阻礙生產性的範圍內施加未滿臨界點的壓力來加快乾燥的情況亦包含於常壓乾燥中。The aerogel of this embodiment can be obtained, for example, by drying a wet gel that has been washed and (if necessary) replaced with a solvent, at a temperature below the critical point of the solvent used for drying, and at atmospheric pressure. The drying temperature varies depending on the type of the solvent to be replaced (the solvent used for cleaning without solvent replacement), but in view of the existence of drying, especially at high temperatures, the evaporation rate of the solvent is accelerated, resulting in a large gel. In the case of cracking, it may be, for example, 20 ° C to 150 ° C, or 60 ° C to 120 ° C. The drying time varies depending on the capacity of the wet gel and the drying temperature, and it can be set to, for example, 4 hours to 120 hours. Furthermore, in the present embodiment, the case where the drying is accelerated by applying a pressure less than the critical point in a range that does not hinder the productivity is also included in the normal-pressure drying.

就抑制因急遽的乾燥造成的氣凝膠的裂紋的觀點而言，本實施形態的氣凝膠形成步驟中可於乾燥步驟之前進行預乾燥。預乾燥溫度例如可為60℃～180℃，亦可為90℃～150℃。預乾燥時間根據氣凝膠的容量及乾燥溫度而不同，例如亦可為1分鐘～30分鐘。From the viewpoint of suppressing cracking of the aerogel due to rapid drying, the aerogel forming step of the present embodiment may be pre-dried before the drying step. The pre-drying temperature may be, for example, 60 ° C to 180 ° C, or 90 ° C to 150 ° C. The pre-drying time varies depending on the capacity of the aerogel and the drying temperature, and may be, for example, 1 minute to 30 minutes.

乾燥步驟中的乾燥方法例如亦可為超臨界乾燥。超臨界乾燥可利用公知的方法來進行。作為進行超臨界乾燥的方法，例如可列舉以濕潤凝膠中所含的溶媒的臨界點以上的溫度及壓力來去除溶媒的方法。或者，作為進行超臨界乾燥的方法，可列舉如下方法：藉由以例如20℃～25℃、5 MPa～20 MPa左右的條件，將濕潤凝膠浸漬於液化二氧化碳中，而將濕潤凝膠中所含的溶媒的全部或一部分置換為臨界點低於該溶媒的二氧化碳，然後將二氧化碳單獨去除，或者將二氧化碳及溶媒的混合物去除。The drying method in the drying step may be, for example, supercritical drying. Supercritical drying can be performed by a known method. Examples of the method for performing supercritical drying include a method of removing a solvent at a temperature and pressure higher than a critical point of a solvent contained in a wet gel. Alternatively, as a method for performing supercritical drying, there can be mentioned a method in which a wet gel is immersed in liquefied carbon dioxide under conditions of, for example, 20 ° C to 25 ° C and about 5 MPa to 20 MPa. All or part of the contained solvent is replaced with carbon dioxide having a critical point lower than the solvent, and then the carbon dioxide is removed alone, or a mixture of carbon dioxide and the solvent is removed.

藉由此種的常壓乾燥或超臨界乾燥而獲得的氣凝膠亦可進而於常壓下，於105℃～200℃下追加乾燥0.5小時～2小時左右。藉此，更容易獲得密度低、具有小的細孔的氣凝膠。追加乾燥亦可於常壓下，於150℃～200℃下進行。The aerogel obtained by such normal-pressure drying or supercritical drying can be further dried at 105 ° C to 200 ° C for about 0.5 to 2 hours under normal pressure. This makes it easier to obtain an aerogel having a low density and small pores. The additional drying may be performed at 150 ° C to 200 ° C under normal pressure.

B：塗層步驟 塗層步驟例如可具備：溶液製備步驟，製備包含塗佈材料及溶媒的塗佈液；滲透步驟，使所獲得的塗佈液滲透至氣凝膠中；以及溶媒去除步驟，自滲透的塗佈液中去除溶媒。B: Coating step The coating step may include, for example, a solution preparation step to prepare a coating liquid including a coating material and a solvent, an infiltration step to infiltrate the obtained coating liquid into the aerogel, and a solvent removal step, The solvent is removed from the permeated coating liquid.

（溶液製備步驟） 藉由向溶媒中添加塗佈材料來製備塗佈液。就對氣凝膠的滲透性的觀點而言，溶媒可使用有機溶媒。就容易於低溫下進行後續步驟中的溶媒去除的觀點而言，有機溶媒可使用蒸氣壓小的有機溶媒，特別是可使用沸點為100℃以下的有機溶媒。作為有機溶媒，具體可使用：甲醇、乙醇、異丙醇、1、4-二噁烷、二氯甲烷、苯、環己烷、乙酸甲酯、乙酸乙酯、丙酮、甲基乙基酮等。(Solution Preparation Step) A coating liquid is prepared by adding a coating material to a solvent. From the viewpoint of permeability to the aerogel, an organic solvent can be used as the solvent. From the viewpoint of easily removing the solvent in the subsequent steps at a low temperature, an organic solvent having a small vapor pressure can be used as the organic solvent, and particularly, an organic solvent having a boiling point of 100 ° C. or lower can be used. As the organic solvent, specifically, methanol, ethanol, isopropanol, 1,4-dioxane, dichloromethane, benzene, cyclohexane, methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, etc. can be used. .

就形成適度的厚度的塗層的觀點而言，塗佈液中的塗佈材料的含量（固體成分）可設為1質量%以上，亦可為5質量%以上，或者可設為40質量%以下，亦可為20質量%以下。即，塗佈材料的含量可設為1質量%～40質量%，亦可為5質量%～20質量%。From the viewpoint of forming a coating with a moderate thickness, the content (solid content) of the coating material in the coating liquid may be 1% by mass or more, may be 5% by mass or more, or may be 40% by mass. Below, it may be 20% by mass or less. That is, the content of the coating material may be 1 to 40% by mass, or 5 to 20% by mass.

就充分確保對氣凝膠的滲透性的觀點而言，塗佈液的黏度於25℃下可設為35 mPa·s以下。就同樣的觀點而言，該黏度可為20 mPa·s以下，亦可為10 mPa·s以下。該黏度的下限並無特別限定，就滲透步驟的製程的概度（likelihood）的觀點而言，可設為1 mPa·s。黏度可利用E型黏度計、振動式黏度計等來進行測定。From the viewpoint of sufficiently ensuring the permeability to the aerogel, the viscosity of the coating liquid can be set to 35 mPa · s or less at 25 ° C. From the same viewpoint, the viscosity may be 20 mPa · s or less, or 10 mPa · s or less. The lower limit of the viscosity is not particularly limited, and may be set to 1 mPa · s from the viewpoint of the likelihood of the process of the infiltration step. The viscosity can be measured with an E-type viscometer, a vibratory viscometer, or the like.

（滲透步驟） 於本步驟中，使所製備的塗佈液以充分地遍及氣凝膠內部的空隙中的方式進行滲透。具體可列舉：使氣凝膠浸漬於塗佈液中的浸漬法、將塗佈液塗佈於氣凝膠的塗佈法等。滲透方法並無限制，只要為與氣凝膠的大小、形狀等相應的較佳的方法即可。本實施形態中，為了將塗佈液滲透至氣凝膠的深部（例如與絕熱對象物相接之側）而使用適度地稀釋的塗佈液。本步驟特別是基於使塗佈材料滲透至氣凝膠的內部來強化氣凝膠的骨架自身這一思想，而非基於在氣凝膠的表面設置樹脂層等這一思想。藉此，除可改善掉粉以外，亦可改善氣凝膠的脆性，因此可獲得絕熱可靠性優異的被絕熱體。(Permeation step) In this step, the prepared coating liquid is permeated so as to sufficiently penetrate the voids inside the aerogel. Specific examples include an immersion method in which an aerogel is immersed in a coating liquid, a coating method in which a coating liquid is applied to an aerogel, and the like. The method of penetration is not limited, as long as it is a preferable method corresponding to the size, shape, and the like of the aerogel. In this embodiment, in order to permeate a coating liquid to a deep part of the aerogel (for example, the side in contact with the object to be insulated), a coating solution that is appropriately diluted is used. This step is based in particular on the idea of strengthening the aerogel skeleton itself by infiltrating the coating material into the aerogel, rather than on the idea of providing a resin layer on the surface of the aerogel. Thereby, in addition to the powder removal, the brittleness of the aerogel can be improved, so that a heat-insulated body having excellent thermal insulation reliability can be obtained.

於浸漬法的情況下，使塗佈液滲透的時間依存於塗佈液的黏度、氣凝膠的潤濕性等，因此，不能一概而論，但可設為至少5秒以上，亦可為10秒以上，抑或可為30秒以上。即便滲透的時間長，亦無特別問題，就作業效率的觀點而言，可設為1分鐘左右。In the case of the dipping method, the time for the coating liquid to penetrate depends on the viscosity of the coating liquid and the wettability of the aerogel. Therefore, it cannot be generalized, but it can be set to at least 5 seconds or 10 seconds. The above may be 30 seconds or more. There is no particular problem even if the penetration time is long, and it can be set to about 1 minute from the viewpoint of work efficiency.

於塗佈法的情況下，作為塗敷方法（塗敷機），可利用：模塗佈機、缺角輪塗佈機、棒塗佈機、吻合式塗佈機、輥塗佈機等。另外，就以塗佈液充分地充滿氣凝膠的空隙的觀點而言，塗佈量可設為氣凝膠的體積的90%～120%。若塗佈量為90%以上，則容易抑制相對於氣凝膠的處理不均，若為120%以下，則於溶媒去除後不易於氣凝膠複合體上殘留多餘的樹脂。In the case of the coating method, as the coating method (coater), a die coater, a notch wheel coater, a rod coater, a staple coater, a roll coater, and the like can be used. In addition, from the viewpoint that the coating solution sufficiently fills the voids of the aerogel, the coating amount may be 90% to 120% of the volume of the aerogel. If the coating amount is 90% or more, it is easy to suppress the processing unevenness with respect to the aerogel, and if it is 120% or less, it is difficult to leave excess resin on the aerogel composite after the solvent is removed.

滲透步驟中的溫度可根據塗佈材料的種類、塗佈液中的塗佈材料的含量等，以塗佈液容易滲透至氣凝膠中的方式適宜調整。例如，藉由以使塗佈液滲透至氣凝膠時的塗佈液的黏度成為35 mPa·s以下的方式調整溫度，可更佳地實施滲透步驟。再者，就兼顧作業效率與良好的滲透性的觀點而言，該溫度例如可設為0℃～80℃，亦可為10℃～60℃，抑或可為20℃～40℃。The temperature in the infiltration step can be appropriately adjusted so that the coating liquid easily penetrates into the aerogel according to the type of the coating material, the content of the coating material in the coating liquid, and the like. For example, by adjusting the temperature so that the viscosity of the coating liquid when the coating liquid permeates into the aerogel becomes 35 mPa · s or less, the permeation step can be performed better. In addition, from the viewpoint of balancing work efficiency and good permeability, the temperature may be, for example, 0 ° C to 80 ° C, may be 10 ° C to 60 ° C, or may be 20 ° C to 40 ° C.

（溶媒去除步驟） 於本步驟中，自滲透有塗佈液的氣凝膠中去除塗佈液中的溶媒。藉此，於氣凝膠中保持多孔性的結構的狀態下，由氣凝膠粒子形成的骨架的表面由塗佈材料被覆。(Solvent Removal Step) In this step, the solvent in the coating liquid is removed from the aerogel in which the coating liquid has penetrated. Thereby, while the porous structure is maintained in the aerogel, the surface of the skeleton formed of the aerogel particles is covered with the coating material.

溶媒的去除依存於氣凝膠的厚度、塗佈材料的種類等，因此，不能一概而論，就容易控制溶媒的蒸發速度的觀點而言，可以50℃～150℃的加熱溫度進行。就同樣的觀點而言，加熱溫度亦可為60～120。加熱時間因加熱溫度而異，就確保作業效率，並充分地加熱至具有導熱抑制性的氣凝膠的內部的觀點而言，可設為1小時～18小時，亦可為1小時～5小時。The removal of the solvent depends on the thickness of the aerogel, the type of coating material, and the like. Therefore, it cannot be generalized. From the viewpoint of easily controlling the evaporation rate of the solvent, it can be performed at a heating temperature of 50 ° C to 150 ° C. From the same viewpoint, the heating temperature may be 60 to 120. The heating time varies depending on the heating temperature. From the viewpoint of ensuring the work efficiency and sufficiently heating the inside of the aerogel having thermal conductivity suppression, it can be set to 1 to 18 hours, or 1 to 5 hours. .

再者，就抑制因伴隨溶媒的揮發的發泡等導致氣凝膠遭到破壞的觀點而言，加熱處理可分多階段進行。例如，亦可進行主要去除溶媒的第一階段加熱（低溫加熱）及主要使樹脂硬化的第二階段加熱（高溫加熱）。加熱溫度及加熱時間只要於所述範圍內適宜設定即可。In addition, from the viewpoint of suppressing destruction of the aerogel due to foaming due to volatilization of the solvent, the heat treatment can be performed in multiple stages. For example, the first-stage heating (low-temperature heating) mainly removing the solvent and the second-stage heating (high-temperature heating) mainly curing the resin may be performed. The heating temperature and the heating time may be appropriately set within the above-mentioned ranges.

C：阻障層形成步驟 於阻障層形成步驟中，例如使含有阻障層形成材料的阻障層形成用組成物與氣凝膠複合體接觸後，視需要進行加熱及乾燥，藉此使阻障層形成於氣凝膠複合體上。於在氣凝膠複合體上設有其他層的情況下，阻障層形成用組成物只要與其他層接觸即可。再者，本步驟與所述塗層步驟不同，並非以使阻障層形成用組成物滲透至氣凝膠複合體內為目的。因而，於與所述塗佈液的對比中，例如阻障層形成用組成物中的阻障層形成材料的含量（固體成分）可設為至少超過40質量%，另外，阻障層形成用組成物的黏度於25℃下可設為至少超過35 mPa·s。再者，於採用阻障層形成用組成物不滲透至氣凝膠複合體中的接觸方法（例如，後述的噴霧塗佈）的情況下，亦可將阻障層形成材料的含量設為40質量%左右，或者將阻障層形成用組成物的黏度設為10 mPa·s左右。C: Barrier layer forming step In the barrier layer forming step, for example, after the barrier layer forming composition containing the barrier layer forming material is brought into contact with the aerogel composite, it is heated and dried as necessary to thereby A barrier layer is formed on the aerogel composite. When another layer is provided on the aerogel composite, the composition for forming a barrier layer may be in contact with the other layer. In addition, this step is different from the coating step, not for the purpose of allowing the composition for forming a barrier layer to penetrate into the aerogel composite. Therefore, in comparison with the coating liquid, for example, the content (solid content) of the barrier layer-forming material in the composition for forming the barrier layer can be set to at least more than 40% by mass. The viscosity of the composition can be set to at least 35 mPa · s at 25 ° C. When a contact method (for example, spray coating to be described later) that does not penetrate the aerogel composite is used for the composition for forming the barrier layer, the content of the barrier layer-forming material may be set to 40. About mass%, or the viscosity of the composition for forming a barrier layer is set to about 10 mPa · s.

接觸方法可根據阻障層形成用組成物的種類、阻障層的厚度、或氣凝膠複合體的斥水性等來適宜選擇。作為接觸方法，例如可列舉：浸漬塗佈、噴霧塗佈、旋轉塗佈、輥塗佈等。其中，就容易抑制阻障層形成用組成物於氣凝膠內部的滲透的觀點而言，可較佳地利用噴霧塗佈。The contact method can be appropriately selected according to the type of the composition for forming the barrier layer, the thickness of the barrier layer, or the water repellency of the aerogel composite. Examples of the contact method include dip coating, spray coating, spin coating, and roll coating. Among them, spray coating can be preferably used from the viewpoint that it is easy to suppress the penetration of the composition for forming the barrier layer into the aerogel.

阻障層形成步驟中，就使阻障層形成用組成物乾燥及固著的觀點而言，亦可實施加熱處理，就去除雜質的觀點而言，亦可進行清洗或乾燥。In the barrier layer formation step, from the viewpoint of drying and fixing the composition for forming the barrier layer, heat treatment may be performed, and from the viewpoint of removing impurities, washing or drying may be performed.

如以上所說明的本實施形態的被絕熱體於絕熱對象物具備作為藉由塗佈材料而骨架得到強化的氣凝膠的氣凝膠複合體。因此，具有氣凝膠自身的優異的低導熱性，並且具有可長期表現出該低導熱性的韌性。就此種優點而言，本實施形態的氣凝膠複合體可應用於作為極低溫容器、太空領域、建築領域、汽車領域、家電領域、半導體領域、產業用設備等各種環境下的絕熱材的用途等。 [實施例]As described above, the object to be insulated of the present embodiment includes an aerogel composite as an aerogel whose skeleton is reinforced by a coating material. Therefore, the aerogel itself has excellent low thermal conductivity and toughness that can exhibit such low thermal conductivity for a long period of time. In view of such advantages, the aerogel composite of this embodiment can be used as a thermal insulation material in various environments such as extremely low-temperature containers, space, construction, automobiles, home appliances, semiconductors, and industrial equipment. Wait. [Example]

以下，藉由實施例對本發明進一步進行詳細說明，但本發明並不限定於該些實施例。 （基材的準備）Hereinafter, the present invention will be further described in detail through examples, but the present invention is not limited to these examples. (Preparation of substrate)

作為基材，準備以下者。 氣凝膠複合體韌性評價用：鋁合金板：A6061P（竹內金屬箔粉工業股份有限公司製造，製品名，尺寸：300 mm×300 mm×0.5 mm，鋁陽極氧化處理） 氣凝膠複合體密度測定用：鋁箔（厚度20 μm） 氣凝膠複合體透過率測定用：載玻片（松浪硝子工業股份有限公司製造，製品名S1214：厚度1.3 mm）As the substrate, the following was prepared. For evaluation of aerogel composite toughness: Aluminum alloy plate: A6061P (manufactured by Takeuchi Metal Foil Powder Co., Ltd., product name, size: 300 mm × 300 mm × 0.5 mm, anodized aluminum) Aerogel composite For density measurement: aluminum foil (thickness 20 μm) For aerogel composite transmittance measurement: glass slide (made by Songlang Glass Industry Co., Ltd., product name S1214: thickness 1.3 mm)

（溶膠塗液的製備） 將200.0質量份的水、作為酸觸媒的0.10質量份的乙酸、作為陽離子系界面活性劑的20.0質量份的CTAB以及作為熱水解性化合物的120.0質量份的脲進行混合，於其中加入作為聚矽氧烷化合物的40.0質量份的所述通式（B）所表示的兩末端二官能烷氧基改質聚矽氧烷化合物（以下，稱為「聚矽氧烷化合物A」）以及作為矽化合物的60.0質量份的MTMS，於25℃下進行2小時反應。之後，於60℃下花費2小時進行溶膠凝膠反應而獲得溶膠塗液。(Preparation of Sol Coating Solution) 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermally hydrolyzable compound The mixture was mixed, and 40.0 parts by mass of a polysiloxane compound represented by the general formula (B) was added to the two-terminal difunctional alkoxy-modified polysiloxane compound (hereinafter referred to as "polysiloxane" The alkane compound A ″) and 60.0 parts by mass of MTMS as a silicon compound were reacted at 25 ° C. for 2 hours. Thereafter, a sol-gel reaction was performed at 60 ° C for 2 hours to obtain a sol coating liquid.

再者，所述「聚矽氧烷化合物A」是以如下方式來合成。首先，於具備攪拌機、溫度計及戴氏（Dimroth）冷卻管的1 L的三口燒瓶中，將100.0質量份的兩末端具有矽烷醇基的二甲基聚矽氧烷（邁圖公司製造，製品名：XC96-723）、181.3質量份的甲基三甲氧基矽烷及0.50質量份的第三丁基胺混合，於30℃下反應5小時。之後，於1.3 kPa的減壓下，於140℃下對所述反應液進行2小時加熱而將揮發成分去除，藉此獲得兩末端二官能烷氧基改質聚矽氧烷化合物（聚矽氧烷化合物A）。The "polysiloxane compound A" was synthesized as follows. First, in a 1 L three-necked flask equipped with a stirrer, a thermometer, and a Dimroth cooling pipe, 100.0 parts by mass of dimethylpolysiloxane (manufactured by Momentive, Inc., product name, having a silanol group at both ends) : XC96-723), 181.3 parts by mass of methyltrimethoxysilane and 0.50 parts by mass of third butylamine were mixed and reacted at 30 ° C for 5 hours. Thereafter, the reaction solution was heated at 140 ° C. for 2 hours under a reduced pressure of 1.3 kPa to remove volatile components, thereby obtaining a difunctional alkoxy-modified polysiloxane compound (polysiloxane) at both ends. Alkanes A).

（塗佈液的製備） 向稀釋溶媒MEK（2-丁酮）76 g中加入矽酮樹脂KR-300（信越化學工業股份有限公司製造，樹脂成分50質量%）40 g及胺系硬化劑KBM-603（信越化學工業股份有限公司製造，樹脂成分100質量%）4 g並混合，從而製備塗佈液中的樹脂含量為20質量%的熱硬化性樹脂塗佈液。另外，變更各成分的量，藉此製備塗佈液中的樹脂含量為5質量%、10質量%或30質量%的塗佈液。再者，各塗佈液的於25℃下的黏度是使用E型黏度計（東機產業股份有限公司製造，RE80H型，轉子1°34'×R24），將樣品量設為1.1 mL，將溫度設為25℃，將轉速設為100 rpm，將測定時間設為1分鐘來進行測定。關於樹脂含量為5質量%及10質量%的塗佈液，處於測定範圍外（黏度充分地低），因此未測定黏度。(Preparation of Coating Solution) To 76 g of dilute solvent MEK (2-butanone), 40 g of silicone resin KR-300 (manufactured by Shin-Etsu Chemical Co., Ltd., resin content 50% by mass) and amine-based hardener KBM were added. -603 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., resin content 100% by mass) and 4 g were mixed to prepare a thermosetting resin coating solution having a resin content of 20% by mass in the coating solution. In addition, the amount of each component was changed to prepare a coating liquid having a resin content in the coating liquid of 5% by mass, 10% by mass, or 30% by mass. In addition, the viscosity at 25 ° C of each coating liquid is an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80H, rotor 1 ° 34 '× R24), and the sample volume is 1.1 mL. The temperature was measured at 25 ° C, the rotation speed was 100 rpm, and the measurement time was 1 minute. Since the coating liquids having a resin content of 5% by mass and 10% by mass were outside the measurement range (the viscosity was sufficiently low), the viscosity was not measured.

（阻障層形成用組成物的製備） 於含有全氫化聚矽氮烷的AZ NL120A-20（AZ電子材料製造（AZ Electronic Materials Manufacturing）股份有限公司製造，製品名）中混合燻製二氧化矽（日本艾羅西爾（Aerosil）股份有限公司製造，艾羅西爾（Aerosil）（商標註冊）R972），從而獲得阻障層形成用組成物。再者，將相對於阻障層的總體積的燻製二氧化矽的含量設為5體積%。(Preparation of Composition for Forming Barrier Layer) AZ NL120A-20 (manufactured by AZ Electronic Materials Manufacturing Co., Ltd., product name) containing fully hydrogenated polysilazane was mixed with smoked silicon dioxide ( Manufactured by Japan Aerosil Co., Ltd. and Aerosil (registered trademark) R972) to obtain a composition for forming a barrier layer. In addition, the content of the smoked silicon dioxide with respect to the total volume of the barrier layer was set to 5% by volume.

（實施例1） 將鋁合金板浸泡於放入至槽（vat）中的溶膠塗液後取出，於60℃下進行30分鐘凝膠化而獲得凝膠層的厚度為100 μm的結構體。之後，將所獲得的結構體轉移至密閉容器中，於60℃下進行12小時熟化。(Example 1) An aluminum alloy plate was immersed in a sol coating solution put into a vat, and then taken out, and gelated at 60 ° C. for 30 minutes to obtain a structure having a thickness of 100 μm as a gel layer. After that, the obtained structure was transferred to a closed container and aged at 60 ° C for 12 hours.

將進行了熟化的結構體浸漬於水2000 mL中，花費30分鐘進行清洗。其次，浸漬於甲醇2000 mL中，於60℃下花費30分鐘進行清洗。一面交換為新的甲醇，一面進而進行2次利用甲醇的清洗。其次，浸漬於甲基乙基酮2000 mL中，於60℃下花費30分鐘進行溶媒置換。一面交換為新的甲基乙基酮，一面進而進行2次利用甲基乙基酮的清洗。將經清洗及溶媒置換的結構體於常壓下，於120℃下乾燥6小時，藉此於鋁合金板上形成具有所述通式（2）及通式（3）所表示的結構的氣凝膠。The aging structure was immersed in 2000 mL of water, and it took 30 minutes to wash. Next, it was immersed in 2000 mL of methanol and washed at 60 ° C for 30 minutes. While changing to new methanol, washing with methanol was performed twice. Next, it was immersed in 2000 mL of methyl ethyl ketone, and the solvent replacement was performed at 60 ° C for 30 minutes. While being exchanged for new methyl ethyl ketone, washing with methyl ethyl ketone was further performed twice. The cleaned and solvent-replaced structure was dried under normal pressure at 120 ° C for 6 hours, thereby forming a gas having the structure represented by the general formula (2) and the general formula (3) on an aluminum alloy plate. gel.

將形成有氣凝膠的鋁合金板浸泡於放入至槽中的塗佈液（樹脂含量：5質量%）中10秒鐘後取出。此時，拭去多餘附著的塗佈液。再者，使塗佈液滲透至氣凝膠時的塗佈液的溫度為25℃。將其放入至乾燥機中，於90℃下加熱1小時，繼而於150℃下加熱1小時，藉此於鋁合金板上形成氣凝膠複合體，獲得評價樣品。The aerogel-formed aluminum alloy plate was immersed in a coating solution (resin content: 5% by mass) placed in a tank for 10 seconds, and then taken out. At this time, excess coating liquid was wiped off. The temperature of the coating liquid when the coating liquid was penetrated into the aerogel was 25 ° C. This was put in a dryer and heated at 90 ° C for 1 hour and then at 150 ° C for 1 hour, thereby forming an aerogel composite on an aluminum alloy plate, and obtaining an evaluation sample.

（實施例2～實施例4） 除如表1所示般變更塗佈液以外，與實施例1同樣地進行而獲得評價樣品。(Example 2 to Example 4) An evaluation sample was obtained in the same manner as in Example 1 except that the coating liquid was changed as shown in Table 1.

（實施例5） 與實施例3同樣地進行而於鋁合金板上形成氣凝膠複合體。之後，使用噴刷（air brush）進而於氣凝膠複合體上塗佈阻障層形成用組成物後，於150℃下進行2小時的加熱硬化，藉此形成阻障層，並設為評價樣品。氣凝膠複合體與阻障層的合計厚度為120 μm。(Example 5) It carried out similarly to Example 3, and the aerogel composite was formed on the aluminum alloy plate. After that, the composition for forming the barrier layer was coated on the aerogel composite by using an air brush, and then heat-cured at 150 ° C for 2 hours to form a barrier layer. sample. The total thickness of the aerogel composite and the barrier layer is 120 μm.

（比較例1） 與實施例1同樣地進行而於鋁合金板上形成氣凝膠，之後塗佈液未滲透而設為評價樣品。(Comparative Example 1) An aerogel was formed on an aluminum alloy plate in the same manner as in Example 1. After that, the coating liquid was not penetrated and was set as an evaluation sample.

（比較例2） 與比較例1同樣地進行而於鋁合金板上形成氣凝膠。之後，進而與實施例5同樣地進行而於氣凝膠上形成阻障層，並設為評價樣品。(Comparative example 2) It carried out similarly to the comparative example 1, and the aerogel was formed on the aluminum alloy plate. Then, it carried out similarly to Example 5, and formed the barrier layer on an aerogel, and set it as the evaluation sample.

[表1] [Table 1]

（韌性評價） 重疊10片各評價樣品，於其上使用金屬製夾具（尺寸10 mm×1 mm×1 mm：1 mm×1 mm的面為樣品接觸面），自氣凝膠複合體側施加200 N的壓縮力。之後，藉由目視來確認是否於評價樣品產生崩壞、裂縫等，並依照以下的基準來評價。將評價結果示於表2中。 A評價：於評價樣品均未產生崩壞及裂縫。 B評價：於評價樣品產生崩壞。 C評價：於一部分評價樣品產生崩壞或裂縫。(Evaluation of toughness) Ten pieces of each evaluation sample were superimposed, and a metal jig was used thereon (size 10 mm × 1 mm × 1 mm: the surface of 1 mm × 1 mm was the sample contact surface), and it was applied from the aerogel composite side Compression force of 200 N. Thereafter, it was visually confirmed whether or not chipping, cracking, and the like occurred in the evaluation sample, and evaluation was performed according to the following criteria. The evaluation results are shown in Table 2. A Evaluation: No chipping or cracking occurred in the evaluation samples. Evaluation B: The evaluation sample was broken. C Evaluation: A part of the evaluation sample was chipped or cracked.

（密度測定） 測定氣凝膠複合體的密度。依照所述順序，於鋁箔上形成氣凝膠複合體或氣凝膠（厚度50 μm），將其作為測定樣品而測定密度。密度的測定是依照JIS Z 8807的幾何學的測定法來進行。再者，體積是設為5 cm×5 cm×50 μm（利用游標卡尺測定），重量是利用電子天平進行秤量，算出測定樣品的密度。將測定結果示於表2中。再者，表中，比較例1及比較例2中表示氣凝膠的密度。(Density measurement) The density of the aerogel composite was measured. In this order, an aerogel composite or an aerogel (50 μm thick) was formed on an aluminum foil, and the density was measured using this as a measurement sample. The density is measured in accordance with the geometrical measurement method of JIS Z 8807. The volume is 5 cm × 5 cm × 50 μm (measured with a vernier caliper), and the weight is measured with an electronic balance to calculate the density of the measurement sample. The measurement results are shown in Table 2. In the table, the density of the aerogel is shown in Comparative Examples 1 and 2.

（透過率測定） 測定氣凝膠複合體的相對於波長500 nm～700 nm的光的透過率。依照所述順序，於載玻片上形成氣凝膠複合體或氣凝膠（厚度50 μm），將其作為測定樣品而測定透過率。透過率的測定是依照JIS K 0115而進行。將測定結果示於表2中。再者，表中的數值自左為700 nm、600 nm、500 nm的結果。另外，載玻片及矽酮樹脂的透過率（%）分別為88、88、88。再者，表中，比較例1及比較例2中表示氣凝膠的透過率。(Transmittance measurement) The transmittance of the aerogel composite with respect to light having a wavelength of 500 nm to 700 nm was measured. An aerogel complex or an aerogel (thickness: 50 μm) was formed on a glass slide in accordance with the procedure described above, and the transmittance was measured as a measurement sample. The transmittance was measured in accordance with JIS K 0115. The measurement results are shown in Table 2. In addition, the values in the table are the results of 700 nm, 600 nm, and 500 nm from the left. In addition, the transmittances (%) of the glass slide and the silicone resin were 88, 88, and 88, respectively. In the table, Comparative Examples 1 and 2 show the aerogel transmittance.

[表2] [Table 2]

實施例的氣凝膠複合體具有優異的韌性。The aerogel composites of the examples have excellent toughness.

再者，圖2是實施例3中所獲得的氣凝膠複合體的剖面SEM照片，圖3是比較例1中所獲得的氣凝膠的剖面SEM照片。關於前者，理解為於保持氣凝膠所具有的三維網眼狀骨架的狀態下，骨架（由氣凝膠粒子形成的氣凝膠）的表面由塗層被覆。鑒於此種剖面以及所測定的密度及透過率，預估實施例的氣凝膠複合體可維持良好的絕熱性。2 is a cross-sectional SEM photograph of the aerogel composite obtained in Example 3, and FIG. 3 is a cross-sectional SEM photograph of the aerogel obtained in Comparative Example 1. Regarding the former, it is understood that the surface of the skeleton (aerogel formed of aerogel particles) is covered with a coating layer while maintaining the three-dimensional mesh-like skeleton possessed by the aerogel. In view of such a cross section and the measured density and transmittance, it is estimated that the aerogel composite of the example can maintain good thermal insulation properties.

1‧‧‧絕熱對象物1‧‧‧ insulation objects

2‧‧‧氣凝膠複合體2‧‧‧ aerogel complex

2a‧‧‧氣凝膠2a‧‧‧ aerogel

2b‧‧‧塗層2b‧‧‧coating

10‧‧‧被絕熱體10‧‧‧ Insulated

圖1是示意性地表示本實施形態的被絕熱體的剖面圖。 圖2是實施例3中所獲得的氣凝膠複合體的剖面掃描式電子顯微鏡（Scanning Electron Microscope，SEM）照片。 圖3是比較例1中所獲得的氣凝膠的剖面SEM照片。FIG. 1 is a cross-sectional view schematically showing a thermal insulation body according to this embodiment. FIG. 2 is a sectional scanning electron microscope (SEM) photograph of the aerogel composite obtained in Example 3. FIG. 3 is a cross-sectional SEM photograph of the aerogel obtained in Comparative Example 1. FIG.

Claims (8)

一種氣凝膠複合體的製造方法，其具備： 使包含塗佈材料及溶媒的塗佈液滲透至氣凝膠中的步驟；以及 自所述滲透的塗佈液中去除所述溶媒的步驟。A method for producing an aerogel composite, comprising: a step of permeating a coating liquid containing a coating material and a solvent into the aerogel; and a step of removing the solvent from the permeated coating liquid. 如申請專利範圍第1項所述的製造方法，其中所述塗佈液的25℃下的黏度為35 mPa·s以下。The manufacturing method according to item 1 of the scope of patent application, wherein the viscosity of the coating liquid at 25 ° C. is 35 mPa · s or less. 如申請專利範圍第1項或第2項所述的製造方法，其中所述塗佈材料包含熱硬化性樹脂。The manufacturing method according to claim 1 or claim 2, wherein the coating material contains a thermosetting resin. 如申請專利範圍第1項至第3項中任一項所述的製造方法，其中所述氣凝膠為作為如下溶膠的縮合物的濕潤凝膠的乾燥物，所述溶膠含有選自由具有水解性官能基或縮合性官能基的矽化合物、及所述具有水解性官能基的矽化合物的水解產物所組成的群組中的至少一種。The manufacturing method according to any one of claims 1 to 3, wherein the aerogel is a dried product of a wet gel as a condensate of a sol containing At least one of the group consisting of a silicon compound having a functional functional group or a condensable functional group, and a hydrolysate of the silicon compound having a hydrolyzable functional group. 一種氣凝膠複合體，其具有： 氣凝膠；以及 塗層，被覆形成所述氣凝膠內部的空隙的氣凝膠粒子的表面的至少一部分。An aerogel composite includes: an aerogel; and a coating layer that coats at least a portion of a surface of an aerogel particle forming a void in the aerogel. 如申請專利範圍第5項所述的氣凝膠複合體，其中密度為0.30 g/cm³ ～1.15 g/cm³ 。The aerogel composite according to item 5 of the patent application scope, wherein the density is 0.30 g / cm ³ to 1.15 g / cm ³ . 如申請專利範圍第5項或第6項所述的氣凝膠複合體，其中相對於波長700 nm的光的透過率為15%以下。The aerogel composite according to item 5 or item 6 of the patent application scope, wherein the transmittance with respect to light having a wavelength of 700 nm is 15% or less. 一種被絕熱體，其於絕熱對象物具備如申請專利範圍第5項至第7項中任一項所述的氣凝膠複合體。A heat-insulated body provided with the aerogel composite according to any one of items 5 to 7 of the scope of patent application on the object to be insulated.