201213260 六、發明說明： 【發明所屬之技術領域】 本發明係一種避免或防止因表面處理之鹼侵蝕造成玻 璃腐鈾的方法，而且還能夠同時改善防火特性。 【先前技術】 不論是酸或鹼對玻璃造成的侵蝕均爲習知之問題，而 且已經有各種旨在減少此種侵蝕的不同方法被提出。例如 其中一種方法在玻璃中加入特殊的添加物，例如添加氧化 鋁及/或氧化硼，另外一種方法是在洗碗機使用的洗滌劑 中加入防蝕添加物。 至於大面積玻璃的應用，目前太多數的作法是使用特 殊的抗腐蝕玻璃。 對具有以鹼金屬矽酸鹽爲基之膨脹層的防火釉及/或 隔熱釉（其特徵爲pH値通常很高）而言，鹼造成的玻璃 腐蝕是一個很嚴重的問題。視使用時間而定，鹼侵蝕的現 象遲早都會出現。 因此本發明的目的是避免防火釉及/或隔熱釉的玻璃 侵蝕，而且不必改用價格較高的玻璃或製作價格較高的釉 【發明內容】 使用具有經特殊表面處理而具有或提高抗腐蝕性之玻 璃板製作防火釉及/或隔熱釉（或防火元件及/或隔熱元 -5- 201213260 件），即可達到本發明的目的。 本發明的另一個內容是提出一種製造這種表面改良之 玻璃的方法。 在以下的說明中，“防火”及“隔熱”是兩個可以彼此互 換使用的名詞。 本發明之透光且最好是透明的防火元件具有至少兩個 玻璃片，在該等玻璃片之間有至少一個由硬化且含水的鹼 金屬聚矽酸鹽構成的透明耐火層。一個適當的保護層（通 常是膨膨脹層）的二氧化矽（Si〇2 ):鹼金屬氧化物（ Me20 )的比例至少是2 : 1，含水量最高是60% (重量百 分比）。根據本發明，與鹼金屬聚矽酸鹽層接觸的玻璃表 面均具有鍍層（阻斷層或擴散防止層），該鍍層主要是由 多價陽離子之氧物及其與玻璃表面之矽酸鹽的反應產物構 成，其中氧化物及反應產物均難溶於鹼性環境中，同時抗 鹼阻斷層的厚度小於l〇〇nm。 由於氧化物及/或其與玻璃表面之矽酸鹽的反應產物 需爲難溶的化合物，因此在本發明中，玻璃面上的鍍層在 60°C的溫度中可以置於pH12(或甚至是pH13)的液態鹼 性介質中24小時，而不會出現光學顯微鏡檢査得出的玻 璃侵蝕。 鍍層材料也稱爲網路形成劑或網路轉換劑。鑛層材料 是一種多價陽離子的氧化物，此種氧化物是難溶於鹼的化 合物，或是會與玻璃表面反應生成難溶於鹼的化合物，因 此具有阻斷層或擴散防止層的作用，也就是能夠減少或最 -6- 201213260 好是完全防止玻璃/保護層的交界面發生鈉離子及鈣離子 與氫離子、及/或鈉離子與鈣離子的離子交換，以及阻斷 對氫氧離子的競爭吸附（尤其是阻斷雜質離子鈉及鈣的競 爭吸附）。 關於這種阻斷層的作用方式是假設其能夠防止矽氧烷 基的氧橋被耐火的鹼性保護層撕斷，因而可以防止Si-O-Me基（Me =鹼金屬，尤其是Na)及矽烷醇基內部***。 但是這個假設並不會對本發明的內容造成任何限制。 爲了使內眼無法看到，這種阻斷層的厚度必須很薄（ < 1 OOnm )，或必須是透明的，同時還必須牢固的附著在 玻璃表面上，因此並不是每一種鍍層方法均適於製造這種 阻斷層。利用所謂的“反應性濺鏟法”可以製造出具有良好 特性的阻斷層。這種方法的優點是可以透過靶材的成分控 制氧化物中各種陽離子的含量。將氧適當的混合到氣體中 ，即可控制氧化反應。 反應性濺鍍法可區分爲兩種，也就是直流及高頻反應 性濺鍍法。對本發明而言，兩種方法均適用。另外一種可 能的方式是使用磁控管濺鑛法。 其他可能的鍍層方法還包括化學氣相沉積法（CVD) 及溶膠-凝膠法。 CVD法是將一適當且略具揮發性的鍍層源（例如 SnCl4或SnCl2Et2) (Et=乙醇，乙氧化物）蒸發，然後在 有氧存在的情況下’在要鍍層的基板上沉積出Sn02。 溶膠-凝膠法最好是使用一種適當的先驅物（例如鋁 201213260 可使用鋁-(2-丙醇）或鋁-(2-丁醇）、錐可使用丙醇锆 、鈦可使用乙醇鈦或鈦-(2-丙醇）或TiCl2Et2作爲先驅 物）以浸泡方式進行（特定的浸入角度及特定的速度進行 ’溫度25°C至30°C，空氣濕度8至10g/cm3)。金屬醇 與水反應形成M-OH基，該等M-OH基可以在脫水時經由 冷凝彼此交聯。形成鍍層後，接著以175 °C進行乾燥，然 後以450°C至最高500°C (或最好不超過48 0t：)的溫度 加熱，之後再冷卻。 CVD法及溶膠-凝膠法的共同缺點是都必須使用特殊 的最初產品，CVD法需使用略具揮發性的化合物，溶膠_ 凝膠法需使用可在氫氧化物中轉變的含金屬先驅物。反之 ，反應性濺鍍則實際上可以使用任何成分，因爲該等成分 主要是由靶材中的金屬及/或合金決定。 在鍍層方法（例如反應性濺鍍法、CVD法、溶膠-凝 膠法）結束之後，可以加上退火或施加熱預應力，以改善 阻斷層在基板上的附著性、化學性及內聚性’而且施加熱 預應力還可以改善玻璃品質。適當的條件如下： —退火應以低於轉變點（Tg)的溫度進行熱處理； …施加熱預應力應以低於軟化點（Ew )的溫度在預 應力下進行。 原則上適當的鍍層包括： --鋁、鉍、硼、鈦、鋅、錫、鍩的氧化物及這些氧 化物的混合物； 201213260 --含氧化鋅的混合氧化物，例如氧化鋁（ZnA10x ) » --摻雜鋁的化合物，例如ZnxSny-AlzOn; --鋁酸鹽、硼酸鹽、鉍酸鹽、鈦酸鹽、鋅酸鹽、錫 酸鹽、鉻酸鹽，尤其是具有多價陽離子的鋁、鉍、硼、鈦 、鋅、錫、锆。 這些化合物可以構成單一的鍍層，也可以疊在一起構 成層系統。 同樣的，亦可使用下列氧化物中至少兩個氧化物構成 的混合物：氧化鋁、氧化硼、氧化鉍、氧化鈦、氧化鋅、 氧化锆、氧化錫。 以下是適當之阻斷層的例子： --氧化銘（AI2O3)、氧化鉍（Bi2〇3)、氧化硼（ B2〇3 )、氧化鈦（Ti02 )、氧化鋅（ZnO )、氧化錫（ Sn02 )、氧化鉻（Zr02)，以及這些氧化物的混合物。 --鋅鋁氧化物（ZnA10x ); --摻雜鋁的化合物，例如ZnxSny-AlzOn; --鋁硼酸鹽、鋁鈦酸鹽、鋁鋅酸鹽、鋁錫酸鹽、鋁 錐酸鹽、硼鋁酸鹽、鉍鋁酸鹽、鉍鈦酸鹽、鉍錫酸鹽、鉍 锆酸鹽、鈦錫酸鹽、鈦锆酸鹽、鋅硼酸鹽、鋅鈦酸鹽、鋅 錫酸鹽、鋅鉻酸鹽、錫鋅酸鹽、錫鉻酸鹽、锆鋁酸鹽、鉻 硼酸鹽、鉻鈦酸鹽、锆鋅酸鹽、及/或锆錫酸鹽。 有利的阻斷層包括：氧化錫（Sn02 )、氧化鋁（ Al2〇3)、氧化鉍（Bi203 )、氧化鈦（Ti〇2)、氧化鋅（ 201213260201213260 VI. Description of the Invention: [Technical Field to Be Invented by the Invention] The present invention is a method for avoiding or preventing uranium from being caused by alkali treatment of surface treatment, and also capable of simultaneously improving fireproof properties. [Prior Art] Erosion of glass by acid or alkali is a matter of conventional practice, and various methods for reducing such erosion have been proposed. For example, one of the methods adds special additives to the glass, such as aluminum oxide and/or boron oxide, and the other is to add an anti-corrosion additive to the detergent used in the dishwasher. As for the application of large-area glass, the current practice is to use special anti-corrosion glass. For fire glazes and/or thermal barriers (which are characterized by a generally high pH )) having an alkali metal silicate-based expansion layer, alkali corrosion caused by alkali is a serious problem. Depending on the time of use, the phenomenon of alkali erosion will occur sooner or later. Therefore, the object of the present invention is to avoid the glass erosion of the fire glaze and/or the heat insulating glaze, and it is not necessary to use a higher-priced glass or a higher-priced glaze. [Invention] Use or have a special surface treatment to have or improve resistance The corrosive glass sheet is made of a fire glaze and/or a heat insulating glaze (or a fireproofing element and/or a heat insulating element-5-201213260) to achieve the object of the present invention. Another aspect of the present invention is to provide a method of making such a surface modified glass. In the following description, "fire protection" and "insulation" are two terms that can be used interchangeably. The light transmissive and preferably transparent fire barrier element of the present invention has at least two glass sheets with at least one transparent refractory layer comprised of a hardened and aqueous alkali metal polyphthalate between the glass sheets. A suitable protective layer (usually an expanded layer) of cerium oxide (Si〇2): the proportion of alkali metal oxide (Me20) is at least 2: 1, and the water content is at most 60% (% by weight). According to the present invention, the surface of the glass in contact with the alkali metal polyphthalate layer has a plating layer (blocking layer or diffusion preventing layer) mainly composed of oxygen of a polyvalent cation and its silicate with a glass surface. The reaction product is composed in which the oxide and the reaction product are hardly soluble in an alkaline environment, and the thickness of the alkali blocking layer is less than 10 nm. Since the oxide and/or its reaction product with the citrate on the surface of the glass needs to be a poorly soluble compound, in the present invention, the plating on the glass surface can be placed at pH 12 (or even pH 13 at a temperature of 60 ° C). ) in a liquid alkaline medium for 24 hours without glass erosion from optical microscopy. Plating materials are also known as network formers or network converters. The mineral layer material is an oxide of a polyvalent cation which is a compound which is hardly soluble in alkali or which reacts with the surface of the glass to form a compound which is insoluble in alkali, and thus has a function of a barrier layer or a diffusion preventing layer. That is, it can reduce or most -6- 201213260. It is completely prevent the sodium ion and the ion exchange of calcium ions and hydrogen ions, and/or sodium ions and calcium ions at the interface of the glass/protective layer, and block the hydrogen and oxygen. Competitive adsorption of ions (especially blocking the competitive adsorption of impurity ions sodium and calcium). The mode of action of this barrier layer is based on the assumption that it prevents the oxygen bridge of the oxiranyl group from being torn off by the refractory alkaline protective layer, thereby preventing the Si-O-Me group (Me = alkali metal, especially Na). And the internal division of the stanol group. However, this assumption does not impose any limitation on the content of the present invention. In order to make the inner eye invisible, the thickness of the barrier layer must be very thin (<100 nm), or it must be transparent, and must also be firmly attached to the glass surface, so not every coating method Suitable for making such a barrier layer. A barrier layer having good characteristics can be produced by the so-called "reactive splashing method". The advantage of this method is that the amount of various cations in the oxide can be controlled by the composition of the target. The oxidation reaction can be controlled by appropriately mixing oxygen into the gas. Reactive sputtering can be distinguished into two types, namely DC and high frequency reactive sputtering. Both methods are applicable to the present invention. Another possible way is to use magnetron sputtering. Other possible coating methods include chemical vapor deposition (CVD) and sol-gel methods. The CVD method is to evaporate a suitable and slightly volatile plating source (e.g., SnCl4 or SnCl2Et2) (Et = ethanol, ethoxylate) and then deposit Sn02 on the substrate to be coated in the presence of oxygen. The sol-gel method preferably uses a suitable precursor (for example, aluminum 201213260 can use aluminum-(2-propanol) or aluminum-(2-butanol), cone can use zirconium propoxide, titanium can use titanium ethoxide. Or titanium-(2-propanol) or TiCl2Et2 as a precursor) is carried out in a soaking manner (specific immersion angle and specific speed are carried out 'temperature 25 ° C to 30 ° C, air humidity 8 to 10 g / cm 3 ). The metal alcohol reacts with water to form an M-OH group which can be cross-linked to each other via condensation upon dehydration. After the plating is formed, it is then dried at 175 ° C, then heated at a temperature of 450 ° C to a maximum of 500 ° C (or preferably not more than 48 0 t:), and then cooled. A common disadvantage of the CVD method and the sol-gel method is that a special initial product must be used. The CVD method requires the use of a slightly volatile compound, and the sol-gel method requires the use of a metal-containing precursor that can be converted in the hydroxide. . Conversely, reactive sputtering can actually use any component because the components are primarily determined by the metal and/or alloy in the target. After the plating method (for example, reactive sputtering, CVD, sol-gel method), annealing or application of thermal pre-stress may be added to improve the adhesion, chemical and cohesiveness of the blocking layer on the substrate. And 'heat prestressing can also improve the quality of the glass. Suitable conditions are as follows: - Annealing should be carried out at a temperature below the transition point (Tg); ... applying a thermal pre-stress should be carried out at a temperature below the softening point (Ew) under pre-stress. Suitable coatings in principle include: - aluminum, bismuth, boron, titanium, zinc, tin, antimony oxides and mixtures of these oxides; 201213260 - mixed oxides containing zinc oxide, such as alumina (ZnA10x) » - an aluminum doped compound, such as ZnxSny-AlzOn; - aluminate, borate, citrate, titanate, zincate, stannate, chromate, especially aluminum with polyvalent cations , bismuth, boron, titanium, zinc, tin, zirconium. These compounds may form a single coating or may be stacked together to form a layer system. Similarly, a mixture of at least two oxides of the following oxides may be used: alumina, boron oxide, cerium oxide, titanium oxide, zinc oxide, zirconium oxide, tin oxide. The following are examples of suitable barrier layers: - oxidized AI2O3, bismuth oxide (Bi2〇3), boron oxide (B2〇3), titanium oxide (Ti02), zinc oxide (ZnO), tin oxide (Sn02) ), chromium oxide (ZrO 2 ), and a mixture of these oxides. - zinc aluminum oxide (ZnA10x); - aluminum doped compounds, such as ZnxSny-AlzOn; - alumino borate, aluminum titanate, aluminum zincate, aluminum stannate, aluminum titanate, boron Aluminate, barium aluminate, barium titanate, barium stannate, barium zirconate, titanium stannate, titanium zirconate, zinc borate, zinc titanate, zinc stannate, zinc chromium An acid salt, a tin zincate, a tin chromate, a zirconium aluminate, a chromium borate, a chromium titanate, a zirconium zincate, and/or a zirconium stannate. Advantageous barrier layers include: tin oxide (Sn02), aluminum oxide (Al2〇3), bismuth oxide (Bi203), titanium oxide (Ti〇2), zinc oxide (201213260)
ZnO )、氧化鉻（Zr02 )、氧化硼（b203 )、以及這些氧 化物的混合物、含氧化鋅的混合氧化物（例如鋅鋁氧化物 (ZnA10x ))、摻雜鋁的化合物（例如ZnxSnyAlzOn )、 鋅錫酸鹽（ZnSnOx )、硼鋁酸鹽、锆鋁酸鹽、锆硼酸鹽 、及/或鉻鋅酸鹽。 當前特別有利的阻斷層是由下列化合物構成：氧化錫 (Sn02 )、氧化鋁（Al2〇3 )、氧化鉍（Bi203 )、氧化鈦 (Ti02)、氧化鋅（ZnO)、氧化錐（Zr02)、以及這些 氧化物的混合物、含氧化鋅的混合氧化物、摻雜鋁的化合 物（例如ZnxSnyAlzOn)、銷酸鹽、鋅錫酸鹽（ZnSnOx) 〇 —或複數個疊在一起的阻斷層的總厚度較佳是在10 至lOOnm、10至60nm、或最好是在10至30nm之間。 有兩種方法可以製造本發明之防火釉，其中一種方法 是在一片玻璃片上鍍上由Si02 : Me20的比例至少是2 : 1 且含水量最高是60% (重量百分比）之含水鹼金屬聚矽 酸鹽構成之可硬化鑄造材料，並在鑄造材料硬化之前、硬 化過程中、或是硬化之後’將第二片玻璃片設置在該鑄造 材料之上，另外一種方法是將彼此間隔一定距離的兩片或 多片玻璃片邊緣封裝’並以可硬化鑄造材料將該等玻璃片 形成的至少一個空間塡滿，然後使鑄造材料硬化，其中玻 璃片的至少一個面（而且最好是至少在順流面上）具有阻 斷層，同時玻璃片之帶有阻斷層的面與硬化爲防火層的鑄 造材料接觸。 -10- 201213260 所謂順流面是指在製造過程中，玻璃片背對錫浴的那 一面。面對錫浴的那一面稱爲浴面》 以Si〇2奈米微粒（分散的熱解Si02)、沉降矽酸、 矽膠、或是這三種Si〇2中的兩種或三種Si〇2的混合物、 以及鹼金屬氧化物（尤其是苛性鉀溶液）反應製成的層適 於作爲具有阻斷層之玻璃片的保護層。WO 2009/155719 有關於這種層的描述。 最好是以反應性直流、高頻、及/或磁控管反應性濺 鍍法將阻斷層鍍上去，接著最好再進行退火處理。 經證實，以這種方式鑛上去的阻斷層不只可以阻止或 至少是減少玻璃腐蝕，而且在起火時還可以防止或至少是 大幅減少保護層的脫落。在起火時，由本發明之具有鍍層 之玻璃片構成的防火元件與塗有底漆之玻璃片（例如按照 WO 99/04970的方式製造的玻璃片）表現出可比較的特性 。本發明的另一個內容是使用含有多價陽離子及氧（如前 面對阻斷層的定義）的鍍層，以減低保護層的附著，因而 使其在起火時比較不易從玻璃表面（包括從玻璃片之火焰 面及背對火焰面的表面）脫落。 【實施方式】 執行本發明的方法 利用反應性濺鍍法製造出不同的阻斷層，並比較經此 處理及未經處理的玻璃片的玻璃腐蝕（白色斑點）的情況 -11 - 201213260 實例1:製造具有一個錫酸鹽層的玻璃 在工業用連續式磁控管設備內利用反應性 焰面（所謂火焰面是指玻璃背對錫浴的那一面 非錫浴面）鍍上一個阻斷層。此處所稱之阻斷 由多個鍍層構成。利用先前技術的方法（例如 EP 1 889 818)在厚度5mm的浮選玻璃片上鍍 層，包括： 玻璃/ 30nm ZnSnOx 玻璃/ 40nm Sn〇2 玻璃/ 4〇nm Sn〇2/3nm ZnxSnyAlzOn 所有的鍍層都是以反應性濺鍍機鍍上i Sn02是以純錫靶、21^11〇；1層是以由53% (重 的鋅及 47% (重量百分比）的錫構成 ZnxSnyAlzOn是以68% (重量百分比）的鋅及 百分比）的錫及2% (重量百分比）的鋁構成 而成。在濺鍍出這些鍍層時，並未出現肉眼可 運送設備造成的）干擾抽氣印記。 實例2:製造具有保護層（Si02:K20 = 5.1:l) 元件 1.器材ZnO), chromium oxide (Zr02), boron oxide (b203), and mixtures of these oxides, mixed oxides containing zinc oxide (such as zinc aluminum oxide (ZnA10x)), aluminum-doped compounds (such as ZnxSnyAlzOn), Zinc stannate (ZnSnOx), boroaluminolate, zirconium aluminate, zirconium borate, and/or chromic zincate. The currently particularly advantageous barrier layer consists of tin oxide (Sn02), alumina (Al2〇3), bismuth oxide (Bi203), titanium oxide (Ti02), zinc oxide (ZnO), and oxidized cone (Zr02). And mixtures of these oxides, mixed oxides containing zinc oxide, aluminum-doped compounds (eg ZnxSnyAlzOn), pinate, zinc stannate (ZnSnOx) 〇 - or a plurality of stacked barrier layers The total thickness is preferably between 10 and 100 nm, between 10 and 60 nm, or preferably between 10 and 30 nm. There are two ways to make the fire glaze of the present invention, one of which is to deposit an aqueous alkali metal polyfluorene with a ratio of SiO 2 : Me20 of at least 2:1 and a water content of up to 60% by weight on a piece of glass. a curable cast material composed of an acid salt, and a second piece of glass is placed on the cast material before, during, or after hardening of the cast material, and another method is to separate the two pieces at a distance from each other. a sheet or a plurality of sheets of glass edge encapsulating 'and filling at least one space formed by the sheets of glass with a hardenable cast material, and then hardening the cast material, wherein at least one side of the glass sheet (and preferably at least in the downstream side) Upper) has a barrier layer while the face of the glass sheet with the barrier layer is in contact with the cast material hardened as a fire barrier. -10- 201213260 The so-called downstream surface refers to the side of the glass that faces the tin bath during the manufacturing process. The side facing the tin bath is called bath surface. It is made of Si〇2 nanoparticle (dispersed pyrolysis SiO2), precipitated tannic acid, tannin, or two or three of these three Si〇2 The layer formed by the reaction of the mixture, together with an alkali metal oxide, in particular a caustic potash solution, is suitable as a protective layer for the glass sheet with the barrier layer. WO 2009/155719 relates to the description of such a layer. Preferably, the blocking layer is plated by reactive DC, high frequency, and/or magnetron reactive sputtering, and preferably annealed. It has been demonstrated that the barrier layer that is mineralized in this manner not only prevents or at least reduces glass corrosion, but also prevents or at least substantially reduces the shedding of the protective layer during a fire. In the event of a fire, the fire resistant element consisting of the coated glass sheet of the present invention exhibits comparable characteristics to the primed glass sheet (e.g., a glass sheet manufactured in accordance with WO 99/04970). Another aspect of the invention is the use of a coating comprising a multivalent cation and oxygen (as defined above for the barrier layer) to reduce the adhesion of the protective layer, thereby making it less susceptible to light from the glass surface (including glass) The flame surface of the piece and the surface facing the flame surface are peeled off. [Embodiment] The method of the present invention is used to produce different barrier layers by reactive sputtering, and the glass corrosion (white spots) of the treated and untreated glass sheets is compared - 11 - 201213260 Example 1 : Manufacturing a glass with a stannate layer in a commercial continuous magnetron apparatus using a reactive flame surface (the so-called flame surface refers to the non-tin bath surface of the glass back to the tin bath) is plated with a barrier layer . The blockage referred to herein is composed of a plurality of plating layers. Coating on a 5 mm thick flotation glass using a prior art method (eg EP 1 889 818), including: glass / 30 nm ZnSnOx glass / 40 nm Sn〇2 glass / 4 〇 nm Sn 〇 2 / 3 nm ZnxSnyAlzOn all coatings are I Sn02 was plated with a reactive sputtering machine with a pure tin target, 21^11 〇; 1 layer was composed of 53% (heavy zinc and 47% by weight of tin). ZnxSnyAlzOn was 68% by weight. Zinc and percentage) tin and 2% (by weight) aluminum. When these coatings are sputtered, there is no interference pumping mark caused by the naked eye transport equipment. Example 2: Manufacturing a protective layer (Si02: K20 = 5.1: l) Components 1. Equipment
Si02分散液：容量1〇公升的反應槽’配 濺鍍機在火 ，也就是指 層也可以是 上不同的鍍 的，其中 量百分比） 的標靶、 30% (重量 的標靶濺鍍 見的（玻璃 的透明防熱 備有攪拌器 -12- 201213260 、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2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，這種真空泵能夠以高效率將很大的容積抽真空 ，並達到約70mbar的真空度。 利用以轉子/定子原理工作的Ultra Turrax攪泮器作 爲分散器。 KOH :容量5公升的攪拌容器 2·各成分的製造：從固態矽酸製造Si02分散液 以Si02 ( BET 50m2/g，初始粒子直徑55nm)作爲沉 降矽酸及熱解矽酸。 將下列成分放入容量10公升的容器中： 去礦物質的水（3.23 kg)，電導率<10从S/cm ; 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）。一邊以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。 -13- 201213260 矽膠（含添加物）： 將下列成分放入容量1〇公升的反應槽中： 矽膠（9.35kg) (BET 50m2/g，初始粒子直徑55nm ，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/cm; 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%。 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。。。 苛性鉀溶液： 將下列成分放入容量5公升的攪拌容器中： KOH ( 1.85kg)，純度 >99.9% ； 去.礦物質的水（1.85 kg)，電導率<1〇从s/cm。 將KOH攪拌至完全溶解。 3.製造隔熱鑄造材料及/或隔熱玻璃 製造以下的si〇2分散液，該等Si〇2分散液含有以下 -14- 201213260 的Si02成分及/或量（以前面“2.各成分的製造”給定的量 爲準）： (a) 100%熱解矽酸 (b ) 1 00%沉降矽酸 (c) 50%熱解矽酸及沉降'砂酸 (d ) 1 00% 矽膠 (e) 50%矽膠及50%熱解矽酸 (f) 50%矽膠及50%沉降矽酸 以前面“2.各成分的製造”給定的KOH溶液的量使上 述Si02源（a)至（f)硬化，即可產生Si02:K20 = 5.1:l 的膨脹層》 使每一個分散液/膠（a)至（f)與苛性鉀溶液反應 。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50至55°C。當溫度達到50 乞時，繼續攪拌30分鐘，使溫度保持在50至55°C，直 到混合物變得非常易於流動爲止。接著接通真空泵，使真 空度達到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，材料即當製作完成， 並可作爲至少兩個或更多個玻璃片之間的塡料。然後將以 這種方式製造的元件在8〇°c的溫度中，以每8小時6mm 的層厚度硬化至透明爲止。表1顯示這種隔熱鑄造材料的 特性： -15- 201213260 表1 : 隔熱鑄造材料 ⑻ (b) ⑹ (e) ω 使用期υ 「hi 3 3 6 5 5 55°C、15分鐘後的黏滯性 [mPa*s] 150 130 60 100 80 55〇C、30分鐘後的黏滯性 [mPa*s] 150 130 60 100 80 分散方式/分散液的製造 Turrax轉子/定子 螺旋槳攪拌器 溶解器齒盤 、30分鐘，然後變成20°C的使用期 實例3 :有鍍層/無鍍層玻璃之錫浴面的特性區別 以下將描述有鍍層及無鍍層玻璃的實施例。 爲評定鍍層特性，應對玻璃進行以下的試驗： A刮痕硬度 用一根承受載重的針以特定的速度劃過鍍層。可造成 肉眼可見之刮刻線的重量稱爲刮痕硬度。 B存放在水中之後的刮痕硬度 先將試體放在20°C的水中30分鐘後，然後按照試驗 A的方式進行刮痕試驗。 C按照ASIM 2486進行的Eriehsen洗滌試驗，目視 評定。 D冷凝水試驗（SWT) -16- 201213260 將試體置於溫度60°C及相對濕度100%之環境中140 小時。 目視評定。 E Zn2 +浸出 按照Kimmel et al. Z.在“玻璃技術報告（ Glastechnische Berichte) 59 ( 1 986) S_ 252ff”提出的平板 法測量Zn2 +浸出。 試驗結果可以說明含鋅層系統對水解的抵抗性。 F鹽酸試驗 將玻璃試體浸泡在濃度〇.01η之HC1中8分鐘（溫度 3 81)，並測量發射率損失（單位：％ )。 G以目視評定鹽酸試驗 按照G的方式將玻璃試體浸泡在鹽酸中。以浸泡邊 緣的可視性作爲評定標準。 Η水膜試驗 使試體的銨層面與一層很薄的水膜接觸24小時。試 驗結果可以說明有鍍層且堆疊在一起的玻璃片在有微量的 水滲入玻璃片之間時的存放特性。以目視方式進行評定。 試驗用的試體： -17- 201213260 對以下的玻璃面進行試驗： (a) 按照實例1之方式鍍層之玻璃（5mm浮選玻璃 )的錫酸鹽層 (b) 5mm浮選玻璃的錫浴面 (c) 5mm浮選玻璃的火焰面 表2列出以本發明之方式鍍層的玻璃與無鍍層玻璃之 錫浴面及非錫浴面的試驗結果的比較。 表2 : 試驗 有鍍層 錫浴面 火焰面 A『gl 34 30 22 B『gl 55 46 38 C (1000次循環） 一道很小的刮痕 數道小刮痕及一道中刮痕 許多小刮痕，多道中刮痕 D 略微變紅 未變紅υ 未變紅D E rmg/25mll 0.18mg 無法測量υ 無法測量υ FAE 0% 0.5% 1% G 無缺陷 無缺陷υ 無缺陷υ H 無缺陷 無缺陷 形成邊緣及斑點 U不重要，因爲沒有鍍層。 從表2可以看出，具有以反應性濺鍍法形成之金屬氧 化物鍍層的玻璃在幾乎所有可測得試驗結果之試驗的表現 均優於沒有金屬氧化物鍍層的玻璃。 實例4 :對隔熱元件的試驗 18- 201213260 透過澆鑄如實例2之隔熱鑄造材料，可以製造出在兩 個玻璃片之間具有一隔熱層的隔熱玻璃。隔熱層與下列部 分接觸： (a) 如實例1利用反應性濺鍍法鍍層之玻璃的不同 的阻斷層及/或擴散阻擋層，其中該等玻璃爲厚度5mm 之浮選玻璃，且在鍍層後經進一步處理（施加熱預應力） 達到E S G品質； (b) 5mmESG的錫浴面； (c) 5mmESG的火焰面。 表3列出具有本發明之阻斷層的玻璃與不同年齡之無 鍍層玻璃的錫浴面及非錫浴面的試驗結果的比較。這個試 驗用的隔熱元件的結構爲防火鑄造材料之層厚度爲6mm 的2x5mm玻璃。以60 °C的溫度使玻璃加速老化。 -19- 201213260 表3 : 玻璃翻 玻璃年齡 玻璃面 試驗時間 [MM] 試驗結果 ESG 5mm 1-6 天 5) 火焰面 15 9至13星期後可看 到玻璃腐蝕4) ESG 5mm >6 天6) 火焰面 1 1至5天後可看到玻 璃腐蝕4) ESG 5mm 1-6 天 5) 錫浴面 15 9至13星期後可看 到玻璃腐蝕4) ESG 5mm >6 天 6) 錫浴面 15 9至13星期後可看 到玻璃腐蝕4) ESG 5mm 含有錫酸鹽(ZnSnOx)1〉 1-6 天 5) 火焰面 197) 19星期後仍未出現 玻璃腐蝕 ESG 5mm 含有錫酸鹽(ZnSnOx)。 >6 天6) 火焰面 197) 19星期後仍未出現 玻璃腐蝕 ESG 5mm 含有氧化錫(Sn〇2)2) 1-6 天 5) 火焰面 197) 19星期後仍未出現 玻璃腐蝕 ESG 5mm 含有氧化錫(Sn02)2) >6 天6) 火焰面 197) 19星期後仍未出現 玻璃腐蝕 ESG 5mm 含有氧化錫及混合氧化錫3) 1-6 天 5) 火焰面 197) 19星期後仍未出現 玻璃腐蝕 ESG 5mm 含有氧化錫及混合氧化錫3) >6 天6) 火焰面 197) 19星期後仍未出現 玻璃腐蝕 阻斷層及/或擴散阻擋層：厚度3 Onm的鋅錫酸鹽 (ZnSnOx )，由成分爲鋅53% (重量百分比）及 錫47% (重量百分比）之標靶所產生。 2) 阻斷層及/或擴散阻擋層：厚度40nm的氧化錫（ Sn〇2)，由成分爲錫100% (重量百分比）之標靶 所產生。 3) 阻斷層及/或擴散阻擋層：玻璃面爲厚度40nm的 氧化錫（Sn〇2)，由成分爲錫100% (重量百分比 -20- 201213260 )之標靶所形成，另外再加上一個厚度3nm的阻 擋層（ZnxSnyAlzOn)，由成分爲鋅68% (重量百 分比）、錫30% (重量百分比）及鋁2% (重量 百分比）之標靶所產生。 4) 玻璃腐鈾會出現白色斑點。 5) 此處之1至6天是指自最後一個製造步驟起的玻 璃。實際的玻璃年齡可能是2至3天。 6) 此處之>6天是指年齡大於6天、並被存放及運送 的玻璃。實際的玻璃年齡估計爲1個月。 7) 到目前爲止的試驗時間，該試驗會繼續進行下去 隔熱層/防水層造成的鹼侵蝕是以白色斑點及條帶（ 試驗前玻璃表面已受損）的方式呈現，以及在玻璃/隔熱 層的交界面出現淡至很濃的白色混濁及雲霧。 實例5 :燃燒試驗 按照EN 1 3 63及1 364規定的方式對尺寸爲120cmx 220cm及構造爲5mm ESG/6mm保護層/5mm ESG的玻璃 進行燃試驗。保護層是以聚二甲基矽氧烷爲基的含有及不 含添加物的聚矽酸鉀（Si〇2:K20 = 5.1:l)，阻斷層是30nmSi02 dispersion: a reaction tank with a capacity of 1 liter liters 'with a sputter in the fire, that is, the layer can also be differently plated, the percentage of which is a percentage of the target, 30% (the weight of the target splash see (Glass transparent heat protection with agitator-12- 201213260, heater and cooling unit, glass straight-through cooler, and vacuum pump, where the glass straight-through cooler has a round bottle with a capacity of 2 liters (as a collection container) The vacuum pump is based on a compressed air device with a Venturi system that can evacuate a large volume with high efficiency and achieve a vacuum of approximately 70 mbar. Utilizing the Ultra Turrax operating on the rotor/stator principle Stirring device as a disperser KOH: Stirring container with a capacity of 5 liters 2. Preparation of each component: SiO 2 dispersion was prepared from solid tannic acid with SiO 2 (BET 50 m 2 /g, initial particle diameter 55 nm) as sedimentation tannic acid and pyrolysis The following ingredients were placed in a container of 10 liter capacity: demineralized water (3.23 kg), conductivity <10 from S/cm; polydimethyl methoxyalkane aqueous latex (〇.〇5kg)(polydimethylsiloxane (50% by weight)); glycerin (1.96 kg), purity >99.9%; KOH (0.06 kg), purity > 99.9%. The solution was stirred well (mixing time was about 5 minutes). While stirring with an Ultraturrax stirrer, 4.7 kg of citric acid powder was slowly poured into the solution. Stirring was continued to disperse until a uniform dispersion was formed. 201213260 Silicone (with additives): The following ingredients are placed in a 1 liter liter reaction tank: Silicone (9.35kg) (BET 50m2/g, initial particle diameter 55nm, SiO2 concentration in water is 50%, with KOH pH値 is adjusted to 9 to 1 1 ); demineralized water (〇.59kg), conductivity <10# S/cm; polydimethyl methoxyalkane aqueous emulsion (〇.〇5kg) (poly 2 Methyl siloxane (50% by weight); glycerin (1.96 kg), purity > 99.9%. Stir the solution of the above ingredients with a stirrer (mixing time is about 5 minutes), then continue stirring and use Heat the module to 50 to 60 ° C. Maintain this temperature and make the latex in a vacuum To boil, to evaporate 1.96 kg of water, then cool to 20 without vacuum. Caustic Potassium Solution: Place the following ingredients in a 5 liter stirred vessel: KOH ( 1.85 kg), purity > 99.9%; demineralized water (1.85 kg), conductivity <1〇 from s/cm. The KOH was stirred until completely dissolved. 3. Manufacturing of heat-insulating casting materials and/or insulating glass to produce the following si〇2 dispersions containing the following SiO 2 components and/or amounts of -14-201213260 (in the previous section "2. The manufacture is based on the given amount: (a) 100% pyrolysis of tannic acid (b) 1 00% sedimentation of tannic acid (c) 50% pyrolysis of tannic acid and sedimentation 'sandic acid (d) 1 00% tannin (e) 50% silicone and 50% pyrogenic tannic acid (f) 50% silicone and 50% precipitated tannic acid The above-mentioned Si02 source (a) is given by the amount of KOH solution given in the previous "2. Manufacture of each component" (f) Hardening to produce an expanded layer of SiO 2 : K20 = 5.1: l Each of the dispersions/gels (a) to (f) is reacted with a caustic potash solution. Turn on the stirrer and stir until the mixture becomes homogeneous. While stirring, heat to 50 to 55 ° C using a heating module. When the temperature reached 50 Torr, stirring was continued for 30 minutes to maintain the temperature at 50 to 55 ° C until the mixture became very easy to flow. The vacuum pump is then switched on to achieve a vacuum of 50 to 90 mbar. The mixture was stirred in vacuo and allowed to cool to 20 °C. After standing in a vacuum for 90 minutes, the material is finished and can serve as a dip between at least two or more glass sheets. The component manufactured in this manner was then hardened to a transparent layer at a temperature of 8 ° C at a layer thickness of 6 mm per 8 hours. Table 1 shows the characteristics of this insulation casting material: -15- 201213260 Table 1: Insulation casting materials (8) (b) (6) (e) ω period of use hi "hi 3 3 6 5 5 55 ° C, after 15 minutes Viscosity [mPa*s] 150 130 60 100 80 55〇C, viscosity after 30 minutes [mPa*s] 150 130 60 100 80 Dispersion / dispersion production Turrax rotor / stator propeller stirrer dissolver The toothed disc, 30 minutes, then becomes the use period of 20 ° C. Example 3: Characteristics of the tin bath surface with coated/uncoated glass The following examples of coated and uncoated glass will be described. To evaluate the coating characteristics, the glass should be evaluated. Carry out the following tests: A. Scratch hardness is used to scratch the coating at a specific speed with a needle that bears the load. The weight of the scratch line visible to the naked eye is called the scratch hardness. B The hardness of the scratch after storage in water After the test piece was placed in water at 20 ° C for 30 minutes, the scratch test was carried out in the same manner as in Test A. C. Eriehsen washing test according to ASIM 2486, visual evaluation. D condensed water test (SWT) -16- 201213260 The test piece is placed at a temperature of 60 ° C and a relative humidity of 100% 140 hours in the environment. Visual evaluation. E Zn2 + leaching Zn2 + leaching was measured according to the plate method proposed by Kimmel et al. Z. in Glastechnische Berichte 59 (1 986) S_ 252ff. Resistance of the zinc layer system to hydrolysis. F hydrochloric acid test The glass sample was immersed in HC1 at a concentration of 〇.01η for 8 minutes (temperature 3 81), and the emissivity loss (unit: %) was measured. The glass test piece was immersed in hydrochloric acid in the manner of G. The visibility of the soaking edge was used as the evaluation standard. The hydrophobic film test allowed the ammonium layer of the test piece to be in contact with a very thin water film for 24 hours. The test result indicates that there is plating. The storage characteristics of the glass sheets stacked together when a small amount of water penetrates between the glass sheets is evaluated visually. Test specimens: -17- 201213260 The following glass surfaces were tested: (a) The stannate layer of the coated glass (5 mm flotation glass) of Example 1 (b) The tin bath surface of the 5 mm flotation glass (c) The flame surface of the 5 mm flotation glass Table 2 lists the plating in the manner of the present invention Comparison of the test results of the tin bath surface and the non-tin bath surface of the glass and the uncoated glass. Table 2: The test has a tin bath surface flame surface A 『gl 34 30 22 B『gl 55 46 38 C (1000 cycles) Small scratches and small scratches and many scratches in the middle. Many scratches D are slightly reddish and not red. Unreddened DE rmg/25mll 0.18mg Cannot be measured υ Unmeasured υ FAE 0% 0.5% 1% G No defects, no defects υ No defects υ H No defects and no defects Forming edges and spots U is not important because there is no plating. As can be seen from Table 2, the glass having the metal oxide plating formed by the reactive sputtering method performed better than the glass without the metal oxide plating in almost all tests in which the test results were measurable. Example 4: Test of Insulating Element 18-201213260 By casting an insulating cast material as in Example 2, an insulating glass having a heat insulating layer between two glass sheets can be manufactured. The insulating layer is in contact with: (a) a different barrier layer and/or diffusion barrier layer of the glass coated by reactive sputtering as in Example 1, wherein the glass is a float glass having a thickness of 5 mm, and After plating, further treatment (heat prestressing) is achieved to achieve ESG quality; (b) 5 mm ESG tin bath surface; (c) 5 mm ESG flame surface. Table 3 shows a comparison of the test results of the tin bath surface and the non-tin bath surface of the glass having the barrier layer of the present invention and the uncoated glass of different ages. The thermal insulation element for this test was constructed as a 2x5 mm glass having a layer thickness of 6 mm for the fire resistant casting material. The glass is accelerated to age at a temperature of 60 °C. -19- 201213260 Table 3: Glass glazing age glass surface test time [MM] Test results ESG 5mm 1-6 days 5) Flame surface 15 After 9 to 13 weeks, glass corrosion can be seen 4) ESG 5mm > 6 days 6 The flame surface can be seen after 1 to 5 days. 4) ESG 5mm 1-6 days 5) Tin bath surface 15 9 to 13 weeks after seeing glass corrosion 4) ESG 5mm > 6 days 6) Tin bath Surface corrosion can be seen after 15 to 13 weeks. 4) ESG 5mm contains stannate (ZnSnOx) 1> 1-6 days 5) Flame surface 197) Glass corrosion does not occur after 19 weeks ESG 5mm contains stannate ( ZnSnOx). >6 days 6) Flame surface 197) No glass corrosion after 19 weeks ESG 5mm Contains tin oxide (Sn〇2) 2) 1-6 days 5) Flame surface 197) No glass corrosion after 19 weeks ESG 5mm Contains tin oxide (Sn02)2) >6 days 6) Flame surface 197) Glass corrosion does not occur after 19 weeks ESG 5mm Contains tin oxide and mixed tin oxide 3) 1-6 days 5) Flame surface 197) 19 weeks later There is still no glass corrosion. ESG 5mm contains tin oxide and mixed tin oxide. 3) > 6 days 6) Flame surface 197) After 30 weeks, there is no glass corrosion blocking layer and/or diffusion barrier: zinc tin with a thickness of 3 Onm The acid salt (ZnSnOx) is produced from a target having a composition of 53% by weight of zinc and 47% by weight of tin. 2) Blocking layer and/or diffusion barrier layer: Tin oxide (Sn 2 ) having a thickness of 40 nm is produced by a target having a composition of 100% by weight of tin. 3) Blocking layer and/or diffusion barrier: the glass surface is tin oxide (Sn〇2) with a thickness of 40 nm, which is formed by the target of 100% tin (weight percentage -20-201213260), plus A 3 nm thick barrier layer (ZnxSnyAlzOn) is produced from a target having a composition of 68% by weight of zinc, 30% by weight of tin, and 2% by weight of aluminum. 4) White sulphate appears in glass humus. 5) The 1 to 6 days here refers to the glass from the last manufacturing step. The actual glass age may be 2 to 3 days. 6) The term “6 days” refers to glass that is stored and transported for more than 6 days. The actual glass age is estimated to be 1 month. 7) The test time to date, the test will continue. The alkali attack caused by the insulation/waterproof layer is presented in the form of white spots and strips (the surface of the glass is damaged before the test), and in the glass/space At the interface of the hot layer, there is a slight white turbidity and cloudiness. Example 5: Burning test A glass test was conducted on a glass having a size of 120 cm x 220 cm and a structure of 5 mm ESG/6 mm protective layer / 5 mm ESG in accordance with the manner specified in EN 1 3 63 and 1 364. The protective layer is polydimethyl siloxane based on potassium polyphthalate with or without additives (Si〇2: K20 = 5.1:1), and the blocking layer is 30 nm.
ZnSnOx、40nm Sn02 及 40nm Sn02/3nm ZnxSnxAlzOn。 試驗結果列於表4。 -21 - 201213260 表4 玻璃麵 阻斷層 保護層 內底漆 脫落 FWK5 ESG 5mm 無 Si02:K20 =5.1:1 姐 自第17分鐘起4 El 17 ESG 5mm 無 Si02:K20 =5.1:1 0.5% PDMS 4rrr. m El 33 ESG 5mm 鋅錫酸鹽(ZnSnCg1 Si02:K20 =5.1:1 -fnj, Ws Arrr. m El 36 ESG 5mm 氧化錫(Sn〇2)2 Si02:K20 =5.1:1 M 4rrr m El 37 ESG 5mm 氧化錫及混合氧化錫3 Si02:K20 =5.1:1 te jw\ ffrrr 無 El 35 見表3的說明1 ) 見表3的說明2 ) 見表3的說明3 ) 4 溫度通道高於初始溫度1 80K以上時發生脫落 5 FWK = EN 1 350卜2定義之防火等級 以上的例子均爲本發明之有利的實施方式’但是本發 明的範圍並不受限於這些實施方式，而是還包括以下之申 請專利範圍之項目的內容。 -22-ZnSnOx, 40 nm Sn02 and 40 nm Sn02/3 nm ZnxSnxAlzOn. The test results are shown in Table 4. -21 - 201213260 Table 4 Glass surface blocking layer Protective layer primer peeling off FWK5 ESG 5mm No SiO2: K20 =5.1:1 Sister from the 17th minute 4 El 17 ESG 5mm No SiO2: K20 =5.1:1 0.5% PDMS 4rrr. m El 33 ESG 5mm Zinc stannate (ZnSnCg1 Si02: K20 = 5.1:1 -fnj, Ws Arrr. m El 36 ESG 5mm Tin oxide (Sn〇2) 2 Si02: K20 =5.1:1 M 4rrr m El 37 ESG 5mm Tin Oxide and Mixed Tin Oxide 3 Si02:K20 =5.1:1 te jw\ ffrrr No El 35 See Table 3 for description 1) See Table 3 for description 2) See Table 3 for description 3) 4 Temperature channel is higher than The occurrence of shedding at an initial temperature of 1 80 K or more 5 FWK = EN 1 350 The definition of the fire rating above is an advantageous embodiment of the invention 'but the scope of the invention is not limited to these embodiments, but is also Includes the content of the following patented scope of the project. -twenty two-