JP2007212365A - Oxygen quenching paint and oxygen concentration measurement system - Google Patents

Oxygen quenching paint and oxygen concentration measurement system Download PDF

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JP2007212365A
JP2007212365A JP2006034519A JP2006034519A JP2007212365A JP 2007212365 A JP2007212365 A JP 2007212365A JP 2006034519 A JP2006034519 A JP 2006034519A JP 2006034519 A JP2006034519 A JP 2006034519A JP 2007212365 A JP2007212365 A JP 2007212365A
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oxygen
light
quenching
paint
quenching paint
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JP4630991B2 (en
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Jiyouyuu Hakozaki
譲優 箱崎
Shinya Kamata
慎矢 鎌田
Keisuke Asai
圭介 浅井
Daiki Nagai
大樹 永井
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Tohoku University NUC
Toyota Motor Corp
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Toyota Motor Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen quenching paint improved in peeling from the coated body or tearing of the paint film itself by expansion/shrinkage of the paint film caused by the temperature change. <P>SOLUTION: The oxygen quenching paint contains pigments and oxygen permeable polymers as a binder which are made to emit light by excitation light, in which the weight mean molecular weight of the oxygen permeable polymers is in a range of 80000-300000. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は酸素消光性塗料及び酸素消光性塗料を用いた酸素濃度計測装置に関する。   The present invention relates to an oxygen quenching paint and an oxygen concentration measuring apparatus using the oxygen quenching paint.

酸素消光性塗料に含有されている色素としては、白金ポルフィリンなどの金属ポルフィリンやルテニウム錯体などの遷移金属錯体などが使用されている。これらの色素に励起光を照射すると、色素分子は励起状態に遷移し、励起状態の色素分子(励起分子)は、基底状態に戻る際に励起光より長い波長の光(ルミネセンス)を発する。しかし、励起分子の周辺に酸素分子が存在すると、励起分子は酸素分子にエネルギを奪われ、酸素分子と励起分子との衝突確率に比例して消光現象が生じる。即ち、色素の発光強度は、色素周辺の雰囲気の酸素濃度によって増減する。従って、この発光強度を光センサ、例えばCCDカメラによって測定すれば色素周辺の酸素濃度を測定することができる。このような酸素濃度計測法を利用した酸素濃度計測装置は、自動車分野と、航空宇宙関係の分野だけでなく様々な分野への応用が期待されている。   As the dye contained in the oxygen-quenching paint, metal porphyrins such as platinum porphyrins, transition metal complexes such as ruthenium complexes, and the like are used. When these dyes are irradiated with excitation light, the dye molecules transition to an excited state, and the excited dye molecules (excitation molecules) emit light (luminescence) having a wavelength longer than that of the excitation light when returning to the ground state. However, when oxygen molecules exist around the excited molecules, the excited molecules lose their energy to the oxygen molecules, and a quenching phenomenon occurs in proportion to the collision probability between the oxygen molecules and the excited molecules. That is, the emission intensity of the dye varies depending on the oxygen concentration in the atmosphere around the dye. Therefore, if this emission intensity is measured by an optical sensor such as a CCD camera, the oxygen concentration around the dye can be measured. An oxygen concentration measuring apparatus using such an oxygen concentration measuring method is expected to be applied not only to the automobile field and aerospace related fields but also to various fields.

特許文献1には、光ファイバの先端に酸素消光性塗料を固定し、その光ファイバを燃料電池内に挿入することによって、燃料電池のカソード極に原料として供給される酸素が電解質膜中を透過しアノード極に漏洩したときの酸素濃度を検出する方法が提案されている。   In Patent Document 1, an oxygen quenching paint is fixed to the tip of an optical fiber, and the optical fiber is inserted into the fuel cell so that oxygen supplied as a raw material to the cathode electrode of the fuel cell passes through the electrolyte membrane. A method of detecting the oxygen concentration when leaking to the anode electrode has been proposed.

特開2004−265667号公報JP 2004-265667 A

しかし、特許文献1では、氷点下から100数十度の環境下で使用される燃料電池の使用環境を考慮していないため、その冷熱変化により光ファイバ先端に固定された酸素消光性塗料の塗膜は、膨張収縮し、被着体である光ファイバからの剥離や、塗膜自体の裂けが生じ、長期に渡って燃料電池内の酸素濃度を検出することができない。さらに、燃料電池内のガス漏れ検査レベル程度の酸素濃度しか測定できず、発電時の酸素濃度を測定することはできない。   However, since Patent Document 1 does not consider the use environment of a fuel cell used in an environment of a few tens of degrees from the freezing point, the coating film of the oxygen quenching paint fixed to the tip of the optical fiber by a change in the cooling temperature. Expands and contracts, peels off from the optical fiber as the adherend, and tears the coating film itself, and cannot detect the oxygen concentration in the fuel cell over a long period of time. Furthermore, only the oxygen concentration at the gas leak inspection level in the fuel cell can be measured, and the oxygen concentration during power generation cannot be measured.

本発明は、冷熱変化時において、被着体に塗布された酸素消光性塗料の塗膜の膨張収縮による被着体からの剥離や、塗膜自体の裂けを改善する酸素消光性塗料を提供する。   The present invention provides an oxygen-quenching coating material that improves peeling from the adherend due to expansion and contraction of the coating film of the oxygen-quenching coating material applied to the adherend and tearing of the coating film itself when the heat changes. .

また本発明は、冷熱変化時において、被着体に酸素消光性塗料を塗布した発光部における膨張収縮による被着体からの剥離や発光部自体の裂けを改善する酸素濃度計測装置を提供する。   The present invention also provides an oxygen concentration measuring apparatus that improves peeling from the adherend and tearing of the light emitting portion itself due to expansion and contraction in a light emitting portion in which an oxygen quenching paint is applied to the adherend during a change in cooling.

本発明の酸素消光性塗料は、励起光によって発光する色素とバインダとしての酸素透過性高分子とを含む酸素消光性塗料において、前記酸素透過性高分子の重量平均分子量が80000〜300000の範囲である。   The oxygen-quenching paint of the present invention is an oxygen-quenching paint containing a dye that emits light by excitation light and an oxygen-permeable polymer as a binder. The weight-average molecular weight of the oxygen-permeable polymer is in the range of 80,000 to 300,000. is there.

また、前記酸素消光性塗料であって、さらに撥水剤を含有することが好ましい。   The oxygen-quenching coating material preferably further contains a water repellent.

また、本発明の酸素濃度計測装置は、被着体に励起光によって発光する色素とバインダとしての酸素透過性高分子とを含む酸素消光性塗料を塗布した発光部と、前記発光部に対して励起光を照射する光照射部と、前記発光部の発光強度を計測する発光計測部と、前記発光計測部によって計測された前記発光部の発光強度から酸素濃度を算出する処理部と、を備え、前記酸素透過性高分子の重量平均分子量が80000〜300000の範囲である。   The oxygen concentration measuring apparatus according to the present invention includes a light-emitting unit in which an oxygen quenching paint including a dye that emits light by excitation light and an oxygen-permeable polymer as a binder is applied to an adherend, and the light-emitting unit. A light irradiation unit that emits excitation light, a light emission measurement unit that measures the light emission intensity of the light emission unit, and a processing unit that calculates an oxygen concentration from the light emission intensity of the light emission unit measured by the light emission measurement unit. The weight average molecular weight of the oxygen permeable polymer is in the range of 80,000 to 300,000.

また、前記酸素濃度計測装置であって、前記酸素消光性塗料は撥水剤をさらに含有することが好ましい。   Moreover, it is the said oxygen concentration measuring apparatus, Comprising: It is preferable that the said oxygen quenching coating material further contains a water repellent.

また、前記酸素濃度計測装置であって、前記発光部にアニール処理が行われるが好ましい。   In the oxygen concentration measuring apparatus, it is preferable that the light emitting unit is annealed.

本発明に係る酸素消光性塗料では、バインダとしての酸素透過性高分子の重量平均分子量を80000〜300000の範囲にすることにより、被着体に塗布された酸素消光性塗料の塗膜の被着体からの剥離や、塗膜自体の裂けを改善させることができる。   In the oxygen-quenching paint according to the present invention, the weight-average molecular weight of the oxygen-permeable polymer as a binder is in the range of 80,000 to 300,000, thereby attaching the coating film of the oxygen-quenching paint applied to the adherend. The peeling from the body and the tearing of the coating film itself can be improved.

また、本発明に係る酸素濃度計測装置では、バインダとしての酸素透過性高分子の重量平均分子量を80000〜300000の範囲にすることにより、被着体に酸素消光性塗料を塗布した発光部と被着体との剥離や、発光部自体の裂けを改善させることができる。特に冷熱変化時での発光部と被着体との剥離や、発光部自体の裂けを改善させることができるため、酸素濃度計測装置の長期間の使用を確保することができる。   In the oxygen concentration measuring apparatus according to the present invention, the weight-average molecular weight of the oxygen-permeable polymer as a binder is in the range of 80,000 to 300,000, so that the light-emitting part coated with an oxygen quenching paint on the adherend and the object to be coated Separation from the wearing body and tearing of the light emitting part itself can be improved. In particular, it is possible to improve the peeling of the light emitting part and the adherend and the tearing of the light emitting part itself at the time of a change in cold temperature, so that long-term use of the oxygen concentration measuring device can be ensured.

本発明の実施の形態について以下説明する。   Embodiments of the present invention will be described below.

まず、本発明の実施形態に係る酸素消光性塗料の一例を以下説明する。   First, an example of an oxygen-quenching paint according to an embodiment of the present invention will be described below.

酸素消光性塗料は、色素と酸素透過性高分子と撥水剤とを水、有機溶媒等の溶媒に溶解又は分散させて構成されている。酸素消光性塗料の調整方法は、特に限定されるものではないが、例えば、まず、有機溶媒中に酸素透過性高分子を溶解させ、次にその混合溶液に色素を溶解させ、さらにその混合溶液に撥水剤を溶解させることが好ましい。また溶解させるための各溶液の攪拌時間としては、好ましくは1〜60分、より好ましくは10〜30分である。また攪拌温度としては、室温付近(25度〜30度)であることが好ましい。   The oxygen-quenching paint is constituted by dissolving or dispersing a dye, an oxygen-permeable polymer, and a water repellent in a solvent such as water or an organic solvent. The method for adjusting the oxygen-quenching paint is not particularly limited. For example, first, the oxygen-permeable polymer is dissolved in an organic solvent, then the dye is dissolved in the mixed solution, and the mixed solution is further dissolved. It is preferable to dissolve the water repellent. Moreover, as stirring time of each solution for making it melt | dissolve, it becomes like this. Preferably it is 1-60 minutes, More preferably, it is 10-30 minutes. The stirring temperature is preferably around room temperature (25 to 30 degrees).

酸素消光性塗料中の色素、酸素透過性高分子、撥水剤の混合重量比は特に制限されるものではないが、酸素消光性塗料の総重量に対して色素は0.9〜4.9重量%、酸素透過性高分子は95〜99重量%、撥水剤は0〜0.1重量%であることが好ましい。   The mixing weight ratio of the dye, the oxygen permeable polymer, and the water repellent in the oxygen quenching paint is not particularly limited, but the dye is 0.9 to 4.9 based on the total weight of the oxygen quenching paint. It is preferable that the weight%, the oxygen-permeable polymer is 95 to 99% by weight, and the water repellent is 0 to 0.1% by weight.

酸素透過性高分子は、重量平均分子量(Mw)が80000〜300000の範囲であれば特に制限されるものではないが、好ましくは90000〜200000の範囲であり、さらに好ましくは90000〜110000の範囲である。酸素透過性高分子は例えば、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂と、ポリフッ化ビニル、ポリフッ化ビニリデン等のフッ素系樹脂と、ポリカーボネート、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリエステル、ポリテトラフルオロエチレン、との内少なくとも1つを使用することができる。酸素透過性高分子の重量平均分子量は、触媒とモノマーの仕込み比、反応温度、使用する溶媒の種類等の重合条件、或いは再沈殿の際の精製条件等を変えることによって調整してもよいが、分子量が特定されている市販品の物でも良い。具体的には、ポリスチレン(AVOCADO社製のポリスチレン、重量平均分子量100000)が挙げられる。酸素透過性高分子の重量平均分子量が80000より小さいと、被着体に塗布された酸素消光性塗料の塗膜強度が低下するため、冷熱変化時において、塗膜の膨張収縮により塗膜の裂けが生じやすくなり、また重量平均分子量が300000より大きいと、塗膜自体の強度が高くなりすぎるため、冷熱変化時において、塗膜の膨張収縮による塗膜自体の裂けが生じ易くなる。一般に平均分子量は、重量平均分子量(Mw)と数平均分子量(Mn)があるが、粘性など塗装に重要な物性量は重量平均分子量の方に依存すると考えられている。実施例で使用した酸素透過性高分子は市販のものであり、重量平均分子量の測定方法については製造者に依存するが、一般的にガスクロマトグラフィ(GPO)を使用する。酸素透過性高分子のガラス転移温度(Tg)としては、好ましくは85度〜200度、より好ましくは100度〜150度の範囲である。   The oxygen-permeable polymer is not particularly limited as long as the weight average molecular weight (Mw) is in the range of 80000-300000, but is preferably in the range of 90000-200000, more preferably in the range of 90000-110,000. is there. Examples of the oxygen permeable polymer include polyolefin resins such as polyethylene and polypropylene, fluorine resins such as polyvinyl fluoride and polyvinylidene fluoride, polycarbonate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyester, and polytetrafluoroethylene. , And at least one of them can be used. The weight average molecular weight of the oxygen permeable polymer may be adjusted by changing the polymerization conditions such as the catalyst / monomer charge ratio, reaction temperature, type of solvent used, or purification conditions during reprecipitation. A commercially available product having a specified molecular weight may also be used. Specific examples include polystyrene (polystyrene manufactured by AVOCADO, weight average molecular weight 100000). If the weight average molecular weight of the oxygen-permeable polymer is less than 80000, the coating strength of the oxygen-quenching paint applied to the adherend will decrease. If the weight average molecular weight is more than 300,000, the strength of the coating film itself becomes too high, and the coating film itself tends to tear due to expansion and contraction of the coating film when the temperature changes. In general, the average molecular weight includes a weight average molecular weight (Mw) and a number average molecular weight (Mn). It is considered that physical properties important for coating such as viscosity depend on the weight average molecular weight. The oxygen-permeable polymer used in the examples is commercially available, and the method for measuring the weight average molecular weight depends on the manufacturer, but generally gas chromatography (GPO) is used. The glass transition temperature (Tg) of the oxygen permeable polymer is preferably in the range of 85 to 200 degrees, more preferably 100 to 150 degrees.

色素としては、励起光により蛍光、燐光等を発光し、酸素消光性を示すものであれば特に制限されるものではない。例えば、白金オクタエチルポルフィリン、白金テトラペンタフルオロフェニルポルフィリンなどの白金ポルフィリン等の金属ポルフィリン錯体、フェナンスロリン・ルテニウム・クロライドなどの遷移金属錯体、ピレン、ペリレンなどの多環式芳香族化合物及びその誘導体を使用することができる。特に発光寿命、発光強度、熱的安定性の点から、白金テトラペンタフルオロフェニルポルフィリン又はフェナンスロリン・ルテニウム・クロライドが好ましく、具体的には、FrontierScientific PorphrinProducts社製のPt(II)meso−tetra penta fluoro phenyl porphine(以下Pt(TFPP))または、GFSケミカル社製のtris(Bathophenanthroline)Ruthenium Dichlorideが挙げられる。   The dye is not particularly limited as long as it emits fluorescence, phosphorescence or the like by excitation light and exhibits oxygen quenching property. For example, platinum porphyrin complexes such as platinum octaethylporphyrin and platinum tetrapentafluorophenylporphyrin, transition metal complexes such as phenanthrolin, ruthenium and chloride, polycyclic aromatic compounds such as pyrene and perylene, and derivatives thereof Can be used. In particular, platinum tetrapentafluorophenylporphyrin or phenanthroline / ruthenium / chloride is preferable from the viewpoint of emission lifetime, emission intensity, and thermal stability. Specifically, Pt (II) meso-tetra penta produced by Frontier Scientific Porphine Products. Fluorophenyl porphine (hereinafter referred to as Pt (TFPP)) or tris (Bathophaneanthroline) Ruthenium Dichloride manufactured by GFS Chemical Company.

撥水剤としては、酸素消光性塗料に撥水性能を付与するものであれば特に制限されるものではないが、塗膜面に対して、接触角が90%以上、好ましくは100%以上であるものが好ましい。具体的には、シリコン系樹脂、アクリル系樹脂、フッ素系樹脂等の撥水樹脂、及びこれらの混合物等が挙げられる。酸素消光性塗料の撥水性能の点から、アクリル系樹脂とフッ素系樹脂の混合物であるモディパー(登録商標)FS720(日本油脂社製)を用いることができる。   The water repellent is not particularly limited as long as it imparts water repellency to the oxygen-quenching paint, but the contact angle with respect to the coating surface is 90% or more, preferably 100% or more. Some are preferred. Specific examples include water-repellent resins such as silicon resins, acrylic resins, and fluorine resins, and mixtures thereof. From the viewpoint of the water-repellent performance of the oxygen-quenching paint, MODIPER (registered trademark) FS720 (manufactured by NOF Corporation), which is a mixture of an acrylic resin and a fluorine resin, can be used.

溶剤としては、揮発性の高い有機溶剤であれば特に制限されるものではない。例えばエタノール等のアルコール類、メチルエチルケトン等のケトン類、酢酸エチル等のエステル類、N−メチルピロリドン等のアミド系溶媒、トルエン溶媒等が挙げられる。揮発性の点、及び色素等との溶解性の点において、トルエンを用いることができる。   The solvent is not particularly limited as long as it is a highly volatile organic solvent. Examples thereof include alcohols such as ethanol, ketones such as methyl ethyl ketone, esters such as ethyl acetate, amide solvents such as N-methylpyrrolidone, and toluene solvents. Toluene can be used in terms of volatility and solubility with pigments.

以上説明した本実施形態に係る酸素消光性塗料により、被着体に酸素消光性塗料を塗布後、冷熱変化により酸素消光性塗料の塗膜が膨張収縮しても、被着体からの剥離や塗膜自体の裂けを防止することができる。また酸素消光性塗料にさらに撥水剤を含有させることにより、塗膜表面上に水滴が付着しても、塗膜表面での水滴の停滞を防止することができる。   After the oxygen quenching paint according to the present embodiment described above is applied, the oxygen quenching paint is applied to the adherend. It is possible to prevent tearing of the coating film itself. Further, by adding a water repellent to the oxygen-quenching paint, it is possible to prevent stagnation of water droplets on the coating film surface even if water droplets adhere to the coating film surface.

本実施形態に係る酸素消光性塗料は、酸素濃度計測装置の発光部、酸素分圧、水検知に使用することができる。   The oxygen-quenching paint according to the present embodiment can be used for a light emitting unit, oxygen partial pressure, and water detection of an oxygen concentration measuring device.

次に、本発明の実施形態に係る酸素濃度計測装置について以下説明する。   Next, an oxygen concentration measuring apparatus according to an embodiment of the present invention will be described below.

図1は、本発明の実施形態に係る酸素濃度計測装置1の構成の一例を示す概略図である。酸素濃度計測装置1は、光照射部10と、発光部14と、発光計測部16と、処理部18とを有する。発光部14は被着体12に塗布されている。また発光計測部16は処理部18に接続されている。光照射部10は、光照射部10の発光タイミングを制御する制御部20を備えているものが好ましい。さらに、発光計測部16は、発光部14の発光のみを計測できるように発光フィルタ22を備えているものが好ましい。   FIG. 1 is a schematic diagram showing an example of the configuration of an oxygen concentration measuring apparatus 1 according to an embodiment of the present invention. The oxygen concentration measurement apparatus 1 includes a light irradiation unit 10, a light emission unit 14, a light emission measurement unit 16, and a processing unit 18. The light emitting unit 14 is applied to the adherend 12. The light emission measuring unit 16 is connected to the processing unit 18. The light irradiation unit 10 preferably includes a control unit 20 that controls the light emission timing of the light irradiation unit 10. Furthermore, it is preferable that the light emission measurement unit 16 includes the light emission filter 22 so that only the light emission of the light emission unit 14 can be measured.

光照射部10から照射された光(励起光)は、被着体12に塗布された発光部14に投光される。投光された光により、発光部14は励起され発光する。発光部14から放射された光は周辺の酸素濃度に応じて発光強度が変化し、発光計測部16により検出され、電気信号に変換して出力される。出力された電気信号は、発光部14の発光強度として処理部18に送られる。処理部18は発光強度に対応する酸素濃度分布データを検出し、この検出結果を画面表示又は、プリント出力する。   Light (excitation light) irradiated from the light irradiation unit 10 is projected onto the light emitting unit 14 applied to the adherend 12. The light emitting unit 14 is excited and emits light by the projected light. The light emitted from the light-emitting unit 14 has a light emission intensity that changes according to the surrounding oxygen concentration, is detected by the light-emission measuring unit 16, is converted into an electrical signal, and is output. The output electrical signal is sent to the processing unit 18 as the light emission intensity of the light emitting unit 14. The processing unit 18 detects oxygen concentration distribution data corresponding to the emission intensity, and displays or prints out the detection result.

光照射部10は、発光部14に用いられる酸素消光性塗料の励起波長の光を放射するものであれば特に制限されるものでない。光照射部10は、例えば、光学フィルタを備えたキセノンランプ、メタルハライドランプ等、又はLEDである。具体的には、浜松ホトニクス社製LED(波長294〜395nm)、日亜化学工業社製LEDのNSPB300A(波長465nm)を使用することができ、酸素消光性塗料の励起波長に応じて選択される。   The light irradiation part 10 will not be restrict | limited especially if the light of the excitation wavelength of the oxygen quenching coating material used for the light emission part 14 is radiated | emitted. The light irradiation unit 10 is, for example, a xenon lamp provided with an optical filter, a metal halide lamp, or an LED. Specifically, Hamamatsu Photonics LED (wavelength 294-395 nm), Nichia Corporation LED NSPB300A (wavelength 465 nm) can be used, and is selected according to the excitation wavelength of the oxygen quenching paint. .

発光部14は、上記で述べた酸素消光性塗料を被着体12に塗布したものである。酸素消光性塗料中の色素が、光照射部10から投光された光により励起され、発光する。例えばPt(TFPP)では、波長400nmの紫色光を吸収し、波長650nm付近の燐光を発するが、発光強度は発光部14の周辺の酸素濃度に依存して消光される。   The light emitting unit 14 is obtained by applying the oxygen quenching paint described above to the adherend 12. The pigment in the oxygen-quenching paint is excited by the light projected from the light irradiation unit 10 and emits light. For example, Pt (TFPP) absorbs violet light having a wavelength of 400 nm and emits phosphorescence having a wavelength of around 650 nm, but the emission intensity is quenched depending on the oxygen concentration around the light emitting portion 14.

酸素消光性塗料は、上記で述べたものと同様のものを使用することができる。例えば、酸素透過性高分子としては、特に、塗布方法として簡便なエアスプレーガンに対応する酸素消光性塗料を調整することができる点から、ポリスチレン(AVOCADO社製のポリスチレン、分子量100000)が好ましく、撥水剤は、撥水性能に優れたモディパー(登録商標)FS720(日本油脂社製)が好ましく、色素は、発光寿命、発光強度、熱的安定性の点から、FrontierScientific PorphrinProducts社製のPt(TFPP)または、GFSケミカル社製のtris(Bathophenanthroline)Ruthenium Dichlorideが好ましい。また酸素消光性塗料の調整法も上記と同様の方法によって調整することができ、酸素消光性塗料中の色素、酸素透過性高分子、撥水剤の混合重量比も同様のものとすることができる。   As the oxygen-quenching paint, the same one as described above can be used. For example, as the oxygen permeable polymer, polystyrene (polystyrene manufactured by AVOCADO, molecular weight 100000) is particularly preferable from the viewpoint that an oxygen quenching paint corresponding to a simple air spray gun can be prepared as a coating method. The water repellent is preferably Modiper (registered trademark) FS720 (manufactured by Nippon Oil & Fats Co., Ltd.), which is excellent in water repellency. TFPP) or tris (Bathophaneanthroline) Ruthenium Dichloride manufactured by GFS Chemical Co. is preferable. The method for adjusting the oxygen quenching paint can also be adjusted by the same method as described above, and the mixing weight ratio of the dye, the oxygen permeable polymer and the water repellent in the oxygen quenching paint should be the same. it can.

図1に示すように、発光部14は被着体12上の酸素濃度を検出する箇所に酸素消光性塗料を塗布し作製される。塗布方法としては、特に制限されるものではないが、エアスプレーガン、デスペンサ、アプリケータ、スクリーン印刷、ロールコート、フローコート等が挙げられる。作業性の点から、特にエアスプレーガンが好ましい。発光部14の厚さは、1μm〜100μm、好ましくは10μm〜60μmである。膜厚が1μmより薄いと発光部14の発光を発光計測部16により検出することが困難となる場合があり、膜厚が80μmより厚いと、発光部14の作成時に発光部14自体に裂けが生じ易くなる場合がある。   As shown in FIG. 1, the light emitting unit 14 is manufactured by applying an oxygen quenching paint to a location on the adherend 12 where the oxygen concentration is detected. The application method is not particularly limited, and examples thereof include an air spray gun, a dispenser, an applicator, screen printing, roll coating, and flow coating. From the viewpoint of workability, an air spray gun is particularly preferable. The thickness of the light emitting portion 14 is 1 μm to 100 μm, preferably 10 μm to 60 μm. If the film thickness is less than 1 μm, it may be difficult to detect the light emission of the light emitting unit 14 by the light emission measuring unit 16. If the film thickness is greater than 80 μm, the light emitting unit 14 itself is torn when the light emitting unit 14 is formed. It may be likely to occur.

さらに被着体12への塗布後、発光部14をアニール処理することが好ましい。アニール処理をすることによって、発光部14の表面が滑らかになり、発光部14の発光むらを低減させることができるため、酸素濃度検出感度を向上させることができる。さらに発光部14の表面状態の均一性が増し、発光部14の塗膜強度の強い弱いのむらを低減させることができるため、冷熱変化時の発光部14の裂け等を防止することができる。アニール処理の条件としては酸素透過性高分子のガラス転移温度(Tg)より高い温度で一定時間保持されれば特に制限されるものではない。酸素透過性高分子として、例えばポリスチレン(Tg=82℃)を用いる場合、温度は85℃〜200℃、好ましくは100℃〜150℃で、保持時間は1分〜120分、好ましくは10分〜60分である。   Furthermore, it is preferable to anneal the light emitting portion 14 after application to the adherend 12. By performing the annealing process, the surface of the light-emitting portion 14 becomes smooth, and unevenness in light emission of the light-emitting portion 14 can be reduced, so that the oxygen concentration detection sensitivity can be improved. Furthermore, since the uniformity of the surface state of the light emitting portion 14 is increased and the unevenness of the coating strength of the light emitting portion 14 is strong and weak, it is possible to prevent tearing of the light emitting portion 14 during a change in cooling. The conditions for the annealing treatment are not particularly limited as long as the annealing treatment is maintained at a temperature higher than the glass transition temperature (Tg) of the oxygen-permeable polymer for a certain period of time. For example, when polystyrene (Tg = 82 ° C.) is used as the oxygen permeable polymer, the temperature is 85 ° C. to 200 ° C., preferably 100 ° C. to 150 ° C., and the holding time is 1 minute to 120 minutes, preferably 10 minutes to 60 minutes.

発光計測部16は発光部14の発光を計測できるものであれば特に制限されるものではない。発光計測部16は、例えばフォトダイオード、CCD等の光電変換素子である。具体的には、CCDを備えるCCDカメラとして、浜松ホトニクス社製のORCA2ER、またはPCO社製のSensicam1600等が挙げられる。また発光フィルタ22は、ISSI社製の645FG07−05(中心波長645nm)、又はケンコー社製SC60(中心波長600nm)等が挙げられ、発光部14の発光波長に応じて選択される。   The light emission measuring unit 16 is not particularly limited as long as it can measure the light emission of the light emitting unit 14. The light emission measuring unit 16 is a photoelectric conversion element such as a photodiode or a CCD. Specifically, as a CCD camera equipped with a CCD, ORCA2ER manufactured by Hamamatsu Photonics, Sensicam 1600 manufactured by PCO, or the like can be given. Examples of the light emission filter 22 include 645FG07-05 (center wavelength: 645 nm) manufactured by ISSI, SC60 (center wavelength: 600 nm) manufactured by Kenko, and the like, and are selected according to the light emission wavelength of the light emitting unit 14.

以上説明した本実施形態に係る酸素濃度計測装置により、発光部14は、冷熱変化により発光部14が膨張収縮しても、被着体12からの剥離や塗膜自体の裂けを防止することができる。従って長期に渡って酸素濃度計測を行うことができる。また酸素消光性塗料に撥水剤を添加することにより、塗膜表面上に水滴が付着しても、塗膜表面での水滴の停滞を防止することができる。   With the oxygen concentration measuring apparatus according to the present embodiment described above, the light emitting unit 14 can prevent peeling from the adherend 12 and tearing of the coating film itself even if the light emitting unit 14 expands and contracts due to a change in cold. it can. Therefore, the oxygen concentration can be measured over a long period. Further, by adding a water repellent to the oxygen-quenching paint, even if water droplets adhere to the surface of the coating film, stagnation of the water droplets on the coating film surface can be prevented.

従って、本実施形態に係る酸素濃度計測装置は、例えば氷点下から100数十度の環境下で使用される燃料電池において、その原料として供給される酸素濃度を測定し燃料電池の性能を評価することや、また上記同様の環境下で使用される現行エンジンの酸素センサにも使用することができる。さらに冷却水の飛散等が起こる工場設備付近での酸素濃度計測にも使用することができる。また耐熱性が必要な可視化エンジンの筒内、エキマニ内の酸素濃度計測にも使用することができる。さらに上記特許文献1で説明したような光ファイバ先端に上記説明した酸素消光性塗料を塗布することも可能であり、燃料電池の性能評価や電気自動車用燃料電池の酸素センサにも使用することができる。   Therefore, the oxygen concentration measuring apparatus according to the present embodiment measures the concentration of oxygen supplied as a raw material and evaluates the performance of the fuel cell, for example, in a fuel cell used in an environment of a few hundred degrees from a freezing point. It can also be used for an oxygen sensor of an existing engine used in the same environment as described above. Furthermore, it can be used for oxygen concentration measurement in the vicinity of factory equipment where cooling water scatters. It can also be used to measure the oxygen concentration in the cylinder and exhaust manifold of a visualization engine that requires heat resistance. Furthermore, it is possible to apply the above-described oxygen quenching paint described above to the tip of the optical fiber as described in Patent Document 1, and it can be used for performance evaluation of fuel cells and oxygen sensors for fuel cells for electric vehicles. it can.

次に本実施形態に係る酸素濃度計測装置の他の実施形態として、燃料電池セルに原料として供給される酸素濃度を本実施形態に係る酸素濃度計測装置を用いて計測する例を示し、以下説明する。   Next, as another embodiment of the oxygen concentration measuring apparatus according to the present embodiment, an example in which the oxygen concentration supplied as a raw material to the fuel cell is measured using the oxygen concentration measuring apparatus according to the present embodiment will be described. To do.

図2は、本発明の他の実施形態に係る酸素濃度計測装置の構成の一例を示す概略図である。酸素濃度計測装置1を構成する光照射部10と、発光計測部16と、処理部18とは上記と同様の構成であるため説明を省略するが、発光部14に用いられる酸素消光性塗料の調整方法及び燃料電池セル3への塗布方法についてより具体的に以下説明する。また燃料電池セル3内の酸素ガス濃度を検出するために、発光部14は酸素ガス流路30内面に形成されている(図3に示す)。   FIG. 2 is a schematic diagram showing an example of the configuration of an oxygen concentration measuring apparatus according to another embodiment of the present invention. Since the light irradiation unit 10, the light emission measurement unit 16, and the processing unit 18 constituting the oxygen concentration measuring device 1 have the same configuration as described above, the description thereof is omitted, but the oxygen quenching paint used in the light emission unit 14 is omitted. The adjustment method and the application method to the fuel cell 3 will be described more specifically below. In addition, in order to detect the oxygen gas concentration in the fuel cell 3, the light emitting section 14 is formed on the inner surface of the oxygen gas flow path 30 (shown in FIG. 3).

まず図2に示す燃料電池セル3は、MEA(膜電極接合体)24と、酸素ガスセパレータ26と、水素ガスセパレータ28とを有する。酸素ガスセパレータ26には、酸素ガスを通過させる酸素ガス流路30が形成されている。酸素ガスは酸素ガス入口32から入り、酸素ガス流路30を通過し酸素ガス出口34から排出される。水素ガスセパレータ28も同様である(図示せず)。酸素ガス流路30内を通過する酸素ガス濃度を検出するために、発光部14は酸素ガス流路30内面に形成されている(図3に示す)。また発光部14に励起光を照射し、発光部14の発光強度を観察するために酸素ガスセパレータ26は、アクリル樹脂や合成石英等の透明板を使用している。   First, the fuel cell 3 shown in FIG. 2 includes an MEA (membrane electrode assembly) 24, an oxygen gas separator 26, and a hydrogen gas separator 28. The oxygen gas separator 26 is formed with an oxygen gas flow path 30 through which oxygen gas passes. Oxygen gas enters from the oxygen gas inlet 32, passes through the oxygen gas flow path 30, and is discharged from the oxygen gas outlet 34. The same applies to the hydrogen gas separator 28 (not shown). In order to detect the concentration of oxygen gas passing through the oxygen gas flow channel 30, the light emitting section 14 is formed on the inner surface of the oxygen gas flow channel 30 (shown in FIG. 3). Further, in order to irradiate the light emitting unit 14 with excitation light and observe the light emission intensity of the light emitting unit 14, the oxygen gas separator 26 uses a transparent plate such as acrylic resin or synthetic quartz.

図3は、酸素ガス流路30内に形成した発光部14の構成の1例として、図2の矢印aに沿って切断した断面を矢印b方向から見た酸素ガス流路30の一部を表したものである。発光部14は、撥水剤を添加していない酸素消光性塗料(以下酸素消光性塗料A)を塗布した部分(塗布部A)と撥水剤を添加した酸素消光性塗料(以下酸素消光性塗料B)を塗布した部分(塗布部B)とを有する。必ずしもこれに限定されるものでなく、酸素消光性塗料Aのみを塗布した部分でもよいし、酸素消光性塗料Bのみを塗布した部分でもよい。   FIG. 3 shows, as an example of the configuration of the light emitting unit 14 formed in the oxygen gas flow path 30, a part of the oxygen gas flow path 30 as viewed from the direction of the arrow b in a cross section cut along the arrow a in FIG. It is a representation. The light-emitting portion 14 includes an oxygen-quenching paint (hereinafter referred to as oxygen-quenching paint A) to which a water-repellent agent is not added and an oxygen-quenching paint (hereinafter referred to as oxygen-quenching property) to which a water-repellent agent is added. And a portion to which the coating material B) is applied (application portion B). However, the present invention is not necessarily limited thereto, and may be a portion where only the oxygen quenching paint A is applied, or a portion where only the oxygen quenching paint B is applied.

酸素消光性塗料A,Bの調整法を具体的に説明するが、これに限定されるものではない。酸素消光性塗料Aは、トルエン等の有機溶媒中に酸素消光性塗料Aの総重量に対して95〜99重量%のポリスチレン等の酸素透過性高分子を加え25度〜30度で、10分〜30分程度攪拌し溶解させ、次にその混合溶液に酸素消光性塗料Aの総重量に対して0.9〜4.9重量%のPt(TFPP)等の色素を加え25度〜30度で、10分〜30分程度攪拌し溶解させたものとする。酸素消光性塗料Bは、トルエン等の有機溶媒中に酸素消光性塗料Bの総重量に対して95〜99重量%のポリスチレン等の酸素透過性高分子を加え25度〜30度で、10分〜30分程度攪拌し溶解させ、次にその混合溶液に酸素消光性塗料Bの総重量に対して0.9〜4.9重量%のPt(TFPP)等の色素を加え25度〜30度で、10分〜30分程度攪拌し溶解させ、さらにその混合溶液に撥水剤としてアクリル系樹脂とフッ素系樹脂の混合物等である撥水剤を加え25度〜30度で、10分〜30分程度攪拌し溶解させたものとする。   Although the adjustment method of the oxygen-quenching paints A and B will be specifically described, it is not limited to this. Oxygen-quenching paint A is an organic solvent such as toluene, and an oxygen-permeable polymer such as polystyrene of 95 to 99% by weight with respect to the total weight of oxygen-quenching paint A is added at 25 to 30 degrees for 10 minutes. Stir for about 30 minutes to dissolve, then add 0.9 to 4.9% by weight of a dye such as Pt (TFPP) to the total weight of the oxygen-quenching coating material A and add 25 to 30 degrees. Then, the mixture is stirred for about 10 to 30 minutes and dissolved. Oxygen-quenching paint B is an organic solvent such as toluene, and an oxygen-permeable polymer such as polystyrene of 95 to 99% by weight based on the total weight of oxygen-quenching paint B is added at 25 to 30 degrees for 10 minutes. Stir for about 30 minutes to dissolve, and then add 0.9 to 4.9% by weight of a dye such as Pt (TFPP) to the total weight of the oxygen-quenching paint B to the mixed solution. Then, a water repellent agent such as a mixture of an acrylic resin and a fluororesin is added as a water repellent agent to the mixed solution for 10 minutes to 30 minutes. It shall be dissolved by stirring for about a minute.

酸素消光性塗料A,Bの塗布方法を具体的に説明するが、これに限定されるものではない。図3に示すように、酸素消光性塗料Bは酸素ガス流路30の幅dに対して隙間が空くように塗布されることが好ましく、さらに酸素ガス流路30の幅dの1/2以下の直径になるよう塗布されることがより好ましい。これは燃料電池の発電反応により生成した水の通り道を確保するためである。燃料電池セル3の発電反応により生成した水の一部は、酸素ガス流路30内に排水されるため、撥水機能を有する酸素消光性塗料Bが酸素ガス流路30の幅dと同じ直径となるように塗布されると、酸素ガス流路内の水の排水を酸素消光性塗料Bが阻害してしまうからである。また塗布部Bは円形である必要はなく、三角形、四角形等でもよい。塗布方法としては、例えば酸素消光性塗料Aを充填したエアスプレーガンを用いて酸素ガス流路30内側面に塗布する際に、予めマスキングテープ等により酸素消光性塗料Bを塗布する箇所を確保し、酸素消光性塗料Aを充填したエアスプレーガンを用いて酸素ガス流路30内側面に塗布した後、マスキングテープ等を剥がし、その箇所に酸素消光性塗料Bを充填したエアスプレーガンを用いて塗布するものが好ましい。さらに塗布後、アニール処理により酸素消光性塗料の塗膜を安定化させることが好ましい。アニール処理の条件としては、特に制限されるものではないが110℃、60分が好ましい。   The method for applying the oxygen-quenching paints A and B will be specifically described, but is not limited thereto. As shown in FIG. 3, the oxygen-quenching coating material B is preferably applied such that a gap is provided with respect to the width d of the oxygen gas flow path 30, and further, ½ or less of the width d of the oxygen gas flow path 30. More preferably, it is applied so as to have a diameter of. This is to ensure the passage of water generated by the power generation reaction of the fuel cell. Since part of the water generated by the power generation reaction of the fuel battery cell 3 is drained into the oxygen gas flow path 30, the oxygen quenching paint B having a water repellent function has the same diameter as the width d of the oxygen gas flow path 30. This is because the oxygen quenching paint B inhibits the drainage of water in the oxygen gas flow path. Moreover, the application part B does not need to be circular, and may be a triangle, a quadrangle, or the like. As a coating method, for example, when applying to the inner side surface of the oxygen gas flow path 30 using an air spray gun filled with the oxygen quenching paint A, a portion where the oxygen quenching paint B is applied with a masking tape or the like is secured in advance. Using an air spray gun filled with oxygen-quenching paint A, the inner surface of oxygen gas flow path 30 was applied, and then the masking tape was peeled off, and an air spray gun filled with oxygen-quenching paint B was used at that location. What is applied is preferred. Furthermore, it is preferable to stabilize the coating film of the oxygen-quenching paint after the application by annealing. The annealing conditions are not particularly limited, but 110 ° C. and 60 minutes are preferable.

以上説明した本発明の他の実施形態に係る酸素濃度計測装置が、氷点下から100数十度の環境下で使用される燃料電池に使用されても、発光部14は酸素ガス流路30内側面から剥離することや、発光部14自体の裂けを生じることがないため、長期間酸素濃度計測装置を使用することができる。また撥水剤を有する塗布部Bを設けることによって、燃料電池の発電反応により生成する水が塗布部Bに付着することがないために、酸素ガス流路30内の酸素ガス濃度を正確に測定することができる。さらにアニール処理によって発光部14の表面を滑らかにすることができるため、より正確な発光強度を計測することができる。上記これらの実施形態に係る酸素濃度計測装置は、燃料電池用の用途に使用されるものに限られない。   Even if the oxygen concentration measuring device according to another embodiment of the present invention described above is used in a fuel cell used in an environment of a few tens of degrees from the freezing point, the light-emitting unit 14 has the oxygen gas channel 30 inner surface. Therefore, the oxygen concentration measuring device can be used for a long period of time. In addition, by providing the application part B having a water repellent agent, water generated by the power generation reaction of the fuel cell does not adhere to the application part B, so that the oxygen gas concentration in the oxygen gas channel 30 is accurately measured. can do. Furthermore, since the surface of the light emitting portion 14 can be smoothed by the annealing treatment, more accurate light emission intensity can be measured. The oxygen concentration measuring apparatus according to the above embodiments is not limited to those used for fuel cell applications.

以下実施例及び比較例を挙げ、本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。   Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(実施例1〜8の酸素消光性塗料の調整及び被着体への塗布)
トルエン100ml溶媒中に酸素透過性高分子としてポリスチレン5000mg(AVOCADO社製、重量平均分子量100000)を加え25度で10分攪拌し溶解させ、次にその混合溶液に色素としてPt(TFPP)75mg(FrontierScientific PorphrinProducts社製)を加え25度で10分攪拌し溶解させ、さらにその混合溶液に撥水剤としてアクリル系樹脂とフッ素系樹脂の混合物であるモディパー(登録商標)FS720を1.5g加え25度で10分攪拌し溶解させ、酸素消光性塗料を調整した。上記酸素消光性塗料をエアスプレーガンにより被着体としてのガラス板に20マイクロmの厚さに塗布したものを実施例1とし、被着体としてのガラス板に80マイクロmの厚さに塗布したものを実施例3とした。また実施例1及び実施例3を高温槽にて酸素雰囲気下110度で1時間アニール処理したものをそれぞれ実施例2及び実施例4とした。実施例5及び実施例7は、上記ポリスチレンの分子量を重量平均分子量280000(AVOCADO社製)として、実施例1及び実施例3と同様に作製した。実施例6及び実施例8は、実施例5及び実施例7を110度で1時間アニール処理したものである。
(Adjustment of oxygen quenching paints of Examples 1 to 8 and application to adherends)
In 100 ml of toluene, 5000 mg of polystyrene (AVOCADO, weight average molecular weight 100000) as an oxygen permeable polymer was added and stirred for 10 minutes at 25 ° C. to dissolve, and then 75 mg (Frontier Scientific) of Pt (TFPP) as a dye in the mixed solution. Porphrin Products, Inc.) was added and stirred for 10 minutes at 25 degrees to dissolve, and 1.5 g of Modiper (registered trademark) FS720, which is a mixture of acrylic resin and fluororesin, was added to the mixed solution as a water repellent. The mixture was stirred for 10 minutes and dissolved to prepare an oxygen quenching paint. The oxygen quenching paint was applied to a glass plate as an adherend to a thickness of 20 μm with an air spray gun as Example 1, and applied to the glass plate as an adherend to a thickness of 80 μm. This was designated as Example 3. Moreover, what annealed Example 1 and Example 3 for 1 hour by 110 degreeC by oxygen atmosphere in the high temperature tank was set as Example 2 and Example 4, respectively. Examples 5 and 7 were prepared in the same manner as in Examples 1 and 3 with the molecular weight of the polystyrene set to a weight average molecular weight of 280000 (manufactured by AVOCADO). In Examples 6 and 8, Example 5 and Example 7 were annealed at 110 degrees for 1 hour.

(比較例1〜4の酸素消光性塗料の調整及び被着体への塗布)
トルエン100ml溶媒中に酸素透過性高分子としてポリスチレン5000mg(AVOCADO社製、重量平均分子量50000)を加え25度で10分攪拌し溶解させ、次にその混合溶液に色素としてPt(TFPP)75mg(FrontierScientific PorphrinProducts社製)を加え25度で10分攪拌し溶解させ、さらにその混合溶液に撥水剤としてモディパー(登録商標)FS720を1.5g加え25度で10分攪拌し溶解させ、酸素消光性塗料を調整した。上記酸素消光性塗料をエアスプレーガンにより被着体としてのガラス板に20μmの厚さに塗布したものを比較例1とし、被着体としてのガラス板に80マイクロmの厚さに塗布したものを比較例3とした。また比較例1及び比較例3を高温槽にて酸素雰囲気下110度で1時間アニール処理したものをそれぞれ比較例2及び比較例4とした。比較例1〜4の作製条件を下記表1に示す。
(Adjustment of oxygen quenching paints of Comparative Examples 1 to 4 and application to adherends)
In 100 ml of toluene, 5,000 mg of polystyrene as an oxygen permeable polymer (AVOCADO, weight average molecular weight 50000) is added and stirred for 10 minutes at 25 ° C. to dissolve, and then 75 mg of Pt (TFPP) (Frontier Scientific) as a dye in the mixed solution. Porphrin Products, Inc.) was added and stirred for 10 minutes at 25 degrees to dissolve, and 1.5 g of Modiper (registered trademark) FS720 as a water repellent was added to the mixed solution and dissolved by stirring for 10 minutes at 25 degrees. Adjusted. The above-mentioned oxygen-quenching paint was applied to a glass plate as an adherend with an air spray gun to a thickness of 20 μm as Comparative Example 1, and applied to a glass plate as an adherend to a thickness of 80 μm. Was designated as Comparative Example 3. Further, Comparative Example 1 and Comparative Example 3 were annealed in an oxygen atmosphere at 110 ° C. for 1 hour in a high-temperature bath, and were designated as Comparative Example 2 and Comparative Example 4, respectively. The production conditions of Comparative Examples 1 to 4 are shown in Table 1 below.

Figure 2007212365
Figure 2007212365

(実施例1〜8、比較例1〜4の高温蒸気曝露試験)
実施例1〜8、比較例1〜4を、温度100度の沸騰水状態のビーカ内の水面上方50mmに設置し、ビーカ内の沸騰水が発生する蒸気中に実施例1〜8、比較例1〜4を2時間放置した。その後の実施例1〜8、比較例1〜4の塗膜表面状態の結果を下記表2に示す。塗膜表面状態の評価は、塗膜表面を走査型共焦点レーザ顕微鏡(オリンパス社製、OLS1200、形状分解能0.01μm)で測定することによって行った。表面状態の程度はディスプレイに表示される画像の滑らかさから判断した。
○:塗膜表面にでこぼこ等がない。
△:塗膜表面にでこぼこした部位がある。
×:塗膜表面の破壊(裂け)又は塗膜全体の剥離。
(Examples 1 to 8 and Comparative Examples 1 to 4 of high temperature steam exposure test)
Examples 1 to 8 and Comparative Examples 1 to 4 were installed 50 mm above the water surface in a beaker in a boiling water state at a temperature of 100 degrees, and Examples 1 to 8 and Comparative Example were in steam generated by boiling water in the beaker. 1-4 were left for 2 hours. The result of the coating-film surface state of Examples 1-8 after that and Comparative Examples 1-4 is shown in following Table 2. Evaluation of the coating film surface state was performed by measuring the coating film surface with a scanning confocal laser microscope (manufactured by Olympus, OLS1200, shape resolution 0.01 μm). The degree of the surface condition was judged from the smoothness of the image displayed on the display.
○: There is no unevenness on the surface of the coating film.
Δ: There are bumpy parts on the surface of the coating film.
X: Destruction (tearing) of the coating film surface or peeling of the entire coating film.

Figure 2007212365
Figure 2007212365

比較例1〜4(酸素透過性高分子の重量平均分子量が50000)は、高温蒸気曝露試験後、塗膜表面自体が破壊され、被着体から剥がれ落ちていた。塗膜厚は20μm及び80μmで試験を行ったものであるが、厚さの違いによる塗膜表面状態に差は見られなかった。さらにアニール処理による効果も見られなかった。一方実施例1,3(酸素透過性高分子の重量平均分子量が100000)及び実施例5,7(酸素透過性高分子の重量平均分子量が280000)は、高温曝露試験後でも塗膜自体の裂けや被着体からの剥離が生じることはなく、また塗膜厚の違いによる塗膜表面状態にも差は見られなかったが、塗膜表面の一部にでこぼこした部位が存在していた。但し例えば酸素濃度計測装置の発光部に使用しても支障をきたす程度ではない。もっとも良い結果を示したのは、アニール処理を行った実施例2,4(酸素透過性高分子の重量平均分子量が100000)及び実施例6,8(酸素透過性高分子の重量平均分子量が280000)であった。高温曝露試験後でも塗膜自体の裂けや被着体からの剥離が生じることなく、塗膜表面にでこぼこの部位も存在していなかった。20μm及び80μmの塗膜の厚さは、酸素濃度計測装置の発光部として使用可能な塗膜厚である。   In Comparative Examples 1 to 4 (the weight average molecular weight of the oxygen-permeable polymer was 50000), the coating film surface itself was destroyed after the high-temperature steam exposure test, and peeled off from the adherend. The coating thickness was tested at 20 μm and 80 μm, but no difference was found in the coating surface state due to the difference in thickness. Furthermore, the effect by annealing treatment was not seen. On the other hand, in Examples 1 and 3 (the weight average molecular weight of the oxygen-permeable polymer is 100,000) and Examples 5 and 7 (the weight average molecular weight of the oxygen-permeable polymer is 280000), the coating itself is torn even after the high-temperature exposure test. No peeling from the adherend occurred, and no difference was observed in the surface state of the coating film due to the difference in coating thickness. However, a part of the coating film surface was uneven. However, even if it is used for the light emitting part of the oxygen concentration measuring device, for example, it does not cause any trouble. The best results were shown in Examples 2 and 4 (the weight-average molecular weight of the oxygen-permeable polymer was 100,000) and Examples 6 and 8 (the weight-average molecular weight of the oxygen-permeable polymer was 280000) after annealing. )Met. Even after the high temperature exposure test, the coating film itself was not torn or peeled off from the adherend, and there were no bumps on the surface of the coating film. The thicknesses of the coating films of 20 μm and 80 μm are coating film thicknesses that can be used as the light emitting part of the oxygen concentration measuring device.

(燃料電池セル用の酸素濃度試験装置の作成方法)
図4に示したように、酸素濃度計測装置1は、光照射部10として日亜化学工業社製LEDのNSPB300A(波長465nm)を用い、発光計測部16としてPCO社製のSensicam1600、また発光フィルタ22は、ISSI社製の645FG07−05(中心波長645nm)を用い、処理部18として、パーソナルコンピュータを用いた。図3に示したように発光部14は、酸素消光性塗料A及び酸素消光性塗料Bをエアスプレーガンによりアクリル樹脂の透明板を使用した酸素ガスセパレータ26内の酸素ガス流路30面内に形成した。塗布厚は20μmとした。酸素消光性塗料Aは、トルエン100ml溶媒中に酸素透過性高分子としてポリスチレン5000mg(AVOCADO社製、重量平均分子量100000)を加え25度で10分攪拌し溶解させ、次にその混合溶液に色素としてPt(TFPP)75mg(FrontierScientific PorphrinProducts社製)を加え25度で10分攪拌し溶解させ調整した。酸素消光性塗料Bは、酸素消光性塗料Aに撥水剤としてアクリル系樹脂とフッ素系樹脂の混合物であるモディパー(登録商標)FS720を1.5g加え25度で10分攪拌し溶解させ調整した。塗布方法は、酸素消光性塗料Aを充填したエアスプレーガンを用いて酸素ガス流路30内側面に塗布する際に、酸素ガス流路30の幅dに対して1/2の大きさのマスキングテープにより酸素消光性塗料Bを塗布する箇所を確保し、酸素消光性塗料Aを充填したエアスプレーガンを用いて酸素ガス流路30内側面に塗布した後、マスキングテープを剥がし、その箇所に酸素消光性塗料Bを充填したエアスプレーガンを用いて塗布した。さらに塗布後、高温槽にて酸素雰囲気下110℃、60分の条件でアニール処理を行った。以上により燃料電池セル用の酸素濃度計測装置を作成した。
(Method for creating an oxygen concentration test device for fuel cells)
As shown in FIG. 4, the oxygen concentration measuring apparatus 1 uses NSPB 300A (wavelength 465 nm) of LED manufactured by Nichia Corporation as the light irradiation unit 10, Sensicam 1600 manufactured by PCO as the light emission measuring unit 16, and a light emission filter For No. 22, 645FG07-05 (center wavelength: 645 nm) manufactured by ISSI was used, and a personal computer was used as the processing unit 18. As shown in FIG. 3, the light-emitting unit 14 has an oxygen-quenching paint A and an oxygen-quenching paint B on the surface of the oxygen gas flow path 30 in the oxygen gas separator 26 using an acrylic resin transparent plate by an air spray gun. Formed. The coating thickness was 20 μm. Oxygen-quenching paint A was added with 5000 mg of polystyrene (produced by AVOCADO, weight average molecular weight 100000) as an oxygen-permeable polymer in 100 ml of toluene and dissolved by stirring at 25 degrees for 10 minutes. Pt (TFPP) 75 mg (manufactured by Frontier Scientific Porbrin Products) was added and stirred for 10 minutes at 25 ° C. to dissolve and adjust. The oxygen-quenching paint B was prepared by adding 1.5 g of MODIPER (registered trademark) FS720, which is a mixture of an acrylic resin and a fluororesin, as a water repellent to the oxygen-quenching paint A and stirring it at 25 ° C. for 10 minutes for dissolution. . When applying to the inner surface of the oxygen gas flow channel 30 using an air spray gun filled with the oxygen quenching paint A, the coating method is a masking that is ½ the width d of the oxygen gas flow channel 30. After securing the location where the oxygen-quenching paint B is applied with a tape and applying it to the inner surface of the oxygen gas flow path 30 using an air spray gun filled with the oxygen-quenching paint A, the masking tape is peeled off and oxygen is applied to the location. It applied using the air spray gun with which the quenching paint B was filled. Further, after the coating, annealing was performed in a high-temperature bath under an oxygen atmosphere at 110 ° C. for 60 minutes. Thus, an oxygen concentration measuring device for fuel cells was created.

(撥水剤を含有した酸素消光性塗料と撥水剤を含有していない酸素消光性塗料の酸素濃度試験)
撥水剤を含有していない酸素消光性塗料(上記酸素消光性塗料A)と撥水剤を含有した酸素消光性塗料(上記酸素消光性塗料B)をそれぞれ被着体としてガラス基板上に塗布し(発光部)、その他上記酸素濃度計測装置1と同様の装置を用いて酸素濃度を測定した。測定条件は、温度297Kで、圧力を100kPa,120kPa,160kPa,180kPa,200kPa,220kPa,240kPaまで変えたときの、100kPa(Pref)の発光強度(Iref)を基準とした発光強度比(Iref/I)を測定し、圧力感度(P/Pref)に影響がないことを確認した。Pは上記各圧力を表し、Iは各圧力での発光強度を表す。
(Oxygen concentration test of oxygen quenching paint containing water repellent and oxygen quenching paint containing no water repellent)
An oxygen-quenching paint that does not contain a water repellent (the oxygen-quenching paint A) and an oxygen-quenching paint that contains a water-repellent agent (the oxygen-quenching paint B) are applied as adherends to a glass substrate. Then, the oxygen concentration was measured using the same device as the oxygen concentration measuring device 1 described above. The measurement conditions were a temperature of 297 K and a light emission intensity ratio (Iref / I) based on a light emission intensity (Iref) of 100 kPa (Pref) when the pressure was changed to 100 kPa, 120 kPa, 160 kPa, 180 kPa, 200 kPa, 220 kPa, and 240 kPa. ) Was measured and it was confirmed that there was no effect on pressure sensitivity (P / Pref). P represents each pressure described above, and I represents the light emission intensity at each pressure.

撥水剤を含有しても酸素消光性塗料の発光強度に影響はなく、撥水剤含有酸素消光性塗料と撥水剤を含有していない酸素消光性塗料の酸素濃度検出感度に差は生じなかった。   Even if it contains a water repellent, it does not affect the emission intensity of the oxygen-quenching paint, and there is a difference in the oxygen concentration detection sensitivity between the water-repellent-containing oxygen-quenching paint and the oxygen-quenching paint that does not contain a water repellent. There wasn't.

本発明の実施形態に係る酸素濃度計測装置1の構成の一例を示す概略図である。It is the schematic which shows an example of a structure of the oxygen concentration measuring apparatus 1 which concerns on embodiment of this invention. 本発明の他の実施形態に係る酸素濃度計測装置の構成の一例を示す概略図である。It is the schematic which shows an example of a structure of the oxygen concentration measuring device which concerns on other embodiment of this invention. 酸素ガス流路30内に形成した発光部14の構成の1例として、図2の矢印aに沿って切断した断面を矢印b方向から見た酸素ガス流路30の一部を表したものである。As an example of the configuration of the light emitting section 14 formed in the oxygen gas flow path 30, a part of the oxygen gas flow path 30 as viewed from the direction of the arrow b is shown as a section cut along the arrow a in FIG. is there. 燃料電池セル用の酸素濃度計測装置を示す図である。It is a figure which shows the oxygen concentration measuring apparatus for fuel cells.

符号の説明Explanation of symbols

1 酸素濃度計測装置、3 燃料電池セル、10 光照射部、12 被着体、14 発光部、16 発光計測部、18 処理部、20 制御部、22 発光フィルタ、24 MEA、26 酸素ガスセパレータ、28 水素ガスセパレータ、30 酸素ガス流路、32 酸素ガス入口、34酸素ガス出口。   DESCRIPTION OF SYMBOLS 1 Oxygen concentration measuring device, 3 Fuel cell, 10 Light irradiation part, 12 Adhering body, 14 Light emission part, 16 Light emission measurement part, 18 Processing part, 20 Control part, 22 Light emission filter, 24 MEA, 26 Oxygen gas separator, 28 hydrogen gas separator, 30 oxygen gas flow path, 32 oxygen gas inlet, 34 oxygen gas outlet.

Claims (5)

励起光によって発光する色素とバインダとしての酸素透過性高分子とを含む酸素消光性塗料において、
前記酸素透過性高分子の重量平均分子量が80000〜300000の範囲であることを特徴とする酸素消光性塗料。
In an oxygen quenching paint containing a dye that emits light by excitation light and an oxygen permeable polymer as a binder,
An oxygen-quenching paint, wherein the oxygen-permeable polymer has a weight average molecular weight in the range of 80,000 to 300,000.
請求項1記載の酸素消光性塗料であって、さらに撥水剤を含有することを特徴とする酸素消光性塗料。   The oxygen-quenching paint according to claim 1, further comprising a water repellent. 被着体に励起光によって発光する色素とバインダとしての酸素透過性高分子とを含む酸素消光性塗料を塗布した発光部と、前記発光部に対して励起光を照射する光照射部と、前記発光部の発光強度を計測する発光計測部と、前記発光計測部によって計測された前記発光部の発光強度から酸素濃度を算出する処理部と、を備え、
前記酸素透過性高分子の重量平均分子量が80000〜300000の範囲であることを特徴とする酸素濃度計測装置。
A light-emitting part in which an oxygen quenching paint including a dye that emits light by excitation light and an oxygen-permeable polymer as a binder is applied to an adherend; a light irradiation part that irradiates the light-emitting part with excitation light; and A light emission measuring unit for measuring the light emission intensity of the light emitting unit, and a processing unit for calculating an oxygen concentration from the light emission intensity of the light emitting unit measured by the light emission measuring unit,
A weight average molecular weight of the oxygen permeable polymer is in the range of 80000-300000.
請求項3記載の酸素濃度計測装置であって、前記酸素消光性塗料は撥水剤をさらに含有することを特徴とする酸素濃度計測装置。   4. The oxygen concentration measuring apparatus according to claim 3, wherein the oxygen quenching paint further contains a water repellent. 請求項3及び4記載の酸素濃度計測装置であって、前記発光部にアニール処理が行われることを特徴とする酸素濃度計測装置。   5. The oxygen concentration measuring apparatus according to claim 3, wherein an annealing process is performed on the light emitting portion.
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JP2013053901A (en) * 2011-09-02 2013-03-21 Gunma Univ Oxygen sensor based on ratio measurement
JP2014118551A (en) * 2012-12-19 2014-06-30 Tohoku Univ Porous structure, oxygen sensor and separation membrane using the same, and method for producing porous structure
JP2014203559A (en) * 2013-04-02 2014-10-27 株式会社島津製作所 Fuel cell and oxygen concentration measuring device using the same
JP2021196206A (en) * 2020-06-10 2021-12-27 株式会社オートマチック・システムリサーチ Element for oxygen gas concentration measurement and sensor provided with element

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013053901A (en) * 2011-09-02 2013-03-21 Gunma Univ Oxygen sensor based on ratio measurement
JP2014118551A (en) * 2012-12-19 2014-06-30 Tohoku Univ Porous structure, oxygen sensor and separation membrane using the same, and method for producing porous structure
JP2014203559A (en) * 2013-04-02 2014-10-27 株式会社島津製作所 Fuel cell and oxygen concentration measuring device using the same
JP2021196206A (en) * 2020-06-10 2021-12-27 株式会社オートマチック・システムリサーチ Element for oxygen gas concentration measurement and sensor provided with element
JP7295574B2 (en) 2020-06-10 2023-06-21 株式会社オートマチック・システムリサーチ Oxygen gas concentration measuring element and sensor provided with the element

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