TW201831418A - Alkali-free glass substrate and preparation method thereof - Google Patents

Alkali-free glass substrate and preparation method thereof Download PDF

Info

Publication number
TW201831418A
TW201831418A TW107113046A TW107113046A TW201831418A TW 201831418 A TW201831418 A TW 201831418A TW 107113046 A TW107113046 A TW 107113046A TW 107113046 A TW107113046 A TW 107113046A TW 201831418 A TW201831418 A TW 201831418A
Authority
TW
Taiwan
Prior art keywords
alkali
glass substrate
free glass
mol
composition
Prior art date
Application number
TW107113046A
Other languages
Chinese (zh)
Other versions
TWI667216B (en
Inventor
張廣濤
王俊峰
李剛
閻冬成
王麗紅
鄭權
Original Assignee
大陸商東旭科技集團有限公司
大陸商東旭集團有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 大陸商東旭科技集團有限公司, 大陸商東旭集團有限公司 filed Critical 大陸商東旭科技集團有限公司
Publication of TW201831418A publication Critical patent/TW201831418A/en
Application granted granted Critical
Publication of TWI667216B publication Critical patent/TWI667216B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/004—Refining agents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses an alkali-free glass substrate and a preparation method thereof. The erosion amount of the alkali-free glass substrate in an HF solution with the concentration of 10% by weight is smaller than 5.5 mg/cm2. The alkali-free glass substrate comprises the following components by using the total molar weight of the components as a reference: 70-74 mol% of SiO2, 11-14 mol% of Al2O3, 0-2.5 mol% of ZnO, 10-17 mol% of Ro and 0.01-2 mol% of RE2O3, wherein RO is at least one of MgO, CaO, SrO and BaO; and RE2O3 is at least one of Y2O3, La2O3, Gd2O3, Ce2O3, Yb2O3 and Lu2O3. The preparation method comprises the following steps: mixing the various components; and then successively fusing, defoaming, homogenizing, forming, cooling, cutting, polishing, washing and drying the components. The alkali-free glass substrate has excellent overall performance.

Description

無鹼玻璃基板及其製備方法Alkali-free glass substrate and preparation method thereof

本發明係有關玻璃製造領域，更特別有關一種無鹼玻璃基板及其製備方法。The invention relates to the field of glass manufacturing, and more particularly to an alkali-free glass substrate and a method for preparing the same.

隨著光電行業的快速發展，對各種顯示元件的需求正在不斷增長，比如主動矩陣液晶顯示（AMLCD）、有機發光二極體（OLED）以及應用低溫多晶矽技術的主動矩陣液晶顯示（LTPS TFT-LCD）元件，這些顯示元件都基於使用薄膜半導體材料生產薄膜電晶體(TFT)技術。主流的矽基TFT可分為非晶矽(a-Si)TFT、多晶矽(p-Si)TFT和單晶矽（SCS）TFT，其中非晶矽(a-Si)TFT為現在主流TFT-LCD應用的技術，非晶矽(a-Si)TFT技術，在生產製程中的處理溫度可以在300~450℃溫度下完成。LTPS多晶矽(p-Si)TFT在製程過程中需要在較高溫度下多次處理，基板必須在多次高溫處理過程中不能發生變形，這就對基板玻璃性能指標提出更高的要求，較佳的應變點高於650℃，更佳的是高於670℃、700℃、720℃，以使基板在面板製程中具有儘量小的熱收縮。同時玻璃基板的膨脹係數需要與矽的膨脹係數相近，盡可能減小應力和破壞，因此基板玻璃較佳的線性熱膨脹係數在2.8×10-6 ~4×10-6 /℃之間。為了便於生產，降低生產成本，作為顯示器基板用的玻璃應該具有較低的熔化溫度和成型溫度。With the rapid development of the optoelectronic industry, the demand for various display elements is continuously increasing, such as active matrix liquid crystal display (AMLCD), organic light emitting diode (OLED), and active matrix liquid crystal display (LTPS TFT-LCD) using low temperature polycrystalline silicon technology. ) Elements, these display elements are based on the use of thin-film semiconductor materials to produce thin-film transistor (TFT) technology. The mainstream silicon-based TFT can be divided into amorphous silicon (a-Si) TFT, polycrystalline silicon (p-Si) TFT, and single crystal silicon (SCS) TFT. Among them, amorphous silicon (a-Si) TFT is the mainstream TFT-LCD. The applied technology, amorphous silicon (a-Si) TFT technology, can be processed at a temperature of 300 ~ 450 ° C in the production process. LTPS polycrystalline silicon (p-Si) TFT needs to be processed multiple times at a higher temperature during the manufacturing process, and the substrate must not be deformed during multiple high-temperature processing. This puts forward higher requirements on the substrate glass performance indicators. The strain point is higher than 650 ° C, and more preferably higher than 670 ° C, 700 ° C, and 720 ° C, so that the substrate has as small a thermal contraction as possible during the panel manufacturing process. At the same time, the expansion coefficient of the glass substrate needs to be similar to that of silicon to minimize stress and damage. Therefore, the preferred linear thermal expansion coefficient of the substrate glass is between 2.8 × 10 -6 to 4 × 10 -6 / ℃. In order to facilitate production and reduce production costs, glass used as a display substrate should have a lower melting temperature and forming temperature.

用於平面顯示的玻璃基板，需要通過濺射、化學氣相沈積（CVD）等技術在底層基板玻璃表面形成透明導電膜、絕緣膜、半導體（多晶矽、無定形矽等）膜及金屬膜，然後通過光蝕刻（Photo-etching）技術形成各種電路和圖形，如果玻璃含有鹼金屬氧化物（Na2 O，K2 O，Li2 O），在熱處理過程中鹼金屬離子擴散進入沈積半導體材料，損害半導體膜特性，因此，玻璃應不含鹼金屬氧化物，首選的是以SiO2 、Al2 O3 、鹼土金屬氧化物RO（RO=Mg、Ca、Sr、Ba）等為主成分的鹼土鋁矽酸鹽玻璃。For glass substrates used for flat display, a transparent conductive film, an insulating film, a semiconductor (polycrystalline silicon, amorphous silicon, etc.) film and a metal film need to be formed on the surface of the underlying substrate glass by sputtering, chemical vapor deposition (CVD), etc., and then Various circuits and patterns are formed by photo-etching technology. If the glass contains alkali metal oxides (Na 2 O, K 2 O, Li 2 O), alkali metal ions diffuse into the deposited semiconductor material during heat treatment and damage Semiconductor film characteristics, therefore, the glass should not contain alkali metal oxides, the first choice is SiO 2 , Al 2 O 3 , alkaline earth metal oxides RO (RO = Mg, Ca, Sr, Ba) and other main components of alkaline earth aluminum Silicate glass.

大多數矽酸鹽玻璃的應變點隨著玻璃形成體含量的增加和改性劑含量的減少而增高，但同時會造成高溫熔化和澄清困難，造成耐火材料侵蝕加劇，增加能耗和生產成本。因此，通過成分改良，使得低溫黏度增大的同時還要保證高溫黏度不會出現大的提升，甚至降低才是提高應變點的最佳突破口。The strain point of most silicate glass increases with the increase of the glass forming body content and the decrease of the modifier content, but at the same time, it will cause difficulties in melting and clarification at high temperatures, increase the erosion of refractory materials, increase energy consumption and production costs. Therefore, by improving the composition, it is necessary to ensure that the low-temperature viscosity is increased, while ensuring that the high-temperature viscosity does not increase greatly, or even lowered. This is the best breakthrough to increase the strain point.

在高鋁無鹼矽酸鹽玻璃體系中，添加氧化硼B2 O3 可以帶來良好的助熔效果，同時有利於提升玻璃耐化性。但是在低溫黏度區，B2 O3 卻使得玻璃應變點顯著降低，如何同時提高玻璃基板的耐化性和應變點溫度成為長期困擾本領域技術人員的一道難題。In high-aluminum alkali-free silicate glass systems, the addition of boron oxide B 2 O 3 can bring good fluxing effects, and at the same time, it is beneficial to improve the chemical resistance of the glass. However, in the low-temperature viscosity region, B 2 O 3 significantly reduces the strain point of the glass. How to simultaneously improve the chemical resistance and the temperature of the strain point of the glass substrate has become a difficult problem for those skilled in the art for a long time.

在玻璃基板的加工過程中，玻璃基板是水平放置的，玻璃在自重作用下，有一定程度的下垂，下垂的程度與玻璃的密度成正比、與玻璃的彈性模量成反比。隨著基板製造向著大尺寸、薄型化方向的發展，製造中玻璃板的下垂必須引起重視。因此應設計組成，使基板玻璃具有盡可能低的密度和盡可能高的彈性模量。During the processing of the glass substrate, the glass substrate is placed horizontally. Under its own weight, the glass sags to a certain degree. The degree of sag is proportional to the density of the glass and inversely proportional to the elastic modulus of the glass. With the development of substrate manufacturing in the direction of large size and thinning, the sag of glass plates in manufacturing must be paid attention to. Therefore, the composition should be designed so that the substrate glass has the lowest possible density and the highest elastic modulus.

隨著智慧手機與平板電腦的普及，開啟了智慧移動的時代。以往的手機局限在通訊功能，但目前包括智慧手機與平板電腦的智慧設備的性能已與筆記型電腦接近，使得讓人們憑藉無線通訊的方便性無時無刻不在執行及享受較高層次的商務及娛樂活動。在這樣的趨勢下，對顯示器性能要求也不斷提高，尤其是對移動智慧設備的畫面品質、在戶外的可視性能要求也正在提升，同時為了減輕掌上型設備的使用負擔，重量變輕、厚度變薄成為不可避免的大趨勢。在這種發展潮流引導下，顯示面板正在向輕薄化、超高清顯示的方向發展，一方面，要求玻璃基板應具有較小的密度；另一方面，面板製程工藝向更高處理溫度發展；同時單片玻璃經過工藝處理，厚度達到0.25mm、0.2mm、0.1mm、0.05mm甚至更薄。使玻璃變薄的方式目前主要是化學減薄，具體的說，使用氫氟酸或氫氟酸緩衝液對玻璃基板進行腐蝕，其薄化原理如下：With the popularity of smart phones and tablets, the era of smart mobile has begun. In the past, mobile phones were limited to communication functions, but the performance of smart devices including smartphones and tablets is now close to that of notebook computers, allowing people to perform and enjoy higher-level business and entertainment activities with the convenience of wireless communications. . Under such a trend, the requirements for display performance are constantly increasing, especially for the picture quality of mobile smart devices and the requirements for outdoor visual performance. At the same time, in order to reduce the use of handheld devices, the weight and thickness of the devices have become lighter. Thin became an inevitable megatrend. Guided by this development trend, display panels are moving towards thinner, ultra-high-definition displays. On the one hand, glass substrates are required to have a smaller density; on the other hand, the panel process technology is being developed to higher processing temperatures. Monolithic glass has been processed to a thickness of 0.25mm, 0.2mm, 0.1mm, 0.05mm or even thinner. The method of making glass thinner is mainly chemical thinning. Specifically, the glass substrate is etched using hydrofluoric acid or a hydrofluoric acid buffer solution. The principle of thinning is as follows:

主要化學反應：4HF+SiO2 =SiF4 +2H2 OMain chemical reaction: 4HF + SiO 2 = SiF 4 + 2H 2 O

次要化學反應：RO+2H+ =R2+ +H2 O（R代表鹼土金屬等）Secondary chemical reaction: RO + 2H + = R 2+ + H 2 O (R stands for alkaline earth metal, etc.)

化學減薄工藝及玻璃基板減薄後的表面品質與基礎玻璃組成有一定關係，現有TFT-LCD基板玻璃在化學減薄過程中頻繁出現「凹坑」、「凹凸點」等不良欠點，增加了生產成本。具有高的化學穩定性的玻璃在減薄後具有更好的表面品質，因此研發高化學穩定性的TFT-LCD基板玻璃，可以減少二次拋光等生產成本，提升產品品質和良品率，對於大型工業化生產有較大益處。但是過慢的氫氟酸或氫氟酸緩衝液腐蝕速率會降低薄化廠生產效率。The chemical thinning process and the surface quality of the glass substrate after thinning have a certain relationship with the base glass composition. The existing TFT-LCD substrate glass frequently suffers from bad defects such as "pits" and "bumps" during the chemical thinning process. Production costs. Glass with high chemical stability has better surface quality after thinning. Therefore, the development of high chemically stable TFT-LCD substrate glass can reduce production costs such as secondary polishing, improve product quality and yield, and for large-scale Industrial production has greater benefits. But too slow corrosion rate of hydrofluoric acid or hydrofluoric acid buffer will reduce the production efficiency of thinning plant.

隨著輕薄化趨勢的發展，在G5代、G6代、G7代、G8代等更高世代玻璃基板生產中，水平放置的玻璃基板由於自重產生的下垂、翹曲成了重要研究課題。對玻璃基板生產者而言，玻璃板材成型後要經過退火、切割、加工、檢驗、清洗等多種環節，大尺寸玻璃基板的下垂將影響在加工點之間運送玻璃的箱體中裝入、取出和分隔的能力。對面板製造商來講，類似的問題同樣存在。較大的垂度或翹曲會導致碎片率提高以及CF製程工藝報警，嚴重影響產品良率。如果在兩端支撐基板兩邊時，玻璃基板的最大下垂量（S）可以表示如下：With the development of thinning and thinning, in the production of higher-generation glass substrates such as G5, G6, G7, and G8, the sagging and warping of glass substrates placed horizontally due to their own weight has become an important research topic. For glass substrate manufacturers, after the glass sheet is formed, it must undergo annealing, cutting, processing, inspection, cleaning and other links. The droop of large-sized glass substrates will affect the loading and unloading of the glass boxes between processing points. And the ability to separate. Similar problems exist for panel makers. A large sag or warpage will lead to an increase in the chip rate and an alarm in the CF process, which will seriously affect the product yield. If the two sides of the substrate are supported at both ends, the maximum sag (S) of the glass substrate can be expressed as follows:

式中，k為常數，ρ為密度，E為彈性模量，l為支撐間隔，t為玻璃基板厚度。其中，(ρ/E)為比模數的倒數。比模數是指材料彈性模量與密度的比值，亦稱為「比彈性模量」或「比剛度」，是結構設計對材料的重要要求之一。比模數較高說明相同剛度下材料重量更輕，或相同品質下剛度更大。由上式可見，當l、t一定時，ρ變小E加大後可以降低下垂量，因此應該使基板玻璃具儘量低的密度和儘量高的彈性模量，即具有儘量大的比模數。減薄後的玻璃由於厚度的急劇減小而出現機械強度降低，更容易變形。降低密度、增大比模數及強度，降低玻璃脆性成為玻璃生產者需要重點考慮的因素。In the formula, k is a constant, ρ is a density, E is an elastic modulus, l is a support interval, and t is a thickness of a glass substrate. Here, (ρ / E) is the inverse of the specific modulus. The specific modulus is the ratio of the material's elastic modulus to the density, also known as "specific elastic modulus" or "specific stiffness", which is one of the important requirements for materials in structural design. Higher specific modulus means that the material is lighter at the same stiffness, or more rigid at the same quality. As can be seen from the above formula, when l and t are constant, ρ becomes smaller and E can be increased to reduce the amount of sag. Therefore, the substrate glass should have the lowest density and the highest modulus of elasticity, that is, the largest specific modulus . The thinned glass has a reduced mechanical strength due to a sharp reduction in thickness and is more likely to deform. Decreasing density, increasing specific modulus and strength, and reducing glass brittleness have become important factors for glass producers to consider.

為了得到無泡的無鹼玻璃基板，利用澄清氣體，從玻璃熔液中驅逐玻璃反應時產生的氣體，另外在均質化熔化時，需要再次利用產生的澄清氣體，增大泡層徑，使其上浮，由此取出殘餘的微小泡。In order to obtain a bubble-free alkali-free glass substrate, the gas generated during the glass reaction is expelled from the glass melt by using a clear gas. In addition, when the homogenization is melted, the clear gas generated must be used again to increase the bubble layer diameter and make it Float up, and remove the remaining microbubbles.

可是，用作平面顯示器用玻璃基板的玻璃熔液的黏度高，需用較高的溫度熔化。在此種的玻璃基板中，通常在1300~1500℃引起玻璃化反應，在1500℃以上的高溫下脫泡、均質化。因此，在澄清劑中，廣泛使用能夠在寬的溫度範圍（1300~1700℃範圍）產生澄清氣體的As2 O3 。However, a glass melt used as a glass substrate for a flat display has a high viscosity and needs to be melted at a relatively high temperature. In such a glass substrate, a vitrification reaction usually occurs at 1300 to 1500 ° C, and defoaming and homogenization are performed at a high temperature of 1500 ° C or higher. Therefore, As 2 O 3 which can generate a clear gas in a wide temperature range (1300 to 1700 ° C.) is widely used in the clarifying agent.

但是，As2 O3 的毒性非常強，在玻璃的製造工序或廢玻璃的處理時，有可能污染環境和帶來健康的問題，其使用正在受到限制。However, As 2 O 3 is very toxic. During the glass manufacturing process or the treatment of waste glass, it may pollute the environment and cause health problems, and its use is being restricted.

曾嘗試用銻澄清來替代砷澄清。然而，銻本身存在引起環境和健康方面的問題。雖然Sb2 O3 的毒性不像As2 O3 那樣高，但是Sb2 O3 仍然是有毒的。而且與砷相比，銻產生澄清氣體的溫度較低，除去此種玻璃氣泡的有效性較低。Attempts have been made to replace arsenic clarification with antimony clarification. However, antimony itself has environmental and health problems. Although Sb 2 O 3 is not as toxic as As 2 O 3 , Sb 2 O 3 is still toxic. And compared with arsenic, antimony produces a clearer gas at a lower temperature, which is less effective at removing such glass bubbles.

中國專利CN105992749A公開了一種通過氫氟酸(HF)蝕刻處理減薄了5μm以上的、板厚為0.4mm以下的無鹼玻璃基板。但是該無鹼玻璃基板的脆性較高，斷裂韌性較低。Chinese patent CN105992749A discloses an alkali-free glass substrate having a thickness of 5 μm or less and a thickness of 0.4 mm or less by hydrofluoric acid (HF) etching. However, the alkali-free glass substrate has high brittleness and low fracture toughness.

中國專利CN105601105A公開了一種玻璃用組合物、低脆性無鹼玻璃及其製備方法和應用，其公開的技術方案使玻璃的韌性和脆性得以改善。但是，所得無鹼玻璃基板無法有效兼顧耐化學腐蝕性、高耐熱性、可加工性和機械強度等綜合性能。Chinese patent CN105601105A discloses a glass composition, low-brittleness alkali-free glass, and a preparation method and application thereof. The disclosed technical solution improves the toughness and brittleness of glass. However, the obtained alkali-free glass substrate cannot effectively balance the comprehensive properties such as chemical resistance, high heat resistance, processability, and mechanical strength.

本發明的目的是為了克服現有的無鹼玻璃基板密度大、彈性模量不夠高、比模數低、難以同時提高耐化性和應變點溫度、生產及加工過程能耗大、成本高以及需要使用有毒的澄清劑的問題，提供一種無鹼玻璃基板及其製備方法以及由該方法製備的無鹼玻璃基板。The purpose of the present invention is to overcome the existing alkali-free glass substrates with high density, insufficient elastic modulus, low specific modulus, difficulty in simultaneously improving chemical resistance and strain point temperature, large energy consumption during production and processing, high cost, and the need The problem of using a toxic clarifying agent provides an alkali-free glass substrate, a method for preparing the same, and an alkali-free glass substrate prepared by the method.

為了實現上述目的，本發明第一方面提供一種無鹼玻璃基板，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量小於5.5mg/cm2 ，In order to achieve the above object, the first aspect of the present invention provides an alkali-free glass substrate, and the erosion amount of the alkali-free glass substrate in a 10% by weight HF solution is less than 5.5 mg / cm 2 ,

以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：70-74mol%的SiO2 、11-14mol%的Al2 O3 、0-2.5mol%的ZnO、10-17mol%的RO和0.01-2mol%的RE2 O3 ，Based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 70-74 mol% SiO 2 , 11-14 mol% Al 2 O 3 , 0-2.5 mol % ZnO, 10-17 mol% RO and 0.01-2 mol% RE 2 O 3 ,

其中，所述RO為MgO、CaO、SrO和BaO中的至少一種；Wherein, the RO is at least one of MgO, CaO, SrO, and BaO;

所述RE2 O3 為Y2 O3 、La2 O3 、Gd2 O3 、Ce2 O3 、Yb2 O3 和Lu2 O3 中的至少一種。The RE 2 O 3 is at least one of Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Ce 2 O 3 , Yb 2 O 3 and Lu 2 O 3 .

較佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量為2-5.5mg/cm2 ，更佳為4.5-5.5mg/cm2 ，Preferably, the erosion amount of the alkali-free glass substrate in a 10% by weight HF solution is 2-5.5 mg / cm 2 , more preferably 4.5-5.5 mg / cm 2 ,

以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：70-73mol%的SiO2 、11.3-13.5mol%的Al2 O3 、0-2.2mol%的ZnO、12.6-16.7mol%的RO和0.01-1.2mol%的RE2 O3 ，或者，Based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 70-73 mol% SiO 2 , 11.3-13.5 mol% Al 2 O 3 , 0-2.2 mol% ZnO, 12.6-16.7 mol% RO and 0.01-1.2 mol% RE 2 O 3 , or,

所述無鹼玻璃基板的組成包括：70.4-73mol%的SiO2 、11.3-13mol%的Al2 O3 、0-2.2mol%的ZnO、12.6-16.7mol%的RO和0.01-0.7mol%的RE2 O3 。The composition of the alkali-free glass substrate includes: 70.4-73 mol% SiO 2 , 11.3-13 mol% Al 2 O 3 , 0-2.2 mol% ZnO, 12.6-16.7 mol% RO, and 0.01-0.7 mol% RE 2 O 3 .

較佳地，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足C值的範圍為0-1.26，更佳為0.58-1.23，再更佳為0.63-1.21，再更佳為0.71-1.18，再更佳為0.86-1.12，其中，C值由下式計算得出：Preferably, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the content of each component in the composition of the alkali-free glass substrate satisfies the C value in the range of 0-1.26 as calculated by the molar percentage. It is more preferably 0.58-1.23, even more preferably 0.63-1.21, even more preferably 0.71-1.18, and even more preferably 0.86-1.12. Among them, the C value is calculated by the following formula:

C=0.5×SiO2 +P1 ×Al2 O3 +P2 ×(CaO+SrO)+P3 ×(MgO+BaO+ZnO)+P4 ×RE2 O3 ，C = 0.5 × SiO 2 + P 1 × Al 2 O 3 + P 2 × (CaO + SrO) + P 3 × (MgO + BaO + ZnO) + P 4 × RE 2 O 3 ,

其中，0.8≤P1 ≤1.3，7≤P2 ≤10，1.5≤P3 ≤3，-35≤P4 ≤-20，Among them, 0.8≤P 1 ≤1.3, 7≤P 2 ≤10, 1.5≤P 3 ≤3, -35≤P 4 ≤-20,

SiO2 、Al2 O3 、MgO、CaO、SrO、BaO、ZnO、RE2 O3 各自代表該成分占無鹼玻璃基板組成中的莫耳百分比。SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, and RE 2 O 3 each represent a mole percentage of the component in the composition of the alkali-free glass substrate.

較佳地，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：SiO2 +Al2 O3 ＞82mol%。Preferably, based on the total mole amount of each component in the composition of the alkali-free glass substrate, the content of each component in the composition of the alkali-free glass substrate is calculated in terms of mole percentages: SiO 2 + Al 2 O 3 ＞ 82mol%.

較佳地，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：CaO/（CaO+SrO）≥0.4，更佳滿足CaO/（CaO+SrO）≥0.5，再更佳滿足CaO/（CaO+SrO）≥0.6。Preferably, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the content of each component in the composition of the alkali-free glass substrate is calculated based on the molar percentage: CaO / (CaO + SrO) ≥ 0.4, which better satisfies CaO / (CaO + SrO) ≥0.5, and even better satisfies CaO / (CaO + SrO) ≥0.6.

較佳地，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：（MgO+BaO）/ΣRO≥0.45，更佳滿足（MgO+BaO）/ΣRO≥0.51，再更佳滿足（MgO+BaO）/ΣRO≥0.58，其中，ΣRO表示MgO、CaO、SrO和BaO的莫耳百分比之和。Preferably, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the content of each component in the composition of the alkali-free glass substrate is calculated in terms of mole percentages to satisfy: (MgO + BaO) / ΣRO≥ 0.45, which satisfies (MgO + BaO) /ΣRO≥0.51, and even more satisfies (MgO + BaO) /ΣRO≥0.58, where ΣRO represents the sum of the mole percentages of MgO, CaO, SrO, and BaO.

較佳地，所述無鹼玻璃基板的組成中的成分還包括澄清劑，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述澄清劑的含量不超過1mol%。Preferably, the components in the composition of the alkali-free glass substrate further include a clarifying agent. Based on the total molar amount of each component in the composition of the alkali-free glass substrate, the content of the clarifying agent does not exceed 1 mol%.

較佳地，所述澄清劑為硫酸鹽、硝酸鹽、氧化錫和氧化亞錫中的至少一種。Preferably, the clarifying agent is at least one of sulfate, nitrate, tin oxide, and stannous oxide.

本發明第二方面提供了製備上述無鹼玻璃基板的方法，該方法包括：將由本發明提供的無鹼玻璃基板的組成中各成分混合，然後依次進行熔融、脫泡、均質化、成型、冷卻、切割、拋光、洗滌和烘乾。According to a second aspect of the present invention, there is provided a method for preparing the above-mentioned alkali-free glass substrate, the method comprising: mixing the components in the composition of the alkali-free glass substrate provided by the present invention, and then sequentially melting, defoaming, homogenizing, forming, and cooling , Cutting, polishing, washing and drying.

本發明協力廠商面提供了由上述方法製備的無鹼玻璃基板。The third party of the present invention provides an alkali-free glass substrate prepared by the above method.

由本發明提供的無鹼玻璃基板或採用本發明提供的方法製備的無鹼玻璃基板具有密度小、機械強度高、比模數高、熱穩定性好、熔化溫度低、兼具高耐化性和高應變點溫度等優良特性。The alkali-free glass substrate provided by the present invention or the alkali-free glass substrate prepared by the method provided by the present invention has low density, high mechanical strength, high specific modulus, good thermal stability, low melting temperature, and high chemical resistance. Excellent characteristics such as high strain point temperature.

此外，由本發明提供的無鹼玻璃基板或採用本發明提供的方法製備的無鹼玻璃基板的組成中的成分不含任何有毒物質，生產過程環境友好，即使澄清劑不使用As2 O3 和/或Sb2 O3 ，製備的無鹼玻璃基板的氣態夾雜物含量也較低，使產線良率得到一定改善，同時可以降低燃料、電力等生產成本，經濟性好。In addition, the components in the composition of the alkali-free glass substrate provided by the present invention or the alkali-free glass substrate prepared by the method provided by the present invention do not contain any toxic substances, and the production process is environmentally friendly, even if the clarifying agent does not use As 2 O 3 and / Or Sb 2 O 3 , the content of gaseous inclusions in the prepared alkali-free glass substrate is also low, which improves the production line yield to a certain extent, and at the same time, it can reduce production costs such as fuel and electricity, and is economical.

在本文中所揭露的範圍的端點和任何值都不限於該精確的範圍或值，這些範圍或值應當理解為包含接近這些範圍或值的值。對於數值範圍來說，各個範圍的端點值之間、各個範圍的端點值和單獨的點值之間，以及單獨的點值之間可以彼此組合而得到一個或多個新的數值範圍，這些數值範圍應被視為在本文中具體公開。The endpoints of the ranges and any values disclosed herein are not limited to that precise range or value, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between the individual point values, one or more new numerical ranges can be obtained by combining each other. These numerical ranges should be considered as specifically disclosed herein.

本發明一方面提供一種無鹼玻璃基板，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量小於5.5mg/cm2 ，One aspect of the present invention is to provide an alkali-free glass substrate whose erosion amount in a 10% by weight HF solution is less than 5.5 mg / cm 2 ,

以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：70-74mol%的SiO2 、11-14mol%的Al2 O3 、0-2.5mol%的ZnO、10-17mol%的RO和0.01-2mol%的RE2 O3 ，Based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 70-74 mol% SiO 2 , 11-14 mol% Al 2 O 3 , 0-2.5 mol % ZnO, 10-17 mol% RO and 0.01-2 mol% RE 2 O 3 ,

其中，所述RO為MgO、CaO、SrO和BaO中的至少一種；Wherein, the RO is at least one of MgO, CaO, SrO, and BaO;

所述RE2 O3 為Y2 O3 、La2 O3 、Gd2 O3 、Ce2 O3 、Yb2 O3 和Lu2 O3 中的至少一種。The RE 2 O 3 is at least one of Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Ce 2 O 3 , Yb 2 O 3 and Lu 2 O 3 .

根據本發明，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量指的是在20℃、單位面積的無鹼玻璃基板在濃度為10重量%的HF溶液中浸泡20分鐘(min)損失的重量。現有的化學減薄工藝及無鹼玻璃基板減薄後的表面品質與玻璃的侵蝕量有一定關係，當侵蝕量過高時，會造成無鹼玻璃基板在化學減薄過程中頻繁出現「凹坑」、「凹凸點」等不良欠點，增加生產成本。當所述侵蝕量小於5.5mg/cm2 時，例如所述侵蝕量可以為1mg/cm2 、2mg/cm2 、2.5mg/cm2 、3mg/cm2 、3.5mg/cm2 、3.86mg/cm2 、3.99mg/cm2 、4mg/cm2 、4.23mg/cm2 、4.27mg/cm2 、4.38mg/cm2 、4.45mg/cm2 、4.46mg/cm2 、4.47mg/cm2 、4.5mg/cm2 、4.63mg/cm2 、4.65mg/cm2 、4.74mg/cm2 、4.82mg/cm2 、4.91mg/cm2 、5mg/cm2 、5.16mg/cm2 和5.4mg/cm2 ，以及任意兩個相鄰侵蝕量之間的任意侵蝕量時，所述無鹼玻璃基板具有較高的化學穩定性，在減薄後具有更好的表面品質，可以減少二次拋光等生產成本，提升產品品質和良品率，對於大型工業化生產有較大益處。According to the present invention, the erosion amount of the alkali-free glass substrate in a 10% by weight HF solution means that the alkali-free glass substrate per unit area is immersed in a 10% by weight HF solution for 20 minutes (min. ) Lost weight. Existing chemical thinning processes and the surface quality of alkali-free glass substrates after thinning have a certain relationship with the amount of glass erosion. When the amount of erosion is too high, it will cause frequent occurrence of "pits" in the process of chemical thinning of alkali-free glass substrates. ", And" defective points "and other bad points increase production costs. When the erosion amount is less than 5.5 mg / cm 2 , for example, the erosion amount may be 1 mg / cm 2 , 2 mg / cm 2 , 2.5 mg / cm 2 , 3 mg / cm 2 , 3.5 mg / cm 2 , 3.86 mg / cm 2 . cm 2, 3.99mg / cm 2, 4mg / cm 2, 4.23mg / cm 2, 4.27mg / cm 2, 4.38mg / cm 2, 4.45mg / cm 2, 4.46mg / cm 2, 4.47mg / cm 2, 4.5mg / cm 2, 4.63mg / cm 2, 4.65mg / cm 2, 4.74mg / cm 2, 4.82mg / cm 2, 4.91mg / cm 2, 5mg / cm 2, 5.16mg / cm 2 and 5.4mg / cm 2 and any amount of erosion between any two adjacent amounts of erosion, the alkali-free glass substrate has higher chemical stability, better surface quality after thinning, and can reduce secondary polishing, etc. Production costs and the improvement of product quality and yield have great benefits for large-scale industrial production.

較佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量小於5.4mg/cm2 ；更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量小於5.3mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量小於5.2mg/cm2 。Preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is less than 5.4 mg / cm 2 ; more preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is less than 5.3 mg / cm 2 ; more preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is less than 5.2 mg / cm 2 .

根據本發明，顯示面板經過工藝處理使基板玻璃及封裝玻璃變薄的方式目前主要是化學減薄，即利用氫氟酸或氫氟酸緩衝液對玻璃基板進行腐蝕，過慢的氫氟酸或氫氟酸緩衝液腐蝕速率會降低薄化廠生產效率。較佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於2mg/cm2 ；更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於2.5mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於3mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於3.5mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於4mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於4.3mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於4.4mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於4.5mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於4.6mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於4.7mg/cm2 ；再更佳地，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量大於4.8mg/cm2 。According to the present invention, the manner in which the display panel undergoes a process to thin the substrate glass and the encapsulation glass is mainly chemical thinning, that is, the glass substrate is corroded by using hydrofluoric acid or a hydrofluoric acid buffer solution. The corrosion rate of the hydrofluoric acid buffer solution will reduce the production efficiency of the thinning plant. Preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is greater than 2 mg / cm 2 ; more preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is greater than 2.5 mg / cm 2 ; more preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is greater than 3 mg / cm 2 ; still more preferably, the alkali-free glass substrate is at 10% by weight of HF The amount of erosion in the solution is greater than 3.5 mg / cm 2 ; still more preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is more than 4 mg / cm 2 ; still more preferably, the alkali-free glass The amount of erosion of the substrate in the 10% by weight HF solution is greater than 4.3 mg / cm 2 ; more preferably, the amount of erosion of the alkali-free glass substrate in the 10% by weight of the HF solution is more than 4.4 mg / cm 2 ; Preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is greater than 4.5 mg / cm 2 ; more preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is greater than 4.6 mg / cm 2 ; more preferably, the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is greater than 4.7 mg / cm 2 ; still more preferably, the alkali-free glass substrate is at The amount of erosion in a 10% by weight HF solution was greater than 4.8 mg / cm 2 .

根據本發明，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：70-74mol%的SiO2 ，例如70mol%的SiO2 、70.4mol%的SiO2 、70.5mol%的SiO2 、70.9mol%的SiO2 、71mol%的SiO2 、71.2mol%的SiO2 、71.4mol%的SiO2 、71.6mol%的SiO2 、71.8mol%的SiO2 、72mol%的SiO2 、72.1mol%的SiO2 、72.3mol%的SiO2 、72.5mol%的SiO2 、72.8mol%的SiO2 、72.9mol%的SiO2 、73mol%的SiO2 、74mol%的SiO2 ，以及任意兩個相鄰莫耳百分含量之間的任意莫耳百分含量的SiO2 。這是因為SiO2 是玻璃形成體，若SiO2 的含量過低，不利於耐化性和耐腐蝕性的增強，會造成膨脹係數過高，導致玻璃容易失透；若SiO2 的含量升高，雖然有助於玻璃輕量化，熱膨脹係數減小，應變點增高，耐化性增高，但是SiO2 的含量過高會造成無鹼玻璃基板的高溫黏度升高，即熔化溫度升高，這樣不利於熔化，一般的窯爐難以滿足常規的高容量熔化技術將物料批量熔化。According to the present invention, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 70-74 mol% SiO 2 , for example, 70 mol% SiO 2 , 70.4 mol% SiO 2 , 70.5 mol% SiO 2 , 70.9 mol% SiO 2 , 71 mol% SiO 2 , 71.2 mol% SiO 2 , 71.4 mol% SiO 2 , 71.6 mol% SiO 2 , 71.8 mol% SiO 2, 72mol% of SiO 2, 72.1mol% of SiO 2, 72.3mol% of SiO 2, 72.5mol% of SiO 2, 72.8mol% of SiO 2, 72.9mol% of SiO 2, 73mol% of SiO 2, 74mol % SiO 2 , and any mole percentage of SiO 2 between any two adjacent mole percentages. This is because SiO 2 is a glass-forming body. If the content of SiO 2 is too low, it is not conducive to the enhancement of chemical resistance and corrosion resistance, which will cause the expansion coefficient to be too high, which will cause the glass to easily devitrify. If the content of SiO 2 is increased, Although it helps to reduce the weight of glass, the coefficient of thermal expansion is reduced, the strain point is increased, and the chemical resistance is increased, but an excessively high content of SiO 2 will cause the high-temperature viscosity of the alkali-free glass substrate to increase, that is, the melting temperature will increase, which is disadvantageous. For melting, ordinary kiln is difficult to meet the conventional high-volume melting technology to melt materials in batches.

較佳情況下，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：70-73mol%的SiO2 ，這樣有利於進一步兼顧所述無鹼玻璃基板的耐化性和高溫黏度。Preferably, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 70-73 mol% of SiO 2 , which is beneficial to further consider the alkali-free glass substrate. Chemical resistance and high temperature viscosity of glass substrates.

另一種較佳情況下，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：70.4-73mol%的SiO2 ，這樣有利於進一步兼顧所述無鹼玻璃基板的耐化性和高溫黏度。In another preferred case, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 70.4-73 mol% SiO 2 , which is beneficial to further take into account the Chemical resistance and high temperature viscosity of alkali-free glass substrate.

根據本發明，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：11-14mol%的Al2 O3 ，例如11mol%的Al2 O3 、11.35mol%的Al2 O3 、11.45mol%的Al2 O3 、11.5mol%的Al2 O3 、11.6mol%的Al2 O3 、11.7mol%的Al2 O3 、11.9mol%的Al2 O3 、12mol%的Al2 O3 、12.1mol%的Al2 O3 、12.2mol%的Al2 O3 、12.4mol%的Al2 O3 、12.5mol%的Al2 O3 、12.8mol%的Al2 O3 、13mol%的Al2 O3 、13.1mol%的Al2 O3 、13.5mol%的Al2 O3 、14mol%的Al2 O3 ，以及任意兩個相鄰莫耳百分含量之間的任意莫耳百分含量的Al2 O3 。當Al2 O3 的含量過低時，玻璃耐熱性難以提升，也容易受到外界水氣及化學試劑的侵蝕；當Al2 O3 的含量升高時，雖然有助於玻璃應變點、機械強度的增高，但Al2 O3 的含量過高玻璃容易出現析晶現象，同時會使得玻璃難以熔化。According to the present invention, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 11-14 mol% Al 2 O 3 , for example, 11 mol% Al 2 O 3 , 11.35mol% Al 2 O 3 , 11.45mol% Al 2 O 3 , 11.5mol% Al 2 O 3 , 11.6mol% Al 2 O 3 , 11.7mol% Al 2 O 3 , 11.9mol% al 2 O 3, 12mol% of al 2 O 3, 12.1mol% of al 2 O 3, 12.2mol% of al 2 O 3, 12.4mol% of al 2 O 3, 12.5mol% of al 2 O 3, 12.8 mol% of Al 2 O 3, 13mol% of Al 2 O 3, 13.1mol% of Al 2 O 3, 13.5mol% of Al 2 O 3, 14mol% of Al 2 O 3, and any two adjacent mole Any molar percentage of Al 2 O 3 between the percentages. When the content of Al 2 O 3 is too low, it is difficult to improve the heat resistance of the glass, and it is also susceptible to attack by external water vapor and chemical reagents. When the content of Al 2 O 3 is increased, although it contributes to the strain point and mechanical strength of the glass Increase, but if the content of Al 2 O 3 is too high, the glass will easily crystallize, and it will make the glass difficult to melt.

較佳情況下，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：11.3-13.5mol%的Al2 O3 ，這樣有利於進一步優化所述無鹼玻璃基板的耐熱性、耐化性和機械強度，並改善析晶性能。Preferably, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 11.3-13.5mol% Al 2 O 3 , which is beneficial to further optimize the The heat resistance, chemical resistance, and mechanical strength of the alkali-free glass substrate are described, and the crystallization performance is improved.

另一種較佳情況下，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：11.3-13mol%的Al2 O3 ，這樣有利於進一步優化所述無鹼玻璃基板的耐熱性、耐化性和機械強度，並改善析晶性能。In another preferred case, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 11.3-13 mol% Al 2 O 3 , which is helpful for further optimization. The alkali-free glass substrate has heat resistance, chemical resistance, and mechanical strength, and improves crystallization performance.

更佳地，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：SiO2 +Al2 O3 ＞82mol%。這樣可以在最大限度地提高所述無鹼玻璃基板的耐化學性、耐腐蝕性、耐熱性、可加工性和機械強度的同時，降低所述無鹼玻璃基板出現析晶現象的概率。More preferably, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the content of each component in the composition of the alkali-free glass substrate satisfies the molar ratio calculation: SiO 2 + Al 2 O 3 ＞ 82mol%. In this way, the chemical resistance, corrosion resistance, heat resistance, processability, and mechanical strength of the alkali-free glass substrate can be maximized, and the probability of crystallization of the alkali-free glass substrate can be reduced.

根據本發明，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：0-2.5mol%的ZnO，例如不含ZnO、0.1mol%的ZnO、0.2mol%的ZnO、0.26mol%的ZnO、0.3mol%的ZnO、0.4mol%的ZnO、0.5mol%的ZnO、0.6mol%的ZnO、0.7mol%的ZnO、0.8mol%的ZnO、0.9mol%的ZnO、1mol%的ZnO、1.1mol%的ZnO、1.2mol%的ZnO、1.3mol%的ZnO、1.4mol%的ZnO、1.5mol%的ZnO、1.6mol%的ZnO、1.7mol%的ZnO、1.8mol%的ZnO、1.9mol%的ZnO、2mol%的ZnO、2.1mol%的ZnO、2.2mol%的ZnO、2.3mol%的ZnO、2.4mol%的ZnO和2.5mol%的ZnO，以及任意兩個相鄰莫耳百分含量之間的任意莫耳百分含量的ZnO。在無鹼玻璃體系中，添加適量ZnO有助於降低析晶溫度，進而抑制析晶，並且可以降低玻璃高溫黏度，有利於消除氣泡，同時在軟化點以下有提升玻璃的強度、硬度、耐化性、降低玻璃熱膨脹係數的作用。在理論上，ZnO在無鹼玻璃中，作為網路外體引入玻璃後，高溫下一般以[ZnO4 ]的形式存在，較[ZnO6 ]玻璃結構更加疏鬆，與不含ZnO的玻璃處於相同的高溫狀態下比較，含ZnO的玻璃黏度更小，原子運動速度更大，無法形成晶核，需要進一步降低溫度，才有利於晶核的形成，因而，降低了玻璃的析晶上限溫度。而ZnO含量過多會使玻璃的應變點大幅度降低，不利於玻璃基板熱穩定性的提升。According to the present invention, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 0-2.5 mol% ZnO, such as ZnO-free and 0.1 mol% ZnO 0.2 mol% ZnO, 0.26 mol% ZnO, 0.3 mol% ZnO, 0.4 mol% ZnO, 0.5 mol% ZnO, 0.6 mol% ZnO, 0.7 mol% ZnO, 0.8 mol% ZnO, 0.9 mol% ZnO, 1 mol% ZnO, 1.1 mol% ZnO, 1.2 mol% ZnO, 1.3 mol% ZnO, 1.4 mol% ZnO, 1.5 mol% ZnO, 1.6 mol% ZnO, 1.7 mol% ZnO, 1.8 mol% ZnO, 1.9 mol% ZnO, 2 mol% ZnO, 2.1 mol% ZnO, 2.2 mol% ZnO, 2.3 mol% ZnO, 2.4 mol% ZnO, and 2.5 mol% ZnO, and Any molar percentage of ZnO between any two adjacent molar percentages. In an alkali-free glass system, adding an appropriate amount of ZnO can help reduce the crystallization temperature, thereby inhibiting crystallization, and can reduce the high-temperature viscosity of the glass, which is beneficial to eliminate air bubbles. At the same time, it can improve the strength, hardness, and chemical resistance of the glass below the softening point. And reduce the thermal expansion coefficient of glass. In theory, after ZnO is introduced into the glass as an outer body of the network in alkali-free glass, it generally exists in the form of [ZnO 4 ] at high temperatures, which is more loose than the glass structure of [ZnO 6 ], and is the same as ZnO-free glass. Compared with the high temperature state, ZnO-containing glass has a lower viscosity and a higher atomic velocity, and cannot form crystal nuclei. It is necessary to further reduce the temperature to facilitate the formation of crystal nuclei, and therefore, the upper crystallization limit temperature of the glass is reduced. Too much ZnO content will greatly reduce the strain point of the glass, which is not conducive to the improvement of the thermal stability of the glass substrate.

較佳情況下，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：0-2.2mol%的ZnO，這樣有利於進一步降低所述無鹼玻璃基板的析晶溫度，同時保障所述無鹼玻璃基板的熱應力均勻分佈。Preferably, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 0-2.2 mol% ZnO, which is beneficial to further reduce the alkali-free glass substrate. The crystallization temperature of the glass substrate, while ensuring that the thermal stress of the alkali-free glass substrate is evenly distributed.

根據本發明，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：10-17mol%的RO，例如10mol%的RO、10.45mol%的RO、11mol%的RO、12mol%的RO、12.41mol%的RO、12.6mol%的RO、13mol%的RO、13.6mol%的RO、13.66mol%的RO、14mol%的RO、14.2mol%的RO、14.4mol%的RO、14.45mol%的RO、14.6mol%的RO、15mol%的RO、15.1mol%的RO、15.37mol%的RO、15.58mol%的RO、15.6mol%的RO、16mol%的RO、16.34mol%的RO、16.7mol%的RO和17mol%的RO，以及任意兩個相鄰莫耳百分含量之間的任意莫耳百分含量的RO，其中，所述RO為MgO、CaO、SrO和BaO中的至少一種。MgO、CaO、SrO、BaO均屬於鹼土金屬氧化物，它們的加入可有效降低玻璃的高溫黏度從而提高玻璃的熔融性及成形性，並可提高玻璃的應變點。此外，MgO、BaO具有提高無鹼玻璃基板的化學穩定性和機械穩定性的特點。但是鹼土金屬氧化物的含量過多會使無鹼玻璃基板的密度增加，裂紋、失透、分相的發生率提高。According to the present invention, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 10-17 mol% RO, such as 10 mol% RO, 10.45 mol% RO , 11mol% RO, 12mol% RO, 12.41mol% RO, 12.6mol% RO, 13mol% RO, 13.6mol% RO, 13.66mol% RO, 14mol% RO, 14.2mol% RO , 14.4mol% RO, 14.45mol% RO, 14.6mol% RO, 15mol% RO, 15.1mol% RO, 15.37mol% RO, 15.58mol% RO, 15.6mol% RO, 16mol% RO, 16.34 mol% RO, 16.7 mol% RO, and 17 mol% RO, and any molar percentage RO between any two adjacent molar percentages, where the RO is MgO At least one of CaO, SrO, and BaO. MgO, CaO, SrO, and BaO are all alkaline earth metal oxides. Their addition can effectively reduce the high temperature viscosity of the glass, thereby improving the meltability and formability of the glass, and can increase the strain point of the glass. In addition, MgO and BaO have the characteristics of improving the chemical and mechanical stability of the alkali-free glass substrate. However, if the content of the alkaline earth metal oxide is too large, the density of the alkali-free glass substrate will increase, and the incidence of cracks, devitrification, and phase separation will increase.

較佳情況下，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：12.6-16.7mol%的RO，其中，所述RO為MgO、CaO、SrO和BaO中的至少一種，這樣有利於進一步提高玻璃的熔融性及成形性，同時更有效地控制無鹼玻璃基板裂紋、失透、分相的發生率。Preferably, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 12.6-16.7mol% RO, wherein the RO is MgO, CaO At least one of SrO, SrO, and BaO, which is helpful to further improve the meltability and formability of the glass, and more effectively control the incidence of cracks, devitrification, and phase separation of the alkali-free glass substrate.

根據本發明，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：CaO/（CaO+SrO）≥0.4，例如CaO/（CaO+SrO）的值可以為0.4、0.5、0.6、0.64、0.67、0.7、0.8、0.85、0.87、0.9、0.91、0.92、0.98和1，以及任意兩個相鄰數值之間的任意數值，較佳滿足CaO/（CaO+SrO）≥0.5，更佳滿足CaO/（CaO+SrO）≥0.6，其中，CaO、SrO各自代表該成分占所述無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比。不同離子半徑的Ca2+ 和Sr2+ 之間相互堆積緊密，相互牽制，使得離子遷移困難，從而提高擴散活化能，而Ca2+ 的半徑比Sr2+ 小，具有更高的電場強度，對其他元素的熱運動阻礙更大，因而適當提高鹼土金屬氧化物中CaO的含量有利於增強其對周圍離子的遷移壓製作用，進而降低無鹼玻璃基板的熱膨脹係數，提高無鹼玻璃基板的化學穩定性。According to the present invention, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the content of each component in the composition of the alkali-free glass substrate is calculated in terms of mole percentages to satisfy: CaO / (CaO + SrO) ≥ 0.4, for example, the value of CaO / (CaO + SrO) can be 0.4, 0.5, 0.6, 0.64, 0.67, 0.7, 0.8, 0.85, 0.87, 0.9, 0.91, 0.92, 0.98, and 1, and any two adjacent values Any value in between, preferably satisfies CaO / (CaO + SrO) ≥0.5, and more preferably satisfies CaO / (CaO + SrO) ≥0.6, wherein CaO and SrO each represent that this component accounts for the composition of the alkali-free glass substrate Molar percentage of the total Molar content of each ingredient. Ca 2+ and Sr 2+ with different ionic radii are densely packed with each other and restrained each other, making ion migration difficult, thereby increasing the diffusion activation energy, while the radius of Ca 2+ is smaller than Sr 2+ and has a higher electric field strength. The thermal movement of other elements is more hindered, so appropriately increasing the content of CaO in the alkaline earth metal oxide is conducive to enhancing its migration and suppression of surrounding ions, thereby reducing the thermal expansion coefficient of the alkali-free glass substrate and improving the chemistry of the alkali-free glass substrate. stability.

根據本發明，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：（MgO+BaO）/ΣRO≥0.45，例如（MgO+BaO）/ΣRO的值可以為0.45、0.46、0.51、0.52、0.53、0.56、0.58、0.6、0.61、0.62、0.66、0.67、0.68、0.69、0.71和0.8以及任意兩個相鄰數值之間的任意數值，較佳滿足（MgO+BaO）/ΣRO≥0.51，更佳滿足（MgO+BaO）/ΣRO≥0.58，其中，MgO、BaO各自代表該成分占無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比，ΣRO表示所述無鹼玻璃基板的組成中鹼土金屬氧化物的莫耳百分含量之和，具體地，ΣRO表示MgO、CaO、SrO和BaO各自占所述無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比之和。多元混合鹼土金屬氧化物的添加，可以使無鹼玻璃基板的膨脹軟化溫度得到顯著提升，並且當鹼土金屬離子半徑相差越大時，混合效應越明顯，因此適當提高鹼土金屬氧化物中MgO、BaO的含量有利於提升玻璃的膨脹軟化溫度，提高玻璃的熱穩定性，在玻璃拉製過程中，擴大工作溫度範圍，使玻璃製備過程中的操作性更好。According to the present invention, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the content of each component in the composition of the alkali-free glass substrate is calculated in terms of mole percentages: (MgO + BaO) / ΣRO≥ 0.45, for example, (MgO + BaO) / ΣRO can be 0.45, 0.46, 0.51, 0.52, 0.53, 0.56, 0.58, 0.6, 0.61, 0.62, 0.66, 0.67, 0.68, 0.69, 0.71 and 0.8 and any two phases Any value between adjacent values is better to satisfy (MgO + BaO) /ΣRO≥0.51, and more preferably (MgO + BaO) /ΣRO≥0.58, where MgO and BaO each represent the composition of the composition in the alkali-free glass substrate Molar percentage of the total mole amount of each component in the composition, ΣRO represents the sum of the molar content of the alkaline earth metal oxide in the composition of the alkali-free glass substrate, and specifically, ΣRO represents each of MgO, CaO, SrO, and BaO The sum of the mole percentages of the total moles of the components in the composition of the alkali-free glass substrate. The addition of multiple mixed alkaline earth metal oxides can significantly increase the expansion and softening temperature of alkali-free glass substrates, and the larger the difference between the alkaline earth metal ion radii, the more obvious the mixing effect. Therefore, the MgO and BaO in the alkaline earth metal oxides are appropriately increased. The content is beneficial to increase the expansion and softening temperature of the glass, improve the thermal stability of the glass, expand the working temperature range during the glass drawing process, and make the operability in the glass preparation process better.

根據本發明，稀土氧化物RE2 O3 在提高玻璃的某些性能方面具有獨特的能力，例如玻璃的抗彎強度、彈性模量、應變點等性能隨稀土氧化物的加入而大幅上升，促使玻璃脆性降低，斷裂韌性大幅增加，並且能夠降低玻璃的高溫黏度，為玻璃大型工業製造帶來巨大便利。鹼土金屬、ZnO等網路外體引入玻璃組成後，過剩的氧原子使得玻璃結構中的橋氧鍵斷裂生成非橋氧，這些非橋氧的存在顯著降低了玻璃的抗彎強度。RE2 O3 的加入促使玻璃的內部結構發生變化，所生成的Si-O-RE化學鍵將玻璃中孤立島狀網路單元重新連接，可以改善玻璃的網路結構，從而可以大幅提高玻璃的抗彎強度、彈性模量、應變點、化學穩定性等性能。但是進一步增加RE2 O3 時，由於可供調整的非橋氧數量減少，過量的RE2 O3 對玻璃的上述性能影響不大。因此，綜合考慮，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：0.01-2mol%的RE2 O3 ，例如0.01mol%的RE2 O3 、0.02mol%的RE2 O3 、0.03mol%的RE2 O3 、0.05mol%的RE2 O3 、0.07mol%的RE2 O3 、0.1mol%的RE2 O3 、0.2mol%的RE2 O3 、0.3mol%的RE2 O3 、0.34mol%的RE2 O3 、0.35mol%的RE2 O3 、0.4mol%的RE2 O3 、0.5mol%的RE2 O3 、0.6mol%的RE2 O3 、0.7mol%的RE2 O3 、0.8mol%的RE2 O3 、0.9mol%的RE2 O3 、1mol%的RE2 O3 、1.2mol%的RE2 O3 、1.3mol%的RE2 O3 、1.5mol%的RE2 O3 、1.8mol%的RE2 O3 、1.9mol%的RE2 O3 和2mol%的RE2 O3 ，以及任意兩個莫耳百分含量之間的任意莫耳百分含量的RE2 O3 ，較佳為0.01-1.2mol%的RE2 O3 ，更佳為0.01-0.7mol%的RE2 O3 ，其中，所述RE2 O3 較佳為Y2 O3 、La2 O3 、Gd2 O3 、Ce2 O3 、Yb2 O3 和Lu2 O3 中的至少一種。從吸收光譜等其他性能綜合考慮，更佳地，Y2 O3 +La2 O3 ＞0mol%，其中，Y2 O3 、La2 O3 各自代表該成分占無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比。According to the present invention, the rare earth oxide RE 2 O 3 has a unique ability to improve certain properties of the glass, such as the bending strength, elastic modulus, strain point and other properties of the glass, which greatly increase with the addition of the rare earth oxide, prompting The brittleness of the glass is reduced, the fracture toughness is greatly increased, and the high-temperature viscosity of the glass can be reduced, which brings great convenience to the large-scale industrial manufacturing of glass. After the introduction of glass components such as alkaline earth metals and ZnO into the glass, excess oxygen atoms break the bridge oxygen bonds in the glass structure to generate non-bridged oxygen. The presence of these non-bridged oxygen significantly reduces the bending strength of the glass. The addition of RE 2 O 3 promotes changes in the internal structure of the glass. The generated Si-O-RE chemical bonds reconnect the isolated island network units in the glass, which can improve the network structure of the glass, which can greatly improve the resistance of the glass. Flexural strength, elastic modulus, strain point, chemical stability and other properties. However, when RE 2 O 3 is further increased, the amount of non-bridged oxygen that can be adjusted is reduced, so the excess of RE 2 O 3 has little effect on the above properties of the glass. Therefore, based on comprehensive considerations, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 0.01-2 mol% of RE 2 O 3 , such as 0.01 mol% of RE 2 O 3 , 0.02 mol% of RE 2 O 3 , 0.03 mol% of RE 2 O 3 , 0.05 mol% of RE 2 O 3 , 0.07 mol% of RE 2 O 3 , 0.1 mol% of RE 2 O 3 , 0.2 mol % RE 2 O 3 , 0.3 mol% RE 2 O 3 , 0.34 mol% RE 2 O 3 , 0.35 mol% RE 2 O 3 , 0.4 mol% RE 2 O 3 , 0.5 mol% RE 2 O 3, 0.6mol% of RE 2 O 3, 0.7mol% of RE 2 O 3, 0.8mol% of RE 2 O 3, 0.9mol% of RE 2 O 3, 1mol% of RE 2 O 3, 1.2mol% of RE 2 O 3 , 1.3 mol% of RE 2 O 3 , 1.5 mol% of RE 2 O 3 , 1.8 mol% of RE 2 O 3 , 1.9 mol% of RE 2 O 3 and 2 mol% of RE 2 O 3 , and RE 2 O 3 at any mole percentage between any two mole percentages, preferably 0.01-1.2 mol% RE 2 O 3 , more preferably 0.01-0.7 mol% RE 2 O 3 Among them, the RE 2 O 3 is preferably at least one of Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Ce 2 O 3 , Yb 2 O 3 and Lu 2 O 3 . From the comprehensive consideration of other properties such as absorption spectrum, more preferably, Y 2 O 3 + La 2 O 3 > 0 mol%, among which Y 2 O 3 and La 2 O 3 each represent each component in the composition of the alkali-free glass substrate. The mole percentage of the total mole of the ingredients.

根據本發明，化學減薄工藝中，使用氫氟酸或氫氟酸緩衝液對玻璃基板進行腐蝕，其薄化原理如下：According to the present invention, in the chemical thinning process, the glass substrate is etched using hydrofluoric acid or a hydrofluoric acid buffer solution, and the principle of thinning is as follows:

主要化學反應：4HF+SiO2 =SiF4 +2H2 OMain chemical reaction: 4HF + SiO 2 = SiF 4 + 2H 2 O

次要化學反應：RO+2H+ =R2+ +H2 O（RO代表二價金屬氧化物等）Secondary chemical reaction: RO + 2H + = R 2+ + H 2 O (RO stands for divalent metal oxide, etc.)

化學減薄工藝及玻璃基板減薄後的表面品質與無鹼玻璃基板的組成配方有一定關係，具有高的化學穩定性的玻璃在減薄後具有更好的表面品質，因此研發高化學穩定性的無鹼玻璃基板，可以減少二次拋光等生產成本，提升產品品質和良品率，對於大型工業化生產有較大益處。較佳情況下，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足C值的範圍為0-1.26，例如C值可以為0.1、0.2、0.3、0.4、0.5、0.58、0.6、0.63、0.7、0.71、0.8、0.84、0.86、0.9、0.92、0.93、0.99、1、1.01、1.03、1.08、1.09、1.1、1.12、1.2、1.21、1.22、1.25和1.26，以及任意兩個C值之間的任意C值，較佳為0.58-1.23，更佳為0.63-1.21，再更佳為0.71-1.18，再更佳為0.86-1.12，其中，C值由下式計算得出：The chemical thinning process and the surface quality of the glass substrate after thinning have a certain relationship with the composition formula of the alkali-free glass substrate. The glass with high chemical stability has better surface quality after thinning, so the development of high chemical stability Alkali-free glass substrates can reduce production costs such as secondary polishing, improve product quality and yield, and have greater benefits for large-scale industrial production. Preferably, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the content of each component in the composition of the alkali-free glass substrate satisfies the value of C in the range of 0-1.226 as a percentage of the mole. For example, the C value can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.58, 0.6, 0.63, 0.7, 0.71, 0.8, 0.84, 0.86, 0.9, 0.92, 0.93, 0.99, 1, 1.01, 1.03, 1.08, 1.09, 1.1, 1.12, 1.2, 1.21, 1.22, 1.25, and 1.26, and any C value between any two C values, preferably 0.58-1.23, more preferably 0.63-1.21, even more preferably 0.71-1.18, and More preferably, it is 0.86-1.12, where the C value is calculated from the following formula:

C=0.5×SiO2 +P1 ×Al2 O3 +P2 ×(CaO+SrO)+P3 ×(MgO+BaO+ZnO)+P4 ×RE2 O3 ，C = 0.5 × SiO 2 + P 1 × Al 2 O 3 + P 2 × (CaO + SrO) + P 3 × (MgO + BaO + ZnO) + P 4 × RE 2 O 3 ,

其中，SiO2 、Al2 O3 、MgO、CaO、SrO、BaO、ZnO、RE2 O3 各自代表該成分占無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比，0.8≤P1 ≤1.3，7≤P2 ≤10，1.5≤P3 ≤3，-35≤P4 ≤-20。當所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算得到的C值滿足上述範圍時，可以使所述無鹼玻璃基板具有優異的耐化性、高溫黏度、耐熱性、機械強度、應變點溫度、熱膨脹係數、抗彎強度和彈性模量等性能，同時可以抑制無鹼玻璃基板裂紋、失透、析晶和分相等現象的出現，即使無鹼玻璃基板獲得更加優異的綜合性能。Among them, SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, and RE 2 O 3 each represent the molar percentage of the component to the total molar amount of each component in the composition of the alkali-free glass substrate, 0.8 ≦ P 1 ≤1.3, 7≤P 2 ≤10, 1.5≤P 3 ≤3, -35≤P 4 ≤-20. When the content of each component in the composition of the alkali-free glass substrate satisfies the above range when the C value calculated by the mole percentage satisfies the above range, the alkali-free glass substrate can have excellent chemical resistance, high temperature viscosity, heat resistance, and mechanical properties Strength, strain point temperature, thermal expansion coefficient, flexural strength, and modulus of elasticity can also suppress the occurrence of cracks, devitrification, crystallization, and equalization of alkali-free glass substrates, even if the alkali-free glass substrates have a more excellent comprehensive performance.

根據本發明，為了得到無泡的無鹼玻璃基板，所述無鹼玻璃基板的組成中的成分還可以包括澄清劑。所述澄清劑的主要作用是協助排除殘餘氣泡，同時需避免無鹼玻璃基板熔製過程中因著色而引起透過率下降。所述澄清劑可以在無鹼玻璃基板熔製過程中高溫分解（氣化）產生氣體或降低玻璃液黏度，促使玻璃液中氣泡消除。所述澄清劑的含量沒有特別的限定，只要足夠將玻璃液中的氣泡全部消除即可，較佳地，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述澄清劑的含量不超過1mol%。According to the present invention, in order to obtain a foam-free alkali-free glass substrate, a component in the composition of the alkali-free glass substrate may further include a clarifying agent. The main function of the clarifying agent is to help to eliminate residual air bubbles, and at the same time to avoid the decrease in transmittance due to coloration during the melting of the alkali-free glass substrate. The clarifying agent can decompose (gasify) at a high temperature during the melting process of the alkali-free glass substrate to generate a gas or reduce the viscosity of the glass liquid, thereby promoting the elimination of bubbles in the glass liquid. The content of the clarifying agent is not particularly limited, as long as it is sufficient to completely eliminate air bubbles in the glass liquid. Preferably, the clarifying agent is based on the total molar amount of each component in the composition of the alkali-free glass substrate. The content is less than 1mol%.

根據本發明，所述澄清劑的種類沒有特別的限定，只要不含砷、綠色、環保、安全、高效即可，可以為本領域常規的各種選擇，為了最大限度降低最終製備的無鹼玻璃基板的氣態夾雜物含量，所述澄清劑較佳為硫酸鹽、硝酸鹽、氧化錫和氧化亞錫中的至少一種。本發明中，即使澄清劑不使用As2 O3 和/或Sb2 O3 也具有較高的透過率和較低的氣態夾雜物含量，因此，根據本發明的較佳實施方式，本發明的無鹼玻璃基板不含As2 O3 和/或Sb2 O3 。According to the present invention, the type of the clarifying agent is not particularly limited, as long as it does not contain arsenic, green, environmental protection, safety, and high efficiency, it can be various conventional choices in the field, in order to minimize the finally prepared alkali-free glass substrate Content of gaseous inclusions, the fining agent is preferably at least one of sulfate, nitrate, tin oxide and stannous oxide. In the present invention, even if the fining agent does not use As 2 O 3 and / or Sb 2 O 3, it has a high transmittance and a low gaseous inclusion content. Therefore, according to a preferred embodiment of the present invention, The alkali-free glass substrate does not contain As 2 O 3 and / or Sb 2 O 3 .

根據本發明，當所述無鹼玻璃在10重量%的HF溶液中的侵蝕量和所述無鹼玻璃基板的組成中各成分含量之間的關係滿足上述條件時，如果加入B2 O3 會形成層狀結構的硼氧三角體[BO3 ]，進入所述無鹼玻璃基板中矽氧網路結構，使所述矽氧網路結構遭到破壞，化學穩定性降低。因此，較佳情況下，所述無鹼玻璃基板的組成中不含B2 O3 ，這樣可以有效保證所述無鹼玻璃基板的熱穩定性、化學穩定性和機械穩定性。According to the present invention, when the relationship between the amount of erosion of the alkali-free glass in a 10% by weight HF solution and the content of each component in the composition of the alkali-free glass substrate satisfies the above conditions, if B 2 O 3 is added, The boron-oxygen triangle [BO 3 ], which forms a layered structure, enters the silicon-oxygen network structure in the alkali-free glass substrate, which causes the silicon-oxygen network structure to be destroyed and the chemical stability to be reduced. Therefore, preferably, the composition of the alkali-free glass substrate does not include B 2 O 3 , which can effectively ensure the thermal stability, chemical stability, and mechanical stability of the alkali-free glass substrate.

在一種較佳的實施方式中，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量為4.6-5.5mg/cm2 ，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：70-73mol%的SiO2 、11.3-13.5mol%的Al2 O3 、0-2.2mol%的ZnO、12.6-16.7mol%的RO和0.01-1.2mol%的RE2 O3 ，0.1-0.3mol%的澄清劑，其中，所述RO為MgO、CaO、SrO和BaO中的至少一種；所述RE2 O3 為Y2 O3 、La2 O3 、Gd2 O3 、Ce2 O3 、Yb2 O3 和Lu2 O3 中的至少一種，並且以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：82mol%≤SiO2 +Al2 O3 ≤84mol%、0.8≤CaO/（CaO+SrO）≤1.0、0.58≤（MgO+BaO）/ΣRO≤0.8、C值的範圍為1.03-1.12，其中，C值由下式計算得出：In a preferred embodiment, the erosion amount of the alkali-free glass substrate in a 10% by weight HF solution is 4.6-5.5 mg / cm 2 , and the total molar amount of each component in the composition of the alkali-free glass substrate is As a benchmark, the composition of the alkali-free glass substrate includes: 70-73 mol% SiO 2 , 11.3-13.5 mol% Al 2 O 3 , 0-2.2 mol% ZnO, 12.6-16.7 mol% RO, and 0.01- 1.2 mol% of RE 2 O 3 , 0.1-0.3 mol% of fining agent, wherein the RO is at least one of MgO, CaO, SrO, and BaO; the RE 2 O 3 is Y 2 O 3 , La 2 At least one of O 3 , Gd 2 O 3 , Ce 2 O 3 , Yb 2 O 3 and Lu 2 O 3 , and based on the total molar amount of each component in the composition of the alkali-free glass substrate, said alkali-free The content of each component in the composition of the glass substrate is calculated in terms of mole percentages: 82mol% ≤SiO 2 + Al 2 O 3 ≤84mol%, 0.8≤CaO / (CaO + SrO) ≤1.0, 0.58≤ (MgO + BaO) / ΣRO≤0.8, the range of C value is 1.03-1.12, where C value is calculated by the following formula:

C=0.5×SiO2 +P1 ×Al2 O3 +P2 ×(CaO+SrO)+P3 ×(MgO+BaO+ZnO)+P4 ×RE2 O3 ，C = 0.5 × SiO 2 + P 1 × Al 2 O 3 + P 2 × (CaO + SrO) + P 3 × (MgO + BaO + ZnO) + P 4 × RE 2 O 3 ,

其中，SiO2 、Al2 O3 、MgO、CaO、SrO、BaO、ZnO、RE2 O3 各自代表該成分占無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比，0.8≤P1 ≤1.3，7≤P2 ≤10，1.5≤P3 ≤3，-35≤P4 ≤-20，ΣRO表示MgO、CaO、SrO和BaO各自占所述無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比之和。Among them, SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, and RE 2 O 3 each represent the molar percentage of the component to the total molar amount of each component in the composition of the alkali-free glass substrate, 0.8 ≦ P 1 ≤ 1.3, 7 ≤ P 2 ≤ 10, 1.5 ≤ P 3 ≤ 3, -35 ≤ P 4 ≤ -20, ΣRO means that MgO, CaO, SrO, and BaO each account for each component in the composition of the alkali-free glass substrate Sum of the mole percentage of the total mole.

在另一種較佳的實施方式中，所述無鹼玻璃基板在10重量%的HF溶液中的侵蝕量為4.6-5.5mg/cm2 ，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成包括：71-72mol%的SiO2 、12-13mol%的Al2 O3 、0-1mol%的ZnO、15-16mol%的RO和0.01-0.3mol%的RE2 O3 ，0.1-0.3mol%的澄清劑，其中，所述RO為MgO、CaO、SrO和BaO中的至少一種；所述RE2 O3 為Y2 O3 、La2 O3 、Gd2 O3 、Ce2 O3 、Yb2 O3 和Lu2 O3 中的至少一種，並且以無鹼玻璃基板的組成中各成分的總莫耳量為基準，所述無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：82mol%≤SiO2 +Al2 O3 ≤84mol%、0.8≤CaO/（CaO+SrO）≤1.0、0.58≤（MgO+BaO）/ΣRO≤0.8、C值的範圍為1.03-1.12，其中，C值由下式計算得出：In another preferred embodiment, the erosion amount of the alkali-free glass substrate in a 10% by weight HF solution is 4.6-5.5 mg / cm 2 , and the total mole of each component in the composition of the alkali-free glass substrate is The amount is based on the composition of the alkali-free glass substrate including: 71-72 mol% of SiO 2 , 12-13 mol% of Al 2 O 3 , 0-1 mol% of ZnO, 15-16 mol% of RO, and 0.01-0.3 mol % RE 2 O 3 , 0.1-0.3 mol% clarifying agent, wherein the RO is at least one of MgO, CaO, SrO and BaO; the RE 2 O 3 is Y 2 O 3 , La 2 O 3 At least one of Gd 2 O 3 , Ce 2 O 3 , Yb 2 O 3 and Lu 2 O 3 , and based on the total molar amount of each component in the composition of the alkali-free glass substrate, the alkali-free glass substrate The content of each component in the composition is calculated according to the mole percentage: 82mol% ≤SiO 2 + Al 2 O 3 ≤84mol%, 0.8≤CaO / (CaO + SrO) ≤1.0, 0.58≤ (MgO + BaO) / ΣRO≤ The range of 0.8 and C value is 1.03-1.12, where the C value is calculated by the following formula:

C=0.5×SiO2 +P1 ×Al2 O3 +P2 ×(CaO+SrO)+P3 ×(MgO+BaO+ZnO)+P4 ×RE2 O3 ，C = 0.5 × SiO 2 + P 1 × Al 2 O 3 + P 2 × (CaO + SrO) + P 3 × (MgO + BaO + ZnO) + P 4 × RE 2 O 3 ,

其中，SiO2 、Al2 O3 、MgO、CaO、SrO、BaO、ZnO、RE2 O3 各自代表該成分占無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比，0.8≤P1 ≤1.3，7≤P2 ≤10，1.5≤P3 ≤3，-35≤P4 ≤-20，ΣRO表示MgO、CaO、SrO和BaO各自占所述無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比之和。Among them, SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, and RE 2 O 3 each represent the molar percentage of the component to the total molar amount of each component in the composition of the alkali-free glass substrate, 0.8 ≦ P 1 ≤ 1.3, 7 ≤ P 2 ≤ 10, 1.5 ≤ P 3 ≤ 3, -35 ≤ P 4 ≤ -20, ΣRO means that MgO, CaO, SrO, and BaO each account for each component in the composition of the alkali-free glass substrate Sum of the mole percentage of the total mole.

根據本發明，當所述澄清劑為硫酸鹽時，所述硫酸鹽可以是硫酸鍶、硫酸鋇和硫酸鈣中的至少一種，較佳為硫酸鋇，這種澄清劑在高溫分解時產生O2 和SO2 ，對玻璃液中的氣泡的長大或溶解起著重要的表面活性劑作用、介面湍動作用、高溫排氣作用和均化作用。當所述澄清劑為硝酸鹽時，所述硝酸鹽可以選自硝酸鍶和/或硝酸鋇，較佳地，所述硫酸鹽與氧化劑硝酸鹽配合使用，以防硫酸鹽發生低溫分解。當所述澄清劑為氧化錫或氧化亞錫時，可以通過錫元素的變價來實現攜氧和釋氧，玻璃配合料在低溫熔解時，低價錫離子（氧化亞錫）吸收氧氣轉變成高價錫離子（氧化錫），達到高溫澄清溫度時，高價錫離子所吸收的氧氣開始釋放，通過其釋放的氧氣來吸收合併玻璃液中其他氣體，最終排出到玻璃液中，在玻璃配合料熔化過程中，氣體與玻璃液之間發生溶解和反應。玻璃液中溶解氣體的飽和度越大，玻璃液中氣泡內分壓越低，則氣體增長的速度也越快，進而使氣泡增大而上升排出。反之，如果氣泡內氣體的分壓大於玻璃液中溶解的氣體的分壓，則氣泡內的氣體將被溶解而使氣泡變小，甚至完全溶解而消失，從而達到使玻璃液澄清的效果。According to the present invention, when the fining agent is a sulfate, the sulfate may be at least one of strontium sulfate, barium sulfate, and calcium sulfate, and preferably barium sulfate. Such a clarifier generates O 2 during high-temperature decomposition. And SO 2 , play an important role in the growth or dissolution of bubbles in the glass liquid, interface turbulence, high temperature exhaust and homogenization. When the clarifying agent is a nitrate, the nitrate may be selected from strontium nitrate and / or barium nitrate. Preferably, the sulfate is used in combination with the oxidant nitrate to prevent low-temperature decomposition of the sulfate. When the fining agent is tin oxide or stannous oxide, oxygen can be carried and released through the valence of tin element. When the glass batch melts at low temperature, the low-cost tin ion (tin oxide) absorbs oxygen and turns into a high price. Tin ions (tin oxide). When the high-temperature clarification temperature is reached, the oxygen absorbed by the high-valent tin ions begins to be released, and the other gases in the molten glass liquid are absorbed by the released oxygen, and finally discharged into the glass liquid, during the glass batch melting process. In the process, gas and glass liquid dissolve and react. The greater the saturation of the dissolved gas in the glass liquid, and the lower the partial pressure of the bubbles in the glass liquid, the faster the gas will grow, and then the bubbles will increase and discharge. Conversely, if the partial pressure of the gas in the bubble is greater than the partial pressure of the dissolved gas in the glass liquid, the gas in the bubble will be dissolved to make the bubble smaller, or even completely dissolved and disappeared, thereby achieving the effect of clarifying the glass liquid.

本發明第二方面提供了製備上述無鹼玻璃基板的方法，該方法包括：將由本發明提供的無鹼玻璃基板的組成中各成分混合，然後依次進行熔融、脫泡、均質化、成型、冷卻、切割、拋光、洗滌和烘乾。According to a second aspect of the present invention, there is provided a method for preparing the above-mentioned alkali-free glass substrate, the method comprising: mixing the components in the composition of the alkali-free glass substrate provided by the present invention, and then sequentially melting, defoaming, homogenizing, forming, and cooling , Cutting, polishing, washing and drying.

較佳情況下，製備上述無鹼玻璃基板的方法包括：將由本發明提供的無鹼玻璃基板的組成中各成分在攪拌的條件下混合均勻，將混合料倒入鉑金坩堝中，然後在1550-1600℃的電阻爐中加熱3-5小時至熔融，並使用鉑金棒攪拌以脫泡、均質化。將熔製好的玻璃液澆注入不銹鋼鑄鐵模具內，成形為規定的塊狀玻璃製品，然後將玻璃製品在退火爐中退火1-3小時，之後關閉電源隨爐冷卻至20-30℃。將玻璃製品進行切割、研磨、拋光，然後用去離子水洗滌乾淨並烘乾。Preferably, the method for preparing the above-mentioned alkali-free glass substrate includes: mixing the components in the composition of the alkali-free glass substrate provided by the present invention under agitation conditions, pouring the mixture into a platinum crucible, and then Heat in a resistance furnace at 1600 ° C for 3-5 hours to melt, and stir with a platinum rod to defoam and homogenize. The molten glass is poured into a stainless steel cast iron mold to form a predetermined block glass product, and then the glass product is annealed in an annealing furnace for 1-3 hours, and then the power is turned off and the furnace is cooled to 20-30 ° C. The glass products are cut, ground, polished, then washed with deionized water and dried.

本發明協力廠商面提供了由上述方法製備的無鹼玻璃基板。The third party of the present invention provides an alkali-free glass substrate prepared by the above method.

較佳地，所述無鹼玻璃基板的厚度不超過1mm，更佳地，所述無鹼玻璃基板的厚度不超過0.7mm。Preferably, the thickness of the alkali-free glass substrate does not exceed 1 mm, and more preferably, the thickness of the alkali-free glass substrate does not exceed 0.7 mm.

以下將通過實施例對本發明進行詳細描述。Hereinafter, the present invention will be described in detail through examples.

以下實施例1-15和對比例1-7中，無鹼玻璃基板的密度按照ASTM C-693中規定的方法測得，單位為g/cm3 。In the following Examples 1-15 and Comparative Examples 1-7, the density of the alkali-free glass substrate is measured according to the method specified in ASTM C-693, and the unit is g / cm 3 .

無鹼玻璃基板在50-350℃的熱膨脹係數通過臥式膨脹儀，按照ASTM E-228中規定的方法測得，單位為10-7 /℃。The thermal expansion coefficient of the alkali-free glass substrate at 50-350 ° C is measured by a horizontal dilatometer according to the method specified in ASTM E-228, and the unit is 10 -7 / ° C.

無鹼玻璃基板的楊氏模量按照ASTM C-623中規定的方法測得，單位為GPa。The Young's modulus of the alkali-free glass substrate is measured in accordance with the method specified in ASTM C-623, and the unit is GPa.

無鹼玻璃基板的退火點和應變點通過三點測試儀，按照ASTM C-336中規定的方法測得，單位為℃。The annealing point and strain point of the alkali-free glass substrate are measured by a three-point tester according to the method specified in ASTM C-336, and the unit is ° C.

無鹼玻璃基板的玻璃高溫黏溫曲線通過旋轉高溫黏度計，按照ASTM C-965中規定的方法測得，其中，200P黏度時對應的溫度記為Tm ，單位為℃；35000P黏度對應的成型溫度記為T35000 ，單位為℃。The high-temperature viscosity-temperature curve of the alkali-free glass substrate is measured by a rotating high-temperature viscometer according to the method specified in ASTM C-965. Among them, the temperature corresponding to the viscosity at 200P is recorded as T m , the unit is ℃; the molding corresponding to the viscosity of 35000P The temperature is recorded as T 35000 in ° C.

無鹼玻璃基板在10重量%的HF溶液中的侵蝕量指的是在20℃，單位面積的無鹼玻璃基板在濃度為10重量%的HF溶液中浸泡20min損失的重量，記為CHF ，單位為mg/cm2 。Erosion-alkali glass substrate in 10 wt% HF solution refers to the 20 ℃, alkali-free glass per area of substrate at a concentration of 10 wt% HF solution soak 20min weight loss, referred to as C HF, The unit is mg / cm 2 .

無鹼玻璃基板中d＞0.1mm氣泡數指每公斤無鹼玻璃基板中泡徑＞0.1mm的氣泡數目。The number of bubbles of d> 0.1mm in the alkali-free glass substrate refers to the number of bubbles of bubble diameter> 0.1mm per kilogram of the alkali-free glass substrate.

實施例1-15和對比例1-7Examples 1-15 and Comparative Examples 1-7

將無鹼玻璃基板的組成中各成分在攪拌的條件下混合均勻，將混合料倒入鉑金坩堝中，然後在1580℃的電阻爐中加熱4小時至熔融，並使用鉑金棒攪拌以脫泡、均質化。將熔製好的玻璃液澆注入不銹鋼鑄鐵模具內，成形為規定的塊狀玻璃製品，然後將玻璃製品在退火爐中退火2小時，之後關閉電源隨爐冷卻至25℃。將玻璃製品進行切割、研磨、拋光，然後用去離子水洗滌乾淨並烘乾，製得厚度為0.5mm的無鹼玻璃基板。The components in the composition of the alkali-free glass substrate are mixed uniformly under stirring conditions, the mixture is poured into a platinum crucible, and then heated in a resistance furnace at 1580 ° C. for 4 hours to be melted, and the platinum rod is used to defoam, Homogenization. The molten glass is poured into a stainless steel cast iron mold to form a predetermined block glass product, and then the glass product is annealed in an annealing furnace for 2 hours, and then the power is turned off and the furnace is cooled to 25 ° C. The glass product is cut, ground, polished, and then washed with deionized water and dried to obtain an alkali-free glass substrate having a thickness of 0.5 mm.

製備實施例1-15和對比例1-7中的無鹼玻璃基板所用的物料、用量以及對製得的無鹼玻璃基板的各種性能的測試結果如表1和表2所示，其中，對比例6中的無鹼玻璃基板按照CN105601105A的實施例4公開的配方製備得到，對比例7中的無鹼玻璃基板按照CN105992749A的實施例3公開的配方製備得到。Table 1 and Table 2 show the test results of the materials, amounts, and various properties of the alkali-free glass substrates prepared in Examples 1-15 and Comparative Examples 1-7. The alkali-free glass substrate in Comparative Example 6 was prepared according to the formula disclosed in Example 4 of CN105601105A, and the alkali-free glass substrate in Comparative Example 7 was prepared according to the formula disclosed in Example 3 of CN105992749A.

實施例1-15和對比例1-7製得的無鹼玻璃基板的C值由下式計算得出：The C value of the alkali-free glass substrate prepared in Examples 1-15 and Comparative Examples 1-7 is calculated from the following formula:

C=0.5×SiO2 +P1 ×Al2 O3 +P2 ×(CaO+SrO)+P3 ×(MgO+BaO+ZnO)+P4 ×RE2 O3 ，C = 0.5 × SiO 2 + P 1 × Al 2 O 3 + P 2 × (CaO + SrO) + P 3 × (MgO + BaO + ZnO) + P 4 × RE 2 O 3 ,

其中，P1 =1，P2 =8，P3 =2，P4 =-30，SiO2 、Al2 O3 、MgO、CaO、SrO、BaO、ZnO、RE2 O3 各自代表該成分占無鹼玻璃基板的組成中各成分的總莫耳量的莫耳百分比。 表1 表2 Among them, P 1 = 1, P 2 = 8, P 3 = 2, P 4 = -30, SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, and RE 2 O 3 each represent the component accounted for The molar percentage of the total molar amount of each component in the composition of the alkali-free glass substrate. Table 1 Table 2

通過表1和表2的結果可以看出，由本發明提供的無鹼玻璃基板或者採用本發明提供的方法製備的無鹼玻璃基板可以同時達到以下的技術指標：在濃度為10重量%的HF溶液的侵蝕量在3.8-5.5mg/cm2 之間；密度小於2.63g/cm3 ；50～350℃的熱膨脹係數小於39×10-7 /℃；黏度為35000P時對應的溫度低於1370℃；黏度為200P時對應的溫度低於1670℃；應變點在750℃以上；楊氏模量大於75GPa；每公斤無鹼玻璃基板中泡徑大於0.1mm的氣泡肉眼不可見，即由本發明提供的無鹼玻璃基板或者採用本發明提供的方法製備的無鹼玻璃基板兼具密度小、機械強度高、比模數高、熱穩定性好、熔化溫度低、耐化性強和應變點溫度高等特點，綜合性能優異。此外，由本發明提供的無鹼玻璃基板或採用本發明提供的方法製備的無鹼玻璃基板的組成中的成分不含任何有毒物質，生產過程環境友好，即使澄清劑不使用As2 O3 和/或Sb2 O3 也具有較低的氣態夾雜物等優點，使產線良率得到一定改善，同時可以降低燃料、電力等生產成本，經濟性好。It can be seen from the results of Tables 1 and 2 that the alkali-free glass substrate provided by the present invention or the alkali-free glass substrate prepared by the method provided by the present invention can simultaneously achieve the following technical indicators: HF solution at a concentration of 10% by weight The amount of erosion is between 3.8-5.5mg / cm 2 ; the density is less than 2.63g / cm 3 ; the thermal expansion coefficient of 50 ～ 350 ℃ is less than 39 × 10 -7 / ℃; the corresponding temperature is lower than 1370 ℃ when the viscosity is 35000P; When the viscosity is 200P, the corresponding temperature is lower than 1670 ° C; the strain point is above 750 ° C; the Young's modulus is greater than 75GPa; bubbles with a bubble diameter greater than 0.1mm per kilogram of the alkali-free glass substrate are not visible to the naked eye, that is, Alkali glass substrates or alkali-free glass substrates prepared by the method provided by the invention have the characteristics of low density, high mechanical strength, high specific modulus, good thermal stability, low melting temperature, strong chemical resistance, and high strain point temperature. Excellent overall performance. In addition, the components in the composition of the alkali-free glass substrate provided by the present invention or the alkali-free glass substrate prepared by the method provided by the present invention do not contain any toxic substances, and the production process is environmentally friendly, even if the clarifying agent does not use As 2 O 3 and / Or Sb 2 O 3 also has the advantages of lower gaseous inclusions, which improves the production line yield to a certain extent, and can reduce production costs such as fuel and electricity, and is economical.

對比例1中的無鹼玻璃基板的C值超出本申請限定的範圍，並且對比例1中含有較少的SiO2 和Al2 O3 的合量、RO的含量過高，製得的無鹼玻璃基板在濃度為10重量%的HF溶液的侵蝕量較高、熱膨脹係數較高、耐化性較差、機械強度較差、密度較高；對比例2中的無鹼玻璃基板的C值以及特定成分之間的配合比值均超出本申請限定的範圍，並且含有較少的SiO2 和Al2 O3 的合量、RO的含量過高，製得的無鹼玻璃基板在濃度為10重量%的HF溶液的侵蝕量較高、熱膨脹係數較高、耐化性較差、機械強度較差、密度較高；對比例3中的無鹼玻璃基板的C值不滿足本申請限定的範圍，RE2 O3 的含量過高，即使其含有較高的SiO2 和Al2 O3 的合量，可以保障在50～350℃的熱膨脹係數較低，但是其在濃度為10重量%的HF溶液的侵蝕量較高、耐化性較差、密度較高，並且使用的無毒澄清劑SrCl2 不能有效澄清無鹼玻璃，導致每公斤無鹼玻璃基板中泡徑大於0.1mm的氣泡數量過多；雖然對比例4中的無鹼玻璃基板的C值以及特定成分之間的配合比值均滿足本申請限定的範圍，並且含有較高的SiO2 和Al2 O3 的合量和適當的RO含量，具有較低的熱膨脹係數、較高的機械強度、較低的密度，但是對比例4中的無鹼玻璃基板在濃度為10重量%的HF溶液的侵蝕量較高，耐化性較差，且熱穩定性關鍵指標應變點溫度過低，同時使用的無毒澄清劑CaF2 不能有效澄清無鹼玻璃，導致每公斤無鹼玻璃基板中泡徑大於0.1mm的氣泡數量過多；對比例5中的無鹼玻璃基板的C值以及特定成分之間的配合比值均滿足本申請限定的範圍，但是含有較低的SiO2 和Al2 O3 的合量，添加了B2 O3 ，無法有效提高無鹼玻璃基板的應變點溫度，難以有效控制其在濃度為10重量%的HF溶液的侵蝕量，不能保證無鹼玻璃基板兼具優良的熱穩定性、化學穩定性和機械穩定性，同時使用的澄清劑Sb2 O3 毒性較大，且不能有效澄清無鹼玻璃，導致每公斤無鹼玻璃基板中泡徑大於0.1mm的氣泡數量較多；對比例6中的無鹼玻璃基板的C值低於本申請限定的範圍，並且對比例6中含有較少的SiO2 以及SiO2 和Al2 O3 的合量、RO和RE2 O3 的含量過高，製得的無鹼玻璃基板的密度較高，熱穩定性關鍵指標應變點溫度過低，機械強度較差；對比例7中含有過低的SiO2 和Al2 O3 的合量、RO的含量過高、且不含ZnO和RE2 O3 以及澄清劑，製得的無鹼玻璃基板在濃度為5重量%的HF溶液的侵蝕量較低（參見CN105992749A的實施例3），但是按照本發明的條件10重量%的HF溶液測試的話，其侵蝕量將會過高，不利於大批量工業生產，熱穩定性關鍵指標應變點溫度過低，且不能有效澄清無鹼玻璃，導致每公斤無鹼玻璃基板中泡徑大於0.1mm的氣泡數量較多。The C value of the alkali-free glass substrate in Comparative Example 1 exceeds the range defined in the present application, and the amount of the combined SiO 2 and Al 2 O 3 and the content of RO in Comparative Example 1 are too high, and the alkali-free produced The glass substrate has a higher erosion amount, a higher thermal expansion coefficient, a lower chemical resistance, a lower mechanical strength, and a higher density in a 10% by weight HF solution; the C value and specific components of the alkali-free glass substrate in Comparative Example 2 The blending ratio between them is beyond the range defined in the present application, and contains a small amount of SiO 2 and Al 2 O 3 , and the content of RO is too high. The alkali-free glass substrate obtained has a concentration of 10% by weight of HF. high erosion amount of the solution, the higher coefficient of thermal expansion, poor chemical resistance, poor mechanical strength, higher density; C for alkali-free glass substrate of Comparative Example 3 did not satisfy the range defined in the present application, RE 2 O 3 is The content is too high, even if it contains a high combined amount of SiO 2 and Al 2 O 3 , it can ensure that the thermal expansion coefficient is low at 50 to 350 ° C., but its erosion amount is higher in a 10% by weight HF solution , poor chemical resistance, higher density, and using no toxic refining agents SrCl 2 Effectively clarify alkali-free glass, resulting in too many bubbles with a bubble diameter greater than 0.1 mm per kilogram of alkali-free glass substrate; although the C value of the alkali-free glass substrate in Comparative Example 4 and the blending ratio between specific components meet the limits of this application Range, and contains a higher combined amount of SiO 2 and Al 2 O 3 and an appropriate RO content, has a lower thermal expansion coefficient, a higher mechanical strength, a lower density, but is alkali-free in Comparative Example 4 The glass substrate has a higher erosion amount in HF solution with a concentration of 10% by weight, poor chemical resistance, and the key point of thermal stability, the strain point temperature is too low, and the non-toxic clarifier CaF 2 used at the same time cannot effectively clarify alkali-free glass, resulting in There are too many bubbles with a bubble diameter greater than 0.1 mm per kilogram of the alkali-free glass substrate; the C value of the alkali-free glass substrate in Comparative Example 5 and the ratio of the specific components meet the range defined in this application, but contain lower the amount of SiO 2 and Al 2 O 3 is bonded, B 2 O 3 is added, can not effectively increase the strain point temperature of the alkali-free glass substrate, it is difficult to effectively control the amount of erosion in an HF solution of a concentration of 10 wt% can not guarantee Alkali glass substrate has both excellent thermal stability, chemical and mechanical stability, while the use of clarifying agents Sb 2 O 3 toxicity, and can not effectively clarify the alkali-free glass, lead alkali glass substrate per kilogram of a bubble The number of bubbles larger than 0.1 mm is larger; the C value of the alkali-free glass substrate in Comparative Example 6 is lower than the range defined in this application, and the comparative example 6 contains less SiO 2 and SiO 2 and Al 2 O 3 The combined amount, the content of RO and RE 2 O 3 are too high, the density of the obtained alkali-free glass substrate is high, the key point of thermal stability, the strain point temperature is too low, and the mechanical strength is poor; Comparative Example 7 contains too low SiO The combined amount of 2 and Al 2 O 3 , the content of RO is too high, and ZnO and RE 2 O 3 are not included, as well as the fining agent. The alkali-free glass substrate prepared has a lower erosion amount in a HF solution with a concentration of 5 wt%. (See Example 3 of CN105992749A), but if the 10% by weight HF solution is tested under the conditions of the present invention, the amount of erosion will be too high, which is not conducive to large-scale industrial production, and the key point of thermal stability, the strain point temperature is too low, And can not effectively clarify alkali-free glass, resulting in alkali-free per kg The glass substrate has a large number of bubbles having a bubble diameter of more than 0.1 mm.

以上詳細描述了本發明的較佳實施方式，但是，本發明並不限於此。在本發明的技術構思範圍內，可以對本發明的技術方案進行多種簡單變型，包括各個技術特徵以任何其它的合適方式進行組合，這些簡單變型和組合同樣應當視為本發明所公開的內容，均屬於本發明的保護範圍。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the content disclosed in the present invention. It belongs to the protection scope of the present invention.

Claims (10)

一種無鹼玻璃基板，其特徵在於，該無鹼玻璃基板在濃度為10重量%的HF溶液中的侵蝕量小於5.5mg/cm2 ， 以無鹼玻璃基板的組成中各成分的總莫耳量為基準，該無鹼玻璃基板的組成包括：70-74mol%的SiO2 、11-14mol%的Al2 O3 、0-2.5mol%的ZnO、10-17mol%的RO和0.01-2mol%的RE2 O3 ，其中，該RO為MgO、CaO、SrO和BaO中的至少一種；該RE2 O3 為Y2 O3 、La2 O3 、Gd2 O3 、Ce2 O3 、Yb2 O3 和Lu2 O3 中的至少一種。An alkali-free glass substrate, characterized in that the amount of erosion of the alkali-free glass substrate in a 10% by weight HF solution is less than 5.5 mg / cm 2 , and the total molar amount of each component in the composition of the alkali-free glass substrate is As a benchmark, the composition of the alkali-free glass substrate includes: 70-74 mol% SiO 2 , 11-14 mol% Al 2 O 3 , 0-2.5 mol% ZnO, 10-17 mol% RO, and 0.01-2 mol% RE 2 O 3 , wherein the RO is at least one of MgO, CaO, SrO, and BaO; the RE 2 O 3 is Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Ce 2 O 3 , Yb 2 At least one of O 3 and Lu 2 O 3 . 如申請專利範圍第1項所述之無鹼玻璃基板，其中，該無鹼玻璃基板在10重量%的HF溶液中的侵蝕量為2-5.5mg/cm2 ，較佳為4.5-5.5mg/cm2 ， 以無鹼玻璃基板的組成中各成分的總莫耳量為基準，該無鹼玻璃基板的組成包括：70-73mol%的SiO2 、11.3-13.5mol%的Al2 O3 、0-2.2mol%的ZnO、12.6-16.7mol%的RO和0.01-1.2mol%的RE2 O3 ，或者，該無鹼玻璃基板的組成包括：70.4-73mol%的SiO2 、11.3-13mol%的Al2 O3 、0-2.2mol%的ZnO、12.6-16.7mol%的RO和0.01-0.7mol%的RE2 O3 。The alkali-free glass substrate according to item 1 of the scope of patent application, wherein the erosion amount of the alkali-free glass substrate in a 10% by weight HF solution is 2-5.5 mg / cm 2 , preferably 4.5-5.5 mg / cm 2 , based on the total molar amount of each component in the composition of the alkali-free glass substrate, the composition of the alkali-free glass substrate includes: 70-73 mol% of SiO 2 , 11.3-13.5 mol% of Al 2 O 3 , 0 -2.2 mol% ZnO, 12.6-16.7 mol% RO and 0.01-1.2 mol% RE 2 O 3 , or the composition of the alkali-free glass substrate includes: 70.4-73 mol% SiO 2 , 11.3-13 mol% Al 2 O 3 , 0-2.2 mol% ZnO, 12.6-16.7 mol% RO, and 0.01-0.7 mol% RE 2 O 3 . 如申請專利範圍第1或2項所述之無鹼玻璃基板，其中，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，該無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足C值的範圍為0-1.26，較佳為0.58-1.23，更佳為0.63-1.21，再更佳為0.71-1.18，再更佳為0.86-1.12，其中，C值由下式計算得出： C=0.5×SiO2 +P1 ×Al2 O3 +P2 ×(CaO+SrO)+P3 ×(MgO+BaO+ZnO)+P4 ×RE2 O3 ，其中，0.8≤P1 ≤1.3，7≤P2 ≤10，1.5≤P3 ≤3，-35≤P4 ≤-20，SiO2 、Al2 O3 、MgO、CaO、SrO、BaO、ZnO、RE2 O3 各自代表該成分占無鹼玻璃基板組成中的莫耳百分比。The alkali-free glass substrate according to item 1 or 2 of the scope of the patent application, wherein, based on the total molar amount of each component in the composition of the alkali-free glass substrate, the content of each component in the composition of the alkali-free glass substrate is as follows The Mohr percentage calculation satisfies the range of C value of 0-1.26, preferably 0.58-1.23, more preferably 0.63-1.21, even more preferably 0.71-1.18, and even more preferably 0.86-1.12, where the C value is The formula calculates: C = 0.5 × SiO 2 + P 1 × Al 2 O 3 + P 2 × (CaO + SrO) + P 3 × (MgO + BaO + ZnO) + P 4 × RE 2 O 3 , where: 0.8≤P 1 ≤1.3, 7≤P 2 ≤10, 1.5≤P 3 ≤3, -35≤P 4 ≤-20, SiO 2 , Al 2 O 3 , MgO, CaO, SrO, BaO, ZnO, RE 2 O 3 each represents the mole percentage of this component in the composition of the alkali-free glass substrate. 如申請專利範圍第1或2項所述之無鹼玻璃基板，其中，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，該無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：SiO2 +Al2 O3 ＞82mol%。The alkali-free glass substrate according to item 1 or 2 of the scope of the patent application, wherein the content of each component in the composition of the alkali-free glass substrate is based on the total molar amount of each component in the composition of the alkali-free glass substrate. The mole percentage calculation satisfies: SiO 2 + Al 2 O 3 > 82 mol%. 如申請專利範圍第1或2項所述之無鹼玻璃基板，其中，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，該無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：CaO/（CaO+SrO）≥0.4，較佳滿足CaO/（CaO+SrO）≥0.5，更佳滿足CaO/（CaO+SrO）≥0.6。The alkali-free glass substrate according to item 1 or 2 of the scope of the patent application, wherein the content of each component in the composition of the alkali-free glass substrate is based on the total molar amount of each component in the composition of the alkali-free glass substrate. The mole percentage calculation satisfies: CaO / (CaO + SrO) ≥0.4, preferably satisfies CaO / (CaO + SrO) ≥0.5, and more preferably satisfies CaO / (CaO + SrO) ≥0.6. 如申請專利範圍第1或2項所述之無鹼玻璃基板，其中，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，該無鹼玻璃基板的組成中各成分的含量按莫耳百分比計算滿足：（MgO+BaO）/ΣRO≥0.45，較佳滿足（MgO+BaO）/ΣRO≥0.51，更佳滿足（MgO+BaO）/ΣRO≥0.58，其中，ΣRO表示MgO、CaO、SrO和BaO的莫耳百分比之和。The alkali-free glass substrate according to item 1 or 2 of the scope of the patent application, wherein the content of each component in the composition of the alkali-free glass substrate is based on the total molar amount of each component in the composition of the alkali-free glass substrate. The mole percentage calculation satisfies: (MgO + BaO) /ΣRO≥0.45, preferably satisfies (MgO + BaO) /ΣRO≥0.51, and more preferably satisfies (MgO + BaO) /ΣRO≥0.58, where ΣRO represents MgO, CaO, The sum of the mole percentages of SrO and BaO. 如申請專利範圍第1或2項所述之無鹼玻璃基板，其中，該無鹼玻璃基板的組成中的成分還包括澄清劑，以無鹼玻璃基板的組成中各成分的總莫耳量為基準，該澄清劑的含量不超過1mol%。The alkali-free glass substrate according to item 1 or 2 of the scope of the patent application, wherein the composition in the composition of the alkali-free glass substrate further includes a clarifying agent, and the total molar amount of each component in the composition of the alkali-free glass substrate is On the basis, the content of the fining agent does not exceed 1 mol%. 如申請專利範圍第7項所述之無鹼玻璃基板，其中，該澄清劑為硫酸鹽、硝酸鹽、氧化錫和氧化亞錫中的至少一種。The alkali-free glass substrate according to item 7 of the scope of patent application, wherein the clarifying agent is at least one of sulfate, nitrate, tin oxide, and stannous oxide. 一種無鹼玻璃基板之製備方法，其特徵在於，該方法包括：將申請專利範圍第1至8項中任一項所述之無鹼玻璃基板的組成中各成分混合，然後依次進行熔融、脫泡、均質化、成型、冷卻、切割、拋光、洗滌和烘乾。A method for preparing an alkali-free glass substrate, characterized in that the method comprises: mixing the components in the composition of the alkali-free glass substrate according to any one of claims 1 to 8 of the scope of the patent application, and then sequentially melting and demelting Soaking, homogenizing, forming, cooling, cutting, polishing, washing and drying. 一種由申請專利範圍第9項所述之製備方法製備的無鹼玻璃基板。An alkali-free glass substrate prepared by the preparation method described in item 9 of the scope of application for a patent.
TW107113046A 2017-04-18 2018-04-17 Alkali-free glass substrate and preparation method thereof TWI667216B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
??201710255130.3 2017-04-18
CN201710255130.3A CN107129142B (en) 2017-04-18 2017-04-18 Alkali-free glass substrate and preparation method thereof

Publications (2)

Publication Number Publication Date
TW201831418A true TW201831418A (en) 2018-09-01
TWI667216B TWI667216B (en) 2019-08-01

Family

ID=59716815

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107113046A TWI667216B (en) 2017-04-18 2018-04-17 Alkali-free glass substrate and preparation method thereof

Country Status (3)

Country Link
CN (1) CN107129142B (en)
TW (1) TWI667216B (en)
WO (1) WO2018192423A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107129142B (en) * 2017-04-18 2021-02-09 东旭光电科技股份有限公司 Alkali-free glass substrate and preparation method thereof
CN108455867A (en) * 2017-12-29 2018-08-28 安徽杜氏高科玻璃有限公司 A kind of preparation method of heat-resistant antifriction glass
CN109320070A (en) * 2018-10-16 2019-02-12 东旭科技集团有限公司 Glass composition, alumina silicate glass and its preparation method and application
CN109231819B (en) 2018-10-16 2021-04-09 东旭光电科技股份有限公司 Alkali-free aluminosilicate glass and preparation method and application thereof
CN109160727B (en) 2018-10-16 2020-10-13 东旭光电科技股份有限公司 Aluminosilicate glass composition, aluminosilicate glass, and preparation method and application thereof
CN110550858B (en) * 2019-07-12 2023-05-23 重庆鑫景特种玻璃有限公司 Float glass clarifier
CN113562979B (en) * 2021-07-09 2022-11-04 山东玻纤集团股份有限公司 Low-expansion-coefficient glass fiber composition and preparation method thereof
CN113880429A (en) * 2021-09-28 2022-01-04 彩虹显示器件股份有限公司 Alkali-free substrate glass and thinning method thereof
CN114163104A (en) * 2021-12-21 2022-03-11 北京工业大学 Melting and clarifying method suitable for ultrahigh-aluminum cover plate glass and transparent glass ceramics

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8187715B2 (en) * 2008-05-13 2012-05-29 Corning Incorporated Rare-earth-containing glass material and substrate and device comprising such substrate
CN102471134B (en) * 2009-07-02 2015-04-15 旭硝子株式会社 Alkali-free glass and method for producing same
JP5914453B2 (en) * 2012-12-28 2016-05-11 ＡｖａｎＳｔｒａｔｅ株式会社 Glass substrate for display and manufacturing method thereof
CN104326662B (en) * 2013-12-31 2017-07-04 东旭集团有限公司 A kind of alkali-free alumina silicate glass of not boracic
JP6575223B2 (en) * 2014-08-27 2019-09-18 Ａｇｃ株式会社 Alkali-free glass
CN105859128B (en) * 2016-04-06 2018-11-27 芜湖东旭光电装备技术有限公司 A kind of glass composition, low surface tension alkali-free glass and its preparation method and application
CN105948489B (en) * 2016-05-04 2019-03-01 东旭科技集团有限公司 Prepare aluminium borosilicate glass composition, aluminium borosilicate glass and its preparation method and application
CN107129142B (en) * 2017-04-18 2021-02-09 东旭光电科技股份有限公司 Alkali-free glass substrate and preparation method thereof

Also Published As

Publication number Publication date
WO2018192423A1 (en) 2018-10-25
CN107129142A (en) 2017-09-05
CN107129142B (en) 2021-02-09
TWI667216B (en) 2019-08-01

Similar Documents

Publication Publication Date Title
TWI667216B (en) Alkali-free glass substrate and preparation method thereof
CN107216032B (en) Composition for glass, aluminosilicate glass, and preparation method and application thereof
TWI675017B (en) Composition used for glass, alkaline earth aluminosilicate glass, making method of alkaline earth aluminosilicate glass, and application of composition or alkaline earth aluminosilicate glass
JP4904062B2 (en) Composition of alkali metal-free glass, formulation and use thereof
JP2013151407A (en) Alkali-free glass
CN109678341B (en) Alkali-free glass composition, alkali-free glass and application
WO2010084670A1 (en) Reinforced glass, and glass
CN105121374A (en) Glass
WO2012063643A1 (en) Alkali-free glass
JP2012106919A (en) Alkali-free glass
CN110668694A (en) Alkali-free glass
CN104326662B (en) A kind of alkali-free alumina silicate glass of not boracic
TW201213267A (en) Photovoltaic low iron flat glass batches containing alkali-free alumino-borosilicate display glass cullet
CN113045197A (en) Glass
WO2019233291A1 (en) Phosphorus-free alkali-free glass batch suitable for float shaping and phosphorus-free alkali-free glass prepared therefrom
WO2020078375A1 (en) Composition for glass, and aluminosilicate glass and preparation method therefor and use thereof
JP7087102B2 (en) Aluminosilicate glass and its preparation method
CN109020195B (en) Aluminosilicate glass and preparation method and application thereof
CN102584008B (en) Formula for light environment-friendly alkali-free boron-alumina silicate glass used in liquid crystal display (LCD)
CN105731790B (en) A kind of alkali-free alumina silicate glass composition, alkali-free alumina silicate glass and its preparation method and application
CN114772928A (en) Alkali-free aluminosilicate substrate glass and preparation method and application thereof
TWI230145B (en) Substrate glass for plate panel display
CN117602823A (en) Composition for alkali-free aluminoborosilicate glass, and preparation method and application thereof
CN118026526A (en) Glass composition, high-performance electronic glass substrate and preparation method thereof