JP2015226906A - Method of evaluating filter - Google Patents
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- JP2015226906A JP2015226906A JP2015140479A JP2015140479A JP2015226906A JP 2015226906 A JP2015226906 A JP 2015226906A JP 2015140479 A JP2015140479 A JP 2015140479A JP 2015140479 A JP2015140479 A JP 2015140479A JP 2015226906 A JP2015226906 A JP 2015226906A
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- 238000000034 method Methods 0.000 title claims description 28
- 239000002245 particle Substances 0.000 claims abstract description 56
- 239000002923 metal particle Substances 0.000 claims abstract description 54
- 239000000706 filtrate Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 104
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 61
- 239000010931 gold Substances 0.000 claims description 58
- 229910052737 gold Inorganic materials 0.000 claims description 57
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 52
- 229910017604 nitric acid Inorganic materials 0.000 claims description 52
- 239000012488 sample solution Substances 0.000 claims description 20
- 238000011156 evaluation Methods 0.000 claims description 14
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- 238000010438 heat treatment Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 39
- 239000002105 nanoparticle Substances 0.000 description 38
- 239000011259 mixed solution Substances 0.000 description 32
- 239000003446 ligand Substances 0.000 description 22
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- GWOLZNVIRIHJHB-UHFFFAOYSA-N 11-mercaptoundecanoic acid Chemical compound OC(=O)CCCCCCCCCCS GWOLZNVIRIHJHB-UHFFFAOYSA-N 0.000 description 13
- 238000005259 measurement Methods 0.000 description 11
- 239000011550 stock solution Substances 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 10
- AGBQKNBQESQNJD-SSDOTTSWSA-N (R)-lipoic acid Chemical compound OC(=O)CCCC[C@@H]1CCSS1 AGBQKNBQESQNJD-SSDOTTSWSA-N 0.000 description 8
- AGBQKNBQESQNJD-UHFFFAOYSA-N alpha-Lipoic acid Natural products OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 description 8
- 235000019136 lipoic acid Nutrition 0.000 description 8
- 229960002663 thioctic acid Drugs 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007781 pre-processing Methods 0.000 description 6
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
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- 238000004090 dissolution Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 238000007865 diluting Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- 229920006393 polyether sulfone Polymers 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000012207 quantitative assay Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
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- QGLWBTPVKHMVHM-MDZDMXLPSA-N (e)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C\CCCCCCCCN QGLWBTPVKHMVHM-MDZDMXLPSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- -1 IPA Chemical compound 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
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- 229920000126 latex Polymers 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 description 1
- 235000019392 nitrosyl chloride Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010206 sensitivity analysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
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- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
本発明は、金属粒子を添加した試料液をろ過し、得られたろ過液中の金属粒子の量に基づき、フィルターの除粒子性能を評価する方法に関する。 The present invention relates to a method for filtering a sample solution to which metal particles are added and evaluating the particle removal performance of a filter based on the amount of metal particles in the obtained filtrate.
半導体デバイスなどの製造工程において利用される純水やアルコールなどの液中の微粒子は、歩留まりを低下させる直接的な原因となるため厳しく管理されている。デバイスの設計寸法が小さくなるに従って、問題となる微粒子サイズも小さくなる。ＩＴＲＳ（International Technology Roadmap for Semiconductors）によると２０１０年のＤＲＡＭハーフピッチ寸法は、４５ｎｍであり、今後さらに微細化が進むと予想され、従って管理微粒子サイズもより小さくなると考えられる。実際に、ＩＴＲＳ２００８からは、分析上の課題が克服されていない中でも、純水中の微粒子に関しては、「Critical particle size」という管理項目が追加されている。そして、ＩＴＲＳ２０１０では、２０１１年には２０ｎｍ、２０１７年には１０ｎｍサイズの微粒子を、４個／ｍＬレベルで管理する指針が示されている。同様に、ＩＰＡ（イソプロピルアルコール）中の微粒子に関しても２０１１年には２０ｎｍサイズの微粒子を１．０Ｅ＋０４（１０，０００）個／ｍＬレベルでの管理することが求められている。 Fine particles in liquids such as pure water and alcohol used in the manufacturing process of semiconductor devices and the like are strictly controlled because they directly cause a decrease in yield. As device design dimensions decrease, the problem particle size also decreases. According to ITRS (International Technology Roadmap for Semiconductors), the DRAM half-pitch size in 2010 is 45 nm, and further miniaturization is expected in the future. Actually, from the ITRS 2008, a management item “Critical particle size” has been added for fine particles in pure water, even though analytical problems have not been overcome. In ITRS 2010, a guideline for managing fine particles having a size of 20 nm in 2011 and 10 nm in 2017 at a level of 4 particles / mL is shown. Similarly, regarding the fine particles in IPA (isopropyl alcohol), in 2011, it is required to manage fine particles having a size of 20 nm at a level of 1.0E + 04 (10,000) / mL.
液中の微粒子数を高度に維持管理するためには、精密ろ過膜（以下、ＭＦ膜（という）や、限外ろ過膜（以下、ＵＦ膜という）などのフィルターが利用されている。一般的に、ＭＦ膜では標準粒子としてＰＳＬ（Polystyrene Latex）のような固体球状粒子を用いてその除去率が９９％程度であるところをもって定格ろ過精度（μｍ）と称している。一方、ＵＦ膜では、タンパク質などの指標物質を用いてろ過を行い、阻止率が９０％に相当する分子量を持って分画分子量としている。従って、両者の分離性能指標をそのまま比較することはできない。しかしながら、最近では半導体業界向けＭＦ膜におけるレーティングが粒子径３０ｎｍ以下に達してきており、事実上ＵＦ膜のレーティングと重なってきている。また、標準粒子としてのＰＳＬ粒子の粒子径下限が２０ｎｍ程度であることなどから、粒子径３０ｎｍ以下の微粒子除去用フィルターに対する新しい除粒子性能評価方法が求められている。 Filters such as microfiltration membranes (hereinafter referred to as MF membranes) and ultrafiltration membranes (hereinafter referred to as UF membranes) are used for highly maintaining and managing the number of fine particles in the liquid. In addition, the MF membrane uses solid spherical particles such as PSL (Polystyrene Latex) as standard particles, and the removal rate is about 99%, which is referred to as the rated filtration accuracy (μm). Filtration is carried out using an indicator substance such as protein, and the molecular weight corresponding to a blocking rate of 90% is used as the fractional molecular weight, so it is not possible to compare the separation performance indicators as they are. The rating of MF membranes for industry has reached a particle size of 30 nm or less, and is effectively overlapping with the rating of UF membranes. Therefore, there is a need for a new particle removal performance evaluation method for fine particle removal filters having a particle diameter of 30 nm or less.
そこで、近年、粒子径３０ｎｍ以下のサイズの微粒子除去用フィルターに対する除粒子性能評価方法として、非特許文献１に挙げられるような金属微粒子を用いた新たな手法が提案されている。この手法では、金ナノ粒子をチャレンジ粒子として、ＤＬＳ（動的光散乱法）やＩＣＰ−ＭＳ（誘導結合プラズマ質量分析装置）を測定装置として用いることでフィルターの除粒子性能を求めている。中でも、保護配位子を変化させることにより金ナノ粒子の親水性／疎水性、およびカチオン性／アニオン性をコントロールし、フィルター（ろ過膜）の吸着特性も評価している。 Therefore, in recent years, a new method using metal fine particles as described in Non-Patent Document 1 has been proposed as a particle removal performance evaluation method for a fine particle removal filter having a particle size of 30 nm or less. In this method, the particle removal performance of the filter is obtained by using gold nanoparticles as challenge particles and using DLS (dynamic light scattering method) or ICP-MS (inductively coupled plasma mass spectrometer) as a measuring device. Above all, the hydrophilic / hydrophobic and cationic / anionic properties of the gold nanoparticles are controlled by changing the protective ligand, and the adsorption characteristics of the filter (filtration membrane) are also evaluated.
ここで、金の高感度分析手法として、ウエハ状の金（金属）分析についての提案もある。特許文献１では、シリコン基板表面を汚染した金、白金、銀、銅の分析において、基板表面にフッ酸蒸気を噴射した後、王水を滴下して基板上の不純物を分解し、その分解回収液を回収して原子吸光分析により分析する方法が開示されている。 Here, there is also a proposal for wafer-like gold (metal) analysis as a high-sensitivity analysis method for gold. In Patent Document 1, in analysis of gold, platinum, silver, and copper contaminating the silicon substrate surface, hydrofluoric acid vapor is sprayed on the substrate surface, and then aqua regia is dropped to decompose impurities on the substrate, and the decomposition and recovery thereof A method is disclosed in which the liquid is collected and analyzed by atomic absorption spectrometry.
また、特許文献２では、シリコンウエハ表面の白金などの金属汚染に対して、ウエハ表面を、王水を純水で希釈して調整した希王水に所定の時間接触させた後、希王水を回収し、これを蒸発乾固して硝酸等に再溶解させ、ＩＣＰ−ＭＳ又は原子吸光分析（Atomic Absorption Spectrometry : AAS）により金属を定量する方法が開示されている。 Further, in Patent Document 2, against the metal contamination such as platinum on the surface of the silicon wafer, the wafer surface is brought into contact with a rare water prepared by diluting aqua regia with pure water for a predetermined time, Is recovered, evaporated to dryness, redissolved in nitric acid or the like, and a method for quantifying the metal by ICP-MS or atomic absorption spectrometry (AAS) is disclosed.
しかし、上記非特許文献１のフィルターの除粒子性能を求める方法に関しては、ＩＣＰ−ＭＳに微粒子状態の金が直接導入された場合、その分散性のばらつきなどにより測定値が変動してしまい、正確な分析値が得られない可能性がある。その結果、フィルターの除粒子性能を正確に評価できない場合が生じ得る。 However, regarding the method for obtaining the particle removal performance of the filter described in Non-Patent Document 1, when gold in a fine particle state is directly introduced into ICP-MS, the measured value fluctuates due to dispersion in the dispersibility and the like. It may not be possible to obtain accurate analysis values. As a result, it may occur that the particle removal performance of the filter cannot be accurately evaluated.
特に、微粒子濃度が低濃度におけるフィルターの除粒子性能を評価する際には、フィルター後のろ過液中の金ナノ粒子濃度がより低濃度になるため、高感度に定量する方法が必要となる。 In particular, when evaluating the particle removal performance of a filter at a low concentration of fine particles, the gold nanoparticle concentration in the filtrate after the filter becomes lower, so a method for quantitative determination with high sensitivity is required.
また、特許文献１および特許文献２における分析は、基板を汚染している金属の分析であり、フィルターの除粒子性能評価とは、目的が異なっており、フィルターの吸着特性などについて考慮しようとする考え方もない。 Further, the analysis in Patent Document 1 and Patent Document 2 is an analysis of a metal that contaminates a substrate, and its purpose is different from the evaluation of the particle removal performance of the filter. There is no way of thinking.
本発明は、低濃度の微粒子を精度良く定量し、フィルターの除粒子性能を正確に評価することを目的とする。 An object of the present invention is to accurately quantify low-concentration fine particles and accurately evaluate the particle removal performance of a filter.
本発明は、媒質液に金属粒子を添加して分散させて試料液を調製する工程と、試料液を評価対象のフィルターに流通して、ろ過液を得る工程と、ろ過液を採取する工程と、採取したろ過液中の金属粒子を薬液に溶解して溶解液を得る工程と、得られた溶解液についてＩＣＰ−ＭＳによって分析し、採取したろ過液中の金属粒子の量を検出する工程と、を含み、得られたろ過液中の金属粒子の量に基づき、前記フィルターを評価することを特徴とする。 The present invention includes a step of preparing a sample solution by adding and dispersing metal particles in a medium solution, a step of distributing the sample solution to a filter to be evaluated to obtain a filtrate, and a step of collecting the filtrate. A step of dissolving a metal particle in the collected filtrate in a chemical solution to obtain a solution, a step of analyzing the obtained solution by ICP-MS, and detecting an amount of the metal particles in the collected filtrate; The filter is evaluated based on the amount of metal particles in the obtained filtrate.
また、前記媒質液は、水溶液であることが好適である。 The medium liquid is preferably an aqueous solution.
また、前記金属粒子は、金粒子であることが好適である。 The metal particles are preferably gold particles.
また、前記金属粒子の粒径は、３０ｎｍ以下であることが好適である。 The metal particles preferably have a particle size of 30 nm or less.
また、前記薬液は、硝酸と、塩酸または塩化物と、を混合して調整されていることが好適である。 The chemical solution is preferably prepared by mixing nitric acid with hydrochloric acid or chloride.
また、前記採取したろ過液について、加熱処理を施す工程をさらに有し、前記溶解液を得る工程では、加熱処理したものに前記薬液を混合して前記溶解液を得ることが好適である。 The collected filtrate further includes a step of performing a heat treatment, and in the step of obtaining the solution, it is preferable to obtain the solution by mixing the chemical solution with the heat-treated product.
また、前記加熱処理は、前記媒質液を蒸発させて金属粒子の残渣物を得る処理であり、前記溶解液を得る工程では、得られた残渣物を薬液で溶解することが好適である。 The heat treatment is a treatment for evaporating the medium liquid to obtain a residue of metal particles. In the step of obtaining the solution, it is preferable to dissolve the obtained residue with a chemical solution.
また、前記溶解液を得る工程では、超音波振動を与えながら前記残渣物を薬液で溶解することが好適である。 In the step of obtaining the dissolution liquid, it is preferable to dissolve the residue with a chemical solution while applying ultrasonic vibration.
また、前記試料液中の金属粒子の量を計測し、（ろ過液中の金属粒子の量）／（試料液中の金属粒子の量）によりろ過膜における粒子除去性能を評価することが好適である。 It is also preferable to measure the amount of metal particles in the sample solution and evaluate the particle removal performance in the filtration membrane by (amount of metal particles in the filtrate) / (amount of metal particles in the sample solution). is there.
本発明によれば、金属粒子を用いて、フィルターの除粒子性能を効果的に評価することができる。 According to the present invention, the particle removal performance of a filter can be effectively evaluated using metal particles.
以下、本発明の実施形態について、図面に基づいて説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
図１は、フィルター１８を評価するための処理システムの概要を示す図である。まず、貯槽１０に、水溶液に金属粒子を添加混合して、金属粒子を分散させた試料液を調整する。水溶液としては、超純水が使用され、これに金ナノ粒子が分散される。特に、金属粒子として、粒子径３０ｎｍ以下の金ナノ粒子を用いることが好適であり、粒子径が、３０ｎｍ、２０ｎｍ、１０ｎｍなどの金ナノ粒子を用いることができる。 FIG. 1 is a diagram showing an outline of a processing system for evaluating the filter 18. First, a sample solution in which metal particles are dispersed is prepared by adding metal particles to an aqueous solution in the storage tank 10. As the aqueous solution, ultrapure water is used, and gold nanoparticles are dispersed therein. In particular, it is preferable to use gold nanoparticles having a particle diameter of 30 nm or less as the metal particles, and gold nanoparticles having a particle diameter of 30 nm, 20 nm, 10 nm, or the like can be used.
また、貯槽１０には、超音波照射装置１２が設けられており、超音波の照射によって金属粒子が水溶液中に確実に分散される。超音波照射装置１２は、各種液体等の混合用のものを適宜採用することができる。 Further, the storage tank 10 is provided with an ultrasonic irradiation device 12, and the metal particles are reliably dispersed in the aqueous solution by the ultrasonic irradiation. As the ultrasonic irradiation device 12, a device for mixing various liquids or the like can be appropriately employed.
貯槽１０内の試料液は、ポンプ１４により、バルブ１６を介し、フィルター１８に供給される。なお、フィルター１８に供給される試料液の圧力は圧力計２０で計測され、フィルター１８における圧損などをチェックする。 The sample liquid in the storage tank 10 is supplied to the filter 18 via the valve 16 by the pump 14. Note that the pressure of the sample liquid supplied to the filter 18 is measured by the pressure gauge 20, and pressure loss in the filter 18 is checked.
フィルター１８は、評価対象である、ＭＦ膜、ＵＦ膜などのろ過膜を利用したものであり、例えば高分子ろ過膜によって原液側とろ過液側が仕切られており、ろ過膜によって原液中の微粒子がろ過除去される。 The filter 18 uses a filtration membrane such as an MF membrane or a UF membrane to be evaluated. For example, the polymer solution membrane separates the stock solution side from the filtrate side, and fine particles in the stock solution are separated by the filtration membrane. Filtered off.
そして、フィルター１８への供給路からバルブ２２を介し、サンプリングされ、前処理手段Ｓ１に供給される。また、フィルター１８で得られたろ液がサンプリングされて前処理手段Ｓ２に供給される。そして、前処理手段Ｓ１，Ｓ２で前処理された、試料液、ろ液が適宜ＩＣＰ−ＭＳ２６に供給され、ここで金属粒子濃度が定量分析される。 Then, the sample is sampled from the supply path to the filter 18 through the valve 22 and supplied to the preprocessing means S1. Further, the filtrate obtained by the filter 18 is sampled and supplied to the pretreatment means S2. Then, the sample solution and filtrate pretreated by the pretreatment means S1 and S2 are appropriately supplied to the ICP-MS 26, where the metal particle concentration is quantitatively analyzed.
ここで、前処理手段Ｓ１，Ｓ２について、図２，３に基づいて説明する。図２は、前処理手段Ｓ１，Ｓ２の一例を示すものである。この例では、サンプリングした被測定液（試料液またはろ液）に薬液を添加する。この薬液は、金属粒子を溶解させるためのものであり、金属粒子として金ナノ粒子を用いた場合には、硝酸と塩酸の混合溶液（濃硝酸に濃塩酸を混合したいわゆる王水など）が好適であるが、塩酸に代えて塩化物を用いる硝酸と塩化物の混合液を用いることもできる。 Here, pre-processing means S1 and S2 will be described with reference to FIGS. FIG. 2 shows an example of the preprocessing means S1 and S2. In this example, a chemical solution is added to the sampled solution to be measured (sample solution or filtrate). This chemical solution is for dissolving metal particles. When gold nanoparticles are used as the metal particles, a mixed solution of nitric acid and hydrochloric acid (so-called aqua regia in which concentrated hydrochloric acid is mixed with concentrated nitric acid) is suitable. However, it is also possible to use a mixed solution of nitric acid and chloride using chloride instead of hydrochloric acid.
すなわち、金を溶解するのは、濃硝酸（ＨＮＯ３）と濃塩酸（ＨＣｌ）が反応して生ずるＮＯＣｌと、Ｃｌ２である。従って、王水に限らずＮＯ３とＣｌを生ずる組み合わせでも可能であり、例えば濃ＨＮＯ３＋ＮａＣｌ／ＮＨ４Ｃｌや、ＮａＮＯ３＋濃ＨＣｌなどを利用することもできる。 That is, gold is dissolved by NOCl and Cl 2 produced by the reaction of concentrated nitric acid (HNO 3 ) and concentrated hydrochloric acid (HCl). Therefore, not only aqua regia but also a combination that generates NO 3 and Cl is possible, and for example, concentrated HNO 3 + NaCl / NH 4 Cl, NaNO 3 + concentrated HCl, or the like can be used.
このように、被測定液に薬液を混合することで、被測定液中の金属粒子（金ナノ粒子）が溶解し、均質な液となる。そして、このように金属粒子が溶解された測定溶液をＩＣＰ−ＭＳ２６で定量分析する。これによって、測定溶液中の溶解金属の濃度を検出することができ、薬液の添加量を考慮して換算することで、溶解液中の金属粒子濃度を定量することができる。 In this way, by mixing the chemical solution with the liquid to be measured, the metal particles (gold nanoparticles) in the liquid to be measured are dissolved, and a homogeneous liquid is obtained. Then, the measurement solution in which the metal particles are dissolved in this way is quantitatively analyzed by ICP-MS26. Thereby, the concentration of the dissolved metal in the measurement solution can be detected, and the metal particle concentration in the solution can be quantified by performing conversion in consideration of the amount of the chemical solution added.
さらに、フィルターにおける処理において、金属粒子と、フィルターの吸着作用がろ過性能に影響を及ぼす。すなわち、試料液に混合されている金属粒子について吸着能力があれば、金属粒子の除去性能は高くなる。しかし、試料液中の金属粒子は、標準粒子であって、実際に除去対象とする粒子ではない。従って、フィルターの除粒子性能の評価を行うのであれば、吸着作用のない場合のろ過性能を評価することが好ましい。 Further, in the processing in the filter, the metal particles and the adsorption action of the filter affect the filtration performance. That is, if the metal particles mixed in the sample solution have an adsorption capability, the metal particle removal performance is enhanced. However, the metal particles in the sample liquid are standard particles and are not actually particles to be removed. Therefore, if the particle removal performance of the filter is evaluated, it is preferable to evaluate the filtration performance when there is no adsorption action.
そこで、金属粒子について保護配位子によりその表面状態を調整し、フィルターにおける吸着作用のない状態でのろ過性能を評価することが好ましい。 Therefore, it is preferable to adjust the surface state of the metal particles with a protective ligand and evaluate the filtration performance in a state where there is no adsorption action in the filter.
図３には、他の前処理例が示されている。この例では、サンプリングした被測定液は、まず加熱乾固される。すなわち、容器に入れた被測定液を１００°Ｃ程度に加熱して、水分を蒸発させ、金属粒子を残渣物として乾固する。次に、残渣物に薬液を添加して、金属粒子からなる残渣物を薬液に溶解しＩＣＰ−ＭＳ２６により測定する測定溶液を得る。そして、得られた測定溶液をＩＣＰ−ＭＳ２６によって定量する。このように加熱乾固工程を設けることによって、金属粒子の濃度が低濃度であっても、ＩＣＰ−ＭＳ２６で定量するときには、高濃度化でき、定量の精度を上げることができる。試料液について、図２の手法によって分析を行い、ろ液について図３に示す加熱乾固工程を含む手法によって分析を行うことも好適である。 FIG. 3 shows another example of preprocessing. In this example, the sampled liquid to be measured is first heated and dried. That is, the liquid to be measured placed in the container is heated to about 100 ° C. to evaporate the water and dry the metal particles as a residue. Next, a chemical solution is added to the residue, and the residue consisting of metal particles is dissolved in the chemical solution to obtain a measurement solution that is measured by ICP-MS26. And the obtained measurement solution is quantified by ICP-MS26. By providing the heating and drying step in this way, even when the concentration of the metal particles is low, when quantifying with the ICP-MS 26, the concentration can be increased and the accuracy of quantification can be increased. It is also preferable to analyze the sample solution by the method of FIG. 2 and analyze the filtrate by the method including the heating and drying step shown in FIG.
なお、ＩＣＰ−ＭＳ２６は、市販のものを利用することができ、特別な手法を用いなくても定量分析を行うことが可能である。複数の濃度の標準試料を用い、カウント値（ＣＰＳ）と金属粒子濃度の検量線を作成しておき、実際の測定の際に得られたカウント値を濃度に換算する。 Note that a commercially available ICP-MS 26 can be used, and quantitative analysis can be performed without using a special technique. Using a standard sample having a plurality of concentrations, a calibration curve of the count value (CPS) and the metal particle concentration is prepared, and the count value obtained in the actual measurement is converted into the concentration.
また、ろ過の原液について、ＩＰＡなどのアルコールを採用し、アルコール中の微粒子の除去性能を評価することも行われる。この場合には、チャレンジ粒子をＩＰＡ中に分散させ、これを定量する必要がある。この場合は、アルコールを蒸発させて、金属粒子を加熱乾固して残渣物を得、得られた残渣物を王水等の薬液で溶解させる。そして、溶解液を必要に応じて希釈し、これをＩＣＰ−ＭＳで分析する。 Moreover, alcohol, such as IPA, is employ | adopted about the undiluted | stock solution of filtration, and evaluation of the removal performance of the microparticles | fine-particles in alcohol is also performed. In this case, it is necessary to disperse the challenge particles in IPA and quantify them. In this case, the alcohol is evaporated, the metal particles are heated to dryness to obtain a residue, and the obtained residue is dissolved with a chemical solution such as aqua regia. And a solution is diluted as needed and this is analyzed by ICP-MS.
この際、上述したように、金属粒子について保護配位子により表面を修飾する場合がある。このような金属粒子の表面状態の調整については、非特許文献２，３等に記載があり、本実施例についても、同様の手法が利用できる。 At this time, as described above, the surface of the metal particles may be modified with a protective ligand. Such adjustment of the surface state of the metal particles is described in Non-Patent Documents 2 and 3 and the like, and the same method can be used for this embodiment.
また、金を表面修飾する際に用いられる配位子としては、MEA(2-mercaptoethanoic Acid)、MPA(3-mercaptopropanoic acid)、TA(thioctic acid)、11-MUDA(11-mercaptoundecanoic acid)、Oleylamine(9-octadecenylamine)、1-Dodecanethiol等が挙げられる。 In addition, as ligands used for surface modification of gold, MEA (2-mercaptoethanoic acid), MPA (3-mercaptopropanoic acid), TA (thioctic acid), 11-MUDA (11-mercaptoundecanoic acid), Oleylamine (9-octadecenylamine), 1-Dodecanethiol and the like.
そして、保護配位子を用いて金属粒子に表面修飾を行った場合に、金属粒子の残渣物の硝酸と塩酸の混合溶液等の薬液への溶解しやすさが、異なってくる。例えば、ＩＰＡ中で、保護配位子によって疎水性の表面修飾を行った場合、親水性の表面修飾を行う場合に比べ、高濃度の硝酸と塩酸の混合溶液によって金属粒子の溶解回収を行うことが好適である。また、溶解を促進するために、超音波照射時間を比較的長くするとよい。 When surface modification is performed on metal particles using a protective ligand, the ease of dissolution of metal particle residues in a chemical solution such as a mixed solution of nitric acid and hydrochloric acid differs. For example, when hydrophobic surface modification is performed with a protective ligand in IPA, metal particles are dissolved and recovered with a mixed solution of nitric acid and hydrochloric acid at a higher concentration than when hydrophilic surface modification is performed. Is preferred. Further, in order to promote dissolution, it is preferable to make the ultrasonic irradiation time relatively long.
例えば、超音波照射時間を一定として硝酸と塩酸の混合溶液の濃度を高くすると、これによって残渣物中の金属粒子の回収率が向上する。また、硝酸と塩酸の混合溶液の濃度を一定として、超音波照射時間を変更した場合、回収率が向上する。例えば、ＩＰＡ中の金ナノ粒子であって、チオクト酸や、１０−カルボキシ−1−デカンチオールなどで表面修飾を行った場合、硝酸と塩酸の混合溶液について、硝酸濃度（ａｓＨＮＯ３）が１．５ｗｔ％かつ塩酸濃度（ａｓＨＣｌ）が２．３ｗｔ％未満になると、回収率が低く、また硝酸濃度（ａｓＨＮＯ３）が７．５ｗｔ％かつ塩酸濃度（ａｓＨＣｌ）が１１．３ｗｔ％以上としても、回収率に変化はない。従って、硝酸と塩酸の混合溶液は、硝酸濃度（ａｓＨＮＯ３）１．５〜７．５ｗｔ％、塩酸濃度（ａｓＨＣｌ）２．３〜１１．３ｗｔ％の範囲とすることが好適である。なお、純水中の金ナノ粒子の場合、硝酸と塩酸の混合溶液は、硝酸濃度（ａｓＨＮＯ３）０．７５ｗｔ％、塩酸濃度（ａｓＨＣｌ）１．１５ｗｔ％程度でも、十分な回収率が得られる。 For example, when the concentration of the mixed solution of nitric acid and hydrochloric acid is increased while keeping the ultrasonic irradiation time constant, this improves the recovery rate of the metal particles in the residue. Further, when the concentration of the mixed solution of nitric acid and hydrochloric acid is kept constant and the ultrasonic irradiation time is changed, the recovery rate is improved. For example, when gold nanoparticles in IPA are surface-modified with thioctic acid or 10-carboxy-1-decanethiol, the nitric acid concentration (asHNO 3 ) of the mixed solution of nitric acid and hydrochloric acid is 1. When 5 wt% and hydrochloric acid concentration (asHCl) are less than 2.3 wt%, the recovery rate is low, and even when the nitric acid concentration (asHNO 3 ) is 7.5 wt% and the hydrochloric acid concentration (asHCl) is 11.3 wt% or more, recovery is possible. There is no change in rate. Therefore, it is preferable that the mixed solution of nitric acid and hydrochloric acid has a nitric acid concentration (asHNO 3 ) of 1.5 to 7.5 wt% and a hydrochloric acid concentration (asHCl) of 2.3 to 11.3 wt%. In the case of gold nanoparticles in pure water, a sufficient recovery rate can be obtained even if the mixed solution of nitric acid and hydrochloric acid has a nitric acid concentration (asHNO 3 ) of 0.75 wt% and a hydrochloric acid concentration (asHCl) of about 1.15 wt%. .
（１）微粒子状態の金の定量分析
図２に示す手法によって、金ナノ粒子の定量を行った。
(1) Quantitative analysis of gold in a fine particle state Gold nanoparticles were quantified by the technique shown in FIG.
金ナノ粒子原液（市販品：ＢＢＩ社製、粒子径２０ｎｍ）を目的値（Ｘｎｇ／Ｌ）になるように超純水で希釈した。この際、一定量の硝酸と塩酸の混合溶液を添加し、混合するために数分間超音波を照射した。この硝酸と塩酸の混合溶液を含む金ナノ粒子希釈溶液（測定溶液）に含まれる金の濃度をＩＣＰ−ＭＳ（横川アナリティカルシステムズ株式会社製、ＨＰ−４５００）で定量した。測定結果の濃度をＹｎｇ／Ｌとする。比較例として、金ナノ粒子原液に硝酸と塩酸の混合溶液を加えず超純水のみで希釈し、それ以外は上述と同様にして分析を行った。結果を表１，２に示す。 A gold nanoparticle stock solution (commercially available product: manufactured by BBI, particle diameter 20 nm) was diluted with ultrapure water so as to have a target value (Xng / L). At this time, a certain amount of a mixed solution of nitric acid and hydrochloric acid was added, and ultrasonic waves were applied for several minutes to mix. The concentration of gold contained in the gold nanoparticle diluted solution (measuring solution) containing the mixed solution of nitric acid and hydrochloric acid was quantified by ICP-MS (Yokogawa Analytical Systems, Inc., HP-4500). The concentration of the measurement result is Yng / L. As a comparative example, the gold nanoparticle stock solution was diluted with only ultrapure water without adding a mixed solution of nitric acid and hydrochloric acid, and the analysis was performed in the same manner as described above except for that. The results are shown in Tables 1 and 2.
なお、硝酸と塩酸の混合溶液については、硝酸（市販品：関東化学社製 Ultrapur、６1ｗｔ％（ａｓＨＮＯ３））と、塩酸（市販品：関東化学社製 Ultrapur、３１ｗｔ％（ａｓＨＣｌ））を体積比で１：３で混合したものを原液として用いた。 In addition, about the mixed solution of nitric acid and hydrochloric acid, nitric acid (commercial product: Ultrapur manufactured by Kanto Chemical Co., 61 wt% (asHNO 3 )) and hydrochloric acid (commercial product: Ultrapur manufactured by Kanto Chemical Co., 31 wt% (asHCl)) by volume The mixture at a ratio of 1: 3 was used as the stock solution.
表１より、本実施例では、目的濃度Ｘ：２８ｎｇ／Ｌに対して、測定値Ｙ：２５．１ｎｇ／Ｌ、ばらつき（標準偏差σ）３σ：１．５ｎｇ／Ｌとなり、精度よく分析されていることがわかる。一方、比較例では、目的濃度Ｘ：４０ｎｇ／Ｌに対して、測定値Ｙ：３５．５ｎｇ／Ｌ、ばらつき（標準偏差σ）３σ：２３．９ｎｇ／Ｌとなり、精度が実施例と比較して劣ることがわかった。 From Table 1, in this example, for the target concentration X: 28 ng / L, the measured value Y is 25.1 ng / L, the variation (standard deviation σ) is 3σ: 1.5 ng / L, and is analyzed with high accuracy. I understand that. On the other hand, in the comparative example, with respect to the target concentration X: 40 ng / L, the measured value Y is 35.5 ng / L, the variation (standard deviation σ) is 3σ: 23.9 ng / L, and the accuracy is compared with the example. I found it inferior.
また、表２より、各測定溶液における均一分散性を表すカウント値（ＣＰＳ）を見ても、本実施例では、５回の測定の全てにおいて安定した値であるの対して、比較例では５回測定の内、３回目と４回目の測定溶液ではＣＰＳがばらついてしまっていることがわかる。これは、測定溶液中に含まれる金ナノ粒子の分散状態が均一でなかったためと考えられる。 Also, from Table 2, the count value (CPS) representing the uniform dispersibility in each measurement solution is a stable value in all of the five measurements in this example, whereas it is 5 in the comparative example. It can be seen that CPS varies in the third and fourth measurement solutions among the repeated measurements. This is presumably because the dispersion state of the gold nanoparticles contained in the measurement solution was not uniform.
（２）金ナノ粒子の表面状態による回収率比較
図３に示す手法によって、金ナノ粒子の定量を行った。
(2) Comparison of recovery rate according to surface condition of gold nanoparticles Gold nanoparticles were quantified by the method shown in FIG.
金ナノ粒子原液（市販品：ＢＢＩ社製、粒子径３０ｎｍ）を一旦加熱乾固させた後、金ナノ粒子を含む残渣物を硝酸と塩酸の混合溶液で溶解し、得られた測定溶液をＩＣＰ−ＭＳによって定量した。なお、ここで使用した硝酸と塩酸の混合溶液原液は、（１）で使用したものと同じものを用いた。 A gold nanoparticle stock solution (commercial product: manufactured by BBI, particle size: 30 nm) was once heated to dryness, and then the residue containing gold nanoparticles was dissolved in a mixed solution of nitric acid and hydrochloric acid. -Quantified by MS. The mixed solution stock solution of nitric acid and hydrochloric acid used here was the same as that used in (1).
具体的には、まず超純水中に種々の金ナノ粒子（３０ｎｍ）を０．５ｎｇ／Ｌになるように添加した金ナノ粒子溶液を調整した。この際、異なる保護配位子によって表面を修飾した。具体的には、上記市販の金ナノ粒子自体は、すでに親水性の保護配位子によって表面修飾されているため、それを２つの疎水性の保護配位子によって表面修飾し、合計３つの表面状態に調整した。 Specifically, first, a gold nanoparticle solution in which various gold nanoparticles (30 nm) were added to ultrapure water so as to be 0.5 ng / L was prepared. At this time, the surface was modified with different protective ligands. Specifically, since the commercially available gold nanoparticle itself is already surface-modified with a hydrophilic protective ligand, it is surface-modified with two hydrophobic protective ligands, resulting in a total of three surfaces. Adjusted to the condition.
本実施例では、保護配位子としては、（ｉ）クエン酸（Citric acid）、（ｉｉ）チオクト酸（thioctic acid）、（ｉｉｉ）１０−カルボキシ−１−デカンチオール（10-Carboxy-1-decanethiol or 11-Mercaptoundecanoic acid）を利用した。 In this example, as the protective ligand, (i) citric acid, (ii) thioctic acid, (iii) 10-carboxy-1-decanethiol (10-Carboxy-1- decanethiol or 11-Mercaptoundecanoic acid) was used.
ここで、前述した通り、上記の金ナノ粒子原液（市販品：ＢＢＩ社製、粒子径３０ｎｍ）については、すでに親水性の（ｉ）クエン酸（Citric acid）で表面修飾されている。そこで、本実施例における親水性の保護配位子で表面修飾された金ナノ粒子としては、上記市販品をそのまま用いた。 Here, as described above, the gold nanoparticle stock solution (commercial product: manufactured by BBI, particle size: 30 nm) has already been surface-modified with hydrophilic (i) citric acid. Therefore, as the gold nanoparticles surface-modified with the hydrophilic protective ligand in this example, the above-mentioned commercially available product was used as it was.
また、上記の疎水性の保護配位子（ｉｉ），（ｉｉｉ）による金ナノ粒子の表面修飾については、具体的に以下の方法で行った。
（ｉｉ）チオクト酸（thioctic acid）による表面修飾方法
［１］ＢＢＩ社製金コロイド（３０ｎｍ，０．１ｗｔ％）を５ｍｌ分取する。
［２］金のモル数に対して１０倍モルとなるように調整したチオクト酸を４５ｍｌ添加する。
［３］１ＮのＮａＯＨにてｐＨ１１に調整する。
［４］１６時間攪拌する。
［５］遠心分離（１１８００ｒｐｍ，１０℃，１０分）により上澄み液を除く。
上記方法により、チオクト酸で表面修飾した金コロイド濃縮液約１ｗｔ％を得た。
（ｉｉｉ）１０−カルボキシ−１−デカンチオール（10-Carboxy-1-decanethiol or 11-Mercaptoundecanoic acid）による表面修飾方法
［１］上記（ｉｉ）により得られた金コロイド濃縮液について、さらに下記の操作を実施。
［２］金のモル数に対して２５倍モルとなるように調整した１０−カルボキシ−１−デカンチオールを４５ｍｌ添加する。
［３］１ＮのＮａＯＨにてｐＨ１１に調整する。
［４］１６時間攪拌する。
［５］遠心分離（１１８００ｒｐｍ，１０℃，１０分）により上澄み液を除く。
上記方法により、１０−カルボキシ−１−デカンチオールで表面修飾した金コロイド濃縮液約１ｗｔ％を得た。
The surface modification of the gold nanoparticles with the hydrophobic protective ligands (ii) and (iii) was specifically performed by the following method.
(Ii) Surface modification method with thioctic acid [1] 5 ml of a gold colloid (30 nm, 0.1 wt%) manufactured by BBI is taken.
[2] 45 ml of thioctic acid adjusted so as to be 10 times the mole of gold is added.
[3] Adjust to pH 11 with 1N NaOH.
[4] Stir for 16 hours.
[5] The supernatant is removed by centrifugation (11800 rpm, 10 ° C., 10 minutes).
By the above method, about 1 wt% of a colloidal gold concentrate surface-modified with thioctic acid was obtained.
(Iii) Surface modification method using 10-Carboxy-1-decanethiol or 11-Mercaptoundecanoic acid [1] The gold colloid concentrate obtained by (ii) above is further subjected to the following operations: Implemented.
[2] 45 ml of 10-carboxy-1-decanethiol adjusted so as to be 25 moles per mole of gold is added.
[3] Adjust to pH 11 with 1N NaOH.
[4] Stir for 16 hours.
[5] The supernatant is removed by centrifugation (11800 rpm, 10 ° C., 10 minutes).
By the above method, about 1 wt% of a colloidal gold concentrate surface-modified with 10-carboxy-1-decanethiol was obtained.
（ｉ）は親水性であり、溶液（液性）として超純水を利用した。配位子（ｉｉ），（ｉｉｉ）は比較的疎水性であり、溶液としてＩＰＡ（イソプロピルアルコール）を利用した。 (I) is hydrophilic, and ultrapure water was used as a solution (liquid property). The ligands (ii) and (iii) are relatively hydrophobic, and IPA (isopropyl alcohol) was used as a solution.
保護配位子で金ナノ粒子表面を修飾した金ナノ粒子を含む試料液を、加熱乾固し、金ナノ粒子を含む残渣物を析出させた。その後残渣物に所定量の硝酸と塩酸の混合溶液を加えてこれを溶解し、これに超純水を加えて希釈し、所定濃度として、ＩＣＰ−ＭＳで定量した。 A sample solution containing gold nanoparticles whose surface was modified with a protective ligand was heated and dried to precipitate a residue containing gold nanoparticles. Then, a predetermined amount of a mixed solution of nitric acid and hydrochloric acid was added to the residue to dissolve it, and ultrapure water was added to the residue to dilute it, and a predetermined concentration was determined by ICP-MS.
ここで、硝酸と塩酸の混合溶液の添加量と、超音波の照射時間を変化させて、回収率への寄与を評価した。その結果を図４に示す。ここで、回収条件１は、硝酸と塩酸の混合溶液の濃度として、硝酸濃度（ａｓＨＮＯ３）１．５ｗｔ％、塩酸濃度（ａｓＨＣｌ）２．３ｗｔ％、超音波照射時間５分、回収条件２は、硝酸と塩酸の混合溶液の濃度として、硝酸濃度（ａｓＨＮＯ３）３．０ｗｔ％、塩酸濃度（ａｓＨＣｌ）４．５ｗｔ％、超音波照射時間１０分、回収条件３は、硝酸と塩酸の混合溶液の濃度として、硝酸濃度（ａｓＨＮＯ３）４．５ｗｔ％、塩酸濃度（ａｓＨＣｌ）６．８ｗｔ％、超音波照射時間１０分である。なお、硝酸と塩酸の混合溶液の濃度は、超純水に（１）の硝酸と塩酸の混合溶液原液を２，４，６ｍＬ添加して、添加後の水量を２０ｍＬに調整することで行った。 Here, the addition amount of the mixed solution of nitric acid and hydrochloric acid and the irradiation time of ultrasonic waves were changed, and the contribution to the recovery rate was evaluated. The result is shown in FIG. Here, the recovery condition 1 is that the concentration of the mixed solution of nitric acid and hydrochloric acid is as follows: nitric acid concentration (asHNO 3 ) 1.5 wt%, hydrochloric acid concentration (asHCl) 2.3 wt%, ultrasonic irradiation time 5 minutes, recovery condition 2 The concentration of the mixed solution of nitric acid and hydrochloric acid is as follows: nitric acid concentration (asHNO 3 ) 3.0 wt%, hydrochloric acid concentration (asHCl) 4.5 wt%, ultrasonic irradiation time 10 minutes, recovery condition 3 is a mixed solution of nitric acid and hydrochloric acid The concentration of nitric acid is 4.5 wt% nitric acid (asHNO 3 ), 6.8 wt% hydrochloric acid (asHCl), and the ultrasonic irradiation time is 10 minutes. The concentration of the mixed solution of nitric acid and hydrochloric acid was determined by adding 2, 4, 6 mL of the mixed solution of nitric acid and hydrochloric acid (1) to ultrapure water and adjusting the amount of water after the addition to 20 mL. .
このように、配位子としてクエン酸（親水性の保護配位子）を用い液性として超純水を用いた上記（ｉ）の例では、回収条件１〜３のいずれにおいても、高い回収率を示しており、加熱乾固後の硝酸と塩酸の混合溶液の添加による溶解について保護配位子の影響がほとんどないことがわかる。一方、配位子としてチオクト酸、１０−カルボキシ−１−デカンチオール（疎水性官能基を有する保護配位子）を用い液性としてＩＰＡを用いた上記（ｉｉ），（ｉｉｉ）の例では、回収条件において、大きな変化がある。すなわち、硝酸と塩酸の混合溶液の濃度がある程度高い必要がある。また、超音波照射時間も長い方がよい。具体的には、回収条件３のように、硝酸と塩酸の混合溶液の濃度として、硝酸濃度（ａｓＨＮＯ３）４．５ｗｔ％、塩酸濃度（ａｓＨＣｌ）６．８ｗｔ％以上で、超音波照射時間１０分以上の場合、回収率が非常に高くなることが分かる。 Thus, in the example of the above (i) in which citric acid (hydrophilic protective ligand) is used as the ligand and ultrapure water is used as the liquid, high recovery is achieved in any of the recovery conditions 1 to 3. It can be seen that there is almost no influence of the protective ligand on dissolution by addition of a mixed solution of nitric acid and hydrochloric acid after heating to dryness. On the other hand, in the above examples (ii) and (iii) using thioctic acid, 10-carboxy-1-decanethiol (protective ligand having a hydrophobic functional group) as a ligand and IPA as a liquid, There are significant changes in recovery conditions. That is, the concentration of the mixed solution of nitric acid and hydrochloric acid needs to be high to some extent. Also, it is better that the ultrasonic irradiation time is longer. Specifically, as in the recovery condition 3, the concentration of the mixed solution of nitric acid and hydrochloric acid is as follows: nitric acid concentration (asHNO 3 ) 4.5 wt%, hydrochloric acid concentration (asHCl) 6.8 wt% or more, and ultrasonic irradiation time 10 It can be seen that the recovery rate is very high when it is more than a minute.
このように、比較的疎水性の保護配位子を用いて金ナノ粒子の表面を修飾して、アルコール中に分散させた試料液を用いた場合には、加熱乾固後に硝酸と塩酸の混合溶液で金ナノ粒子を溶解することは可能であるが、高濃度の硝酸と塩酸の混合溶液を用いることが必要であり、超音波照射を行うことが好適であることがわかった。 In this way, when a sample solution in which the surface of the gold nanoparticle is modified with a relatively hydrophobic protective ligand and dispersed in alcohol is used, a mixture of nitric acid and hydrochloric acid is mixed after heating to dryness. Although it is possible to dissolve the gold nanoparticles with a solution, it was necessary to use a mixed solution of high-concentration nitric acid and hydrochloric acid, and it was found preferable to perform ultrasonic irradiation.
（３）フィルターの除粒子性能評価
図１に示すシステムを用い、試料液をろ過処理し、フィルターの除粒子性能を評価した。
(3) Particle removal performance evaluation of filter Using the system shown in FIG. 1, the sample solution was filtered and the particle removal performance of the filter was evaluated.
粒子径３０ｎｍの金ナノ粒子を超純水で希釈した原水をフィルター：ＰＥＳ（ポリエーテルサルフォン）製ＵＦ膜（分画分子量：１５０，０００）に通水させた。この際、ＵＦ膜の通水条件は、通水方式：デッドエンド、ろ過流速：５．０ｍ／ｄａｙ、ろ過流量：２７Ｌ／ｈ（４５０ｍｌ／ｍｉｎ）とした。フィルター前後の原水（Ｓ１）およびろ過液（Ｓ２）をサンプリングした。サンプリングした原水はそのまま硝酸と塩酸の混合溶液原液を添加して、金ナノ粒子を溶解し、その後超純水で所定濃度に希釈して、ＩＣＰ−ＭＳで定量した。一方、サンプリングしたろ過液は、一旦加熱乾固した後、硝酸と塩酸の混合溶液原液で溶解し、超純水で所定濃度に調整してＩＣＰ−ＭＳで定量した。なお、硝酸と塩酸の混合溶液の濃度は、硝酸濃度（ａｓＨＮＯ３）１．５ｗｔ％、塩酸濃度（ａｓＨＣｌ）２．３ｗｔ％、超音波照射時間は１０分とした。 Raw water obtained by diluting gold nanoparticles having a particle diameter of 30 nm with ultrapure water was passed through a filter: PES (polyethersulfone) UF membrane (fraction molecular weight: 150,000). At this time, the water flow conditions of the UF membrane were water flow method: dead end, filtration flow rate: 5.0 m / day, filtration flow rate: 27 L / h (450 ml / min). The raw water before and after the filter (S1) and the filtrate (S2) were sampled. The sampled raw water was directly added with a mixed solution of nitric acid and hydrochloric acid to dissolve the gold nanoparticles, and then diluted to a predetermined concentration with ultrapure water and quantified by ICP-MS. On the other hand, the sampled filtrate was once heated to dryness, dissolved in a mixed solution stock solution of nitric acid and hydrochloric acid, adjusted to a predetermined concentration with ultrapure water, and quantified by ICP-MS. The concentration of the mixed solution of nitric acid and hydrochloric acid was nitric acid concentration (asHNO 3 ) 1.5 wt%, hydrochloric acid concentration (asHCl) 2.3 wt%, and the ultrasonic irradiation time was 10 minutes.
この結果を表３に示す。 The results are shown in Table 3.
（４）フィルターの除粒子性能評価（ＩＰＡ）
図１に示すシステムに対応する実験装置を用い、ＩＰＡ中に金ナノ粒子を分散させた試料液（原水）をろ過処理し、フィルターの除粒子性能を評価した。すなわち、貯槽１０に所定量の原水を貯留し、ここに窒素ガスを圧送して、全量をフィルター１８に供給してろ過処理した。そして、原水（Ｓ１）を予めサンプリングすると共に、ろ過液をサンプリングした。
(4) Particle removal performance evaluation of filters (IPA)
Using a test apparatus corresponding to the system shown in FIG. 1, a sample solution (raw water) in which gold nanoparticles were dispersed in IPA was filtered, and the particle removal performance of the filter was evaluated. That is, a predetermined amount of raw water was stored in the storage tank 10, nitrogen gas was pumped therein, and the entire amount was supplied to the filter 18 for filtration. And while sampling raw | natural water (S1) previously, the filtrate was sampled.
粒子径２０ｎｍの金ナノ粒子（ＢＢＩ社製）をＩＰＡ（(株)徳山製、トクソーＩＰＡ ＳＥ（商品名））で希釈するとともに、金ナノ粒子の表面を保護配位子で修飾して得た原水をフィルター１８に通水させた。 Obtained by diluting gold nanoparticles (BBI) having a particle size of 20 nm with IPA (manufactured by Tokuyama Co., Ltd., Toxo IPA SE (trade name)) and modifying the surface of the gold nanoparticles with a protective ligand The raw water was passed through the filter 18.
なお、保護配位子としては、上述した（ｉｉｉ）１０−カルボキシ−１−デカンチオールを利用した。 As the protective ligand, (iii) 10-carboxy-1-decanethiol described above was used.
また、フィルター１８としては、膜種：ＭＦ膜、材質：ＵＰＥ（超高分子量ポリエチレン）、除粒子径：５ｎｍの、日本インテグリス(株)製、オプチマイザーＤＬＥ ディスポーザブルフィルター（商品名）を利用した。 As the filter 18, an Optimizer DLE disposable filter (trade name) manufactured by Nihon Integris Co., Ltd., having a membrane type: MF membrane, a material: UPE (ultra high molecular weight polyethylene), and a particle removal diameter: 5 nm was used.
この際、ＭＦ膜の通水条件は、通水方式：全量ろ過、通水圧力：０．１ＭＰａ、ろ過流量：６７ｍＬ／ｍｉｎとした。フィルター前後の原水（Ｓ１）およびろ過液（Ｓ２）をサンプリングした。サンプリングした原水は、加熱乾固し、金ナノ粒子を含む残渣物を析出させ、その後残渣物に所定量の硝酸と塩酸の混合溶液を加えてこれを溶解し、これに超純水を加えて希釈し、所定濃度として、ＩＣＰ−ＭＳで定量した。一方、サンプリングしたろ過液は、一旦加熱乾固した後、硝酸と塩酸の混合溶液原液で溶解し、超純水で所定濃度に調整してＩＣＰ−ＭＳで定量した。なお、回収条件としては、上述の回収条件３を採用した。また、硝酸と塩酸の混合溶液の濃度は、硝酸濃度（ａｓＨＮＯ３）４．５ｗｔ％、塩酸濃度（ａｓＨＣｌ）６．８ｗｔ％、超音波照射時間は１０分とした。 At this time, the water flow conditions of the MF membrane were water flow method: total filtration, water flow pressure: 0.1 MPa, filtration flow rate: 67 mL / min. The raw water before and after the filter (S1) and the filtrate (S2) were sampled. The sampled raw water is heated to dryness to precipitate a residue containing gold nanoparticles, and then a predetermined amount of a mixed solution of nitric acid and hydrochloric acid is added to the residue to dissolve it, and ultrapure water is added to this. It diluted and quantified by ICP-MS as predetermined concentration. On the other hand, the sampled filtrate was once heated to dryness, dissolved in a mixed solution stock solution of nitric acid and hydrochloric acid, adjusted to a predetermined concentration with ultrapure water, and quantified by ICP-MS. Note that the above-mentioned recovery condition 3 was adopted as the recovery condition. The concentration of the mixed solution of nitric acid and hydrochloric acid was nitric acid concentration (asHNO 3 ) 4.5 wt%, hydrochloric acid concentration (asHCl) 6.8 wt%, and the ultrasonic irradiation time was 10 minutes.
この結果を表４に示す。 The results are shown in Table 4.
このように、このフィルターの微粒子捕捉率は、９９．９８％であることがわかった。従って、本実施例により、ＩＴＲＳにおける２０ｎｍ粒子の管理指標（１．０Ｅ＋０４個／ｍＬ）を満たすレベルでのフィルターの評価が可能であることがわかった。 Thus, the fine particle capture rate of this filter was found to be 99.98%. Therefore, according to the present example, it was found that the filter can be evaluated at a level satisfying the management index (1.0E + 04 particles / mL) of 20 nm particles in ITRS.
このように、本実施形態の手法によって、液中に存在する粒子径３０ｎｍ以下、例えば２０ｎｍの微粒子についてのフィルターの除粒子性能を評価することが可能となった。 As described above, the method of this embodiment makes it possible to evaluate the particle removal performance of the filter for fine particles having a particle diameter of 30 nm or less, for example, 20 nm, present in the liquid.
１０ 貯槽、１２ 超音波照射装置、１４ ポンプ、１６ バルブ、１８ フィルター、２０ 圧力計、２２，２４ バルブ、２６ ＩＣＰ−ＭＳ。 10 storage tanks, 12 ultrasonic irradiation devices, 14 pumps, 16 valves, 18 filters, 20 pressure gauges, 22, 24 valves, 26 ICP-MS.
本発明は、媒質液に粒径３０ｎｍ以下の金粒子を添加して分散させて試料液を調製する工程と、試料液を評価対象の、粒子径３０ｎｍ以下の微粒子除去用のフィルターに流通して、ろ過液を得る工程と、ろ過液を採取する工程と、前記試料液に、硝酸と、塩酸または塩化物と、を混合して調整された薬液を添加し、試料液中の金粒子を溶解して溶解液を得る工程と、採取したろ過液について、加熱処理を施して前記媒質液を蒸発させて金粒子の残渣物を得る工程と、前記残渣物を、硝酸と、塩酸または塩化物と、を混合して調整された薬液で溶解して溶解液を得る工程と、得られたそれぞれの溶解液についてＩＣＰ−ＭＳによって分析し、前記試料液および採取したろ過液中の金粒子の量を検出する工程と、を含み、前記試料液および得られたろ過液中の金粒子の量に基づき、前記フィルターを評価することを特徴とする。 The present invention includes a step of preparing a sample liquid by adding and dispersing gold particles having a particle diameter of 30 nm or less in a medium liquid, and distributing the sample liquid to a filter for removing fine particles having a particle diameter of 30 nm or less. The step of obtaining the filtrate, the step of collecting the filtrate, the chemical solution prepared by mixing nitric acid and hydrochloric acid or chloride is added to the sample solution, and the gold particles in the sample solution are dissolved. A step of obtaining a dissolved solution, a step of subjecting the collected filtrate to a heat treatment to evaporate the medium solution to obtain a residue of gold particles, and the residue of nitric acid and hydrochloric acid or chloride. , And a step of obtaining a solution by dissolving with an adjusted chemical solution, and analyzing each obtained solution by ICP-MS, and determining the amount of gold particles in the sample solution and the collected filtrate. wherein the step of detecting, the said sample solution and to obtain Based on the amount of gold particles in the filtrate, and evaluating the filter.
また、前記媒質液は、純水、超純水またはアルコールであることが好適である。 The medium liquid is preferably pure water, ultrapure water, or alcohol .
また、前記残渣物を前記薬液で溶解して溶解液を得る工程では、超音波振動を与えながら前記残渣物を前記薬液で溶解することが好適である。 Further, in the step of obtaining a solution by dissolving the residue in the chemical solution, it is preferable to dissolve in the liquid chemical to the residue while applying ultrasonic vibration.
また、（ろ過液中の金粒子の量）／（試料液中の金粒子の量）によりろ過膜における粒子除去性能を評価することが好適である。 Further, it is preferable to evaluate the particle removal performance in filtration membrane by (amount of gold particles in the filtrate) / (amount of gold particles in the sample liquid).
Claims (9)
試料液を評価対象のフィルターに流通して、ろ過液を得る工程と、
ろ過液を採取する工程と、
採取したろ過液中の金属粒子を薬液に溶解して溶解液を得る工程と、
得られた溶解液についてＩＣＰ−ＭＳによって分析し、採取したろ過液中の金属粒子の量を検出する工程と、
を含み、
得られたろ過液中の金属粒子の量に基づき、前記フィルターを評価することを特徴とするフィルターの評価方法。 Adding metal particles to the medium liquid and dispersing it to prepare a sample liquid;
Distributing the sample liquid to the filter to be evaluated to obtain a filtrate; and
Collecting the filtrate,
A step of dissolving the metal particles in the collected filtrate in a chemical solution to obtain a solution,
Analyzing the obtained solution by ICP-MS and detecting the amount of metal particles in the collected filtrate;
Including
A method for evaluating a filter, wherein the filter is evaluated based on an amount of metal particles in the obtained filtrate.
前記媒質液は、水溶液であることを特徴とするフィルターの評価方法。 The method for evaluating a filter according to claim 1,
The method for evaluating a filter, wherein the medium liquid is an aqueous solution.
前記金属粒子は、金粒子であることを特徴とするフィルターの評価方法。 In the evaluation method of the filter according to any one of claims 1 to 2,
The method for evaluating a filter, wherein the metal particles are gold particles.
前記金属粒子の粒径は、３０ｎｍ以下であることを特徴とするフィルターの評価方法。 In the evaluation method of the filter according to any one of claims 1 to 3,
The method for evaluating a filter, wherein the metal particles have a particle size of 30 nm or less.
前記薬液は、硝酸と、塩酸または塩化物と、を混合して調整されていることを特徴とするフィルターの評価方法。 In the evaluation method of the filter according to any one of claims 1 to 4,
The method for evaluating a filter, wherein the chemical solution is prepared by mixing nitric acid and hydrochloric acid or chloride.
前記採取したろ過液について、加熱処理を施す工程をさらに有し、
前記溶解液を得る工程では、加熱処理したものに前記薬液を混合して前記溶解液を得ることを特徴とするフィルターの評価方法。 The filter evaluation method according to claim 5,
The collected filtrate further has a step of heat treatment,
In the step of obtaining the solution, the chemical solution is mixed with a heat-treated product to obtain the solution.
前記加熱処理は、前記媒質液を蒸発させて金属粒子の残渣物を得る処理であり、
前記溶解液を得る工程では、得られた残渣物を薬液で溶解することを特徴とするフィルターの評価方法。 The filter evaluation method according to claim 6,
The heat treatment is a treatment for evaporating the medium liquid to obtain a residue of metal particles,
In the step of obtaining the solution, the obtained residue is dissolved with a chemical solution.
前記溶解液を得る工程では、超音波振動を与えながら前記残渣物を薬液で溶解することを特徴とするフィルターの評価方法。 The filter evaluation method according to claim 7,
In the step of obtaining the dissolving solution, the residue is dissolved with a chemical solution while applying ultrasonic vibration.
前記試料液中の金属粒子の量を計測し、（ろ過液中の金属粒子の量）／（試料液中の金属粒子の量）によりフィルターにおける粒子除去性能を評価することを特徴とするフィルターの評価方法。 In the filter evaluation method according to any one of claims 1 to 8,
The amount of metal particles in the sample solution is measured, and the particle removal performance of the filter is evaluated by (amount of metal particles in the filtrate) / (amount of metal particles in the sample solution). Evaluation method.
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