201210811 六、發明說明： 【發明所屬之技術領域】 本發明係一種隔熱裝置及製造這種隔熱裝置的方法， 尤其是一種可捲起之鍍層薄膜形式的隔熱裝置，以及將這 種隔熱裝置應用於隔熱元件。 【先前技術】 已知有各種不同形式的透光隔熱元件，而且均可作爲 構件使用。大部分的隔熱元件都是以玻璃片作爲載體，但 也有些隔熱元件是以其他的透光材料（例如塑膠）作爲載 體。應用於外牆封裝之構件、分隔室內空間之構件（例如 隔牆及門）、以及船舶及離岸設施之封裝構件的隔熱需達 到特別高的品質要求。DE C3 1 9 00 054提出之熱絕緣透光 複合玻璃的特徵是，在兩個玻璃面之間設置一層乾燥的含 水鹼金屬矽酸鹽。當複合玻璃受熱時，例如起火時，這個 由鹼金屬矽酸鹽構成的膨脹層就會起泡，同時鹼金屬矽酸 鹽層中的水分會蒸發。此時膨脹層會變得使熱輻射無法穿 透，並能夠在一段時間內有效的阻止熱輻射穿透。雖然至 少有一片玻璃片破裂，玻璃構件仍會附著在起泡的泡沬層 上。爲了改善隔熱效果，可以將多個玻璃片及鹼金屬矽酸 鹽構成的膨脹層一個接一個排在一起。 熱絕緣複合玻璃的製造有兩種方法’一種方法是在一 個玻璃面塗上一層很薄的液態鹼金屬矽酸鹽’然後去除過 多的水分（例如加熱）’另一種方法是利用—種酸性成分 -5- 201210811 (例如矽酸）使鹼金屬矽酸鹽硬化（EP 0 620 78 1 )。 另外一種已知的方法是在鹼液（例如ΚΟΗ )的作用下 使透過聚醇穩定化的熱解Si02硬化（見DE 197 20 269)。 同樣屬於已知方法的利用沉降矽酸及/或矽膠的鹼液硬化 ，以製造隔熱元件（見WO 2009/155719)。 以上提及的所有方法的一個共同點是在玻璃上直接形 成膨脹層，因此必須運送已製造完成的玻璃。此外，先前 技術的鑄造法主要是適用於終端材料的製造。 EP 1 43 1 027提出一種埋在構件中的隔熱裝置，其中 隔熱裝置具有至少一種混合薄膜系統，該混合薄膜系統至 少有一個薄膜被鍍上膨脹材料。薄膜系統最好是至少有— 種成分是以矽酸鹽爲基，且其Si02及Na20的克分子比例較 佳是在2.0至6.5之間、或最好是在3至5.〇之間。以這種方 法製造的鍍層的缺點是易脆、及/或帶有裂縫及/或氣泡、 或含有很多的剩餘水分。 【發明內容】 本發明的目的是提出一種混合薄膜形式的隔熱裝置， 該隔熱裝置需具有良好的隔熱特性及很好的光學値，而且 還要易於運送、儲存及層壓^ 本發明的其他目的是提出一種適於用來製造混合薄膜 用的隔熱鑄造材料，以及製造這種混合薄膜的方法，以及 應用混合薄膜製造隔熱裝置，例如隔熱玻璃。 爲達到上述目的，本發明之混合薄膜系統包括至少— -6 - 201210811 個載體膜及至少一個膨脹層，其中膨膜層是由具有下列成 分的含水矽酸鹽構成： 3 5 %至60% (重量百分比）的水； —種鹼金屬矽酸鹽，相當於： (i) 30至55 % (重量百分比）的二氧化砂’含有最多 5%、或最好是最多3% (重量百分比）的多價陽離子氧化 物； (i i )最多1 8 % (重量百分比）的鹼金屬氧化物’例 如氧化鈉、氧化鉀、氧化鋰、以及這些氧化物的混合物： 0.1至10% (重量百分比）的矽氧烷’其中爲獲得透明 玻璃，最多只能加入〇. 2 5至3 % (重量百分比）、或最好是 最多0.25至2.5% (重量百分比）的矽氧烷； 5至23% (重量百分比）的聚醇； 0至2% (重量百分比）的氨（以1〇〇%氨爲準）； 其中二氧化矽與鹼金屬氧化物的克分子比例是6.0: 1 至2.0: 1、或最好是5.2: 1至2.0: 1，而且以上成分合計 至少佔膨脹層的99% (重量百分比）。 在本發明中，所謂多價陽離子氧化物是指Al2〇3、 B203、Sn〇2、Ti〇2、ZnO、以及這些氧化物的混合物、含 鋅的混合氧化物，尤其是摻雜鋁的混合氧化物，例如 Zn2SnAl203、鋅錫氧化物（ZnSnOx )或鈉-鉀-鋅錫氧化物 (Na-K-ZnSnOx) 〇 加入鹼溶液使含有Si〇2的分散液硬化，即可產生本發 明之包括至少一個載體膜及至少一個膨脹層的混合薄膜系 201210811 統，其中該含有S i Ο 2的分散液是由下列成分組成： 35至52% (重量百分比）的以〇2 (可含有最多5%、或 最好是最多3% (重量百分比）的多價陽離子氧化物： 30至50% (重量百分比）的水； 0.5至0.7% (重量百分比）的ΚΟΗ ; 〇至13% (重量百分比）的烷基矽氧烷’其中爲獲得透 明產物，最多只能加入3% (重量百分比）的烷基矽氧烷； 0至6% (重量百分比）的氨（以32%的含水溶液爲準 )： 7.5至30% (重量百分比）的甘油及/或乙二醇； 其中以上成分合計至少佔分散液的99% (重量百分比 )、或最好是佔1 〇 〇 % (重量百分比）。 加入鹼溶液使分散液硬化，硬化層的含水量爲35%至 60% (重量百分比），二氧化矽與鹼金屬氧化物的克分子 比例是6.0: 1至2.0: 1、或最好是5·2: 1至2.0: 1。 載體膜最好具有很高的彈性。具有高彈性的優點是可 以提高以混合薄膜製造之隔熱裝置的力學特性，並使其可 以被捲起來運送，前提是具有足夠的彈性或可撓性。載體 膜最好還具有很高的透明性及良好的光學特性。 有一種初始材料特別適於應用在混合薄膜，其硬化是 在有去泡劑及聚醇的情況下，Si02與氫氧離子（尤其是透 過氫氧化鉀溶液）反應的結果。WO 2009/155719已有提出 —種適當的系統。 一個令人訝異的發現是，這種系統可以在很廣的應用 -8- 201210811 範圍符合各種要求》除去泡作用外，必要時亦可同時產生 內底漆之作用的去泡劑（一種矽氧烷）可以促進製造過程 中膨脹層的排氣，也就是促進澆鑄在薄膜上的過程中及澆 鑄後膨脹層的排氣，這樣就可以加快澆鑄的速度，及/或 在成分混合的過程中及/或澆鑄時，使所產生的氣泡小到 在乾燥過程或硬化過程中會消失（也就是說目視無法看見 )° 底漆會使膨脹層在燃燒側的薄膜或燃燒側的玻璃片上 的附著力變小，因此在起火時，膨脹層會大面積的從薄膜 /玻璃片上分離，以避免導致脫落。由於使用內底漆的關 係，因此無需事先在玻璃片上塗底漆。此外，內底漆還可 以改善薄膜的分離，這對於製造無薄膜的玻璃構件是很有 利的。 WO 2009/1 55719有揭示在膨脹層之成分內作爲去泡劑 及底漆、而且不會對膨脹層的最終特性造成不利影響的含 矽化合物。這一類化合物主要是矽氧烷。 以下是特別有利之矽氧烷的例子：烷基矽氧烷，尤其 是帶有短烷基（例如線性或分枝的C1至C4烷基，具有5至 350個、15至3 5 0個、或最好是90至3 50個單體單元）的聚 單烷基矽氧烷或聚二烷基矽氧烷，其中線性矽氧烷在一端 或兩端（在α位置及/或ω位置）的聚合鏈可以被烷基（ 尤其是甲烷基）或其他有機基取代。一種特別有利的矽氧 烷是聚二甲基矽氧烷（亦可寫爲聚[氧（二甲基矽）]或α-(三甲基矽）-ω-甲基聚[氧（二甲基矽）])(Mw=1000 201210811 至30000、6000至30000、或最好是1 0000至25000，密度 0.9至〇.98g/cm3、或最好是〇.98g/cm3 )。這種矽氧烷可以 同時作爲去泡劑及內底漆。這種矽氧烷可以被單獨使用， 亦可以混合形式被使用。其他適當的聚二甲基矽氧烷還包 括 Dimeticon/Dimethicon (砂靈）、E900、砂油等。例如 Dow Corning Corporation, Midland, Michigan, USA '201210811 VI. Description of the Invention: [Technical Field] The present invention relates to a heat insulating device and a method of manufacturing the same, and more particularly to a heat insulating device in the form of a rollable coating film, and the like The thermal device is applied to the thermal insulation element. [Prior Art] Various types of light-transmissive heat insulating members are known and can be used as members. Most of the insulation elements are made of glass sheets, but some of the insulation elements are made of other light-transmissive materials (such as plastic). Insulation of components used in exterior wall packaging, components that separate indoor spaces (such as partitions and doors), and packaging components for ships and offshore facilities require particularly high quality requirements. The thermally insulating, light-transmissive composite glass proposed by DE C3 1 9 00 054 is characterized in that a layer of dry alkali metal silicate is provided between the two glass faces. When the composite glass is heated, such as during a fire, the expanded layer of alkali metal silicate is foamed while the water in the alkali metal silicate layer evaporates. At this point, the intumescent layer becomes incapable of penetrating the heat radiation and is effective in preventing the penetration of the heat radiation for a period of time. Although at least one piece of glass breaks, the glass member adheres to the foamed layer of foam. In order to improve the heat insulating effect, a plurality of glass sheets and an expanded layer composed of an alkali metal silicate may be arranged one after another. There are two methods for the manufacture of thermally insulating composite glass. One method is to apply a thin layer of liquid alkali metal citrate on a glass surface and then remove excess moisture (eg, heat). Another method is to use an acidic component. -5- 201210811 (eg citric acid) hardens alkali metal silicates (EP 0 620 78 1 ). Another known method is to harden the pyrolytic SiO 2 stabilized by the polyhydric alcohol under the action of an alkali liquid such as hydrazine (see DE 197 20 269). It is also known in the art to harden the lye with precipitated tannic acid and/or silicone to produce a thermal insulation element (see WO 2009/155719). A common feature of all of the above mentioned methods is the direct formation of an intumescent layer on the glass, so that the finished glass must be transported. In addition, prior art casting methods are primarily applicable to the manufacture of terminal materials. EP 1 43 1 027 proposes a thermal insulation device embedded in a component, wherein the thermal insulation device has at least one mixed membrane system, at least one of which is plated with an intumescent material. Preferably, the film system is at least one component based on a phthalate salt, and preferably has a molar ratio of SiO 2 and Na 20 of from 2.0 to 6.5, or preferably from 3 to 5. Coatings made by this method have the disadvantage of being brittle, and/or having cracks and/or bubbles, or containing a lot of residual moisture. SUMMARY OF THE INVENTION The object of the present invention is to provide a heat insulating device in the form of a mixed film, which has good heat insulating properties and good optical flaws, and is also easy to transport, store and laminate. Other objects are to propose an insulating casting material suitable for use in the manufacture of mixed films, and a method of manufacturing such a mixed film, and a hybrid film manufacturing heat insulating device such as heat insulating glass. To achieve the above object, the mixed film system of the present invention comprises at least - -6 - 201210811 carrier films and at least one intumescent layer, wherein the expanded layer is composed of an aqueous niobate having the following composition: 3 5 % to 60% ( Percent by weight of water; an alkali metal silicate, equivalent to: (i) 30 to 55 % by weight of sulphur dioxide' containing up to 5%, or preferably up to 3% by weight a polyvalent cation oxide; (ii) up to 18% by weight of an alkali metal oxide such as sodium oxide, potassium oxide, lithium oxide, and a mixture of these oxides: 0.1 to 10% by weight of ruthenium Oxane' wherein to obtain clear glass, at most 〇. 2 5 to 3% by weight, or preferably at most 0.25 to 2.5% by weight of decane; 5 to 23% (% by weight) Polyol; 0 to 2% by weight of ammonia (based on 1% ammonia); wherein the molar ratio of cerium oxide to alkali metal oxide is 6.0: 1 to 2.0: 1, or most Good is 5.2: 1 to 2.0: 1, and the above ingredients total at least 99% (by weight) layer. In the present invention, the polyvalent cation oxide means Al2〇3, B203, Sn〇2, Ti〇2, ZnO, and a mixture of these oxides, a mixed oxide containing zinc, especially a mixture of doped aluminum. An oxide such as Zn2SnAl203, zinc tin oxide (ZnSnOx) or sodium-potassium-zinc tin oxide (Na-K-ZnSnOx) is added to the alkali solution to harden the dispersion containing Si〇2, thereby producing the present invention. A mixed film of at least one carrier film and at least one intumescent layer is 201210811, wherein the dispersion containing S i Ο 2 is composed of the following components: 35 to 52% by weight of 〇2 (may contain up to 5%) Or preferably up to 3% by weight of polyvalent cation oxide: 30 to 50% by weight of water; 0.5 to 0.7% by weight of ruthenium; 〇 to 13% by weight Alkyl oxane' where a transparent product is obtained, up to 3% by weight of alkyl oxane can be added; 0 to 6% by weight of ammonia (based on 32% aqueous solution): 7.5 to 30% by weight of glycerin and/or ethylene glycol; The above components are at least 99% by weight, or preferably 1% by weight, based on the total amount of the dispersion. The alkali solution is added to harden the dispersion, and the water content of the hardened layer is 35% to 60% (weight Percentage), the molar ratio of cerium oxide to alkali metal oxide is 6.0: 1 to 2.0: 1, or preferably 5·2: 1 to 2.0: 1. The carrier film preferably has a high elasticity. The advantage of elasticity is that the mechanical properties of the thermal insulation device made of the mixed film can be improved and can be rolled up and transported, provided that it has sufficient elasticity or flexibility. The carrier film preferably has high transparency and Good optical properties. A starting material is particularly suitable for use in mixed films where the hardening is the result of the reaction of SiO 2 with hydroxide ions (especially through a potassium hydroxide solution) in the presence of defoamers and polyols. WO 2009/155719 has proposed an appropriate system. One surprising finding is that such a system can be used in a wide range of applications -8-201210811 to meet various requirements, in addition to the bubble effect, if necessary, simultaneously produce The defoaming agent (a kind of decane) which acts as a primer can promote the venting of the intumescent layer during the manufacturing process, that is, to promote the process of casting on the film and the venting of the intumescent layer after casting, so that the casting can be accelerated. Speed, and / or during the mixing of the components and / or casting, the resulting bubbles are so small that they disappear during the drying process or hardening process (that is, visually invisible) ° The primer will cause the intumescent layer to burn The adhesion on the side film or the glass sheet on the burning side becomes small, so that in the event of a fire, the intumescent layer is largely separated from the film/glass sheet to avoid falling off. Due to the use of the inner primer, there is no need to apply a primer to the glass sheet beforehand. In addition, the inner primer can also improve the separation of the film, which is advantageous for the manufacture of film-free glass members. WO 2009/1 55719 discloses ruthenium containing compounds which act as defoamers and primers within the composition of the intumescent layer without adversely affecting the final properties of the intumescent layer. This class of compounds is mainly oxoxane. The following are examples of particularly advantageous oxanes: alkyl oxanes, especially with short alkyl groups (for example linear or branched C1 to C4 alkyl groups, having 5 to 350, 15 to 350, Or preferably from 90 to 3 50 monomer units of polymonoalkyl oxa oxide or polydialkyl decane, wherein the linear decane is at one or both ends (in the alpha position and / or ω position) The polymeric chain can be substituted with an alkyl group (especially a methyl group) or other organic group. A particularly advantageous oxoxane is polydimethyl methoxyalkane (also written as poly[oxy(dimethyl hydrazine)] or alpha-(trimethylhydrazine)-ω-methyl poly[oxygen (dimethyl) Base)])) (Mw = 1000 201210811 to 30,000, 6000 to 30,000, or preferably 1 0000 to 25000, density 0.9 to 98.98 g/cm3, or preferably 〇.98 g/cm3). This decane can be used as both a defoamer and an inner primer. Such a decane can be used singly or in a mixed form. Other suitable polydimethyl siloxanes include Dimeticon/Dimethicon, E900, sand oil, and the like. For example, Dow Corning Corporation, Midland, Michigan, USA '
Bayer Industrieprodukte GmbH & Co. KG,Leverkusen, DE 、Wacker-Chemie GmbH, Munchen, DE、Acros Organics, Belgien等公司均有生產適當的聚二甲基矽氧烷。 根據本發明，必要時聚矽氧烷的氨鹽還可含有自由氨 或添加氨、可改善分散液或膨脹層之光學特性的其他添加 物、及/或可降低分散液或膨脹層在硬化前的黏性的添加 .物、及/或延長分散液或膨脹層的使用期的添加物。 二氧化矽是熱解Si02及/或沉降8丨02及/或矽膠，可以 用聚醇將二氧化矽穩定化，而且二氧化矽最好是被聚醇穩 定化，同時二氧矽可以被鹼液（例如KOH )固化。矽氧烷 對這種成分的二氧化矽可以產生較好的排氣作用，因而使 加工速度加快，也就是使加工時間變短。 透過使用矽膠及熱解矽酸及/或沉降矽酸的混合物， 可以在很大的範圍內改變使用期，而且由於使用本發明建 議的以矽氧烷爲基的去泡劑，因此可以不受邊緣限制調整 對薄膜鍍層而言非常重要的隔熱鑄造材料的黏性及/或抗 蠕變性。 硬化的膨脹層的另外一個特徵是其防火性優於其他類 -10- 201210811 似但不含矽氧烷之膨脹層的防火性° 可以透過加入鹼液被固化的適當的Si〇2分散液是由以 下成分構成： 35至52% (重量百分比）的Si02，含有最多5%、或最 好是最多3% (重量百分比）的多價陽離子氧化物； 30至50% (重量百分比）的水； 0.5至0.7% (重量百分比）的KOH : 〇至13% (重量百分比）的烷基矽氧烷，其中爲獲得透 明產物，最多只能加入3% (重量百分比）的烷基矽氧烷； 〇至6% (重量百分比）的氨（以32%的含水溶液爲準 )·* 7.5至30% (重量百分比）的聚醇，尤其是甘油及/或 乙二醇； 其中以上成分合計至少佔分散液的99% (重量百分比 )、或最好是佔1〇〇% (重量百分比）。 處於硬化狀態之膨脹層的二氧化矽與鹼金屬氧化物的 克分子比例是5.2: 1至2.0: 1、或最好是3.5: 1至2.5: 1 。這個克分子比例可表明聚矽酸鹽或聚矽酸鹽及其內含之 奈米尺寸（也就是肉眼看不到的尺寸）之二氧化矽微粒的 混合物的特徵。這固化的層的含水量最好是35至60% (重 量百分比）’二氧化矽的含量是30至55 % (重量百比）， 鹼金屬氧化物（M20)的含量最多不超過18 % (重量百分 比），聚醇（尤其是甘油）的含量通常是5至23 % (重量百 分比）’其中驗金屬氧化物可以是氧化鈉、氧化鉀、氧化 -11 - 201210811 鋰、或這些氧化物的混合物。 經證實，從硬度的角度來看，如果聚醇含量低於10% (重量百分比），在完全硬化的狀態下’ Si02 : Κ20的比 例（克分子比例）的臨界値爲5.2 : 1。因此必須將製造完 成後被直接捲起的產品加熱，以便經過儲存後能夠無缺陷 的被捲開。如果克分子比例是2.0 : 1，則可以一直維持很 高的彈性，但是隔熱效果並不是很好。 爲了在克分子比例較高的情況下，無需加熱也可以達 到很好的可捲起性及可捲開性，可以用部分硬化或預硬化 取代使產品達到最終硬度及變成透明的完全硬化。此時膨 脹層仍呈現乳白色混濁狀，但是比較有彈性。如果只最預 硬化或是要製造板狀材料，甚至可以使用最高達6.0的克 分子比例。 聚醇（例如乙二醇，丙二醇，甘油）可使熱解或沉降 矽酸及/或矽膠穩定化。 這些添加物可提供調整彈性的另外一種可能性。膨脹 層內所含的聚醇（尤其是甘油）愈多，膨脹層就愈軟，因 此克分子量的可選擇範圍就愈廣。甘油含量最好是至少 1 0% (重量百分比），但最多不超過22% (重量百分比） ，因爲甘油含量過高在起火時可能會導致熱斑的出現。 可以加入鹼液使這種穩定化矽酸固化，例如加入 NaOH或ΚΟΗ，其中ΚΟΗ比NaOH更適合，及/或可以力卩入網 路形成劑（例如氧化鋁或氧化硼）使矽酸固化。 最好是以沉降矽酸及矽膠作爲Si02的來源。雖然矽膠 -12- 201210811 內及/或沉降矽酸表面上的OH基密度大於熱解Si02，而且 一次粒子及二次粒子的粒徑也不同於熱解矽酸，但是沉降 矽酸及/或矽膠的使用期及澆鑄黏性都很容易被控制。只 要在50至500mPas 〃的範圍內改變混合比例，即可控制澆 鑄黏性。 可以將矽氧烷加到含矽酸鹽或二氧化矽的成分中，或 是加到砂化成分（驗液）中，也可以在製造隔層的過程中 加入矽氧烷。由於使用Si 〇2微粒分散液時，一種有利的方 式是使分散液排氣，因此最好是在分散液中加入去泡劑。 另外一種可能性是在分散液與硬化成分混合的過程中加入 去泡劑，不過這種作法對於不含矽酸的分散液並不適合。 由於對沉降矽酸及矽膠的混合物而言，含Si〇2的分散液通 常不需要排氣，因此可以將去泡劑加到分散液及/或鹼溶 液中，或是在混合的過程中作爲第三種成分加到沉降矽酸 及矽膠中。 以矽化層的質量爲準，矽氧烷的添加量是0.1至10% ( 重量百分比）。透明薄膜或玻璃的矽氧烷添加量是0.25至 3.0% (重量百分比）、或最好是0.25至2.5% (重量百分比 )。但是部分透明或不透明的透光薄膜或玻璃的矽氧烷添 加量可以達到1 0% (重量百分比）。 一種適於用來製造隔熱層的非晶形沉降矽酸的Si〇2含 量至少是98.5% (重量百分比）、98_8% (重量百分比）、 或最好是至少99.1% (重量百分比），BET表面大約是2〇 至1001112^。3丨〇2含量約35至42%(重量百分比）的分散液 -13- 201210811 的BET可以是80至100m2/g，濃度較高的分散液的BET可以 是20至80m2/g。一次粒子平均粒徑通常是10至70nm、或最 好是20至40nm，如果硬化後所有微粒均位於低於可見頻譜 之粒徑分佈內，則可以使用較大的一次粒子平均粒徑。 Si02的二次粒子的粒徑僅對硬化速度有影響（較小的微粒 硬化速度較慢），對分散液及/或膨脹層並不會有影響。 可加入鹼液固化的適當的Si 〇2分散液是由以下的成分 組成： 35至52% (重量百分比）的Si02 (可以含有最多5%、 或最好是最多3% (重量百分比）的多價陽離子氧化物）： 3 0至5 0% (重量百分比）的水； 0.5至0.7% (重量百分比）的KOH ; 0至13% (重量百分比）的烷基矽氧烷，其中爲獲得透 明產物，最多只能加入3% (重量百分比）的烷基矽氧烷； 0至6% (重量百分比）的氨（以32%的含水溶液爲準 )； 7.5至3 0% (重量百分比）的甘油及/或乙二醇； 其中以上成分合計至少佔分散液的99% (重量百分比 )、或最好是佔1 〇〇% (重量百分比）； 例如： 47.0至48.5% (重量百分比）的Si02; 3 3.8至30.9% (重量百分比）的水； 0.6 + /-0.1% (重量百分比）的KOH; 0至10% (重量百分比）的烷基矽氧烷； -14- 201210811 0至2.5% (重量百分比）的氨（以32%的含水溶液爲準 )； 7.5至3 0% (重量百分比）的甘油及/或乙二醇。 以下是一種很有利的分散液的成分： 47.0% (重量百分比）的Si〇2 ; 32.8% (重量百分比）的水； 0.6% (重量百分比）的KOH ; 0.25至3% (重量百分比）的烷基矽氧烷’尤其是聚二 甲基矽氧烷； 〇至〇 . 5 % (重量百分比）的氨（以3 2 %的含水溶液爲準 )； 7.5至3 0% (重量百分比）的甘油及/或乙二醇。 另外一種很有利的分散液的成分是： 48.2% (重量百分比）的Si02 ; 30.9% (重量百分比）的水； 0.5% (重量百分比）的KOH ; 0.25至3% (重量百分比）的烷基矽氧烷，尤其是聚二 甲基矽氧烷； 〇至0.5% (重量百分比）的氨（以32%的含水溶液爲準 )； 7.5至3 0% (重量百分比）的甘油及/或乙二醇。 聚醇（尤其是甘油及/或乙二醇）及KOH的作用是使 分散液中的Si02微粒穩定化。此外聚醇還具有降低凝固點 及提高彈性的作用。 -15- 201210811 經證實一種有利的方式是Si02的含量爲45至50% (重 量百分比），因爲在這樣的Si02含量下，可以加入足量的 KOH作爲溶體，而且仍然可以產生高濃度的膨脹層。濃度 最高可達52% (重量百分比），但是自濃度49至50% (重 量百分比）起，對於分散器的性能會有較高的要求。 膨脹層內的氨有助於改善膨脹層的特性，可以將絕對 量（也就是以100% NH3計算的量）相當於0.1至2% (重量 百分比）、或最好是〇.8至0.9% (重量百分比）的氨加到 分散液及/或硬化劑中，而且氨可以部分或完全鍵合在聚 砂氧院上。 經證實，一種適當的方式是，Si02分散液的含水氨溶 液（32% (重量百分比））的含量最多是6% (重量百分比 )、或最好是最多2.5% (重量百分比），最少則是0.1% ( 重量百分比）、或最好是最少0.5% (重量百分比）。 可以按照WO 2009/1 5571 9描述的方式製作分散液，此 專利之關於此部分的內容亦包括在本發明中。 製造膨脹鍍層材料的方法是使分散液及/或矽膠與氫 氧化鉀溶液反應並固化。一種有利的方式（但並非一定要 這樣做）是在沒有脫水的情況下進行固化。 製造本發明的混合薄膜是利用一種鍍層方法將膨脹鍍 層材料鍍在載體膜上，然後硬化。硬化過程通常是在烘箱 中以批次或連續方式進行。烘箱的溫度通常是60至8 5 °C、 或最好是70至8 0°C。可以在脫水的情況下進行硬化，例如 在“乾燥的”空氣或“乾燥的”惰性氣體中進行硬化，但基於 -16- 201210811 兩個原因，在脫水的情況下進行硬化並不理想：第一個原 因是含水量會降低，因此起火時可能導致不良後果’第二 個原因是表面的硬化速度會變得過快’因此可能導致不均 勻性。因此最好是在潮濕的環境中進行硬化，尤其是在潮 濕的保護氣體中或加上一層覆蓋膜的情況下進行硬化，硬 化後可將這層覆蓋膜去除，亦可將覆蓋膜留在膨脹層上， 使其成爲混合薄膜的一部分。 硬化過程可以在一個步驟中完成，也可以分成兩個階 段完成，其中第一個階段是預硬化，也就是只將膨脹層硬 化到達到運送及處理所需的穩定化程度，第二個階段是進 行最終硬化，也就是硬化到最終硬度及變成透明》可以在 薄膜上達到最終硬度，例如在以捲起的形完成運送工作後 ，捲開並切割成平坦的薄膜，也可以在玻璃片之間形成膨 脹層後再達到最終硬度。兩階段硬化對於克分子比例爲 6·0: 1至4.0: 1的薄膜特別適合。 可以根據甘油含量及所希望的柔軟性/彈性，在5.2 : 1 至2.0: 1的範圍內調整膨脹層內二氧化矽與鹼金屬氧物的 克分子比例，如果聚醇含量很低（大約1 0% (重量百分比 ))，則可以在3.5: 1至2.5: 1的範圍內調整。 透過以下的方法可以在很大範圍內控制膨脹層及混合 薄膜的加工特性及最終特性： (i )改變沉降矽酸及/或熱解矽酸與矽膠的比例； (ii)改變Si02與鹼金屬氧化物（尤其是κ20)的克 分子比例（也稱爲莫耳比例）； -17- 201210811 (Hi)調整聚醇（尤其是甘油）的含量； (iv )加入必要時亦可作爲內底漆的去泡劑，以及加 入矽氧烷。 這樣就可以控制加工特性，例如透過（i )控制使用 期及黏性，另外也可以透過（ii )改變黏性及透過（ii ) 及（Hi)改變彈性及起火時的特性，由於有矽氧烷（iv) 的存在，因此這些改變不會對光學特性造成不良影響》 必要時可加入氨達到進一步改的目的。 如果膨脹層需與玻璃直接接觸，可以添加不溶於鹼性 介質的多價陽離子氧化物，以減少玻璃腐蝕。 可以在膨脹鍍層混合之前，將去泡劑（iv )添加到含 二氧化矽或矽酸鹽的成分及/或硬化劑中，及/或可以將去 泡劑（iv )加到已混合的成分（並熱鑄造材料）中。由於 適合作爲去泡劑的矽氧烷通常也具有內底漆的作用，因此 無需以底漆對載體元件（也就是載體膜及/或鍍上混合薄 膜的玻璃）進行預處理。但是本發明的內容外亦包括除了 內底漆外，另外再使用外底漆，或是以外底漆取代內底漆 (例如去去泡劑不具備或是僅有很微弱的內底漆作用）。 在本發明中，這種（外）底漆層稱爲輔助層。 由於加工特性（例如黏性及使用期）具有良好的可調 整性，因此可以用不同的鍍層方法鍍上膨脹層。例如浸泡 法是使薄膜的一個面以固定的速度與一可澆注材料的表面 接觸，刮板塗覆法是利用幫浦及噴嘴將可鑄造材料配料在 薄膜的一個面上，然後再以刮板均勻的（形成規定的層厚 -18 - 201210811 度）塗覆在這個薄膜面上，滾壓塗覆法是利用兩個彼此間 隔一事先設定之距離並緩慢朝對方滾動的滾筒（其中一個 滾筒塗有可澆注材料），將可澆注材料塗在以固定速度通 過兩個滾筒之間隙的薄膜上。一種非常有利的方式是利用 縫隙式噴嘴塗覆，此種方法可透過噴嘴與薄膜的距離調整 層厚度。 所謂的預配料鍍層方法對大部分情況都是很有利的鍍 層方法，尤其是利用縫隙式噴嘴塗覆的鍍層方法。對以上 提及的所有方法而言，適當的黏性範圍是在50至500mPas ，本發明的隔熱鑄造材料可達到這個黏性範圍》 以上所有的鏟層方法在完成後都接著在烘箱中以高溫 進行批次或連續的預硬化及/或硬化。例如以60至85 °C、 或最好是70至80 °C的溫度進行1至3小時的預硬化。接著以 相同的溫度進行4至8小時的硬化。以上條件適於層厚度約 0.5至1.5mm的膨脹層。硬化及預硬化都是在烘箱中進行， 例如對流爐、紅外線爐或輻射爐。 以上提及的方法都無需在塗覆之前先使膨脹鍍層排氣 。即使沒有排氣，也可以經由去泡劑的使用達到所需的光 學品質。 塗覆之後將帶有鍍層的薄膜放到烘箱中以高溫硬化。 如前面所述，可以在脫水的環境中進行硬化，也就是在乾 燥的空氣或情性氣體中進行硬化，或較佳是在有水分的環 境中進行硬化。如果要在有水分存在的情況下進行硬化， 環境氛圍（例如氮氣）中的含水量至少要等於要硬化之膨 -19- 201210811 脹層的含水量。 另外一種可能的方法是在硬化之前在高溫中將加上一 層覆蓋膜。這個覆蓋膜可以留在混合薄膜複合物內，也可 以在硬化後被去除。視膨脹層及覆蓋膜的特性而定，可以 爲只在硬化及運送過程中使用的覆蓋膜加上一個降低黏著 力的銨層，例如加上一個離型層（例如矽化層）。在邊緣 區域最好是將覆蓋層與載體膜隔離。這樣做的好處是，載 體膜在邊緣區域不會被鍍上隔熱鑄造材料，因此薄膜在邊 緣區域可以被熱封裝、熱焊接、或是在塗上密封劑（例如 熱溶黏膠）後可以被黏著住。最好是在加上覆蓋膜之前先 在邊緣區域塗上密封劑，且其厚度應大致與隔熱鑄造材料 的厚度相同，以確保覆蓋膜能夠均勻的覆蓋在膨脹層上。 事後不應留在複合物內的覆蓋膜可以是透明、不透明、或 不透光的。 用於隔熱時，載體膜必須是可以耐熱的。可以使用塑 膠或金屬製造載體膜。載體膜最好還能夠提高隔熱元件的 力學穩定性。應用於隔熱玻璃的載體膜最好是透光且透明 的薄膜。聚乙烯醇縮丁醛薄膜是一種已應用於隔熱玻璃的 薄膜，其具有隔熱玻璃要求的特性，例如抗斷裂性，而且 能夠提高隔熱玻璃的隔音效果。其他可使用、但最好不要 留在玻璃複合物內的載體膜的例子有聚對苯二甲酸乙二酯 (PET)、聚氯乙烯（PVC)、聚乙烯（PE)、聚丙烯（ PP )、聚氨酯（PUR)。 對於要捲起來運送的薄膜而言，最好是具有覆蓋膜， -20- 201210811 或是其載體膜的兩個面對膨脹層有不同的附著特性，這樣 在捲開薄膜時就不會造成膨脹層斷裂。 混合薄膜非常適於用來製造隔熱玻璃。在這種情況下 ，混合薄膜（必要時應去除載體膜及/或覆蓋膜）是被置 於兩個玻璃片之間’並與玻璃片結合。可以使用以加熱或 化學方式被整個或部分施以預應力的玻璃片。 製造隔熱玻璃時，應利用捲開裝置將被捲起及預硬化 或硬化的混合薄膜拉緊，然後將捲開裝置送入一個塗覆單 元，並使載體膜位於下面，膨脹層位於上面。然後將一個 玻璃片放在膨脹層上，並施壓使玻璃片與膨脹層結合。然 後將玻璃元件開端的混合薄膜切掉，如果混合薄膜有超出 玻璃元件尾端，亦應將超出尾端的部分切掉。 接著將與混合薄膜結合的玻璃片移出第一塗覆單元， 並將玻璃面向下送入第二塗覆單元。視所希望達到的特性 及薄膜性質而定，可以將載體膜扯下，也可將載體膜留在 膨脹層上。接著將第二個玻璃片或一個同樣帶有膨脹層的 玻璃片（必要時帶有被扯下的薄膜）放到膨脹層上。接著 施加壓力使位於上方的玻璃片與位於下方並帶有膨脹層的 玻璃片結合在一起。 如前面所述，構造方式爲載體膜-膨脹層-覆蓋膜的薄 膜可以將覆蓋膜去除，也可以將覆蓋膜得在複合物內。如 果要將覆蓋膜留在玻璃複合物內，則覆蓋膜最好是具有與 載體膜相同的特性。 可以按照前面所述的兩階段方法製造具有此種薄膜的 -21 - 201210811 玻璃複合物，其中薄膜的定位並無任關係，也就是說覆蓋 膜或載體膜何者先與玻璃片結合並無任何區別。也可以用 直接方式製造玻璃複合物，也就是說將混合薄膜的一個面 (例如載體膜側）置於第一玻璃片上，然後將第二玻璃片 放到混合薄膜的另一個面上（例如覆蓋膜側），其中可以 在這兩個步驟完成後均施以壓力，或是僅在放上第二玻璃 片後施以壓力。 雙面均被薄膜覆蓋的膨脹層的優點是，可以阻止或至 少是減輕（視薄膜的滲透性而定）玻璃的鹼侵蝕。 對某些薄膜而言，一種有利的作法是，在將薄膜埋在 兩個玻璃片之間後’在真空下將玻璃複合物加熱，加熱溫 度通常是60至85°C、或最好是70至80°C »這樣做的好處是 可以強化薄膜與玻璃的結合。但由於膨脹層需盡可能保有 含水量及均勻的水分分佈，這種作法通常僅用在以帶有覆 蓋膜並被其封住的混合薄膜製作的玻璃複合物，而且覆蓋 膜要留在玻璃複合物內。如果要將這種作法應用於其他的 玻璃複合物，則必須先弄清楚混合薄膜的密封程度及/或 可以使用多大的真空度及真空持續的時間有多長，以確保 膨脹不會受損》對具有完整的邊緣封裝薄膜的玻璃複合物 而言，適當的溫度範圍如前面所述，適當的真空度爲50至 150mbar、或最好是50至75mbar。真空步驟並非對所有的 薄膜都有利，但很適於應用在聚乙烯醇縮丁醛薄膜。 如果是僅經過預硬化的薄膜，在完成邊緣側密封後， 應以60至85°C、或最好是70至80°C的溫度加熱玻璃複合物 -22- 201210811 4至6小時，使其硬化。 如果預硬化或硬化的混合薄膜已經具有“固定的尺寸’ ，也就是說其大小已經不能改變，則可以進行上述的步驟 。將膨脹層朝上的載體膜送入塗覆單元。接著將一個玻璃 片放在膨脹層上，並施加壓力使其與膨脹層結合。將與混 合薄膜結合的玻璃片移出塗覆單元，並將玻璃片向下送入 第二塗覆單元中。視所希望達到的特性及薄膜性質而定， 可以將載體膜扯下，也可以將載體膜留在膨脹層上。接著 將第二個玻璃片或一個同樣帶有膨脹層的玻璃片（必要時 帶有被扯下的薄膜）放到膨脹層上。接著施加壓力使位於 上方的玻璃片與位於下方並帶有膨脹層的玻璃片結合在一 起。 可以根據需要的玻璃片厚度及/或膨脹層厚度重複進 行上述的塗覆過程。在達到需要的厚度後，就可以用膠帶 或聚合密封劑將玻璃片露空的邊緣封住。 本發明的方法可以用來製造混合薄膜形式的隔熱元件 ’其中在運送及/或儲存時，混合薄膜被製成片形式或捲 起形式，而且在應用於玻璃製品時可以被黏在玻璃片上。 接著加上至少一個封裝甩的玻璃片，即可將複合物封住。 玻璃複合物可以具有一個以上的混合薄膜，及/或至少具 有其在每一個玻璃片上的膨脹層，以及多個被至少一個混 合薄膜隔開的玻璃片。 爲了達到較高的隔熱値，隔熱元件最好是由多個分別 設置在兩個載體元件之間的膨脹層構成，其中載體元件可 -23- 201210811 以是薄膜或玻璃片。 如果混合薄膜的尺寸與玻璃的尺寸不同，可以在混合 薄膜被加到玻璃片上之前或之後、或是在玻璃複合物製造 兀成後’將混合薄膜裁剪成所希望的尺寸。本發明的內容 還包括製造大尺寸的坡璃複合物，然後再切割成所需要的 尺寸’並將其側邊密封住’這樣就成爲適於作爲隔熱元件 用的複合玻璃》 例如可以利用丁基材料、聚矽氧材料、聚硫化物、熱 熔膠、或一種快速硬化的橡膠聚合物進行密封。 混合薄膜具有很高的光學品質及透光率，當然前提是 混合薄膜具有適當的載體膜。混合薄膜具有很好的抗老化 性及隔熱特性。混合薄膜可以被塑造成不同形式，因此其 至少要能夠在加熱至40至6(TC後，可以無缺點的被捲起。 混合薄膜非常適於以單層或多層的方式塗覆在一個玻 璃片上’例如塗覆在一個浮選玻璃板或被施加預應力的玻 璃片上，然後（必要時可先去除載體膜）再被另一個玻璃 片覆蓋住。這個過程可以重複多次，以製造出比較厚的三 明治式系統。 爲供日後使用，可以將雙面都帶有一層塑膠膜或可撕 下的矽化紙、且邊緣區被密封住的混合薄膜捲成圓筒狀， 以節省儲存空間。 雖然用來製造薄膜是一種很重要的應用方式，但是也 可以利用前面說明的鍍層方法將調好黏性的分散液直接製 造成玻璃片，而且該等玻璃片可以已具有所需要之尺寸的 -24- 201210811 玻璃片，也可以需要再切割成所需尺寸的玻璃複合物。 【實施方式】 執行本發明的方法 以下的實例可以清楚的說明本發明的內容。 實例1 : 以不同種類的Si02製造透明隔熱膜 1.器材：Companies such as Bayer Industrieprodukte GmbH & Co. KG, Leverkusen, DE, Wacker-Chemie GmbH, Munchen, DE, Acros Organics, Belgien, etc. all produce suitable polydimethyloxane. According to the present invention, if desired, the ammonium salt of the polyoxyalkylene may further contain free ammonia or other additives added with ammonia, which may improve the optical properties of the dispersion or the expanded layer, and/or may reduce the dispersion or the expanded layer before hardening. The addition of a viscous material, and/or an extension of the life of the dispersion or expansion layer. Cerium dioxide is pyrolyzed SiO 2 and / or precipitated 8 丨 02 and / or yttrium, cerium oxide can be stabilized with polyalcohol, and cerium oxide is preferably stabilized by polyalcohol, while dioxin can be alkali The liquid (eg KOH) solidifies. The cerium oxide of this composition can produce a good venting action, thereby speeding up the processing, that is, making the processing time shorter. By using a mixture of silicone and pyrolysis of citric acid and/or precipitated citric acid, the period of use can be varied over a wide range, and since the defoaming agent based on the oxime which is proposed by the present invention is used, it is not The edge limit adjusts the viscosity and/or creep resistance of the thermally insulating cast material that is important to the film coating. Another feature of the hardened intumescent layer is that it is superior in fire resistance to other types of -10-201210811 but does not contain a buffer layer of siloxane. The appropriate Si 〇 2 dispersion that can be cured by the addition of lye is It is composed of the following components: 35 to 52% by weight of SiO 2 , containing up to 5%, or preferably up to 3% by weight, of polyvalent cation oxide; 30 to 50% by weight of water; 0.5 to 0.7% by weight of KOH: 〇 to 13% by weight of alkyl siloxane, wherein at least 3% by weight of alkyl oxane can be added to obtain a transparent product; Up to 6% by weight of ammonia (based on 32% aqueous solution) · * 7.5 to 30% by weight of polyalcohol, especially glycerol and/or ethylene glycol; wherein the above components are at least dispersed 99% (by weight) of the liquid, or preferably 1% by weight (% by weight). The molar ratio of cerium oxide to alkali metal oxide in the expanded layer in the hardened state is 5.2:1 to 2.0:1, or preferably 3.5:1 to 2.5:1. This molar ratio may indicate the characteristics of a mixture of polycaprate or polysilicate and its contained nanometer size (i.e., size invisible to the naked eye) of cerium oxide particles. The water content of the cured layer is preferably from 35 to 60% by weight, the content of cerium oxide is from 30 to 55% by weight, and the content of alkali metal oxide (M20) is at most not more than 18% ( Percentage by weight), the content of polyalcohol (especially glycerol) is usually 5 to 23% by weight. The metal oxide can be sodium oxide, potassium oxide, oxidized -11 - 201210811 lithium, or a mixture of these oxides. . It has been confirmed that, from the viewpoint of hardness, if the content of the polyol is less than 10% by weight, the critical enthalpy of the ratio (molar ratio) of 'SiO 2 : Κ 20 in the fully hardened state is 5.2 : 1. Therefore, it is necessary to heat the product which is directly rolled up after the completion of the manufacture so as to be unwound after being stored. If the molar ratio is 2.0: 1, the elasticity can be maintained at all times, but the insulation effect is not very good. In order to achieve good roll-up and roll-off without heating, a partial hardening or pre-hardening can be used to achieve a final hardness and complete curing. At this time, the swelling layer still showed a milky white turbidity, but it was more elastic. If the most pre-hardened or plate-like material is to be produced, even a molar ratio of up to 6.0 can be used. Polyalcohols (e.g., ethylene glycol, propylene glycol, glycerin) can stabilize pyrolysis or sedimentation of citric acid and/or tannin. These additives provide another possibility to adjust the elasticity. The more polyalcohol (especially glycerol) contained in the swelling layer, the softer the intumescent layer, so the wider range of molecular weight options is. The glycerin content is preferably at least 10% by weight, but not more than 22% by weight, because the glycerin content may cause hot spots when it is on fire. The stabilized tannic acid can be cured by the addition of a lye, such as NaOH or hydrazine, wherein hydrazine is more suitable than NaOH, and/or the network former (e.g., alumina or boron oxide) can be forced to cure the citric acid. It is preferable to use tantalum citrate and tannin as a source of SiO 2 . Although the density of OH groups on the surface of tantalum-12-201210811 and/or the surface of tantalum acid is greater than that of pyrolytic SiO2, and the particle size of primary particles and secondary particles is different from that of pyrolytic tannin, it is precipitated with tannic acid and/or tannin. The life and casting viscosity are easily controlled. The casting viscosity can be controlled by changing the mixing ratio within the range of 50 to 500 mPas 〃. The decane can be added to the cerium or cerium oxide-containing component, or added to the sanding component (test), or the siloxane can be added during the production of the barrier. Since an advantageous method of using the Si 〇 2 fine particle dispersion is to vent the dispersion, it is preferred to add a defoaming agent to the dispersion. Another possibility is to add a defoaming agent during the mixing of the dispersion with the hardening component, although this practice is not suitable for dispersions which do not contain citric acid. Since the Si含2-containing dispersion generally does not require venting for the mixture of precipitated citric acid and yttrium, the defoaming agent can be added to the dispersion and/or the alkali solution, or as a mixture process. The third component is added to the precipitated tannic acid and tannin. The amount of the deuterium oxide added is 0.1 to 10% by weight based on the mass of the deuterated layer. The amount of the siloxane to be added to the transparent film or glass is 0.25 to 3.0% by weight, or preferably 0.25 to 2.5% by weight. However, the partially transparent or opaque light transmissive film or glass may have a neodymite addition amount of 10% by weight. An amorphous precipitated tantalum acid suitable for use in the manufacture of a thermal barrier layer has a Si 〇 2 content of at least 98.5% by weight, 98 8% by weight, or preferably at least 99.1% by weight, BET surface. It is about 2〇 to 1001112^. The BET of the 3丨〇2 content of about 35 to 42% by weight of the dispersion -13-201210811 may be 80 to 100 m2/g, and the BET of the higher concentration dispersion may be 20 to 80 m2/g. The primary particle average particle size is usually from 10 to 70 nm, or preferably from 20 to 40 nm, and if all of the particles are located within a particle size distribution below the visible spectrum after hardening, a larger primary particle average particle size can be used. The particle size of the secondary particles of SiO 2 has only an effect on the hardening rate (smaller particle hardening rate is slow) and does not affect the dispersion and/or the expansion layer. A suitable Si 〇 2 dispersion which can be added with lye solidification consists of the following components: 35 to 52% by weight of SiO 2 (may contain up to 5%, or preferably up to 3% by weight) Valence cation oxide): 30 to 50% by weight of water; 0.5 to 0.7% by weight of KOH; 0 to 13% by weight of alkyl siloxane, in order to obtain a transparent product , can only add up to 3% (by weight) of alkyl oxane; 0 to 6% (by weight) of ammonia (based on 32% aqueous solution); 7.5 to 30% (by weight) of glycerol And/or ethylene glycol; wherein the above components together account for at least 99% by weight of the dispersion, or preferably 1% by weight; for example: 47.0 to 48.5% by weight of SiO 2 ; 3 3.8 to 30.9% by weight of water; 0.6 + /-0.1% by weight of KOH; 0 to 10% by weight of alkyl siloxane; -14- 201210811 0 to 2.5% (weight Percentage of ammonia (based on 32% aqueous solution); 7.5 to 30% (by weight) of glycerin and / or B Alcohol. The following are a very advantageous composition of the dispersion: 47.0% by weight of Si〇2; 32.8% by weight of water; 0.6% by weight of KOH; 0.25 to 3% by weight of alkane Alkoxyoxane 'especially polydimethyloxane; 〇 to 〇. 5 % by weight of ammonia (based on 32% aqueous solution); 7.5 to 30% by weight of glycerol And / or ethylene glycol. Another very advantageous composition of the dispersion is: 48.2% by weight of SiO 2 ; 30.9% by weight of water; 0.5% by weight of KOH; 0.25 to 3% by weight of alkyl hydrazine Oxyalkane, especially polydimethyloxane; 〇 to 0.5% by weight of ammonia (based on 32% aqueous solution); 7.5 to 30% (by weight) of glycerol and/or ethylene alcohol. The action of the polyalcohol (especially glycerin and/or ethylene glycol) and KOH is to stabilize the SiO 2 particles in the dispersion. In addition, the polyalcohol has a function of lowering the freezing point and increasing the elasticity. -15- 201210811 It has been found that an advantageous method is that the content of SiO 2 is 45 to 50% by weight, because at such SiO 2 content, a sufficient amount of KOH can be added as a solution, and still a high concentration of expansion can be produced. Floor. Concentrations up to 52% by weight, but from a concentration of 49 to 50% (by weight), there is a high requirement for the performance of the disperser. The ammonia in the intumescent layer contributes to the improvement of the properties of the intumescent layer, and the absolute amount (i.e., the amount calculated as 100% NH3) is equivalent to 0.1 to 2% by weight, or preferably 0.8 to 0.9%. (% by weight) of ammonia is added to the dispersion and/or hardener, and the ammonia may be partially or completely bonded to the polyoxo. It has been confirmed that a suitable method is that the aqueous ammonia solution (32% by weight) of the SiO 2 dispersion is at most 6% by weight, or preferably at most 2.5% by weight, at least 0.1% by weight, or preferably at least 0.5% by weight. The dispersion can be made in the manner described in WO 2009/1 5571 9 and the contents of this patent are also included in the present invention. The method of making the expanded coating material is to react and solidify the dispersion and/or silicone with a potassium hydroxide solution. An advantageous way (but not necessarily) is to cure without dehydration. The hybrid film of the present invention is produced by plating an expanded plating material onto a carrier film by a plating method and then hardening. The hardening process is usually carried out in a batch or continuous manner in an oven. The temperature of the oven is usually 60 to 85 ° C, or preferably 70 to 80 ° C. Hardening can be carried out in the case of dehydration, for example in "dry" air or "dry" inert gas, but for two reasons -16-201210811, hardening in the case of dehydration is not ideal: first The reason is that the water content will decrease, so the fire may cause adverse consequences. The second reason is that the hardening speed of the surface will become too fast', which may lead to unevenness. Therefore, it is best to harden in a humid environment, especially in a humid protective gas or with a cover film. After hardening, the cover film can be removed, and the cover film can be left in expansion. On the layer, make it part of the hybrid film. The hardening process can be done in one step or in two stages, the first of which is pre-hardening, that is, only the hardened layer is hardened to the degree of stabilization required for shipping and handling, and the second stage is Final hardening, ie hardening to final hardness and becoming transparent, can achieve final hardness on the film, for example after winding up in a rolled up shape, rolling up and cutting into a flat film, or between glass sheets The final hardness is achieved after the formation of the intumescent layer. Two-stage hardening is particularly suitable for films having a molar ratio of 6·0:1 to 4.0:1. The molar ratio of cerium oxide to alkali metal oxide in the expanded layer can be adjusted in the range of 5.2:1 to 2.0:1 depending on the glycerin content and the desired softness/elasticity, if the polyol content is very low (about 1 0% (% by weight) can be adjusted from 3.5: 1 to 2.5: 1. The processing characteristics and final characteristics of the intumescent layer and the mixed film can be controlled in a wide range by: (i) changing the ratio of precipitated tannic acid and/or pyrolysis of tannic acid to tannin; (ii) changing SiO 2 and alkali metal The molar ratio of oxides (especially κ20) (also known as the molar ratio); -17- 201210811 (Hi) adjusts the content of polyalcohols (especially glycerol); (iv) can also be used as an inner primer if necessary Defoamer, as well as the addition of decane. In this way, the processing characteristics can be controlled, for example, by (i) controlling the pot life and viscosity, and also by (ii) changing the viscosity and changing the elasticity and the characteristics of the fire through (ii) and (Hi) due to the oxygenation. The presence of an alkane (iv), so these changes do not adversely affect the optical properties. If necessary, ammonia can be added for further modification. If the intumescent layer is to be in direct contact with the glass, a polyvalent cation oxide insoluble in an alkaline medium may be added to reduce glass corrosion. The defoaming agent (iv) may be added to the ceria- or cerium-containing component and/or hardener before the expansion coating is mixed, and/or the defoaming agent (iv) may be added to the mixed component. (and hot casting materials). Since the oxime which is suitable as a defoaming agent usually also has the effect of an inner primer, it is not necessary to pretreat the carrier member (i.e., the carrier film and/or the glass coated with the mixed film) with a primer. However, the content of the present invention also includes the use of an outer primer in addition to the inner primer, or the replacement of the inner primer in the outer primer (for example, the defoaming agent does not have or has only a weak inner primer). . In the present invention, this (outer) primer layer is referred to as an auxiliary layer. Due to the good adjustability of the processing characteristics (such as viscosity and service life), the expansion layer can be plated by different plating methods. For example, the immersion method is to make one surface of the film contact with the surface of a castable material at a fixed speed. The squeegee coating method uses the pump and the nozzle to make the castable material on one side of the film, and then scrapes the plate. Uniform (forming a defined layer thickness of -18 - 201210811 degrees) is applied to this film surface, and the roll coating method utilizes two rollers that are spaced apart from each other by a predetermined distance and slowly roll toward each other (one of which is coated with a roller) With a pourable material), the castable material is applied to the film passing through the gap between the two rolls at a fixed speed. A very advantageous way is to use a slit nozzle coating which adjusts the layer thickness through the distance of the nozzle from the film. The so-called pre-dosing method is a very advantageous coating method for most cases, especially the coating method using slit nozzle coating. For all of the above mentioned methods, the appropriate viscosity range is from 50 to 500 mPas, and the insulating cast material of the present invention can achieve this viscosity range. All of the above shovel methods are followed by an oven in the oven. Batch or continuous pre-hardening and/or hardening at elevated temperatures. For example, pre-hardening is carried out at a temperature of 60 to 85 ° C, or preferably 70 to 80 ° C for 1 to 3 hours. The hardening is then carried out at the same temperature for 4 to 8 hours. The above conditions are suitable for an intumescent layer having a layer thickness of about 0.5 to 1.5 mm. Both hardening and pre-hardening are carried out in an oven, such as a convection oven, an infrared furnace or a radiant furnace. None of the above mentioned methods require the expanded coating to be vented prior to coating. Even without venting, the desired optical quality can be achieved through the use of defoamers. After coating, the coated film is placed in an oven and hardened at a high temperature. As described above, the hardening can be carried out in a dehydrated environment, i.e., in a dry air or an inert gas, or preferably in a moisture-containing environment. If hardening is to be carried out in the presence of moisture, the water content in the ambient atmosphere (eg nitrogen) must be at least equal to the water content of the expansion layer to be hardened. Another possible method is to add a cover film at high temperatures prior to hardening. This cover film may remain in the mixed film composite or may be removed after hardening. Depending on the properties of the intumescent layer and the cover film, an adhesion-reducing ammonium layer can be added to the cover film used only during hardening and transport, for example by adding a release layer (e.g., a deuterated layer). Preferably, the cover layer is isolated from the carrier film in the edge region. The advantage of this is that the carrier film is not plated with insulating material in the edge region, so the film can be thermally encapsulated, thermally welded, or coated with a sealant (eg hot melt adhesive) in the edge region. Being stuck. Preferably, the sealant is applied to the edge region prior to the addition of the cover film and should be approximately the same thickness as the heat insulating cast material to ensure uniform coverage of the cover film over the expanded layer. The cover film that should not remain in the composite afterwards may be transparent, opaque, or opaque. For thermal insulation, the carrier film must be heat resistant. The carrier film can be made of plastic or metal. The carrier film preferably also enhances the mechanical stability of the thermal insulation element. The carrier film applied to the insulating glass is preferably a light transmissive and transparent film. The polyvinyl butyral film is a film which has been applied to heat insulating glass, which has characteristics required for heat insulating glass, such as fracture resistance, and can improve the sound insulating effect of the heat insulating glass. Other examples of carrier films that can be used, but preferably do not remain in the glass composite, are polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP). , polyurethane (PUR). For the film to be rolled up, it is preferable to have a cover film, -20-201210811 or the two facing facing layers of the carrier film have different adhesion characteristics, so that it does not cause expansion when the film is unwound. The layer is broken. Mixed films are very suitable for making insulating glass. In this case, the mixed film (the carrier film and/or the cover film should be removed if necessary) is placed between the two glass sheets' and bonded to the glass sheet. Glass sheets that are pre-stressed in whole or in part by heating or chemically can be used. In the manufacture of insulating glass, the rolled film and the pre-hardened or hardened mixed film should be tensioned by means of a take-up device, and then the unwinding device is fed into a coating unit with the carrier film underneath and the intumescent layer on top. A glass piece is then placed over the intumescent layer and pressed to bond the glass sheet to the intumescent layer. The mixed film at the beginning of the glass element is then cut away. If the mixed film has beyond the end of the glass element, the portion beyond the trailing end should also be cut away. The glass sheet combined with the mixed film is then removed from the first coating unit and the glass is fed face down into the second coating unit. Depending on the desired properties and film properties, the carrier film can be pulled off or the carrier film can be left on the intumescent layer. A second piece of glass or a piece of glass, also with a layer of tearing down, if necessary, is placed on the intumescent layer. Pressure is then applied to bond the upper glass piece to the underlying glass sheet with the intumescent layer. As described above, the film of the carrier film-intumescent layer-cover film may be removed from the cover film, or the cover film may be obtained in the composite. If the cover film is to be left in the glass composite, the cover film preferably has the same characteristics as the carrier film. The 21 - 201210811 glass composite having such a film can be produced according to the two-stage method described above, wherein the positioning of the film is irrelevant, that is, the cover film or the carrier film is first combined with the glass sheet without any difference. . It is also possible to manufacture the glass composite in a straightforward manner, that is to say placing one side of the mixed film (for example the carrier film side) on the first glass sheet and then placing the second glass sheet on the other side of the mixed film (for example covering Membrane side), wherein pressure can be applied after both steps are completed, or pressure is applied only after the second glass piece is placed. An advantage of the intumescent layer, which is covered by the film on both sides, is that the alkali attack of the glass can be prevented or at least reduced (depending on the permeability of the film). For some films, it is advantageous to heat the glass composite under vacuum after burying the film between two glass sheets, typically at a temperature of 60 to 85 ° C, or preferably 70. Up to 80 ° C » The benefit of this is that it strengthens the bond between the film and the glass. However, since the intumescent layer needs to have a water content and a uniform water distribution as much as possible, this method is usually only used for a glass composite made of a mixed film with a cover film and sealed by it, and the cover film is left in the glass composite. Inside. If you want to apply this method to other glass composites, you must first understand the degree of sealing of the mixed film and / or how much vacuum can be used and how long the vacuum lasts to ensure that the expansion will not be damaged. For glass composites having a complete edge encapsulating film, a suitable temperature range is as previously described, with a suitable degree of vacuum of 50 to 150 mbar, or preferably 50 to 75 mbar. The vacuum step is not advantageous for all films, but is well suited for use in polyvinyl butyral films. In the case of a pre-cured film only, after completion of the edge-side sealing, the glass composite -22-201210811 should be heated at a temperature of 60 to 85 ° C, or preferably 70 to 80 ° C for 4 to 6 hours. hardening. If the pre-hardened or hardened hybrid film already has a "fixed size", that is to say its size has not changed, the above steps can be carried out. The carrier film with the expanded layer facing up is fed into the coating unit. The sheet is placed on the intumescent layer and pressure is applied to bond it to the intumescent layer. The glass sheet bonded to the mixed film is removed from the coating unit and the glass sheet is fed down into the second coating unit as desired. Depending on the properties and the properties of the film, the carrier film can be torn off or the carrier film can be left on the intumescent layer. The second glass piece or a piece of glass with the same expansion layer (with tearing down if necessary) The film is placed on the intumescent layer. Pressure is then applied to bond the upper glass sheet to the underlying glass sheet with the intumescent layer. The above can be repeated depending on the desired thickness of the glass sheet and/or the thickness of the intumescent layer. Coating process. After the desired thickness is reached, the exposed edge of the glass sheet can be sealed with tape or a polymeric sealant. The method of the invention can be used to manufacture Insulating element in the form of a film, wherein the mixed film is formed into a sheet form or a rolled up form during transport and/or storage, and can be adhered to the glass sheet when applied to a glass article. Next, at least one package is added. The glass sheet can be sealed. The glass composite can have more than one mixed film, and/or at least have an intumescent layer on each of the glass sheets, and a plurality of glass separated by at least one mixed film. In order to achieve a higher thermal insulation, the insulating element is preferably composed of a plurality of intumescent layers respectively disposed between the two carrier elements, wherein the carrier element can be a film or a glass sheet, -23-201210811. The size of the mixed film is different from the size of the glass, and the mixed film can be cut to a desired size before or after the mixed film is applied to the glass sheet, or after the glass composite is fabricated. The present invention also includes Manufacture of large-sized slab composites, and then cut to the required size 'and seal the sides thereof' so that it is suitable as a thermal insulation element The composite glass used can be sealed, for example, by using a butyl material, a polyfluorene material, a polysulfide, a hot melt adhesive, or a rapidly hardening rubber polymer. The mixed film has high optical quality and light transmittance, of course. The premise is that the mixed film has a suitable carrier film. The mixed film has good aging resistance and heat insulation properties. The mixed film can be molded into different forms, so it must be able to be heated at least 40 to 6 (after TC, no The disadvantages are rolled up. The hybrid film is very suitable for coating on a glass sheet in a single or multi-layer manner, for example on a flotation glass plate or a pre-stressed glass sheet, and then (if necessary) The carrier film is then covered by another glass sheet. This process can be repeated several times to create a thicker sandwich system. For later use, both sides can be covered with a plastic film or peeled off. The paper and the mixed film in which the edge regions are sealed are rolled into a cylindrical shape to save storage space. Although the film is an important application, it is also possible to directly form a viscous dispersion into a glass sheet by the plating method described above, and the glass sheets can already have the required size - 24- 201210811 Glass sheets can also be re-cut into glass composites of the required size. [Embodiment] The method of the present invention is carried out. The following examples will clearly illustrate the contents of the present invention. Example 1: Making transparent insulation film with different kinds of SiO2 1. Equipment:
Si〇2分散液：容量10公升的反應槽，配備有攪拌器、 加熱器及冷卻單元、玻璃直通式冷卻器、以及真空泵，其 中玻璃直通式冷卻器具有一個容量兩公升的圓形瓶（作爲 收集容器）。 真空泵是以具有文居里系統的壓縮空器裝置爲基礎。 這種真空泵能夠很大的容積（相對於空氣量）抽到很高的 真空度（約70mbar)。 利用以轉子/定子原理工作的Ultra Turrax攪拌器作爲 分散器》 K10H :容量5公升的攪拌容器 2.使用材料： 以固態矽酸製作Si02分散液，成分如下： 固態 Si02 ( 4.7kg); 去礦物質的水（3.23kg)，電導率<i〇 v S ; -25- 201210811 聚二甲基矽氧烷的含水乳膠（〇.〇5kg)(聚二甲基矽 氧烷佔50% (重量百分比））； 甘油（1.96kg)，純度 >99.9% ; KOH ( 0.06kg )，純度 >99.9%。 以Si〇2 ( BET 50m2/g，初始粒子直徑55nm)作爲沉降 矽酸及熱解矽酸。 矽膠 矽膠（9.3 5kg ) ( BET 5 0m2/g，初始粒子直徑55nm， 濃度50%的含水分散液，以KOH將pH値調整爲9至11); 去礦物質的水（〇.59kg)，電導率<l〇//S: 聚二甲基矽氧烷的含水乳膠（0.05kg )(聚二甲基矽 氧烷佔50% (重量百分比））； 甘油（1.96kg )，純度 >99.9% » 在製造過程中有1.9 6kg的水從上述混合物中被蒸發掉 〇 苛性鉀溶液，由以下成分組成： KOH ( 2.69kg )，純度 >99.9%; 去礦物質的水（2.6 9kg)，電導率<l〇yS。 3.製造初始材料 3.1以固態Si02製作Si02分散液 將下列成分放入容量10公升的容器中： 去礦物質的水（3.23kg)，電導率cio^s: -26- 201210811 聚二甲基矽氧烷的含水乳膠（〇.〇5kg)(聚二甲基矽 氧烷佔50% (重量百分比））； 甘油（1.96kg)，純度 >99.9% ; KOH ( 0.06kg)，純度>99.9%。 利用攪拌器將上述成分構成的溶液攪拌均勻（攪拌時 間約5分鐘）。 —邊以Ultraturrax攪拌器攪拌，一邊慢慢將4.7kg的矽 酸粉末倒入溶液中。繼續攪拌使其分散，直到形成均勻的 分散液爲止。 3.2製造摻有添加物的矽膠 將下列成分放入容量10公升的反應槽中： 矽膠（9.35kg) ( BET 50m2/g，初始粒子直徑55nm，Si〇2 dispersion: a 10 liter reaction tank equipped with a stirrer, a heater and a cooling unit, a glass straight-through cooler, and a vacuum pump, wherein the glass straight-through cooler has a two-liter round bottle (as Collection container). The vacuum pump is based on a compressed air device with a Venturi system. This vacuum pump is capable of pumping a very high vacuum (about 70 mbar) with a large volume (relative to the amount of air). Utilizing the Ultra Turrax agitator operating on the rotor/stator principle as a disperser" K10H: Stirring vessel with a capacity of 5 liters 2. Materials used: SiO 2 dispersion was prepared from solid tannic acid with the following composition: Solid Si02 (4.7 kg); Substance water (3.23kg), conductivity <i〇v S ; -25- 201210811 Polydimethyl methoxy alkane aqueous emulsion (〇.〇5kg) (polydimethyl methoxy oxane accounted for 50% (weight Percentage)); glycerol (1.96 kg), purity >99.9%; KOH (0.06 kg), purity > 99.9%. Si〇2 (BET 50 m2/g, initial particle diameter 55 nm) was used as the precipitated tannic acid and pyrolytic tannic acid. Silicone rubber (9.3 5kg) (BET 5 0m2 / g, initial particle diameter 55nm, 50% concentration of aqueous dispersion, pH 値 adjusted to 9 to 11 with KOH); demineralized water (〇.59kg), conductance Rate <l〇//S: aqueous emulsion of polydimethyloxane (0.05 kg) (polydimethylsiloxane (50% by weight)); glycerol (1.96 kg), purity >99.9 % » In the manufacturing process, 1.9 6 kg of water is evaporated from the above mixture. The caustic potash solution consists of the following components: KOH ( 2.69 kg ), purity >99.9%; demineralized water (2.6 9 kg), Conductivity < l〇yS. 3. Manufacture of starting material 3.1 Preparation of SiO 2 dispersion from solid SiO 2 The following ingredients were placed in a container of 10 liter capacity: demineralized water (3.23 kg), conductivity cio^s: -26- 201210811 polydimethyl hydrazine Aqueous emulsion of oxane (〇.5kg) (polydimethylsiloxane (50% by weight)); glycerol (1.96kg), purity >99.9%; KOH (0.06kg), purity>99.9 %. The solution of the above components was stirred uniformly by a stirrer (stirring time was about 5 minutes). - While stirring with an Ultraturrax mixer, slowly pour 4.7 kg of citric acid powder into the solution. Stirring is continued to disperse until a uniform dispersion is formed. 3.2 Manufacture of tannins with additives The following ingredients were placed in a reaction tank of 10 liters capacity: tannin (9.35 kg) (BET 50 m2/g, initial particle diameter 55 nm,
Si02在水中的濃度爲50%，以KOH將pH値調整爲9至1 1 ); 去礦物質的水（〇_59kg)，電導率<10#S; 聚二甲基矽氧烷的含水乳膠（0.05kg)(聚二甲基矽 氧烷佔50% (重量百分比））； 甘油（1.96kg)，純度>99.9%。The concentration of SiO2 in water is 50%, the pH is adjusted to 9 to 1 1 with KOH); the demineralized water (〇_59kg), the conductivity <10#S; the water content of polydimethyl siloxane Latex (0.05 kg) (polydimethylsiloxane) 50% by weight; glycerol (1.96 kg), purity > 99.9%.
利用攪拌器將上述成分構成的溶液攪拌均勻（攪拌時 間約5分鐘），然後繼續攪拌並利用加熱模組加熱至50至 60°C。保持這個溫度，在真空中使乳膠達到沸騰，以便將 1.96kg的水蒸發掉。然後在沒有真空的情況下冷卻至20°C -27- 201210811 3.3製作苛性鉀溶液 將下列成分放入容量5公升的攪拌容器中： KOH ( 2.69kg)，純度 >99.9% ; 去礦物質的水（2.69 kg)，電導率<10yS。 將KOH攪拌至完全溶解。 4.製造隔熱鑄造材料 製造以下的Si02分散液，該等Si02分散液含有以下的 Si〇2成分及/或量（以前面給定的量爲準）： (a) 100%熱解矽酸（根據3.1 ) (b ) 100%沉降矽酸（根據3.1 ) (c) 50%熱解矽酸及50%沉降矽酸（根據3.1) (d) 100%矽膠（根據3.2) (e ) 50%矽膠（根據3.2 )及50%熱解矽酸（根據3.1 ) (f) 50%矽膠（根據3.2 )及50%沉降矽酸（根據3.1 ) 以前面3.3給定的1<：011溶液的量使上述3丨02源（&)至 (f)硬化’即可產生Si〇2: Κ·2〇 = 3.2: 1的膨膜層。 使每一個分散液/膠（a)至（f)與苛性鉀溶液（根據 3.3)反應。接通攪拌器進行攪拌，直到混合物變均勻爲 止。一邊攪拌，一邊利用加熱模組加熱至5 0至5 5 °C。當溫 度達到5〇°C時，繼續攪拌45分鐘，使溫度保持在50至55t： ’直到混合物變黏稠爲止。接著接通真空泵，使真空度達 -28- 201210811 到50至90mbar。在真空中攪拌混合物，使其冷卻至20°C。 在真空中放置90分鐘後，材料即告製作完成，並可作鏟材 被鑛在薄膜或矽化紙上。 表1顯示按照實例1第4點的方式製造的隔熱鑄造材料 的特性： 表1 : 隔熱鑄造材料 (a) (b) ⑹ (e) (f) 使用期以55t加熱 30分鐘再冷卻至 20°C 3h 3h 6h 5h 5h 黏滞性以55°C加熱 15分鐘 150mPa*s 130mPa*s 60mPa*s 100mPa*s 80mPa*s 黏滯性以55°C加熱 45分鐘 500mPa*s 400mPa*s 280mPa*s 350mPa*s 300mPa*s 分散方式/分散液 的製造 Turrax 轉子 / 定子 Turrax 轉子 / 定子 螺旋槳攪拌 器 溶解器齒盤 溶解器齒盤 5 .利用縫隙式噴嘴將防火鑄造材料塗在薄膜上，以製造混 合薄膜，然後硬化形成膨脹層 將隔熱鑄造材料裝到塗覆噴嘴的儲存容器。接著使待 塗覆的PET膜循著捲開裝置->塗覆工作台->乾燥爐->捲繞 裝置的轨道通過。 將薄膜及塗覆噴嘴之間的縫隙調整爲1mm，以調整塗 覆厚度。利用厚度規在薄膜的右外側及左外側測量厚度。 根據軌道速度調整配料幫浦的給料量。將軌道速度調 整爲0.1 m/s，因爲速度過快會造成塗覆厚度過薄或濕膜出 現裂痕等塗覆缺點。 啓動捲繞裝置及配料幫浦即進入塗覆過程。 膨脹層的硬化是在乾燥通道內進行，乾燥通道內充滿 -29- 201210811 以略爲過壓（l〇Pa)注入的保護氣體（氮氣）。乾燥通道 的溫度爲80°C。 在乾燥通道的出口處檢驗混合薄膜的透明性。 6.特性 以光學顯微鏡檢査，確定所有的層都是透明的，而且 沒有氣泡。 實例2 : 製造透明封閉的隔熱膜 按照實例1第1至第4點的方式製造隔熱鑄造材料。 將隔熱鑄造材料裝到塗覆噴嘴的儲存容器。接著使待 塗覆的PET膜循著捲開裝置->塗覆工作台->塗覆滾筒->乾 燥爐-> 捲繞裝置的軌道通過，以及使覆蓋膜循著捲開裝 置->塗覆滾筒->乾燥爐_>捲繞裝置的軌道通過。 利用熱熔膠配料器進行邊緣密封，熱熔膠配料機的任 務是在加上覆蓋膜之前，將熱熔膠直接塗在載體膜未被膨 脹層蓋住的邊緣上。熱熔膠配料機的調整方式和塗覆厚度 的調整方式一樣（參見後面的說明）。 將薄膜及塗覆噴嘴之間的縫隙調整爲1mm，以調整塗 覆厚度。利用厚度規在薄膜的右外側及左外側測量厚度。 根據軌道速度調整配料幫浦的給料量。將軌道速度調 整爲0.1 m/s，因爲速度過快會造成塗覆厚度過薄或濕膜出 現裂痕等塗覆缺點。 -30- 201210811 啓動捲繞裝置及配料幫浦即進入塗覆過程。 膨脹層的硬化是在乾燥通道內進行’乾燥通道內充滿 以略爲過壓（1 〇Pa )注入的保護氣體（氮氣），雖然保護 氣體氛圍並非此乾燥過程必須有的條件。乾燥通道內的溫 度爲80°C。 在乾燥通道的出口處檢驗混合薄膜的透明性及邊緣的 密封性。 實例3 : 使用混合薄膜製造耐熱的玻璃片 將被捲起的混合薄膜固定在捲開裝置上拉緊，然後將 捲開裝置送入一個塗覆單元，並使混合薄膜位於下面，膨 脹層位於上面。然後將一個淨化過的玻璃片平放在膨脹層 上，並以塗覆滾筒施壓使玻璃片與膨脹層結合。然後將玻 璃元件開端及尾端的混合薄膜切掉。 接著將與混合薄膜結合的玻璃片移出，並將玻璃面向 下平放在另一個塗覆單元上。將PET膜扯下，接著將另一 個玻璃片或一個同樣帶有膨脹層的玻璃片（必要時帶有被 扯下的薄膜）放到膨脹層上。接著以塗覆滾筒對位於上方 的玻璃片施加壓力，以使位於上方的玻璃片與位於下方並 帶有膨脹層的玻璃片結合在一起。 可以根據需要的玻璃片厚度及/或膨脹層厚度重複進 行上述的塗覆過程v在達到需要的厚度後，就可以用膠帶 或聚合密封劑將玻璃片露空的邊緣封住。 -31 - 201210811 實例4 : 透過改變可鑄造之隔熱材料及/或不含甘油的膨脹層的克 分子比例，以影響特性 按照實例1第4點（f)的方式製作矽酸分散液，其所 含的Si 02有5 0% (重量百分比）來自矽膠，另外50% (重 量百分比）來自沉降矽酸，但是甘油的含量被水取代，加 入苛性鉀溶液溶液，調整到各個不同的克分子比例（Si02 ：K20 )。 試驗結果顯不於表2。 表2 : 克分子比例 (Si02:K20) 變成透明的乾 燥時間80t 薄膜的硬度 應用 2:1 60min 很軟及有彈性 薄膜可以被捲起 2.5:1 75min 很軟及有彈性 薄膜可以被捲起 3:1 90min 軟及有彈性 薄膜可以被捲起 3.5:1 1 lOmin 軟及有彈性 薄膜可以被捲起 4:1 180min 易脆，有一定的彈性 薄膜片可以被堆壘 4.5:1 300min 易脆，有一定的彈性 薄膜片可以被堆壘 5:1 480min 硬及易破裂 薄膜片可以被堆壘 可能的Si02 : Κ2〇克分子比例是從Si02 2 : 1 Κ20到 Si02 5.2 : 1 Κ20。但是對薄膜而言，在甘油含量爲10% ( 重量百分比））的情況下，有利的克分子比例是從Si02 2.5 : 1 K20到 Si02 3.5 : 1 K20。 實例5 : 透過甘油含量影響特性 按照實例1第4點（f)的方式製作矽酸分散液/矽膠， -32- 201210811 其中較高/較低的甘油含量是因爲部分甘油被較少/較多的 水取代，並加入苛性鉀溶液（50% (重量百分比））將克 分子比例調整爲Si 02 4.5: 1 K20。試驗結果顯示於表3。 表3 : 隔熱鑄造材料 的甘油含量(％) 變成透明的乾 燥時間80°C 薄膜的硬度 應用 0% 480min 硬及易破裂 薄膜片可以被堆壘 5% 465min 硬及易破裂 薄膜片可以被堆壘 10% 430min 易脆，有一定的彈性 薄膜片可以被堆壘 15% 370min 軟及有彈性 薄膜可以被捲起 20% 315min 軟及有彈性 薄膜可以被捲起 25% 270min 很軟及有彈性 薄膜可以被捲起 30% 240min 很軟及有彈性 薄膜可以被捲起 透過添加甘油，即使克分子比例高於Si02 4 : 1 Κ20， 也可以使薄膜變得很軟及有彈性，以便能夠將薄膜捲起來 。此外還可以降低薄膜的寒冷敏感性。 實例6 : 本發明製造的玻璃複合物在燃燒試驗中表現的特性 表4顯示燃燒試驗的結果，此燃燒試驗是按照規範ΕΝ 1363/1364的規定進行。 -33- 201210811The solution of the above ingredients was stirred uniformly by a stirrer (mixing time was about 5 minutes), and then stirring was continued and heated to 50 to 60 ° C by a heating module. Maintaining this temperature, the latex is boiled in a vacuum to evaporate 1.96 kg of water. Then cool to 20 ° C without vacuum -27- 201210811 3.3 Preparation of Caustic Potassium Solution Place the following ingredients in a 5 liter stirred vessel: KOH ( 2.69 kg), purity >99.9%; demineralized Water (2.69 kg), conductivity < 10yS. The KOH was stirred until completely dissolved. 4. Production of Insulating Casting Materials The following SiO 2 dispersions were prepared, and the SiO 2 dispersions contained the following Si 〇 2 components and/or amounts (based on the amounts given above): (a) 100% pyrogenic decanoic acid (according to 3.1) (b) 100% sedimentation of tannic acid (according to 3.1) (c) 50% pyrogenic tannic acid and 50% precipitated tannic acid (according to 3.1) (d) 100% tannin (according to 3.2) (e) 50% Silicone (according to 3.2) and 50% pyrolysis of tannic acid (according to 3.1) (f) 50% silicone (according to 3.2) and 50% sedimentation of tannic acid (according to 3.1) with the amount of 1 <: 011 solution given in 3.3 above The above 3 丨 02 source (&) to (f) hardening 'produces Si 〇 2: Κ · 2 〇 = 3.2: 1 swelled layer. Each of the dispersions/gels (a) to (f) was reacted with a caustic potash solution (according to 3.3). Turn on the stirrer and stir until the mixture becomes uniform. While stirring, use a heating module to heat to 50 to 55 °C. When the temperature reached 5 ° C, stirring was continued for 45 minutes to maintain the temperature at 50 to 55 t: ' until the mixture became viscous. The vacuum pump is then turned on to a vacuum of -28-201210811 to 50 to 90 mbar. The mixture was stirred in vacuo and allowed to cool to 20 °C. After being placed in a vacuum for 90 minutes, the material is finished and can be used as a shovel on the film or crepe paper. Table 1 shows the properties of the insulating cast materials manufactured in accordance with the method of point 4 of Example 1: Table 1: Insulation casting materials (a) (b) (6) (e) (f) Heating for 55 minutes during use for 30 minutes and then cooling to 20°C 3h 3h 6h 5h 5h Viscosity heating at 55°C for 15 minutes 150mPa*s 130mPa*s 60mPa*s 100mPa*s 80mPa*s Viscosity heating at 55°C for 45 minutes 500mPa*s 400mPa*s 280mPa *s 350mPa*s 300mPa*s Manufacture of dispersion/dispersion Turrax rotor / stator Turrax rotor / stator propeller stirrer dissolver toothed disk dissolver sprocket 5. Apply the fireproof casting material to the film with a slit nozzle A hybrid film is produced and then hardened to form an intumescent layer to load the insulating casting material into a storage container for the coating nozzle. The PET film to be coated is then passed through the track of the winding device - > coating station - > drying oven - > winding device. The gap between the film and the coating nozzle was adjusted to 1 mm to adjust the coating thickness. The thickness was measured on the right outer side and the left outer side of the film using a thickness gauge. The dosing amount of the dosing pump is adjusted according to the orbital speed. Adjust the orbital speed to 0.1 m/s because too fast a speed can cause coating defects such as excessive coating thickness or cracking of the wet film. The winding device and the batching pump are started to enter the coating process. The hardening of the intumescent layer is carried out in a drying tunnel filled with a protective gas (nitrogen gas) injected with a slight overpressure (10 Pa) at -29-201210811. The drying channel temperature is 80 °C. The transparency of the mixed film was examined at the exit of the drying tunnel. 6. Characteristics With optical microscopy, it was determined that all layers were transparent and free of air bubbles. Example 2: Production of a transparent closed heat-insulating film An insulating cast material was produced in the same manner as in the first to fourth points of Example 1. The insulating cast material is loaded into a storage container that coats the nozzle. The PET film to be coated is then passed through a roll-off device->coating table->coating drum->drying furnace-> track of the winding device, and the cover film is followed by the unwinding device -> Coating drum-> Drying furnace_> The track of the winding device passes. The edge seal is carried out using a hot melt glue dispenser which is required to apply the hot melt directly to the edge of the carrier film which is not covered by the expansion layer prior to the application of the cover film. The hot melt dispensing machine is adjusted in the same way as the coating thickness (see description below). The gap between the film and the coating nozzle was adjusted to 1 mm to adjust the coating thickness. The thickness was measured on the right outer side and the left outer side of the film using a thickness gauge. The dosing amount of the dosing pump is adjusted according to the orbital speed. Adjust the orbital speed to 0.1 m/s because too fast a speed can cause coating defects such as excessive coating thickness or cracking of the wet film. -30- 201210811 Start the winding device and the batching pump into the coating process. The hardening of the intumescent layer is carried out in the drying channel. The drying channel is filled with a protective gas (nitrogen gas) injected with a slight overpressure (1 〇Pa), although the protective gas atmosphere is not a necessary condition for this drying process. The temperature in the drying channel was 80 °C. The transparency of the mixed film and the sealing of the edges were examined at the exit of the drying tunnel. Example 3: Fabrication of a heat-resistant glass sheet using a mixed film. The rolled film was fixed to a take-up device and tensioned, and then the take-up device was fed into a coating unit with the mixed film underneath and the intumescent layer on top. . A cleaned glass piece is then placed flat on the intumescent layer and pressed with a coating roll to bond the glass piece to the intumescent layer. The mixed film at the beginning and the end of the glass element is then cut away. The glass sheet bonded to the mixed film is then removed and the glass is placed flat on the other coating unit. The PET film is torn off, and then another glass piece or a piece of glass (including a film torn with it) having the same expanded layer is placed on the intumescent layer. The coated glass is then used to apply pressure to the upper glass sheet to bond the upper glass sheet to the underlying glass sheet with the intumescent layer. The coating process described above can be repeated depending on the desired thickness of the glass sheet and/or the thickness of the intumescent layer. v After the desired thickness is achieved, the exposed edges of the glass sheet can be sealed with tape or polymeric sealant. -31 - 201210811 Example 4: A tantalum acid dispersion was prepared in accordance with the method of Example 4, point 4 (f), by changing the molar ratio of the castable insulating material and/or the glycerin-free swelling layer. 50% (% by weight) of the Si 02 contained is from tannin, and another 50% by weight is from the tannic acid, but the content of glycerin is replaced by water, and the solution of caustic potash is added to adjust the ratio of different moles. (Si02: K20). The test results are not as shown in Table 2. Table 2: molar ratio (Si02:K20) becomes transparent drying time 80t film hardness application 2:1 60min very soft and elastic film can be rolled up 2.5:1 75min very soft and elastic film can be rolled up 3 :1 90min soft and flexible film can be rolled up 3.5:1 1 lOmin soft and elastic film can be rolled up 4:1 180min brittle, a certain elastic film can be piled up 4.5:1 300min brittle, There are certain elastic film sheets that can be stacked 5:1 480min. Hard and easily ruptured film sheets can be stacked. Possible SiO 2 : Κ 2 〇 molecular ratio is from SiO 2 2 : 1 Κ 20 to SiO 2 5.2 : 1 Κ 20. However, for the film, in the case of a glycerin content of 10% by weight, the favorable molar ratio is from SiO 2 2.5 : 1 K20 to Si02 3.5 : 1 K20. Example 5: Effect of glycerin content on the formation of tannic acid dispersion / silicone according to the method of Example 4, point 4 (f), -32- 201210811 wherein the higher/lower glycerin content is due to less/more glycerin Replace the water with a caustic potash solution (50% by weight) to adjust the molar ratio to Si 02 4.5: 1 K20. The test results are shown in Table 3. Table 3: Glycerin content (%) of heat-insulating casting material Transparent drying time 80 °C Hardness of film applied 0% 480min Hard and easily ruptured film can be piled up 5% 465min Hard and easily ruptured film can be piled 10% 430min brittle, a certain elastic film can be piled up 15% 370min soft and elastic film can be rolled up 20% 315min soft and elastic film can be rolled up 25% 270min very soft and elastic film Can be rolled up 30% 240min. A soft and flexible film can be rolled up and added with glycerin. Even if the molar ratio is higher than SiO 4 4 : 1 Κ20, the film can be made soft and elastic so that the film can be rolled. stand up. It also reduces the cold sensitivity of the film. Example 6: Characteristics of the glass composite produced by the present invention in the burning test Table 4 shows the results of the burning test which was carried out in accordance with the specification ΕΝ 1363/1364. -33- 201210811
:寸1^ 輻射ΕΝ 13 501-23) 4.5 KW/m2 6.1 KW/m2 9.5 KW/m2 8.5 KW/m2 防火等級 Si02/K20 5.0:1 EW60 EW90/EI15 EW 120/EI 30 EW 60/EI30 -1 EW 15 EW35 防火等級 Si02/K20 3.2:1 EW 60 EW90/EI15 EW 120/EI 30 EW 60/EI 30 j 玻璃尺寸 lmxlm lmxlm lmxlm lmxlm 1 0.5mx0.5m i 0.5mx0.5m 薄膜厚度，數量2) 1x1.5mm 2x1.5mm 4x1.5mm 3x1.5mm 1x0.5mm 2x0.5mm 玻璃厚度” 2x5mm ESG 2x5mm ESG 2x5mm ESG 4x3mm ESG 2x3mm浮選玻璃 3x3mm浮選玻璃 試驗 編號11-2 編號II 3-4 編號ΠΙ 5-6 編號IV 7-8 編號V9 編號v 10 mlT鎰qqe^HSIi:^5^ln(^E*/r、®^N^^ss5OXId^-ffl"-K®_^s$#Milli#3H^^N^sl^Miw(ro ° s^00^ ^ 。經海OSA辉經海觊&s-RilMaq:闺伥¾¾长酿#只勸呢11向却-OSHh遊(I 。鷀她¥捏^除掛雖ssel/δει M3陛珉 -34- 201210811 雖然以上是以本發明的有利的實施方式對本發明的內 容進行說明，但此處要明確指出的是，本發明的內容並不 受上述實施方式限制，而且能夠在以下的申請專利範圍內 以其他的方式被實現。 -35-: inch 1^ radiation ΕΝ 13 501-23) 4.5 KW/m2 6.1 KW/m2 9.5 KW/m2 8.5 KW/m2 fire rating Si02/K20 5.0:1 EW60 EW90/EI15 EW 120/EI 30 EW 60/EI30 -1 EW 15 EW35 Fire rating Si02/K20 3.2:1 EW 60 EW90/EI15 EW 120/EI 30 EW 60/EI 30 j Glass size lmxlm lmxlm lmxlm lmxlm 1 0.5mx0.5m i 0.5mx0.5m Film thickness, quantity 2) 1x1 .5mm 2x1.5mm 4x1.5mm 3x1.5mm 1x0.5mm 2x0.5mm Glass thickness" 2x5mm ESG 2x5mm ESG 2x5mm ESG 4x3mm ESG 2x3mm flotation glass 3x3mm flotation glass test number 11-2 No. II 3-4 No. ΠΙ 5- 6 No. IV 7-8 No. V9 No. v 10 mlT镒qqe^HSIi:^5^ln(^E*/r,®^N^^ss5OXId^-ffl"-K®_^s$#Milli#3H^ ^N^sl^Miw(ro ° s^00^ ^. After the sea OSA Huijing Haishu & s-RilMaq: 闺伥3⁄43⁄4 long brewing # only persuade 11 to but - OSHh swim (I. 鹚 she ¥ pinch Although ssel/δει M3陛珉-34- 201210811 is described above, although the content of the present invention has been described in terms of an advantageous embodiment of the present invention, it is expressly pointed out that the content of the present invention is not implemented as described above. Limited by method, and can be within the scope of the following patent application Other ways are implemented. -35-