TW201414683A - Molten salt for use in toughening glass, production method of toughened glass, and life extension method of molten salt for use in toughening glass - Google Patents

Molten salt for use in toughening glass, production method of toughened glass, and life extension method of molten salt for use in toughening glass Download PDF

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TW201414683A
TW201414683A TW102133701A TW102133701A TW201414683A TW 201414683 A TW201414683 A TW 201414683A TW 102133701 A TW102133701 A TW 102133701A TW 102133701 A TW102133701 A TW 102133701A TW 201414683 A TW201414683 A TW 201414683A
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molten salt
glass
potassium
added
potassium nitrate
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Taku Yamada
Kazuyoshi Kurashima
Kunio Watanabe
Toshifumi Nihei
Jun Irisawa
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions

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  • Organic Chemistry (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)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)

Abstract

Given a molten salt containing potassium nitrate used for chemically toughening glass, the purpose of the present invention is to provide a molten salt with a well-extended use life. This molten salt for use in toughening glass is used for forming a compressive stress layer on a glass surface by means of ion exchange, contains potassium nitrate and further contains carbonate anions and/or phosphate anions.

Description

玻璃強化用熔融鹽、強化玻璃之製造方法及玻璃強化用熔融鹽之壽命延長方法 Method for producing molten salt for glass reinforcement, method for producing tempered glass, and method for extending life of molten salt for glass reinforcement

本發明係關於一種玻璃強化用熔融鹽、強化玻璃之製造方法、及玻璃強化用熔融鹽之壽命延長方法。 The present invention relates to a molten salt for glass reinforcement, a method for producing tempered glass, and a method for extending the life of molten salt for glass reinforcement.

於數位相機、行動電話及PDA(Personal Digital Assistants，個人數位助理)等顯示器裝置等之覆蓋玻璃及顯示器之玻璃基板中，使用利用離子交換等進行化學強化處理之玻璃(以下，亦稱為化學強化玻璃)。雖玻璃之理論強度較高，但由於損傷而導致強度大幅下降。與未強化之玻璃相比，化學強化玻璃之機械強度較高，而防止玻璃表面受到損傷，因此較佳用於該等用途。 In a glass substrate covering a glass or a display such as a digital camera, a mobile phone, or a display device such as a PDA (Personal Digital Assistants), a glass that is chemically strengthened by ion exchange or the like (hereinafter, also referred to as chemical strengthening) is used. glass). Although the theoretical strength of glass is high, the strength is greatly reduced due to damage. Chemically strengthened glass is preferred for such applications because it has a higher mechanical strength than the unreinforced glass and prevents damage to the glass surface.

利用離子交換之化學強化處理係藉由將玻璃中所含有之較小之離子半徑之金屬離子(例如Na離子)與更大之離子半徑之金屬離子(例如，K離子)進行置換，而於玻璃表面產生壓縮應力層而使玻璃強度提高之處理。 The chemical strengthening treatment by ion exchange is performed by replacing a metal ion (for example, Na ion) having a smaller ionic radius contained in the glass with a metal ion (for example, K ion) having a larger ionic radius. A process in which a compressive stress layer is formed on the surface to increase the strength of the glass.

於玻璃組成中含有Na2O之情形時，將玻璃浸漬於含有K離子之熔融鹽(無機鉀鹽)中，將玻璃中之Na離子與熔融鹽中之K離子進行離子交換。熔融鹽可使用強化處理溫度下成為熔融狀態之無機鉀鹽，但其中使用硝酸鉀之情況較多。 When Na 2 O is contained in the glass composition, the glass is immersed in a molten salt (inorganic potassium salt) containing K ions, and the Na ions in the glass are ion-exchanged with the K ions in the molten salt. As the molten salt, an inorganic potassium salt which is in a molten state at a strengthening treatment temperature can be used, but potassium nitrate is often used therein.

可列舉表面壓縮應力(Compressive Stress：CS)作為化學強化玻璃之評價方法之一種。以硝酸鉀為主成分之化學強化用熔融鹽於化學強 化處理後可賦予玻璃最高之CS值僅限於使用未供於離子交換之熔融鹽(新的熔融鹽)時，實際上根據累積玻璃處理面積，獲得之CS值緩慢下降。 Compressive Stress (CS) can be cited as one of the evaluation methods of chemically strengthened glass. Chemically strengthened molten salt containing potassium nitrate as a main component The highest CS value that can be imparted to the glass after the treatment is limited to the use of the molten salt (new molten salt) that is not supplied for ion exchange, and the CS value obtained is actually gradually decreased according to the cumulative glass treated area.

CS值下降之主要原因在於：硝酸鉀熔融鹽被因離子交換而自玻璃中溶出之Na離子稀釋，因此可知Na離子濃度與CS值下降存在關聯。因此，考慮到如下方法，即若無法獲得某固定值以上之CS值，則將熔融鹽之全部或一部分交換成新的熔融鹽。然而，於該方法中，有熔融鹽之交換頻率變高而高成本化或者由於交換時之停工時間而導致處理效率下降之擔憂。 The main reason for the decrease in the CS value is that the potassium nitrate molten salt is diluted by the Na ions eluted from the glass by ion exchange, and thus it is known that the Na ion concentration is correlated with the decrease in the CS value. Therefore, a method is considered in which, if a CS value of a certain fixed value or more is not obtained, all or a part of the molten salt is exchanged into a new molten salt. However, in this method, there is a concern that the exchange frequency of the molten salt becomes high and the cost is high or the processing efficiency is lowered due to the downtime at the time of exchange.

因此，對延長熔融鹽之使用壽命(life)之方法進行研究。例如於非專利文獻1中揭示有一種方法，其藉由於硝酸鉀熔融鹽中預先添加二氧化矽而緩和由Na離子引起之影響。 Therefore, research has been conducted on a method of prolonging the life of a molten salt. For example, Non-Patent Document 1 discloses a method for alleviating the influence by Na ions by adding cerium oxide to the molten salt of potassium nitrate in advance.

先前技術文獻Prior technical literature 非專利文獻Non-patent literature

非專利文獻1：Nagaoka Gijutsu Kagaku Daigaku Kenkyu Hokoku (1982), 4, 1-4。 Non-Patent Document 1: Nagaoka Gijutsu Kagaku Daigaku Kenkyu Hokoku (1982), 4, 1-4.

然而，關於非專利文獻1所記載之利用添加二氧化矽之效果，僅記載如下主旨：於對於摻雜二氧化矽0.1%，相對於硝酸鉀之硝酸鈉以0.2%，即Na離子為500ppm之極少量混合存在之情形時熔融鹽之壽命變長，關於Na離子量較多之情形，並未提及。 However, regarding the effect of adding cerium oxide described in Non-Patent Document 1, only the following is described: 0.1% for doped ceria, 0.2% for sodium nitrate, and 500 ppm for Na ions. The life of the molten salt becomes long in the case where a very small amount of mixing exists, and the case where the amount of Na ions is large is not mentioned.

因此，本發明之目的在於提供一種關於玻璃之化學強化所使用之含有硝酸鉀之熔融鹽，其使用壽命得以充分延長之熔融鹽。 Accordingly, an object of the present invention is to provide a molten salt containing a potassium nitrate-containing molten salt used for chemical strengthening of glass, which has a sufficiently long service life.

本發明者等人反覆進行銳意研究，結果發現，於含有硝酸鉀之 熔融鹽中，以含有碳酸陰離子及磷酸陰離子中之至少一者之方式，於玻璃之化學強化處理前預先添加碳酸鉀及磷酸鉀中之1種以上，藉此可延長熔融鹽之使用壽命，從而完成本發明。 The inventors of the present invention repeatedly conducted intensive studies and found that they contained potassium nitrate. In the molten salt, one or more of potassium carbonate and potassium phosphate are added in advance before the chemical strengthening treatment of the glass so as to contain at least one of a carbonate anion and a phosphate anion, thereby prolonging the service life of the molten salt. The present invention has been completed.

即，本發明係如下所述。 That is, the present invention is as follows.

<1>一種玻璃強化用熔融鹽，其係用於藉由離子交換而於玻璃表面形成壓縮應力層者，且含有硝酸鉀，進而含有碳酸陰離子及磷酸陰離子中之至少一者。 <1> A molten salt for glass reinforcement which is used for forming a compressive stress layer on a glass surface by ion exchange, and contains potassium nitrate, and further contains at least one of a carbonate anion and a phosphate anion.

<2>如上述<1>之玻璃強化用熔融鹽，其含有硝酸鉀、碳酸陰離子及磷酸陰離子。 <2> The molten salt for glass reinforcement according to <1> above, which contains potassium nitrate, a carbonate anion, and a phosphate anion.

<3>如上述<1>或<2>之玻璃強化用熔融鹽，其中上述碳酸陰離子為碳酸鉀之陰離子種，上述磷酸陰離子為正磷酸鉀及焦磷酸鉀中之至少一種之陰離子種。 <3> The molten salt for glass reinforcement according to <1> or <2> above, wherein the carbonate anion is an anion species of potassium carbonate, and the phosphate anion is an anion species of at least one of potassium orthophosphate and potassium pyrophosphate.

<4>如上述<3>之玻璃強化用熔融鹽，其中上述碳酸鉀之含量相對於上述硝酸鉀為3.5~24莫耳%。 <4> The molten salt for glass reinforcement according to <3> above, wherein the content of the potassium carbonate is 3.5 to 24 mol% based on the potassium nitrate.

<5>如上述<3>或<4>之玻璃強化用熔融鹽，其中上述正磷酸鉀之含量相對於上述硝酸鉀為0.8~13.5莫耳%。 <5> The molten salt for glass reinforcement according to <3> or <4> above, wherein the content of the potassium orthophosphate is 0.8 to 13.5 mol% based on the potassium nitrate.

<6>如上述<3>至<5>中任一項之玻璃強化用熔融鹽，其中上述焦磷酸鉀之含量相對於上述硝酸鉀為3.5~9.0莫耳%。 The molten salt for glass reinforcement according to any one of the above-mentioned items, wherein the content of the potassium pyrophosphate is 3.5 to 9.0 mol% based on the potassium nitrate.

<7> 一種強化玻璃之製造方法，其包括使用如上述<1>至<6>中任一項之玻璃強化用熔融鹽而於玻璃表面形成壓縮應力層之步驟。 <7> A method of producing a tempered glass, comprising the step of forming a compressive stress layer on a surface of a glass by using the molten salt for glass reinforcement according to any one of the above <1> to <6>.

<8>一種玻璃強化用熔融鹽之壽命延長方法，其係用於藉由離子交換而於玻璃表面形成壓縮應力層之玻璃強化用熔融鹽之壽命延長的方法，且 於含有硝酸鉀之強化處理前之熔融鹽中，以含有碳酸陰離子及磷酸陰離子中之至少一者之方式，混合碳酸鉀及磷酸鉀中之至少一者。 <8> A method for extending the life of a molten salt for glass reinforcement, which is a method for extending the life of a molten salt for glass reinforcement which forms a compressive stress layer on a glass surface by ion exchange, and At least one of potassium carbonate and potassium phosphate is mixed with at least one of a carbonate anion and a phosphate anion in the molten salt before the strengthening treatment containing potassium nitrate.

根據本發明之熔融鹽，可抑制或緩和因自玻璃溶出之Na離子濃度之增加而產生之表面壓縮應力(CS)之下降，可延長熔融鹽之使用壽命。其結果，熔融鹽之交換頻率下降，而可使化學強化處理低成本化或提高處理量。 According to the molten salt of the present invention, the decrease in the surface compressive stress (CS) due to the increase in the concentration of Na ions eluted from the glass can be suppressed or alleviated, and the service life of the molten salt can be prolonged. As a result, the frequency of exchange of the molten salt is lowered, and the chemical strengthening treatment can be reduced in cost or the amount of treatment can be increased.

圖1係表示於硝酸鉀熔融鹽中未添加其他無機鉀鹽而進行化學強化處理之情形時，熔融鹽中之Na離子濃度與CS值之關係的圖表。 Fig. 1 is a graph showing the relationship between the concentration of Na ions in the molten salt and the CS value in the case where the inorganic potassium salt is not added to the potassium nitrate molten salt and chemically strengthened.

圖2係表示於硝酸鉀熔融鹽中添加正磷酸鉀而進行化學強化處理之情形時，相對於硝酸鉀之Na添加量與獲得之CS值之關係的圖表。 Fig. 2 is a graph showing the relationship between the amount of Na added to potassium nitrate and the obtained CS value when potassium orthophosphate is added to the potassium nitrate molten salt for chemical strengthening treatment.

圖3係表示正磷酸鉀向熔融鹽之添加量與熔融鹽之壽命比的關係之圖表。 Fig. 3 is a graph showing the relationship between the amount of potassium orthophosphate added to the molten salt and the life ratio of the molten salt.

圖4係表示於硝酸鉀熔融鹽中添加碳酸鉀而進行化學強化處理之情形時，相對於硝酸鉀之Na添加量與獲得之CS值之關係的圖表。 Fig. 4 is a graph showing the relationship between the amount of Na added to potassium nitrate and the obtained CS value in the case where potassium carbonate is added to the potassium nitrate molten salt to carry out chemical strengthening treatment.

圖5係表示碳酸鉀向熔融鹽之添加量與熔融鹽之壽命比的關係之圖表。 Fig. 5 is a graph showing the relationship between the amount of potassium carbonate added to the molten salt and the life ratio of the molten salt.

圖6係表示於硝酸鉀熔融鹽中添加焦磷酸鉀而進行化學強化處理 之情形時，相對於硝酸鉀之Na添加量與獲得之CS值之關係的圖表。 Figure 6 shows the chemical strengthening treatment by adding potassium pyrophosphate to the molten salt of potassium nitrate. In the case of the relationship, the relationship between the amount of Na added to potassium nitrate and the obtained CS value.

圖7係表示焦磷酸鉀向熔融鹽之添加量與熔融鹽之壽命比之關係的圖表。 Fig. 7 is a graph showing the relationship between the amount of potassium pyrophosphate added to the molten salt and the life ratio of the molten salt.

圖8係表示添加於熔融鹽中之正磷酸鉀、焦磷酸鉀及碳酸鉀之陰離子種之總離子交換能力與熔融鹽之壽命比之關係的圖表。 Fig. 8 is a graph showing the relationship between the total ion exchange capacity of the anion species of potassium orthophosphate, potassium pyrophosphate and potassium carbonate added to the molten salt and the life ratio of the molten salt.

圖9係表示於硝酸鉀熔融鹽中添加二氧化矽而進行化學強化處理之情形時，相對於硝酸鉀之Na添加量與獲得之CS值之關係的圖表。 Fig. 9 is a graph showing the relationship between the amount of Na added to potassium nitrate and the obtained CS value in the case where cerium oxide is added to the potassium nitrate molten salt to carry out chemical strengthening treatment.

圖10係表示二氧化矽向熔融鹽之添加量與熔融鹽之壽命比之關係的圖表。 Fig. 10 is a graph showing the relationship between the amount of cerium oxide added to the molten salt and the life ratio of the molten salt.

以下，對本發明詳細地進行說明。 Hereinafter, the present invention will be described in detail.

再者，於本說明書中，「質量%」與「重量%」同義。 In addition, in the present specification, "% by mass" is synonymous with "% by weight".

<熔融鹽> <Molten salt>

本發明之玻璃強化用熔融鹽(以下，亦稱為本發明之熔融鹽)含有無機鉀鹽。作為無機鉀鹽，較佳為具有進行化學強化之玻璃之變形點(通常500~600℃)以下之熔點者，於本發明中，含有硝酸鉀(熔點330℃)作為主成分。若硝酸鉀為主成分，則就於玻璃之變形點以下成為熔融狀態，且於使用溫度區域中容易操作之方面而言較佳。此處，所謂主成分意指含有50質量%以上。 The molten salt for glass reinforcement of the present invention (hereinafter also referred to as the molten salt of the present invention) contains an inorganic potassium salt. The inorganic potassium salt is preferably a melting point of a chemically strengthened glass (normally 500 to 600 ° C) or less. In the present invention, potassium nitrate (melting point: 330 ° C) is contained as a main component. When potassium nitrate is a main component, it is preferably in a molten state below the deformation point of the glass, and is preferable in terms of ease of handling in the use temperature region. Here, the main component means 50% by mass or more.

本發明之熔融鹽除含有作為主成分之硝酸鉀外，進而含有碳酸陰離子及磷酸陰離子中之至少一者。藉此，與未含有碳酸陰離子及磷酸陰離子之情形相比，可延長熔融鹽之使用壽命。 The molten salt of the present invention contains at least one of a carbonate anion and a phosphate anion in addition to potassium nitrate as a main component. Thereby, the service life of the molten salt can be prolonged as compared with the case where the carbonate anion and the phosphate anion are not contained.

若於化學強化處理中連續使用相同之熔融鹽，則與利用未供於化學強化處理之熔融鹽(以下，亦稱為「初期狀態之熔融鹽」、或「新的熔融鹽」)進行化學強化之情形相比，可賦予玻璃之CS值根據累積玻璃處理面積而緩慢下降。 When the same molten salt is continuously used in the chemical strengthening treatment, it is chemically strengthened with a molten salt (hereinafter, also referred to as "a molten salt in an initial state" or a "new molten salt") which is not subjected to chemical strengthening treatment. In contrast, the CS value that can be imparted to the glass is slowly decreased depending on the cumulative glass treated area.

於本發明中，於進行化學強化處理前之熔融鹽中，以含有碳酸陰離子及磷酸陰離子中之至少一者之方式，預先混合碳酸鉀及磷酸鉀中之1種以上，而進行化學強化處理，藉此，於鈉溶出初期，藉由預先存在於熔融鹽中之碳酸陰離子、磷酸陰離子而捕獲鈉，從而玻璃表面附近之鈉離子濃度下降。進而，若碳酸陰離子、磷酸陰離子之鈉鹽超過飽和溶解度量，則析出，因此抑制熔融鹽中之鈉離子濃度上升。可認為藉由上述作用，可延長熔融鹽之壽命。 In the present invention, one or more of potassium carbonate and potassium phosphate are preliminarily mixed with at least one of a carbonate anion and a phosphate anion in the molten salt before the chemical strengthening treatment, and chemical strengthening treatment is performed. Thereby, in the initial stage of sodium elution, sodium is trapped by the carbonate anion and the phosphate anion which are present in the molten salt in advance, and the sodium ion concentration in the vicinity of the glass surface is lowered. Further, when the sodium salt of the carbonate anion or the phosphate anion exceeds the saturation solubility measurement, it precipitates, thereby suppressing an increase in the sodium ion concentration in the molten salt. It is considered that the life of the molten salt can be prolonged by the above action.

就對利用添加之碳酸鉀或磷酸鉀等之壽命延長能力進行定量比較‧評價而言，可認為以下述方式進行。例如於正磷酸鉀之情形時，構成正磷酸鉀之陰離子為PO4 3-，因此為3價之陰離子。陰離子之價數越大，吸引陽離子之力越強，且變得容易保持陽離子。 The quantitative comparison of the life extension ability by the added potassium carbonate or potassium phosphate, etc., was considered to be carried out in the following manner. For example, in the case of potassium orthophosphate, the anion constituting potassium orthophosphate is PO 4 3- and thus is a trivalent anion. The larger the valence of the anion, the stronger the force for attracting the cation and the easier it is to retain the cation.

於正磷酸鉀中存在3個1價之陽離子K+，但根據磷酸之酸解離常數(pKa1=1.83、pka2=6.43、pka3=11.46)，認為於熔融鹽中與Na離子交換的是3個鉀中之1個，正磷酸鉀每1莫耳之潛在之Na-K離子交換能力可藉由下述式進行評價：潛在之Na-K離子交換能力=(陰離子種之價數)×(可交換之K離子量)=3×1=3。 There are three monovalent cations K + in potassium orthophosphate, but according to the acid dissociation constant of phosphoric acid (pKa1=1.83, pka2=6.43, pka3=11.46), it is considered that 3 potassium is exchanged with Na ions in the molten salt. One of them, the potential Na-K ion exchange capacity per 1 mole of potassium orthophosphate can be evaluated by the following formula: potential Na-K ion exchange capacity = (valence of anion species) × (exchangeable The amount of K ions) = 3 × 1 = 3.

藉此，向熔融鹽添加之正磷酸鉀之總離子交換能力可藉由下述式算出：總離子交換能力=(正磷酸鉀添加量)×(潛在之Na-K離子交換能力)。 Thereby, the total ion exchange capacity of potassium orthophosphate added to the molten salt can be calculated by the following formula: total ion exchange capacity = (addition amount of potassium orthophosphate) × (potential Na-K ion exchange capacity).

可認為該總離子交換能力越高，與玻璃進行離子交換之熔融鹽中之Na離子進而與添加之無機鉀鹽之K離子進行離子交換的概率變得越高，從而緩和由熔融鹽中之鈉引起之離子交換阻礙，而有助於延長熔融鹽之壽命。 It is considered that the higher the total ion exchange capacity, the higher the probability that the Na ions in the molten salt ion-exchanged with the glass and the K ion of the added inorganic potassium salt are ion exchanged, thereby alleviating the sodium in the molten salt. The ion exchange caused by the hindrance helps to prolong the life of the molten salt.

於本發明中，為了定量評價熔融鹽之使用壽命(life)而使用以下 之指標。首先，所謂所需之CS值係定義為將利用初期狀態之包含硝酸鉀之熔融鹽獲得之CS值設為100%時之90%以上的CS值。然後，將於化學強化處理中無法獲得所需之CS值時，即，相對於所需之CS值，CS值下降10%以上時之熔融鹽中之Na離子濃度定義為熔融鹽的使用壽命。 In the present invention, in order to quantitatively evaluate the life of the molten salt, the following is used. Indicators. First, the CS value required is defined as a CS value of 90% or more when the CS value obtained by using the molten salt containing potassium nitrate in the initial state is 100%. Then, when the desired CS value cannot be obtained in the chemical strengthening treatment, that is, the Na ion concentration in the molten salt when the CS value is decreased by 10% or more with respect to the required CS value is defined as the service life of the molten salt.

再者，熔融鹽之壽命可以下述方式進行評價。首先，為了模擬製作反覆進行化學強化處理後之狀態，而有意圖地將作為Na離子源之特定量之硝酸鈉添加於熔融鹽中。然後，利用添加有Na離子源之熔融鹽對玻璃進行化學強化處理，處理後之玻璃之CS值低於所需之CS值時，根據硝酸鈉之添加量算出Na離子濃度，可將其設為熔融鹽壽命之指標。 Further, the life of the molten salt can be evaluated in the following manner. First, in order to simulate the state in which the chemical strengthening treatment is repeated, a specific amount of sodium nitrate as a source of Na ions is intentionally added to the molten salt. Then, the glass is chemically strengthened by the molten salt to which the Na ion source is added, and when the CS value of the treated glass is lower than the required CS value, the Na ion concentration is calculated based on the amount of sodium nitrate added, and it can be set as An indicator of the life of molten salt.

於本發明之熔融鹽含有碳酸鉀之情形時，其含量較佳為相對於熔融鹽中之硝酸鉀為3.5莫耳%~24莫耳%(5.0質量%~30質量%)，更佳為8.0莫耳%~24莫耳%(10.9質量%~30質量%)，特佳為16.0莫耳%~24莫耳%(21.5質量%~30質量%)。 When the molten salt of the present invention contains potassium carbonate, the content thereof is preferably from 3.5 mol% to 24 mol% (5.0% by mass to 30% by mass) based on the potassium nitrate in the molten salt, more preferably 8.0. Mohr%~24 mol% (10.9 mass%~30 mass%), especially preferably 16.0 mol%~24 mol% (21.5 mass%~30 mass%).

只要相對於硝酸鉀之碳酸鉀之添加量為30質量%以下，則無因熔點較高之碳酸鉀而導致熔融鹽中之固相量增加之虞，而操作性良好。又，無於離子交換處理中產生溫度不均之虞，而可對玻璃整體均勻地進行離子交換。 When the amount of potassium carbonate added to potassium nitrate is 30% by mass or less, there is no increase in the amount of solid phase in the molten salt due to potassium carbonate having a high melting point, and the workability is good. Further, it is possible to uniformly perform ion exchange on the entire glass without causing temperature unevenness in the ion exchange treatment.

作為磷酸鉀，可列舉：正磷酸鉀(K3PO4)、焦磷酸鉀(K4P2O7)、偏磷酸鉀，就相對於添加之陰離子種之總離子交換能力之壽命延長效率的方面而言，較佳為正磷酸鉀。 Examples of the potassium phosphate include potassium orthophosphate (K 3 PO 4 ), potassium pyrophosphate (K 4 P 2 O 7 ), and potassium metaphosphate, and the lifetime is extended with respect to the total ion exchange capacity of the added anionic species. In terms of aspect, potassium orthophosphate is preferred.

於添加正磷酸鉀作為磷酸鉀之情形時，正磷酸鉀可為水合物，亦可為經脫水處理者。又，熔融鹽中之正磷酸鉀之含量較佳為相對於硝酸鉀為0.8莫耳%~13.5莫耳%(1.5質量%~25質量%)，更佳為1.5莫耳%~13.5莫耳%(3.0質量%~25質量%)，進而較佳為3.0莫耳%~13.5 莫耳%(6.0質量%~25質量%)，特佳為6.0莫耳%~13.5莫耳%(11.5質量%~25質量%)。只要下限為該範圍，則可將獲得所需之CS值之熔融鹽壽命延長2倍以上，故而較佳。 When potassium orthophosphate is added as the potassium phosphate, the potassium orthophosphate may be a hydrate or may be a dehydrated one. Further, the content of potassium orthophosphate in the molten salt is preferably from 0.8 mol% to 13.5 mol% (1.5 mass% to 25% by mass), more preferably from 1.5 mol% to 13.5 mol%, relative to potassium nitrate. (3.0% by mass to 25% by mass), and further preferably 3.0% by mole to 13.5 Molar% (6.0% by mass to 25% by mass), particularly preferably 6.0% by mole to 13.5% by mole (11.5% by mass to 25% by mass). When the lower limit is in this range, the life of the molten salt which obtains the desired CS value can be more than doubled, which is preferable.

又，正磷酸鉀之熔點較高(>1000℃)，從而於化學強化所使用之溫度區域(<500℃)中溶解於硝酸鉀之量極少。因此，若添加過剩量，則沈澱物沈積於容器之底部而熔融鹽之操作性變差。因此，若相對於硝酸鉀，正磷酸鉀為25質量%以下，則可控制正磷酸鉀之固相之比率，而可充分地確保化學強化能使用之液相容積，且無熔融鹽中之磷酸鉀沈澱物接觸於玻璃而導致玻璃表面腐蝕之虞，故而較佳。 Further, the potassium orthophosphate has a high melting point (>1000 ° C), so that the amount of potassium nitrate dissolved in the temperature region (<500 ° C) used for chemical strengthening is extremely small. Therefore, if an excessive amount is added, deposits are deposited on the bottom of the container and the handleability of the molten salt is deteriorated. Therefore, when the potassium orthophosphate is 25% by mass or less with respect to potassium nitrate, the ratio of the solid phase of potassium orthophosphate can be controlled, and the liquid phase volume for chemical strengthening can be sufficiently ensured, and the phosphoric acid in the molten salt is not obtained. It is preferred that the potassium precipitate is in contact with the glass to cause corrosion of the surface of the glass.

於添加焦磷酸鉀作為磷酸鉀之情形時，較佳為相對於熔融鹽中之硝酸鉀，焦磷酸鉀為3.5莫耳%~9.0莫耳%(10.5質量%~25質量%)，更佳為7.5莫耳%以上(21.0質量%以上)。只要下限為該範圍，則可將獲得所需之CS值之熔融鹽壽命延長2倍以上，故而較佳。 When potassium pyrophosphate is added as potassium phosphate, it is preferably 3.5 mol% to 9.0 mol% (10.5 mass% to 25% by mass) relative to potassium nitrate in the molten salt, more preferably 7.5 mol% or more (21.0 mass% or more). When the lower limit is in this range, the life of the molten salt which obtains the desired CS value can be more than doubled, which is preferable.

又，焦磷酸鉀亦與正磷酸鉀同樣地存在如下之虞，即若因添加過剩量而粉末接觸於化學強化用玻璃，則腐蝕玻璃表面，因此較佳為將焦磷酸鉀之含量之上限設為25質量%。 Further, potassium pyrophosphate also has the same effect as potassium orthophosphate, that is, if the powder is contacted with the glass for chemical strengthening due to the excessive amount of addition, the surface of the glass is corroded. Therefore, it is preferable to set the upper limit of the content of potassium pyrophosphate. It is 25% by mass.

再者，亦可併用上述碳酸鉀與磷酸鉀。於該情形時，只要碳酸鉀與磷酸鉀各自之添加量分別滿足上述範圍，則亦可為任意組合。 Further, the above potassium carbonate and potassium phosphate may also be used in combination. In this case, any combination of potassium carbonate and potassium phosphate may be any combination as long as it satisfies the above range.

本發明之熔融鹽除含有硝酸鉀、碳酸鉀及磷酸鉀以外，亦可於不阻礙本發明之效果之範圍內含有其他化學物種，例如可列舉：硫酸鈉、硫酸鉀、氯化鈉、氯化鉀等鹼硫酸鹽、或鹼氯化鹽等。再者，亦可組合該等複數種使用。 The molten salt of the present invention may contain other chemical species in addition to potassium nitrate, potassium carbonate and potassium phosphate, and may, for example, be sodium sulfate, potassium sulfate, sodium chloride or chlorinated, without damaging the effects of the present invention. An alkali sulfate such as potassium or an alkali chloride or the like. Furthermore, it is also possible to combine these plural kinds of uses.

<熔融鹽之製造方法> <Method for Producing Molten Salt>

本發明之熔融鹽可藉由下述所示之步驟而製造。 The molten salt of the present invention can be produced by the steps shown below.

步驟1：硝酸鉀熔融鹽之製備 Step 1: Preparation of potassium nitrate molten salt

步驟2：其他無機鉀鹽向熔融鹽之添加 Step 2: Addition of other inorganic potassium salts to molten salt

(步驟1) (step 1)

於步驟1中，將硝酸鉀投入容器中，加熱至熔點以上之溫度而使硝酸鉀熔融，藉此製備熔融鹽。硝酸鉀之熔點為330℃，沸點為500℃，因此以該範圍內之溫度進行熔融。特別是就可賦予玻璃之表面壓縮應力與應力層深度之平衡及強化時間之方面而言，更佳為將熔融溫度設為350~470℃。 In the step 1, potassium nitrate is put into a vessel and heated to a temperature higher than the melting point to melt the potassium nitrate, thereby preparing a molten salt. Potassium nitrate has a melting point of 330 ° C and a boiling point of 500 ° C, so it is melted at a temperature within this range. In particular, it is preferable to set the melting temperature to 350 to 470 ° C in terms of the balance between the compressive stress on the surface of the glass and the depth of the stress layer and the strengthening time.

使硝酸鉀熔融之容器可使用金屬、石英、陶瓷等。其中，就耐久性之觀點而言，較理想為金屬材質，就耐蝕性之觀點而言，較理想為不鏽鋼(SUS，Steel Use Stainless，日本不鏽鋼標準)材質。 A metal, quartz, ceramic, or the like can be used for the container in which potassium nitrate is melted. Among them, from the viewpoint of durability, it is preferably made of a metal material, and from the viewpoint of corrosion resistance, it is preferably made of stainless steel (SUS, Steel Use Stainless).

(步驟2) (Step 2)

於步驟2中，於步驟1中製備之硝酸鉀熔融鹽中添加碳酸鉀、磷酸鉀等硝酸鉀以外之無機鉀鹽，一面將溫度保持在固定範圍，一面藉由攪拌葉片等，以整體變均勻之方式進行混合。於併用碳酸鉀與磷酸鉀之情形時，添加順序並無限定，可首先添加任一種，亦可同時添加。溫度較佳為硝酸鉀之熔點以上，即330℃以上，更佳為350~500℃。又，攪拌時間較佳為1分鐘~10小時，更佳為10分鐘~2小時。其後，進行靜置直至析出物沈澱。於該析出物中含有超過飽和溶解度之碳酸鉀或磷酸鉀，又，含有碳酸陰離子之鈉鹽、磷酸陰離子之鈉鹽。 In the step 2, an inorganic potassium salt other than potassium nitrate such as potassium carbonate or potassium phosphate is added to the potassium nitrate molten salt prepared in the first step, and the temperature is maintained in a fixed range, and the whole is uniformly uniform by stirring the blade or the like. The way to mix. In the case of using potassium carbonate and potassium phosphate in combination, the order of addition is not limited, and either one may be added first or may be added at the same time. The temperature is preferably above the melting point of potassium nitrate, i.e., 330 ° C or higher, more preferably 350 to 500 ° C. Further, the stirring time is preferably from 1 minute to 10 hours, more preferably from 10 minutes to 2 hours. Thereafter, it was allowed to stand until the precipitate precipitated. The precipitate contains potassium carbonate or potassium phosphate having a saturated solubility, and further contains a sodium salt of a carbonate anion and a sodium salt of a phosphate anion.

如上所述，可製造本發明之熔融鹽。 As described above, the molten salt of the present invention can be produced.

<化學強化處理> <Chemical strengthening treatment>

繼而，對使用本發明之熔融鹽之化學強化處理方法進行說明。 Next, a chemical strengthening treatment method using the molten salt of the present invention will be described.

化學強化處理係藉由將玻璃浸漬於熔融鹽中，將玻璃中之金屬離子與熔融鹽中之離子半徑較大之金屬離子進行置換而進行。藉由該離子交換而使玻璃表面之組成發生變化，而使壓縮應力產生於玻璃表面層，藉此可強化玻璃。 The chemical strengthening treatment is carried out by immersing the glass in a molten salt to replace metal ions in the glass with metal ions having a large ionic radius in the molten salt. By the ion exchange, the composition of the glass surface is changed, and the compressive stress is generated in the glass surface layer, whereby the glass can be strengthened.

本發明中之化學強化處理可藉由繼上述熔融鹽之製造方法(步驟1、步驟2)後之以下所示之步驟而進行。 The chemical strengthening treatment in the present invention can be carried out by the following steps following the above-described method for producing the molten salt (Step 1, Step 2).

步驟3：玻璃之化學強化處理 Step 3: Chemical strengthening treatment of glass

步驟4：熔融鹽之廢棄 Step 4: Disposal of molten salt

(步驟3) (Step 3)

於步驟3中將玻璃預熱，並將於上述步驟1及步驟2中製備之熔融鹽調整至進行化學強化之溫度。繼而，將預熱之玻璃浸漬於熔融鹽中特定時間後，將玻璃自熔融鹽中提起，進行放置冷卻。再者，較佳為於化學強化處理前，對玻璃進行根據用途之形狀加工，例如切割、端面加工及開孔加工等機械加工。 The glass is preheated in step 3, and the molten salt prepared in the above steps 1 and 2 is adjusted to a temperature at which chemical strengthening is performed. Then, after immersing the preheated glass in the molten salt for a specific period of time, the glass is lifted from the molten salt and left to stand for cooling. Further, it is preferred to process the glass according to the shape of the application before the chemical strengthening treatment, for example, machining such as cutting, end surface processing, and drilling.

玻璃之預熱溫度雖取決於浸漬於熔融鹽中之溫度，但通常較佳為100℃以上。 The preheating temperature of the glass depends on the temperature immersed in the molten salt, but is usually preferably 100 ° C or more.

化學強化溫度較佳為被強化玻璃之變形點(通常500~600℃)以下，為了獲得更高之壓縮應力層深度(Depth of Layer：DOL)，特佳為350℃以上。 The chemical strengthening temperature is preferably below the deformation point of the tempered glass (usually 500 to 600 ° C), and is preferably 350 ° C or more in order to obtain a higher Depth of Layer (DOL).

玻璃向熔融鹽之浸漬時間較佳為10分鐘~12小時，進而較佳為30分鐘~10小時。只要在該範圍內，則可獲得強度與壓縮應力層之深度之平衡優異之化學強化玻璃。 The immersion time of the glass to the molten salt is preferably from 10 minutes to 12 hours, more preferably from 30 minutes to 10 hours. When it is within this range, a chemically strengthened glass excellent in the balance between the strength and the depth of the compressive stress layer can be obtained.

(步驟4) (Step 4)

若反覆進行步驟3，則由於熔融鹽-玻璃間之離子交換，熔融鹽中之Na離子濃度變高，因此隨著玻璃處理面積增加，熔融鹽之離子交換能力下降，而變得無法獲得所需之CS值。因此，於步驟4中，藉由測定熔融鹽中之Na離子濃度、或者化學強化後之表面壓縮應力(CS)值，從而判斷是否可繼續使用熔融鹽而進行化學強化處理，或者是否廢棄熔融鹽。 When the step 3 is repeated, the concentration of Na ions in the molten salt becomes high due to the ion exchange between the molten salt and the glass. Therefore, as the glass treatment area increases, the ion exchange capacity of the molten salt decreases, and the desired content becomes impossible. The CS value. Therefore, in step 4, by measuring the Na ion concentration in the molten salt or the surface compressive stress (CS) value after chemical strengthening, it is judged whether or not the molten salt can be continuously used for chemical strengthening treatment, or whether the molten salt is discarded. .

<玻璃> <glass>

本發明所使用之玻璃只要含有鈉即可，只要為具有可成形且可進行利用化學強化處理之強化之組成者，則可使用各種組成者。具體而言，例如可列舉：鈉鈣玻璃、鋁矽酸鹽玻璃、硼矽酸玻璃、鉛玻璃、鹼鋇玻璃、硼矽酸鋁玻璃等。 The glass used in the present invention may be any one as long as it contains sodium, and any composition can be used as long as it has a composition which can be formed and can be strengthened by chemical strengthening treatment. Specific examples thereof include soda lime glass, aluminosilicate glass, borosilicate glass, lead glass, alkali bismuth glass, and aluminum borosilicate glass.

玻璃之製造方法並無特別限定，可藉由如下方式而製造：將所需之玻璃原料投入連續熔融爐中，使玻璃原料於較佳為1500~1600℃下進行加熱熔融，澄清後，供給於成形裝置，之後將熔融玻璃成形為板狀，並進行緩冷卻。 The method for producing the glass is not particularly limited, and it can be produced by introducing a desired glass raw material into a continuous melting furnace, heating and melting the glass raw material at preferably 1500 to 1600 ° C, clarifying, and then supplying it. The forming apparatus then forms the molten glass into a plate shape and performs gentle cooling.

再者，就玻璃之成形而言，可採用各種方法。例如可採用下拉法(例如，溢流下拉法、流孔下引法及再曳引法等)、浮式法、滾壓法及按壓法等各種成形方法。 Further, various methods can be employed for the formation of the glass. For example, various forming methods such as a down-draw method (for example, an overflow down-draw method, a flow-down method, and a re-drawing method), a floating method, a rolling method, and a pressing method can be employed.

玻璃之厚度並無特別限制，為了有效地進行化學強化處理，玻璃之厚度通常較佳為5mm以下，更佳為3mm以下。 The thickness of the glass is not particularly limited, and in order to effectively perform chemical strengthening treatment, the thickness of the glass is usually preferably 5 mm or less, more preferably 3 mm or less.

作為本發明之化學強化用玻璃之組成，並無特別限定，例如可列舉以下之玻璃之組成。 The composition of the glass for chemical strengthening of the present invention is not particularly limited, and examples thereof include the composition of the following glass.

(i)於以莫耳%表示之組成中含有SiO2 50~80%、Al2O3 2~25%、Li2O 0~10%、Na2O 0~18%、K2O 0~10%、MgO 0~15%、CaO 0~5%及ZrO2 0~5%之玻璃 (i) SiO 2 50 to 80%, Al 2 O 3 2 to 25%, Li 2 O 0 to 10%, Na 2 O 0 to 18%, K 2 O 0~ in the composition expressed by mol% 10%, MgO 0~15%, CaO 0~5% and ZrO 2 0~5% glass

(ii)以莫耳%表示之組成含有SiO2 50~74%、Al2O3 1~10%、Na2O 6~14%、K2O 3~11%、MgO 2~15%、CaO 0~6%及ZrO2 0~5%，且SiO2及Al2O3之含量之合計為75%以下、Na2O及K2O之含量之合計為12~25%、MgO及CaO之含量之合計為7~15%之玻璃 (ii) The composition expressed in mole % contains SiO 2 50-74%, Al 2 O 3 1~10%, Na 2 O 6-14%, K 2 O 3-11%, MgO 2-15%, CaO 0~6% and ZrO 2 0~5%, and the total content of SiO 2 and Al 2 O 3 is 75% or less, and the total content of Na 2 O and K 2 O is 12 to 25%, MgO and CaO. The total content is 7~15% glass

(iii)以莫耳%表示之組成含有SiO2 68~80%、Al2O3 4~10%、Na2O 5~15%、K2O 0~1%、MgO 4~15%及ZrO2 0~1%之玻璃 (iii) The composition expressed in mole % contains SiO 2 68-80%, Al 2 O 3 4-10%, Na 2 O 5-15%, K 2 O 0~1%, MgO 4-15%, and ZrO 2 0~1% glass

(iv)以莫耳%表示之組成含有SiO2 67~75%、Al2O3 0~4%、Na2O 7~15%、K2O 1~9%、MgO 6~14%及ZrO2 0~1.5%，且SiO2及Al2O3 之含量之合計為71~75%、Na2O及K2O之含量之合計為12~20%，於含有CaO之情形時其含量未達1%之玻璃 (iv) The composition expressed in mole % contains SiO 2 67 to 75%, Al 2 O 3 0 to 4%, Na 2 O 7 to 15%, K 2 O 1 to 9%, MgO 6 to 14%, and ZrO. 20 to 1.5%, and the total content of SiO 2 and Al 2 O 3 is 71 to 75%, and the total content of Na 2 O and K 2 O is 12 to 20%. When CaO is contained, the content is not Up to 1% glass

玻璃亦可根據需要於化學強化處理前進行研磨。作為研磨方法，例如可列舉一面供給研磨漿料一面利用研磨墊進行研磨之方法，就研磨漿料而言，可使用含有研磨材與水之研磨漿料。作為研磨材，較佳為氧化鈰(ceria)及二氧化矽。 The glass can also be ground prior to chemical strengthening treatment as needed. As the polishing method, for example, a method of polishing the polishing slurry while polishing the slurry is used, and in the polishing slurry, a polishing slurry containing the polishing material and water can be used. As the abrasive, ceria and ceria are preferred.

於研磨玻璃之情形時，藉由清洗液對研磨後之玻璃進行清洗。作為清洗液，較佳為中性清潔劑及水，更佳為於利用中性清潔劑清洗後利用水進行清洗。作為中性清潔劑，可使用市售者。 In the case of grinding the glass, the ground glass is cleaned by a cleaning liquid. As the cleaning liquid, a neutral detergent and water are preferred, and it is more preferred to wash with water after washing with a neutral detergent. As a neutral detergent, a commercially available person can be used.

藉由清洗液對藉由上述清洗步驟而清洗之玻璃基板進行最終清洗。作為清洗液，例如可列舉：水、乙醇及異丙醇等。其中，較佳為水。 The glass substrate cleaned by the above-described cleaning step is subjected to final cleaning by a cleaning liquid. Examples of the washing liquid include water, ethanol, and isopropyl alcohol. Among them, water is preferred.

上述最終清洗後，使玻璃乾燥。乾燥條件只要考慮於清洗步驟中使用之清洗液、及玻璃之特性等而選擇最佳之條件即可。 After the final cleaning described above, the glass is dried. The drying conditions may be selected in consideration of the conditions of the cleaning liquid used in the washing step and the characteristics of the glass.

實施例Example

以下對本發明之實施例具體地進行說明，但本發明並不限定於該等。 The embodiments of the present invention are specifically described below, but the present invention is not limited thereto.

(玻璃組成) (glass composition)

就進行化學強化之玻璃而言，使用鈉鈣玻璃及鋁矽酸鹽玻璃2種玻璃。 For the glass to be chemically strengthened, two types of glass, soda lime glass and aluminosilicate glass, are used.

鈉鈣玻璃(以莫耳%表示之組成)：SiO2 72.0%、Al2O3 1.1%、Na2O3 12.6%、K2O 0.2%、MgO 5.5%、CaO 8.6% Soda lime glass (composition expressed as % by mole): SiO 2 72.0%, Al 2 O 3 1.1%, Na 2 O 3 12.6%, K 2 O 0.2%, MgO 5.5%, CaO 8.6%

鋁矽酸鹽玻璃(以莫耳%表示之組成)：SiO2 64.4%、Al2O3 8.0%、Na2O3 12.5%、K2O 4.0%、MgO 10.5%、CaO 0.1%、SrO 0.1%、BaO 0.1%、ZrO2 2.5% Aluminosilicate glass (composition expressed as % by mole): SiO 2 64.4%, Al 2 O 3 8.0%, Na 2 O 3 12.5%, K 2 O 4.0%, MgO 10.5%, CaO 0.1%, SrO 0.1 %, BaO 0.1%, ZrO 2 2.5%

(玻璃之評價) (evaluation of glass)

玻璃之評價係藉由測定表面壓縮應力(CS)與壓縮應力層深度(DOL)而進行。CS及DOL係藉由使用表面應力計(折原製作所製造之FSM-6000LE)對玻璃表面與內部之折射率差進行測定而求出。 The evaluation of the glass was carried out by measuring the surface compressive stress (CS) and the compressive stress layer depth (DOL). CS and DOL were obtained by measuring the difference in refractive index between the surface of the glass and the inside using a surface stress meter (FSM-6000LE manufactured by Ohara Co., Ltd.).

[實施例1：正磷酸鉀之添加] [Example 1: Addition of potassium orthophosphate] (實施例1A-1~1A-6) (Examples 1A-1 to 1A-6) (實施例1A-1) (Example 1A-1)

於SUS製之杯中加入硝酸鉀250g，利用加熱套加熱至430℃而製備熔融鹽。於以上述方式製備之熔融鹽中添加正磷酸鉀三水合物30.4g(相對於硝酸鉀之K3PO4含量：4.4mol%)，使用攪拌馬達、4片螺旋葉片攪拌2小時，靜置2小時。其後，將鈉鈣玻璃預熱至100℃，浸漬於430℃之熔融鹽中4小時而進行化學強化處理。其後，利用100℃之離子交換水清洗玻璃，於60℃下乾燥2小時。分別測定化學強化處理後之該玻璃之CS、DOL。 250 g of potassium nitrate was added to a cup made of SUS, and the molten salt was prepared by heating to 430 ° C with a heating mantle. To the molten salt prepared in the above manner, 30.4 g of potassium orthophosphate trihydrate (content of K 3 PO 4 relative to potassium nitrate: 4.4 mol%) was added, and the mixture was stirred for 2 hours using a stirring motor and 4 spiral blades, and allowed to stand 2 hour. Thereafter, the soda lime glass was preheated to 100 ° C, and immersed in a molten salt of 430 ° C for 4 hours to carry out a chemical strengthening treatment. Thereafter, the glass was washed with ion-exchanged water at 100 ° C and dried at 60 ° C for 2 hours. The CS and DOL of the glass after the chemical strengthening treatment were measured, respectively.

(實施例1A-2) (Example 1A-2)

於實施例1A-1中進行化學強化處理之熔融鹽中添加硝酸鈉0.93g，使用攪拌馬達、4片螺旋葉片攪拌2小時，靜置2小時。其後，將鈉鈣玻璃預熱至100℃，浸漬於430℃之熔融鹽中4小時而進行化學強化處理。利用100℃之離子交換水清洗玻璃，於60℃下乾燥2小時。其後，分別測定CS、DOL。 To the molten salt subjected to the chemical strengthening treatment in Example 1A-1, 0.93 g of sodium nitrate was added, and the mixture was stirred for 2 hours using a stirring motor and four spiral blades, and allowed to stand for 2 hours. Thereafter, the soda lime glass was preheated to 100 ° C, and immersed in a molten salt of 430 ° C for 4 hours to carry out a chemical strengthening treatment. The glass was washed with ion-exchanged water at 100 ° C and dried at 60 ° C for 2 hours. Thereafter, CS and DOL were measured, respectively.

(實施例1A-3) (Example 1A-3)

於實施例1A-2中進行化學強化處理之熔融鹽中進而添加硝酸鈉0.92g(硝酸鈉之添加量之合計為1.85g)，使用攪拌馬達、4片螺旋葉片攪拌2小時，靜置2小時。其後，將鈉鈣玻璃預熱至100℃，浸漬於430℃之熔融鹽中4小時而進行化學強化處理。利用100℃之離子交換水清洗玻璃，於60℃下乾燥2小時。其後，分別測定CS、DOL。 Further, 0.92 g of sodium nitrate (the total amount of sodium nitrate added was 1.85 g) was added to the molten salt subjected to the chemical strengthening treatment in Example 1A-2, and the mixture was stirred for 2 hours using a stirring motor and four spiral blades, and allowed to stand for 2 hours. . Thereafter, the soda lime glass was preheated to 100 ° C, and immersed in a molten salt of 430 ° C for 4 hours to carry out a chemical strengthening treatment. The glass was washed with ion-exchanged water at 100 ° C and dried at 60 ° C for 2 hours. Thereafter, CS and DOL were measured, respectively.

(實施例1A-4) (Example 1A-4)

於實施例1A-3中進行化學強化處理之熔融鹽中進而添加硝酸鈉0.94g(硝酸鈉之添加量之合計為2.79g)，使用攪拌馬達、4片螺旋葉片攪拌2小時，靜置2小時。將鈉鈣玻璃預熱至100℃，浸漬於430℃之熔融鹽中4小時而進行化學強化處理。利用100℃之離子交換水清洗玻璃，於60℃下乾燥2小時。其後，分別測定CS、DOL。 Further, 0.94 g of sodium nitrate (the total amount of sodium nitrate added was 2.79 g) was added to the molten salt subjected to the chemical strengthening treatment in Example 1A-3, and the mixture was stirred for 2 hours using a stirring motor and four spiral blades, and allowed to stand for 2 hours. . The soda lime glass was preheated to 100 ° C, and immersed in a molten salt of 430 ° C for 4 hours to carry out a chemical strengthening treatment. The glass was washed with ion-exchanged water at 100 ° C and dried at 60 ° C for 2 hours. Thereafter, CS and DOL were measured, respectively.

(實施例1A-5) (Example 1A-5)

於實施例1A-4中進行化學強化處理之熔融鹽中進而添加硝酸鈉1.93g(硝酸鈉之添加量之合計為4.72g)，使用攪拌馬達、4片螺旋葉片攪拌2小時，靜置2小時。將鈉鈣玻璃預熱至100℃，浸漬於430℃之熔融鹽中4小時而進行化學強化處理。利用100℃之離子交換水清洗玻璃，於60℃下乾燥2小時。其後，分別測定CS、DOL。 Further, 1.93 g of sodium nitrate (the total amount of sodium nitrate added was 4.72 g) was added to the molten salt subjected to the chemical strengthening treatment in Example 1A-4, and the mixture was stirred for 2 hours using a stirring motor and four spiral blades, and allowed to stand for 2 hours. . The soda lime glass was preheated to 100 ° C, and immersed in a molten salt of 430 ° C for 4 hours to carry out a chemical strengthening treatment. The glass was washed with ion-exchanged water at 100 ° C and dried at 60 ° C for 2 hours. Thereafter, CS and DOL were measured, respectively.

(實施例1A-6) (Example 1A-6)

於實施例1A-5中進行化學強化處理之熔融鹽中進而添加硝酸鈉4.87g(硝酸鈉之添加量之合計為9.59g)，使用攪拌馬達、4片螺旋葉片攪拌2小時，靜置2小時。將鈉鈣玻璃預熱至100℃，浸漬於430℃之熔融鹽中4小時而進行化學強化處理。利用100℃之離子交換水清洗玻璃，於60℃下乾燥2小時。其後，分別測定CS、DOL。 Further, 4.87 g of sodium nitrate (the total amount of sodium nitrate added was 9.59 g) was added to the molten salt subjected to the chemical strengthening treatment in Example 1A-5, and the mixture was stirred for 2 hours using a stirring motor and four spiral blades, and allowed to stand for 2 hours. . The soda lime glass was preheated to 100 ° C, and immersed in a molten salt of 430 ° C for 4 hours to carry out a chemical strengthening treatment. The glass was washed with ion-exchanged water at 100 ° C and dried at 60 ° C for 2 hours. Thereafter, CS and DOL were measured, respectively.

(實施例1B-1~1B-6) (Examples 1B-1 to 1B-6)

將玻璃變更為鋁矽酸鹽玻璃，除此以外，以與實施例1A-1~1A-6相同之方式製備熔融鹽，進行化學強化處理，分別測定CS、DOL。 A molten salt was prepared in the same manner as in Examples 1A-1 to 1A-6 except that the glass was changed to aluminosilicate glass, and chemical strengthening treatment was carried out to measure CS and DOL, respectively.

[比較例1：僅硝酸鉀] [Comparative Example 1: potassium nitrate only] (比較例1A-1~1A-6) (Comparative Example 1A-1~1A-6)

使用未添加正磷酸鉀三水合物而僅硝酸鉀之熔融鹽，除此以外，以與實施例1A-1~1A-6相同之方式進行化學強化處理，分別測定CS、DOL。(比較例1B-1~1B-6) Chemical strengthening treatment was carried out in the same manner as in Examples 1A-1 to 1A-6 except that the molten salt of potassium orthophosphate trihydrate and only potassium nitrate was added, and CS and DOL were measured, respectively. (Comparative Example 1B-1 to 1B-6)

使用未添加正磷酸鉀三水合物而僅硝酸鉀之熔融鹽，除此以 外，以與實施例1B-1~1B-6相同之方式進行化學強化處理，分別測定CS、DOL。 Use a molten salt of potassium nitrate which is not added with potassium orthophosphate trihydrate, except Further, chemical strengthening treatment was carried out in the same manner as in Examples 1B-1 to 1B-6, and CS and DOL were measured, respectively.

[實施例2：添加正磷酸鉀] [Example 2: Adding potassium orthophosphate] (實施例2A-1~2A-6) (Examples 2A-1 to 2A-6)

將正磷酸鉀三水合物之添加量設為6.7g(相對於硝酸鉀之K3PO4含量：1mol%)，除此以外，以與實施例1A-1~1A-6相同之方式進行化學強化處理，分別測定CS、DOL。 The chemistry was carried out in the same manner as in Examples 1A-1 to 1A-6 except that the amount of potassium orthophosphate trihydrate added was 6.7 g (K 3 PO 4 content relative to potassium nitrate: 1 mol%). Strengthen the treatment and measure CS and DOL separately.

(實施例2B-1~2B-6) (Examples 2B-1 to 2B-6)

將正磷酸鉀三水合物之添加量設為6.7g(相對於硝酸鉀之K3PO4含量：1mol%)，除此以外，以與實施例1B-1~1B-6相同之方式進行化學強化處理，分別測定CS、DOL。 The chemistry was carried out in the same manner as in Examples 1B-1 to 1B-6 except that the amount of potassium orthophosphate trihydrate added was 6.7 g (K 3 PO 4 content relative to potassium nitrate: 1 mol%). Strengthen the treatment and measure CS and DOL separately.

[實施例3：添加正磷酸鉀] [Example 3: Adding potassium orthophosphate] (實施例3A-1~3A-6) (Examples 3A-1 to 3A-6)

將正磷酸鉀三水合物之添加量設為43.2g(相對於硝酸鉀之K3PO4含量：6mol%)，除此以外，以與實施例1A-1~1A-6相同之方式進行化學強化處理，分別測定CS、DOL。 Chemicals were carried out in the same manner as in Examples 1A-1 to 1A-6 except that the amount of potassium orthophosphate trihydrate added was 43.2 g (K 3 PO 4 content relative to potassium nitrate: 6 mol%). Strengthen the treatment and measure CS and DOL separately.

(實施例3B-1~3B-6) (Examples 3B-1 to 3B-6)

將正磷酸鉀三水合物之添加量設為43.2g(相對於硝酸鉀之K3PO4含量：6mol%)，除此以外，以與實施例1B-1~1B-6相同之方式進行化學強化處理，分別測定CS、DOL。 The chemistry was carried out in the same manner as in Examples 1B-1 to 1B-6 except that the amount of potassium orthophosphate trihydrate added was 43.2 g (K 3 PO 4 content relative to potassium nitrate: 6 mol%). Strengthen the treatment and measure CS and DOL separately.

將實施例1~3之測定結果示於表1，將比較例1之測定結果示於表2。 The measurement results of Examples 1 to 3 are shown in Table 1, and the measurement results of Comparative Example 1 are shown in Table 2.

[實施例4：添加碳酸鉀] [Example 4: Addition of potassium carbonate] (實施例4A-1) (Example 4A-1)

於SUS製之杯中加入硝酸鉀250g，利用加熱套加熱至430℃而製備熔融鹽。於以上述方式製備之熔融鹽中添加碳酸鉀29.7g(相對於硝酸鉀之K2CO3含量：8mol%)，使用攪拌馬達、4片螺旋葉片攪拌10小時，靜置2小時。其後，將鈉鈣玻璃預熱至100℃，浸漬於430℃之熔融鹽中4小時而進行化學強化處理。其後，利用100℃之離子交換水清洗玻璃，於60℃下乾燥2小時。分別測定化學強化處理後之該玻璃之CS、DOL。 250 g of potassium nitrate was added to a cup made of SUS, and the molten salt was prepared by heating to 430 ° C with a heating mantle. To the molten salt prepared in the above manner, 29.7 g of potassium carbonate (K 2 CO 3 content relative to potassium nitrate: 8 mol%) was added, and the mixture was stirred for 10 hours using a stirring motor and four spiral blades, and allowed to stand for 2 hours. Thereafter, the soda lime glass was preheated to 100 ° C, and immersed in a molten salt of 430 ° C for 4 hours to carry out a chemical strengthening treatment. Thereafter, the glass was washed with ion-exchanged water at 100 ° C and dried at 60 ° C for 2 hours. The CS and DOL of the glass after the chemical strengthening treatment were measured, respectively.

(實施例4A-2~4A-6) (Examples 4A-2 to 4A-6)

於以與實施例1A-2~1A-6相同之方式進行化學強化處理之熔融鹽中依序添加硝酸鈉，進行化學強化處理，分別測定CS、DOL。 Sodium nitrate was sequentially added to the molten salt subjected to chemical strengthening treatment in the same manner as in Examples 1A-2 to 1A-6, and chemical strengthening treatment was carried out to measure CS and DOL, respectively.

(實施例4B-1~4B-6) (Examples 4B-1 to 4B-6)

將玻璃變更為鋁矽酸鹽玻璃，除此以外，以與實施例4A-1~4A-6相同之方式製備熔融鹽，進行化學強化處理，分別測定CS、DOL。 A molten salt was prepared in the same manner as in Examples 4A-1 to 4A-6 except that the glass was changed to aluminosilicate glass, and chemical strengthening treatment was carried out to measure CS and DOL, respectively.

[實施例5：添加碳酸鉀] [Example 5: Addition of potassium carbonate] (實施例5A-1~5A-6) (Examples 5A-1 to 5A-6)

將碳酸鉀之添加量設為18.0g(相對於硝酸鉀之K2CO3含量：5mol%)，除此以外，以與實施例4A-1~4A-6相同之方式進行化學強化處理，分別測定CS、DOL。 Chemical strengthening treatment was carried out in the same manner as in Examples 4A-1 to 4A-6 except that the amount of potassium carbonate added was 18.0 g (K 2 CO 3 content relative to potassium nitrate: 5 mol%). Determine CS and DOL.

(實施例5B-1~5B-6) (Examples 5B-1 to 5B-6)

將碳酸鉀之添加量設為18.0g(相對於硝酸鉀之K2CO3含量：5mol%)，除此以外，以與實施例4B-1~4B-6相同之方式進行化學強化處理，分別測定CS、DOL。 Chemical strengthening treatment was carried out in the same manner as in Examples 4B-1 to 4B-6 except that the amount of potassium carbonate added was 18.0 g (K 2 CO 3 content relative to potassium nitrate: 5 mol%). Determine CS and DOL.

[實施例6：添加碳酸鉀] [Example 6: Addition of potassium carbonate] (實施例6A-1~6A-6) (Examples 6A-1 to 6A-6)

將碳酸鉀之添加量設為55.6g(相對於硝酸鉀之K2CO3含量：14mol%)，除此以外，以與實施例4A-1~4A-6相同之方式進行化學強化處理，分別測定CS、DOL。 Chemical strengthening treatment was carried out in the same manner as in Examples 4A-1 to 4A-6 except that the amount of potassium carbonate added was 55.6 g (K 2 CO 3 content relative to potassium nitrate: 14 mol%). Determine CS and DOL.

(實施例6B-1~6B-6) (Examples 6B-1 to 6B-6)

將碳酸鉀之添加量設為55.6g(相對於硝酸鉀之K2CO3含量：14mol%)，除此以外，以與實施例4B-1~4B-6相同之方式進行化學強化處理，分別測定CS、DOL。 Chemical strengthening treatment was carried out in the same manner as in Examples 4B-1 to 4B-6 except that the amount of potassium carbonate added was 55.6 g (K 2 CO 3 content relative to potassium nitrate: 14 mol%). Determine CS and DOL.

將實施例4~6之測定結果示於表3。 The measurement results of Examples 4 to 6 are shown in Table 3.

[實施例7：添加焦磷酸鉀] [Example 7: Addition of potassium pyrophosphate] (實施例7A-1~7A-6) (Examples 7A-1 to 7A-6) (實施例7A-1) (Example 7A-1)

於SUS製之杯中加入硝酸鉀250g，利用加熱套加熱至430℃而製備熔融鹽。於以上述方式製備之熔融鹽中添加焦磷酸鉀三水合物30.4g(相對於硝酸鉀之K4P2O7含量：4.4mol%)，使用攪拌馬達、4片螺旋葉片攪拌2小時，靜置2小時。其後，將鈉鈣玻璃預熱至100℃，浸漬於430℃之熔融鹽中4小時而進行化學強化處理。其後，利用100℃之離子交換水清洗玻璃，於60℃下乾燥2小時。分別測定化學強化處理後之該玻璃之CS、DOL。 250 g of potassium nitrate was added to a cup made of SUS, and the molten salt was prepared by heating to 430 ° C with a heating mantle. 30.4 g of potassium pyrophosphate trihydrate (content of K 4 P 2 O 7 relative to potassium nitrate: 4.4 mol%) was added to the molten salt prepared in the above manner, and stirred by a stirring motor and 4 spiral blades for 2 hours. Set for 2 hours. Thereafter, the soda lime glass was preheated to 100 ° C, and immersed in a molten salt of 430 ° C for 4 hours to carry out a chemical strengthening treatment. Thereafter, the glass was washed with ion-exchanged water at 100 ° C and dried at 60 ° C for 2 hours. The CS and DOL of the glass after the chemical strengthening treatment were measured, respectively.

(實施例7A-2~7A-6) (Examples 7A-2 to 7A-6)

於以與實施例1A-2~1A-6相同之方式進行化學強化處理之熔融鹽中依序添加硝酸鈉，進行化學強化處理，分別測定CS、DOL。 Sodium nitrate was sequentially added to the molten salt subjected to chemical strengthening treatment in the same manner as in Examples 1A-2 to 1A-6, and chemical strengthening treatment was carried out to measure CS and DOL, respectively.

(實施例7B-1~7B-6) (Examples 7B-1 to 7B-6)

將玻璃變更為鋁矽酸鹽玻璃，除此以外，以與實施例7A-1~7A-6相同之方式製備熔融鹽，進行化學強化處理，分別測定CS、DOL。 A molten salt was prepared in the same manner as in Examples 7A-1 to 7A-6 except that the glass was changed to aluminosilicate glass, and chemical strengthening treatment was carried out to measure CS and DOL, respectively.

[實施例8：添加焦磷酸鉀] [Example 8: Addition of potassium pyrophosphate] (實施例8A-1~8A-6) (Examples 8A-1 to 8A-6)

將焦磷酸鉀三水合物之添加量設為6.7g(相對於硝酸鉀之K4P2O7含量：1mol%)，除此以外，以與實施例7A-1~7A-6相同之方式進行化學強化處理，分別測定CS、DOL。 In the same manner as in Examples 7A-1 to 7A-6, the amount of potassium pyrophosphate trihydrate added was 6.7 g (K 4 P 2 O 7 content relative to potassium nitrate: 1 mol%). Chemical strengthening treatment was carried out to measure CS and DOL, respectively.

(實施例8B-1~8B-6) (Examples 8B-1 to 8B-6)

將焦磷酸鉀三水合物之添加量設為6.7g(相對於硝酸鉀之K4P2O7含量：1mol%)，除此以外，以與實施例7B-1~7B-6相同之方式進行化學強化處理，分別測定CS、DOL。 In the same manner as in Examples 7B-1 to 7B-6, the amount of potassium pyrophosphate trihydrate added was 6.7 g (K 4 P 2 O 7 content relative to potassium nitrate: 1 mol%). Chemical strengthening treatment was carried out to measure CS and DOL, respectively.

[實施例9：添加焦磷酸鉀] [Example 9: Addition of potassium pyrophosphate] (實施例9A-1~9A-6) (Examples 9A-1 to 9A-6)

將焦磷酸鉀三水合物之添加量設為43.2g(相對於硝酸鉀之K4P2O7含量：6mol%)，除此以外，以與實施例7A-1~7A-6相同之方式進行 化學強化處理，分別測定CS、DOL。 In the same manner as in Examples 7A-1 to 7A-6, the amount of potassium pyrophosphate trihydrate added was 43.2 g (K 4 P 2 O 7 content relative to potassium nitrate: 6 mol%). Chemical strengthening treatment was carried out to measure CS and DOL, respectively.

(實施例9B-1~9B-6) (Examples 9B-1 to 9B-6)

將焦磷酸鉀三水合物之添加量設為43.2g(相對於硝酸鉀之K4P2O7含量：6mol%)，除此以外，以與實施例7B-1~7B-6相同之方式進行化學強化處理，分別測定CS、DOL。 In the same manner as in Examples 7B-1 to 7B-6, the amount of potassium pyrophosphate trihydrate added was 43.2 g (K 4 P 2 O 7 content relative to potassium nitrate: 6 mol%). Chemical strengthening treatment was carried out to measure CS and DOL, respectively.

將實施例7~9之測定結果示於表4。 The measurement results of Examples 7 to 9 are shown in Table 4.

(熔融鹽之壽命之評價) (Evaluation of the life of molten salt)

基於比較例1之結果，將於硝酸鉀熔融鹽中未添加其他無機鉀鹽而進行化學強化處理之情形時，熔融鹽中之Na離子濃度(將NaNO3設 為A(mol)，將KNO3設為B(mol)時之A/(A+B)之值)與CS之關係匯總於圖1。根據圖1之結果可知，關於化學強化玻璃之CS，與鈉鈣玻璃(比較例1A)相比，鋁矽酸鹽玻璃(比較例1B)同樣可獲得較高之值。因此，以下，為了證實無機鉀鹽向熔融鹽之添加效果，而使用利用鋁矽酸鹽玻璃之結果進行以後之考察。 Based on the result of Comparative Example 1, when other inorganic potassium salts were not added to the potassium nitrate molten salt for chemical strengthening treatment, the concentration of Na ions in the molten salt (NaNO 3 was set to A (mol), and KNO 3 was used. The relationship between the value of A/(A+B) when B (mol) is set and CS is summarized in Fig. 1. From the results of Fig. 1, it can be seen that the CS of the chemically strengthened glass can obtain a higher value than the soda lime glass (Comparative Example 1A) as compared with the soda lime glass (Comparative Example 1A). Therefore, in the following, in order to confirm the effect of adding an inorganic potassium salt to a molten salt, the result of using an aluminosilicate glass was examined later.

然後，於比較例1B中，由初期狀態之熔融鹽(比較例1B-1)賦予之CS值為864MPa，因此將自其降低了約10%之CS值(800MPa)設為劣化狀態之基準。即，將CS值成為800MPa時之熔融鹽中之Na離子含量(相對於硝酸鈉之添加量(mol%))設為熔融鹽之壽命之指標，而於以後進行評價。 In the comparative example 1B, since the CS value of the molten salt in the initial state (Comparative Example 1B-1) was 864 MPa, the CS value (800 MPa) from which it was reduced by about 10% was used as a criterion for the deterioration state. In other words, the Na ion content (addition amount (mol%) relative to sodium nitrate) in the molten salt when the CS value is 800 MPa is taken as an index of the life of the molten salt, and is evaluated later.

(正磷酸鉀向熔融鹽之添加效果) (Addition of potassium orthophosphate to molten salt)

基於實施例1B、實施例2B、及實施例3B之結果，將於硝酸鉀熔融鹽中添加正磷酸鉀而進行化學強化處理之情形時，相對於硝酸鉀(KNO3)之Na添加量(質量ppm)與獲得之CS的關係匯總於圖2。為了進行比較，亦一併表示於僅硝酸鉀，即未添加無機鉀鹽之情形時之關係(比較例1B)。 Based on the results of Example 1B, Example 2B, and Example 3B, when potassium orthophosphate was added to the potassium nitrate molten salt for chemical strengthening treatment, Na addition amount (mass) relative to potassium nitrate (KNO 3 ) The relationship between ppm and the obtained CS is summarized in Figure 2. For comparison, the relationship was also shown in the case of only potassium nitrate, that is, when no inorganic potassium salt was added (Comparative Example 1B).

然後，根據圖2之各關係，藉由直線近似，分別算出CS值成為800MPa時之熔融鹽中之Na離子含量(相對於硝酸鈉之添加量(mol%))。進而，根據該Na離子含量，將於熔融鹽中未添加硝酸鉀以外之無機鉀鹽之情形(比較例1B-1)設為熔融鹽壽命之基準(1.00倍)，而算出壽命比。 Then, according to the respective relationships of FIG. 2, the Na ion content (relative to the amount of sodium nitrate added (mol%)) in the molten salt when the CS value was 800 MPa was calculated by linear approximation. Further, in the case where the inorganic potassium salt other than potassium nitrate was not added to the molten salt (Comparative Example 1B-1), the life ratio was calculated based on the life of the molten salt (1.00 times).

又，藉由上述之方法，算出對應於正磷酸鉀添加量之總離子交換能力。正磷酸鉀之陰離子之價數為3，因此若將可交換之鉀離子數設為1，則潛在之Na-K離子交換能力為3。 Further, the total ion exchange capacity corresponding to the amount of potassium orthophosphate added was calculated by the above method. The valence of the anion of potassium orthophosphate is 3, so if the number of exchangeable potassium ions is set to 1, the potential Na-K ion exchange capacity is 3.

總離子交換能力=(正磷酸鉀添加量)×(潛在之Na-K離子交換能力) Total ion exchange capacity = (addition of potassium orthophosphate) × (potential Na-K ion exchange capacity)

將以上之結果示於表5。 The above results are shown in Table 5.

進而，將相對於硝酸鉀之正磷酸鉀之添加量(mol%)、與熔融鹽之壽命比(將僅硝酸鉀之熔融鹽之壽命設為1.00倍時之比)的關係示於圖3。 Further, the relationship between the amount (mol%) of potassium orthophosphate added to potassium nitrate and the life ratio of molten salt (the ratio of the life of the molten salt of only potassium nitrate to 1.00) is shown in Fig. 3 .

根據圖2可知，於熔融鹽中未添加正磷酸鉀之情形時，隨著熔融鹽中之Na量增加，強化玻璃之CS之下降明顯(比較例1B)，相對於此，藉由預先將正磷酸鉀添加於熔融鹽中，從而CS之下降變得非常緩慢(實施例1B、2B及3B)。又，根據圖3可知，伴隨著正磷酸鉀之添加量之增加，熔融鹽之壽命延長效果提高。 As can be seen from Fig. 2, when potassium orthophosphate was not added to the molten salt, as the amount of Na in the molten salt increased, the decrease in CS of the tempered glass was remarkable (Comparative Example 1B), whereas it was positive in advance. Potassium phosphate was added to the molten salt so that the drop in CS became very slow (Examples 1B, 2B and 3B). Further, as is clear from Fig. 3, the effect of prolonging the life of the molten salt is enhanced as the amount of potassium orthophosphate added is increased.

根據以上情況可知，正磷酸鉀之添加對熔融鹽之長壽命化起到明顯效果。 From the above, it can be seen that the addition of potassium orthophosphate has a significant effect on the long life of the molten salt.

(碳酸鉀向熔融鹽之添加效果) (Addition effect of potassium carbonate to molten salt)

基於實施例4B、實施例5B、及實施例6B之結果，將於硝酸鉀熔融鹽中添加碳酸鉀而進行化學強化處理之情形時，相對於硝酸鉀(KNO3)之Na添加量(質量ppm)與獲得之CS之關係匯總於圖4。為了進行比較，亦一併表示於僅硝酸鉀，即未添加無機鉀鹽之情形時之關係(比較例1B)。 Based on the results of Example 4B, Example 5B, and Example 6B, when potassium carbonate was added to the molten salt of potassium nitrate for chemical strengthening treatment, the amount of Na added relative to potassium nitrate (KNO 3 ) (ppm by mass) The relationship with the obtained CS is summarized in Figure 4. For comparison, the relationship was also shown in the case of only potassium nitrate, that is, when no inorganic potassium salt was added (Comparative Example 1B).

根據圖4之各關係，以與上述相同之方式，藉由直線近似，而算出CS值成為800MPa時之熔融鹽中之Na離子含量，進而根據Na離子含 量算出壽命比。 According to the relationship of FIG. 4, in the same manner as described above, the Na ion content in the molten salt when the CS value becomes 800 MPa is calculated by linear approximation, and further, according to the Na ion content. Calculate the life ratio.

又，藉由上述之方法，算出對應於碳酸鉀添加量之總離子交換能力。碳酸鉀之陰離子之價數為2，因此若將可交換之鉀離子數設為1，則潛在之Na-K離子交換能力為2。 Further, the total ion exchange capacity corresponding to the amount of potassium carbonate added was calculated by the above method. The valence of the anion of potassium carbonate is 2, so if the number of exchangeable potassium ions is set to 1, the potential Na-K ion exchange capacity is 2.

總離子交換能力=(碳酸鉀添加量)×(潛在之Na-K離子交換能力) Total ion exchange capacity = (potassium carbonate addition) × (potential Na-K ion exchange capacity)

將以上之結果示於表6。 The above results are shown in Table 6.

進而，將相對於硝酸鉀(KNO3)之碳酸鉀之添加量(mol%)與熔融鹽之壽命比(將僅硝酸鉀之熔融鹽之壽命設為1.00倍時之比)的關係示於圖5。 Further, the relationship between the amount of potassium carbonate added (mol%) relative to potassium nitrate (KNO 3 ) and the life ratio of molten salt (the ratio when the lifetime of the molten salt of only potassium nitrate is 1.00 times) is shown in the figure. 5.

根據圖4可知，於熔融鹽中未添加碳酸鉀之情形時，隨著熔融鹽中之Na量變多，強化玻璃之CS之下降明顯(比較例1B)，相對於此，藉由預先將碳酸鉀添加於熔融鹽中，從而CS之下降變緩慢(實施例4B、5B及6B)。又，根據圖5可知，伴隨著碳酸鉀之添加量之增加，熔融鹽之壽命延長效果提高。 As can be seen from Fig. 4, when potassium carbonate is not added to the molten salt, as the amount of Na in the molten salt increases, the decrease in CS of the tempered glass is remarkable (Comparative Example 1B), whereas potassium carbonate is previously used. It was added to the molten salt so that the decrease in CS became slow (Examples 4B, 5B and 6B). Further, as is clear from Fig. 5, the effect of prolonging the life of the molten salt is enhanced as the amount of potassium carbonate added is increased.

根據以上情況可知，碳酸鉀之添加對熔融鹽之長壽命化起到明顯效果。 From the above, it can be seen that the addition of potassium carbonate has a significant effect on the long life of the molten salt.

(焦磷酸鉀向熔融鹽之添加效果) (Addition effect of potassium pyrophosphate to molten salt)

基於實施例4B、實施例5B、及實施例6B之結果，將於硝酸鉀熔融鹽中添加焦磷酸鉀而進行化學強化處理之情形時，相對於硝酸鉀 (KNO3)之Na添加量(質量ppm)與獲得之CS的關係匯總於圖6。為了進行比較，亦一併表示於僅硝酸鉀，即未添加無機鉀鹽之情形時之關係(比較例1B)。 Based on the results of Example 4B, Example 5B, and Example 6B, Na addition amount (mass) relative to potassium nitrate (KNO 3 ) when potassium pyrophosphate was added to the potassium nitrate molten salt for chemical strengthening treatment The relationship between ppm and the obtained CS is summarized in Figure 6. For comparison, the relationship was also shown in the case of only potassium nitrate, that is, when no inorganic potassium salt was added (Comparative Example 1B).

根據圖6之各關係，以與上述相同之方式，藉由直線近似而算出CS值成為800MPa時之熔融鹽中之Na離子含量，進而根據Na離子含量算出壽命比。 According to the respective relationships of Fig. 6, in the same manner as described above, the Na ion content in the molten salt when the CS value was 800 MPa was calculated by linear approximation, and the life ratio was calculated from the Na ion content.

又，藉由上述之方法，算出對應於焦磷酸鉀添加量之總離子交換能力。焦磷酸鉀之陰離子之價數為4，因此若將可交換之鉀離子數設為1，則潛在之Na-K離子交換能力為4。 Further, the total ion exchange capacity corresponding to the amount of potassium pyrophosphate added was calculated by the above method. The valence of the anion of potassium pyrophosphate is 4, so if the number of exchangeable potassium ions is set to 1, the potential Na-K ion exchange capacity is 4.

總離子交換能力=(焦磷酸鉀添加量)×(潛在之Na-K離子交換能力) Total ion exchange capacity = (potassium pyrophosphate added) × (potential Na-K ion exchange capacity)

將以上之結果示於表7。 The above results are shown in Table 7.

進而，將相對於硝酸鉀(KNO3)之焦磷酸鉀之添加量(mol%)與熔融鹽之壽命比(將僅硝酸鉀之熔融鹽之壽命設為1.00倍時之比)的關係示於圖7。 Further, the relationship between the amount (mol%) of potassium pyrophosphate added to potassium nitrate (KNO 3 ) and the life ratio of molten salt (the ratio when the lifetime of the molten salt of only potassium nitrate is 1.00 times) is shown in Figure 7.

根據圖6可知，於熔融鹽中未添加焦磷酸鉀之情形時，隨著熔融鹽中之Na量變多，強化玻璃之CS之下降明顯(比較例1B)，相對於此，藉由預先將焦磷酸鉀添加於熔融鹽中，從而CS之下降變緩慢(實施例7B、8B及9B)。又，根據圖7可知，伴隨著焦磷酸鉀之添加量之 增加，熔融鹽之壽命延長效果提高。 As can be seen from Fig. 6, when potassium pyrophosphate was not added to the molten salt, as the amount of Na in the molten salt increased, the decrease in CS of the tempered glass was remarkable (Comparative Example 1B), whereas the coke was previously Potassium phosphate was added to the molten salt so that the drop in CS became slow (Examples 7B, 8B and 9B). Moreover, it can be seen from Fig. 7 that the amount of potassium pyrophosphate added is Increasing, the life of the molten salt is prolonged.

根據以上情況可知，焦磷酸鉀之添加對熔融鹽之長壽命化起到明顯效果。 From the above, it can be seen that the addition of potassium pyrophosphate has a significant effect on the long life of the molten salt.

總結上述情況，將添加於熔融鹽中之磷酸鉀或碳酸鉀等各無機鉀鹽(陰離子種)之總離子交換能力(添加之陰離子種之價數×添加量(mol%))與熔融鹽之壽命比(將僅硝酸鉀之熔融鹽之壽命設為1.00倍時之比)的關係示於圖8。 In summary, the total ion exchange capacity (the valence of the added anion species × the amount of addition (mol%)) of each inorganic potassium salt (anionic species) such as potassium phosphate or potassium carbonate added to the molten salt and the molten salt are The relationship between the life ratio (the ratio when the life of the molten salt of only potassium nitrate is set to 1.00 times) is shown in Fig. 8 .

根據圖8可知，藉由預先將該等無機鉀鹽添加於以硝酸鉀為主成分之玻璃強化用熔融鹽中，可實現壽命之長期化。其中，利用正磷酸鉀之壽命延長效果明顯。 As can be seen from Fig. 8, the inorganic potassium salt is added to the molten salt for glass reinforcement containing potassium nitrate as a main component in advance, whereby the life can be prolonged. Among them, the effect of prolonging the life of potassium orthophosphate is obvious.

[比較例2：添加二氧化矽粉末] [Comparative Example 2: addition of cerium oxide powder] (比較例2A-1~2A-4) (Comparative Example 2A-1~2A-4) (比較例2A-1) (Comparative Example 2A-1)

於SUS製之杯中加入硝酸鉀250g，利用加熱套加熱至430℃而製備熔融鹽。於以上述方式製備之熔融鹽中添加二氧化矽粉末0.2g(相對於硝酸鉀之SiO2含量：0.1質量%)，使用攪拌馬達、4片螺旋葉片攪拌2小時，靜置2小時。其後，將鈉鈣玻璃預熱至100℃，浸漬於430℃之熔融鹽中4小時而進行化學強化處理。其後，利用100℃之離子交換水清洗玻璃，於60℃下乾燥2小時。分別測定化學強化處理後之該玻璃之CS、DOL。 250 g of potassium nitrate was added to a cup made of SUS, and the molten salt was prepared by heating to 430 ° C with a heating mantle. To the molten salt prepared in the above manner, 0.2 g of cerium oxide powder (SiO 2 content relative to potassium nitrate: 0.1% by mass) was added, and the mixture was stirred for 2 hours using a stirring motor and four spiral blades, and allowed to stand for 2 hours. Thereafter, the soda lime glass was preheated to 100 ° C, and immersed in a molten salt of 430 ° C for 4 hours to carry out a chemical strengthening treatment. Thereafter, the glass was washed with ion-exchanged water at 100 ° C and dried at 60 ° C for 2 hours. The CS and DOL of the glass after the chemical strengthening treatment were measured, respectively.

(比較例2A-2~2A-4) (Comparative Example 2A-2~2A-4)

於以與實施例7A-2~7A-4相同之方式進行化學強化處理之熔融鹽中依序添加硝酸鈉，進行化學強化處理，分別測定CS、DOL。 Sodium nitrate was sequentially added to the molten salt subjected to chemical strengthening treatment in the same manner as in Examples 7A-2 to 7A-4, and chemical strengthening treatment was carried out to measure CS and DOL, respectively.

(比較例2B-1~2B-4) (Comparative Example 2B-1~2B-4)

將玻璃變更為鋁矽酸鹽玻璃，除此以外，以與比較例2A-1~2A-4相同之方式製備熔融鹽，進行化學強化處理，分別測定CS、DOL。 A molten salt was prepared in the same manner as in Comparative Examples 2A-1 to 2A-4 except that the glass was changed to aluminosilicate glass, and chemical strengthening treatment was carried out to measure CS and DOL, respectively.

[比較例3：添加二氧化矽粉末] [Comparative Example 3: Addition of cerium oxide powder] (比較例3A-1~3A-4) (Comparative Example 3A-1 to 3A-4)

將二氧化矽粉末之添加量設為25.1g(相對於硝酸鉀之SiO2含量：10質量%)，除此以外，以與比較例2A-1~2A-4相同之方式進行化學強化處理，分別測定CS、DOL。 Chemical strengthening treatment was carried out in the same manner as in Comparative Examples 2A-1 to 2A-4 except that the amount of the cerium oxide powder was changed to 25.1 g (the SiO 2 content of potassium nitrate: 10% by mass). Determine CS and DOL separately.

(比較例3B-1~3B-4) (Comparative Example 3B-1 to 3B-4)

將二氧化矽粉末之添加量設為25.1g(相對於硝酸鉀之SiO2含量：10質量%)，除此以外，以與比較例2B-1~2B-4相同之方式進行化學強化處理，分別測定CS、DOL。 Chemical strengthening treatment was carried out in the same manner as in Comparative Examples 2B-1 to 2B-4 except that the amount of the cerium oxide powder was changed to 25.1 g (the SiO 2 content of potassium nitrate: 10% by mass). Determine CS and DOL separately.

將比較例2A、2B、3A及3B之測定結果示於表8。 The measurement results of Comparative Examples 2A, 2B, 3A, and 3B are shown in Table 8.

(二氧化矽向熔融鹽之添加效果) (addition effect of cerium oxide to molten salt)

基於比較例2B、3B之結果，將於硝酸鉀熔融鹽中添加二氧化矽而進行化學強化處理之情形時，相對於硝酸鉀(KNO3)之Na添加量(質 量ppm)與獲得之CS的關係匯總於圖9。為了進行比較，亦一併表示於僅硝酸鉀，即未添加無機鉀鹽之情形時之關係(比較例1B)。 Based on the results of Comparative Examples 2B and 3B, when the cerium oxide was added to the molten salt of potassium nitrate to carry out chemical strengthening treatment, the amount of Na added (mass ppm) relative to potassium nitrate (KNO 3 ) and the obtained CS were The relationship is summarized in Figure 9. For comparison, the relationship was also shown in the case of only potassium nitrate, that is, when no inorganic potassium salt was added (Comparative Example 1B).

然後，根據圖9之各關係，藉由直線近似，分別算出CS值成為800MPa時之熔融鹽中之Na離子含量(相對於硝酸鈉之添加量(mol%))。進而，根據該Na離子含量，將於熔融鹽中未添加硝酸鉀以外之無機鉀鹽之情形(比較例1B-1)設為熔融鹽壽命之基準(1.00倍)而算出壽命比。 Then, according to each relationship of FIG. 9, the Na ion content (addition amount (mol%) with respect to sodium nitrate) in the molten salt when the CS value was 800 MPa was calculated by linear approximation. In addition, in the case where the inorganic potassium salt other than potassium nitrate was not added to the molten salt (Comparative Example 1B-1), the life ratio was calculated based on the reference (1.00 times) of the molten salt life.

將以上之結果示於表9。 The above results are shown in Table 9.

進而，將二氧化矽之添加量(相對於硝酸鉀KNO3之二氧化矽SiO2之添加量(質量%))與熔融鹽之壽命比(將僅硝酸鉀之熔融鹽之壽命設為1.00倍時之比)的關係示於圖10。 Further, the ratio of the amount of addition of cerium oxide (the amount of cerium oxide SiO 2 added (mass%) relative to potassium nitrate KNO 3 ) to the molten salt is set to 1.00 times the life of the molten salt of only potassium nitrate. The relationship of time ratio is shown in Fig. 10.

根據圖9可知，於熔融鹽中未添加無機鹽之情形時，隨著熔融鹽中之Na量變多，強化玻璃之CS之下降明顯(比較例1B)，即便將二氧化矽預先添加於熔融鹽中，CS之下降亦明顯(比較例2B、3B)。又，根據圖10可知，即便二氧化矽之添加量增加，亦基本上無法確認熔融鹽之壽命延長效果。 According to Fig. 9, when the inorganic salt is not added to the molten salt, as the amount of Na in the molten salt increases, the CS of the tempered glass decreases significantly (Comparative Example 1B), even if cerium oxide is previously added to the molten salt. The decrease in CS was also significant (Comparative Examples 2B, 3B). Further, as is clear from Fig. 10, even if the amount of addition of cerium oxide is increased, the effect of prolonging the life of the molten salt cannot be confirmed.

根據上述情況可知，二氧化矽之添加未對熔融鹽之長壽命化起到效果。 From the above, it is understood that the addition of cerium oxide does not contribute to the long life of the molten salt.

參照特定之實施態樣詳細地說明了本發明，但業者明確可於不偏離本發明之精神與範圍而進行各種變更或修正。本申請案係基於 2012年9月18日提出申請之日本專利申請案(日本專利特願2012-205039)者，將其內容作為參照而併入本文中。 The present invention has been described in detail with reference to the specific embodiments thereof, and it is obvious that various changes and modifications may be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2012-205039, filed on Sep.

產業上之可利用性Industrial availability

根據本發明之熔融鹽，可於保持賦予玻璃之CS值與先前相同程度之情況下使熔融鹽之交換頻率下降，而反覆應用於玻璃之化學強化處理。其結果，於玻璃之化學強化處理中可低成本化或提高處理量。 According to the molten salt of the present invention, the exchange frequency of the molten salt can be lowered while maintaining the CS value of the glass to be the same as before, and the chemical strengthening treatment of the glass can be repeatedly applied. As a result, it is possible to reduce the cost or increase the amount of treatment in the chemical strengthening treatment of glass.

Claims (8)

一種玻璃強化用熔融鹽，其係用於藉由離子交換而於玻璃表面形成壓縮應力層者，且含有硝酸鉀，進而含有碳酸陰離子及磷酸陰離子中之至少一者。 A molten salt for glass reinforcement for forming a compressive stress layer on a glass surface by ion exchange, and containing potassium nitrate, and further containing at least one of a carbonate anion and a phosphate anion. 如請求項1之玻璃強化用熔融鹽，其含有硝酸鉀、碳酸陰離子及磷酸陰離子。 The molten salt for glass reinforcement according to claim 1, which comprises potassium nitrate, a carbonate anion, and a phosphate anion. 如請求項1或2之玻璃強化用熔融鹽，其中上述碳酸陰離子為碳酸鉀之陰離子種，上述磷酸陰離子為正磷酸鉀及焦磷酸鉀中之至少一者之陰離子種。 The molten salt for glass reinforcement according to claim 1 or 2, wherein the carbonate anion is an anion species of potassium carbonate, and the phosphate anion is an anion species of at least one of potassium orthophosphate and potassium pyrophosphate. 如請求項3之玻璃強化用熔融鹽，其中上述碳酸鉀之含量相對於上述硝酸鉀為3.5~24莫耳%。 The molten salt for glass reinforcement according to claim 3, wherein the content of the potassium carbonate is 3.5 to 24 mol% with respect to the potassium nitrate. 如請求項3或4之玻璃強化用熔融鹽，其中上述正磷酸鉀之含量相對於上述硝酸鉀為0.8~13.5莫耳%。 The molten salt for glass reinforcement according to claim 3 or 4, wherein the content of the potassium orthophosphate is 0.8 to 13.5 mol% based on the potassium nitrate. 如請求項3至5中任一項之玻璃強化用熔融鹽，其中上述焦磷酸鉀之含量相對於上述硝酸鉀為3.5~9.0莫耳%。 The molten salt for glass reinforcement according to any one of claims 3 to 5, wherein the content of the potassium pyrophosphate is 3.5 to 9.0 mol% based on the potassium nitrate. 一種強化玻璃之製造方法，其包括使用如請求項1至6中任一項之玻璃強化用熔融鹽而於玻璃表面形成壓縮應力層之步驟。 A method of producing a tempered glass, comprising the step of forming a compressive stress layer on a surface of a glass using the molten salt for glass reinforcement according to any one of claims 1 to 6. 一種玻璃強化用熔融鹽之壽命延長方法，其係用於藉由離子交換而於玻璃表面形成壓縮應力層之玻璃強化用熔融鹽之壽命延長方法，且於含有硝酸鉀之強化處理前之熔融鹽中，以含有碳酸陰離子及磷酸陰離子中之至少一者之方式混合碳酸鉀及磷酸鉀中之至少一者。 A method for prolonging the life of a molten salt for glass reinforcement, which is a method for extending the life of a molten salt for glass reinforcement which forms a compressive stress layer on a glass surface by ion exchange, and a molten salt before the strengthening treatment containing potassium nitrate At least one of potassium carbonate and potassium phosphate is mixed in such a manner as to contain at least one of a carbonate anion and a phosphate anion.
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