200922897 九、發明說明 【發明所屬之技術領域】 本發明關於用於玻璃的蝕刻液組成物，更詳細地說係 關於供構成平面顯示器的玻璃用的蝕刻液組成物。 【先前技術】 本發明的用於玻璃的蝕刻液組成物係用於替代或改善 先前所使用的主材料爲氫氟酸（HF )的蝕刻劑。先前所使 用的主材料爲氫氟酸的鈾刻劑用於在對玻璃表面進行触刻 的同時，去除殘留在表面上的污染源，但是由於氫氟酸所 具備的強氧化能力，導致玻璃的透明度下降及表面粗糕度 增加、設備腐蝕等。因此，少量使用或完全替代氫氟酸的 硏究已持續很久。 其中，比較具代表性的方法係混合含有氟化氫銨及氟 離子的無機鹽、無機酸及有機酸以抑制過度腐蝕。但由於 其氧化能力差’清洗能力急劇下降’所以難以適用於大規 模生產。 【發明內容】 本發明的目的在於提供一種供構成平面顯示器的玻璃 用的蝕刻液組成物’其既能減少氣氟酸的使用量’又具有 強而穩定的蝕刻能力’且蝕刻品質良好。 本發明的另一目的在於提供一種供構成平面顯不器的 玻璃用的蝕刻液組成物，其使得派渣（sludge )產生量減 -5- 200922897 少，廢水處理費用降低，被鈾刻的玻璃的透明度和均勻度 良好，蝕刻效率（蝕刻張數）提高。 本發明提供一種供構成平面顯示器的玻璃用的蝕刻液 組成物，該飩刻液組成物係由下述部分組成：5重量％〜20 重量％的HF ; 1 0重量％〜5 0重量％的一種以上的無機酸， 該無機酸選自 H2S〇4、H3PO4 ' HC1、H2CO3 ' HNO3 或 HCl〇4 ; 0.5重量％~10重量％的羧酸；0.01重量％〜5重量％ 的作爲第一添加劑的無機硝酸鹽；及餘量的水。本發明的 玻璃用的蝕刻液組成物較佳地亦包含0.00 5重量1重量 %的作爲第二添加劑的氟系表面活性劑。在此，該“氟系 表面活性劑”是指表面活性劑中作爲親油性基團的烴部分 的氫係被氟取代的表面活性劑。 本發明的蝕刻液組成物的應用方法沒有特別限定。例 如’根據被處理玻璃的大小，蝕刻方式包括：適用於較小 尺寸（2代尺寸以下，3 70 x470、590x670 )玻璃的浸漬起 泡（Dip-bubble )方式；及適用於大尺寸（3代尺寸以上 )玻璃的噴灑（spray )方式。浸漬起泡方式是在通風的蝕 刻槽中浸漬被處理玻璃且通常不維持恆定溫度進行蝕刻的 方法’其直接適用於隨鈾刻升高的溫度以進行蝕刻；噴灑 方式是在槽外對被處理玻璃進行噴灑且維持恆定溫度進行 蝕刻的方法。 上述蝕刻液組成物中，HF爲玻璃蝕刻的主材料，將 作爲玻璃成分的氧化物轉換成氟化物，且進行蝕刻之使用 量爲5重量％〜2 0重量％。當HF爲5重量％以下時，初期 200922897 蝕刻能力較差，蝕刻時間長。當超過20重量％時，初期触 刻能力顯著增加，產生蝕刻斑點。 上述一種以上的無機酸作爲輔材料，與玻璃成分中的 陽離子結合，形成水溶性淤渣，防止淤渣再附著到玻璃表 面上，提高溶液的氧化能力，從而提高蝕刻能力，防止因 溶液的黏度增加而導致凹痕（dent)和劃痕（scratch)擴 大。選自 H2S04、H3P〇4 ' HC1、h2co3、hno3 或 hcio4 的一種以上的無機酸的使用量爲10重量％〜50重量％。在 使用量爲1 〇重量％以下時，淤渣量增多，初期蝕刻能力差 。在使用量爲5 0重量％以上時，蝕刻斑點加深，突起缺陷 和表面粗糙度增加。 上述羧酸具有下述效果：抑制初期急劇的酸度變化， 直接與殘留在玻璃表面上的污染物反應，降低蝕刻後殘留 的淤渣的黏結性。上述之飽和或不飽和脂肪酸較佳地係飽 和脂肪酸或具有1或2個雙鍵的脂肪酸。上述羧酸的種類 沒有特別限定，但通常爲具有1〜16個碳原子和1〜3個羧 酸基的羧酸。例如，可爲甲酸、乙酸、枸櫞酸、乙二酸、 馬來酸、丙二酸、丁二酸、蘋果酸、甲基丙烯酸、丙酸、 山梨酸、檸檬酸、十一碳烯酸、新癸酸、油酸、葡萄糖酸 、乙醇酸或彼等的混合物。羧酸的使用量爲〇 . 5重量％〜 1 0重量％。在使用量爲0.5重量％以下時’不具備降低淤 渣黏結性的效果，從而因淤渣引起的設備污染加重；在使 用量爲1 0重量％以上時，難以調節酸度’蝕刻能力下降。 作爲第一添加劑的含有Ν〇3·離子的無機硝酸鹽可提高 200922897 溶液的氧化能力’從而提高蝕刻能力，產生微小氣泡（ microbubble)，所以能夠防止游渣附著在玻璃表面上，能 夠將指紋或其他有機物直接溶解。同時，亦具有通過氟離 子的再生反應以提高試劑壽命的效果。例如，使用NaN03 ' KN〇3 ' FeN〇3 ' A1 ( N03) 3 等的 M(N03) n 無機鹽， 較佳之使用量爲0.01重量％~5重量％。 作爲第二添加劑的氟系表面活性劑係吸附在玻璃表面 上，使得所生成的淤渣快速脫落且不會再次附著。同時， 能夠顯著提局清洗效率。作爲第二添加劑的氟系表面活性 劑可爲 RfCH2CH2SCH2CH2C02Li、 (RfCH2CH20)P(〇)(〇NH4)2、（RfCH2CH20)2P(0)(0NH4)、 RfCH2CH20(CH2CH20)yH、RfCH2CH2S03X、 RfCH2CH2NHS03X或彼等的混合物（上述式中，y爲8〜 15的整數’ X是Η或NH4，Rf是F(CF2CF2) z，其中z 爲3〜8的整數）。表面活性劑的使用量較佳地爲0.005 重量％〜1重量％。在表面活性劑達到1重量％以上時，產 生大量泡沬，效率降低。 Μ ί隹測本發明的供構成平面顯示器的玻璃用的蝕刻液 組成物是通過下述的反應機制所形成的，但其並不用於特 別限定本發明的保護範圍。據推測，蝕刻反應機制係分爲 兩個階段：在第一階段中，組成物成分中的H F與作爲玻 璃成分的Si〇2、Α12〇3、CaO、ROx結合，其中一部分轉化 爲氣相的I、siF4而揮發，另一部分則轉化爲H20和 HzSiF6而溶解到試劑中，另有—部分轉化爲不溶性鹽，即 200922897 A1F3、CaF2及RFX。在第二階段中，該不溶性鹽的陽離子 和無機酸的陰離子結合，生成 A12(S04)3、CaS04、 R(S04)x、A1(N03)3、Ca(N03)2、R(N03)x、A1C13、CaCl2 、RC1 x ' Al(C〇3) 3、Ca(C〇3)2、R(C03 )x ' AIPO4、 Ca3(P04)2、R(P〇4)x及HF，其轉化爲水溶性鹽，從而導致 淤渣量減少，淤渣之間的黏結性下降，粒子變小，可減少 設備污染，所生成的HF可再次參與蝕刻。 發明效果 本發明提供的玻璃用的蝕刻液組成物具有下述之效果 :經本發明的玻璃用的蝕刻液組成物處理的玻璃的透明度 和表面粗糙度等蝕刻品質良好，蝕刻能力穩定，使用壽命 延長，蝕刻效率（蝕刻張數）提高。 【實施方式】 下述係根據實施例以詳細說明本發明。該等實施例係 用於例示本發明，不能被解釋爲限定本發明的專利權利範 圍。 實施例1至6 蝕刻方法 準備以下述表1所示的比例混合H F /硝酸鈉/無機酸（ 硫酸、磷酸、鹽酸）/乙醇酸/氟系表面活性劑/去離子水以 生成蝕刻液組成物’並維持於3 0 r下。爲去除污染物，在 200922897 LCD製程中對上下板密合間注入有液晶的飩刻用無鹼玻璃 (日本電氣硝子股份有限公司的NEG OA-21，尺寸： 3 70 x470 ’厚度：l.26t ( 1260 μιη))，測定各規定部分的 厚度，投入到蝕刻液中。蝕刻量設定如下：事先，預備噴 灑1 0分鐘左右，測定蝕刻能力，然後噴灑與所需蝕刻量 (1.26t— 0.8t，即460μιη )相應的時間，進行鈾刻。 在本發明使用的噴灑裝置中，下部設置有儲藏罐，該 儲藏罐採用適合使用於強酸（pHSl)環境的耐酸性（特 氟隆：teflon )材質製成，最大能夠存儲30 L溶液，使用 具有強磁吸力的磁力泵（1 00 L/分鐘），通過按照圓形噴 射的全錐型（full cone type )垂直噴灑噴嘴，將溶液均勻 噴射到玻璃的兩個表面上。裝置由玻璃投入口、蝕刻區域 、清洗區域及出口構成，並使用透明PVC，能夠用肉眼確 認蝕刻程序，從而能夠用肉眼發現程序中產生的問題並調 節蝕刻過程。清洗區域採用排出方式，而不採用再循迴方 式，從而將清洗所引起的玻璃污染最小化，控制部分可使 用觸控面板（touchpanel)以進行自動和手動調節。爲防 止玻璃蝕刻時發熱所引起之試劑溫度上升，可將該程序設 計成可自動進行加熱和冷卻調節。 分析方法 在清洗機中使用純水清洗被蝕刻的玻璃，經過清洗、 乾燥程序後，測定各部分的厚度，計算蝕刻量、蝕刻速度 及每秒飩刻速度。並且，利用三波長燈檢查被蝕刻的玻璃 -10- 200922897 ’計算突起缺陷率，進行大致觀察，比較縱向斑點、突起 斑點、透明度。圖7示出實施例3、實施例6及比較例的 表面照片。 凹痕擴大率係經如下計算：任意製作出幾個不同尺寸 的凹痕，測定其尺寸之後，以一定的厚度（0.8t )進行蝕 刻。然後，找出蝕刻前凹痕尺寸爲100 μηι〜200 μπι的擴大 凹痕，測定尺寸，根據下面的數學式，計算出擴大率。將 實施例4、實施例5及比較例的凹痕擴大率如圖6所示。 凹痕擴大率（％)= 蝕刻後尺寸-蝕刻前尺寸 蝕刻前尺寸 χΙΟΟ 粗糙度係通過使用稱 α-STEP IQ (生產商：KLA Tencor，美國）設備測定被蝕刻的玻璃表面粗糙度加以 確定。實施例3和實施例5的粗糙度圖見圖1和圖2。上 述附圖中，橫軸表示粗糙度測定長度（距離）且縱軸表示 被蝕刻的玻璃的高低。 淤渣比例係以下述方式表示：對一定量的玻璃（ 400μηι )進行蝕刻後，靜置一定時間（30分鐘），測出沉 澱的淤渣量，將測出的淤渣量與比較例進行比較，表示爲 相對値。將實施例2、實施例6及比較例的淤渣量的照片 示於圖4。 使用壽命是經相同的溶液鈾刻一定量（累積蝕刻量 4000 μπι )的玻璃後的蝕刻能力與初期蝕刻能力之比所測 定。將實施例2、實施例4及比較例的使用壽命圖示於圖 -11 - 200922897 表1示出針對蝕刻斑點、凹痕擴大率、表面粗糙度、 淤渣比例及使用壽命的相對檢測値。 比較例 作爲玻璃蝕刻液，使用1 7重量％的氫氟酸水溶液；除 此之外，採用與實施例1至6相同的方式實施蝕刻。蝕刻 斑點、凹痕擴大率、表面粗糙度、淤渣比例及使用壽命的 相對檢測値如表1所示。圖3是示出粗糙度的圖。 【圖式簡單說明】 圖1和圖2分別是實施例3和實施例5的粗糙度圖。 圖3是比較例的粗糙度圖。 圖4是實施例2、實施例6及比較例的淤渣量照片。 圖5是實施例2、實施例4及比較例的使用壽命圖。 圖6是實施例4、實施例5及比較例的凹痕擴大率圖 〇 圖7是實施例3、實施例6及比較例的表面照片。 -12-BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching liquid composition for glass, and more particularly to an etching liquid composition for a glass constituting a flat display. [Prior Art] The etching liquid composition for glass of the present invention is used to replace or improve the etchant in which the main material used previously is hydrofluoric acid (HF). The uranium engraving agent used as the main material of hydrofluoric acid was used to remove the residual source on the surface while the glass surface was touched, but the transparency of the glass was caused by the strong oxidizing ability of hydrofluoric acid. Decrease and increase in surface roughness, equipment corrosion, etc. Therefore, research on the small amount of use or complete replacement of hydrofluoric acid has been going on for a long time. Among them, a more representative method is to mix inorganic salts, inorganic acids and organic acids containing ammonium hydrogen fluoride and fluoride ions to suppress excessive corrosion. However, due to its poor oxidizing ability, the cleaning ability is drastically reduced, it is difficult to apply to large-scale production. DISCLOSURE OF THE INVENTION An object of the present invention is to provide an etching liquid composition for glass which constitutes a flat panel display, which can reduce the amount of use of fluorofluoric acid and has a strong and stable etching ability, and has excellent etching quality. Another object of the present invention is to provide an etchant composition for a glass constituting a flat display, which reduces the amount of sludge generated by -5 to 200922897, reduces the cost of wastewater treatment, and is etched by uranium. The transparency and uniformity are good, and the etching efficiency (number of etching sheets) is improved. The present invention provides an etchant composition for glass for constituting a flat panel display, the etchant composition being composed of 5% by weight to 20% by weight of HF; 10% by weight to 5% by weight of 5% by weight More than one inorganic acid selected from the group consisting of H2S〇4, H3PO4 'HC1, H2CO3 'HNO3 or HCl〇4; 0.5% by weight to 10% by weight of carboxylic acid; 0.01% by weight to 5% by weight of the first additive Inorganic nitrate; and the balance of water. The etchant composition for glass of the present invention preferably further contains 0.005 wt.% by weight of a fluorine-based surfactant as a second additive. Here, the "fluorosurfactant" means a surfactant in which a hydrogen portion of a hydrocarbon portion which is a lipophilic group in the surfactant is substituted with fluorine. The application method of the etching liquid composition of the present invention is not particularly limited. For example, 'depending on the size of the glass to be treated, the etching method includes: Dip-bubble method suitable for smaller size (2 generation size, 3 70 x 470, 590x670) glass; and suitable for large size (3 generations) Above the size) spray of glass. The immersion foaming method is a method of immersing the treated glass in a ventilated etching bath and generally not maintaining a constant temperature for etching. It is directly applicable to etching at an elevated temperature with uranium engraving; the spraying method is treated outside the tank. A method in which the glass is sprayed and maintained at a constant temperature for etching. In the etching liquid composition, HF is a main material for glass etching, and an oxide which is a glass component is converted into a fluoride, and the amount of etching is 5% by weight to 20% by weight. When HF is 5% by weight or less, the initial 200922897 has a poor etching ability and a long etching time. When it exceeds 20% by weight, the initial contact ability is remarkably increased to cause etching spots. The above-mentioned one or more inorganic acids are used as auxiliary materials to combine with the cations in the glass component to form a water-soluble sludge, thereby preventing the sludge from adhering to the surface of the glass, thereby improving the oxidizing ability of the solution, thereby improving the etching ability and preventing the viscosity of the solution. The increase leads to an increase in dents and scratches. The amount of one or more inorganic acids selected from the group consisting of H2S04, H3P〇4 'HC1, h2co3, hno3 or hcio4 is from 10% by weight to 50% by weight. When the amount used is 1% by weight or less, the amount of sludge increases, and the initial etching ability is poor. When the amount used is 50% by weight or more, the etching spots are deepened, and the protrusion defects and surface roughness are increased. The carboxylic acid has an effect of suppressing a sudden change in acidity in the initial stage and directly reacting with the contaminants remaining on the surface of the glass to lower the adhesion of the sludge remaining after the etching. The above saturated or unsaturated fatty acid is preferably a saturated fatty acid or a fatty acid having 1 or 2 double bonds. The kind of the above carboxylic acid is not particularly limited, but is usually a carboxylic acid having 1 to 16 carbon atoms and 1 to 3 carboxylic acid groups. For example, it may be formic acid, acetic acid, citric acid, oxalic acid, maleic acid, malonic acid, succinic acid, malic acid, methacrylic acid, propionic acid, sorbic acid, citric acid, undecylenic acid, Neodecanoic acid, oleic acid, gluconic acid, glycolic acid or a mixture thereof. The amount of the carboxylic acid used is 〇 5% by weight to 10% by weight. When the amount of use is 0.5% by weight or less, the effect of reducing the stickiness of the sludge is not obtained, so that the equipment contamination due to the sludge is increased; when the amount is 10% by weight or more, it is difficult to adjust the acidity'. The inorganic nitrate containing Ν〇3· ions as the first additive can improve the oxidizing ability of the solution of 200922897', thereby improving the etching ability and generating microbubbles, so that the slag can be prevented from adhering to the glass surface, and the fingerprint or the fingerprint can be Other organic matter dissolves directly. At the same time, it also has the effect of enhancing the life of the reagent by the regeneration reaction of fluorine ions. For example, an M(N03)n inorganic salt such as NaN03 'KN〇3 'FeN〇3 ' A1 (N03) 3 is used, and it is preferably used in an amount of 0.01% by weight to 5% by weight. The fluorine-based surfactant as the second additive is adsorbed on the surface of the glass, so that the generated sludge quickly falls off and does not adhere again. At the same time, it can significantly improve the cleaning efficiency. The fluorine-based surfactant as the second additive may be RfCH2CH2SCH2CH2C02Li, (RfCH2CH20)P(〇)(〇NH4)2, (RfCH2CH20)2P(0)(0NH4), RfCH2CH20(CH2CH20)yH, RfCH2CH2S03X, RfCH2CH2NHS03X or the like A mixture (in the above formula, y is an integer of 8 to 15 'X is hydrazine or NH4, and Rf is F(CF2CF2) z, wherein z is an integer of 3 to 8). The surfactant is preferably used in an amount of from 0.005% by weight to 1% by weight. When the surfactant reaches 1% by weight or more, a large amount of foam is generated and the efficiency is lowered. The etching liquid composition for glass constituting the flat panel display of the present invention is formed by the following reaction mechanism, but it is not intended to particularly limit the scope of the present invention. It is speculated that the etching reaction mechanism is divided into two stages: in the first stage, HF in the composition of the composition is combined with Si〇2, Α12〇3, CaO, ROx as a glass component, and a part thereof is converted into a gas phase. I, siF4 volatilizes, the other part is converted to H20 and HzSiF6 and dissolved into the reagent, and the other part is converted into insoluble salt, namely 200922897 A1F3, CaF2 and RFX. In the second stage, the cation of the insoluble salt and the anion of the inorganic acid combine to form A12(S04)3, CaS04, R(S04)x, A1(N03)3, Ca(N03)2, R(N03)x , A1C13, CaCl2, RC1 x 'Al(C〇3) 3, Ca(C〇3)2, R(C03)x 'AIPO4, Ca3(P04)2, R(P〇4)x and HF, their transformation It is a water-soluble salt, which leads to a decrease in the amount of sludge, a decrease in the adhesion between the sludges, a decrease in the particles, a reduction in equipment contamination, and the generated HF can be involved in the etching again. Advantageous Effects of Invention The etching liquid composition for glass provided by the present invention has an effect that the glass treated with the etching liquid composition for glass of the present invention has good etching quality such as transparency and surface roughness, stable etching ability, and prolonged service life. The etching efficiency (number of etching sheets) is increased. [Embodiment] Hereinafter, the present invention will be described in detail based on examples. The examples are intended to illustrate the invention and are not to be construed as limiting the scope of the invention. Examples 1 to 6 Etching method Preparation HF / sodium nitrate / inorganic acid (sulfuric acid, phosphoric acid, hydrochloric acid) / glycolic acid / fluorine-based surfactant / deionized water was mixed in the ratio shown in Table 1 below to form an etching liquid composition. 'And maintained at 3 0 r. In order to remove contaminants, in the LCD process of 200922897, the alkali-free glass for engraving with liquid crystal was injected into the close-up of the upper and lower plates (Nippon Electric Glass Co., Ltd. NEG OA-21, size: 3 70 x470 'thickness: l.26t ( 1260 μιη)), the thickness of each predetermined portion was measured and put into an etching solution. The etching amount was set as follows: In advance, the preliminary etching was performed for about 10 minutes, the etching ability was measured, and then uranium engraving was performed by spraying a time corresponding to the required etching amount (1.26 t - 0.8 t, i.e., 460 μm). In the spraying device used in the present invention, the lower portion is provided with a storage tank which is made of an acid-resistant (Teflon: teflon) material suitable for use in a strong acid (pHSl) environment, and is capable of storing up to 30 L of solution, using A strong magnetic suction magnetic pump (100 L/min) sprayed the solution evenly onto both surfaces of the glass by a full cone type vertical spray nozzle sprayed in a circular shape. The device consists of a glass inlet, an etched area, a cleaning area, and an outlet. Transparent PVC is used to visually confirm the etching process, so that problems generated in the program can be visually recognized and the etching process can be adjusted. The cleaning area is drained instead of recirculating, minimizing glass contamination caused by cleaning, and the control section can use touch panels for automatic and manual adjustment. To prevent the temperature rise of the reagent caused by heat generated during glass etching, the program can be designed to automatically perform heating and cooling adjustments. Analytical method The etched glass was cleaned with pure water in a washing machine. After washing and drying procedures, the thickness of each portion was measured, and the etching amount, etching rate, and etching speed per second were calculated. Further, the etched glass was examined by a three-wavelength lamp -10-200922897', and the projection defect rate was calculated, and the longitudinal observation, the projection spot, and the transparency were compared. Fig. 7 shows surface photographs of Example 3, Example 6, and Comparative Example. The dent enlargement ratio was calculated as follows: dents of several different sizes were arbitrarily formed, and after measuring the size, etching was performed at a certain thickness (0.8 t). Then, an enlarged dent having a dimple size of 100 μηι to 200 μπι before etching was found, and the size was measured, and the enlargement ratio was calculated according to the following mathematical formula. The dimple enlargement ratios of Example 4, Example 5, and Comparative Example are shown in Fig. 6 . Dent enlargement ratio (%) = post-etch size - pre-etch size Pre-etch size χΙΟΟ Roughness is determined by measuring the surface roughness of the etched glass using a device called α-STEP IQ (manufacturer: KLA Tencor, USA). The roughness diagrams of Example 3 and Example 5 are shown in Figures 1 and 2. In the above drawings, the horizontal axis represents the roughness measurement length (distance) and the vertical axis represents the height of the etched glass. The sludge ratio is expressed as follows: after etching a certain amount of glass (400 μηι), it is allowed to stand for a certain period of time (30 minutes), and the amount of sludge deposited is measured, and the measured amount of sludge is compared with the comparative example. , expressed as relative ambiguity. A photograph of the amount of sludge of Example 2, Example 6 and Comparative Example is shown in Fig. 4 . The service life is determined by the ratio of the etching ability of the same solution uranium engraved to a certain amount (cumulative etching amount of 4000 μπι) of glass and the initial etching ability. The service life diagrams of Example 2, Example 4, and Comparative Example are shown in Figures -11 - 200922897. Table 1 shows the relative detection flaws for etching spots, dent expansion ratio, surface roughness, sludge ratio, and service life. Comparative Example Etching was carried out in the same manner as in Examples 1 to 6 except that a glass etchant was used in an amount of 17% by weight of a hydrofluoric acid aqueous solution. The relative detection of etch spots, dent enlargement ratio, surface roughness, sludge ratio and service life is shown in Table 1. FIG. 3 is a diagram showing roughness. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 are roughness diagrams of Example 3 and Example 5, respectively. Fig. 3 is a roughness diagram of a comparative example. 4 is a photograph of the amount of sludge in Example 2, Example 6, and Comparative Example. Fig. 5 is a graph showing the service life of Example 2, Example 4, and Comparative Example. Fig. 6 is a graph showing the dimple enlargement ratios of Example 4, Example 5, and Comparative Example. Fig. 7 is a surface photograph of Example 3, Example 6, and Comparative Example. -12-