200538733 九、發明說明： 【發明所屬之技術領域】 本發明有關用為測定含在工業 硬度的硬度測定用試藥者。 ” 活用水等中的 【先前技術】200538733 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a tester for measuring the hardness contained in industrial hardness. [Prior art] in domestic water, etc.
如周知，對鋼爐、溫水器、或冷卻器等冷教機 ^水糸統巾，為防止冷熱機㈣的㈣（seaie = 要性，連接有為了去除工業用水、 寸者的必 含硬度成分（Ca2+及Mg2+)之裝置，例士 、'原水中所 脂的硬水軟化裝置連接—料 使用離子交換樹 r 1逆按万、、、Ό水糸統中，將原水中之硬产 刀（Ca及]^)取代為如+，並將所得經過軟化處理之:作 為給水以供給冷熱機器類。 ★錢用前述硬水軟化裝置時，如該裝置内部所收容的 離子交換樹脂劣化、或離子交換樹脂之再生不充分時，則 給水中之硬度成分的Na+取代即變成不足夠。因而，需要 在。又置冷熱機器類的地域或場所之原水硬度等預先設定能 合δ午的硬度’並定期性測定經過硬水軟化裝置後的給水中 之硬度。並且’如給水中之硬度超過容許值上限（以下，簡 %「官制硬度」。）時，則判斷為已經發生硬度漏洩，並進 订#子交換樹脂之交換或是再生等，以給水能符合既定之 硬度範圍方式來處理。 欲判別給水中之硬度的方法而言，揭示有（參照專利文 獻Ϊ、2、3。）例如，將含有豔麗華黑τ (Eriochrome black Τ’ EBT)作為色素的非水系之硬度測定用試藥，添加於從給 316886 ,200538733 水採取的被測定水中，以作為被測定水之色相之指標的方 法二被測定水之色相，在定性方面，係由硬度成分與硬度 測定用試藥中所含色素互相反應後所生成的整合（如b) 2合物、與未反應（free)之色素間的存在比例而決定。具 體而言，如作為色素而使用Εβτ時，隨著被測定水中之硬 度之升高，被測定水之色相即從起初的藍色變色為藍紫 色，（以下，將呈現藍紫色的色相時之硬度，簡稱「變色開 籲始點」。）、再經過紅紫色而到達紅色（以下，將呈現紅色的 色相時之硬度，簡稱「變色終點」）。 於是，如著眼於此種被測定水中的硬度所引起的色相 愛化以判別硬度漏戌時，則事先訂定管制硬度之同時，按 该官制硬度能存在變色開始點與變色終點之間的方式，決 定硬度測定用試藥中之ΕΒΤ之調配比例、測定時之硬度測 疋用試藥之添加量以及被測定水之容量等的測定條件後， 再進行實施測定作業。 _ 如此，如以被測定水中之硬度所對應的色相變化作為 硬度漏洩之指標時，作為色相之測定方法而言，通常採用： 藉由肉眼之觀察的目視測定、或藉由透射率測定或吸光度 測定的機械測定。如實施目視測定時，則當被測定水之色 相從藍紫色變色為紅色時，判斷為已發生硬度漏洩。又， 如實施機械式測定時，則根據表示硬度與透射率（或吸光度） 之關係的檢量線而硬度即直接顯示於測定器上，當硬度達 到官制硬度時’判斷為已發生硬度漏洩。不管採用任一種 測疋方法，如欲能確貫判斷硬度漏洩時，則需要在管制硬 316886 、200538733 度附近時被測定水能敏銳地變色。 ^而，以來之硬度測定用試藥中，由於變色開始點盘 點之間的差幅(以下，簡稱「變色差幅」。 在官制硬度附近的變色遲鈍之^ 又在稭由比色的目視測定 守，在硬度漏洩之判斷上，產生有個人差異。 [專利文獻1]日本專利特開平丨卜64323號公報。 [專利文獻2]日本專利特開2GG2-1818G2號公報。 [專利文獻3]日本專利特開·2_1818()3號公報。 【發明内容】 [發明所欲解決之課題] …本發明所欲解決之課題，在於開發—種被敎水能於 g制硬度附近敏銳地變色的硬度測定用試藥。 [用於解決課題之手段] 為了解決前述課題起見，經本發明人精心研究之結果 發現，當硬度成分與硬度測定用試藥中所含色素起反應所 籲生^之螫合化合物、與未反應之色素按特定比例存在時， 如掌握被測定水開始變色呈現藍紫色的定量性關係的同 時，使用調配有能與硬度成分優先反應以生成螫合化合物 的特色螫合劑之鹼金屬鹽的硬度測定用試藥，則可解=前 述課題的事實，終於完成本發明。 亦即，申請專利範圍第1項之發明之特徵為·含有選 自盤麗華黑T(EBT)或卡碼飢特（Ca Imagi te)[卜（1 一 hydroxy-4-inthy 卜 2-pj则 y]azo)-2iaphth〇l-4-su]i〇nic ac〗d](卜（1-羥基間甲基苯偶氮基）-2 —萘酚—4 —磺酸）中的 316886 7 200538733 色素、二乙醇胺、二醇化人 、 t 4 r - ° ，以及螫合劑之鹼金屬鹽。 項之硬度測定用試m中申請專利範圍第1 , Φ ^ ^ 八忠σ劑係有機系胺基羧酸。 再者，申凊專利範圍第3 用試藥，其特徵為十 ==發明’係-種硬度測定 測定用” U〜圍第1項或第2項之硬度 利疋用5式樂係以一液所構成者。 [發明之效果] 掛色因本t月，則被測定水將在管制硬度附近敏銳地 贫色，因而可確實判別硬度漏m之，優先於色素、 螫合劑之驗金屬鹽先盘〜 ” 救八 /皮疋水中之硬度成分反應而生成 物’其他所剩餘的硬度成分則與色素進行反應而 5物之故，冑色差幅即變成狹窄，結杲，被測定水 將在管制硬度附近敏銳地變色。再者，由於該硬度測定用 试樂係以-液所構成之故，可簡化試藥之處理及使用。 【實施方式】 _ [發明之最佳實施形態] 其次，就本發明之實施形態加以說明。本發明之硬度 =定用試藥係一液、且非水系，而其特徵為··除EBT(豔麗 華黑T)或卡碼凱特（Caimagite)中的色素、三乙醇胺 (triethan〇lamine)、二醇化合物（glyc〇1 c〇mp㈤nd)之 外，尚含有螫合劑之鹼金屬鹽。 EBT或卡碼凱特，係在鹼之pH領域中，與硬度成分形 成螫合化合物，即可從藍色明顯變色為紅色的色素，而可 以分別單獨、或混合之方式使用。色素之調配比例並無特 316886 200538733 別限定，推外处士 μ 仅此在管制硬度附近使被測定水敏銳地變色來 看旦。如按被測定水中之硬度測定用試藥濃度能成為〇· 24 重里％之方式添力σ色素時，硬度測定用試藥中較佳為〇. 1 至1.0重量％、更佳為〇1至〇·5重量％。 ’ 三乙醇胺，係為了維持pH於10附近以使色素之顯色 安定化所用者。二乙醇胺之調配比例並無特別限定，惟從 為了抑制試藥中的三乙醇胺之滚結、且從保持試藥之適當 黏性來看，硬度測定用試藥中較佳為10至80重量％、更2 為30至50重量％。 -享化a物，係作為硬度測定用試藥之溶劑所用者。 二醇化合物而言’可例舉··乙二醇（ethylenegiyc〇i)、丙 :醇（㈣ Pyleneglyc()1)、二乙二醇（diethyienegiyc〇i) 寻，此寺二醇化合物可以單獨或混合2種以上之方式使 用。此中’從能抑制色素之分解之同時，為防止三乙醇胺 之凌結的觀點來看，特佳為乙：醇（ethylenegiy⑽。二 醇化合物之調配比例並無特別限定，惟從在試藥中作為不 深液而使窃其作用的觀點來看，硬度測定用試藥中較佳為 至80重量％、更佳為3〇至5〇重量％。 /構成螫合劑之驗金屬鹽的螫合劑而言，可使用：有機 乐螫合劑或無機系螫合劑。有機系螫合劑而言，可例舉. 乙二胺四乙酸⑽TA)、反式—二胺基環己烧四乙酸 (CjDTA)。，〇雙（2-fe基乙基）乙二醇四乙酸（哪等的 胺基幾酸、檸檬酸、葡糖酸# ’此等酸可以單獨，或、、曰八 2種以上之方式使用。無機系螫合劑而言，可例舉：焦： 316SS6 9 '200538733 酸、多磷酸、偏磷酸等周知之磷酸化合物。此中，從較色 素為優先能與硬度成分反應的螫合生成能（chela忱^ formation energy)的觀點來看，較佳為有機系螫合劑，而 有機系螫合劑中，則較佳為胺基叛酸。胺基繞酸中厂從前 述螫合生成能及經濟性之觀點來看，特佳為edta。 構成螫合劑之鹼金屬鹽的鹼金屬鹽而言，可例舉：h (鈉）及K⑷。EDTA之驗金屬鹽而言，可例舉：職a .鹽）、浙八-!((鉀鹽）、EDTA一2Na(二鈉鹽）、edta_2k(二鉀 鹽）、EDTA-3Na(三納鹽）、職一3K(三卸鹽）、職屬（四 納鹽）、EDTA-4K(四鉀鹽）等，此中，從添加於被測定水中 時的優異溶解性之觀點來看，特佳為、娜一施 以及EDTA-4Na。螫合劑之驗金屬鹽之調配比例並無特別限 定，惟從能在管制硬度附近使被測定水敏銳地變色的觀點 來看，較佳為按照能在被測定水中添加相當於「管制硬度 -0.1至2. 0卿」之量方式’含在硬度測定用試荜中。 本發明之硬度測定用試藥中，可不用螫合劑之驗 1屬’或加以混合以含有在抗衡離子（咖化刚）中具有 驗金屬的陽離子交換劑。卜卜話眼 丁 乂俠剎此種％離子交換劑而言，較佳為 具有硬度成分之解離常數丨的古 _ 吊数小的吕能基者，可例舉··苯乙稀 石頁S夂納等。此種陽離子交換劑之調配比例，較佳為與整合 劑之鹼金屬鹽者有同樣之調配比例。 本發明之硬度測定用試藥中，除色素、三乙醇胺、乙 一醇化合物以及螫合劑之鹼金屬鹽以外，在不影響本發明 效果之範_，尚可適當調配如㈣㈣Mslungagent)、 ]〇 3.16S86 ,200538733 曰感J劣化防止劑、消泡劑等的添加劑。掩蔽劑，係 六被測疋水中之妨礙離子（例如，以、如、a 1等）形妓a 物而⑽測定水之顯色安定化者，可例舉：三乙醇胺 KCN(氰化等’此中，從排水時之安全性的觀點來看，和 佳為使用二乙醇胺。增感劑，係因將被測定水中之Ca2+^ 代為Mg而使被測定水之顯色性增加敏感者，例如，較隹 為使用EDTA-Mg(鎂鹽）。增感劑之調配比例並無特別限 籲疋准彳之此於官制硬度附近使被測定水敏銳地變色的觀點 來看，較佳為能於被測定水中添加管制硬度之等量以上之 方式，在硬度測定用試藥中含有增感劑。劣化防止劑，係 即使硬度測定用試藥置放於5〇。〇以上的高溫下時仍能防 止色素之劣化者，例如，較佳為使用山梨酸鉀。消泡劑， 係為消去收谷於測定容器内的被測定水中之泡沫者，而較 佳為使用非離子表面活性劑（例如，聚環氧乙烷辛基苯基 s迷）。 _ 本發明之硬度測定用試藥，係將色素、三乙醇胺、二 醇化合物以及螫合劑之鹼金屬鹽，及對應需求之添加劑均 勻加以混合，即可製造。例如，將二醇化合物與三乙醇胺 均勻混合，接著，將螫合化合物之鹼金屬鹽，對應需求之 Λ]、'加9彳依此順序添加並混合’最後添加色素並混合，即可 製造均勻的硬度測定用試藥。 再者，本發明之硬度測定用試藥，係將色素、三乙醇 胺、二醇化合物以及螫合劑之鹼金屬鹽加以混合，即可作 成一液之試藥，而實施被測定水中之硬度測定。在此，一 316886 · ,200538733 液之试樂’係指含有硬度測定上所需要的構成成分，並作 成個’合液的硬度測定用試藥之意。因而，如使用此種硬 f /則疋用5式樂時’與將各構成成分分別添加並混合使用的 f月形相比，為能簡化處理及使用，故不需要複雜的測定步 驟。 —接著，在將未調配有鉗化劑之鹼金屬鹽的以往之硬度 測=用试藥添加於被測定水的情形，對被測定水之色相變 化說明本發明人所獲知的事實，根據該事實，兹就本發明 =效果及較佳的適用方法加以說明。首先，如未存在有硬 的破敎水中添加採用EBT作為色素的硬 =物 Π:， 二“：之未反應狀態存在之故，被測定水是呈現藍色。 物.去生成的整合化合物與未反應色素係按螫合化人 物.未反應色素，至30:80至7〇之 化口 測定水即從藍色變色為藍紫色。再者十對’破 的螫合化合物之存在比例增高者對未反應色素 為紅紫色，而如未反應色素全部二色變色 僅存有螫合化合物時，被測、，。果 如從對被測定水中所添加的色素旦丈」達終點。 之事實時，可解釋為當所添加的色素：：考賴所獲知 素變色比例）與硬度成分起反鹿而生' a的2G至3⑽（色 定水即開始變色而呈現誌妙色a攻★合化合物時，被測 _生成螫合化合物時，：測定：::= 色素之中的 色。於是，如作為管制硬度而 :&色而王現紅 疋例如】呢/公升（亦即， 3ί6886 .12 ，200538733 1 ppm )時，假設對被測定水中添加相當於硬度j卯阳的色素 %，由於以硬度0· 2至0· 3ppm作為變色開始點而被測定水 將呈現藍紫色並開始變色之故，從變色開始點（硬度〇.2 至0· 3ppm)至變色終點（硬度ippm)為止的變色差幅將有相 當於硬度0· 7至0· 8ppm之程度。 亦即，假設對被測定水添加相當於管制硬度量之色 素，則由於管制硬度之20至30%之硬度下被測定水將開始 _變色之故，如被測定水中之硬度在變色差幅之中的情形， 在測定被測定水之色相時，難於判別究竟硬度是接近管制 硬度，或是比管制硬度低很多的硬度。因而，如欲確實作 出判斷時需要使變色差幅作成狹窄，又，由於將變色差幅 作成狹窄，即可確實判別硬度漏洩。 .於是，本發明中，由於作為硬度測定用試藥之構成成 分而調配有螫合劑之鹼金屬鹽之故，螫合劑即優先於色素 而與被測疋水中之硬度成分生成螫合化合物，由於剩餘之 籲硬度成分與色素起反應而生成螫合化合物之故，將變色差 中田作成狹窄，使被測定水能在管制硬度附近敏銳地變色。 具體而言，與前述同樣，按設定管制硬度為丨ppm之方 式’在被測定水中添加相當於硬度〇· 5ppm之螫合劑之鹼金 屬鹽、及相當於硬度〇· 5ppm程度之色素時，則螫合劑之鹼 金屬鹽即優先與相當於硬度〇. 5ppm程度之硬度成分反應 m生成螫合化合物，然後所剩餘之硬度成分即與色素起反 應。此時的變色開始點為0· 6至0. 65ppn〗，而變色終點為 lppm。因而，變色差幅將成為相當於0· 35至0. 4ppm程度。 316886 200538733 如比較有使用與無使用螫合劑之驗金屬鹽的前述2個例 ^在更度測疋用試樂中調配有螫合劑之鹼金屬鹽的情 形二變色差幅縮窄為相當於〇·37至0.42卿程度。亦即， 在刚述後者之例中，在將變色終點作成與前者同樣的狀態 下使’交色開始點接近變色終點側，藉以縮窄變色差幅。如 此，本發明中，如適當變更螫合劑之鹼金屬鹽與色素之調 配比例即可自由設定變色差幅，由此可在管制硬度附近 鲁使被測定水敏銳地變色。此發明的效果，如將管制硬度設 立愈同，愈會顯著呈現，較以來之硬度測定用試藥，尚可 減少色素之調配量。 如使用本發明之硬度測定用試藥以提升硬度之測定精 確度時’較佳為預先決定：硬度測定用試藥中所含色素濃 度及螫合劑之鹼金屬鹽之濃度、測定時的硬度測定用試藥 之添加置、所採取的被測定水之容量等測定條件之後，再 行測疋。具體而言，當被測定水中添加硬度測定用試藥時， 鲁較佳為被測定水中含有：色素〇· 〇〇〇24至〇· 〇〇24重量％、 二乙酵胺〇· 05重量％以上、螫合劑之鹼金屬鹽0. 00006至 〇· 0012重I %之方式操作。又，色素在硬度測定用試藥中 之濃度’更佳為按下式所計算的濃度。 [數1] 硬度測定用試藥中濃产（重量卩，）一變色開始點(ppin)x仏水里(inl)x色素之分子量X ]〇 色素變色比例(%)χ試藥添加量(mg)x碳酸妈分子量 如上所說明，如使用本發明之硬度測定用試藥，則由 .14 3168N6 '200538733 於能在管制硬度附近使被測定水敏銳地變色之故，护另，、高 合於依比色的目視測定用，㈣樣亦可適用為機械=適 用。又，本發明，可將供給於冷熱機器類為止的 冷溫水系内之水、或鍋爐用水等作為硬度之測定對象°。因 而，例如，不揭限於經過前述硬水軟化裝置後的軟化處理 水，尚可將經過硬水軟化裝置前之原水作為硬度之測定對 象。 鲁[貫施例] 以上，藉由實施例再詳細說明本發明，惟本發明並不 因實施例而有所限定。 (檢水之調製） 如表1所示’調製將硬度作成〇mg/公升、〇· 6mg/公升、 〇· 8mg/公升、1· 〇mg/公升、L 2mg/公升、〗· 4呢/公升、丨· 6mg/ 公升、2. Omg/公升以及4· 〇mg/公升之9水準，將Μ鹼度（Μ alkalinity)作成5mg/公升、40mg/公升以及120mg/公升之 _ 3水準的檢水。又，在硬度之調整上，為了識別Ca2+與Mgn 之相對比例相異時的色相之不同起見，按分別之莫耳比能 成為Ca2+ : Mg2+=4 : 1、1: 2之方式，調製在同一硬度下而 Ca2+與Mg2+之相對比例相異的2種檢水。當調製檢水時，硬 度係藉由ICP(感應耦合高頻電漿）加以確認、μ鹼度係使用 1 /50Ν硫酸，依滴定加以確認。 (硬度測定用試藥之調製） 知：此成為表2所示組成之方式，分別調配ΕΒΤ、三乙 S手胺、乙二醇、EDTA-Na以及EDTAUa，並充分攪拌溶解， 15 16SS6 200538733 以調製4種硬度測定用試藥。 (實施例1至5以及比較例1至3) 於lOOral燒杯中裝入檢水50ml，使用微型注射器 (nncro synnge)將硬度測定用試藥滴下121//丨於檢水 中，並輕盪燒杯。檢水立即顯色。顯色丨分鐘後觀察色相。 表1中表示其結果。又，將根據表丨結果所導出之各試驗 區之變色開始點、變色終點以及變色差幅表示於表3中。 在此種試驗中，於各檢水中滴下的硬度測定用試藥之中， EBT及EDTA-4Na之硬度相當濃度係以CaC〇3(碳 ^«*^2.2rag/^(EDTA_4Na^0.7rag/^；^ =L 5mg/ A 升）、試藥 2 為 3· 5mg/公升（EDTA-4Na 為 ι· 〇mg/ 公升、EBT為2 5mg/公升）、而試藥3及試藥$ 公升⑽為2.5mg/公升)。 mg/ [表1]As is well known, in order to prevent the cold and hot machine from being damaged by cold and hot machines such as steel furnaces, warm water heaters, or coolers, etc. (seaie = essential, it must be connected with the hardness required to remove industrial water and inches). The components (Ca2 + and Mg2 +) are connected to the hard water softening device in the raw water-using the ion exchange tree r 1 to reverse the pressure in the water system, the hard-boiled knife in the raw water ( Ca and] ^) are replaced by +, and the obtained softened: used as water to supply hot and cold equipment. ★ When using the aforementioned hard water softening device, if the ion exchange resin contained in the device deteriorates, or ion exchange When the regeneration of the resin is not sufficient, the substitution of Na + of the hardness component in the water becomes insufficient. Therefore, it is necessary to set the hardness of raw water in areas and places such as cold and hot equipment in advance to set a hardness that can be δ midday and periodically. The hardness in the feedwater after passing through the hard water softening device is measured. If the hardness in the feedwater exceeds the upper limit of the allowable value (hereinafter, "%" official hardness "), it is judged that a hardness leak has occurred, and enters the order # The exchange or regeneration of the sub-exchange resin is handled in such a way that the feed water can meet the predetermined hardness range. Methods to determine the hardness of the feed water are disclosed (see Patent Documents Ϊ, 2, 3). For example, Eriochrome black τ (Eriochrome black Τ 'EBT) is a non-aqueous hardness test reagent used as a pigment. It is added to the water to be measured from 316886, 200538733 water as an indicator of the hue of the water to be measured. The hue of water is measured. In terms of qualitative characteristics, it refers to the ratio of the presence of a combination of the hardness component and the pigment contained in the test reagent for hardness measurement (such as b) and the unreacted pigment. Specifically, if Eβτ is used as a pigment, as the hardness of the water to be measured increases, the hue of the water to be measured changes from the original blue to blue-violet, (hereinafter, blue-violet The hardness at the time of hue is referred to as "the beginning point of discoloration."), And then passes through red and purple to reach red (hereinafter, the hardness at the time of red hue will be referred to as "the end point of discoloration"). Therefore, when focusing on the love of the hue caused by the hardness in the water to be measured to determine the hardness leak, while setting the control hardness in advance, there can be a way between the beginning point of the color change and the end point of the color change. Determine the measurement conditions such as the ratio of EBT in the test reagent for hardness measurement, the amount of test reagent added for hardness measurement, and the volume of water to be measured, and then perform the measurement. _ So, if the When the change in hue corresponding to the hardness in water is used as an indicator of hardness leakage, as a method for measuring the hue, a visual measurement by visual observation or a mechanical measurement by transmittance measurement or absorbance measurement are usually used. In the visual measurement, when the hue of the water to be measured changes from blue-purple to red, it is determined that hardness leakage has occurred. When a mechanical measurement is performed, the hardness is directly displayed on the measuring device based on a calibration curve showing the relationship between hardness and transmittance (or absorbance). When the hardness reaches the official hardness, it is judged that hardness leakage has occurred. Regardless of which method is used, if you want to be able to determine the hardness leak accurately, you need to measure the water near the 316886 and 200538733 degrees to control the measured water can change sharply. ^ In the previous test reagents for measuring hardness, the difference between the starting points of the discoloration (hereinafter referred to as the "discoloration difference range"). The sluggishness of discoloration near the official hardness ^ was measured visually by colorimetry There is a personal difference in the judgment of hardness leakage. [Patent Document 1] Japanese Patent Laid-Open Publication No. 64323. [Patent Document 2] Japanese Patent Laid-Open Publication No. 2GG2-1818G2. [Patent Literature 3] Japan Patent Publication No. 2_1818 () 3. [Summary of the Invention] [Problems to be Solved by the Invention] ... The problem to be solved by the present invention is to develop a hardness that can be discolored sharply around the hardness of g made by water. [Means for measuring the problem] [Means for solving the problem] In order to solve the foregoing problem, as a result of careful study by the present inventors, it was found that when the hardness component reacts with the pigment contained in the reagent for measuring the hardness, it is called ^ 螫When the compound and the unreacted pigment are present in a specific ratio, if the quantitative relationship between the measured water to start discoloring and blue-violet is grasped, the formulation can be used to preferentially react with the hardness component to generate The test reagent for measuring the hardness of the alkali metal salt of the special compound of the compound can be solved = the fact that the above-mentioned problem is solved, and the present invention has finally been completed. Lihua black T (EBT) or Ca Imagi te [b (1 -hydroxy-4-inthy b 2-pj y] azo) -2iaphth〇l-4-su] i〇nic ac〗 d 316886 7 200538733 in ((1-hydroxy-m-tolylphenylazo) -2-naphthol-4—sulfonic acid) pigments, diethanolamine, glycolated humans, t 4 r-°, and the mixture of Alkali metal salt. In the test for hardness measurement, the scope of patent application is the first, Φ ^ ^ Bazhong σ agent is an organic amine carboxylic acid. Furthermore, the third application of the patent scope of the patent application is characterized by ten == Invention 'system-for hardness measurement and measurement "U ~ The hardness profit of item 1 or item 2 is composed of 5 fluids with one fluid. [Effect of the invention] Hanging color because of this month, The water to be measured will be acutely poor near the controlled hardness, so the hardness leakage can be accurately determined, and it takes precedence over the metal salt test of pigments and mixtures. The hardness component in the reaction reacts to produce the product 'Other remaining hardness components react with the pigment and the five substances cause the color difference to become narrow and crusted, and the measured water will sharply change color near the regulated hardness. Furthermore, Since the test music for hardness measurement is composed of -liquid, the handling and use of the test drug can be simplified. [Embodiment] _ [Best Embodiment of the Invention] Next, the embodiment of the present invention will be described. The hardness of the present invention is a one-agent test solution and non-aqueous system, and is characterized by the exception of pigments, triethanolamine (triethanolamine) in EBT (Brilliant Black T) or Caimagite, In addition to the diol compound (glyco1 commpnd), it also contains an alkali metal salt of a coupler. EBT or Carmate Kate, in the pH range of alkali, form a compound with hardness components, which can change color from blue to red, and can be used separately or in combination. There is no special color mixing ratio. 316886 200538733 Special limitation, extrapolation μ This only makes the measured water sharply change color near the controlled hardness. When adding a sigma pigment in such a way that the concentration of the test reagent for hardness measurement in the water to be measured becomes 0.24% by weight, the test reagent for hardness measurement is preferably from 0.1 to 1.0% by weight, more preferably from 0 to 1 0.5% by weight. 'Triethanolamine is used to maintain the pH around 10 to stabilize the color development of the pigment. The blending ratio of diethanolamine is not particularly limited, but in order to suppress the rolling of triethanolamine in the test reagent and to maintain the proper viscosity of the test reagent, the test reagent for hardness measurement is preferably 10 to 80% by weight. And more 2 is 30 to 50% by weight. -Henhwa-a is used as a solvent for hardness test reagents. As for the diol compound, it can be exemplified by ethylene glycol (ethylenegiyco), propylene: alcohol (㈣ Pyleneglyc () 1), and diethylene glycol (diethyienegiyco). This diol compound can be used alone or Use by mixing 2 or more methods. Among them, from the viewpoint of inhibiting the decomposition of pigments and preventing triethanolamine from stagnation, it is particularly preferred to be ethylenegiy⑽. The compounding ratio of the diol compound is not particularly limited, but it is used in the test drug. From the standpoint of not having a deep solution and its effect, the hardness test reagent is preferably 80% by weight, and more preferably 30 to 50% by weight. For example, an organic compound or an inorganic compound can be used. For an organic compound, ethylene diamine tetraacetic acid (TA), trans-diaminocyclohexane tetraacetic acid (CjDTA) can be used. 〇 Bis (2-feylethyl) ethylene glycol tetraacetic acid (what kind of amino citric acid, citric acid, gluconic acid # 'These acids can be used alone, or, eight or more than two ways For inorganic-based admixtures, examples include: coke: 316SS6 9 '200538733 acid, polyphosphoric acid, metaphosphoric acid and other well-known phosphoric acid compounds. Here, from the coloring matter, it is preferred to react with the hardness component to generate the compounding energy ( From the viewpoint of chela formation energy, organic couplers are preferred, and among organic couplers, amine-based acid is preferred. Amine-based acid production from the above-mentioned coupling energy and economy From the viewpoint, edta is particularly preferred. For the alkali metal salt constituting the alkali metal salt of the coupler, there may be mentioned: h (sodium) and K⑷. For the metal test salt of EDTA, there may be mentioned: job a. Salt), Zheba-! ((Potassium salt), EDTA-2Na (disodium salt), edta_2k (dipotassium salt), EDTA-3Na (three sodium salt), Duyi 3K (three unloading salt), staff ( Four nano-salts), EDTA-4K (tetra-potassium salt), etc. Among them, from the viewpoint of excellent solubility when added to the water to be measured, particularly preferred are Na and Shi. The mixing ratio of the EDTA-4Na. Coupler metal test salt is not particularly limited, but from the standpoint of being able to sharply change the color of the water to be measured near the controlled hardness, it is preferable to add the equivalent of " Controlled hardness -0.1 to 2.0 "" Included in the test for hardness measurement. In the test reagent for hardness measurement of the present invention, it is not necessary to test the genus of the admixture "or mixed to contain the counter ion (Cahuagang) has a metal-examining cation exchanger. As a% ion exchanger such as Bu Ding Yan Xia Xia, it is preferably a Lunengji with a small dissociation constant of the hardness component. For example: styrene styrene sulphonate, etc. The formulation ratio of this cation exchanger is preferably the same as that of the alkali metal salt of the integrator. In the test reagent for hardness measurement of the present invention, In addition to the alkali metal salts of pigments, triethanolamine, glycol compounds, and couplers, in the range that does not affect the effect of the present invention, such as ㈣㈣Mslungagent), can be appropriately blended], 〇3.16S86, 200538733 Additives like defoamers. Masking agent, which is an obstructing ion (for example, as, a, etc.) in the six tested water, and is used to determine the color stability of water, for example: triethanolamine KCN (cyanation, etc.) Among them, from the viewpoint of safety during drainage, Hejia uses diethanolamine. The sensitizer is a person who is sensitive to increase the coloration of the water to be measured by replacing Ca2 + ^ in the water to be measured with, for example, Mg. It is better to use EDTA-Mg (magnesium salt). The blending ratio of the sensitizer is not particularly limited. From the viewpoint of sharply discoloring the water to be measured near the official hardness, it is preferably The method of adding the same or more amount of controlled hardness in the water to be measured contains a sensitizer in the test reagent for hardness measurement. An agent for preventing deterioration can be used even when the test reagent for hardness measurement is placed at a high temperature of 50,000 or more. To prevent deterioration of the pigment, for example, potassium sorbate is preferably used. The defoaming agent is used to eliminate foam in the water to be measured, which is collected in the measuring container, and a nonionic surfactant (for example, Polyethylene oxide octylphenyl s fan). _ The present invention The test reagent for hardness measurement can be produced by uniformly mixing pigments, triethanolamine, diol compounds, and alkali metal salts of a coupler with additives as required. For example, a diol compound can be uniformly mixed with triethanolamine, and then Add the alkali metal salt of the compound to the corresponding requirement Λ], 'Add 9 彳 in this order and add and mix' and finally add the pigment and mix to produce a uniform test reagent for hardness measurement. Furthermore, the present invention The test reagent for hardness measurement is a mixture of pigment, triethanolamine, diol compound, and alkali metal salt of a coupler, which can be used as a one-liquid test reagent to measure the hardness in the measured water. Here, a 316886 · , 200538733 The test of liquid 'means that it contains the constituents required for hardness measurement, and it is intended to be used as a test solution for the measurement of the hardness of liquid mixtures. Therefore, if this kind of hard f / 'Compared to the f-shaped crescent, which adds and mixes each component separately, in order to simplify handling and use, a complicated measurement procedure is not required. — Next, the unadjusted The conventional hardness test of the alkali metal salt of the agent = the case where the test agent is added to the water to be measured, and the change in the hue of the water to be measured explains the facts known to the inventors. Based on this fact, the present invention = effects and comparison The best applicable method will be explained. First, if there is no hard broken water, the hard substance using EBT as a pigment is added: Ⅱ :, and the water is blue because the unreacted state exists. The integrated compounds and unreacted pigments that are generated are combined according to the characters. The unreacted pigments are measured from the mouth of 30:80 to 70, and the water changes from blue to blue-violet. In addition, ten pairs of 'broken crickets' Those who have a higher proportion of the compound will be red-purple to the unreacted pigments, and if all the unreacted pigments are two-color discolored and only the compound is stored, it will be measured. To the end. The fact can be interpreted as when the added pigment :: the ratio of the known pigment discoloration) and the hardness component are born against the deer's 2G to 3⑽ (the color fixation of the water will begin to change color and present a wonderful color a ★ When combining compounds, when measuring _ generating compound compounds, measure ::: = color in pigments. So, as a control hardness, & color and Wang Xianhong 疋 For example]? / Liter (ie, 3ί6886 .12, 200538733 1 ppm), suppose that the pigment% corresponding to hardness j 卯 yang is added to the water to be measured. Since the hardness of 0.2 to 0.3 ppm is used as the starting point of color change, the measured water will appear blue-violet and start to change color. Therefore, the discoloration difference from the start point of the discoloration (hardness 0.2 to 0.3 ppm) to the end point of the discoloration (hardness ippm) will have a degree corresponding to a hardness of 0.7 to 0.8 ppm. That is, it is assumed that Adding pigment equivalent to the regulated hardness in the measurement water, because the measured water will start to change color at a hardness of 20 to 30% of the regulated hardness. If the hardness of the measured water is within the range of discoloration, When measuring the hue of water, it is difficult to tell exactly The degree of hardness is close to the regulated hardness, or a hardness much lower than the regulated hardness. Therefore, if you want to make a judgment, you need to make the color difference difference narrow, and because you make the color difference difference narrow, you can definitely determine the hardness leak. Therefore, in the present invention, since an alkali metal salt of a coupler is prepared as a constituent of the test reagent for hardness measurement, the coupler has priority over the pigment to form a compound with the hardness component in the test water. Because the hardness component reacts with the pigment to form a compound, the color change difference Nakada is narrowed so that the water to be measured can change sharply near the regulated hardness. Specifically, as described above, the regulated hardness is set to 丨Method of ppm 'When an alkali metal salt equivalent to a hardness of 0.5 ppm and a pigment equivalent to a hardness of approximately 0.5 ppm are added to the water to be measured, the alkali metal salt of the adhesive is preferentially equal to hardness. A hardness component of about 5 ppm reacts with m to form a compound, and then the remaining hardness component reacts with the pigment. The discoloration at this time starts The point is 0.6 to 0.65ppn, and the end point of discoloration is 1ppm. Therefore, the discoloration difference will be equivalent to about 0.35 to 0.4ppm. 316886 200538733 If you compare the metal test salt with and without the use of a coupler The aforementioned two examples ^ In the case of the test music for the test, the alkali metal salt with a coupler was adjusted. The discoloration difference narrowed to approximately 0.37 to 0.42. That is, in the latter case, In the example, the discoloration end point is made the same as the former, and the 'crossing start point is close to the discoloration end point side to narrow the discoloration difference. Thus, in the present invention, the alkali metal salt of the coupler and the pigment The proportion of discoloration can be set freely by adjusting the ratio, so that the measured water can be discolored sharply near the controlled hardness. The effect of this invention will be more pronounced if the control hardness is set to be the same. Compared with the previous test reagents for hardness measurement, the amount of pigments can be reduced. If the hardness test reagent of the present invention is used to improve the accuracy of hardness measurement, it is preferably determined in advance: the concentration of the pigment contained in the hardness test reagent and the concentration of the alkali metal salt of the coupler, and the hardness measurement during the measurement. After measuring conditions such as the addition of the test reagent and the volume of the water to be measured, the test is performed. Specifically, when a test reagent for hardness measurement is added to the water to be measured, Lu preferably contains the pigments: 0.0000 to 240.0% by weight, and diethylenamine 0.05% by weight. Above, the alkali metal salt of the coupler is operated in a manner of 0.000006 to 0.0012 weight I%. The concentration of the pigment in the test reagent for hardness measurement is more preferably a concentration calculated by the following formula. [Enum. 1] Concentration (weight）) of the test reagent for hardness measurement-a discoloration start point (ppin) x 仏 water (inl) x the molecular weight of the pigment X] 〇 pigment discoloration ratio (%) × the amount of test reagent added ( mg) x Carbonic acid molecular weight is as described above. If the test reagent for hardness measurement of the present invention is used, it is from .14 3168N6 '200538733 to make the measured water sharply change color near the regulated hardness. For visual measurement by colorimetry, the sample can also be applied as mechanical = applicable. In addition, in the present invention, the water to be supplied to the hot and cold water systems up to the hot and cold equipment, the boiler water, and the like can be used as the hardness measurement object °. Therefore, for example, without being limited to the softened water after passing through the aforementioned hard water softening device, the raw water before passing through the hard water softening device may be used as a measurement object for hardness. [贯 实施 例] In the above, the present invention will be described in detail through the examples, but the present invention is not limited by the examples. (Preparation of water detection) As shown in Table 1, 'modulation made the hardness to 0 mg / liter, 0.6 mg / liter, 0.8 mg / liter, 1.0 mg / liter, L 2 mg / liter, and 4? / Lithium, 丨 · 6mg / liter, 2.0 mg / liter, and 4.0 mg / liter at 9 levels. Make M alkalinity to 5mg / liter, 40mg / liter, and 120mg / liter _ 3 level inspection. water. In addition, in the adjustment of hardness, in order to identify the difference in hue when the relative ratio of Ca2 + and Mgn is different, the Mohr ratio can be Ca2 +: Mg2 + = 4: 1, 1: 2, respectively. Under the same hardness, Ca2 + and Mg2 + have different relative water ratios. When preparing water detection, the hardness is confirmed by ICP (inductively coupled high-frequency plasma), and the μ alkalinity is confirmed by titration with 1 / 50N sulfuric acid. (Preparation of test reagents for hardness measurement) Known: This is the method with the composition shown in Table 2. EBT, triethylamine, ethylene glycol, EDTA-Na, and EDTAUa are prepared separately, and fully stirred to dissolve. 15 16SS6 200538733 to Four kinds of reagents for hardness measurement were prepared. (Examples 1 to 5 and Comparative Examples 1 to 3) A 100ral beaker was charged with 50 ml of water, and a test reagent for hardness measurement was dropped into the water using a micro syringe (nncro synnge), and the beaker was gently shaken. The water test shows color immediately. After color development, observe the hue after 1 minute. The results are shown in Table 1. In addition, Table 3 shows the start point, end point, and color difference of each test area derived from the results in Table 丨. In this kind of test, among the reagents for measuring hardness dropped in each test water, the hardness equivalent concentration of EBT and EDTA-4Na is based on CaC03 (carbon ^ «* ^ 2.2rag / ^ (EDTA_4Na ^ 0.7rag / ^; ^ = L 5mg / A liter), reagent 2 is 3.5mg / liter (EDTA-4Na is ι · 〇mg / liter, EBT is 2.5mg / liter), and reagent 3 and reagent $ liter⑽ (2.5 mg / liter). mg / [Table 1]
16 200538733 [表2 ] 調配成分 試藥1 試藥2 試藥3 試藥4 硬 度 測 定 用 試 藥 之 組 重 量 % EBT 0. 26 0. 44 0. 44 0. 44 三乙醇胺 49. 31 49. 19 49· 78 49. 13 乙二醇 49. 31 49· 19 49· 78 49. 13 EDTA-Mg 1. 0 1. 0 0 1· 3 EDTA-4Na 0. 12 0. 18 0 0 [表3 ] 試藥 水質 變色開始點 (mg/公升） 變色終點 〇Hg/紗) 變色幅 (呢/紗) Μ驗度 (mg/公升） Ca : Mg 實施例1 試藥1 120 1 2 1. 1 2.2 1. 1 實施例2 試藥1 40 1 2 1. 1 2. 2 1· 1 實施例3 試藥1 5 1 2 1· 0 2· 0 1. 0 實施例4 試藥1 40 4 1 1. 1 2.2 1. 1 實施例5 試藥2 40 4 1 1. 6 3. 5 1. 9 比較例1 試藥3 40 1 2 0.9 3. 7 2. 8 比較例2 試藥3 40 4 1 2. 9 7. 5 4. 6 比較例3 試藥4 40 4 1 0.6 2. 5 1· 9 由表3可知，實施例1至4之變色差幅較比較例1至 3者為狹窄的事實。從此事實，如就此種實施例而言，例 316886 200538733 如’將管制硬度設定為2· Offlg/公升時，如硬度測定用試藥 中含有EDTA-4Na，則檢水將在硬度2· 〇mg/公升附近敏銳地 變色，藉此可確實判別硬度漏洩之情形。又，如比較試藥 1(實施例1至3)與試藥2(實施例5)即可知變色開始點及 變色終點均互相差異，且試藥1者之變色差幅較為狹窄的 事貫。因此’如就此種實施例而言，如改變EDTA-4Na與 EBT之e周配比例時’則可自由控制變色開始點、變色終點 以及變色差幅。16 200538733 [Table 2] Formulated ingredient test 1 test 2 test 3 test 4 group weight% of test reagent for hardness measurement EBT 0. 26 0. 44 0. 44 0. 44 triethanolamine 49. 31 49. 19 49 · 78 49. 13 Ethylene glycol 49. 31 49 · 19 49 · 78 49. 13 EDTA-Mg 1. 0 1. 0 0 1 · 3 EDTA-4Na 0. 12 0. 18 0 0 [Table 3] Test Discoloration start point (mg / litre) Discoloration end point (Hg / yarn) Discoloration width (thickness / yarn) M test (mg / liter) Ca: Mg Example 1 Reagent 1 120 1 2 1. 1 2.2 1. 1 Example 2 Test reagent 1 40 1 2 1. 1 2. 2 1 · 1 Example 3 Test reagent 1 5 1 2 1 · 0 2 · 0 1. 0 Example 4 Test reagent 1 40 4 1 1. 1 2.2 1.1 Example 5 Reagent 2 40 4 1 1. 6 3. 5 1. 9 Comparative Example 1 Reagent 3 40 1 2 0.9 3. 7 2. 8 Comparative Example 2 Reagent 3 40 4 1 2. 9 7 5 4. 6 Comparative Example 3 Reagent 4 40 4 1 0.6 2. 5 1 · 9 As can be seen from Table 3, the discoloration difference of Examples 1 to 4 is narrower than that of Comparative Examples 1 to 3. From this fact, for this example, for example, 316886 200538733 If 'the regulated hardness is set to 2 · Offlg / litre, if the test reagent for hardness measurement contains EDTA-4Na, the water test will be at a hardness of 2.0mg The color is sharply changed near the liter / litre, so that the leak of hardness can be accurately determined. In addition, when comparing reagent 1 (Examples 1 to 3) and reagent 2 (Example 5), it can be seen that the discoloration start point and the discoloration end point are different from each other, and the discoloration difference of the reagent 1 is narrow. Therefore, 'as in this embodiment, if the e-period ratio of EDTA-4Na to EBT is changed', the start point of the color change, the end point of the color change, and the color change margin can be freely controlled.
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