經濟部中央棣準局員工消费合作社印製 293087 五、發明説明（1 ) (產業上之利用範圍） 本發明乃關於：超音波式液體濃度測定裝置者。進一 步詳言之，即本發明乃關於：在極高精度下，亦可進行迅 速之測定之超音波式液體濃度測定裝置者。 (以往之技術） .作爲測定液體濃度之裝置之一，乃有超音波式液體濃 度測定裝置，爲一般所知。在此，所謂液體之濃度，乃指 :兩種以上成分之液晶互相之液狀混合物中之特定成分液^ 體之濃度·，或被溶解在液體中之成分固體之濃度。 惟近年來在使用於電子工業之液體工業藥品之領域， 正確測定液體濃度之要求，已達到更高水準之高精度水平 。在此，所謂被使用於電子工業之液體工業藥品，乃有： 矽晶片（s i 1 i c (D n wa f e r )洗淨用藥品、配線圖型顯像用 藥品、各種蝕刻劑等。 惟實際上例如：誤差範圍〔（測定値—眞正之値）/ 眞正之値丄XI 〇 〇〕在±〇 · 〇 4%，而於極爲高精度二 下之測定爲可能之液體濃度測定裝置，況且在線上（〇 η line)所作之自動測定亦爲可能，且可適用於工業製造裝 置者，卻尙未出現。 此外，作爲可獲得高精度之測定法，亦有所謂之化學 滴定法（chemical titration)惟此法亦缺乏迅速性’ 不適合使用於工業製造裝置。 · 本紙張尺度逍用中國國家橾準（CNS > A4規格（210 X 297公釐J 4 - I I II - - I - n 1--- I (锖先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央樣準局貝工消费合作社印装 A7 B7 五、發明説明（2 ) (本發明擬解決之問題） 本發明擬解決之課題，乃在提供：於極高之精度下， 亦可進行迅速之測定之超音波式液體濃度測定裝置者。 (解決上述問題之方法） 具有超音波收發信部及超音波反射部之超音波式液體 濃度測定裝置，乃爲周知者，已廣供市售及使用。惟在以 往之裝置中，其極高精度下之測定乃爲困難。本發明人等 曾對其降低精度之原因加以詳細之撿討。結果發現，附著 於超音波收發信部及超音波反射部之氣泡乃爲其主要原因 ，卻除該氣泡將可實現極高之測定精度；因此乃有本發明 之開發及提出。 亦即，本發明乃爲在具有超音波收發信部及超音波反 射部之超音波式液體澳度測定裝置中，備有：去除附著於 超音波收發信部及超音波反射部之氣泡所用之氣泡去除機 構之超音波式液體濃度測定裝置者° 下面1細加以說明。 本發明之具有超音波收發信部及超音波反射部之超音 波式液體濃度測定裝置，將可使用具有周知之構成者：並 此等亦已廣爲在市上銷售者。在此，所謂超音波式液體濃 度測定裝置，乃爲：具有被設置在濃度測定用液體中之超 音波收發信部及超音波反射部，而從超音波發信部發出超 音波，並將從超音波反射部反射回來之超音波超音波收信 部加以接收，再由測定發信至收信間之時間來求出超音波 本紙張尺度適用中國國家標準（0奶）八4规格（210父297公釐_)5 . -------4 I 裝 I:---^---訂------{ (請先閲讀背面之注意事項再填寫本頁) A7 B7 298087 五、發明説明（3 ) 在液體中之傳播速度，利用該傳播速度乃依存於液體濃度 之性質，來求出液體之濃度之裝置者。 I ^ I裝 ^ | 訂 (請先閲讀背面之注意事項再填寫本頁) 本發明之最大之特徵乃在：此種超音波式液體濃度測 定裝置乃爲具有：去除附著於超音波收發信部及超音波反 射部之氣泡所用之氣泡去除機構者。由於設置該機構，在 極高精度下之測定，將成爲可能。 .作爲去除附著於超音波收發信部及超音波反射部之氣 泡所用之氣泡去除機構，具體言，亦可舉出：從被設在超 音波收發信部及超音波反射部之近旁之噴嘴（1)，向超+ 音波發信部（2)及超音波反射部（3)，噴出濃度測定 用液體者（圖1 )。噴出濃度測定用液體之方法，則以泵 對濃度測定用液體加壓，再從噴嘴噴出即可。至於，噴嘴 之形狀及大小以及液體之噴出量，則未有特別之限制，關 鍵乃在可去除附著於超音波收發信部及超音波反射部之氣 泡即可；例如用具有0 · 5〜5mm之口徑，而被設置在 經濟部中央標準局貝工消費合作社印製 距離超音波收發信部及超音波反射部約2〜5 c m之位置 之噴嘴，J〜1 Ο β /分鐘程度之流量，將濃度測定用液 體向超音波收發.信部及超音波反射部噴出即可。此外，在 濃度測定中，乃以一定之流量來常時噴出爲宜。 下面說明實施本發明時之較爲理想之黄施形態。 第1 ，使用以白金測溫電阻器所成之溫度計，來測定 濃度測定用液體之溫度，以校正超音波之傳播速度對液溫 之影響爲佳。此外，溫度計之元件乃應儘可能使用小型者 ，例如5 m m以下者爲宜：進一步，則以1 m m以下者爲 本紙張尺度適用中國國家梂準（CNS ) A4規格（210X297公羡J 6 — 經濟部中央橾準局員工消費合作社印製 293087 A1 B7 五、發明説明（4 ) 佳。 第2 ，進行上述之溫度校正時，亦宜校正：溫度計所 得測定溫度與實際上之液溫之時間性反應延遲。其具體方 法則可舉出：於濃度運算部，附溫度計所得液體之測定溫 度，延遲0〜1 6 0眇鐘前之超音波傳播速度資料，來進 行濃度運算之方法。 .第3 ，宜將超音波式液體濃度測定裝置之設置環境溫 度保持於一定。尤其是，通過超音波收發信部及溫度計所 受到之環境溫度之影響，乃有不能忽視者。作爲其對策/ 亦可舉出：例如，在設置有超音波收發信部及溫度計之凸 綠部分，施以隔熱材被覆之方法；或者將超音波式液體濃 度測定裝置全體，設置在恆溫室之方法等。此外，在後者 之情形，恆溫室之溫度之變動幅度亦宜維持在±1 . o°c 以內。 第4 ，使用具有從液體之超音波傳播速度信號及溫度 信號獲得液體澳度信號之轉換機構之超音波式液體滇度測 定裝置時丄宜將該轉換機構部分之溫度保持爲一定。其方 法乃可舉出例如：將轉換機構部分設置在恆溫槽內之方法 。所保持之溫度，通常宜在2 0〜3 0 °C，最好則在2 3 〜2 7。(：，變動幅度宜維持在± 1 . 〇 °C以內。 第5 ，宜將測定用液體中之溶存氣體濃度保持於一定 。溶存氣體之澳度保持於一定之方法，則可舉出：例如將 測定之用液體以3 5〜4 0 °C之一定溫度保持5〜2小時 後，再供作濃度測定之用之方法。 本紙張尺度適用中國國家梂準（匸呢）人4规格（210’乂297公釐-)7- I ^ I裝 ^ ； 訂 ^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央梂隼局工消費合作社印製 A7 B7 五、發明説明（5 ) 此外’將上述第1〜第5之形態任意組合兩種以上’ 亦爲可行。 本發明作爲測定對象所得之液體之種類，雖無特別之 限制：惟作爲本發明之適用例子，則可舉出：電子工業所 使用之液體工業藥品，亦即矽晶片洗淨用藥品、配線圖型 顯像用藥品、各種蝕刻劑等：具體言則可舉出：16卜31^-thyL ammonium h y d r ο X i d e水溶液、氟氧水溶液等。 並且，將兩種以上之成分液體加以混合以調配具有目 的成分比率之混合液時，以本發明之超音波式液體濃度測 定裝置來監視混合液之濃度，將所得之濃度測定値加以回 饋（feed back)，以成爲可自動調節成分液供給量之系 統，由此可調配在極高精度下自動具有目的濃度之混合液 體。 (作用） 依據本發明，則可將對測定値之氣泡之影響，完全加 以剔除，变即可在極高之精度下，迅速測定液體濃度。 (實施例） 下面，以實施例來說明本發明。 (實施例1 ) 使用：從設置於超音波收發信部（2 )及超音波反射 部（3 )近旁之噴嘴（1 )，可向超音波收發信部（2 ) 本紙張尺度逍用中國國家榡準（CNS ) A4規格（210X297公麈_) 8 - I - I I -II 1- I - - - n - n (請先閱讀背面之注意事項再填寫本頁)Printed by the Employee Consumer Cooperative of the Central Department of Economics of the Ministry of Economic Affairs 293087 V. Description of the invention (1) (Scope of use in the industry) The present invention relates to: an ultrasonic type liquid concentration measuring device. In further detail, the present invention relates to an ultra-sonic liquid concentration measuring device that can perform rapid measurement under extremely high precision. (Conventional technology) As one of the devices for measuring the liquid concentration, there is an ultrasonic type liquid concentration measuring device, which is generally known. Here, the so-called liquid concentration refers to: the concentration of a specific component liquid in a liquid mixture of two or more liquid crystals with each other, or the concentration of a component solid dissolved in a liquid. However, in the field of liquid industrial medicines used in the electronics industry in recent years, the requirements for the accurate determination of liquid concentration have reached a higher level of high precision. Here, the liquid industrial chemicals used in the electronics industry include: silicon wafer (Si 1 ic (D n wa fer) cleaning chemicals, wiring pattern imaging chemicals, various etchants, etc. But in fact For example: the error range [(measurement value-眞 正 之 値) / 眞 正 瀤 丄 XI 〇〇] is within ± 〇 · 〇4%, and the measurement under extremely high accuracy is possible as a liquid concentration measuring device, and online (〇η line) automatic measurement is also possible, and it can be applied to industrial manufacturing equipment, but it has not appeared. In addition, as a measurement method that can obtain high precision, there is also the so-called chemical titration method (chemical titration). This method also lacks rapidity. It is not suitable for use in industrial manufacturing equipment. · This paper standard is used in China National Standards (CNS &A; A4 specifications (210 X 297 mm J 4-II II--I-n 1 --- I (Read the precautions on the back first and then fill out this page) Order A7 B7 printed by Beigong Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economy V. Description of the invention (2) (Problems to be solved by the invention) Problems to be solved by the invention Is providing: Ultrasonic liquid concentration measuring device that can perform rapid measurement under extremely high accuracy. (Method for solving the above problem) Ultrasonic liquid concentration measuring device with ultrasonic transmission and reception unit and ultrasonic reflection unit is It is well-known and widely available on the market. However, in the conventional device, the measurement under extremely high accuracy is difficult. The inventors have carefully investigated the reasons for the reduced accuracy. As a result, The air bubbles attached to the ultrasonic transceiver and the ultrasonic reflection part are the main reasons, but except for the air bubbles, extremely high measurement accuracy can be achieved; therefore, the invention has been developed and proposed. That is, the invention is Ultrasonic liquid measuring device with ultrasonic transmission and reception unit and ultrasonic reflection unit is equipped with: Ultrasonic system with bubble removing mechanism for removing air bubbles attached to ultrasonic transmission and reception unit and ultrasonic reflection unit The liquid concentration measuring device is described in detail below: The ultrasonic type liquid concentration measuring device of the present invention having an ultrasonic transmission and reception unit and an ultrasonic reflection unit, Well-known components can be used: and these are also widely sold in the market. Here, the so-called ultrasonic-type liquid concentration measuring device means that it has an ultrasonic transmission and reception device installed in a liquid for concentration measurement And the ultrasonic reflection part, and the ultrasonic wave is sent from the ultrasonic transmission part, and the ultrasonic reception part reflected by the ultrasonic reflection part is received, and then the time between sending and receiving is measured. Calculate the paper standard of the ultrasound book to apply the Chinese national standard (0 milk) 8 4 specifications (210 father 297 mm_) 5. ------- 4 I Pack I: --- ^ --- order- ---- {(Please read the precautions on the back before filling out this page) A7 B7 298087 5. Description of the invention (3) The propagation speed in the liquid, the use of the propagation speed depends on the nature of the liquid concentration to find Device for concentration of liquid. I ^ I 装 ^ | Order (please read the precautions on the back before filling out this page) The biggest feature of the present invention is that this ultrasonic liquid concentration measuring device is to have: remove the attachment to the ultrasonic transceiver And the bubble removing mechanism used in the bubble of the ultrasonic reflection part. Due to the installation of this mechanism, measurement under extremely high accuracy will become possible. . As a bubble removing mechanism for removing bubbles adhering to the ultrasonic transmission and reception unit and the ultrasonic reflection unit, specifically, the nozzles provided near the ultrasonic transmission and reception unit and the ultrasonic reflection unit ( 1), the person who ejects the liquid for concentration measurement to the ultrasonic + sonic signal transmitting unit (2) and the ultrasonic wave reflecting unit (3) (Fig. 1). In the method of ejecting the liquid for concentration measurement, the liquid for concentration measurement is pressurized by a pump and then ejected from the nozzle. As for the shape and size of the nozzle and the amount of liquid ejected, there are no special restrictions. The key is to remove the air bubbles attached to the ultrasonic transceiver and ultrasonic reflection part; for example, use a 0.5-5 ~ 5mm The diameter of the nozzle is set at a nozzle printed at a position about 2 to 5 cm away from the ultrasound transmission and reception department and the ultrasound reflection department at the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Send and receive the liquid for concentration measurement to the ultrasonic wave. The signal part and the ultrasonic reflection part can be ejected. In addition, in the concentration measurement, it is advisable to spray at a constant flow rate at all times. The following is a description of the preferred yellow application form when implementing the present invention. First, a thermometer made of platinum temperature measuring resistors is used to measure the temperature of the liquid for concentration measurement, in order to correct the influence of the propagation speed of ultrasonic waves on the liquid temperature. In addition, the components of the thermometer should be as small as possible, for example, those below 5 mm are suitable: further, the paper size below 1 mm is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public envy J 6 — Printed 293087 A1 B7 by Employee Consumer Cooperative of Central Central Bureau of Economic Affairs of the Ministry of Economic Affairs 5. Invention description (4) is good. Second, when performing the above temperature correction, it is also appropriate to correct: the time between the measured temperature obtained by the thermometer and the actual liquid temperature The reaction is delayed. The specific method can be: in the concentration calculation section, the measured temperature of the liquid with a thermometer is delayed, and the method of performing the concentration calculation by delaying the ultrasonic propagation speed data before 0 ~ 1 6 0 clock. It is advisable to keep the installation ambient temperature of the ultrasonic liquid concentration measuring device at a certain level. In particular, the influence of the ambient temperature on the ultrasonic transceiver and the thermometer cannot be ignored. As a countermeasure / Out: For example, in the convex green part where the ultrasonic transceiver and thermometer are installed, a method of covering with a heat-insulating material; or measuring the concentration of the ultrasonic liquid The method of setting the whole device and installing it in a constant temperature room, etc. In addition, in the latter case, the temperature variation range of the constant temperature room should also be maintained within ± 1.o ° c. Fourth, use the ultrasonic wave propagation speed from the liquid When the signal and temperature signal are obtained by the ultrasonic type liquid temperature measuring device of the conversion mechanism of the liquid Ao degree signal, the temperature of the conversion mechanism part should be kept constant. The method can be exemplified by: The method in the tank. The temperature to be kept is usually in the range of 2 0 ~ 3 0 ° C, preferably in the range of 2 3 ~ 2 7. (:, the variation range should be kept within ± 1.0 ° C. 5th, It is advisable to keep the concentration of dissolved gas in the measurement liquid at a certain level. The method to maintain the degree of dissolved gas at a certain level can be exemplified by, for example, maintaining the measurement liquid at a certain temperature of 3 5 ~ 4 0 ° C for 5 ~ After 2 hours, it will be used as a method for concentration determination. This paper scale is applicable to the Chinese National Standard (匸 呢) person 4 specifications (210 '297 mm-) 7- I ^ I installed ^; order ^ (please Read the notes on the back before filling out this page) The A7 B7 is printed by the Industrial and Consumer Cooperative of Central Jeju Bureau of the Ministry of Economy. V. Description of the invention (5) In addition, it is also feasible to 'arbitrarily combine two or more of the first to fifth forms above.' There is no particular restriction on the type: as an applicable example of the present invention, liquid industrial chemicals used in the electronics industry, that is, silicon wafer cleaning chemicals, wiring pattern imaging chemicals, and various etchant Etc .: Specific examples include: 16 ^ 31 ^ -thyL ammonium hydr ο X ide aqueous solution, oxyfluoride aqueous solution, etc. In addition, when two or more component liquids are mixed to prepare a mixed liquid having a target component ratio, The ultrasonic liquid concentration measuring device of the present invention monitors the concentration of the mixed liquid, and feeds back the obtained concentration measurement value to become a system that can automatically adjust the supply amount of the component liquid, thus it can be adjusted to extremely high precision The mixed liquid with the desired concentration is automatically loaded. (Function) According to the present invention, it is possible to completely eliminate the influence of bubbles on the measurement value, and the liquid concentration can be quickly measured with extremely high accuracy. (Examples) Next, the present invention will be described with examples. (Embodiment 1) Use: From the nozzle (1) installed near the ultrasonic transceiver (2) and the ultrasonic reflector (3), the paper standard can be easily used by the ultrasonic transceiver (2). Standard (CNS) A4 specification (210X297 餈 _) 8-I-II -II 1- I---n-n (please read the precautions on the back before filling this page)
<1T A7 B7 293087 五、發明説明（6 ) 及超音波反射部（3 )噴出濃度測定用液體之超音波式液 體濃度測定裝置（圖1 )，來測定：Tetramethyl απιιηοη-ί u m h y d r d X i d e 水溶液 之浪度 。此外 ，將濃 度測定 用液體 以泵予加壓，並從具有2mm 口徑，被設置於距離超音波 收發信部（2 )及超音波反射部（3 )約3 c m之位置之 噴嘴，將合計4 · 05/分鐘左右之濃度測定用液體，向 超音波收發信部（2 )及超音波反射部（3 )噴出。惟未 使用前述之理想實施形態（1 )〜（5 )，即進行測定。 約每隔1 0分鐘之間隔，反5作5次之測定。結果表示於 表1 。 (請先g讀背面之注意事項再填寫本頁) 裝_ 測定時 表 1 (實施例1 ) 測定値（w t % ) 誤差（％ ) * 訂 經濟部中央標準局員工消费合作社印裝 第1次 第2次 第3次 第4次 第5次 3 7 9 8 3 8 0 2 3 7 8 6 3 7 9 0 3 7 9 2 + 〇 + 0 -0 -0 —〇 0 1 3 0 2 9 0 3 8 0 2 1 0 1 3< 1T A7 B7 293087 V. Description of the invention (6) and ultrasonic reflection part (3) Ultrasonic liquid concentration measuring device (FIG. 1) that ejects liquid for concentration measurement to measure: Tetramethyl απιιηοη-ί umhydrd X ide aqueous solution Waves. In addition, the liquid for concentration measurement is pressurized by a pump, and the nozzle with a caliber of 2 mm, which is installed at a position about 3 cm away from the ultrasonic transceiver (2) and the ultrasonic reflection part (3), totals 4 · The liquid for concentration measurement around 05 / min is ejected to the ultrasonic transmission / reception unit (2) and the ultrasonic reflection unit (3). However, the measurement is performed without using the aforementioned ideal embodiments (1) to (5). At intervals of about 10 minutes, the measurement is repeated 5 times. The results are shown in Table 1. (Please read the precautions on the back first and then fill out this page) Installation _ Table 1 during measurement (Example 1) Measurement value (wt%) Error (%) * Ordered by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperatives for the first time 2 times 3 times 4 times 5 times 3 7 9 8 3 8 0 2 3 7 8 6 3 7 9 0 3 7 9 2 + 〇 + 0 -0 -0 -〇0 1 3 0 2 9 0 3 8 0 2 1 0 1 3
本紙張尺度適用中國國家操準（CNS ) A4规格（210X297公簸J B7 五、發明説明（7 ) 表 2 (比較例1 ) 測定時 測定値（w t % ) 誤差（％ ) * 1 第1次 2.385 第2次 2.383 第 3.次 2.374 第4次 2.375 第5次 2.381 2 +0.240 5 +0.168 0 -0.231 6 一 0 . 1 6 4 2 +0.071 (請先閲讀背面之注意事項再填寫本頁} 經濟部中央橾準局貝工消费合作社印裝 * 1誤差：{(測定値一眞正之値）/眞正之値} X 1 0 0 眞正之値乃使用以化學滴定法所得之値（ 2 . 3795wt%) ° (發明之空果） 如上面所說明，由本發明將可提供：在極高精度下， 可迅速進行測定之超音波式液體濃度測定裝置。 (附圖之簡單說明） 〔圇1〕本發明之超音波式液體濃度測定裝置之一例之圖 本紙張尺度遠用中國國家標準（CNS ) A4规格（210X297公羡 293087 A7 B7 五、發明説明（8 ) (附圖中編號之說明） 1 ......噴嘴， 號 信 ， 發部 收射 波反 音波 超音 " 超 • *tisc S3 本 之 置 裝 定 測 度 濃 式 波 音 超 泵 _ - - I - 1«| ?11 II - - I I — n (請先閲讀背面之注意事項再填寫本頁) Λ 經濟部中央標準局員工消费合作社印製 本紙張尺度適用中國國家標準（〇阳）人4規格（210父297公釐）11-This paper scale is applicable to China National Standards (CNS) A4 specifications (210X297 public bumps J B7. V. Invention description (7) Table 2 (Comparative Example 1) Measurement value (wt%) Error (%) * 1 1st 2.385 2nd time 2.383 2. 3.74 2.374 4th 2.375 5th 2.381 2 +0.240 5 +0.168 0 -0.231 6 1 0. 1 6 4 2 +0.071 (please read the precautions on the back before filling this page) Printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs * 1 Error: {(Determination of the value of the positive value) / Value of the value of the positive value X 1 0 0 Value of the value of the positive value is the value obtained by chemical titration (2.379% by weight) ) ° (empty fruit of the invention) As explained above, the present invention will provide: an ultra-sonic liquid concentration measuring device that can rapidly measure with extremely high accuracy. (Simple description of the drawings) [囵 1] This An example of the invention of a supersonic liquid concentration measurement device. The paper size is far from the Chinese National Standard (CNS) A4 specification (210X297 public enlightenment 293087 A7 B7. V. Description of the invention (8) (instructions numbered in the drawings) 1. ..... Nozzle, signal, transmitter radio wave antisonic supersonic "" • * tisc S3 is installed with a fixed-measure thick Boeing superpump _--I-1 «|? 11 II--II — n (please read the precautions on the back before filling this page) Λ Central Bureau of Standards The paper standard printed by the employee consumer cooperative applies the Chinese National Standard (〇yang) Ren 4 specifications (210 father 297 mm) 11-