200912278 九、發明說明： 【發明所屬之技術領域】 本發明是關於利用流動狀態下互相接觸之二液之折射 率分佈而測定分析對象液之目標參數值（例如液中分析對 象成分之濃度）之方法及其系統。 ' 【先前技術】 一般在半導體及液晶顯示裝置等的製造步驟中，要正 ，確、簡單且迅速地測定所使用之處理用藥劑水溶液中所含 藥劑之濃度，是在這些製造領域廣汎被需求之課題。例如s， 在半導體之領域，矽晶圓洗淨步驟及光蝕刻步驟上使用的 酸（氟酸、硝酸、醋酸、磷酸、鹽酸、硫酸等）之混合物等 處理液，在製品成品率之提高，安全性及作業效率等的觀 點而言，這些處理液中酸濃度之管理是不可缺少的，所以 有對此目的之濃度分析與根據此濃度分析而自動供給心 維持目標濃度的自動化之需求。此處之處理液是無機電解 ，質，沒有紅外線吸收特性’因此不能利用有機化合物之定 性及定量上一般所利用的紅外線吸收特性，所以向來是利 用離子層析法的分析法及離子選擇性電極等的利用電極的 電化干刀析法。但是離子層析法之分析法及離子選擇性電 =等的利用電極的電化學方法，需要將要做濃度分析的處 液稀釋，理液之前處理，每一樣品之處理所需之時 s長’不單不能做連續十生同時做複數種成分之定量，且容 二受其他成分之影響，有缺乏安定性之_。另—方面谷 •文之早成分系之濃度測定法，已知有中和滴定等的化學濕 320122 5 200912278 式法。但是中和滴定等的化學濕式法中，也θ泰 藥及樣品之前處理或後處理等，而有 =而要分析試 嘁（專利文獻1中之先前技術攔）。 、之問 [專利文獻1]日本特開平6-265471號公報 [專利文獻2]曰本特開平4_213〇44號公報 【發明内容】 [發明要解決的課題] 在專利文獻1中，有開示測定混酸中酸濃度 作為可將在半導體及液晶顯示裝置#的製造步驟上所使用 的處理用藥劑中之混酸之酸濃度，正確地對複數 續料定量，是將敎對象之混酸導人於測透光用的^ 式檢測槽（flow cell)中，由數據處理裝置的微處理機，將經 A/D轉換ϋ轉換為數位信號之受光元件之混酸之透光強度 信號，而以此演算出各波長之個別吸光度，再由此演算^ 得各個波長之光的吸光度及多元分析法求得之標準線，而 演算混酸中之酸濃度。 但像這樣利用如此多元迴歸分析⑽hiple analysis)手法的時候，如各成分有特有之不同吸收波長時 可以得到良好的結果，但Μ有時就有不能得到可以滿意 的結果之問題。此外，還有濃度低時精度不好，通常濃度 低於1%時則有不能分析的問題。此外，這個手法還有需 要實施複雜的計算處理而必須使用微處理機之問題。 此外，在專利文獻2中，有提案利用被測定物質在液 中的濃度分.佈的測定手法。具體而言，該手法是含有將液 320122 6 200912278 體流過疎水性多孔質管狀體之内外之步驟。如此，在存在 外侧之液中之被測定物質經由該管狀體之孔而滲入内側之 液中’在該液内形成濃度分佈（徑方向）。如此在形成被檢 測物質之濃度分佈之狀況下’對内侧之液照射光線，則由 於濃度分佈而有折射率之變化，而有所照射光線之光束 控、受光量或集光點之位置之變化。被測定物質之濃度則 由此變化而決定（段落號碼〇〇〇6等）。 f. \' 但疋這個手法如前所述，是以疎水性多孔質管狀體由 外往内，將被測定物質之移動作為前提者。因此要測某一 物質日τ，母-人扁要選擇使該物質有效透過的疎水性多孔質 管狀體的材質。此外，内部之液體也需要選擇比被測定物 質表示更為疎水十生，而被測定物質會擴散、溶解而呈現濃 度分佈者（段落號碼_4)。如此，要測定某被測定物質時， =要選擇適合於該被測絲質的疎水性多孔質管狀體及液 體，又條件設定也需要隨被測定物f之種類及濃度而決 二，。更有要使用經過疎水化處理的多孔質管狀 -心 而要叹置在多孔質管狀體之内外使液體流動的 ^路4，而引起系統構成複雜化之問題。 度的=本目的，為提供一種可簡便地分析濃 分之吸收波Μ^對象成分之吸收波長與樣品中其他成 長範圍内的情形下，皮長不在所使用的波 形下都能夠對該分析之rr象成分濃度鱗 定要使用微處理機也可：辰度進：分析’並且不- 」做，辰度分析。此外，本發明之第二 320122 7 200912278 :的二=供簡單的測定系統構成的手法，其係 要 ，成液中▲度分#之細微的狀況也可做分析對象成 標參數值之測定，並且不需要 77目 之特殊構件。不而要使用如疎水性多孔質管狀體 [解決課題之手段] 本發明者首先注視第—個專利文獻上的問題，是起因 ^利用物質的吸收而做濃度之敎之點，而精心研究基於 / ^古 …俊本發明者着眼於作為物性之折 射率後，以不同於第二個專利 ώ 能&* 予刃又馱上的手法，做成流動狀 =使折料不同的二液在不會完全混合的狀態下將兩液 =至測疋部’在該測定部中測定兩液在流動狀態形成的 ^折射率分佈引起的光強度差，據此光強度差而決定分析 子象成分之濃度’發現這樣劃時代的手法’而完成了本發 明。 本發明⑴是一種測定系統，是利用起因於第一液與第 二液之光學雜(折㈣分則起的光強度的差異）而決定 分析對象物之目標參數值者，其具有 可以導入液體的流路（流穿式檢測槽卬〇〜 cell)17); +液體導入部（第一切換閥13、第二切換閥15)，係在導 入第一液於該流路（流穿式檢測槽17)内後，導人第二液而 使其在該流路（流穿式檢測槽⑺内與第__液接觸而形成界 面領域； 向該界面領域照射光線的光照射部（光源18)， 測定向界面領域照射的光（光強度）的光測定部（受光 8 320122 200912278 部 19)， 其中，光照射部（光源18)是使第一液與第二液的界面 領域呈交叉的方式而照射的。 本發明（2)是發明（1)之測定系統，其光照射部（光源18) 可向界面領域，順著這些液之流向（例如與流向略成平行） 照射光線的。 本發明（3)是發明⑴或發明⑺的測定系統，再具有決 定分析對象物之目標參數值的目標參數值決定手段（數據 處理部22)，該決定手段包括： 適用於將前述目標參數值已知之複數個不同組成的第 三液取代前述第二液時所得複數個組成的光強度而作成的 前述目標翏數值/光強度之標準線，藉此，如分析對象物 為别逑第二液本身時即決定第二液之前述目標來數值；以 ^如分析對象是調配於第二液時，.則依據前述第二液中之 :速目標參數值而決定前述分析對象物中之前述目標參數 ”本:月⑴至發明(3)之任-項的測定系統， 其中/34目標參數值是前述分析對象物中之對 分之浪度，或前述分析對象物之折’ 本發明（5)是發明⑴至發明⑷的制^度。 流穿式檢測槽（流穿式檢測槽17)。Ά錢，其流路為 本發明（6)是一種決定分析 法，是利用第一液與第二液 象I之目標參數值的方 方法係包括下列步驟： 、予特性之差異者，該 320122 200912278 ,第.V驟是在流路（流穿式檢測槽17)内導入第一液 後再導入第一液，使其與第一液在該流路（流穿式檢測槽 17)内接觸而形成界面領域； 第#驟疋使第一液與第二液之界面領域交叉（貫通） 而向該界面領域照射光線； 第三步驟是向界面領域測定所照射的光（光強度）。 、夜邻本疋發明⑹之方法’其第二步驟是向前述之接 液和順者這些液之流動方向照射光線。 驟，：:：⑻是發明(6)或發明⑺之方法，再有第四步 數個不L驟#包括：適用於將前述目標參數值已知之複 Γ=ΐ的第三液取代前述第二液時所得複數個組成 如分析對象物為前述第度之標準線，藉此， 述分析對象成分之前即決定前述第二液中前 調配於第二液時，則依據;述===對象物是 數值。 决疋爾析對象物中之前述目標參 本發明（9)為發明（8)之方法，再 與前述分析對象物反應而生成*前过有八^五步驟，係將含有 率不同之異折射率成分的上〜象成分之折射 液混合者， 風刀之第四液，且與第二 並在第四步驟中，依據前述第 時所測定的光強度，而決定前述分析二液混合 數值。 士象物之削述目標參 320222 10 200912278 述目：是發明(6)至發明(9)之任-方法，”，前 :度’或前述分析對象物之折析對象成分之漠 定義其切請專利之範圍及本說明書中的各用进之 疋義。「界面領域」就是，指笛 "Τ妁各用-之 領域，有明確分界線的界面之二界面之 :分:非連續性變化的界面及連續性二=第::： 先」表不測定有闕光的、某種參/員域測疋 (光量）、光束徑變化量、》二;^//=度 是指與液體流動之方向呈平行及 力率刀佈」 的分佈。「目桿夹數佶θ S垂直之方向之折射率 所含之化合物;:#^^;'7可料於分㈣象物（液） 制，可舉例如，==可以’並無特別的限 分析對象液之折:之二析對ΐ”之漠度，或 如工薇設備的概念，又，各構要」二曰疋指裝置，包含 ,^ 谷構成要素不只是物理性之一體 存=中化者’也包含各構成要素在物理上是分割或分散 【實施方式】 [貫施發明最佳的形態】 在下文’參照附圖而說明本發明之最 。本 不r文之最佳形態所限制。即，最= 畢兄疋舉例表不者，只要與本發明之巾請專利範圍 性思想實質上有相同構成.，並有同樣作 塞 物都包含在本發明之技術性範圍之内。例如 320122 11 200912278 f是測定分析對象成分濃度當做分析對象液t的「目標參 」，。但目標參數」則並不限於分析對象成分濃度。又， ^敢佳形態'中，是由與順著液體流動呈平行之方向照射 光= '，而決定分析對象液之目標參數值而構成。但是，例 體流動方向成垂直的方向照射光線，或與液體流動 方向成斜角的方向照射光線也可以。 首先說明有關本發明之漢度測定系統的測定原理。向 來之、濃度測定法，例如專利文獻i之測定對象之吸光度， 是表示物質對特定波長之光之吸收強度的量度，是與濃度 成比例的參數。此處該文獻是以線上濃度分析為目標，而 測定流經流穿式檢測槽之液體的吸光度，但吸光度本身並 :需要在液體流動狀態，可在靜止狀態測定的物性值。另 面本發明之利用二液之折射率分佈之光強度（差）， 是，體只在流動狀態下才會出現的信號，在這一點上即有 顯著的=同。更有，向來的濃度測定法，是利用吸光度或 IR吸，等之物質之吸收而做濃度測定，而相對於此，本發 月之;辰度列定法，是利用液體之折射率的濃度谢定，在這 一點上t不同。此外，以示差折射率法之濃度測定，需 要在對照單元中導人做為比較對象的液體，要線上適用 時，導入流路需要有分支，使-機器構成變成煩雜。 第1圖表示本發明之原理圖。首先，第一液與第二液 乂相互接觸的狀恕（即兩液並不完全混合的狀態）被導入於 流穿式檢測槽中。此時，如第一液與第二液有濃度差（密度 差）時，界面領域會形成透鏡狀態。此時該透鏡會隨折射^ 320122 12 200912278 之差而變化光之收聚或發散之程度。具體而言，第 遭度>第-液之濃度的時候，第二液之濃度越高，光強度 •越大(收聚:，相反地’第二液之濃度< 第-液之濃度時， 弟-液之浪度越南’光強度越小（發散）。如此，在該透鏡 照射光線下，在流穿式檢測槽下游處測定光強度。缺後夫 照事先準備的各種濃度之該分析對象成分之標準線（濃户 度)、，由測定之光強度決定樣品液中該分析對象成： f中口存在插杰八性樣式，將測定對象液 分時（多成分系），分別加以說明。 種成 《一成分系》 ，品液中之成分為—種成分時’該成分（分象 之測定以如下手法實行。 丁豕成刀） (第一步驟） 將含有已知濃度之分析對象成 入乘載液中。鈇德f空u 旱液間斷性地導 m、，、後在他穿式檢測槽内對乘载液/ 界面與該等液之流向略成平行之方向照光，在於 :下游處受光，而測定光強度。將此操作對於複數:不1 k度之標準液實施’做成該分析對象成分之濃度::：同 之標準線。 权及對先強度 在此，乘载液只要與樣品液不反應的物質 节 特別的限制，例如樣品液為水系時，也不必是水季；無 :也可以。又，從光強度信號放大之觀點上二系選用有機 乘載液，與標準液及樣品液有密度差 =之 奴可使用 320122 13 200912278 純水、酒精等的一般性溶媒 多成分系。 本項目所記述者，也適用於 液體的流量並無特別的限制，但過於緩慢則由 混合而使信號強度寬度增大，或由於幫浦的機械特性而 信號強度發生不均之問題之情形，所以通常是纟3⑼至 200” 1/min之範圍實施。流體之壓力，也沒有特別的限 制，但太低就會在流體中含氣泡，會產生不能做安定的測 定之問題的情形，過高就會|生流路之㈣問題的情形， 所以通常是在（U i 10MPa之範圍實施。流體之溫度，因 為對測定之信號強度有影響，故需要以不產生溫度變化的 方式將液體導人檢測器。所利用的波長也沒有限制，以讯 定對象之液體之折射率之差較大的波長為佳。本項目所= 述者，也適用於下面所說明之多成分系。 (第二步驟） 將樣品液’性地導人乘載㈣，然後在流穿式檢測 槽内對乘㈣/樣品液之界面順著與該等液之流向略成平 灯之方向,¾光，在流穿式檢測槽下游處受光，測^光強度。 然後與在第-步财做成的標準線對照，依據所測定的光 強度決定樣品液中之分析對象成分之濃度。 《多成分系》 樣:m液中的成分為多成分時，其中一成分（分析對象成 分）之測定是依如下手法實行。在多成分系時，對該多成分 系要使用含有與分析對象成分有反應性之反應性成分之溶 液此處所明的「反應性成分」，是與分析對象成分會反應 320122 14 200912278 的成分，並在反應後會生成與該分析對象成分折射率不同 之異折射率成分之成分。選擇這種反應性之反應性成分之 理由，是因生成之成分之折射率與該其反應之分析對象成 分之折射率相同，就不會有折射率之差，而不能辨別光強 度差之故。此外，反應性成分要選擇不受分析對象成分以 外之成分之濃度變化之影響者為佳（換言之，在分析對象成 分以外之成分之濃度有不同時，也不會對分析對象成分之 標準線之直線性有影響的反應性成分為佳）。在表1表示分 析對象成分與反應性成分之組合例以供參考。 【表1】 表1 分析對象成分 樣品液中之其他成分 反應性成分 異折射率成分 氨 過氧化氫 醋酸或鹽酸 醋酸銨 或氯化銨 鹽酸 過氧化氫 氨 或氫氧化納 氯化銨 為了說明上之方便起見，下面以多成分系之2成分系 {第一成分（分析對象成分）及第二成分}為例，說明多成分 系樣品液中一成分濃度之測定手法。 {第一步驟（第一標準線及第二標準線的製作）} 將含有已知濃度之第一成分（分析對象成分）之第一標 準液間斷性地導入於乘載液中。然後對流穿式檢測槽之乘 載液/第一標準液之界面領域順著與其流向略成平行之方 向照光，在流穿式檢測槽下游處受光，測定光強度。將此 15 320122 200912278 操作對於複數個不同濃度之第一標 成分（分析對象成分）之漠度對光強度 '二做成該第一 用複數個组成之已知漠度之第二成分 標準線。同樣 第二成分之濃度對光強度之第二標準線標準液，製成 {第二步騾（第三標準線的製作）丨 (1)第三標準液之調製 含有1=3::=::(分_成分)與 此關於分析對象成分之第一成分，：互準液。在 ⑺含應性成分之溶液(反應性成分溶液):;Γ。 反庫性二與第一成分(分析對象成分)會反應的 ^應]生成刀之溶液。此時，該反應性成分之 ;要大於樣品中第-成分(分析對象成分)之可能:最大 (3)第二標準線之製作 成八液間斷性地導入於乘载液間。再將反應性 間斷性地導入。如第2圖所示，在乘載液間導入 液時’要使第三標準液挾在乘载液與乘載液之間 眭2 A ’但要在第二標準液間導入反應性成分溶液 D要使混合液（第三標準液與反應性成分溶液之混合液） 二第一‘準液與第二標準液之間的方式導入。然後對流 牙、才欢/貝J槽之第二標準液/混合液之界面領域（第2圖中 之A)順著往液流之方向略平行地照射光，在流穿式檢測槽 '轉處又光’測定來自該界面領域之光強度。將此操作實 320122 16 200912278 施於不同濃度之複數種標準液，製成與反應性成分反應的 第一成分（分析對象成分）之濃度對光強度的第三標準線。 {第三步驟（樣品液中之成分濃度決定 (1)使用樣品液之光強度測定 將樣品液間斷性地導入於乘載液間。再將反應性成分 溶，間斷性地導入於樣品液間。如第3圖所示，在乘載液 ^樣°°液日守，要使樣品液挾在乘載液與乘載液間之方 式V入’而要將反應性成分溶液導入於樣品液時，則要使 2合液（樣品液與反應性成分溶液之混合液）挾在樣品液鱼 ί品液之間的方式導人。然後對流穿式檢測槽之乘載液;; =之/面領域(第3圖中之X)與樣品液/混合液之界 光:員二二：中之γ)順著往液流之方向略平行地照射 么光:;測槽下游處受光’測定來自…界面領 (2) 樣品液中第一成分（分析對象成分）之濃度決定 翏照在第二步驟製成的第 領域的光強度，決定樣品液 八據來自γ界面 之濃度。 履中的第一成分（分析對象成分） (3) 樣品液中第二成分之濃度決定 以第4圖所示，說明第二成 4圖（1)所示，泉昭在第 _ /又決叱手法。如第 >…在弟一步驟製成 自X界面領域的光強戶：1 ，線’依據來 姐名 尤強度（Lm)，決定樣品液中第士、八,\ 對象成幻之理論最大濃度(L〜)巾上―,分(分析 示，依據前述⑺所決定的第—成分=如/ 4圖⑺所 成刀（刀析對象成分）之濃度 320122 17 200912278 (C!) ’決定第一成分貢獻之光強度（Li)。然後來自χ界面 領域的光強度（Lm)減去第一成分貢獻之光強度（Li)，而決定 第一成分貝獻之光強度（L2)。然後如第4圖（3)所示，對照 在第一步驟製成的第二標準線，依據所決定的第二成分貢 獻之光強度（L2) ’決定樣品液中第二成分之濃度。 其次依據第5圖說明有關本最佳形態之濃度測定系統 之全體構成。第5圖是該濃度測定系統的示意圖，是流液 主入为析裝置之一種。該系統是由測定部s與控制·數據 處理部P所構成。 士 ^先，測定部S具備：乘載液及樣品液等的流路之主 机路s 1 〇，使乘載液及樣品液以規定流量往下游輸送的筹 、幫浦11，支撐規定量的樣品液（在製作標準線時是標準 用的支撐f 12;在主流路管1〇 0流動的乘載液中將標 支撐^ 12内之樣品液間斷地導入之第一切換閥13 ;在 ，支撐s 12之下游處設置做為反應性成分溶液之流路 之反應性成分溶液流路管Η ;要將與主流路管1〇沒有接 =「非接通狀態」與使主流路管中流動的液體與反庫性 換二液的:接通狀態」互相切換的第二切 ~ Μ生成为洛液以規定流量送往主流路管10 所設：二二:在第一切換閥13與第二切換閥15之下游 液體之流動；：：：17;與在流穿式檢測槽17内流動的 穿式檢測槽17^平行时向照射光的m·隔著流 光元件m等 光源18相對之位置上設置的受光部（受 、此外逛備有儲存乘載液之乘载液儲存部c， 320122 18 200912278 及儲存反應性成分溶液之反應性成分儲存部r 中雖，有顯示，其構成是例如由半導體生產步驟中之舉 之主管、線’樣品液會自動導入於樣品支撐管12。、 另一方面，控制.數據處理部p具備：實行 閥13及第二切換閥15之切換控制，及第一幫浦U及第二 幫浦16之流量控制的控制部21 ;依據測定部s之信 決定分析對象成分之濃度等的數據處理部22;要記憶伊準 η等的濃度等之決定上必要的資訊及測定數據等的數 據部23 ;等。控制·數據處理部s，典型的是個 腦，由CPU、R0M及RAM所構成。 電 此外’在測定部s與控制.數據處理部p之間，裝備 有放大來自又光部19的光強度信號之增幅器％，盥將此 增幅器30之輪出變換為數位信號的a/d轉換器 以下說明本發明之特徵性構成要素。 首先’第6圖為表示流穿式檢測槽17,光源18及受 光部19的位置關係圖(表示乘載液中挾有樣品液之狀態 圖）。該圖中’乘載液（圖中之W或樣品液（圖中之石）由下 方被導向於流穿式檢測槽17之左側後，由左向右流經流穿 式仏測槽17内，由流穿式檢測槽17右侧往下方排出。此 時，光源18是配置於流穿式檢測槽的左彻！，由光源18發 出之光之絲，會與在流穿式檢測槽17内流動之液體之流 向略成平行的位置。受光部19隔著流穿式檢測槽17與光 源18相對而配置於流穿式檢測槽17之右侧。圖中之a為 乘載液與樣品液之界面領域。 320122 19 200912278 流穿式檢測槽17為有 至少有-部分對於該流路之一部 體貝^定容器，其流路 光源18-該流路之一部八 、體抓向可使光經由 巧。等並無特 或圓錐形容器。其剖面形狀也無限制，可:圓; 會產生全反射的材料為佳。-般廣為使 】的材質’如透光面具有光透過型石英㈣、石^ 透過性氟樹月旨的容器等都可以使用 ^ : 部…裝備有透明t: 1之位置與面對受光 受光=部乂9宜為具有輸出因應光強度之電信號機能的 :==1:立置是只要在能接受來自流穿式檢 測槽17之下_ 不受_’典型的是在流穿式檢 雖❹^ 但如與流穿式檢測槽17之距離短，則 雖感度變而，但會受散射光的影響而使光強度差變小 :離=感度變低，但光強度差則會增大。受光部 :而=:=件但光強度差會變小。所以需要隨使用條 數據6圖及第7圖詳細說明本最佳形態之控制. 1處理〇實行光強度測定處理及濃度決定處理之一例 第一成分及第二成分)之測定}。這畢竟是-例， 二的順序等並不受其限制。例如，在第6圖中，將第二 <切換為石側之時間，是在第1 13切換為㈣之前 320122 20 200912278 貝行，但視流量大小，可將其順序倒過來實行。 弟6圖為本最佳形態之光強度測定處理100之流程 圖。百先在步驟102 ’控制部21參照數據記憶部23，依據 在該Z憶部23所記憶（操作者預先存入者）之設定流量，驅 動控制第-幫浦n，使流量為其設定流量。由此乘載液開 始乂 n又疋/瓜1在主流路管j 〇中流動。其次在步驟i ，控 制。卩21參妝數據記憶部23，依據該記憶部所記憶（操 作者預先存入者）设定之流量，驅動控制第二幫浦〗6，使 流量為，設定流量。但第二切換閥15在「非接通狀態」， 所以雖是以該流量而驅動控制，但反應性成分溶液不會注 入於主流路f 1G中，而被排出於系外。其次在步驟106, 控制部21判定有沒有達到將樣品液導入系内之時間，亦 P有/又有達到將第一切換閥】3之切換時間。在步驟1 % 為州時，在步驟1〇8，控制部以控制第一切換閥u往a 側（與主流路管10接通之側）切換。由此，樣品支撐管12 =之樣品液被第-幫浦引出之結果，成為被挾在乘載液與 乘載液間之狀態而往下游方向流動。其次在步驟ιι〇，控 ^部21狀是否達料把反應性成分溶液導人於系内之 、間亦即’疋否達到要切換第二切換閥15之時間。當 二,％ ’反f性成分溶液(與樣品液之混合液)需要被挾在 :品液與樣品液之間，所以需要考量樣品液之先端通過第 換ϋ,之時間及樣品液之後端通過第二切換閥15之 寺間· >瓜速等，而決定被每庇 確只月匕使反應性成分溶液會被挾在 才取品液間之時間。JL攻左牛 ^ 八在步驟112，控制部112控制將第 320122 21 200912278 二閥15往〇：側（與主流路管1〇接通狀態之側）切換。由此 反應性成分溶液被導入於主流路管1〇内，在該導入點逐次 舆樣品液混合。如此，前述之樣品液被導入於主流路管1〇 内時，在切換前後，會以該液（樣品液）完全取代在主流路 管、1〇内流動的液體（乘載液），而反應性成分溶液被導入於 主流路管10時’（並非液之取代）是成為在主流路管1〇内 μ動之液體（樣品液）與該液（反應性成分溶液）混合之形 態。其次，在步驟114’控制部12判定是否達到要終止往 主流路管10之反應性成分溶液之供給，亦即，是否達到要 將第二閥15切換為々侧（與主流路管10成為非接通狀能之 側)^時間。在步驟114為yes時，在步驟116，控制部 將第二閥15控制向Θ侧（與主流路管1〇成為非接通狀態之 側）切換。由此而終止反應性成分溶液往主流路管W之供 給。其次在步驟118，控制部12要判定是否達到要線j 品液往主流路f 1〇之供給，亦即，是否達到要把第一門 切^者B側（與主流路管1〇成為非接通狀態之側 間。在步驟118為yes時，在舟驟彳 ^ ' 望β 步驟12〇,控制部山控制 弟-閥U在Β側（與主流路管1〇成為非接通狀態之側）切 換。由此而終止樣品液往主流路管1〇之供給。在 控制部112看準第一、、ρ,丨宕w ,驟122， 有早弟測疋對象界面領域（乘载液 到達流穿式檢測槽17之時間， β 。口液） 關光強度X之資；。在步:124取^^^^ 貝汛在步驟124，控制部112看 =象界面領域(樣品液+反應性成分溶液之淚合液；： «口液）到達流穿式檢測槽17之時間，取得受光部Η測定的 320122 22 200912278 有關光強度γ之資訊。這些資訊之取得時間，可考量例如 切換閥的時間及流速等而決定。然後在步驟126，控制部 Π2將在㈣122 &步釋124所取得之資訊記憶在數據記 憶部23。在步驟1〇6、步驟11〇、步驟114及步驟ιΐ8有 110時’須循環該處理至出現yes為止。 ，第7圖是本最佳形態之濃度決定處理之流程圖。 首先在步驟202 ’數據處理部22參照數據記憶部23所記 憶之有關第-成分之標準線數據，依據第6圖之步驟122 所測疋之光強度X之值，決定第—成分之理論最大濃度。 其次在步驟204，數據處理部22再參照在數據記憶部^ 所記憶之有關第-成分之標準線數據，依據第6圖之步驟 124所測定的光強度γ之值，決定第—成分之漢度。其次 f步驟2G6,數據處理部22參照有關第—成分之標準線數 f，決定第一成分貢獻之光強度與第二成分貢獻之光強 度:然後在步驟2G8，數據處理部22參照數據記憶部23 斤★己L之第一成分之標準線數據，依據在步驟所決定 的第二成分貢獻之光強度，而決定第二成分之濃度。 八f 6圖與第7圖是關於樣品液中之第-成分及第二成 刀之:f決定處理的，但在製成標準線時也是同樣的處 要f作第-成分之標準線時，使用複數個組成 辰度的第—成分溶液取代樣品液，要製作第二成分 ^不準線& ’使用複數個組成之已知濃度的第二成分溶 要依據第-成分與反應性成分之反應物（不同折射率成 为）而製作第一成分之標準線時，使用複數個組成之已知濃 320122 23 200912278 度的第一成分與第二成分（此時第二成分之濃度可以是— 定濃度，也可以是不同濃度）之混合物取代樣品液。 [實施例] 《實施例〗（一成分系）》 藍準線之劁祚 1) 調製0、〇.〇5、〇1、〇q、曾甘咖产 、_ · · 0.5莫耳浪度之氨水溶液，做 為製作第—標準線之標準液，並調製G.G5、0.1、0.3、 0.5莫耳濃度之過氧化氫做為第二標準線之標準液。 2) 以純水做為乘驗，將1)之液以llGG/zl/min的速度導 入於測疋盗，測定所產生的界面領域之信號強度。 )由2)所仔的仏號強度與各標準液之濃度，製成標準線（有 關氨水溶液之第―標㈣—第9圖，有關過氧化氫的第 二標準線'^第10圖）。 ^度之測定 1)=、二做樣品液之下表所列示調製莫耳濃度之氨水溶液 1)與過氧化氫水溶液（供試品幻之信號強度，依 ，在則步驟製成的第—標準線及第二標準線算出各別的 濃度。其結果示於表2。 【表2】 表2 fit fJr' 〇 Γ 一•一 調製莫耳濃度 0J50 -------- :PK1信號濃度 0.00150 异出莫耳濃唐 0.144 ~ 0.200 0.00560 0.202 — 《實施例 2(多成分系）》 320122 24 200912278 標準液之調盤 1) 調製 0、0.05、0.1、0.3、〇 5 朴 曲 ^ 為製作第一標準線之標準7 *耳展度之氨水溶液，佐 夜’並調製〇〇5、 0.5莫耳濃度之過氧化氫# ·05 0·1、0.3、 1做為製作第二標準飧 做為 2) 以表3所示之组合，轉^準線之;示準液1 製作第三標準線之標準液。’風混合溶液 【表3】 表 成分 標準液1 氨 0.080 過氧化氫 0.416 樣品液之調f200912278 IX. Description of the Invention: [Technical Field] The present invention relates to measuring a target parameter value (for example, a concentration of a component to be analyzed in a liquid) of an analysis target liquid by using a refractive index distribution of two liquids in contact with each other in a flowing state. Method and system. [Prior Art] Generally, in the manufacturing steps of semiconductors, liquid crystal display devices, and the like, it is necessary to accurately, accurately, and rapidly measure the concentration of the drug contained in the aqueous solution for treatment used, which is widely used in these manufacturing fields. The topic of demand. For example, in the field of semiconductors, the treatment liquids such as a mixture of acid (fluoric acid, nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, etc.) used in the wafer cleaning step and the photo-etching step are improved in the yield of the product. From the viewpoints of safety, work efficiency, and the like, the management of the acid concentration in these treatment liquids is indispensable, and there is a need for concentration analysis for this purpose and automation for automatically supplying the heart to maintain the target concentration based on the concentration analysis. The treatment liquid here is inorganic electrolysis, and has no infrared absorption characteristics. Therefore, the qualitative and quantitative infrared absorption characteristics generally used for the organic compound cannot be utilized. Therefore, the ion chromatography method and the ion selective electrode have conventionally been used. Electrochemical dry knife analysis using electrodes. However, the ion chromatography method and the ion-selective electro-electrical method using an electrode require dilution of the solution to be subjected to concentration analysis, and prior treatment of the solution, and the time required for the treatment of each sample is ' Not only can we not do the continuous ten-year and do the quantitative determination of multiple components at the same time, and the capacity is affected by other components, and there is a lack of stability. In addition, the concentration measurement method of the early component of the article is known as chemical wetness such as neutralization titration. 320122 5 200912278 Formula method. However, in the chemical wet method such as neutralization titration, etc., it is also possible to pre-treat or post-treat the sample of the Thai medicine and the sample, and to analyze the test (the prior art block in Patent Document 1). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The acid concentration in the mixed acid is used to accurately quantify the acid concentration of the mixed acid in the processing agent used in the manufacturing process of the semiconductor and the liquid crystal display device #, and to introduce the mixed acid of the target to the tester. In the flow cell of the light type, the microprocessor of the data processing device converts the light-transmitting intensity signal of the mixed acid of the light-receiving element converted into the digital signal by the A/D conversion ,, thereby calculating each The individual absorbances of the wavelengths are calculated from the absorbance of the light of each wavelength and the standard line obtained by the multivariate analysis method, and the acid concentration in the mixed acid is calculated. However, when such a multi-regression analysis (10) hiple analysis technique is used as described above, good results can be obtained if the components have different absorption wavelengths, but sometimes there is a problem that satisfactory results cannot be obtained. In addition, there is a problem that the accuracy is not good when the concentration is low, and the problem is not analyzed when the concentration is less than 1%. In addition, this approach has the problem of having to implement complex computational processing and having to use a microprocessor. Further, in Patent Document 2, there is a proposal for a method of measuring the concentration of a substance to be measured in a liquid. Specifically, the method comprises the step of flowing the liquid 320122 6 200912278 into the inside and outside of the hydrophobic porous tubular body. In this manner, the substance to be measured in the liquid in the outer side penetrates into the liquid inside through the pores of the tubular body, and a concentration distribution (diameter direction) is formed in the liquid. Thus, in the case where the concentration distribution of the substance to be detected is formed, the light is irradiated to the inner liquid, and the refractive index changes due to the concentration distribution, and the beam control, the amount of received light, or the position of the light collecting point of the irradiated light are changed. . The concentration of the substance to be measured is determined by this change (paragraph number 〇〇〇6, etc.). f. \' However, as mentioned above, the hydrophobic porous tubular body is moved from the outside to the inside, and the movement of the substance to be measured is premised. Therefore, to measure a certain material day τ, the mother-person flat should select the material of the hydrophobic porous tubular body that effectively transmits the substance. In addition, the internal liquid also needs to be selected to be more immersed than the substance to be measured, and the substance to be measured is diffused and dissolved to exhibit a concentration distribution (paragraph number _4). When measuring a certain substance to be measured, it is necessary to select a hydrophobic porous tubular body and a liquid suitable for the silk to be measured, and the condition setting needs to be determined in accordance with the type and concentration of the object to be measured f. Further, it is necessary to use a porous tubular-heart that has been hydrotreated, and to sigh the inside of the porous tubular body to allow the liquid to flow, which causes a problem of complication of the system. For the purpose of providing a simple analysis of the absorption wavelength of the absorption component of the concentration and other growth ranges in the sample, the skin length can not be analyzed under the waveform used. Rr like the concentration of the composition of the scale must use the microprocessor can also be: Chen Jinjin: analysis 'and not -" to do, Chen degree analysis. In addition, the second 320122 7 200912278 of the present invention is a method for constructing a simple measurement system, and the subtle condition of the ▲ degree score in the liquid can also be used to determine the value of the target parameter of the analysis object. And no special components of 77 mesh are needed. It is not necessary to use a hydrophobic porous tubular body. [Means for Solving the Problem] The present inventors first looked at the problem in the first patent document, and it is the point at which the concentration of the substance is absorbed by the absorption of the substance, and the research is based on / ^古...The inventor of the present invention focused on the refractive index of the physical property, and made it different from the second patent & & & * 予 予 = = = = = = = = = = = = = = = = = In the state where the two liquids are not completely mixed, the difference in light intensity caused by the refractive index distribution formed by the two liquids in the flowing state is measured in the measuring portion, and the analyte component is determined based on the difference in light intensity. The present invention has been completed by the concentration 'discovering such an epoch-making technique'. The present invention (1) is a measurement system that determines a target parameter value of an analysis target by using an optical impurity (a difference in light intensity between the first liquid and the second liquid), which has a liquid inputable Flow path (flow-through detection tank cell ~ cell) 17); + liquid introduction portion (first switching valve 13, second switching valve 15), is introduced into the first liquid in the flow path (flow-through detection After the inside of the groove 17), the second liquid is guided to form an interface region in the flow path (the flow-through detecting groove (7) is in contact with the first liquid; the light irradiation portion that irradiates the light to the interface region (light source 18) a light measuring unit (light receiving light 8 320122 200912278 part 19) that measures light (light intensity) irradiated to the interface area, wherein the light irradiation unit (light source 18) intersects the interface area of the first liquid and the second liquid The present invention (2) is the measurement system of the invention (1), wherein the light-irradiating portion (light source 18) can illuminate the light in the interface region along the flow direction of the liquid (for example, slightly parallel to the flow direction). The invention (3) is the measurement system of the invention (1) or the invention (7), and further has Determining a target parameter value determining means (data processing unit 22) for analyzing a target parameter value of the object, the determining means comprising: applying a third liquid having a plurality of different compositions whose known target parameter values are known to replace the second liquid a standard line of the target target value/light intensity created by a plurality of components of light intensity, whereby the target value of the second liquid is determined when the object to be analyzed is the second liquid itself; When the object is formulated in the second liquid, the determination of the target parameter in the analysis object is determined according to the speed target parameter value in the second liquid. The measurement of the term (1) to the invention (3) The system, wherein the /34 target parameter value is the halving of the halving in the analysis object, or the folding of the aforementioned analysis object. The invention (5) is the manufacturing degree of the invention (1) to the invention (4). (Flowthrough detection tank 17). The flow path is the invention (6) is a determination analysis method, and the method for using the target parameter values of the first liquid and the second liquid image I includes the following steps: Difference in characteristics 320122 200912278, the first step is to introduce the first liquid into the flow path (flow-through detecting tank 17) and then introduce the first liquid into the flow path with the first liquid (flow-through detecting tank 17). The internal contact forms an interface field; the first step is to make the interface between the first liquid and the second liquid intersect (through) and irradiate the light to the interface field; the third step is to measure the irradiated light to the interface field (light intensity) The method of the invention of the invention (6) is the second step of illuminating the light in the direction of the flow of the liquid and the liquid. The method of the invention (6) or the invention (7), Further, there are a plurality of steps in the fourth step. Including: a plurality of components obtained by substituting the third liquid having the known target parameter value of retanning = ΐ for the second liquid, for example, the object to be analyzed is the aforementioned standard. The line, whereby the second liquid is pre-distributed to the second liquid before the analysis target component is determined, and the object is a numerical value. The above-mentioned object of the invention is the method of the invention (8), and the method of the invention (8) is further reacted with the object to be analyzed to generate * before the step of 5^5, which is a heterorefringence having a different content rate. The composition of the upper-to-image component of the refractive index is mixed with the fourth liquid of the air knife, and in the fourth step, in the fourth step, the analysis of the two-liquid mixing value is determined based on the light intensity measured in the first time. The description of the target of the icon is 320222 10 200912278. It is the method of invention (6) to invention (9) - method, ", before: degree" or the definition of the component of the object of analysis of the aforementioned analysis object Please refer to the scope of the patent and the meaning of each use in this manual. The "interface field" is the area of the interface where the flute is used, and the interface with the clear boundary line is divided into two: interface: discontinuity The interface and continuity of change two = the first::: first" table does not measure the light, a certain parameter / member field measurement (light quantity), beam diameter change, "two"; ^ / / = degree means The direction of liquid flow is in a parallel and force distribution. "The compound contained in the refractive index in the direction perpendicular to the θ θ S;; #^^; '7 can be obtained from the sub-fourth image (liquid), for example, == can be 'no special' Limit the analysis of the liquid of the object: the second analysis of the indifference to the ΐ", or the concept of the equipment of the weiwei, and the various structures must be "two-finger device, including, ^ the composition of the valley is not only a physical body The "neutralizer" also includes physical division or dispersion of each constituent element. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described with reference to the drawings. This is not limited by the best form of the text. That is, the most = 毕 疋 疋 疋 , , , , 疋 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 For example, 320122 11 200912278 f is a "target parameter" for measuring the concentration of the component to be analyzed as the liquid t to be analyzed. However, the target parameter is not limited to the concentration of the analyte component. Further, in the "dough form", the target parameter value of the analysis target liquid is determined by irradiating light = ' in a direction parallel to the liquid flow. However, it is also possible that the flow direction of the sample is irradiated with light in a vertical direction or in a direction oblique to the direction in which the liquid flows. First, the measurement principle of the Handu measurement system of the present invention will be described. In the conventional concentration measurement method, for example, the absorbance of the object to be measured in Patent Document i is a measure indicating the absorption intensity of a substance with respect to light of a specific wavelength, and is a parameter proportional to the concentration. Here, the document aims at the online concentration analysis, and measures the absorbance of the liquid flowing through the flow-through detection tank, but the absorbance itself is a physical property value that can be measured at a stationary state in the liquid flow state. Further, the light intensity (difference) of the refractive index distribution using the two liquids of the present invention is a signal which appears only when the body is in a flowing state, and at this point, there is a significant = the same. In addition, the concentration measurement method is based on the absorption of substances such as absorbance or IR absorption, and the concentration is measured. In contrast, the present invention is based on the concentration of the refractive index of the liquid. D, at this point t is different. Further, in the concentration measurement by the differential refractive index method, it is necessary to introduce a liquid as a comparison object in the comparison unit, and when it is applied on the line, the introduction flow path needs to have a branch, making the -machine configuration complicated. Figure 1 shows the schematic of the invention. First, the first liquid and the second liquid are in contact with each other (i.e., the state in which the two liquids are not completely mixed) are introduced into the flow-through detecting tank. At this time, if there is a difference in density (density difference) between the first liquid and the second liquid, a lens state is formed in the interface field. At this time, the lens changes the degree of light collection or divergence with the difference of the refractive index 320122 12 200912278. Specifically, when the concentration of the first solution is the concentration of the first liquid, the higher the concentration of the second liquid is, the larger the light intensity is (collecting: conversely, the concentration of the second liquid < the concentration of the first liquid At the same time, the younger-liquid wave of Vietnam's light intensity is smaller (divergence). Thus, under the lens illumination light, the light intensity is measured downstream of the flow-through detection tank. The standard line (concentration degree) of the component to be analyzed is determined by the measured light intensity. The analysis object in the sample liquid is: f. The mouth of the mouth has a singularity, and the liquid is measured (multi-component system), respectively To describe the composition of the "one component", when the component in the liquid is the component - the component (the measurement of the image is carried out as follows: Ding Yucheng knife) (first step) The analysis object containing the known concentration Into the carrier liquid. The dry liquid is intermittently guided by m, and then in the direction of the carrier liquid/interface in a direction slightly parallel to the flow of the liquid in the wear-through detection tank, : The light is measured at the downstream, and the light intensity is measured. This operation is for the plural: The concentration of the component to be analyzed is not the same as the standard concentration of the component: When the sample liquid is water, it does not have to be a water season; no: Yes. Also, from the viewpoint of light intensity signal amplification, the second choice is the organic carrier liquid, and the density difference between the standard solution and the sample solution = slave can use 320122 13 200912278 General solvent multi-component system such as pure water, alcohol, etc. The flow rate of liquids used in this project is not particularly limited, but if it is too slow, the signal intensity width is increased by mixing, or The mechanical characteristics of the pump and the problem of uneven signal intensity, so it is usually implemented in the range of 纟3 (9) to 200" 1 / min. The pressure of the fluid is not particularly limited, but if it is too low, it will contain bubbles in the fluid. , it will produce a problem that cannot be determined by stability. If it is too high, it will be the case of (4) problem, so it is usually implemented in the range of U i 10MPa. The temperature of the fluid is because of the measurement. Since the signal intensity has an influence, it is necessary to introduce the liquid into the detector in such a manner that no temperature change occurs. The wavelength to be used is also not limited, and the wavelength at which the difference in refractive index of the liquid of the target object is large is preferable. = The above is also applicable to the multi-component system described below. (Second step) The sample liquid is 'studyly loaded (4), and then the interface of the multiplication (four)/sample liquid is followed in the flow-through detection tank. The flow direction of the liquid is slightly flat, 3⁄4 light, and is received at the downstream of the flow-through detection tank to measure the light intensity. Then, according to the standard line made in the first step, according to the measured light intensity The concentration of the component to be analyzed in the sample solution is determined. "Multi-component system" Sample: When the component in the m-liquid is a multi-component, the measurement of one component (analytical component) is carried out as follows. In the case of a multi-component system, a "reactive component" as described herein which contains a reactive component reactive with the component to be analyzed is a component which reacts with the component to be analyzed 320122 14 200912278. Further, after the reaction, a component of a refractive index component different in refractive index from the component to be analyzed is generated. The reason for selecting such a reactive reactive component is that the refractive index of the component to be formed is the same as the refractive index of the component to be analyzed, and there is no difference in refractive index, and the difference in light intensity cannot be discerned. . Further, it is preferable that the reactive component is selected from the influence of the concentration change of the component other than the component to be analyzed (in other words, when the concentration of the component other than the component to be analyzed is different, the standard line of the component to be analyzed is not Linear reactive influential reactive components are preferred). Table 1 shows an example of the combination of the analyte component and the reactive component for reference. [Table 1] Table 1 Other components in the sample liquid of the analysis component Reactive composition component Ammonia hydrogen peroxide or ammonium acetate hydrochloride or ammonium chloride hydrochloride hydrogen peroxide or sodium hydroxide ammonium chloride For the sake of convenience, the measurement method of the concentration of one component in the multi-component sample liquid will be described below by taking the two components of the multi-component system {the first component (analytical component) and the second component} as an example. {First Step (Production of First Standard Line and Second Standard Line)} The first standard liquid containing the first component (analytical component) of a known concentration is intermittently introduced into the carrier liquid. Then, the interface region of the carrier liquid/first standard solution of the flow-through detecting tank is irradiated in a direction slightly parallel to the flow direction thereof, and is received at the downstream of the flow-through detecting tank to measure the light intensity. The operation of this 15 320122 200912278 operation is performed for a plurality of different concentrations of the first component (analytical component), and the light intensity '2' is the second component standard line of the first component of the known composition. Similarly, the concentration of the second component to the second standard line standard of light intensity is made {the second step 制作 (production of the third standard line) 丨 (1) the third standard solution contains 1=3::=: : (minutes_components) With regard to the first component of the analyte component, the: collimation liquid. (7) A solution containing a suitable component (reactive component solution): Γ. The anti-depositive two reacts with the first component (analytical component) to form a solution of the knife. At this time, the reactive component is larger than the first component (analytical component) in the sample: maximum (3) The second standard line is formed into an intermittently introduced liquid between the carrier liquids. The reactivity was introduced intermittently. As shown in Fig. 2, when introducing liquid between the carrier liquids, 'make the third standard liquid 眭2 A ' between the carrier liquid and the carrier liquid, but introduce a reactive component solution between the second standard liquid. D is to introduce a mixture (the mixture of the third standard solution and the reactive component solution) between the first 'pre-liquid and the second standard solution. Then, the interface area of the second standard solution/mixture solution of the flow tooth, the huayue/bean J groove (A in the second figure) is irradiated with light in the direction parallel to the flow direction, and is turned in the flow-through detection groove. At the same time, light intensity is measured from the interface field. This operation was carried out by applying a plurality of standard solutions of different concentrations to a third standard line of the concentration of the first component (analytical component) reacting with the reactive component against the light intensity. {Third Step (Determining the concentration of the components in the sample solution (1) Using the light intensity measurement of the sample solution, the sample liquid is intermittently introduced between the carrier liquids. The reactive components are dissolved and intermittently introduced between the sample liquids. As shown in Fig. 3, in the case of the carrier liquid, the liquid is to be immersed in the mode of the carrier liquid and the carrier liquid, and the reactive component solution is introduced into the sample liquid. At the same time, the two liquid mixture (mixture of the sample liquid and the reactive component solution) is immersed in the sample liquid, and then the carrier liquid is passed through the flow detection tank; The surface area (X in Figure 3) and the sample liquid/mixture boundary light: member 22: medium γ) illuminate in a direction slightly parallel to the direction of the liquid flow:; From the interface (2) The concentration of the first component (analytical component) in the sample solution determines the light intensity of the first field produced in the second step, and determines the concentration of the sample liquid from the γ interface. The first component (analytical component) in the process (3) The concentration of the second component in the sample solution is determined as shown in Fig. 4, and the second figure is shown in Fig. 1 (1). technique. For example, the first step in the brother's step is made from the X-interface field: 1 , the line 'based on the name of the sister's name (Lm), determines the sample liquid in the Dshi, eight, \ object into the magic theory Concentration (L~) towel on the ―, (analysis, according to the above-mentioned (7), the first component = such as / 4 Figure (7), the concentration of the knife (the object of the analysis) 320122 17 200912278 (C!) 'Decision The light intensity (Li) contributed by a component. Then the light intensity (Lm) from the χ interface field is subtracted from the light intensity (Li) contributed by the first component, and the light intensity (L2) of the first component is determined. As shown in Fig. 4 (3), the concentration of the second component in the sample liquid is determined according to the determined light intensity (L2) of the second component determined in the second standard line produced in the first step. 5 is a view showing the overall configuration of the concentration measuring system according to the present preferred embodiment. Fig. 5 is a schematic view of the concentration measuring system, which is a type of flow-in main-injection device. The system is controlled by the measuring unit s and the control data processing. In the first part, the measuring unit S includes a flow of a carrier liquid, a sample liquid, or the like. The host road s 1 〇, the carrier liquid and the sample liquid are transported downstream by a predetermined flow rate, and the pump 11 supports a predetermined amount of sample liquid (the standard support f 12 is used in the production of the standard line; in the mainstream road) The first switching valve 13 that intermittently introduces the sample liquid in the standard support 12 into the carrier liquid flowing in the tube 1〇0; the reactivity of the flow path as the reactive component solution is set downstream of the support s 12 Component solution flow path tube; to be connected to the main line tube 1〇 = "non-on state" and the liquid flowing in the main flow tube and the anti-reservoir exchange liquid: the on state" The second cut ~ Μ is generated as a liquid to be sent to the main flow pipe 10 at a prescribed flow rate: 22: the flow of the liquid downstream of the first switching valve 13 and the second switching valve 15;:::17; The transmissive detecting groove 17 in the type detecting groove 17 is a light-receiving portion provided at a position facing the light source 18 such as the streamer element m when the light is irradiated in parallel (accepted by the storage of the carrier liquid) Carrier liquid storage unit c, 320122 18 200912278 and storage of reactive components for storing reactive component solution In the part r, it is shown that the configuration is, for example, the main line of the semiconductor production step, and the sample liquid is automatically introduced into the sample support tube 12. On the other hand, the control data processing unit p includes: 13 and the switching control of the second switching valve 15, and the control unit 21 for the flow control of the first pump U and the second pump 16, and the data processing unit 22 for determining the concentration of the analysis target component based on the information of the measuring unit s; It is necessary to memorize the information necessary for the determination of the concentration or the like of the y, and the like, the data unit 23 for measuring data, etc. The control/data processing unit s is typically a brain, and is composed of a CPU, a ROM, and a RAM. Further, between the measuring unit s and the control/data processing unit p, an amplifier % for amplifying the light intensity signal from the light-receiving portion 19 is provided, and the rotation of the amplifier 30 is converted into a/ for the digital signal. d Converter The following describes the characteristic constituent elements of the present invention. First, Fig. 6 is a view showing the positional relationship between the flow-through detecting groove 17, the light source 18 and the light receiving portion 19 (a state diagram showing the sample liquid in the carrier liquid). In the figure, the 'carrier liquid (the W in the figure or the sample liquid (the stone in the figure) is guided from the lower side to the left side of the flow-through detecting groove 17, and flows from the left to the right through the flow-through detecting groove 17 The light source 18 is disposed on the right side of the flow-through detecting groove 17. The light source 18 is disposed in the flow-through detecting groove, and the light emitted by the light source 18 is connected to the flow-through detecting groove 17 The flow of the liquid flowing therein is slightly parallel. The light receiving portion 19 is disposed on the right side of the flow-through detecting groove 17 with the flow-through detecting groove 17 interposed therebetween. In the figure, a is a carrier liquid and a sample. The interface area of the liquid. 320122 19 200912278 The flow-through detection tank 17 has at least one part of the container for the flow path, and the flow path light source 18 - one part of the flow path The light can be passed through. There is no special or conical container. The cross-sectional shape is not limited. It can be: round; the material that will produce total reflection is better. The material that is widely used, such as the light-transmissive surface, has light. The transmissive quartz (4), the stone, the transparent fluorinated tree container, etc. can be used. ^ : The part... is equipped with a transparent t: 1 position and Faced with light receiving light = part 乂 9 should be the function of the electrical signal with output light intensity: = = 1: stand up as long as it can be accepted from the flow through detection slot 17 _ not _ 'typically in Although the flow-through type inspection is ❹^, if the distance from the flow-through detection groove 17 is short, the sensitivity is changed, but the light intensity difference is small due to the influence of the scattered light: the deviation is low, but the light intensity is low. The difference will increase. The light receiving part: but =: = but the light intensity difference will become smaller. Therefore, it is necessary to describe the control of the best form in detail with the use of the data 6 and Fig. 7. 1 Processing 〇 Performing light intensity measurement Determination of the first component and the second component in one of the treatment and concentration determination processes}. This is, after all, an example, the order of the two, etc. is not limited by it. For example, in Fig. 6, the time when the second < switch to the stone side is switched to the front row of 320122 20 200912278 before the first 13 is switched to (4), but depending on the flow rate, the order can be reversed. Figure 6 is a flow chart of the light intensity measuring process 100 of the best mode. In step 102, the control unit 21 refers to the data storage unit 23, and drives and controls the first-stage n according to the set flow rate stored in the Z-memory unit 23 (the operator pre-stored), so that the flow rate sets the flow rate thereof. . As a result, the carrier liquid starts to flow, and the melon/melon 1 flows in the main flow path j 〇. Next, in step i, control. The 参21 makeup data storage unit 23 drives and controls the second pump 6 based on the flow rate set by the memory unit (the operator pre-stored), and sets the flow rate to set the flow rate. However, since the second switching valve 15 is in the "non-on state", the control is driven by the flow rate, but the reactive component solution is not injected into the main flow path f1G and is discharged outside the system. Next, in step 106, the control unit 21 determines whether or not the time for introducing the sample liquid into the system is reached, and the switching time of the first switching valve 3 is also reached. When the step 1% is the state, in step 1〇8, the control unit switches to control the first switching valve u to the a side (the side connected to the main flow path 10). As a result, the sample liquid of the sample support tube 12 = is extracted by the first pump, and is caused to flow in the downstream direction between the carrier liquid and the carrier liquid. Next, in the step ιι, the control unit 21 is configured to introduce the reactive component solution into the system, that is, the time to switch the second switching valve 15 is reached. When the second, the % 'anti-f component solution (mixed with the sample solution) needs to be smashed between: the product liquid and the sample liquid, so it is necessary to consider the apex of the sample liquid through the ϋ change, the time and the back end of the sample liquid By the second switching valve 15, the temple, the speed of the melon, and the like, it is determined that the reaction component solution is smashed between the liquids and the liquids. JL attacking the left mouse ^8 In step 112, the control unit 112 controls to switch the 320122 21 200912278 two-valve 15 to the 〇: side (the side close to the main line 1 〇 state). Thereby, the reactive component solution is introduced into the main flow path 1 ,, and the sample liquid is successively mixed at the introduction point. When the sample liquid is introduced into the main flow tube 1 in this manner, the liquid (sample liquid) completely replaces the liquid (the carrier liquid) flowing in the main flow tube and the 1 〇 before and after the switching, and the reaction is performed. When the component solution is introduced into the main flow pipe 10 (not the liquid substitution), the liquid (sample liquid) which is moved in the main pipe 1 is mixed with the liquid (reactive component solution). Next, at step 114', the control unit 12 determines whether or not the supply of the reactive component solution to be terminated to the main flow conduit 10 is reached, that is, whether or not the second valve 15 is to be switched to the crotch side (to become non-mainstream with the main flow pipe 10). Turn on the side of the energy level) ^ time. When the step 114 is yes, in step 116, the control unit switches the second valve 15 to the side of the side (the side where the main line pipe 1 is turned off). Thereby, the supply of the reactive component solution to the main flow path W is terminated. Next, in step 118, the control unit 12 determines whether or not the supply of the product line to the main line f1〇 is reached, that is, whether the first door is cut to the side B (the main line is not the same as the main line). When the step is 118, when the boat is yes, the control unit is in the process of step β〇, and the control unit is controlled to be on the side of the valve (the main pipe 1 is in a non-on state). The side is switched, thereby terminating the supply of the sample liquid to the main flow tube 1 . The control unit 112 looks at the first, ρ, 丨宕w, and step 122, and has the interface area of the early detection target (the carrier liquid The time to reach the flow-through detection tank 17, β. mouth liquid) the light intensity X; in step: 124 take ^^^^ bei in step 124, the control unit 112 see = image interface field (sample liquid + The tearing liquid of the reactive component solution;: the time when the liquid is reached by the light-receiving unit, and the information about the light intensity γ is obtained by the light-receiving unit. The acquisition time of these information can be considered, for example, switching. The time and flow rate of the valve are determined, etc. Then at step 126, the control unit 将2 will be obtained at (iv) 122 & step 94 The information is stored in the data storage unit 23. When there are 110 in step 1, step 6, step 11, step 114, and step ΐ8, the process must be cycled until yes appears. Figure 7 is the density determination process of the best mode. First, in step 202, the data processing unit 22 refers to the standard line data of the first component stored in the data storage unit 23, and determines the first component based on the value of the light intensity X measured in step 122 of FIG. The theoretical maximum concentration. Next, in step 204, the data processing unit 22 refers to the standard line data of the first component stored in the data memory unit, and determines the value of the light intensity γ measured in step 124 of FIG. The second component is the second component. The data processing unit 22 determines the light intensity of the first component contribution and the light intensity of the second component contribution by referring to the standard line number f of the first component: then, in step 2G8, the data is The processing unit 22 refers to the standard line data of the first component of the data storage unit 23, and determines the concentration of the second component based on the light intensity contributed by the second component determined in the step. Eight f 6 and seventh Figure Regarding the first component in the sample solution and the second forming tool: f determines the treatment, but when the standard line is made to be the same as the standard line of the first component, the plural number of constituents is used. - the component solution is substituted for the sample solution, and the second component is to be prepared. The second component is dissolved in a known concentration. The reactant according to the first component and the reactive component (different refractive index becomes) is used. When the standard line of the first component is produced, the first component and the second component of the known composition having a concentration of 320122 23 200912278 degrees are used (the concentration of the second component may be a constant concentration or a different concentration). The mixture replaces the sample solution. [Examples] "Embodiment" (one component system)" Blue guideline 劁祚 1) Modulation 0, 〇.〇5, 〇1, 〇q, Zenggan coffee production, _ · · 0.5 mole wave Aqueous ammonia solution is used as a standard solution for the preparation of the first standard line, and hydrogen peroxide of G.G5, 0.1, 0.3, and 0.5 molar concentration is prepared as the standard solution of the second standard line. 2) Using pure water as a test, the liquid of 1) is introduced into the thief at a speed of llGG/zl/min, and the signal intensity of the generated interface field is measured. 2) The standard line is prepared from the strength of the nickname and the concentration of each standard solution (the first to the standard of the ammonia solution (four) - the figure 9 and the second standard line of the hydrogen peroxide '^10] . The measurement of the degree 1) =, the second is the ammonia solution prepared by the sample liquid under the sample concentration 1) and the aqueous hydrogen peroxide solution (the signal intensity of the test product, according to the steps made in the step - The standard line and the second standard line are used to calculate the respective concentrations. The results are shown in Table 2. [Table 2] Table 2 fit fJr' 〇Γ One-to-one modulation molar concentration 0J50 -------- : PK1 The signal concentration is 0.00150. The molar concentration is 0.144 ~ 0.200 0.00560 0.202 - "Example 2 (multi-component system)" 320122 24 200912278 Standard liquid adjustment plate 1) Modulation 0, 0.05, 0.1, 0.3, 〇 5 朴曲 ^ Make the standard of the first standard line 7 * Aurora aqueous solution of argon, Zuo night 'and modulate 〇〇 5, 0.5 molar concentration of hydrogen peroxide # · 05 0·1, 0.3, 1 as the second standard 飧2) According to the combination shown in Table 3, turn the standard line; show the standard liquid 1 to make the standard liquid of the third standard line. 'Wind mixed solution 【Table 3】 Table Ingredients Standard solution 1 Ammonia 0.080 Hydrogen peroxide 0.416 Sample solution
焉準ST7 0.201 0.416 樣品液，是-般所使用的氨水、過所 的洗淨液，係以含有氨0.16莫耳濃产 飞及」，屯水所」 耳濃度的調配做為對象。、 &氧化氫0.42 ; 金盧反應性成分水溶液夕 調製含有0.2莫耳濃度之醋酸做為會與樣 反應之含有反應性成分水溶液。 4 第一標準線輿第二標準綠夕_作 以純水做為乘载液，將1}之標準液以 _ 道入於a、日，丨抑、， 遂1100/i 1/mi: 導入於,敎在界面領域所產生的信號強度 使用該㈣強度與各標準液之濃度，製成闕於 二 準線及關於過氧化氫之第二標準線⑽於氨之 圖，關於過氧化氳水溶液之標準線—第1〇圖）。”’弟 320122 25 200912278 竿s標車線之製成 以純水做為乘載液，將2)之標準液以流速11 〇〇 // l/min 導入於檢測器，再將含有反應性成分水溶液以流速500 # Ι/min導入’使其與該標準液混合，與樣品液之流速做為 1100 // Ι/min而流動。然後使用該信號強度與各標準液之濃 度，製成氨與過氧化氫之混合液中之關於氨之第三標準線 (第11圖）。 樣品液中之成分濃度之決定 將樣品液導入於測定器，測定樣品液之第一界面領域 (pKl)及第二界面領域（ρΚ2)之信號強度。然後依據ρκ2之 L號強度，參知、弟二標準線而決定氨濃度。再依據ρκ 1之 信號強度，參照第一標準線及第二標準線，決定過氧化氫 之浪度.。其結果示於表4。 【表4】 表4焉 ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST ST , & hydrogen oxide 0.42; aqueous solution of the reaction component of Jinlu, prepared with acetic acid having a concentration of 0.2 mol as an aqueous solution containing a reactive component which reacts with the sample. 4 The first standard line, the second standard, the green day _ is made of pure water as the carrier liquid, and the standard solution of 1} is entered into a, day, depreciation, and 遂1100/i 1/mi: The signal intensity generated by the 敎 in the interface field is determined by using the intensity of the (iv) and the concentration of each standard solution to form a second standard line (10) on the second line of hydrogen peroxide, and an aqueous solution of cerium peroxide. The standard line - the first picture). "'Dai 320122 25 200912278 竿s standard car line made of pure water as the carrier liquid, 2) standard solution is introduced into the detector at a flow rate of 11 〇〇 / / l / min, and then contains the reactive component aqueous solution Introduce 'at a flow rate of 500 #Ι/min to mix it with the standard solution, and flow the flow rate of the sample solution to 1100 // Ι/min. Then use the signal intensity and the concentration of each standard solution to make ammonia and The third standard line for ammonia in the mixture of hydrogen peroxide (Fig. 11). Determination of the concentration of the components in the sample solution. The sample solution is introduced into the measuring device, and the first interface area (pKl) and the second of the sample liquid are measured. The signal intensity of the interface field (ρΚ2). Then, according to the intensity of L of ρκ2, the ammonia concentration is determined by the reference and the second standard line. Based on the signal strength of ρκ 1, the first standard line and the second standard line are determined. The degree of oxidation of hydrogen peroxide. The results are shown in Table 4. [Table 4] Table 4
[發明之效果] e本發明之構成並非以往之濃度測定法之物質的吸收， :: 依物質之折射率差而做濃度測定，所以⑴如在吸收特 J似的複數個物質存在時而要做一物質之濃度決定的， 迴歸分析有固難的濃度決^，也可以容易實行，⑺ 射率有稍微之差就可以檢測，所以湘物質吸收之濃度 320122 26 200912278 測定法即有困難，濃度低於ι%的分析對象液，也可以以 :感度做分析(例如在0.1%位數也可以)，達到如此的效 的业此外如依本發明就不必建立液中的濃度分佈之微細 、、兄也可以做分析對象成分之目標參數值之測定，且 I必使用像疎水性多孔質管狀物之特殊構件，而達到簡翠 系統構成之效果。 [產業上之可利用性] 性的2 =使/做為—般性的參數測統（例如—般 的展度计），並且亦可使用在各種領域 領域）做為參數測定系統。 千绎骽衣以 【圖式簡單說明】 第1圖為表示本發明之原理圖。 第2圖為表示在乘載液間導 與乘載液間挟有第三標準液之狀態圖弟。乘載液 第3圖為表示乘載液間導入樣品液時 液間挾有樣品液之狀態圖。 戰U栽[Effects of the Invention] e The composition of the present invention is not the absorption of a substance in the conventional concentration measurement method. :: The concentration is measured depending on the difference in refractive index of the substance. Therefore, (1) when a plurality of substances which absorb the specific J are present, If the concentration of a substance is determined, the concentration analysis of the regression analysis can be easily implemented. (7) The fluorescence rate can be detected with a slight difference. Therefore, the concentration of the absorption of the substance is 320122 26 200912278. The analysis target liquid of less than 1% can also be analyzed by sensitivity (for example, 0.1% digits), and it is not necessary to establish a fine concentration distribution in the liquid according to the present invention. The brother can also measure the target parameter value of the analysis target component, and I must use the special component like the hydrophobic porous tubular material to achieve the effect of the Jiancui system. [Industrial Applicability] Sexuality 2 = Make/as a general parameter measurement (for example, a general spread meter), and can also be used in various fields as a parameter measurement system. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the present invention. Fig. 2 is a diagram showing the state in which a third standard liquid is interposed between the carrier liquid and the carrier liquid. The carrier liquid Fig. 3 is a view showing the state of the sample liquid between the liquids when the sample liquid is introduced between the carrier liquids. Battle U
第4圖⑴至（3)為表示在第一成分與第二成分人 液中二第二成分之濃度決定手法之說明圖。 & D ^圖為本最佳狀態之濃度測定系統之全體構成圖。 弟6圖為表示本最佳形態之測定系(流穿 源及受光部）之位置關係圖。 先 J 7圖為本最佳形態之光強度測定處理之流程圖。 弟8圖為本最佳形態之濃度測定處理之流程圖。 第9圖為實施例！及實施例2之第一標準線（氨）。 320122 27 200912278Fig. 4 (1) to (3) are explanatory diagrams showing the method of determining the concentration of the second component in the first component and the second component human solution. The <D^ diagram is a general composition diagram of the concentration measurement system in an optimum state. Fig. 6 is a view showing the positional relationship between the measurement system (flow through source and light receiving portion) of the present preferred embodiment. First, the J 7 diagram is a flow chart of the light intensity measurement process of the best form. Figure 8 is a flow chart of the concentration measurement process of the best mode. Figure 9 is an example! And the first standard line (ammonia) of Example 2. 320122 27 200912278
10圖為實施例1及實施例2之第 二標準線（過氧化 第11圖為實施例2之第三標準線（氨）。 【主要元件符號說明】 10 主流路管 11 第一幫浦 12 樣品支撐管 13 第~切換閥 14 反應性成分溶液流路管 15 第二切換閥 16 第二幫浦 17 流穿式檢測槽 18 光源 19 受光部（受光元件） 21 控制部 22 數據處理部 23 數據記憶部 30 增幅器 31 A/D轉換器 a 乘載液 β 樣品液 A 界面領域 C 乘載液儲存部 Ci 濃度值 U 第一成分貢獻之光強度 l2 第二成分貢獻 之光強度 Lm 光強度 L lmax 理論最大濃度 s 測定部 P 控制·數據處理部 R 反應性成分館存部 X、Y 光強度 28 320122Figure 10 is a second standard line of Example 1 and Example 2 (peroxidation Figure 11 is the third standard line (ammonia) of Example 2. [Main component symbol description] 10 Main flow pipe 11 First pump 12 Sample support tube 13 to switching valve 14 Reactive component solution flow tube 15 Second switching valve 16 Second pump 17 Flow-through detecting tank 18 Light source 19 Light receiving unit (light receiving element) 21 Control unit 22 Data processing unit 23 Data Memory unit 30 Amplifier 31 A/D converter a Multi-carrier liquid β Sample liquid A Interface field C Multi-carrier liquid storage unit Ci Concentration value U Light intensity contributed by the first component l2 Light intensity of the second component contribution Lm Light intensity L Lmax theoretical maximum concentration s measuring unit P control data processing unit R reactive component library X, Y light intensity 28 320122