JP2013122483A

JP2013122483A - Component concentration monitoring method and component concentration monitoring device using the same

Info

Publication number: JP2013122483A
Application number: JP2011270013A
Authority: JP
Inventors: Keisuke Kano; 佳祐加納; Nobuaki Saito; 暢朗斎藤; Masashi Inoue; 将司井上; Wataru Nikaido; 亙二階堂
Original assignee: Tokai Senko KK
Current assignee: Tokai Senko KK
Priority date: 2011-12-09
Filing date: 2011-12-09
Publication date: 2013-06-20
Anticipated expiration: 2031-12-09
Also published as: JP5894424B2

Abstract

PROBLEM TO BE SOLVED: To provide a component concentration monitoring method capable of continuously and constantly obtaining a change in component concentrations of a process liquid for use in an immobilization proces without producing an extra cost for titration reagent and disposal of a titration waste liquid, and quickly dealing with a concentration change of the process liquid in operation, and to provide a component concentration monitoring device using the method.SOLUTION: A conductivity and a refractive index under a series of temperature conditions are measured to define each correlationship using a plurality of aqueous solutions formed by combining known concentrations of boric acid and potassium iodide. A practical temperature T, a practical conductivity σ, and a practical refractive index n of the process liquid subject to the monitor are measured. A concentration X of the boric acid and a concentration Y of the potassium iodide of the process liquid subject to the monitor are obtained from the values using the correlationship and predetermined expressions (1) and (2).

Description

本発明は、偏光子の製造段階において固定化工程で使用される処理液の成分濃度、具体的には、ホウ酸及びヨウ化カリウムを成分として含有する処理液の成分濃度をモニタするための成分濃度モニタ方法及びこの方法を使用する成分濃度モニタ装置に関するものである。 The present invention relates to a component for monitoring the component concentration of a treatment liquid used in an immobilization process in the production stage of a polarizer, specifically, the component concentration of a treatment liquid containing boric acid and potassium iodide as components. The present invention relates to a concentration monitoring method and a component concentration monitoring apparatus using this method.

画像表示装置、例えば、液晶ディスプレイ（ＬＣＤ）に用いられる偏光子としては、一般に、ヨウ素染色されたポリビニルアルコール系フィルムが用いられる。これらの偏光子の製造は、一般に、ポリビニルアルコール系フィルムを延伸製膜後、膨潤工程、染色工程、固定化工程、水洗工程及び乾燥工程を経て行われる。 As a polarizer used for an image display device, for example, a liquid crystal display (LCD), a polyvinyl alcohol film dyed with iodine is generally used. In general, these polarizers are produced by stretching a polyvinyl alcohol film, followed by a swelling process, a dyeing process, an immobilizing process, a washing process, and a drying process.

上記各工程の中で、染色工程は、ヨウ素及びヨウ化カリウムを含有した水溶液を用いてポリビニルアルコール系フィルムをヨウ素で染色する。また、続く固定化工程は、ヨウ素で染色されたポリビニルアルコール系フィルムをホウ酸水溶液に浸漬してポリビニルアルコール分子間を架橋する。 Among the above steps, the dyeing step dyes the polyvinyl alcohol film with iodine using an aqueous solution containing iodine and potassium iodide. In the subsequent immobilization step, the polyvinyl alcohol film dyed with iodine is immersed in an aqueous boric acid solution to crosslink between the polyvinyl alcohol molecules.

しかし、この固定化工程において、単にホウ酸水溶液中でポリビニルアルコール分子間を架橋するだけでは、コントラスト斑が少なく、且つ、高コントラストの偏光子を得ることができない。 However, in this immobilization process, merely cross-linking polyvinyl alcohol molecules in an aqueous boric acid solution has few contrast spots and a high-contrast polarizer cannot be obtained.

そこで、下記特許文献１及び下記特許文献２においては、ヨウ素で染色されたポリビニルアルコール系フィルムをホウ酸水溶液に浸漬しながらフィルムを縦方向に更に延伸することが提案されている。 Therefore, in the following Patent Document 1 and Patent Document 2, it has been proposed to further stretch the film in the longitudinal direction while immersing the polyvinyl alcohol film dyed with iodine in an aqueous boric acid solution.

この延伸操作においては、固定化工程の処理液であるホウ酸水溶液に少量のヨウ化カリウムを共存させることが好ましく、下記特許文献１及び下記特許文献２の各実施例においては、処理浴中のホウ酸濃度に対して一定の割合でヨウ化カリウムが混合されている。 In this stretching operation, it is preferable that a small amount of potassium iodide is allowed to coexist in the boric acid aqueous solution that is the treatment liquid in the immobilization step. In each of the following Patent Document 1 and Patent Document 2, the treatment bath contains Potassium iodide is mixed at a constant ratio with respect to the boric acid concentration.

特開平１０−２８８７０９号公報
特開平１１−０４９８７８号公報 JP-A-10-288709
Japanese Patent Application Laid-Open No. 11-049878

ところで、上記偏光子製造の各工程は、工業的には連続して行われ、延伸操作を伴う固定化工程には、染色工程を経て染色液を含浸したポリビニルアルコール系フィルムが連続して導入される。一方、固定化工程からは、ホウ酸で架橋され、且つ、固定化工程の処理液が付着したポリビニルアルコール系フィルムが連続して導出される。 By the way, each process of the said polarizer manufacture is performed continuously industrially, and the polyvinyl-alcohol-type film which impregnated the dyeing liquid through the dyeing | staining process is continuously introduce | transduced into the fixing process accompanied by extending | stretching operation. The On the other hand, from the immobilization step, a polyvinyl alcohol-based film that is cross-linked with boric acid and to which the treatment liquid in the immobilization step is attached is continuously derived.

従って、固定化工程の処理液の成分濃度は、経時的に変化することとなり、処理液中のホウ酸及びヨウ化カリウムの濃度と比率が一定にならない。このことにより、ホウ酸水溶液によるポリビニルアルコール分子間の架橋が均一にならず、得られた偏光子の品質を不安定にして歩留りを低下させる。 Therefore, the component concentration of the treatment liquid in the immobilization process changes with time, and the concentration and ratio of boric acid and potassium iodide in the treatment liquid are not constant. As a result, the cross-linking between the polyvinyl alcohol molecules by the boric acid aqueous solution is not uniform, resulting in unstable quality of the obtained polarizer and a decrease in yield.

従来は、処理液の成分濃度の変化を操業中に行う間欠的な手分析により把握していた。しかし、このような間欠的な測定では、連続工程において常時変化する成分濃度に十分に対応することができないという問題を有していた。また、これらの手分析は、主に滴定法などで行われており、滴定試薬が必要となるだけでなく、その滴定廃液の処理も必要となる。よって、従来の手分析では、ランニングコストが高くなるという問題も有していた。 Conventionally, changes in the component concentration of the treatment liquid have been grasped by intermittent manual analysis performed during operation. However, such intermittent measurement has a problem that it cannot sufficiently cope with a component concentration that constantly changes in a continuous process. Moreover, these manual analyzes are mainly performed by a titration method or the like, and not only a titration reagent is required but also a treatment of the titration waste liquid is required. Therefore, the conventional manual analysis has a problem that the running cost becomes high.

そこで、本発明は、上記の諸問題に対処して、滴定試薬や滴定廃液の処分などに余分なコストをかけることなく、固定化工程で使用される処理液の成分濃度の変化を連続して常時把握できるようにして、操業中の処理液の濃度変化に素早く対応できる成分濃度モニタ方法及びこの方法を使用する成分濃度モニタ装置を提供することを目的とする。 Therefore, the present invention addresses the above-mentioned problems and continuously changes the component concentration of the treatment liquid used in the immobilization process without incurring extra costs for disposal of the titration reagent and the titration waste liquid. It is an object of the present invention to provide a component concentration monitoring method capable of always grasping and quickly responding to a change in the concentration of a processing liquid during operation, and a component concentration monitoring apparatus using this method.

上記課題の解決にあたり、本発明者らは、処理液の各成分濃度を求めるにあたり、滴定試薬や滴定廃液の処分などを必要とせず、連続して各成分濃度を測定できる導電率或いは屈折率を採用することを検討した。しかし、導電率或いは屈折率の測定値は、互いの成分濃度及び濃度比率に影響を受け、単に処理液の導電率或いは屈折率を求めるだけでは、正確な各成分濃度が得られないことが判明した。 In solving the above problems, the present inventors do not require disposal of titration reagents or titration waste liquids, etc. in determining the concentration of each component of the treatment liquid, and have an electrical conductivity or refractive index that allows continuous measurement of each component concentration. Considered adoption. However, the measured values of conductivity or refractive index are affected by each other's component concentration and concentration ratio, and it has been found that simply determining the conductivity or refractive index of the treatment liquid does not give accurate component concentrations. did.

そこで、本発明者らは、鋭意研究の結果、固定化工程の処理液の温度、導電率及び屈折率に関するデータベースを作成しておき、測定対象である処理液の温度、導電率及び屈折率を組み合わせることにより、ホウ酸濃度及びヨウ化カリウム濃度をそれぞれ独立して測定できることを実験的に見出した。 Therefore, as a result of intensive studies, the inventors have created a database on the temperature, conductivity, and refractive index of the treatment liquid in the immobilization process, and determined the temperature, conductivity, and refractive index of the treatment liquid to be measured. It was experimentally found that the boric acid concentration and potassium iodide concentration can be measured independently by combining them.

すなわち、本発明に係る処理液の成分濃度モニタ方法は、請求項１の記載によると、ホウ酸及びヨウ化カリウムを成分として含有する処理液の成分濃度モニタ方法において、
一連の既知濃度のホウ酸と一連の既知濃度のヨウ化カリウムとの組合せからなる複数の水溶液を用いて、当該複数の水溶液に対して、それぞれ、一連の温度条件における導電率を測定して各水溶液の温度と導電率との相関関係１を定めると共に、前記複数の水溶液に対して、それぞれ、前記一連の温度条件における屈折率を測定して各水溶液の温度と屈折率との相関関係２を定める第１ステップと、
モニタ対象となる処理液のホウ酸濃度及びヨウ化カリウム濃度を求めるにあたり、当該処理液の実測温度Ｔ、実測導電率σ及び実測屈折率ｎを測定する第２ステップと、
前記複数の水溶液に対して、それぞれ、前記相関関係１を用いて、前記実測温度Ｔにおける各水溶液の導電率を求めると共に、前記複数の水溶液に対して、それぞれ、前記相関関係２を用いて、前記実測温度Ｔにおける各水溶液の屈折率を求める第３ステップと、
この第３ステップで求めた各水溶液の導電率及び屈折率、並びに、各水溶液のホウ酸濃度及びヨウ化カリウム濃度を用いて、前記実測温度Ｔにおける各ホウ酸濃度に対する導電率と屈折率との相関関係３を定めると共に、前記実測温度Ｔにおける各ホウ酸濃度に対する導電率とヨウ化カリウム濃度との相関関係４を定める第４ステップと、
各ホウ酸濃度に対する前記相関関係３の中から前記実測導電率σ及び前記実測屈折率ｎに共通の近似値を有する２つの相関関係３−１（ホウ酸濃度Ｘ１における相関関係）及び相関関係３−２（ホウ酸濃度Ｘ２における相関関係）を選択し、これらの相関関係から、それぞれ、前記実測導電率σに対する屈折率ｎ１及び屈折率ｎ２を求める第５ステップと、
各ホウ酸濃度に対する前記相関関係４の中から前記ホウ酸濃度Ｘ１と前記ホウ酸濃度Ｘ２に対する２つの相関関係４−１（ホウ酸濃度Ｘ１における相関関係）及び相関関係４−２（ホウ酸濃度Ｘ２における相関関係）を選択し、これらの相関関係から、それぞれ、前記実測導電率σに対するヨウ化カリウム濃度Ｙ１及びヨウ化カリウム濃度Ｙ２を求める第６ステップと、
前記ホウ酸濃度Ｘ１、ホウ酸濃度Ｘ２、ヨウ化カリウム濃度Ｙ１、ヨウ化カリウム濃度Ｙ２、屈折率ｎ１、屈折率ｎ２及び実測屈折率ｎを用いて、下記の式（１）及び式（２）から、
Ｘ＝Ｘ１＋（Ｘ２−Ｘ１）×（ｎ−ｎ１）／（ｎ２−ｎ１）‥‥‥（１）
Ｙ＝Ｙ１＋（Ｙ２−Ｙ１）×（ｎ−ｎ１）／（ｎ２−ｎ１）‥‥‥（２）
前記モニタ対象となる処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを求める第７ステップとを有することを特徴とする。 That is, the component concentration monitoring method for a treatment liquid according to the present invention is the component concentration monitoring method for a treatment solution containing boric acid and potassium iodide as components, according to claim 1,
Using a plurality of aqueous solutions composed of a combination of a series of known concentrations of boric acid and a series of known concentrations of potassium iodide, each of the plurality of aqueous solutions was measured for conductivity under a series of temperature conditions, respectively. The correlation 1 between the temperature of the aqueous solution and the conductivity is determined, and the refractive index under the series of temperature conditions is measured for each of the plurality of aqueous solutions, and the correlation 2 between the temperature and the refractive index of each aqueous solution is obtained. A first step to define;
A second step of measuring the measured temperature T, measured conductivity σ, and measured refractive index n of the treatment liquid in determining the boric acid concentration and potassium iodide concentration of the treatment liquid to be monitored;
For each of the plurality of aqueous solutions, the correlation 1 is used to determine the conductivity of each aqueous solution at the measured temperature T, and for each of the plurality of aqueous solutions, the correlation 2 is used. A third step for obtaining a refractive index of each aqueous solution at the measured temperature T;
Using the conductivity and refractive index of each aqueous solution obtained in this third step, and the boric acid concentration and potassium iodide concentration of each aqueous solution, the conductivity and refractive index for each boric acid concentration at the measured temperature T A fourth step of determining a correlation 3 and determining a correlation 4 between the conductivity and the potassium iodide concentration for each boric acid concentration at the measured temperature T;
Among the correlations 3 for each boric acid concentration, two correlations 3-1 (correlation at boric acid concentration X1) and correlation 3 having approximate values common to the measured conductivity σ and the measured refractive index n -2 (correlation in boric acid concentration X2), and from these correlations, respectively, a fifth step for obtaining a refractive index n1 and a refractive index n2 with respect to the measured conductivity σ,
Two correlations 4-1 (correlation in boric acid concentration X1) and correlation 4-2 (boric acid concentration) with respect to boric acid concentration X1 and boric acid concentration X2 among correlations 4 with respect to each boric acid concentration (Correlation in X2) is selected, and from these correlations, a sixth step for determining potassium iodide concentration Y1 and potassium iodide concentration Y2 with respect to the measured conductivity σ, respectively,
Using the boric acid concentration X1, boric acid concentration X2, potassium iodide concentration Y1, potassium iodide concentration Y2, refractive index n1, refractive index n2, and measured refractive index n, the following equations (1) and (2) From
X = X1 + (X2-X1) * (n-n1) / (n2-n1) (1)
Y = Y1 + (Y2−Y1) × (n−n1) / (n2−n1) (2)
And a seventh step of obtaining a boric acid concentration X and a potassium iodide concentration Y of the treatment liquid to be monitored.

また、本発明に係る処理液の成分濃度モニタ方法は、請求項２の記載によると、ホウ酸及びヨウ化カリウムを成分として含有する処理液の成分濃度モニタ方法において、
一連の既知濃度のホウ酸と一連の既知濃度のヨウ化カリウムとの組合せからなる複数の水溶液を用いて、当該複数の水溶液に対して、それぞれ、一連の温度条件における導電率を測定して各水溶液の温度と導電率との相関関係１を定めると共に、前記複数の水溶液に対して、それぞれ、前記一連の温度条件における屈折率を測定して各水溶液の温度と屈折率との相関関係２を定める第１ステップと、
モニタ対象となる処理液のホウ酸濃度及びヨウ化カリウム濃度を求めるにあたり、当該処理液の実測温度Ｔ、実測導電率σ及び実測屈折率ｎを測定する第２ステップと、
前記複数の水溶液に対して、それぞれ、前記相関関係１を用いて、前記実測温度Ｔにおける各水溶液の導電率を求めると共に、前記複数の水溶液に対して、それぞれ、前記相関関係２を用いて、前記実測温度Ｔにおける各水溶液の屈折率を求める第３ステップと、
この第３ステップで求めた各水溶液の導電率及び屈折率、並びに、各水溶液のホウ酸濃度及びヨウ化カリウム濃度を用いて、前記実測温度Ｔにおける各ヨウ化カリウム濃度に対する導電率と屈折率との相関関係５を定めると共に、前記実測温度Ｔにおける各ヨウ化カリウム濃度に対する導電率とホウ酸濃度との相関関係６を定める第４ステップと、
各ヨウ化カリウム濃度に対する前記相関関係５の中から前記実測導電率σ及び前記実測屈折率ｎに共通の近似値を有する２つの相関関係５−１（ヨウ化カリウム濃度Ｙ３における相関関係）及び相関関係５−２（ヨウ化カリウム濃度Ｙ４における相関関係）を選択し、これらの相関関係から、それぞれ、前記実測導電率σに対する屈折率ｎ３及び屈折率ｎ４を求める第５ステップと、
各ヨウ化カリウム濃度に対する前記相関関係６の中から前記ホウ酸濃度Ｘ３と前記ホウ酸濃度Ｘ４に対する２つの相関関係６−１（ヨウ化カリウム濃度Ｙ３における相関関係）及び相関関係６−２（ヨウ化カリウム濃度Ｙ４における相関関係）を選択し、これらの相関関係から、それぞれ、前記実測導電率σに対するホウ酸濃度Ｘ３及びホウ酸濃度Ｘ４を求める第６ステップと、
前記ホウ酸濃度Ｘ３、ホウ酸濃度Ｘ４、ヨウ化カリウム濃度Ｙ３、ヨウ化カリウム濃度Ｙ４、屈折率ｎ３、屈折率ｎ４及び実測屈折率ｎを用いて、下記の式（３）及び式（４）から、
Ｘ＝Ｘ３＋（Ｘ４−Ｘ３）×（ｎ−ｎ３）／（ｎ４−ｎ３）‥‥‥（３）
Ｙ＝Ｙ３＋（Ｙ４−Ｙ３）×（ｎ−ｎ３）／（ｎ４−ｎ３）‥‥‥（４）
前記モニタ対象となる処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを求める第７ステップとを有することを特徴とする。 The component concentration monitoring method for a treatment liquid according to the present invention is the component concentration monitoring method for a treatment solution containing boric acid and potassium iodide as components, according to claim 2,
Using a plurality of aqueous solutions composed of a combination of a series of known concentrations of boric acid and a series of known concentrations of potassium iodide, each of the plurality of aqueous solutions was measured for conductivity under a series of temperature conditions, respectively. The correlation 1 between the temperature of the aqueous solution and the conductivity is determined, and the refractive index under the series of temperature conditions is measured for each of the plurality of aqueous solutions, and the correlation 2 between the temperature and the refractive index of each aqueous solution is obtained. A first step to define;
A second step of measuring the measured temperature T, measured conductivity σ, and measured refractive index n of the treatment liquid in determining the boric acid concentration and potassium iodide concentration of the treatment liquid to be monitored;
For each of the plurality of aqueous solutions, the correlation 1 is used to determine the conductivity of each aqueous solution at the measured temperature T, and for each of the plurality of aqueous solutions, the correlation 2 is used. A third step for obtaining a refractive index of each aqueous solution at the measured temperature T;
Using the electrical conductivity and refractive index of each aqueous solution obtained in this third step, and the boric acid concentration and potassium iodide concentration of each aqueous solution, the electrical conductivity and refractive index for each potassium iodide concentration at the measured temperature T And a fourth step for determining a correlation 6 between conductivity and boric acid concentration for each potassium iodide concentration at the measured temperature T,
Two correlations 5-1 (correlation at the potassium iodide concentration Y3) and correlation having approximate values common to the measured conductivity σ and the measured refractive index n out of the correlation 5 with respect to each potassium iodide concentration Selecting a relationship 5-2 (correlation in the potassium iodide concentration Y4), and obtaining a refractive index n3 and a refractive index n4 with respect to the measured conductivity σ from these correlations, respectively,
Two correlations 6-1 (correlation in potassium iodide concentration Y3) and correlation 6-2 (iodine in correlation with boric acid concentration X3 and boric acid concentration X4) out of correlation 6 with respect to each potassium iodide concentration. (Correlation in potassium hydride concentration Y4) is selected, and from these correlations, a sixth step for obtaining boric acid concentration X3 and boric acid concentration X4 with respect to the measured conductivity σ, respectively,
Using the boric acid concentration X3, boric acid concentration X4, potassium iodide concentration Y3, potassium iodide concentration Y4, refractive index n3, refractive index n4, and measured refractive index n, the following equations (3) and (4) From
X = X3 + (X4-X3) * (n-n3) / (n4-n3) (3)
Y = Y3 + (Y4-Y3) * (n-n3) / (n4-n3) (4)
And a seventh step of obtaining a boric acid concentration X and a potassium iodide concentration Y of the treatment liquid to be monitored.

また、本発明に係る処理液の成分濃度モニタ方法は、請求項３の記載によると、ホウ酸及びヨウ化カリウムを成分として含有する処理液の成分濃度モニタ方法において、
一連の既知濃度のホウ酸と一連の既知濃度のヨウ化カリウムとの組合せからなる複数の水溶液を用いて、当該複数の水溶液に対して、それぞれ、一連の温度条件における導電率を測定して各水溶液の温度と導電率との相関関係１を定めると共に、前記複数の水溶液に対して、それぞれ、前記一連の温度条件における屈折率を測定して各水溶液の温度と屈折率との相関関係２を定める第１ステップと、
モニタ対象となる処理液のホウ酸濃度及びヨウ化カリウム濃度を求めるにあたり、当該処理液の実測温度Ｔ、実測導電率σ及び実測屈折率ｎを測定する第２ステップと、
前記複数の水溶液に対して、それぞれ、前記相関関係１を用いて、前記実測温度Ｔにおける各水溶液の導電率を求めると共に、前記複数の水溶液に対して、それぞれ、前記相関関係２を用いて、前記実測温度Ｔにおける各水溶液の屈折率を求める第３ステップと、
この第３ステップで求めた各水溶液の導電率及び屈折率、並びに、各水溶液のホウ酸濃度及びヨウ化カリウム濃度を用いて、前記実測温度Ｔにおける各ホウ酸濃度に対する導電率と屈折率との相関関係７を定めると共に、前記実測温度Ｔにおける各ホウ酸濃度に対するヨウ化カリウム濃度と屈折率との相関関係８を定める第４ステップと、
各ホウ酸濃度に対する前記相関関係７の中から前記実測導電率σ及び前記実測屈折率ｎに共通の近似値を有する２つの相関関係７−１（ホウ酸濃度Ｘ５における相関関係）及び相関関係７−２（ホウ酸濃度Ｘ６における相関関係）を選択し、これらの相関関係から、それぞれ、前記実測屈折率ｎに対する導電率σ５及び導電率σ６を求める第５ステップと、
各ホウ酸濃度に対する前記相関関係８の中から前記ホウ酸濃度Ｘ５と前記ホウ酸濃度Ｘ６に対する２つの相関関係８−１（ホウ酸濃度Ｘ５における相関関係）及び相関関係８−２（ホウ酸濃度Ｘ６における相関関係）を選択し、これらの相関関係から、それぞれ、前記実測屈折率ｎに対するヨウ化カリウム濃度Ｙ５及びヨウ化カリウム濃度Ｙ６を求める第６ステップと、
前記ホウ酸濃度Ｘ５、ホウ酸濃度Ｘ６、ヨウ化カリウム濃度Ｙ５、ヨウ化カリウム濃度Ｙ６、導電率σ５、導電率σ６及び実測導電率σを用いて、下記の式（５）及び式（６）から、
Ｘ＝Ｘ５＋（Ｘ６−Ｘ５）×（σ−σ５）／（σ６−σ５）‥‥‥（５）
Ｙ＝Ｙ５＋（Ｙ６−Ｙ５）×（σ−σ５）／（σ６−σ５）‥‥‥（６）
前記モニタ対象となる処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを求める第７ステップとを有することを特徴とする。 The component concentration monitoring method for a treatment liquid according to the present invention is the component concentration monitoring method for a treatment solution containing boric acid and potassium iodide as components according to claim 3,
Using a plurality of aqueous solutions composed of a combination of a series of known concentrations of boric acid and a series of known concentrations of potassium iodide, each of the plurality of aqueous solutions was measured for conductivity under a series of temperature conditions, respectively. The correlation 1 between the temperature of the aqueous solution and the conductivity is determined, and the refractive index under the series of temperature conditions is measured for each of the plurality of aqueous solutions, and the correlation 2 between the temperature and the refractive index of each aqueous solution is obtained. A first step to define;
A second step of measuring the measured temperature T, measured conductivity σ, and measured refractive index n of the treatment liquid in determining the boric acid concentration and potassium iodide concentration of the treatment liquid to be monitored;
For each of the plurality of aqueous solutions, the correlation 1 is used to determine the conductivity of each aqueous solution at the measured temperature T, and for each of the plurality of aqueous solutions, the correlation 2 is used. A third step for obtaining a refractive index of each aqueous solution at the measured temperature T;
Using the conductivity and refractive index of each aqueous solution obtained in this third step, and the boric acid concentration and potassium iodide concentration of each aqueous solution, the conductivity and refractive index for each boric acid concentration at the measured temperature T A fourth step of determining a correlation 7 and determining a correlation 8 between the potassium iodide concentration and the refractive index for each boric acid concentration at the measured temperature T;
Among the correlations 7 for each boric acid concentration, two correlations 7-1 (correlation at boric acid concentration X5) and correlation 7 having approximate values common to the measured conductivity σ and the measured refractive index n. -2 (correlation in boric acid concentration X6), and from these correlations, respectively, a fifth step for obtaining conductivity σ5 and conductivity σ6 with respect to the measured refractive index n;
Two correlations 8-1 (correlation in boric acid concentration X5) and correlation 8-2 (boric acid concentration) with respect to boric acid concentration X5 and boric acid concentration X6 out of correlation 8 with respect to each boric acid concentration (Correlation in X6) is selected, and from these correlations, a sixth step for obtaining a potassium iodide concentration Y5 and a potassium iodide concentration Y6 with respect to the measured refractive index n, respectively,
Using the boric acid concentration X5, boric acid concentration X6, potassium iodide concentration Y5, potassium iodide concentration Y6, conductivity σ5, conductivity σ6, and measured conductivity σ, the following equations (5) and (6) From
X = X5 + (X6-X5) × (σ−σ5) / (σ6-σ5) (5)
Y = Y5 + (Y6−Y5) × (σ−σ5) / (σ6−σ5) (6)
And a seventh step of obtaining a boric acid concentration X and a potassium iodide concentration Y of the treatment liquid to be monitored.

また、本発明に係る処理液の成分濃度モニタ方法は、請求項４の記載によると、ホウ酸及びヨウ化カリウムを成分として含有する処理液の成分濃度モニタ方法において、
一連の既知濃度のホウ酸と一連の既知濃度のヨウ化カリウムとの組合せからなる複数の水溶液を用いて、当該複数の水溶液に対して、それぞれ、一連の温度条件における導電率を測定して各水溶液の温度と導電率との相関関係１を定めると共に、前記複数の水溶液に対して、それぞれ、前記一連の温度条件における屈折率を測定して各水溶液の温度と屈折率との相関関係２を定める第１ステップと、
モニタ対象となる処理液のホウ酸濃度及びヨウ化カリウム濃度を求めるにあたり、当該処理液の実測温度Ｔ、実測導電率σ及び実測屈折率ｎを測定する第２ステップと、
前記複数の水溶液に対して、それぞれ、前記相関関係１を用いて、前記実測温度Ｔにおける各水溶液の導電率を求めると共に、前記複数の水溶液に対して、それぞれ、前記相関関係２を用いて、前記実測温度Ｔにおける各水溶液の屈折率を求める第３ステップと、
この第３ステップで求めた各水溶液の導電率及び屈折率、並びに、各水溶液のホウ酸濃度及びヨウ化カリウム濃度を用いて、前記実測温度Ｔにおける各ヨウ化カリウム濃度に対する導電率と屈折率との相関関係９を定めると共に、前記実測温度Ｔにおける各ヨウ化カリウム濃度に対するホウ酸濃度と屈折率との相関関係１０を定める第４ステップと、
各ヨウ化カリウム濃度に対する前記相関関係９の中から前記実測導電率σ及び前記実測屈折率ｎに共通の近似値を有する２つの相関関係９−１（ヨウ化カリウム濃度Ｙ７における相関関係）及び相関関係９−２（ヨウ化カリウム濃度Ｙ８における相関関係）を選択し、これらの相関関係から、それぞれ、前記実測屈折率ｎに対する導電率σ７及び導電率σ８を求める第５ステップと、
各ヨウ化カリウム濃度に対する前記相関関係１０の中から前記ヨウ化カリウム濃度Ｙ７と前記ヨウ化カリウム濃度Ｙ８に対する２つの相関関係１０−１（ヨウ化カリウム濃度Ｙ７における相関関係）及び相関関係１０−２（ヨウ化カリウム濃度Ｙ８における相関関係）を選択し、これらの相関関係から、それぞれ、前記実測屈折率ｎに対するホウ酸濃度Ｘ７及びホウ酸濃度Ｘ８を求める第６ステップと、
前記ホウ酸濃度Ｘ７、ホウ酸濃度Ｘ８、ヨウ化カリウム濃度Ｙ７、ヨウ化カリウム濃度Ｙ８、導電率σ７、導電率σ８及び実測導電率σを用いて、下記の式（７）及び式（８）から、
Ｘ＝Ｘ７＋（Ｘ８−Ｘ７）×（σ−σ７）／（σ８−σ７）‥‥‥（７）
Ｙ＝Ｙ７＋（Ｙ８−Ｙ７）×（σ−σ７）／（σ８−σ７）‥‥‥（８）
前記モニタ対象となる処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを求める第７ステップとを有することを特徴とする。 Moreover, according to the description of claim 4, the component concentration monitoring method for the treatment liquid according to the present invention is the component concentration monitoring method for the treatment solution containing boric acid and potassium iodide as components.
Using a plurality of aqueous solutions composed of a combination of a series of known concentrations of boric acid and a series of known concentrations of potassium iodide, each of the plurality of aqueous solutions was measured for conductivity under a series of temperature conditions, respectively. The correlation 1 between the temperature of the aqueous solution and the conductivity is determined, and the refractive index under the series of temperature conditions is measured for each of the plurality of aqueous solutions, and the correlation 2 between the temperature and the refractive index of each aqueous solution is obtained. A first step to define;
A second step of measuring the measured temperature T, measured conductivity σ, and measured refractive index n of the treatment liquid in determining the boric acid concentration and potassium iodide concentration of the treatment liquid to be monitored;
For each of the plurality of aqueous solutions, the correlation 1 is used to determine the conductivity of each aqueous solution at the measured temperature T, and for each of the plurality of aqueous solutions, the correlation 2 is used. A third step for obtaining a refractive index of each aqueous solution at the measured temperature T;
Using the electrical conductivity and refractive index of each aqueous solution obtained in this third step, and the boric acid concentration and potassium iodide concentration of each aqueous solution, the electrical conductivity and refractive index for each potassium iodide concentration at the measured temperature T And a fourth step of determining a correlation 10 between the boric acid concentration and the refractive index for each potassium iodide concentration at the measured temperature T,
Two correlations 9-1 (correlation at potassium iodide concentration Y7) and correlation having approximate values common to the measured conductivity σ and the measured refractive index n out of the correlation 9 with respect to each potassium iodide concentration Selecting the relationship 9-2 (correlation in the potassium iodide concentration Y8), and obtaining the conductivity σ7 and the conductivity σ8 with respect to the measured refractive index n from these correlations, respectively,
Among the correlations 10 for each potassium iodide concentration, two correlations 10-1 (correlation at the potassium iodide concentration Y7) and correlation 10-2 with respect to the potassium iodide concentration Y7 and the potassium iodide concentration Y8. (Correlation in potassium iodide concentration Y8) is selected, and from these correlations, a sixth step for obtaining boric acid concentration X7 and boric acid concentration X8 for the measured refractive index n, respectively,
Using the boric acid concentration X7, boric acid concentration X8, potassium iodide concentration Y7, potassium iodide concentration Y8, conductivity σ7, conductivity σ8, and measured conductivity σ, the following equations (7) and (8) From
X = X7 + (X8−X7) × (σ−σ7) / (σ8−σ7) (7)
Y = Y7 + (Y8−Y7) × (σ−σ7) / (σ8−σ7) (8)
And a seventh step of obtaining a boric acid concentration X and a potassium iodide concentration Y of the treatment liquid to be monitored.

また、本発明は、請求項５の記載によると、請求項１から４のいずれか１つに記載の処理液の成分濃度モニタ方法であって、前記第７ステップで算出した前記モニタ対象となる処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙについて、各対応の所定の管理値からずれΔＸ及びΔＹを算出する第８ステップを有することを特徴とする。 According to a fifth aspect of the present invention, there is provided the processing liquid component concentration monitoring method according to any one of the first to fourth aspects, which is the monitoring target calculated in the seventh step. For the boric acid concentration X and potassium iodide concentration Y of the treatment liquid, there is an eighth step of calculating deviations ΔX and ΔY from the corresponding predetermined management values.

また、本発明に係る処理液の成分濃度モニタ装置は、請求項６の記載によると、前記モニタ対象となる処理液の実測温度Ｔを検出する温度検出手段と、
前記処理液の実測導電率σを検出する導電率検出手段と、
前記処理液の実測屈折率ｎを検出する屈折率検出手段と、
前記実測温度Ｔ、前記実測導電率σ及び前記実測屈折率ｎを用いて前記処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを演算する濃度演算手段と、
前記ホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを表示する表示手段とを備え、
請求項１〜４のいずれか１つに記載の成分濃度モニタ方法を用いて算出した前記処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを前記表示手段にモニタすることを特徴とする。 The component concentration monitoring device for a processing liquid according to the present invention, according to claim 6, includes a temperature detection means for detecting the measured temperature T of the processing liquid to be monitored,
Conductivity detecting means for detecting the measured conductivity σ of the treatment liquid;
A refractive index detection means for detecting the measured refractive index n of the treatment liquid;
Concentration calculating means for calculating boric acid concentration X and potassium iodide concentration Y of the treatment liquid using the measured temperature T, the measured conductivity σ, and the measured refractive index n;
Display means for displaying the boric acid concentration X and the potassium iodide concentration Y;
A boric acid concentration X and a potassium iodide concentration Y of the treatment liquid calculated by using the component concentration monitoring method according to any one of claims 1 to 4 are monitored on the display means.

また、本発明に係る処理液の成分濃度モニタ装置は、請求項７の記載によると、前記モニタ対象となる処理液の実測温度Ｔを検出する温度検出手段と、
前記処理液の実測導電率σを検出する導電率検出手段と、
前記処理液の実測屈折率ｎを検出する屈折率検出手段と、
前記実測温度Ｔ、前記実測導電率σ及び前記実測屈折率ｎを用いて前記処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを演算する濃度演算手段と、
前記処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙについて各対応の所定の管理値からのずれΔＸ及びΔＹを演算するずれ演算手段と、
前記ホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを表示する表示手段とを備え、
請求項５に記載の成分濃度モニタ方法を用いて算出した前記処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙ、並びに、各対応の所定の管理値からのずれΔＸ及びΔＹを前記表示手段にモニタすることを特徴とする。 In addition, according to the seventh aspect of the present invention, the component concentration monitoring device for the processing liquid includes a temperature detection means for detecting the measured temperature T of the processing liquid to be monitored,
Conductivity detecting means for detecting the measured conductivity σ of the treatment liquid;
A refractive index detection means for detecting the measured refractive index n of the treatment liquid;
Concentration calculating means for calculating boric acid concentration X and potassium iodide concentration Y of the treatment liquid using the measured temperature T, the measured conductivity σ, and the measured refractive index n;
Deviation calculation means for calculating deviations ΔX and ΔY from the corresponding predetermined control values for the boric acid concentration X and potassium iodide concentration Y of the treatment liquid;
Display means for displaying the boric acid concentration X and the potassium iodide concentration Y;
The boric acid concentration X and potassium iodide concentration Y of the treatment liquid calculated by using the component concentration monitoring method according to claim 5, and deviations ΔX and ΔY from the corresponding predetermined management values are displayed on the display means. It is characterized by monitoring.

本発明に係る処理液の成分濃度モニタ方法によれば、これまで間欠的に滴定法で手分析されていた固定化工程で使用される処理液の成分濃度の変化を連続して常時把握することが可能になる。このことにより、操業中の処理液の濃度変化に素早く対応できる生産体制を確立することができる。 According to the component concentration monitoring method for a processing solution according to the present invention, it is possible to continuously grasp the change in the component concentration of the processing solution used in the immobilization process that has been intermittently manually analyzed by the titration method. Is possible. This makes it possible to establish a production system that can quickly respond to changes in the concentration of the processing liquid during operation.

すなわち、本発明によって、ポリビニルアルコール系フィルムの固定化工程において、経時的に変化する処理液のホウ酸濃度とヨウ化カリウム濃度を常に求め、各対応の所定の管理値からのずれを把握することにより、素早く当該所定の管理値に調整することができる。 That is, according to the present invention, the boric acid concentration and potassium iodide concentration of the treatment liquid that changes with time are always obtained in the fixing process of the polyvinyl alcohol film, and the deviation from the corresponding control value is grasped. Thus, the predetermined management value can be quickly adjusted.

従って、固定化工程で使用される処理液の成分濃度を常に安定した状態に管理することができ、ポリビニルアルコール系フィルムに架橋するホウ酸の量が常に安定して得られた偏光子の品質の安定と歩留りの向上が可能となる。 Therefore, the component concentration of the treatment liquid used in the immobilization process can be always managed in a stable state, and the amount of boric acid cross-linked to the polyvinyl alcohol film can always be stably obtained. Stability and yield can be improved.

更に、本発明において、固定化工程に使用される処理液のホウ酸濃度とヨウ化カリウム濃度を求める際、及び、各所定の管理値とのずれを算出する際には、いずれもコンピュータ等の演算手段を使用して高速に処理することで、処理液の成分濃度をリアルタイムでモニタすることが可能になる。 Furthermore, in the present invention, when calculating the boric acid concentration and potassium iodide concentration of the treatment liquid used in the immobilization step, and calculating the deviation from each predetermined control value, both By processing at high speed using the computing means, it becomes possible to monitor the component concentration of the processing liquid in real time.

よって、本発明は、滴定試薬や滴定廃液の処分などに余分なコストをかけることなく、固定化工程で使用される処理液の成分濃度の変化を連続して常時把握できるようにして、操業中の処理液の濃度変化に素早く対応できる成分濃度モニタ方法及びこの方法を使用する成分濃度モニタ装置を提供することができる。 Therefore, the present invention is capable of continuously grasping changes in the component concentration of the treatment liquid used in the immobilization process continuously without incurring extra costs for disposal of the titration reagent and the titration waste liquid. It is possible to provide a component concentration monitoring method capable of quickly responding to changes in the concentration of the treatment liquid and a component concentration monitoring apparatus using this method.

本発明に係る処理液の成分濃度モニタ装置の一実施形態を示す構成図である。It is a block diagram which shows one Embodiment of the component concentration monitoring apparatus of the process liquid which concerns on this invention. 本発明に係る処理液の成分濃度モニタ方法の実施例１を示す工程図である。It is process drawing which shows Example 1 of the component density | concentration monitoring method of the process liquid which concerns on this invention. 実施例１において各ホウ酸濃度に対する導電率と屈折率との相関関係３を示すグラフである。6 is a graph showing a correlation 3 between conductivity and refractive index with respect to each boric acid concentration in Example 1. 実施例１において各ホウ酸濃度に対する導電率とヨウ化カリウム濃度との相関関係４を示すグラフである。It is a graph which shows the correlation 4 of the electrical conductivity with respect to each boric acid density | concentration in Example 1, and potassium iodide density | concentration. 実施例１において相関関係３−１及び相関関係３−２を用いて処理液のホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを算出する方法の説明図である。In Example 1, it is explanatory drawing of the method of calculating the boric acid density | concentration X and the potassium iodide density | concentration Y of a process liquid using the correlation 3-1 and the correlation 3-2. 本発明に係る処理液の成分濃度モニタ方法の実施例２を示す工程図である。It is process drawing which shows Example 2 of the component density | concentration monitoring method of the process liquid which concerns on this invention. 本発明に係る処理液の成分濃度モニタ方法の実施例３を示す工程図である。It is process drawing which shows Example 3 of the component density | concentration monitoring method of the process liquid which concerns on this invention. 本発明に係る処理液の成分濃度モニタ方法の実施例４を示す工程図である。It is process drawing which shows Example 4 of the component density | concentration monitoring method of the process liquid which concerns on this invention.

本発明は、偏光子の連続的な製造において、ポリビニルアルコール系フィルムの固定化工程に用いられる処理液の成分濃度モニタ方法及びこの方法を使用する成分濃度モニタ装置に関するものである。以下、本発明に係る処理液の成分濃度モニタ装置の一実施形態を図面に基づいて説明する。 The present invention relates to a component concentration monitoring method for a treatment liquid used in a step of fixing a polyvinyl alcohol film in continuous production of a polarizer, and a component concentration monitoring device using this method. Hereinafter, an embodiment of a component concentration monitoring apparatus for a processing solution according to the present invention will be described with reference to the drawings.

図１は、ポリビニルアルコール系フィルムの固定化工程を行う処理装置１００を示している。当該処理装置１００は、固定化ユニット１０と、モニタユニット２０とにより構成されている。固定化ユニット１０は、処理槽１１と、２組のマングル１２、１３と、循環ポンプ１４とを備えている。 FIG. 1 shows a processing apparatus 100 that performs a process for fixing a polyvinyl alcohol film. The processing apparatus 100 includes an immobilization unit 10 and a monitor unit 20. The immobilization unit 10 includes a processing tank 11, two sets of mangles 12 and 13, and a circulation pump 14.

処理槽１１は、ポリビニルアルコール系フィルムＦを固定化処理するための処理液Ｌを貯えており、この処理液Ｌは、循環ポンプ１４の駆動により循環配管１５ａ及び１５ｂによって、それぞれ別経路で液循環を行っている。なお、処理槽１１の内部に設置された複数本のロール１６は、被処理物であるポリビニルアルコール系フィルムＦを導入するためのガイドロールである。 The treatment tank 11 stores a treatment liquid L for immobilizing the polyvinyl alcohol film F, and the treatment liquid L is circulated in separate paths by circulation pipes 15a and 15b by driving the circulation pump 14, respectively. It is carried out. In addition, the several roll 16 installed in the inside of the processing tank 11 is a guide roll for introducing the polyvinyl alcohol-type film F which is a to-be-processed object.

２組のマングル１２、１３のうちマングル１２は、２本のロール間にポリビニルアルコール系フィルムＦをニップして処理槽１１に導入する。一方、マングル１３は、２本のロール間にポリビニルアルコール系フィルムＦをニップして処理槽１１から導出する。ここで、マングル１２の送出速度を遅く、マングル１３の送出速度を早くしてその比率を制御する。このことにより、処理槽１１中のポリビニルアルコール系フィルムＦは、処理槽１１内の複数本のロール１６間を通過しながら所定の倍率に延伸されると共に架橋される。 Of the two sets of mangles 12, 13, the mangle 12 introduces a polyvinyl alcohol film F between two rolls and introduces it into the treatment tank 11. On the other hand, the mangle 13 nips the polyvinyl alcohol-based film F between two rolls and leads out from the processing tank 11. Here, the sending speed of the mangle 12 is slowed down, and the sending speed of the mangle 13 is fastened to control the ratio. Thus, the polyvinyl alcohol film F in the treatment tank 11 is stretched at a predetermined magnification while being passed between the plurality of rolls 16 in the treatment tank 11 and is crosslinked.

モニタユニット２０は、導電率センサ２１と、屈折率センサ２２と、マイクロコンピュータ２３と、モニタ２４とを備えている。なお、本実施形態においては、屈折率センサ２２の内部に温度センサ２２ａが内蔵されているが、これらを別個の装置としても差し支えない。導電率センサ２１及び温度センサ２２ａを内蔵した屈折率センサ２２は、循環配管１５ａから分岐して処理液Ｌを循環する検出配管２５に設置されている。 The monitor unit 20 includes a conductivity sensor 21, a refractive index sensor 22, a microcomputer 23, and a monitor 24. In the present embodiment, the temperature sensor 22a is built in the refractive index sensor 22, but these may be used as separate devices. The refractive index sensor 22 including the conductivity sensor 21 and the temperature sensor 22a is installed in a detection pipe 25 that branches from the circulation pipe 15a and circulates the processing liquid L.

導電率センサ２１は、処理液Ｌの導電率を検出しマイクロコンピュータ２３に出力する。なお、本実施形態では、導電率センサ３１として、株式会社堀場アドバンスドテクノ製導電率計ＨＥ−４８０Ｈが採用されている。 The conductivity sensor 21 detects the conductivity of the processing liquid L and outputs it to the microcomputer 23. In this embodiment, a conductivity meter HE-480H manufactured by Horiba Advanced Techno Co., Ltd. is employed as the conductivity sensor 31.

屈折率センサ２２は、処理液Ｌの屈折率を検出しマイクロコンピュータ２３に出力する。なお、本実施形態では、屈折率センサ２２として温度センサを内蔵したＳｃｈｍｉｄｔ＋ＨａｅｎｓｃｈＧｍｂＨ＆Ｃｏ．製屈折率計ｉＰＲ−ＦＲ２が採用されており、検出した屈折率と共に処理液温度を検出しマイクロコンピュータ２３に出力する。 The refractive index sensor 22 detects the refractive index of the processing liquid L and outputs it to the microcomputer 23. In the present embodiment, Schmidt + Haensch GmbH & Co., Which incorporates a temperature sensor as the refractive index sensor 22. A refractometer iPR-FR2 is employed, and the processing liquid temperature is detected together with the detected refractive index and output to the microcomputer 23.

また、検出配管２５には、導電率センサ２１、屈折率センサ２２及び検出配管２５の内部を洗浄するための洗浄水を供給する洗浄水導入口２５ａと洗浄水排出口２５ｂが設けられている。更に、検出配管２５には、導電率センサ２１及び屈折率センサ２２を校正するための校正液を供給する校正液導入口２５ｃと校正液排出口２５ｄが設けられ、各校正液は、校正用ポンプ２６で各センサに供給される。 Further, the detection pipe 25 is provided with a cleaning water introduction port 25a and a cleaning water discharge port 25b for supplying cleaning water for cleaning the inside of the conductivity sensor 21, the refractive index sensor 22 and the detection pipe 25. Further, the detection pipe 25 is provided with a calibration solution inlet 25c and a calibration solution discharge port 25d for supplying a calibration solution for calibrating the conductivity sensor 21 and the refractive index sensor 22, and each calibration solution is supplied with a calibration pump. 26 to each sensor.

マイクロコンピュータ２３は、後述の成分濃度モニタ方法の工程図（図２〜図８参照）に従い、コンピュータプログラムを実行する。当該コンピュータプログラムは、マイクロコンピュータ２３のＲＯＭに当該マイクロコンピュータにより読み出し可能に記憶されている。 The microcomputer 23 executes a computer program in accordance with process diagrams (see FIGS. 2 to 8) of a component concentration monitoring method described later. The computer program is stored in the ROM of the microcomputer 23 so as to be readable by the microcomputer.

モニタ２４は、マイクロコンピュータ２３により演算された所定のデータ（後述する）をモニタ画面に表示する。 The monitor 24 displays predetermined data (described later) calculated by the microcomputer 23 on the monitor screen.

このように構成した処理装置１００において、固定化ユニット１０では、長尺のポリビニルアルコール系フィルムＦが、前工程である染色工程を経て染色液を含浸した状態で、連続して処理槽１１に導入される。或いは、染色工程後に水洗工程を有する場合であっても、ポリビニルアルコール系フィルムＦが、水洗工程を経て含水した状態で、連続して処理槽１１に導入される。 In the processing apparatus 100 configured as described above, in the immobilization unit 10, the long polyvinyl alcohol film F is continuously introduced into the processing tank 11 in a state of being impregnated with the dyeing liquid through the dyeing process which is the previous process. Is done. Or even if it is a case where it has a water washing process after a dyeing process, the polyvinyl-alcohol-type film F is continuously introduce | transduced into the processing tank 11 in the state containing water through the water washing process.

ここで、処理槽１１中の処理液Ｌは、上述のように、ホウ酸及びヨウ化カリウムを成分として含有する水溶液であり、その成分濃度は、要求される固定化（架橋）の程度により適宜決定される。従って、特に限定するものではないが、一般に、処理液の重量に対して、ホウ酸濃度は１〜１０重量％程度、ヨウ化カリウム濃度は１〜１５重量％程度である。また、処理液の温度は、通常３０〜９０℃程度であり、浸漬時間は、通常１００〜１２００秒程度である。 Here, as described above, the treatment liquid L in the treatment tank 11 is an aqueous solution containing boric acid and potassium iodide as components, and the concentration of the components is appropriately determined depending on the required degree of immobilization (crosslinking). It is determined. Therefore, although not particularly limited, generally, the boric acid concentration is about 1 to 10% by weight and the potassium iodide concentration is about 1 to 15% by weight with respect to the weight of the treatment liquid. Moreover, the temperature of a process liquid is about 30-90 degreeC normally, and immersion time is about about 100-1200 second normally.

本実施形態においては、処理液Ｌの温度及び各成分濃度は、設定された処理温度Ｔｔ、設定されたホウ酸濃度の管理値Ｘｔ及び設定されたヨウ化カリウム濃度の管理値Ｙｔに各々正確に管理されなければならない。 In the present embodiment, the temperature of the processing liquid L and the concentration of each component are the set processing temperature Tt, the set boric acid concentration management value Xt, and the set potassium iodide concentration management value Yt. Each must be managed accurately.

しかし、上述のように、処理液Ｌには、連続して染色液を含浸したポリビニルアルコール系フィルムＦが導入されるため、染色液中のヨウ化カリウムが混入する。或いは、染色工程後に水洗工程を行う場合であっても、含水したポリビニルアルコール系フィルムＦが導入されるため、処理液Ｌの成分濃度が低下する。また、染色工程と固定化工程との処理温度が異なる場合もあり、処理液Ｌの温度が変化しやすくなる。 However, as described above, since the polyvinyl alcohol film F continuously impregnated with the staining liquid is introduced into the treatment liquid L, potassium iodide in the staining liquid is mixed therein. Or even if it is a case where a water washing process is performed after a dyeing process, since the water-containing polyvinyl alcohol-type film F is introduce | transduced, the component density | concentration of the process liquid L falls. Moreover, the process temperature of a dyeing process and an immobilization process may differ, and the temperature of the process liquid L tends to change.

一方、処理液Ｌの成分であるホウ酸がポリビニルアルコール系フィルムＦに選択的に吸着され当該フィルムを架橋する。また、処理液Ｌの一部がポリビニルアルコール系フィルムＦに付着して次工程の水洗工程に向けて導出される。従って、処理液Ｌの成分濃度は経時的に変化しており、このことが処理液の成分濃度の管理を困難にしている。 On the other hand, boric acid which is a component of the treatment liquid L is selectively adsorbed on the polyvinyl alcohol film F to crosslink the film. Further, a part of the treatment liquid L adheres to the polyvinyl alcohol film F and is led out for the next water washing step. Therefore, the component concentration of the treatment liquid L changes with time, which makes it difficult to manage the component concentration of the treatment liquid.

本発明においては、処理液Ｌの導電率及び屈折率が、それぞれ、処理液Ｌ中のホウ酸濃度或いはヨウ化カリウム濃度によって変化することを利用して、処理液Ｌの各成分濃度をモニタするものである。しかし、上述のように、処理液Ｌの導電率及び屈折率は、いずれも、処理液Ｌの温度、並びに、ホウ酸及びヨウ化カリウムの濃度比率によって互いに影響を受ける。 In the present invention, the concentration of each component of the processing liquid L is monitored by utilizing the fact that the conductivity and refractive index of the processing liquid L change depending on the boric acid concentration or potassium iodide concentration in the processing liquid L, respectively. Is. However, as described above, the conductivity and refractive index of the processing liquid L are both affected by the temperature of the processing liquid L and the concentration ratio of boric acid and potassium iodide.

例えば、処理液Ｌのホウ酸濃度及びヨウ化カリウム濃度が一定であっても、処理液Ｌの温度が変化すると処理液Ｌの導電率及び屈折率は、いずれも変化する。また、一定の処理温度においても、ホウ酸濃度及びヨウ化カリウム濃度の比率が変化すると処理液Ｌの導電率及び屈折率は、いずれも変化する。 For example, even if the boric acid concentration and potassium iodide concentration of the treatment liquid L are constant, when the temperature of the treatment liquid L changes, both the conductivity and the refractive index of the treatment liquid L change. Even at a constant treatment temperature, the conductivity and refractive index of the treatment liquid L both change when the ratio of boric acid concentration and potassium iodide concentration changes.

そこで、本発明においては、ホウ酸及びヨウ化カリウムをそれぞれ既知濃度で含有した複数の水溶液に対して、温度を変化させた際の導電率及び屈折率を測定し、これらの測定データを基にしてモニタ対象である処理液Ｌに含まれるホウ酸及びヨウ化カリウムの濃度をそれぞれ正確にモニタするものである。 Therefore, in the present invention, for a plurality of aqueous solutions each containing boric acid and potassium iodide at known concentrations, the electrical conductivity and refractive index when the temperature is changed are measured, and based on these measurement data. Thus, the concentrations of boric acid and potassium iodide contained in the treatment liquid L to be monitored are each accurately monitored.

以下、本発明に係る処理液の成分濃度モニタ方法を各実施例において説明する。 Hereinafter, the component concentration monitoring method of the processing liquid according to the present invention will be described in each embodiment.

図２は、本実施例１に係る処理液の成分濃度モニタ方法を示す工程図である。図２の各工程に従って本実施例１を説明する。上述のように、この処理液Ｌのホウ酸濃度の管理値はＸｔであり、ヨウ化カリウム濃度の管理値はＹｔとする。また、処理液Ｌの温度の管理値はＴｔとして制御されている。 FIG. 2 is a process diagram illustrating the component concentration monitoring method for the processing liquid according to the first embodiment. The first embodiment will be described according to the steps in FIG. As described above, the management value of the boric acid concentration of the treatment liquid L is Xt, and the management value of the potassium iodide concentration is Yt. Further, the management value of the temperature of the processing liquid L is controlled as Tt.

ステップＳ１：
まず、処理液Ｌの温度、導電率及び屈折率に関するデータベースを作成する。具体的には、一連の既知濃度のホウ酸と一連の既知濃度のヨウ化カリウムとの組合せからなる複数の水溶液を準備する。例えば、ホウ酸濃度は、上述のように、通常使用される１〜１０重量％の全範囲として、１〜１０重量％の間で１重量％間隔の１０水準とする。一方、ヨウ化カリウム濃度は、上述のように、通常使用される１〜１５重量％の全範囲のうち、特に使用される３〜１２重量％の間で１重量％間隔の１０水準とする。このようにホウ酸濃度１０水準とヨウ化カリウム濃度１０水準との組み合わせからなる１００種類の水溶液を準備する。 Step S1:
First, a database relating to the temperature, conductivity, and refractive index of the processing liquid L is created. Specifically, a plurality of aqueous solutions comprising a combination of a series of known concentrations of boric acid and a series of known concentrations of potassium iodide are prepared. For example, as described above, the boric acid concentration is set to 10 levels at intervals of 1% by weight between 1 to 10% by weight as the entire range of 1 to 10% by weight that is normally used. On the other hand, as described above, the potassium iodide concentration is set to 10 levels at intervals of 1% by weight among the generally used 1 to 15% by weight of the entire range of 3 to 12% by weight. Thus, 100 types of aqueous solution which consists of a combination of 10 levels of boric acid concentration and 10 levels of potassium iodide are prepared.

次に、これら１００種類の水溶液に対して、それぞれ、温度を３０〜９０℃の間で５℃間隔の１３水準に変化させて、各水溶液の導電率及び屈折率を正確に測定する。導電率の測定には、通常の液体試料の測定方法を使用すればよく、一般に、導電率計を使用する。例えば、上記実施形態の導電率センサ２１に使用した株式会社堀場アドバンスドテクノ製導電率計ＨＥ−４８０Ｈを使用してもよい。但し、導電率の測定値には、処理液Ｌの温度の影響を考慮して適宜補正を行う。 Next, with respect to these 100 kinds of aqueous solutions, the temperature is changed to 13 levels at intervals of 5 ° C. between 30 to 90 ° C., and the conductivity and refractive index of each aqueous solution are accurately measured. For the measurement of conductivity, an ordinary liquid sample measurement method may be used, and generally a conductivity meter is used. For example, HORIBA Advanced Techno's conductivity meter HE-480H used for the conductivity sensor 21 of the above embodiment may be used. However, the measured conductivity value is appropriately corrected in consideration of the influence of the temperature of the processing liquid L.

一方、屈折率の測定には、通常の液体試料の測定方法を使用すればよく、一般に、屈折率計を使用する。例えば、上記実施形態の屈折率センサ２２に使用した温度センサを内蔵したＳｃｈｍｉｄｔ＋ＨａｅｎｓｃｈＧｍｂＨ＆Ｃｏ．製屈折率計ｉＰＲ−ＦＲ２を使用してもよい。但し、屈折率の測定値には、処理液Ｌの温度の影響を考慮して適宜補正を行う。 On the other hand, for the measurement of the refractive index, an ordinary method for measuring a liquid sample may be used, and a refractometer is generally used. For example, Schmidt + Haensch GmbH & Co., which incorporates the temperature sensor used in the refractive index sensor 22 of the above embodiment. A refractometer iPR-FR2 may be used. However, the measured value of the refractive index is appropriately corrected in consideration of the influence of the temperature of the processing liquid L.

このようにして測定したデータは、１００種類の水溶液に対する温度と導電率との相関関係１、及び、１００種類の水溶液に対する温度と屈折率との相関関係２として後述のステップＳ３において使用する。 The data measured in this way is used in step S3, which will be described later, as correlation 1 between temperature and conductivity for 100 types of aqueous solutions and correlation 2 between temperature and refractive index for 100 types of aqueous solutions.

ステップＳ２：
次に、モニタ対象となる処理液Ｌの実測温度Ｔ、実測導電率σ及び実測屈折率ｎをそれぞれ測定する。処理液Ｌの実測温度Ｔの測定には、どのような温度計を使用してもよいが、本実施例１においては、上述のように、屈折率センサ２２に内蔵した温度センサ２２ａを使用した。測定は、実測導電率σ及び実測屈折率ｎの測定と連動して固定化処理の進行に伴い、一定時間間隔、或いは連続して行う。 Step S2:
Next, the measured temperature T, measured conductivity σ, and measured refractive index n of the treatment liquid L to be monitored are measured. Any thermometer may be used to measure the measured temperature T of the treatment liquid L, but in the first embodiment, as described above, the temperature sensor 22a built in the refractive index sensor 22 is used. . The measurement is performed at regular time intervals or continuously as the immobilization process proceeds in conjunction with the measurement of the measured conductivity σ and the measured refractive index n.

処理液Ｌの実測導電率σ及び実測屈折率ｎの測定は、本実施例１においては、上述の導電率センサ２１及び屈折率センサ２２を使用する。また、実測導電率σ及び実測屈折率ｎの測定値は、処理液Ｌの温度の影響を考慮して適宜補正する。測定は、実測温度Ｔの測定と連動して固定化処理の進行に伴い、一定時間間隔、或いは連続して行う。 In the first embodiment, the above-described conductivity sensor 21 and refractive index sensor 22 are used to measure the measured conductivity σ and measured refractive index n of the treatment liquid L. The measured values of the measured conductivity σ and the measured refractive index n are corrected as appropriate in consideration of the influence of the temperature of the processing liquid L. The measurement is performed at regular time intervals or continuously as the immobilization process proceeds in conjunction with the measurement of the actual temperature T.

ステップＳ３：
次に、上記ステップＳ２で測定した処理液Ｌの実測温度Ｔを用いて、上記１００種類の水溶液に対する実測温度Ｔにおける導電率と屈折率を求める。各水溶液の実測温度Ｔにおける導電率は、上記ステップＳ１で求めた温度と導電率との相関関係１から比例計算等により求める。また、各水溶液の実測温度Ｔにおける屈折率は、上記ステップＳ１で求めた温度と屈折率との相関関係２から比例計算等により求める。 Step S3:
Next, using the measured temperature T of the treatment liquid L measured in step S2, the conductivity and refractive index at the measured temperature T for the 100 types of aqueous solutions are obtained. The conductivity at the measured temperature T of each aqueous solution is obtained by proportional calculation or the like from the correlation 1 between the temperature and the conductivity obtained in step S1. Further, the refractive index at the measured temperature T of each aqueous solution is obtained by proportional calculation or the like from the correlation 2 between the temperature and the refractive index obtained in step S1.

ステップＳ４：
次に、上記ステップＳ３で求めた上記１００種類の水溶液の実測温度Ｔにおける導電率及び屈折率、並びに、上記１００種類の水溶液のホウ酸濃度及びヨウ化カリウム濃度を用いて、実測温度Ｔにおける１０水準のホウ酸濃度それぞれに対する導電率と屈折率との相関関係３を求める。得られた１０本の相関曲線の一部を図３に示す。また、同様にして実測温度Ｔにおける１０水準のホウ酸濃度それぞれに対する導電率とヨウ化カリウム濃度（各図においてはＫＩ濃度という。以下同じ）との相関関係４を求める。得られた１０本の相関曲線の一部を図４に示す。 Step S4:
Next, using the conductivity and refractive index at the measured temperature T of the 100 kinds of aqueous solutions obtained at step S3, and the boric acid concentration and potassium iodide concentration of the 100 kinds of aqueous solutions, 10 at the measured temperature T are obtained. Correlation 3 between conductivity and refractive index for each level of boric acid concentration is determined. A part of the obtained 10 correlation curves is shown in FIG. Similarly, a correlation 4 between the conductivity and the potassium iodide concentration (referred to as KI concentration in each figure; the same applies hereinafter) for each of the 10 levels of boric acid concentration at the measured temperature T is obtained. A part of the obtained 10 correlation curves is shown in FIG.

ステップＳ５：
次に、上記ステップＳ４で求めた導電率と屈折率との相関関係３（本実施例１においては、１０水準のホウ酸濃度に対応する１０本の相関曲線）の中から、処理液Ｌの実測導電率σ及び実測屈折率ｎに共通の近似値を有する２本の相関曲線を選択する。 Step S5:
Next, from the correlation 3 (10 correlation curves corresponding to 10 levels of boric acid concentration in Example 1) between the conductivity and the refractive index obtained in step S4, the treatment liquid L Two correlation curves having an approximate value common to the measured conductivity σ and the measured refractive index n are selected.

図３において、処理液Ｌの実測導電率σ及び実測屈折率ｎを示す位置を点Ａとする。この点Ａの両側にある２本の相関曲線３−１及び相関曲線３−２は、点Ａの実測導電率σ及び実測屈折率ｎに共通の近似値を有している。ここで、相関曲線３−１は、ホウ酸濃度Ｘ１に対する導電率と屈折率との相関関係を示しており、相関曲線３−２は、ホウ酸濃度Ｘ２に対する導電率と屈折率との相関関係を示している。 In FIG. 3, a position where the measured conductivity σ and measured refractive index n of the treatment liquid L are indicated as point A. The two correlation curves 3-1 and 3-2 on both sides of the point A have approximate values common to the measured conductivity σ and the measured refractive index n at the point A. Here, the correlation curve 3-1 shows the correlation between the conductivity and the refractive index with respect to the boric acid concentration X1, and the correlation curve 3-2 shows the correlation between the conductivity and the refractive index with respect to the boric acid concentration X2. Is shown.

次に、選択した２本の相関曲線３−１及び相関曲線３−２を用いて、それぞれ、処理液Ｌの実測導電率σに対応する屈折率を求める。まず、相関曲線３−１からホウ酸濃度Ｘ１における実測導電率σに対応する屈折率ｎ１を求め、同様に、相関曲線３−２からホウ酸濃度Ｘ２における実測導電率σに対応する屈折率ｎ２を求める（図３参照）。 Next, using the two selected correlation curves 3-1 and 3-2, the refractive indexes corresponding to the measured conductivity σ of the treatment liquid L are obtained. First, the refractive index n1 corresponding to the measured conductivity σ at the boric acid concentration X1 is obtained from the correlation curve 3-1, and similarly, the refractive index n2 corresponding to the measured conductivity σ at the boric acid concentration X2 is calculated from the correlation curve 3-2. Is obtained (see FIG. 3).

ステップＳ６：
次に、上記ステップＳ４で求めた導電率とヨウ化カリウム濃度との相関関係４（本実施例１においては、１０水準のホウ酸濃度に対応する１０本の相関曲線）の中から、上記ステップＳ５で選定したホウ酸濃度Ｘ１及びホウ酸濃度Ｘ２に対応する２本の相関曲線４−１及び相関曲線４−２を選択する。ここで、相関曲線４−１は、ホウ酸濃度Ｘ１に対する導電率とヨウ化カリウム濃度との相関関係を示しており、相関曲線４−２は、ホウ酸濃度Ｘ２に対する導電率とヨウ化カリウム濃度との相関関係を示している。 Step S6:
Next, from the correlation 4 (10 correlation curves corresponding to 10 levels of boric acid concentration in Example 1) between the conductivity and the potassium iodide concentration obtained in step S4, the above step is performed. Two correlation curves 4-1 and 4-2 corresponding to the boric acid concentration X1 and the boric acid concentration X2 selected in S5 are selected. Here, the correlation curve 4-1 shows the correlation between the conductivity and the potassium iodide concentration with respect to the boric acid concentration X1, and the correlation curve 4-2 shows the conductivity and the potassium iodide concentration with respect to the boric acid concentration X2. The correlation is shown.

次に、選択した２本の相関曲線４−１及び相関曲線４−２を用いて、それぞれ、処理液Ｌの実測導電率σに対応するヨウ化カリウム濃度を求める。まず、相関曲線４−１からホウ酸濃度Ｘ１における実測導電率σに対応するヨウ化カリウム濃度Ｙ１を求め、同様に、相関曲線４−２からホウ酸濃度Ｘ２における実測導電率σに対応するヨウ化カリウム濃度Ｙ２を求める（図４参照）。 Next, using the selected two correlation curves 4-1 and 4-2, the potassium iodide concentration corresponding to the measured conductivity σ of the treatment liquid L is obtained. First, the potassium iodide concentration Y1 corresponding to the measured conductivity σ at the boric acid concentration X1 is obtained from the correlation curve 4-1, and similarly, the iodine corresponding to the measured conductivity σ at the boric acid concentration X2 is calculated from the correlation curve 4-2. The potassium halide concentration Y2 is obtained (see FIG. 4).

ステップＳ７：
次に、上記ステップＳ５で求めたホウ酸濃度Ｘ１、ホウ酸濃度Ｘ２、屈折率ｎ１、屈折率ｎ２、上記ステップＳ６で求めたヨウ化カリウム濃度Ｙ１、ヨウ化カリウム濃度Ｙ２、及び、処理液Ｌの実測屈折率ｎを用いて、処理液Ｌのホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを求める。具体的には、これまでに求めたＸ１、Ｘ２、Ｙ１、Ｙ２、ｎ１、ｎ２及び実測屈折率ｎの関係を図５に示す。この図５の関係から下記の式（１）及び式（２）が導かれる。よって、処理液Ｌのホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙは、これらの式の比例計算により求めることができる。 Step S7:
Next, the boric acid concentration X1, the boric acid concentration X2, the refractive index n1, the refractive index n2 obtained in step S5, the potassium iodide concentration Y1, the potassium iodide concentration Y2 obtained in step S6, and the treatment liquid L. The boric acid concentration X and the potassium iodide concentration Y of the treatment liquid L are obtained using the measured refractive index n. Specifically, FIG. 5 shows the relationship between X1, X2, Y1, Y2, n1, n2 and the actually measured refractive index n obtained so far. The following formulas (1) and (2) are derived from the relationship shown in FIG. Therefore, the boric acid concentration X and the potassium iodide concentration Y of the treatment liquid L can be obtained by proportional calculation of these equations.

Ｘ＝Ｘ１＋（Ｘ２−Ｘ１）×（ｎ−ｎ１）／（ｎ２−ｎ１）‥‥‥（１）
Ｙ＝Ｙ１＋（Ｙ２−Ｙ１）×（ｎ−ｎ１）／（ｎ２−ｎ１）‥‥‥（２）
ステップＳ８：
次に、上記ステップＳ７で求めた処理液Ｌのホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙの値について、ホウ酸濃度の管理値Ｘｔ及びヨウ化カリウム濃度の管理値ＹｔからのずれΔＸ及びΔＹを算出する。 X = X1 + (X2-X1) * (n-n1) / (n2-n1) (1)
Y = Y1 + (Y2−Y1) × (n−n1) / (n2−n1) (2)
Step S8:
Next, regarding the boric acid concentration X and potassium iodide concentration Y of the treatment liquid L obtained in step S7, the boric acid concentration control value Xt And deviations ΔX and ΔY from the control value Yt of the potassium iodide concentration are calculated.

このようにして求めた、処理液Ｌの成分濃度Ｘ及びＹ、並びに、各管理値からのずれΔＸ及びΔＹにより固定化工程の進行中に処理液濃度をモニタし、適正な管理値に修正することができる。なお、上記各ステップのうち、ステップＳ２〜ステップＳ７、或いは、ステップＳ２〜ステップＳ８を順次繰り返すことにより、連続して固定化工程の処理液Ｌの各成分濃度を常にモニタすることができる。 The processing liquid concentration is monitored during the immobilization process by the component concentrations X and Y of the processing liquid L and the deviations ΔX and ΔY from the respective management values, and corrected to an appropriate management value. be able to. It should be noted that among the above steps, step S2 to step S7 or step S2 to step S8 are sequentially repeated, so that the concentration of each component of the treatment liquid L in the immobilization process can be continuously monitored.

図６は、本実施例２に係る処理液の成分濃度モニタ方法を示す工程図である。本実施例２においても上記実施例１と同様に、処理液Ｌのホウ酸濃度の管理値はＸｔであり、ヨウ化カリウム濃度の管理値はＹｔとする。また、処理液Ｌの温度の管理値はＴｔとして制御されている。 FIG. 6 is a process diagram illustrating the component concentration monitoring method for the processing liquid according to the second embodiment. Also in the second embodiment, similarly to the first embodiment, the management value of the boric acid concentration of the treatment liquid L is Xt, and the management value of the potassium iodide concentration is Yt. Further, the management value of the temperature of the processing liquid L is controlled as Tt.

本実施例２においては、ステップＳ１１〜ステップＳ１３を上記実施例１のステップＳ１〜ステップＳ３と同様にして行った。 In the second embodiment, steps S11 to S13 were performed in the same manner as steps S1 to S3 in the first embodiment.

ステップＳ１４：
ステップＳ１３で求めた上記１００種類の水溶液の実測温度Ｔにおける導電率及び屈折率、並びに、上記１００種類の水溶液のホウ酸濃度及びヨウ化カリウム濃度を用いて、実測温度Ｔにおける１０水準のヨウ化カリウム濃度それぞれに対する導電率と屈折率との相関関係５を求める。また、同様にして実測温度Ｔにおける１０水準のヨウ化カリウム濃度それぞれに対する導電率とホウ酸濃度との相関関係６を求める。 Step S14:
Using the conductivity and refractive index at the measured temperature T of the 100 aqueous solutions obtained at step S13 and the boric acid concentration and potassium iodide concentration of the 100 aqueous solutions, 10 levels of iodide at the measured temperature T Correlation 5 between conductivity and refractive index for each potassium concentration is obtained. Similarly, a correlation 6 between the conductivity and the boric acid concentration for each of 10 levels of potassium iodide concentration at the actually measured temperature T is obtained.

ステップＳ１５：
次に、上記ステップＳ１４で求めた導電率と屈折率との相関関係５の中から、処理液Ｌの実測導電率σ及び実測屈折率ｎに共通の近似値を有する２本の相関曲線を選択する。上記実施例１と同様にして２本の相関曲線５−１及び相関曲線５−２を選択する。ここで、相関曲線５−１は、ヨウ化カリウム濃度Ｙ３に対する導電率と屈折率との相関関係を示しており、相関曲線５−２は、ヨウ化カリウム濃度Ｙ４に対する導電率と屈折率との相関関係を示している。 Step S15:
Next, two correlation curves having approximate values common to the measured conductivity σ and the measured refractive index n of the treatment liquid L are selected from the correlation 5 between the conductivity and the refractive index obtained in step S14. To do. In the same manner as in the first embodiment, two correlation curves 5-1 and 5-2 are selected. Here, the correlation curve 5-1 shows the correlation between the conductivity and the refractive index with respect to the potassium iodide concentration Y3, and the correlation curve 5-2 shows the relationship between the conductivity and the refractive index with respect to the potassium iodide concentration Y4. Correlation is shown.

次に、選択した２本の相関曲線５−１及び相関曲線５−２を用いて、それぞれ、処理液Ｌの実測導電率σに対応する屈折率を求める。まず、相関曲線５−１からヨウ化カリウム濃度Ｙ３における実測導電率σに対応する屈折率ｎ３を求め、同様に、相関曲線５−２からヨウ化カリウム濃度Ｙ４における実測導電率σに対応する屈折率ｎ４を求める。 Next, using the two selected correlation curves 5-1 and 5-2, the refractive index corresponding to the measured conductivity σ of the processing liquid L is obtained. First, the refractive index n3 corresponding to the measured conductivity σ at the potassium iodide concentration Y3 is obtained from the correlation curve 5-1, and similarly, the refraction corresponding to the measured conductivity σ at the potassium iodide concentration Y4 is calculated from the correlation curve 5-2. The rate n4 is obtained.

ステップＳ１６：
次に、上記ステップＳ１４で求めた導電率とホウ酸濃度との相関関係６の中から、上記ステップＳ１５で選定したヨウ化カリウム濃度Ｙ３及びヨウ化カリウム濃度Ｙ４に対応する２本の相関曲線６−１及び相関曲線６−２を選択する。ここで、相関曲線６−１は、ヨウ化カリウム濃度Ｙ３に対する導電率とホウ酸濃度との相関関係を示しており、相関曲線６−２は、ヨウ化カリウム濃度Ｙ４に対する導電率とホウ酸濃度との相関関係を示している。 Step S16:
Next, two correlation curves 6 corresponding to the potassium iodide concentration Y3 and the potassium iodide concentration Y4 selected in the step S15 from the correlation 6 between the conductivity and the boric acid concentration obtained in the step S14. -1 and correlation curve 6-2 are selected. Here, the correlation curve 6-1 shows the correlation between the conductivity and the boric acid concentration with respect to the potassium iodide concentration Y3, and the correlation curve 6-2 shows the conductivity and the boric acid concentration with respect to the potassium iodide concentration Y4. The correlation is shown.

次に、選択した２本の相関曲線６−１及び相関曲線６−２を用いて、それぞれ、処理液Ｌの実測導電率σに対応するホウ酸濃度を求める。まず、相関曲線６−１からヨウ化カリウム濃度Ｙ３における実測導電率σに対応するホウ酸濃度Ｘ３を求め、同様に、相関曲線６−２からヨウ化カリウム濃度Ｙ４における実測導電率σに対応するホウ酸濃度Ｘ４を求める。 Next, using the two selected correlation curves 6-1 and 6-2, the boric acid concentration corresponding to the measured conductivity σ of the treatment liquid L is obtained. First, the boric acid concentration X3 corresponding to the measured conductivity σ at the potassium iodide concentration Y3 is obtained from the correlation curve 6-1. Similarly, the measured conductivity σ at the potassium iodide concentration Y4 is determined from the correlation curve 6-2. Obtain the boric acid concentration X4.

ステップＳ１７：
次に、上記ステップＳ１５で求めたヨウ化カリウム濃度Ｙ３、ヨウ化カリウム濃度Ｙ４、屈折率ｎ３、屈折率ｎ４、上記ステップＳ１６で求めたホウ酸濃度Ｘ３、ホウ酸濃度Ｘ４、及び、処理液Ｌの実測屈折率ｎを用いて、処理液Ｌのホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを求める。具体的には、上記実施例１と同様にしてＸ３、Ｘ４、Ｙ３、Ｙ４、ｎ３、ｎ４及び実測屈折率ｎの関係から下記の式（３）及び式（４）が導かれる。よって、処理液Ｌのホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙは、これらの式の比例計算により求めることができる。 Step S17:
Next, the potassium iodide concentration Y3, potassium iodide concentration Y4, refractive index n3, refractive index n4 determined in step S15, boric acid concentration X3, boric acid concentration X4 determined in step S16, and treatment liquid L The boric acid concentration X and the potassium iodide concentration Y of the treatment liquid L are obtained using the measured refractive index n. Specifically, the following formulas (3) and (4) are derived from the relationship between X3, X4, Y3, Y4, n3, n4 and the measured refractive index n in the same manner as in the first embodiment. Therefore, the boric acid concentration X and the potassium iodide concentration Y of the treatment liquid L can be obtained by proportional calculation of these equations.

Ｘ＝Ｘ３＋（Ｘ４−Ｘ３）×（ｎ−ｎ３）／（ｎ４−ｎ３）‥‥‥（３）
Ｙ＝Ｙ３＋（Ｙ４−Ｙ３）×（ｎ−ｎ３）／（ｎ４−ｎ３）‥‥‥（４）
次に、ステップＳ１８は、上記実施例１のステップＳ８と同様にして行った。 X = X3 + (X4-X3) * (n-n3) / (n4-n3) (3)
Y = Y3 + (Y4-Y3) * (n-n3) / (n4-n3) (4)
Next, Step S18 was performed in the same manner as Step S8 in Example 1 above.

このようにして求めた、処理液Ｌの成分濃度Ｘ及びＹ、並びに、各管理値からのずれΔＸ及びΔＹにより固定化工程の進行中に処理液濃度をモニタし、適正な管理値に修正することができる。なお、上記各ステップのうち、ステップＳ１２〜ステップＳ１７、或いは、ステップＳ１２〜ステップＳ１８を順次繰り返すことにより、連続して固定化工程の処理液Ｌの各成分濃度を常にモニタすることができる。 The processing liquid concentration is monitored during the immobilization process by the component concentrations X and Y of the processing liquid L and the deviations ΔX and ΔY from the respective management values, and corrected to an appropriate management value. be able to. In addition, among each said step, step S12-step S17 or step S12-step S18 are repeated sequentially, and each component density | concentration of the process liquid L of an immobilization process can always be monitored continuously.

図７は、本実施例３に係る処理液の成分濃度モニタ方法を示す工程図である。本実施例３においても上記実施例１と同様に、処理液Ｌのホウ酸濃度の管理値はＸｔであり、ヨウ化カリウム濃度の管理値はＹｔとする。また、処理液Ｌの温度の管理値はＴｔとして制御されている。 FIG. 7 is a process diagram illustrating the component concentration monitoring method for the processing liquid according to the third embodiment. In the third embodiment, similarly to the first embodiment, the management value of the boric acid concentration of the treatment liquid L is Xt, and the management value of the potassium iodide concentration is Yt. Further, the management value of the temperature of the processing liquid L is controlled as Tt.

本実施例３においては、ステップＳ２１〜ステップＳ２３を上記実施例１のステップＳ１〜ステップＳ３と同様にして行った。 In the third embodiment, steps S21 to S23 were performed in the same manner as steps S1 to S3 in the first embodiment.

ステップＳ２４：
ステップＳ２３で求めた上記１００種類の水溶液の実測温度Ｔにおける導電率及び屈折率、並びに、上記１００種類の水溶液のホウ酸濃度及びヨウ化カリウム濃度を用いて、実測温度Ｔにおける１０水準のホウ酸濃度それぞれに対する導電率と屈折率との相関関係７を求める。また、同様にして実測温度Ｔにおける１０水準のホウ酸濃度それぞれに対するヨウ化カリウム濃度と屈折率との相関関係８を求める。 Step S24:
Using the conductivity and refractive index of the 100 types of aqueous solutions obtained in step S23 at the measured temperature T and the boric acid concentration and potassium iodide concentration of the 100 types of aqueous solutions, 10 levels of boric acid at the measured temperature T are used. Correlation 7 between conductivity and refractive index for each concentration is obtained. Similarly, a correlation 8 between the potassium iodide concentration and the refractive index for each of the ten levels of boric acid concentration at the actually measured temperature T is obtained.

ステップＳ２５：
次に、上記ステップＳ２４で求めた導電率と屈折率との相関関係７の中から、処理液Ｌの実測導電率σ及び実測屈折率ｎに共通の近似値を有する２本の相関曲線を選択する。上記実施例１と同様にして２本の相関曲線７−１及び相関曲線７−２を選択する。ここで、相関曲線７−１は、ホウ酸濃度Ｘ５に対する導電率と屈折率との相関関係を示しており、相関曲線７−２は、ホウ酸濃度Ｘ６に対する導電率と屈折率との相関関係を示している。 Step S25:
Next, two correlation curves having approximate values common to the measured conductivity σ and the measured refractive index n of the treatment liquid L are selected from the correlation 7 between the conductivity and the refractive index obtained in step S24. To do. In the same manner as in Example 1, two correlation curves 7-1 and 7-2 are selected. Here, the correlation curve 7-1 shows the correlation between the conductivity and the refractive index with respect to the boric acid concentration X5, and the correlation curve 7-2 shows the correlation between the conductivity and the refractive index with respect to the boric acid concentration X6. Is shown.

次に、選択した２本の相関曲線７−１及び相関曲線７−２を用いて、それぞれ、処理液Ｌの実測屈折率ｎに対応する導電率を求める。まず、相関曲線７−１からホウ酸濃度Ｘ５における実測屈折率ｎに対応する導電率σ５を求め、同様に、相関曲線７−２からホウ酸濃度Ｘ６における実測屈折率ｎに対応する導電率σ６を求める。 Next, using the two selected correlation curves 7-1 and 7-2, the electrical conductivity corresponding to the measured refractive index n of the processing liquid L is obtained. First, the electrical conductivity σ5 corresponding to the measured refractive index n at the boric acid concentration X5 is obtained from the correlation curve 7-1. Similarly, the electrical conductivity σ6 corresponding to the measured refractive index n at the boric acid concentration X6 is obtained from the correlation curve 7-2. Ask for.

ステップＳ２６：
次に、上記ステップＳ２４で求めたヨウ化カリウム濃度と屈折率との相関関係８の中から、上記ステップＳ２５で選定したホウ酸濃度Ｘ５及びホウ酸濃度Ｘ６に対応する２本の相関曲線８−１及び相関曲線８−２を選択する。ここで、相関曲線８−１は、ホウ酸濃度Ｘ５に対するヨウ化カリウム濃度と屈折率との相関関係を示しており、相関曲線８−２は、ホウ酸濃度Ｘ６に対するヨウ化カリウム濃度と屈折率との相関関係を示している。 Step S26:
Next, two correlation curves 8− corresponding to the boric acid concentration X5 and the boric acid concentration X6 selected in step S25 are selected from the correlation 8 between the potassium iodide concentration and the refractive index obtained in step S24. 1 and the correlation curve 8-2 are selected. Here, the correlation curve 8-1 shows the correlation between the potassium iodide concentration and the refractive index with respect to the boric acid concentration X5, and the correlation curve 8-2 shows the potassium iodide concentration and the refractive index with respect to the boric acid concentration X6. The correlation is shown.

次に、選択した２本の相関曲線８−１及び相関曲線８−２を用いて、それぞれ、処理液Ｌの実測屈折率ｎに対応するヨウ化カリウム濃度を求める。まず、相関曲線８−１からホウ酸濃度Ｘ５における実測屈折率ｎに対応するヨウ化カリウム濃度Ｙ５を求め、同様に、相関曲線８−２からホウ酸濃度Ｘ６における実測屈折率ｎに対応するヨウ化カリウム濃度Ｙ６を求める。 Next, the potassium iodide concentration corresponding to the measured refractive index n of the treatment liquid L is obtained using the two selected correlation curves 8-1 and 8-2. First, the potassium iodide concentration Y5 corresponding to the measured refractive index n at the boric acid concentration X5 is obtained from the correlation curve 8-1. Similarly, the iodine corresponding to the measured refractive index n at the boric acid concentration X6 is obtained from the correlation curve 8-2. The potassium halide concentration Y6 is determined.

ステップＳ２７：
次に、上記ステップＳ２５で求めたホウ酸濃度Ｘ５、ホウ酸濃度Ｘ６、導電率σ５、導電率σ６、上記ステップＳ２６で求めたヨウ化カリウム濃度Ｙ５、ヨウ化カリウム濃度Ｙ６、及び、処理液Ｌの実測導電率σを用いて、処理液Ｌのホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを求める。具体的には、上記実施例１と同様にしてＸ５、Ｘ６、Ｙ５、Ｙ６、ｎ５、ｎ６及び実測導電率σの関係から下記の式（５）及び式（６）が導かれる。よって、処理液Ｌのホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙは、これらの式の比例計算により求めることができる。 Step S27:
Next, the boric acid concentration X5, boric acid concentration X6, electrical conductivity σ5, electrical conductivity σ6 obtained in step S25, potassium iodide concentration Y5, potassium iodide concentration Y6 obtained in step S26, and treatment liquid L The boric acid concentration X and the potassium iodide concentration Y of the treatment liquid L are obtained using the measured conductivity σ. Specifically, the following equations (5) and (6) are derived from the relationship between X5, X6, Y5, Y6, n5, n6 and the measured conductivity σ in the same manner as in the first embodiment. Therefore, the boric acid concentration X and the potassium iodide concentration Y of the treatment liquid L can be obtained by proportional calculation of these equations.

Ｘ＝Ｘ５＋（Ｘ６−Ｘ５）×（σ−σ５）／（σ６−σ５）‥‥‥（５）
Ｙ＝Ｙ５＋（Ｙ６−Ｙ５）×（σ−σ５）／（σ６−σ５）‥‥‥（６）
次に、ステップＳ２８は、上記実施例１のステップＳ８と同様にして行った。 X = X5 + (X6-X5) × (σ−σ5) / (σ6-σ5) (5)
Y = Y5 + (Y6−Y5) × (σ−σ5) / (σ6−σ5) (6)
Next, Step S28 was performed in the same manner as Step S8 of Example 1 above.

このようにして求めた、処理液Ｌの成分濃度Ｘ及びＹ、並びに、各管理値からのずれΔＸ及びΔＹにより固定化工程の進行中に処理液濃度をモニタし、適正な管理値に修正することができる。なお、上記各ステップのうち、ステップＳ２２〜ステップＳ２７、或いは、ステップＳ２２〜ステップＳ２８を順次繰り返すことにより、連続して固定化工程の処理液Ｌの各成分濃度を常にモニタすることができる。 The processing liquid concentration is monitored during the immobilization process by the component concentrations X and Y of the processing liquid L and the deviations ΔX and ΔY from the respective management values, and corrected to an appropriate management value. be able to. It should be noted that among the above steps, step S22 to step S27 or step S22 to step S28 are sequentially repeated, so that the concentration of each component of the treatment liquid L in the immobilization process can be continuously monitored.

図８は、本実施例４に係る処理液の成分濃度モニタ方法を示す工程図である。本実施例４においても上記実施例１と同様に、処理液Ｌのホウ酸濃度の管理値はＸｔであり、ヨウ化カリウム濃度の管理値はＹｔとする。また、処理液Ｌの温度の管理値はＴｔとして制御されている。 FIG. 8 is a process diagram illustrating the component concentration monitoring method for the processing liquid according to the fourth embodiment. Also in the fourth embodiment, similarly to the first embodiment, the control value of the boric acid concentration of the treatment liquid L is Xt, and the control value of the potassium iodide concentration is Yt. Further, the management value of the temperature of the processing liquid L is controlled as Tt.

本実施例４においては、ステップＳ３１〜ステップＳ３３を上記実施例１のステップＳ１〜ステップＳ３と同様にして行った。 In the fourth embodiment, steps S31 to S33 are performed in the same manner as steps S1 to S3 in the first embodiment.

ステップＳ３４：
ステップＳ３３で求めた上記１００種類の水溶液の実測温度Ｔにおける導電率及び屈折率、並びに、上記１００種類の水溶液のホウ酸濃度及びヨウ化カリウム濃度を用いて、実測温度Ｔにおける１０水準のヨウ化カリウム濃度それぞれに対する導電率と屈折率との相関関係９を求める。また、同様にして実測温度Ｔにおける１０水準のヨウ化カリウム濃度それぞれに対するホウ酸濃度と屈折率との相関関係１０を求める。 Step S34:
Using the conductivity and refractive index of the 100 types of aqueous solutions obtained in step S33 at the measured temperature T and the boric acid concentration and potassium iodide concentration of the 100 types of aqueous solutions, 10 levels of iodide at the measured temperature T are used. Correlation 9 between conductivity and refractive index for each potassium concentration is obtained. Similarly, the correlation 10 between the boric acid concentration and the refractive index for each of the 10 levels of potassium iodide concentration at the measured temperature T is obtained.

ステップＳ３５：
次に、上記ステップＳ３４で求めた導電率と屈折率との相関関係９の中から、処理液Ｌの実測導電率σ及び実測屈折率ｎに共通の近似値を有する２本の相関曲線を選択する。上記実施例１と同様にして２本の相関曲線９−１及び相関曲線９−２を選択する。ここで、相関曲線９−１は、ヨウ化カリウム濃度Ｙ７に対する導電率と屈折率との相関関係を示しており、相関曲線９−２は、ヨウ化カリウム濃度Ｙ８に対する導電率と屈折率との相関関係を示している。 Step S35:
Next, two correlation curves having a common approximate value for the measured conductivity σ and the measured refractive index n of the treatment liquid L are selected from the correlation 9 between the conductivity and the refractive index obtained in step S34. To do. In the same manner as in the first embodiment, two correlation curves 9-1 and 9-2 are selected. Here, the correlation curve 9-1 shows the correlation between the conductivity and the refractive index with respect to the potassium iodide concentration Y7, and the correlation curve 9-2 shows the relationship between the conductivity and the refractive index with respect to the potassium iodide concentration Y8. Correlation is shown.

次に、選択した２本の相関曲線９−１及び相関曲線９−２を用いて、それぞれ、処理液Ｌの実測屈折率ｎに対応する導電率を求める。まず、相関曲線９−１からヨウ化カリウム濃度Ｙ７における実測屈折率ｎに対応する導電率σ７を求め、同様に、相関曲線９−２からヨウ化カリウム濃度Ｙ８における実測屈折率ｎに対応する導電率σ８を求める。 Next, using the two selected correlation curves 9-1 and 9-2, the electrical conductivity corresponding to the measured refractive index n of the processing liquid L is obtained. First, the electrical conductivity σ7 corresponding to the measured refractive index n at the potassium iodide concentration Y7 is obtained from the correlation curve 9-1. Similarly, the electrical conductivity corresponding to the measured refractive index n at the potassium iodide concentration Y8 is obtained from the correlation curve 9-2. The rate σ8 is obtained.

ステップＳ３６：
次に、上記ステップＳ３４で求めたホウ酸濃度と屈折率との相関関係１０の中から、上記ステップＳ３５で選定したヨウ化カリウム濃度Ｙ７及びヨウ化カリウム濃度Ｙ８に対応する２本の相関曲線１０−１及び相関曲線１０−２を選択する。ここで、相関曲線１０−１は、ヨウ化カリウム濃度Ｙ７に対するホウ酸濃度と屈折率との相関関係を示しており、相関曲線１０−２は、ヨウ化カリウム濃度Ｙ８に対するホウ酸濃度と屈折率との相関関係を示している。 Step S36:
Next, two correlation curves 10 corresponding to the potassium iodide concentration Y7 and the potassium iodide concentration Y8 selected in step S35 out of the correlation 10 between the boric acid concentration and the refractive index obtained in step S34. -1 and correlation curve 10-2 are selected. Here, the correlation curve 10-1 shows the correlation between the boric acid concentration and the refractive index with respect to the potassium iodide concentration Y7, and the correlation curve 10-2 shows the boric acid concentration and the refractive index with respect to the potassium iodide concentration Y8. The correlation is shown.

次に、選択した２本の相関曲線１０−１及び相関曲線１０−２を用いて、それぞれ、処理液Ｌの実測屈折率ｎに対応するホウ酸濃度を求める。まず、相関曲線１０−１からヨウ化カリウム濃度Ｙ７における実測屈折率ｎに対応するホウ酸濃度Ｘ７を求め、同様に、相関曲線１０−２からヨウ化カリウム濃度Ｙ８における実測屈折率ｎに対応するホウ酸濃度Ｘ８を求める。 Next, using the two selected correlation curves 10-1 and 10-2, the boric acid concentration corresponding to the measured refractive index n of the treatment liquid L is obtained. First, the boric acid concentration X7 corresponding to the measured refractive index n at the potassium iodide concentration Y7 is obtained from the correlation curve 10-1, and similarly, it corresponds to the measured refractive index n at the potassium iodide concentration Y8 from the correlation curve 10-2. Obtain the boric acid concentration X8.

ステップＳ３７：
次に、上記ステップＳ３５で求めたヨウ化カリウム濃度Ｙ７、ヨウ化カリウム濃度Ｙ８、導電率σ７、導電率σ８、上記ステップＳ３６で求めたホウ酸濃度Ｘ７、ホウ酸濃度Ｘ８、及び、処理液Ｌの実測導電率σを用いて、処理液Ｌのホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙを求める。具体的には、上記実施例１と同様にしてＸ７、Ｘ８、Ｙ７、Ｙ８、ｎ７、ｎ８及び実測導電率σの関係から下記の式（７）及び式（８）が導かれる。よって、処理液Ｌのホウ酸濃度Ｘ及びヨウ化カリウム濃度Ｙは、これらの式の比例計算により求めることができる。 Step S37:
Next, the potassium iodide concentration Y7, potassium iodide concentration Y8, electrical conductivity σ7, electrical conductivity σ8 determined in step S35, boric acid concentration X7, boric acid concentration X8 determined in step S36, and treatment liquid L The boric acid concentration X and the potassium iodide concentration Y of the treatment liquid L are obtained using the measured conductivity σ. Specifically, the following equations (7) and (8) are derived from the relationship between X7, X8, Y7, Y8, n7, n8 and the measured conductivity σ in the same manner as in the first embodiment. Therefore, the boric acid concentration X and the potassium iodide concentration Y of the treatment liquid L can be obtained by proportional calculation of these equations.

Ｘ＝Ｘ７＋（Ｘ８−Ｘ７）×（σ−σ７）／（σ８−σ７）‥‥‥（７）
Ｙ＝Ｙ７＋（Ｙ８−Ｙ７）×（σ−σ７）／（σ８−σ７）‥‥‥（８）
次に、ステップＳ３８は、上記実施例１のステップＳ８と同様にして行った。 X = X7 + (X8−X7) × (σ−σ7) / (σ8−σ7) (7)
Y = Y7 + (Y8−Y7) × (σ−σ7) / (σ8−σ7) (8)
Next, Step S38 was performed in the same manner as Step S8 of Example 1 above.

このようにして求めた、処理液Ｌの成分濃度Ｘ及びＹ、並びに、各管理値からのずれΔＸ及びΔＹにより固定化工程の進行中に処理液濃度をモニタし、適正な管理値に修正することができる。なお、上記各ステップのうち、ステップＳ３２〜ステップＳ３７、或いは、ステップＳ３２〜ステップＳ３８を順次繰り返すことにより、連続して固定化工程の処理液Ｌの各成分濃度を常にモニタすることができる。 The processing liquid concentration is monitored during the immobilization process by the component concentrations X and Y of the processing liquid L and the deviations ΔX and ΔY from the respective management values, and corrected to an appropriate management value. be able to. In addition, among each said step, step S32-step S37 or step S32-step S38 are repeated sequentially, and each component density | concentration of the process liquid L of an immobilization process can always be monitored continuously.

上記実施形態及び上記各実施例においては、これまで間欠的に滴定法で手分析されていた固定化工程で使用される処理液の成分濃度の変化を連続して常時把握することが可能になる。このことにより、操業中の処理液の濃度変化に素早く対応できる生産体制を確立することができる。 In the above-described embodiment and each of the above-described examples, it is possible to continuously grasp the change in the component concentration of the processing liquid used in the immobilization process that has been intermittently manually analyzed by the titration method until now. . This makes it possible to establish a production system that can quickly respond to changes in the concentration of the processing liquid during operation.

なお、本発明の実施にあたり、上記各実施例に限らず、次のような変形例が挙げられる。例えば、上記各実施例においては、ホウ酸濃度１０水準、ヨウ化カリウム濃度１０水準とした１００種類の水溶液に対して、温度を１３水準とした導電率及び屈折率のデータベースを作成した。しかし、データベースは、これらの数に限定されるものではなく、データ数は任意に選定して差し支えない。 In implementing the present invention, not only the above-described embodiments but also the following modifications may be mentioned. For example, in each of the above examples, a database of conductivity and refractive index with a temperature of 13 levels was created for 100 types of aqueous solutions having a boric acid concentration of 10 levels and a potassium iodide concentration of 10 levels. However, the database is not limited to these numbers, and the number of data may be arbitrarily selected.

例えば、処理液Ｌの各管理値Ｘｔ、Ｙｔ及びＴｔを中心として、これらの変化が生じうる範囲を認識し、これらの範囲においてのみデータベースを作成するようにしてもよい。また、変化が微妙な領域においては、データの間隔を更に細かくすることにより、より正確なモニタが可能となる。 For example, it is also possible to recognize a range in which these changes can occur around the management values Xt, Yt, and Tt of the processing liquid L, and create a database only in these ranges. Further, in a region where the change is subtle, more accurate monitoring can be performed by further reducing the data interval.

本発明は、ホウ酸及びヨウ化カリウムを成分として含有する処理液の成分濃度をモニタする成分濃度モニタ方法及び成分濃度モニタ装置に関するものであり、当該処理液の各成分濃度及び各管理値からのずれを連続して正確にモニタすることができる。このことにより、これらの情報を基にして、連続処理で行われ常時変化する処理液の各成分濃度を適正な管理値に修正することが容易となる。 The present invention relates to a component concentration monitoring method and a component concentration monitoring apparatus for monitoring the component concentration of a treatment liquid containing boric acid and potassium iodide as components, and each component concentration and each control value of the treatment liquid The deviation can be monitored continuously and accurately. This makes it easy to correct the concentration of each component of the processing liquid that is constantly changed and continuously changed to an appropriate management value based on these pieces of information.

よって、液晶ディスプレイ（ＬＣＤ）などの画像表示装置に用いられる偏光子の製造において、生産性と歩留まりが高まると共に、より性能の良い偏光子を製造することができ、偏光子を利用する産業全般に寄与することができる。 Therefore, in the manufacture of polarizers used in image display devices such as liquid crystal displays (LCDs), productivity and yield can be increased, and polarizers with higher performance can be manufactured. Can contribute.

また、本発明に係る成分濃度モニタ方法は、導電率及び屈折率を利用して成分濃度を検知する方法において、各成分濃度が互いに影響を及ぼし合う場合であっても、他の成分の影響を排除して正確な成分濃度を求める方法に関するものである。よって、本発明の方法は、ホウ酸及びヨウ化カリウムを成分として含有する処理液に限らず、各成分濃度が導電率及び屈折率を利用して測定できる場合であって、各成分濃度が互いに影響を及ぼし合う２種類の成分を含有する他の処理液に関しても利用することができる。 In addition, the component concentration monitoring method according to the present invention is a method for detecting a component concentration using conductivity and refractive index. Even when each component concentration affects each other, the effect of other components is detected. The present invention relates to a method for eliminating and obtaining an accurate component concentration. Therefore, the method of the present invention is not limited to a treatment liquid containing boric acid and potassium iodide as components, but is a case where the concentration of each component can be measured using conductivity and refractive index. It can utilize also about the other process liquid containing the two types of component which has influence.

これらのことにより、本発明に係る成分濃度モニタ方法は、広範囲の産業で使用される各種処理液の成分濃度のモニタにも応用することができる。 As a result, the component concentration monitoring method according to the present invention can be applied to monitor the component concentrations of various processing liquids used in a wide range of industries.

１０…固定化ユニット、１１…処理槽、１２、１３…マングル、１４…循環ポンプ、
１５ａ、１５ｂ…循環配管、１６…ロール、
２０…モニタユニット、２１…導電率センサ、２２…屈折率センサ、２２ａ…温度センサ、２３…マイクロコンピュータ、２４…モニタ、２５…検出配管、２６…校正用ポンプ、
１００…処理装置。 DESCRIPTION OF SYMBOLS 10 ... Immobilization unit, 11 ... Processing tank, 12, 13 ... Mangle, 14 ... Circulation pump,
15a, 15b ... circulation piping, 16 ... roll,
DESCRIPTION OF SYMBOLS 20 ... Monitor unit, 21 ... Conductivity sensor, 22 ... Refractive index sensor, 22a ... Temperature sensor, 23 ... Microcomputer, 24 ... Monitor, 25 ... Detection piping, 26 ... Calibration pump,
100: Processing device.

Claims

In the component concentration monitoring method of the treatment liquid containing boric acid and potassium iodide as components,
Using a plurality of aqueous solutions composed of a combination of a series of known concentrations of boric acid and a series of known concentrations of potassium iodide, each of the plurality of aqueous solutions was measured for conductivity under a series of temperature conditions, respectively. The correlation 1 between the temperature of the aqueous solution and the conductivity is determined, and the refractive index under the series of temperature conditions is measured for each of the plurality of aqueous solutions, and the correlation 2 between the temperature and the refractive index of each aqueous solution is obtained. A first step to define;
A second step of measuring the measured temperature T, measured conductivity σ, and measured refractive index n of the treatment liquid in determining the boric acid concentration and potassium iodide concentration of the treatment liquid to be monitored;
For each of the plurality of aqueous solutions, the correlation 1 is used to determine the conductivity of each aqueous solution at the measured temperature T, and for each of the plurality of aqueous solutions, the correlation 2 is used. A third step for obtaining a refractive index of each aqueous solution at the measured temperature T;
Using the conductivity and refractive index of each aqueous solution obtained in this third step, and the boric acid concentration and potassium iodide concentration of each aqueous solution, the conductivity and refractive index for each boric acid concentration at the measured temperature T A fourth step of determining a correlation 3 and determining a correlation 4 between the conductivity and the potassium iodide concentration for each boric acid concentration at the measured temperature T;
Among the correlations 3 for each boric acid concentration, two correlations 3-1 (correlation at boric acid concentration X1) and correlation 3 having approximate values common to the measured conductivity σ and the measured refractive index n -2 (correlation in boric acid concentration X2), and from these correlations, respectively, a fifth step for obtaining a refractive index n1 and a refractive index n2 with respect to the measured conductivity σ,
Two correlations 4-1 (correlation in boric acid concentration X1) and correlation 4-2 (boric acid concentration) with respect to boric acid concentration X1 and boric acid concentration X2 among correlations 4 with respect to each boric acid concentration (Correlation in X2) is selected, and from these correlations, a sixth step for determining potassium iodide concentration Y1 and potassium iodide concentration Y2 with respect to the measured conductivity σ, respectively,
Using the boric acid concentration X1, boric acid concentration X2, potassium iodide concentration Y1, potassium iodide concentration Y2, refractive index n1, refractive index n2, and measured refractive index n, the following equations (1) and (2) From
X = X1 + (X2-X1) * (n-n1) / (n2-n1) (1)
Y = Y1 + (Y2−Y1) × (n−n1) / (n2−n1) (2)
And a seventh step of obtaining a boric acid concentration X and a potassium iodide concentration Y of the treatment liquid to be monitored.

In the component concentration monitoring method of the treatment liquid containing boric acid and potassium iodide as components,
Using a plurality of aqueous solutions composed of a combination of a series of known concentrations of boric acid and a series of known concentrations of potassium iodide, each of the plurality of aqueous solutions was measured for conductivity under a series of temperature conditions, respectively. The correlation 1 between the temperature of the aqueous solution and the conductivity is determined, and the refractive index under the series of temperature conditions is measured for each of the plurality of aqueous solutions, and the correlation 2 between the temperature and the refractive index of each aqueous solution is obtained. A first step to define;
A second step of measuring the measured temperature T, measured conductivity σ, and measured refractive index n of the treatment liquid in determining the boric acid concentration and potassium iodide concentration of the treatment liquid to be monitored;
For each of the plurality of aqueous solutions, the correlation 1 is used to determine the conductivity of each aqueous solution at the measured temperature T, and for each of the plurality of aqueous solutions, the correlation 2 is used. A third step for obtaining a refractive index of each aqueous solution at the measured temperature T;
Using the electrical conductivity and refractive index of each aqueous solution obtained in this third step, and the boric acid concentration and potassium iodide concentration of each aqueous solution, the electrical conductivity and refractive index for each potassium iodide concentration at the measured temperature T And a fourth step for determining a correlation 6 between conductivity and boric acid concentration for each potassium iodide concentration at the measured temperature T,
Two correlations 5-1 (correlation at the potassium iodide concentration Y3) and correlation having approximate values common to the measured conductivity σ and the measured refractive index n out of the correlation 5 with respect to each potassium iodide concentration Selecting a relationship 5-2 (correlation in the potassium iodide concentration Y4), and obtaining a refractive index n3 and a refractive index n4 with respect to the measured conductivity σ from these correlations, respectively,
Two correlations 6-1 (correlation in potassium iodide concentration Y3) and correlation 6-2 (iodine in correlation with boric acid concentration X3 and boric acid concentration X4) out of correlation 6 with respect to each potassium iodide concentration. (Correlation in potassium hydride concentration Y4) is selected, and from these correlations, a sixth step for obtaining boric acid concentration X3 and boric acid concentration X4 with respect to the measured conductivity σ, respectively,
Using the boric acid concentration X3, boric acid concentration X4, potassium iodide concentration Y3, potassium iodide concentration Y4, refractive index n3, refractive index n4, and measured refractive index n, the following equations (3) and (4) From
X = X3 + (X4-X3) * (n-n3) / (n4-n3) (3)
Y = Y3 + (Y4-Y3) * (n-n3) / (n4-n3) (4)
And a seventh step of obtaining a boric acid concentration X and a potassium iodide concentration Y of the treatment liquid to be monitored.

In the component concentration monitoring method of the treatment liquid containing boric acid and potassium iodide as components,
Using a plurality of aqueous solutions composed of a combination of a series of known concentrations of boric acid and a series of known concentrations of potassium iodide, each of the plurality of aqueous solutions was measured for conductivity under a series of temperature conditions, respectively. The correlation 1 between the temperature of the aqueous solution and the conductivity is determined, and the refractive index under the series of temperature conditions is measured for each of the plurality of aqueous solutions, and the correlation 2 between the temperature and the refractive index of each aqueous solution is obtained. A first step to define;
A second step of measuring the measured temperature T, measured conductivity σ, and measured refractive index n of the treatment liquid in determining the boric acid concentration and potassium iodide concentration of the treatment liquid to be monitored;
For each of the plurality of aqueous solutions, the correlation 1 is used to determine the conductivity of each aqueous solution at the measured temperature T, and for each of the plurality of aqueous solutions, the correlation 2 is used. A third step for obtaining a refractive index of each aqueous solution at the measured temperature T;
Using the conductivity and refractive index of each aqueous solution obtained in this third step, and the boric acid concentration and potassium iodide concentration of each aqueous solution, the conductivity and refractive index for each boric acid concentration at the measured temperature T A fourth step of determining a correlation 7 and determining a correlation 8 between the potassium iodide concentration and the refractive index for each boric acid concentration at the measured temperature T;
Among the correlations 7 for each boric acid concentration, two correlations 7-1 (correlation at boric acid concentration X5) and correlation 7 having approximate values common to the measured conductivity σ and the measured refractive index n. -2 (correlation in boric acid concentration X6), and from these correlations, respectively, a fifth step for obtaining conductivity σ5 and conductivity σ6 with respect to the measured refractive index n;
Two correlations 8-1 (correlation in boric acid concentration X5) and correlation 8-2 (boric acid concentration) with respect to boric acid concentration X5 and boric acid concentration X6 out of correlation 8 with respect to each boric acid concentration (Correlation in X6) is selected, and from these correlations, a sixth step for obtaining a potassium iodide concentration Y5 and a potassium iodide concentration Y6 with respect to the measured refractive index n, respectively,
Using the boric acid concentration X5, boric acid concentration X6, potassium iodide concentration Y5, potassium iodide concentration Y6, conductivity σ5, conductivity σ6, and measured conductivity σ, the following equations (5) and (6) From
X = X5 + (X6-X5) × (σ−σ5) / (σ6-σ5) (5)
Y = Y5 + (Y6−Y5) × (σ−σ5) / (σ6−σ5) (6)
And a seventh step of obtaining a boric acid concentration X and a potassium iodide concentration Y of the treatment liquid to be monitored.

In the component concentration monitoring method of the treatment liquid containing boric acid and potassium iodide as components,
Using a plurality of aqueous solutions composed of a combination of a series of known concentrations of boric acid and a series of known concentrations of potassium iodide, each of the plurality of aqueous solutions was measured for conductivity under a series of temperature conditions, respectively. The correlation 1 between the temperature of the aqueous solution and the conductivity is determined, and the refractive index under the series of temperature conditions is measured for each of the plurality of aqueous solutions, and the correlation 2 between the temperature and the refractive index of each aqueous solution is obtained. A first step to define;
A second step of measuring the measured temperature T, measured conductivity σ, and measured refractive index n of the treatment liquid in determining the boric acid concentration and potassium iodide concentration of the treatment liquid to be monitored;
For each of the plurality of aqueous solutions, the correlation 1 is used to determine the conductivity of each aqueous solution at the measured temperature T, and for each of the plurality of aqueous solutions, the correlation 2 is used. A third step for obtaining a refractive index of each aqueous solution at the measured temperature T;
Using the electrical conductivity and refractive index of each aqueous solution obtained in this third step, and the boric acid concentration and potassium iodide concentration of each aqueous solution, the electrical conductivity and refractive index for each potassium iodide concentration at the measured temperature T And a fourth step of determining a correlation 10 between the boric acid concentration and the refractive index for each potassium iodide concentration at the measured temperature T,
Two correlations 9-1 (correlation at potassium iodide concentration Y7) and correlation having approximate values common to the measured conductivity σ and the measured refractive index n out of the correlation 9 with respect to each potassium iodide concentration Selecting the relationship 9-2 (correlation in the potassium iodide concentration Y8), and obtaining the conductivity σ7 and the conductivity σ8 with respect to the measured refractive index n from these correlations, respectively,
Among the correlations 10 for each potassium iodide concentration, two correlations 10-1 (correlation at the potassium iodide concentration Y7) and correlation 10-2 with respect to the potassium iodide concentration Y7 and the potassium iodide concentration Y8. (Correlation in potassium iodide concentration Y8) is selected, and from these correlations, a sixth step for obtaining boric acid concentration X7 and boric acid concentration X8 for the measured refractive index n, respectively,
Using the boric acid concentration X7, boric acid concentration X8, potassium iodide concentration Y7, potassium iodide concentration Y8, conductivity σ7, conductivity σ8, and measured conductivity σ, the following equations (7) and (8) From
X = X7 + (X8−X7) × (σ−σ7) / (σ8−σ7) (7)
Y = Y7 + (Y8−Y7) × (σ−σ7) / (σ8−σ7) (8)
And a seventh step of obtaining a boric acid concentration X and a potassium iodide concentration Y of the treatment liquid to be monitored.

The method includes an eighth step of calculating deviations ΔX and ΔY from the corresponding predetermined management values for the boric acid concentration X and the potassium iodide concentration Y of the treatment liquid to be monitored calculated in the seventh step. The component concentration monitoring method for a processing liquid according to any one of claims 1 to 4.

Temperature detecting means for detecting the measured temperature T of the processing liquid to be monitored;
Conductivity detecting means for detecting the measured conductivity σ of the treatment liquid;
A refractive index detection means for detecting the measured refractive index n of the treatment liquid;
Concentration calculating means for calculating boric acid concentration X and potassium iodide concentration Y of the treatment liquid using the measured temperature T, the measured conductivity σ, and the measured refractive index n;
Display means for displaying the boric acid concentration X and the potassium iodide concentration Y;
A treatment liquid characterized by monitoring the boric acid concentration X and potassium iodide concentration Y of the treatment liquid calculated using the component concentration monitoring method according to claim 1 on the display means. Component concentration monitoring device.

Temperature detecting means for detecting the measured temperature T of the processing liquid to be monitored;
Conductivity detecting means for detecting the measured conductivity σ of the treatment liquid;
A refractive index detection means for detecting the measured refractive index n of the treatment liquid;
Concentration calculating means for calculating boric acid concentration X and potassium iodide concentration Y of the treatment liquid using the measured temperature T, the measured conductivity σ, and the measured refractive index n;
Deviation calculation means for calculating deviations ΔX and ΔY from the corresponding predetermined control values for the boric acid concentration X and potassium iodide concentration Y of the treatment liquid;
Display means for displaying the boric acid concentration X and the potassium iodide concentration Y;
The boric acid concentration X and potassium iodide concentration Y of the treatment liquid calculated by using the component concentration monitoring method according to claim 5, and deviations ΔX and ΔY from the corresponding predetermined management values are displayed on the display means. A component concentration monitoring apparatus for a processing liquid, characterized by monitoring.