1300477 九、發明說明： 【發明所屬之技術領域】 本發明係關於用以將液體試料施以前處理後，對其含 有成分進行螢光X射線分析之螢光X射線分析用試料保持 具以及利用此保持具之螢光X射線分析方法與裝置。 【先前技術】 自以往，關於將液體試料施以前處理以對其含有成分 進行螢光X射線分析之技術而言，已有藉由將液體試料滴 注於濾紙上使其乾燥的方式使其含有成分濃縮並保持之濾 紙滴注法。但是，由於濾紙的厚度達到數100 /im，以致產 生多量的一次X射線之散射線使得背景雜訊(background) 提高。又，依濾紙的液體吸收力，每次只能滴注50至100 //1左右之液體試料，若含有成分為微量時，即使在不致使 濾紙過度變形的範圍内反複滴注與乾燥，自濃縮於濾紙的 含有成分所產生而被引入到偵測器的螢光X射線之強度仍 然不足。換言之，分析圖線的斜率（即表示於液體試料中 含有成分的濃度之分析圖線式中，有關螢光X射線強度之 常數）不夠小。因此，如下列式（1 )、（ 2 )所示的偵測極 限（LLD)，例如在為環境分析所需的重元素領域中僅為數 lOOppb左右，所以是不夠充分的。 LLD= 3xbx σ Bg ...... ( 1 ) σΒ〇- (W ( lOOOxt)) 1/2 ······ (2) 於此，b為分析圖線斜率，IBG為背景雜訊之X射線強 度（kcps)，t為測定時間（s )，故為求在有限的測定時間 内且在一定的施加電壓、電流的情況下，使偵測極限提高， 有如下2種方法：其一，係將液體試料中的含有成分濃縮， 提高靈敏度，以改善分析圖線斜率（即是將分析圖線之值 減小。換言之，將更多的含有成分濃縮，使得由其所產生 1300477 且被引入到偵測器的螢光x射線之強度增大）之方法，其 二為使背景雜訊之X射線強度減小的方法。 基於上述方法，為使偵測極限提高，已經存在有於厚 度0.5 Zim左右之聚合物薄膜上形成碳等之蒸鍍膜，並將液 體試料滴注於形成有此蒸鍍膜的部位上令其乾燥以保持其 含有成分之技術（請參照特開2003-90810號公報）。 然而，由於此種蒸鍍膜非常薄，且為將液體試料均勻 濃縮，蒸鍍膜的直徑達於約2腿，故單次能滴注的量低於 對濾紙之滴注量。因此，使用較濾紙為薄的聚合物薄膜或 蒸鍍膜，雖然能降低背景雜訊，但由於所得螢光X射線之 強度未增大，所以其偵測極限之提升程度仍嫌不足。另外， 若使用小面積的蒸鍍膜，即使反複滴注與乾燥以使較多含 有成分濃縮，亦不僅不能穩定地保持，且因含有成分之結 晶化等造成多量的散射線產生，所以存在有背景雜訊增高 之虞。又，若為了增加滴注量以使其螢光X射線之強度增 大，而將蒸鍍膜之面積加大時，則會導致其濃縮不均勻、 螢光X射線之產生不均勻或不穩定（請參照上述公報第 【0019】段落）。 【發明内容】 發明所欲解決之問題 本發明係鑑於上述情形而完成的，其目的在於提供用 以將液體試料施以前處理後，對其含有成分進行螢光X射 線分析之螢光X射線分析用試料保持具以及利用此保持具 之螢光X射線分析方法與裝置，其中，藉著抑制背景雜訊， 並均勻地產生較大強度的螢光X射線之方式，而能充分提 高偵測極限。 解決問題之方式 為達成上述目的，依本發明第一實施態樣的螢光X射 1300477 線分析用試料保持具，係用以將液體試料施以前處理後對 其含有成分進行螢光X射線分析，前述保持具包含環狀台 座、具備固定於該台座之周邊部以及令X射線透射之透射 部且其厚度為10 /im以下之疏水性薄膜、貼附於該疏水性薄 膜上且其厚度為1泖以上100泖以下之片狀液體吸收材， 將該液體試料滴注於該液體吸收材上而使其乾燥，藉以保 持該含有成分。 依本發明之第一實施態樣，首先，待照射一次X射線 的疏水性薄膜以及液體吸收材皆為非常薄的，所以能將散 射線減少以致抑制背景雜訊。另一方面，貼附於疏水性薄 膜的具有適當厚度之液體吸收材能保持足夠量的液體試料 而均勻地使其濃縮，所以能均勻產生強度為更大的螢光X 射線。因此，能將债測極限十分提昇。 於本發明的第一實施態樣中，使用聚酯（例如為聚對 苯二曱酸乙酯）、聚丙稀或聚亞胺等以形成前述疏水性薄膜 者為較佳，而前述液體吸收材，係可使用紙，且使用含有 如滑石（talc，滑石的粉末）等多孔質粉末的紙者為更佳。 依本發明第二實施態樣的螢光X射線分析方法，係使 用如第一實施態樣中的螢光X射線分析用試料保持具，藉 由將液體試料滴注於前述液體吸收材上而使其乾燥，以保 持前述液體試料之含有成分，接著將一次X射線照射至前 述液體吸收材的部位，以偵測所得二次X射線之強度。 依本發明第三實施態樣的螢光X射線分析裝置，係使 用如第一實施態樣中的螢光X射線分析用試料保持具，包 含照射一次X射線的X射線源，其係對著將液體試料滴注 後使其乾燥而保持該液體試料的含有成分於該液體吸收材 之一部位，隨後將一次X射線照射該部位，以及偵測機構， 其測定自該液體吸收材之部位所產生的二次X射線之強 度。 1300477 依本發明之第二、第三實施態樣，由於其使用第一實 施態樣中的螢光X射線分析用試料保持具，故能獲得與第 一實施態樣相同之作用效果。 【實施方式】 以下將參照圖式詳細說明依本發明的較佳實施形態。 第一實施態樣 首先將關於本發明之第一實施態樣的螢光X射線分析 用試料保持具加以說明。此試料保持具係用以將液體試料 施以前處理後，對其含有成分進行螢光X射線分析，如圖 1所示，此試料保持具包含為將疏水性薄膜穩定固定之環 狀台座2，其係由如聚乙浠、聚苯乙烯等樹脂材料所形成， 具有固定於前述台座2的周邊部3a以及令X射線透射之透 射部3b，且其厚度為10娜以下之疏水性薄膜3，被貼附於 此疏水性薄膜3之透射部3b且其厚度為1聊以上100 /im以 下之片狀液體吸收材4,將液體試料滴注於此液體吸收材4 上而使其乾燥，以使液體試料之含有成分濃縮並保持之。 圖3顯示一縱剖面圖，在此疏水性薄膜3係由厚度1.5 卿的聚對苯二曱酸乙酯所形成，係其直徑與台座2之直徑 為略相同的圓形（為圖示以及了解方便，在圖中表示的尺 吋較小），而週邊部3a與台座2粘著保持。除了周邊部3a 的部分以外係為令X射線透射的透射部3b。在圖1與後述 圖2中，台座2的内周係隱藏於疏水性薄膜3之下方，所 以以破線表示之，但實際上是透明而可看到其内周。又， 在此液體吸收材4係如吸油面紙般由含有滑石的厚度為數 卿之紙所形成，其係直徑1.8 cm之圓形，並將如霧狀膠水 (其成分為丙稀酸橡膠（10%)、有機溶劑（54%)、以及異 乙烷氣體（36%)，所使用喷射用高壓氣體為二曱醚）喷射 到液體吸收材4之背面，並將其貼附在疏水性薄膜3的中 1300477 央處。為貼附所使用的粘著劑應不限於此霧狀橡膠，只要 不妨礙分析者即可。另外，為圖示以及了解方便，圖中所 表示之各部分厚度與實際尺吋係相異的。 在使用此試料保持具5之前處理中，如圖2所示，將 液體試料滴注於液體吸收材4上。在此，由於在液體吸收 材4之下方以及周圍設有疏水性薄膜3，所以液體試料1 不會從液體吸收材4溢出到其下方或周圍，並且藉由其表 面張力可以將液體試料滴注200//1以上600//1左右。接 著，將已滴注液體試料1的試料保持具5予以乾燥，藉此 令液體試料1之含有成分吸附到液體吸收材4而保持之。 結果，其外觀如其滴注前的圖1。在此狀態下將一次X射 線照射到試料保持具5之液體吸收材4的部位而進行螢光 X射線分析（有關將試料保持具5載置於螢光X射線分析 裝置之試料台的方法，請參照後述說明）。 圖4係將習知使用濾紙滴注法而將其滴注量設成其上 限之100//1而進行分析所得之定性光譜，與使用本實施態 樣之試料保持具，並經將其滴注量設成500// 1之前處理後 進行分析所得之定性光譜加以重疊表示。由此一圖表得 知，使用依本實施態樣的試料保持具，可將背景雜訊抑制 到使用習知濾紙之情況的一半以下，同時，亦可獲得其強 度更大之螢光X射線。 另外，在使用本實施態樣之試料保持具且將滴注量設 為500// 1之情況之下，將其各種元素之偵測極限表示如表 1300477 [表i] 單位：ppb 元素 偵測極很 元素 偵測極限 B 30ppm Zn 18 F Ippm As 16 Na 76 Se 24 P 56 Sr 25 K 12 Mo 27 V 34 Ag 152 Cr 26 Cd 182 Μη 16 Sn 40 Fe 18 Sb 43 Co 17 Ba 105 Ni 20 T1 81 Cu 19 Pb 76 以往使用之濾紙滴注法的背景雜訊為很高，且其滴注 量之極限在50〜100// 1左右，因此其偵測極限，即使較良 好的金屬元素，也僅有數1 OOppb，所以，由表1得知，依 本實施態樣之試料保持具，其偵測極限有提高至少約一個 _ 位數以上。另外，將表1所示數據與前述日本專利公開公 報特開2003-90810號中表1所示之數據相比照，雖然對 Cr而言係稍微有劣化的情形，但對其他所有的元素而言， 得有更良好之數據。 如上所述，依本實施態樣之螢光X射線分析用試料保 持具，首先，由於一次X射線所照射之疏水性薄膜3以及 液體吸收材4皆為足夠地薄的，所以能將散射線減少以抑 制背景雜訊。另一方面，由於藉由貼付在疏水性薄膜3上 且具有適當厚度之液體吸收材4,能將充分量的液體試料1 11 1300477 保持且使其均勻地濃縮，故能均勻地產生其強度更大之螢 光X射線。因此，能夠將偵測極限充分提高。 在此，由於將液體吸收材4貼付於疏水性薄膜3上而隨 時產生一定的張力，所以，比如當含有成分極為微量之情 況下，即使反複滴注和乾燥操作使其含有成分大量地濃 縮，仍然可均勻且穩定地保持含有成分。又，當使用習知 - 具有小面積之鍍膜時，由於結晶化等理由，欲使含有成分 充分且均勻地濃縮不容易，但依本實施態樣之保持具，藉 ‘ 由其具有適當的厚度、面積之片狀液體吸收材4，能使含 有成分充分且均勻地濃縮，因此，即使對B、F、Na、P等 之輕元素而言，亦能充分且穩定地進行定量分析。 第二實施態樣 接著，說明依本發明之第二實施態樣的螢光X射線分 析方法。此分析方法所使用之螢光X射線分析裝置，係本 發明之第三實施態樣，如圖5所示，其係使用第一實施態 樣中的螢光X射線分析用試料保持具5的裝置，其包含試 料台16，將試料保持具5直接或介於試料架13載置於其 上、X射線光源14，如X射線管等，其藉由將液體試料1 (圖3)滴注而使其乾燥，以將液體試料1的含有成分保 持於液體吸收材4上的部位，並將一次X射線24照射至 此部位、以及偵測機構15，其係如X射線偵測器等，即測 , 量由液體吸收材4上的前述部位所產生的螢光X射線等的 二次X射線25之強度。 — 使用上述裝置的第二實施態樣中之螢光X射線分析方 法，係使用第一實施態樣中的螢光X射線分析用試料保持 具5之方法，如上述，藉由將液體試料1 (請參照圖3)滴 注於液體吸收材4 (請參照圖3)上而使其乾燥，以保持液 體試料1之含有成分，經此前處理後，將此試料保持具5 整體載置於試料架（中空杯狀）13之開口部，隨後將此試 12 1300477 料架13載置於試料台16上，其中，前述試料架13係由 A1或Ti製成並具有底部，其形狀呈圓筒狀。 使用這樣的試料架13之原因在於，為避免物體會靠 近疏水性薄膜之透射部3b的背面近旁，以致降低背景雜 訊，以及為降低貫通透射部3b的背面之一次X射線24在 裝置内側成為散射線所造成之影響。另外，前述試料架13 - 可為無底部且單純的圓筒狀。 又，如圖6所示，當在試料台16設有與台座2之孔 略為相同大小的貫通孔16a之情況下，可不使用試料架而 將試料保持具5直接載置於試料台16上。 以上係為說明由試料上方照射一次X射線之所謂上方 · 照射的情況，但在由試料下方照射一次X射線的所謂下方 照射之情況下，如圖7所示，由於試料台16上設有令一次 X射線24通過之貫通孔16a，所以能將試料保持具5直接 向下載置於試料台16，加上，為降低散射線之影響，令中 空杯13由上方朝下以覆蓋試料保持具5亦可。又如圖8所 示，使用藉由旋轉將試料移送至一次X射線所照射之分析 位置的試料轉台以作為試料台時，將試料保持具5以使液 體吸收材4朝下的方式放入試料架（支撐杯）17中，其中， 此試料架17係為具有底部且呈圓筒狀，其底部設置有孔 _ 17a，且其外周下部的直徑為逐漸變狹小，令此試料架17 • 的徑小部分卡止在設於試料轉台16上的具略相同直徑之 貫通孔16a。 — 於此，本發明並不限於上述之實施態樣。熟習該項技 術者當了解的是，上述實施例在此僅為例示性而非為限制 性，亦即，在不脫離本發明實質精神及範圍之内，上述所 述及之各構成要件及各處理過程之組合的其他變化例及修 正例均為本發明所涵蓋。 發明的效果 13 1300477 如上述說明，將一次X射線24照射至載置於試料台 16的試料保持具5上之液體吸收材4的部位，並測量其所 產生之二次X射線25的強度。 依第二、第三實施態樣中的方法、裝置，因為使用第 一實施態樣中的螢光X射線分析用試料保持具5，所以能 獲得與第一實施態樣相同之作用效果。 【圖式簡單說明】 圖1為本發明第一實施態樣之螢光X射線分析用試料 保持具的立體圖。 圖2表示將液體試料滴注於同上試料保持具的狀態之 立體圖。 圖3為同上試料保持具之剖面圖。 圖4表示將使用上述試料保持具進行分析的定性光 譜，與使用習知濾紙進行分析的定性光譜做比較所得之圖 表。 圖5係本發明的第三實施態樣之螢光X射線分析裝置 的示意圖，係於本發明的第二實施態樣之螢光X射線分析 方法中所使用。 圖6係將試料保持具載置於試料台的方法之變化例的 縱剖面圖。 圖7係將試料保持具載置於試料台的方法之另一變化 例的縱剖面圖。 圖8係將試料保持具載置於試料台的方法之更另一變 化例的縱剖面圖。 【主要元件符號說明】 1液體試料 2台座 14 1300477 3疏水性薄膜 3a周邊部 3b透射部 4液體吸收材 5試料保持具 13 試料架 14 X射線光源 15 偵測機構 16 試料台 16 a貫通孔 17試料架（支撐杯） 17a孔 24 —次X射線 25二次X射線[Technical Field] The present invention relates to a sample holder for fluorescent X-ray analysis for performing a fluorescent X-ray analysis on a component containing a liquid sample before being treated, and using the same Fluorescent X-ray analysis methods and devices for holding. [Prior Art] Conventionally, a technique for performing a fluorescent X-ray analysis on a liquid sample prior to application of a liquid sample has been carried out by dripping a liquid sample onto a filter paper and drying it. A filter paper drip method in which the ingredients are concentrated and maintained. However, since the thickness of the filter paper reaches several hundred / im, a large amount of scattered X-ray rays are generated to increase the background noise. Moreover, depending on the liquid absorption force of the filter paper, only a liquid sample of about 50 to 100 //1 can be instilled at a time, and if the component is contained in a small amount, the drip and dry are repeated even in a range where the filter paper is not excessively deformed. The intensity of the fluorescent X-rays generated by the contained components concentrated on the filter paper and introduced into the detector is still insufficient. In other words, the slope of the analysis line (i.e., the constant of the intensity of the fluorescent X-rays in the analysis chart indicating the concentration of the component contained in the liquid sample) is not sufficiently small. Therefore, the detection limit (LLD) as shown in the following formulas (1) and (2) is, for example, only about 10,000 ppb in the field of heavy elements required for environmental analysis, and thus is insufficient. LLD= 3xbx σ Bg ...... ( 1 ) σΒ〇- (W ( lOOOxt)) 1/2 ······ (2) Here, b is the slope of the analysis line, and IBG is the background noise. The X-ray intensity (kcps) and t are the measurement time (s). Therefore, in order to increase the detection limit in a limited measurement time and with a certain applied voltage and current, there are two methods: First, the content of the liquid sample is concentrated to increase the sensitivity to improve the slope of the analysis line (that is, the value of the analysis line is reduced. In other words, more of the contained components are concentrated, so that 1300477 is generated by The method of increasing the intensity of the fluorescent x-rays introduced into the detector, and the second method of reducing the X-ray intensity of the background noise. Based on the above method, in order to increase the detection limit, a vapor deposition film of carbon or the like is formed on the polymer film having a thickness of about 0.5 Zim, and the liquid sample is dropped on the portion where the vapor deposition film is formed to dry it. A technique for maintaining the composition thereof (refer to Japanese Laid-Open Patent Publication No. 2003-90810). However, since the vapor-deposited film is very thin and the liquid sample is uniformly concentrated, the diameter of the vapor-deposited film is about 2 legs, so that the amount of single-injection can be less than the amount of dripping onto the filter paper. Therefore, the use of a thinner polymer film or a vapor-deposited film as a filter paper can reduce the background noise, but since the intensity of the obtained fluorescent X-rays is not increased, the detection limit is still insufficient. In addition, when a small-area vapor-deposited film is used, even if it is repeatedly dripped and dried to concentrate a large amount of components, it is not stable, and a large amount of scattered rays are generated due to crystallization of components, and therefore there is a background. The increase in noise. Further, if the amount of the vapor-deposited film is increased in order to increase the amount of the dripping, and the area of the vapor-deposited film is increased, the concentration is uneven, and the generation of the fluorescent X-rays is uneven or unstable ( Please refer to paragraph [0019] of the above bulletin. DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a fluorescent X-ray analysis for performing fluorescent X-ray analysis of a component thereof after a liquid sample is treated. A sample holder and a fluorescent X-ray analysis method and apparatus using the same, wherein the detection limit can be sufficiently improved by suppressing background noise and uniformly generating a large intensity of fluorescent X-rays . Means for Solving the Problem In order to achieve the above object, a sample holder for a fluorescent X-ray 1300477 line analysis according to a first embodiment of the present invention is used for performing a fluorescent X-ray analysis on a component of a liquid sample before being treated. The holder includes an annular pedestal, a hydrophobic film having a peripheral portion fixed to the pedestal and a transmission portion for transmitting X-rays and having a thickness of 10 / im or less, attached to the hydrophobic film, and having a thickness of A sheet-like liquid absorbing material of 100 Å or more and 100 Å or less is dropped onto the liquid absorbing material and dried to maintain the contained component. According to the first embodiment of the present invention, first, the hydrophobic film to be irradiated with X-rays and the liquid absorbing material are both very thin, so that the scattered ray can be reduced to suppress background noise. On the other hand, the liquid absorbing material having an appropriate thickness attached to the hydrophobic film can uniformly concentrate the liquid sample by a sufficient amount, so that the fluorescent X-ray having a higher intensity can be uniformly generated. Therefore, the limit of the debt test can be greatly improved. In the first embodiment of the present invention, it is preferred to use a polyester (for example, polyethylene terephthalate), polypropylene or polyimide to form the aforementioned hydrophobic film, and the liquid absorbing material. It is preferable to use paper and use a paper containing a porous powder such as talc (talc, talc). According to the fluorescent X-ray analysis method of the second embodiment of the present invention, the sample holder for fluorescent X-ray analysis according to the first embodiment is used, by dropping a liquid sample onto the liquid absorbing material. It is dried to maintain the components contained in the liquid sample, and then an X-ray is irradiated to the portion of the liquid absorbing material to detect the intensity of the obtained secondary X-ray. According to a third aspect of the present invention, a fluorescent X-ray analysis apparatus uses a sample holder for fluorescent X-ray analysis as in the first embodiment, and includes an X-ray source that irradiates one X-ray, which is opposed to The liquid sample is dripped and dried to maintain a component of the liquid sample in a portion of the liquid absorbing material, and then the X-ray is irradiated to the portion, and a detecting mechanism is determined from the portion of the liquid absorbing material. The intensity of the generated secondary X-rays. According to the second and third embodiments of the present invention, since the sample holder for the fluorescent X-ray analysis in the first embodiment is used, the same effects as those of the first embodiment can be obtained. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. First Embodiment First, a sample holder for a fluorescent X-ray analysis according to a first embodiment of the present invention will be described. The sample holder is used for performing a fluorescent X-ray analysis on the components contained in the liquid sample, and as shown in FIG. 1 , the sample holder includes an annular pedestal 2 for stably fixing the hydrophobic film. It is formed of a resin material such as polyacetonitrile or polystyrene, and has a hydrophobic film 3 fixed to the peripheral portion 3a of the pedestal 2 and the transmissive portion 3b for transmitting X-rays, and having a thickness of 10 nautical or less. The sheet-like liquid absorbing material 4 which is attached to the transmissive portion 3b of the hydrophobic film 3 and has a thickness of 1 or more and 100 / im or less is dripped onto the liquid absorbing material 4 and dried. The contents of the liquid sample are concentrated and maintained. Figure 3 shows a longitudinal section in which the hydrophobic film 3 is formed of a polyethylene terephthalate having a thickness of 1.5 Å, which is slightly rounded in diameter to the diameter of the pedestal 2 (for illustration and For convenience, the scale shown in the figure is small, and the peripheral portion 3a is adhered to the pedestal 2. In addition to the portion of the peripheral portion 3a, it is a transmissive portion 3b that transmits X-rays. In Fig. 1 and Fig. 2 which will be described later, the inner periphery of the pedestal 2 is hidden under the hydrophobic film 3, so that it is indicated by a broken line, but actually it is transparent and the inner circumference can be seen. Further, the liquid absorbing material 4 is formed of a paper containing a talc having a thickness of several tens of grams, such as an oil-absorbing paper, which is a circular shape having a diameter of 1.8 cm, and will be a mist-like glue (the composition of which is acrylic rubber ( 10%), an organic solvent (54%), and an isohexane gas (36%), using a high-pressure gas for spraying as a dimethyl ether), are sprayed onto the back surface of the liquid absorbing material 4, and are attached to the hydrophobic film. 3 of the 1300477 central office. The adhesive to be used for attachment should not be limited to the mist rubber as long as it does not interfere with the analyst. In addition, for the sake of illustration and convenience, the thickness of each part shown in the figure is different from the actual ruler system. In the treatment before the sample holder 5 is used, as shown in Fig. 2, the liquid sample is dropped onto the liquid absorbing material 4. Here, since the hydrophobic film 3 is provided below and around the liquid absorbing material 4, the liquid sample 1 does not overflow from the liquid absorbing material 4 to the bottom or the periphery thereof, and the liquid sample can be dripped by the surface tension thereof. 200//1 or more and 600//1 or so. Then, the sample holder 5 to which the liquid sample 1 has been dropped is dried, whereby the components contained in the liquid sample 1 are adsorbed to the liquid absorbing material 4 and held. As a result, its appearance is as shown in Fig. 1 before the drip. In this state, a portion of the liquid absorbing material 4 of the sample holder 5 is irradiated with X-rays to perform a fluorescent X-ray analysis (a method of placing the sample holder 5 on a sample stage of the fluorescent X-ray analyzer). Please refer to the description below.) Fig. 4 is a qualitative spectrum obtained by analyzing a dropping amount of the filter paper by using a filter paper dripping method to an upper limit of 100//1, and using the sample holder of the present embodiment, and dropping the same The qualitative spectrum obtained by the analysis after the treatment was set to 500//1 was superimposed and expressed. As can be seen from the graph, by using the sample holder according to the embodiment, the background noise can be suppressed to less than half of that of the conventional filter paper, and at the same time, the stronger X-rays can be obtained. In addition, in the case where the sample holder of the present embodiment is used and the drip amount is set to 500//1, the detection limits of various elements are expressed as Table 1300477 [Table i] Unit: ppb Element detection Very elemental detection limit B 30ppm Zn 18 F Ippm As 16 Na 76 Se 24 P 56 Sr 25 K 12 Mo 27 V 34 Ag 152 Cr 26 Cd 182 Μη 16 Sn 40 Fe 18 Sb 43 Co 17 Ba 105 Ni 20 T1 81 Cu 19 Pb 76 The background noise of the filter paper dripping method used in the past is very high, and the limit of the amount of dripping is about 50~100//1, so the detection limit is even better than the metal element. There are several OOppbs. Therefore, as shown in Table 1, according to the sample holder of the present embodiment, the detection limit is increased by at least about one _ digit. In addition, the data shown in Table 1 is compared with the data shown in Table 1 of the above-mentioned Japanese Laid-Open Patent Publication No. 2003-90810, although it is slightly deteriorated for Cr, but for all other elements. , have better data. As described above, according to the sample holder for the fluorescent X-ray analysis of the present embodiment, first, since the hydrophobic film 3 and the liquid absorbing material 4 irradiated by one X-ray are sufficiently thin, the scattering line can be obtained. Reduce to suppress background noise. On the other hand, since the liquid absorbent material 4 having a suitable thickness is attached to the hydrophobic film 3, a sufficient amount of the liquid sample 1 11 1300477 can be held and uniformly concentrated, so that the strength can be uniformly produced more uniformly. Big fluorescent X-rays. Therefore, the detection limit can be sufficiently improved. Here, since the liquid absorbing material 4 is attached to the hydrophobic film 3 and a certain tension is generated at any time, for example, when the content of the component is extremely small, even if the components are concentrated in a large amount by repeated dripping and drying operations, The contained components are still uniformly and stably maintained. Further, when a conventional coating having a small area is used, it is not easy to sufficiently and uniformly concentrate the contained component due to crystallization or the like, but the holder according to the embodiment has a suitable thickness. The sheet-like liquid absorbing material 4 having an area can sufficiently and uniformly concentrate the contained components. Therefore, even for light elements such as B, F, Na, and P, quantitative analysis can be performed sufficiently and stably. Second Embodiment Next, a fluorescent X-ray analysis method according to a second embodiment of the present invention will be described. The fluorescent X-ray analysis apparatus used in the analysis method is a third embodiment of the present invention, as shown in FIG. 5, which uses the sample holder 5 for fluorescent X-ray analysis in the first embodiment. The apparatus comprises a sample stage 16 on which the sample holder 5 is placed directly or on the sample holder 13 and an X-ray source 14, such as an X-ray tube, etc., by instilling the liquid sample 1 (Fig. 3) And drying it to hold the contained component of the liquid sample 1 on the liquid absorbing material 4, and irradiating the X-ray 24 to the portion and the detecting mechanism 15, such as an X-ray detector or the like, that is, The intensity of the secondary X-ray 25 such as fluorescent X-rays generated by the aforementioned portion on the liquid absorbing material 4 is measured. - a method of using the fluorescent X-ray analysis method in the second embodiment of the above apparatus, using the sample holder 5 for the fluorescent X-ray analysis in the first embodiment, as described above, by using the liquid sample 1 (Please refer to Fig. 3), the liquid absorbing material 4 (please refer to Fig. 3) is dripped and dried to maintain the components contained in the liquid sample 1, and after the previous treatment, the sample holder 5 is placed on the sample as a whole. The opening of the rack (hollow cup) 13 is then placed on the sample stage 16 of the sample 12 1300477, wherein the sample rack 13 is made of A1 or Ti and has a bottom, and the shape is a cylinder shape. The reason for using such a sample holder 13 is to reduce the background noise in order to prevent the object from approaching the back surface of the transmissive portion 3b of the hydrophobic film, and to reduce the amount of primary X-rays 24 on the back side of the transmissive portion 3b on the inside of the device. The effect of scattered rays. Further, the sample rack 13 - may have a bottomless shape and a simple cylindrical shape. Further, as shown in Fig. 6, when the sample stage 16 is provided with the through hole 16a having the same size as the hole of the pedestal 2, the sample holder 5 can be directly placed on the sample stage 16 without using the sample holder. The above is a description of the so-called upper-side irradiation in which the X-rays are irradiated once over the sample. However, in the case of so-called downward irradiation in which X-rays are irradiated once under the sample, as shown in Fig. 7, the sample table 16 is provided with a Since the X-ray 24 passes through the through hole 16a, the sample holder 5 can be directly placed on the sample stage 16 for loading. In addition, in order to reduce the influence of the scattered line, the hollow cup 13 is covered from the top to the bottom to cover the sample holder 5. Also. Further, as shown in FIG. 8, when the sample turret which is transferred to the analysis position irradiated by one X-ray by rotation is used as a sample stage, the sample holder 5 is placed in such a manner that the liquid absorbing material 4 faces downward. In the rack (support cup) 17, wherein the sample rack 17 has a bottom and is cylindrical, the bottom of which is provided with a hole _ 17a, and the diameter of the lower portion of the outer periphery is gradually narrowed, so that the sample rack 17 A small portion of the diameter is locked to the through hole 16a having a substantially the same diameter provided on the sample turret 16. - Here, the present invention is not limited to the above-described embodiments. It will be understood by those skilled in the art that the above-described embodiments are intended to be illustrative and not limiting, that is, without departing from the spirit and scope of the invention, Other variations and modifications of the combinations of processes are encompassed by the present invention. Advantageous Effects of Invention 13 1300477 As described above, the primary X-rays 24 are irradiated to the portion of the liquid absorbing material 4 placed on the sample holder 5 of the sample stage 16, and the intensity of the secondary X-rays 25 generated therefrom is measured. According to the method and apparatus of the second and third embodiments, the sample holder 5 for the fluorescent X-ray analysis in the first embodiment is used, so that the same effects as those of the first embodiment can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view of a sample holder for fluorescent X-ray analysis according to a first embodiment of the present invention. Fig. 2 is a perspective view showing a state in which a liquid sample is dropped on the same sample holder. Figure 3 is a cross-sectional view of the same sample holder. Fig. 4 is a graph showing a qualitative spectrum of analysis using the sample holder described above, which is compared with a qualitative spectrum analyzed by a conventional filter paper. Fig. 5 is a view showing a fluorescent X-ray analyzing apparatus according to a third embodiment of the present invention, which is used in the fluorescent X-ray analyzing method of the second embodiment of the present invention. Fig. 6 is a longitudinal sectional view showing a variation of the method of placing the sample holder on the sample stage. Fig. 7 is a longitudinal sectional view showing another modification of the method of placing the sample holder on the sample stage. Fig. 8 is a longitudinal sectional view showing still another modification of the method of placing the sample holder on the sample stage. [Main component symbol description] 1 liquid sample 2 pedestal 14 1300477 3 hydrophobic film 3a peripheral portion 3b transmission portion 4 liquid absorbing material 5 sample holder 13 sample holder 14 X-ray source 15 detection mechanism 16 sample stage 16 a through hole 17 Sample rack (support cup) 17a hole 24 - secondary X-ray 25 secondary X-ray
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