200819728 九、發明說明： t發明所屬之技術領域3 技術領域 本發明係有關於一種紫外線防禦效果之評估方法及評 5 估裝置。 L先前技術3 背景技術 10 15 用以防止因紫外線而造成曬傷的化妝品（所謂的防曬 商品），表示其紫外線防禦效果的標準係使用SpF(Sun Protection Factor :防曬係數)值。前述spF值係表示保護肌 膚免於紫外線之曬傷而可防曬之效果的指數，且spF值係藉 由將使用防曬商品時引起微微泛紅所需之紫外線量，除以 未使用防《商品時5丨起微微泛紅所f之紫外線量的值來進 行定義。例如’若使用SPF值為_防曬化妝品，則在曝曬 於素淨肌膚曬傷時的1G倍之紫外線下時，會與素淨肌膚產 生同樣Μ(紅斑）。狀卿值時非制可能會因季節 所而異之太陽光’㈣制非常近於太陽光之人工光(太陽 隔日再調查是否產生紅 光=器)。測定法係將，之紫外線分別照射於(: 有製品的肌膚與塗有製品的肌膚， 20 斑 商品的紫外線防二值，可一 時間。因此’希望開發出一種例如可使用於開發階段： 5 200819728 品的紫外線防禦效果評估等，可在活體外簡便地進行與以 上述方法所得之活體内SPF值(in vivo SPF值）之高相關的活 體外SPF(in vitro SPF)預測值算出方法。 至今，以活體外測定來進行紫外線防禦效果之評估方 5法，已知有··將以有機溶劑稀釋後之試料置入石英槽，测 定其紫外線之吸光度或透過率的稀釋溶液法；以及在石英 板上將試料形成為均一厚度的薄膜，測定其紫外線之吸光 度或透過率的薄膜法等。前述習知方法在把握紫外線吸收 劑之吸收最大波長及防禦波長區域等特性上雖有意義，但 10卻無法預測SPF值。此係由於該等紫外線防禦效果之評估方 法大幅悖離了測定活體内SPF值的方法之故。又，顯示spF 值之生體反應與紫外線之波長有關，有容易引起紅斑反應 之紫外線波長，也有不易引起紅斑反應之紫外線波長，必 須依各波長考慮各波長對生體的影響。 對於上述2個問超點，在非專利文獻1中，將試料塗布 於作為皮膚代替膜之醫療用膠帶上，測定試料之分光透射 光譜，藉由Diffey & Robson式對前述測定結果進行運算， 而運异出SPF值。前述Diffey & R〇bs〇n式係對於作為人類生 體反應之紅斑反應的波長相關，藉由使用非專利文獻2所揭 20示之紅斑係數而取得對應，可成功地解決上述課題。 然而，由於活體内SPF值有個體差異、部位差異、年齡 差異、性別差異及皮膚類型差異等各種因素存在，所以會 有難以僅藉由紅斑係數之一例而正確預測SPF值的問題。 因此，已有-種評估方法，其係不僅採用紅斑係數， 6 200819728 還從活體内SPF值為已知之多數試料與分光透射光t普的關 係，導出統計上可得出高相關的運算式，即使對於未知的 試料，也可以預測SPF值的評估方法（例如，參照專利文獻 1)。藉由前述評估方法，可以高精準度得出活體外SPF預測 5 值’也可解決因個體差異、部位差異、年齡差異、性別差 異及皮膚類型差異等所產生的參差不齊因素。 非專利文獻 1 ·· Journal of the Society of c〇smetic Chemists(1989) 40;33?127-133 非專利文獻2 : CIE Journal(1987) 6;l，17-22 10 專利文獻1 :特許第3337832號公報 L發明内容：1 發明揭示 發明所欲解決之課題 但是，上述專利文獻1所揭示之紫外線防禦效果的評估 15方法，雖可以高精準度預測至SPF值30左右，但會有無法對 於SPF值30以上之試料進行正確預測的問題。近年來，以 SPF值50以上的製品為主流，推測將來會有spF值更高的製 品投入市場。 又，最近有許多關於紫外線吸收劑因紫外光而造成光 20劣化現象的報告。因此，即使在活體外SPF預測值之算出方 法中，重現與活體内SPF值之測定條件相同的光照射條件而 正確地估計SPF值降低之相當量，也是在正確預測卿值時 不可或缺的一環。 本發明係蓥於上述各點而作成者，本發明之目的在於 7 200819728 種藉由活體外測定而進行的紫外線 方法及使_方狀紫料㈣效料評料置果之汗估 映出因照射光而引起的試料光劣化現象， 提供一 係可反200819728 IX. INSTRUCTION DESCRIPTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to an evaluation method and evaluation device for an ultraviolet protection effect. L. Prior Art 3 Background Art 10 15 A cosmetic (so-called sunscreen product) for preventing sunburn caused by ultraviolet rays, and a standard for indicating the ultraviolet protection effect thereof is a SpF (Sun Protection Factor) value. The aforementioned spF value is an index indicating the effect of protecting the skin from the sunburn caused by ultraviolet rays, and the spF value is obtained by dividing the amount of ultraviolet rays required to cause slight redness when using the sunscreen product, and dividing the unused anti-products. 5 The value of the amount of ultraviolet light that is slightly reddish is defined. For example, if the SPF value is _ sunscreen cosmetics, it will produce the same sputum (erythema) as it is when it is exposed to ultraviolet light at 1G times that of sunburn. When the value is unclear, the sun may be different depending on the season. (4) The artificial light that is very close to the sun (the sun will investigate whether it produces red light every other day). In the measurement method, the ultraviolet rays are respectively irradiated (: the skin of the product and the skin coated with the product, and the ultraviolet protection of the 20-spot product can be used for a while. Therefore, it is hoped that a development can be made, for example, for the development stage: 5 In 2008, the evaluation of the UV-defense effect of the product can easily calculate the in vitro SPF (in vitro SPF) predicted value in relation to the in vivo SPF value (in vivo SPF value) obtained by the above method. In the method of evaluating the ultraviolet protection effect by in vitro measurement, it is known that a sample diluted with an organic solvent is placed in a quartz bath, and a dilute solution method for measuring the absorbance or transmittance of ultraviolet rays is known; The sample is formed into a film having a uniform thickness, and a film method for measuring the absorbance or transmittance of ultraviolet rays, etc. The conventional method is useful in grasping characteristics such as the maximum absorption wavelength and the defensive wavelength region of the ultraviolet absorber, but 10 The SPF value cannot be predicted. This method is based on the evaluation method of the ultraviolet defense effect, which greatly deviates from the method of measuring the SPF value in vivo. Therefore, the bio-reaction of the spF value is related to the wavelength of the ultraviolet ray, the ultraviolet ray wavelength which easily causes the erythema reaction, and the ultraviolet ray wavelength which does not easily cause the erythema reaction, and the influence of each wavelength on the living body must be considered according to each wavelength. In the non-patent document 1, the sample is applied to a medical tape as a skin substitute film, and the spectral transmission spectrum of the sample is measured, and the measurement result is calculated by the Diffey & Robson formula. The SPF value is different. The aforementioned Diffey & R〇bs〇n type system is related to the wavelength of the erythema reaction which is a human bio-reaction, and is obtained by using the red spot coefficient shown in 20 of Non-Patent Document 2, and can be successfully obtained. To solve the above problems. However, since there are various factors such as individual differences, site differences, age differences, gender differences, and skin type differences in the living body, there is a problem that it is difficult to correctly predict the SPF value by only one example of the red spot coefficient. Therefore, there is an evaluation method that uses not only the red spot coefficient, but also the SPF value from the living body. The relationship between the majority of the sample and the spectrally transmitted light is derived, and a statistically high correlation equation can be derived, and the evaluation method of the SPF value can be predicted even for an unknown sample (for example, refer to Patent Document 1). The evaluation method can be used to obtain the in vitro SPF prediction value of 5', which can also solve the jagged factors caused by individual differences, site differences, age differences, gender differences and skin type differences. Non-Patent Document 1 ·· Journal of the Society of c〇smetic Chemists (1989) 40; 33? 127-133 Non-Patent Document 2: CIE Journal (1987) 6; l, 17-22 10 Patent Document 1: Patent No. 3337832 L. (1) The present invention discloses a method for evaluating the ultraviolet protection effect disclosed in Patent Document 1, but it is possible to predict the SPF value by about 30 with high accuracy, but it is impossible to perform a sample having an SPF value of 30 or more. Correctly predicted problems. In recent years, products with an SPF value of 50 or higher are the mainstream, and it is estimated that products with higher spF values will be put on the market in the future. Further, there have been many recent reports on the deterioration of light 20 caused by ultraviolet light by ultraviolet light absorbers. Therefore, even in the method of calculating the in vitro SPF predicted value, it is indispensable to accurately estimate the equivalent value of the SPF value by reproducing the same light irradiation condition as the measurement condition of the SPF value in the living body. A ring. The present invention is made in view of the above points, and the object of the present invention is to determine the cause of the ultraviolet light method by in vitro measurement and the sweat of the fruit of the squarish squarish material (4). The photodegradation phenomenon of the sample caused by the irradiation of light provides a reversible
^ ^ 並且即使在SPF 高相關者 值較高的試料中，也可顯示與活體内spF值較 解決課題之手段 本發明之紫外線防禦效果之評估方法包含有：第工步 驟，係藉由以包含有紫外線之光源的光照射事先設定之^ 照射時間，而敎測定試料之分光透射光譜的經時變化 者；第2步驟，係根據前述第丨步驟所得之測定結果，進行 10因應前述測定試料之前述分光透射光譜經時變化的修正 者；及第3步驟，係使用根據前述第2步驟所得之修正結果， 算出前述測定試料之最終活體外SPF預測值者。 本發明之紫外線防禦效果之評估裝置包含有^經時變 化測又機構，係藉由以包含有紫外線之光源的光照射事先 15言=之光照射時間’而測定測定試料之分光透射光譜的經 時變化者；修正機構，係根據前述敎機構所得之測定結 果進行因應别述測定試料之前述分光透射光譜經時變化 的修正者；及SPF預測值算出機構，係使用根據前述修正機 構所得之修正結果，算出前述測定試料之最終活體外 20 預測值者。 ' 發明之效果 根據本發明，可提供一種藉由活體外測定而進行的紫 外線防禦效果之評估方法及使用該方法之紫外線防禦效果 的。平估裝置，係可反映出因照射光而引起的試料光劣化現 8 200819728 象，並且，即使在SPF值較高的試料中，也可顯示與活體内 SPF值較高相關者。 圖式簡單說明 第1圖係顯示本實施型態之紫外線防禦效果評估裝置 5 之概略構成之一例的圖。 第2圖係顯示本實施型態之紫外線防禦效果評估裝置 之機能構成之一例的圖。 第3圖係顯示本實施型態之標準試料中之已知活體内 SPF值及所預測之活體外gjpF值之相關的圖。 10 第4(a)、（b)圖係顯示本實施型態之紫外線防禦效果之 評估方法的流程圖。 L實施方式】 實施發明之最佳型態 以下，與圖示一併說明本發明之最佳實施型態。 15 本實施型態之紫外線防禦效果之評估方法、及使用前 述方法之紫外線防禦效果之評估裝置係進行正式測定，而 前述正式測定係由例如以下步驟所構成：第丨步驟，係藉由 以包含有紫外線之光源的光照射事先設定之光照射時間， 而測定測定試料之分光透射光譜的經時變化者；第2步驟， 20係進行因應所得之分光透射光譜經時變化的修正者；及第3 步驟，係算出測定試料之最終活體外SPF預測值者。 另外，在第1步驟中，也可進行預備測定，而前述預備 測定包含有例如以下步驟：以290至400nm之紫外線依每 lnm測定測定試料之分光透射光譜；以及從所得之分光透射 9 200819728 光譜決定後述之正式測定的光照射時間。以下，說明前述 方法及裝置。 (評估裝置之概略構成例） 第1圖係顯示本貫施型態之紫外線防禦效果評估裝置 5 之概略構成之一例的圖。 -芩知、第1圖，紫外線防禦效果之評估裝置1〇大致構成為 包含有·光源11，濾波器12 ;光纖13 ;照射埠14 ;皮膚代 替膜16;分光器17;光檢測器18;及電算機19。前述紫外 線防禦效果之評估裝置10係將後述之紫外線防禦效果的評 10 估方法使用於測定試料的裝置。 光源11在本實施型態中適合使用氙氣燈，但並不限定 於此。又，光源11係連接於後述之電算機19，由電算機19 控制光源11的ΟΝ/OFF。 濾波器12位於來自於光源11之光的行進方向附近，使 15光源丨1所發出的光線為例如290至400nm波長之UVB及UVA 紫外線等預定之紫外線區域。此係為了再現活體内SpF測定 現場之光源而進行照射。又，上述使光線為29〇至4〇〇11111波 長之UVB及UVA紫外線的濾波器12，宜使用WG320濾波器 及UG11濾波器（皆為schott社製），但並不限定於該等， 2〇 了因應所1¾之紫外線區域而使用適宜的濾、波器。 光纖13位於來自於濾波器12之光的行進方向附近，可 將透過濾波器12之紫外線導向照射埠14。 由照射埠14照射上述紫外線，以預定間隔固定照射埠 14與光檢測器18，並將以預定量及方法塗布有試料15之皮 200819728 膚代替膜16，固定於相對於照射埠14為一定距離之位置。 若以光行進之方向為順序來表示，則以照射埠14、試料15、 皮膚代替膜16、分光器17及光檢測器18之順序來配置。另 外，前述至皮膚代替膜16之配置係以international 5 SUN PROTECTION FACTOR(SPF) TEST METHOD, February 2003所規定之活體内SPF測定法為基準。 皮膚代替膜16係塗布有測定試料15而代替活體内SPF 測定之生體的皮膚者，宜由290至400nm之不吸收紫外線的 素材所構成，在非專利文獻1中，揭示了使用醫療用膠帶作 10為皮膚代替膜的方法。在本實施型態中，宜使用PMMA(聚 甲基丙浠酸曱酉旨）樹脂板(Plexiglas™，Schonberg GmbH & Co· KG社製），但並非限定於此。 光檢測器18係將290至400nm之範圍的光以1 nm間隔藉 由分光器17進行分光，將各強度轉換成電壓，更進行a/d 15 轉換輸出至電算機19。而在紫外線防禦效果之評估裝置1〇 中，光檢測器18檢測透過上述測定試料15及皮膚代替膜16 的光線。 電算機19從光檢測器18輸入各lnm之分光強度，進行 下述之處理，算出正式測定之光照射時間及最終活體外SPF 20 預測值。又，電算機19如上所述地控制光源11之ON/OFF。 另外，電算機19接收來自於光檢測器18之資料，將資 料進行處理，以使前述資料從前述内容變成用戶較容易瞭 解的型態，並可將結果顯示於畫面、將結果列印在記錄紙 上、或是將結果保存於記憶媒體中。又，電算機19可使用 11 200819728 例如一般用之個人電腦4，可藉由來自於用戶以輸入機構 等之指示等，來實行上述之評估裴置10的各機能。 (評估裝置之機能構成例） 第2圖係顯示本實施型態之紫外線防禦效果評估裝置 5 之機能構成之一例的圖。 參照第2圖，紫外線防禦效果之評估裝置1〇大致包含 有：輸入機構21 ;輸出機構22 ;儲存機構23 ;分光透射光 譜測定機構24 ;照射時間設定機構25 ;經時變化測定機構 26，修正機構27，SPF預測值异出機構28 ;及控制機構29。 1〇 輸入機構21係設置於例如電算機19，負責處理來自於 用戶等之評估開始指示、或使輸出機構22輸出測定結果等 的各種資料輸入。另外’輸入機構21係由例如鍵盤或滑氣 等指向裝置等所構成。 又，輸出機構22係設置於例如電算機19，進行由輸入 15 機構21所輸入之内容或根據輸入内容所實行之内容等的顯 示、輸出。另外，輸出機構22係由顯示器或揚聲器等所構 成。此外，輸出機構22也可具有印表機等的機能，在前述 情況下，可將簡單的測定結果或算出結果等印刷於紙等印 刷媒體，而提供給用戶等。 20 且，儲存機構23係設置於例如電算機19，可儲存以分 光透射光谱測定機構24所測疋之結果、或由照射時間設定 機構25所設定之照射時間、經時變化測定機構26所測定之 結果、由修正機構27所得之修正資訊、SPF預測值算出機構 28所算出之結果等的各種資料。 12 200819728 又，分光透射光譜測定機構24可藉由例如光檢測器i8 等依各1 nm測定290至400nm之紫外線對於測定試料丨5之分 光透射光譜。亦即，分光透射光譜測定機構24係進行用以 測定正式測定之光照射時間的預備測定。又，照射時間設 5 定機構25作為電算機19的機能，可根據由上述之分光透射 光譜測定機構24之預備測定而得的分光透射光譜，來設定 光照射時間。另外’關於詳細的預備測定，容後再述。 又，經時變化測定機構26作為電算機19的機能，可藉 由照射由照射時間設定機構25所設定之光照射時間的光， 10 來測定測定試料15之分光透射光譜的經時變化。另外，經 時變化設定機構26可測定測定試料15之分光透射光譜因光 劣化而產生的經時變化。藉此，可算出反映出因照射光而 產生之試料光劣化現象的活體外SPF預測值。 且，修正機構27作為電算機19的機能，可根據由經時 15 變化測定機構26所得之測定結果，進行因應測定試料15之 分光透射光譜之經時變化的修正。此外，SPF預測值算出機 構28作為電算機19的機能，可使用由修正機構27所得之修 正結果，來算出測定試料之最終活體外SPF預測值。 另外，控制機構29作為電算機19的機能，可進行評估 20 裝置10之各構成部全部的控制。具體而言，例如根據由用 戶等來自於輸入機構21之指示，進行分光透射光譜之測定 或照射時間之設定、光劣化測定、因應分光透射光譜之經 時變化的修正、活體外SPF預測值之算出等的控制。又，控 制機構29作為電算機19的機能，可進行光源11之On/off 13 200819728 的控制。另外，關於正式測定之詳細情形，容後再述。 (關於預備測定） 在此，如下所述，在預備測定時，光檢測器18會依預 定之波長間隔測定例如290至40〇11111之紫外線區域的分光透 5射光譜。另外，預定之波長間隔係例如各lnm或各5nm等， 但在本發明中並無特別限定。因此，在以下說明中，舉一 例如依各lnm而測定者。又，為了依各lnm而進行測定，需 要感度特性可配合前述波長區域之光檢測器18及分光器 17，但並非特別限定者。不過，為了依各lnm測定分光透射 10光譜，分光器I7之波長分解能須在lnm以下。 紫外線防禦效果之評估裝置及評估方法中，測定試料 之分光透射光譜時，SPF值越高的試料，試料對於紫外線吸 收的效果越高，結果透射光量會變少。因此，為了對於spF 值超過50的高SPF值試料也能高精準度地預測spF值，需要 15具微弱光檢測感度優異的光檢測器。至今，光檢測器一般 係使用光二極體陣列及CCD等，但是，近年來由於微弱光 檢測技術的進步，利用提高檢測感度之光電倍增管的情形 也變多了，比起迄今之光二極體陣列及CCd，從理論上來 看檢測感度較高係非常明顯之事，但須因應所檢測之光的 2〇波長區域而選定光電倍增管的光電性表面之素材。在本實 施型悲中，藉由使用在290至400nm之紫外線區域具優異感 度特性的光電倍增管，可測定至高SPF值的試料。 (預備測定與光照射時間之決定） 在本實施型態中，在正式測定之前先進行測定試料之 200819728 分光透射光譜的預備測定。從前述預備測定所得之試料的 分光透射光譜，決定正式測定之光照射時間。決定前述光 照射時間的方法係始於根據活體内SPF值為已知之標準今式 料的測定結果，先算出暫定活體外SPF預測值。 5 對於活體内SPF值為已知之複數標準試料，測定分光透 射光譜，從各波長之透射光強度將前述光譜與已知之活體 内SPF值的相關關係進行多變量分析。分析方法係從由前述 多變量分析所求出之數值與活體内SPF值的關係而描出之 點群所構成的檢量線、及測定試料之分光透射光譜的結 10 果，求出接近活體内SPF值之暫定活體外SPF預測值者。 又，本實施型態之多變量分析之特徵在於使用習知分 析法之PLS(Partial Least Squares :部分最小平方）回歸分析 法。通常所使用之複回歸分析法係利用使用於分析之全部 參數而進行回歸分析的方法，在原理上可使用於包含多種 15 因素之資料分析。但是，在說明變數較目的變數為多時’ 因為進行過度的擬合，而無法得到適當的回歸式。另一方 面，本實施型態所使用之PLS回歸分析係在有多數說明變數 時可建構預測模型的一種方法。PLS回歸分析中，預測為最 終目標，在實際上無須限制所測量之因素數時，為非常有 2〇 用的方法，例如，如本次使用於分光光譜之資料等時即非 常有用。 第3圖係顯示本實施型態之標準試料中之已知活體内 SPF值及所預測之活體外spf值之相關的圖。 參照第3圖，第3圖係關於活體内SPF值為已知之標準試 15 200819728 料，藉由上述PLS回歸分析法預測spF值的結果。橫軸為已 知的活體内SPF值，縱軸為活體外spF預測值。 另外，第3圖之縱軸所示之活體外spF預測值係經過預 備測定及後述之正式測定，藉由考慮試料之光劣化現象而 5預測的結果’如相關係數(R2=0.9743)所示，為活體外SPF 值之預測精準度高者。 測定試料之光照射時間係重現使用實際生體而進行之 活體内SPF測定現場的條件，暫定活體外SPF預測值越高， 則光照射時間也越長，而與活體外SPF預測值成比例關係地 1〇设定。因此，在活體内SPF值之測定現場，根據 lMED(Minimal Erythema Dose :皮膚最低致紅量）而進行計 算。在此，1MED係指在活體内SPF值之測定現場，引起被 試驗者被試驗部位之最小紅斑量所需的紫外線光量。 由於使用於活體内SPF值測定現場之紫外線燈（太陽光 15源模擬器），光源之光量及光譜分布皆規格化，故1MED主 要係以時間單位來表現。此係在SPF測定現場時，於被試驗 部位以無塗布試料之狀態進行確認者。 如上所述，雖有各人之個體差異、部位差異、年齡差 異、性別差異及皮膚型態差異等參差不齊的原因，但在本 20 實施型態中，將1MED假定為5秒(0.083分）至90秒（1.5分）之 範圍内。由於前述假設條件，本實施型態之正式測定時之 光照射時間為暫定活體外SPF預測值χ0·08(分）以上、小於暫 定活體外SPF預測值χ1·5(分）。從資料的再現性等觀點來 看，本實施型態中，更宜使1MED為10秒至60秒的範圍，更 16 200819728 以20秒至50秒之範圍為佳。以前述換算來計算光照射時 間’則在預備測定時暫定活體外spF預測值為5〇、1MED為 30秒(0.5分）的情況下，進行5〇χ〇5=25分的光照射。 上述光照射時間的算出係以電算機19進行，又，在後 5述之正式測定中，電算機19控制光源11而使之為預定之光 照射時間。 (正式測定與因應光劣化之修正） 正式測定係將290至400nm之紫外線照射於測定試 料’並持續從上述預備測定之結果算出的光照射時間。此 10時’測定測定試料之分光透射光譜的經時變化，進行因應 測定試料之光劣化變化的修正處理，並且算出最終之活體 外SPF預測值。 在此，測定試料之光劣化現象係指因為有機系紫外線 吸收劑接受光照射而引起異性化等，而使本來的紫外線吸 15收能力降低。亦即，因為光劣化現象，而使測定試料之SPF 值降低（例如，參照 Photodegradation of Sunscreen Chemicals : Solvent Consideration，Cosmetics & Toiletries (1990) 105:41-44) 〇 即使在活體内SPF值測定現場，也會持續地進行光照 20射，因此即使在生體皮膚上的試料，也會產生前述光劣化 現象。在本評估系統中，可確認為伴隨著光照射之試料透 射光譜變化、即透射光量增加的現象。 再現試料之光劣化的目的在於測定持續光照射條件下 之为光透射光請的時間變化，考慮來自於預備測定所得、 17 200819728 未反映光劣化之暫定活體外SPF預測值因光劣化而引起的 相當於低下的部分，而算出高精準度的最終活體外spF預測 值。 正式測定時之測定試料分光透射光譜的經時變化檢 5測，係以秒為單位控制從上述預備測定所求出之光照射時 間，並且，可在别述光照射時間中之任意各時間取得分光 透射光譜資料。 具體而s，在電异機19之處理中，可以秒為單位設定 光妝射日守間的條件為幾分幾秒。又，即使對於前述光照射 10時間中之經時光譜變化，也可以各1分或將照射時間均等為 10等份的時間間隔等任意時間間隔來取得。宜對於預定之 光照射時間進行均等地時間分割而為6個以上(也包含時間 為0之光照射開始時），更以取得11個以上之光譜資料為 仏之間的光瑨資料越多，越能詳細地把握試料的光劣化 15畅幵》，因此可提高預測的精準度。 此N*為了正確地取得光照射時測定試料之光劣化現 象，不變動測定試料及裝置全體。將完全固定之同一個時 Η欠化f月幵乂取得作為光譜資料，在提高預測 精準度係非常 重要之事。 20 «上述正式測定之測定試料的分光透射光譜之經時變 化檢測結果，進彳千㈤ > 哭订因應測定試料光劣化變化的修正處理。 月〕^正處理係藉由從290至400nm之紫外線區域中之試料 '光透射光邊之時間平均光譜來預測活體外Spf預測值 而達成。 18 200819728 如上述之預備測定所說明，只要決定測定試料之分光 透射光譜，便可以某種程度之精準度決定活體外SPF預測 值。亦即，除了把握伴隨正式測定時之測定試料光劣化的 分光透射光譜時間變化情形，採用何種分光透射光譜於決 5 定測定試料之活體外SPF預測值，在高精準度之測定上係非 常重要之事。 若採用時間為零、即光照射開始時之分光透射光譜資 料，則可得到與預備測定時之暫定活體外SPF預測值相同的 值。但是，該數值未能反映持續光照射下測定試料的光劣 10 化現象，故會預測出較本來應預測之SPF值還高的數值。 又，若採用正式測定時光照射時間結束時之最後的分光透 射光譜資料，則為因為光劣化而結束充分變化、即已接受 過剩的光照射條件的光譜資料，因此會預測出較本來之測 定試料SPF值還低之值的SPF值。 15 由於上述情形，為了反映本來的時間變化分布，宜藉 由分光透射光譜之時間積分，算出與皮膚暴露於同時間之 現象一樣的總透射光量，並預測活體外SPF值。 然而，有鑑於計算處理的繁雜，在本實施型態中，對 於時間變化之分光透射光譜資料，導入稱為時間平均光譜 20 的計算方法。若使用前述時間平均光譜的想法而算出活體 外SPF預測值，則可建構出可求出與活體内SPF值相關性高 的最終活體外SPF預測值的方法。 在此所示之時間平均光譜係指將從以任意次數所取得 之光照射開始時的光譜資料，至光照射時間最後的光譜資 19 200819728 料為止的全部資料’使依各波長之分光透射強度平均化處 理者。 具體而言，最終活體外SPF預測值係對於上述活體内 SPF值為已知之複數標準㈣測定分光透射光譜，藉由從依 5各波長之透射光強度，將前述光譜與已知之活體内SPF值的 相關關係以PLS回歸分析法進行分析，並從藉由上述而導出 的檢量線、及將正式測定所得之分光透射光譜依時間平均 修正後的結果而算出前述最終活體外SPF預測值。 藉由導入上述算出方法，從容易受光劣化影響的測定 10試料至不易受光劣化現象影響的測定試料，皆可用同樣的 計算方法預測最終活體外SPF值。 (紫外線防禦效果之評估方法的流程） 第4圖係顯示本實施型態之紫外線防禦效果之評估方 法的流程圖。 15 關於上述之紫外線防禦效果之評估方法，整理如以下 步驟。參照第4(a)圖，說明在正式測定前先進行之預備測定 的流程。 依各1 nm測定290至400nm之紫外線區域中的試料之分 光透射光譜(S101)。 使用藉由多變量回歸分析法將活體内SPF值為已知之 標準試料的分光透射光譜、及活體内SPF值的相關所求$ # 檢量線，從分光透射光譜算出測定試料之暫定活體外spF 預測值(S102)。 相對於暫定活體外SPF預測值[A]，將光照射時間決定 20 200819728 為[Α]χ0·08(分）以上、小於[Α]χ1·5(分）的範圍内（S103)。 參照第4(b)圖，說明在預備測定後進行的正式測定的流 程。 將光持續照射於測定試料上S103所決定之時間，依各 5 任意之經過時間取得分光透射光譜資料(S151)。 對於所得之各經過時間的分光透射光譜進行時間平均 化處理，算出已修正測定試料之光劣化的時間平均光譜 (S152)。 使用所得之時間平均光譜、及S102所求出之檢量線， 10 算出最終活體外SPF預測值(S153)。 在此，在上述實施型態中，係對於在正式測定前進行 預定測定的處理進行說明，但例如在有以本測定系統評估 與過去同樣的樣本的實際成效時、即使沒有測定實際成效 也可從有測定實際成效之類似處方例而容易預測時（例 15 如，當曾以氧化鈦10%預測為SPF20、同樣之5%預測為 SPF10時，可將氧化鈦7%之處方預測為SPF14等）、又從經 驗可知活體内SPF值時等情況下，可因應需要而省略預備測 定。亦即，為了進行高精準度的預測，預備測定很重要， 但可因應須縮短處理時間等之各種條件而將之省略。 20 實施例 藉由實施例，更詳細地說明本實施型態。另外，以下 之實施例顯示進行預備測定之例。 [實施例1] (測定條件） 21 200819728 在上述實施型態所表示之測定裝置中，藉由使氣氣燈 光源所發出之光線分別透過WG320濾波器及UG11渡波哭 (皆為SCHOTT社製），得到290至400nm波長之光線。關於皮 膚代替膜，使用PMMA(聚甲基丙烯酸曱酿）樹脂板 5 (Plexiglas™，Schonberg GmbH & Co. KG社製），配置於相對 於光源1至2mm的照射距離。此時，UV-B之強度為2.0Med/ 分。塗布在PMMA樹脂板上之試料量為〇.75mg/cm2，祥量 預定量之試料後，對於PMMA樹脂板表面以手指塗勻丨分鐘 而進行塗布。在塗布後，以25°C之條件，進行15分鐘的試 10料乾燥。又，在預備測定時，對於1MED進行30秒的光照射。 (試料測定） 在上述測定條件中，對於活體内SPF值為未知的試料A 進行測定。預備測定的結果，暫定活體外SPF預測值為 29·8 ’故正式測定之光照射時間決定為29.8χ〇·5=14·9分（14 15分54秒）。在正式測定時，進行前述光照射時間的持續照 射。又’以等間隔使光照射時間14分54秒為5等分，取得包 含光照射開始時合計為6點之光譜資料。對於前述6點之光 譜資料’依各波長算出時間平均光譜，得到最終活體外SPF 預測值21.9。前述最終活體外SpF值近似於後來所得之活體 20内SPF值22·5。對於試料A之活體内SPF值以及暫定及最終 活體外SPF預測值顯示於表1。 22 200819728 表1 測定試料 暫定活體外 SPF預測值 最終活體外 SPF預測值 實施例1 29.8 21.9 _ —-—_ 比較例1 A — 24.6 比較例2 一 40.5 實施例2 70.5 62.4 比較例3 B 一 33.3 比較例4 一 84.6 實施例3 32.9 32.2 比較例5 C 一 26.0 —- 比較例6 — 81.7 31.5 [實施例2]^ ^ and even in the sample with high SPF high correlation value, it can display the solution with the in vivo spF value. The method for evaluating the ultraviolet protection effect of the present invention includes: the first step, by including The light having the ultraviolet light source is irradiated with the irradiation time set in advance, and the time-dependent change of the spectral transmission spectrum of the sample is measured; and the second step is performed according to the measurement result obtained in the above-mentioned second step, and the sample is subjected to the above-mentioned measurement. The correction of the spectral transmission spectrum with time is changed; and the third step is to calculate the final in vitro SPF prediction value of the measurement sample by using the correction result obtained in the second step. The evaluation device for the ultraviolet protection effect of the present invention comprises a mechanism for measuring the spectral transmission of the sample by irradiating the light irradiation time of the light source with the light source containing the ultraviolet light. The correction means is a correctionr for determining the temporal change of the spectral transmission spectrum of the sample according to the measurement result obtained by the enthalpy mechanism; and the SPF prediction value calculation means using the correction obtained by the correction mechanism As a result, the final in vitro 20 predicted value of the above-described measurement sample was calculated. Effect of the Invention According to the present invention, it is possible to provide an evaluation method of the ultraviolet defense effect by in vitro measurement and an ultraviolet protection effect using the same. The flattening device can reflect the photodegradation of the sample due to the irradiation of light, and even in the sample with a high SPF value, the correlation with the SPF value in the living body can be displayed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a schematic configuration of an ultraviolet protection effect evaluation device 5 of the present embodiment. Fig. 2 is a view showing an example of the functional configuration of the ultraviolet protection effect evaluation device of the present embodiment. Fig. 3 is a graph showing the correlation between the known in vivo SPF value and the predicted in vitro gjpF value in the standard sample of this embodiment. 10 Sections 4(a) and (b) show a flow chart showing the evaluation method of the ultraviolet protection effect of this embodiment. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the invention will be described together with the drawings. 15 The evaluation method of the ultraviolet protection effect of the present embodiment and the evaluation device for the ultraviolet protection effect using the above method are performed, and the above-mentioned formal measurement is constituted by, for example, the following steps: the third step is to include The light having the ultraviolet light source is irradiated with the light irradiation time set in advance, and the time-dependent change of the spectral transmission spectrum of the measurement sample is measured; and in the second step, 20 is the correction of the time-dependent change of the spectral transmission spectrum obtained; and In the third step, the final in vitro SPF predicted value of the sample is calculated. Further, in the first step, preliminary measurement may be performed, and the preliminary measurement includes, for example, a step of measuring a spectral transmission spectrum of the measurement sample per 1 nm by ultraviolet rays of 290 to 400 nm; and a spectral transmission from the obtained spectral transmission 9 200819728 The light irradiation time of the official measurement described later is determined. Hereinafter, the above method and apparatus will be described. (Schematic configuration example of the evaluation device) Fig. 1 is a view showing an example of a schematic configuration of the ultraviolet protection effect evaluation device 5 of the present embodiment. - 芩 、 第 第 第 第 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线And computer 19. The ultraviolet light defense effect evaluation device 10 is a device for measuring a sample using a method for estimating the ultraviolet protection effect to be described later. The light source 11 is suitably a xenon lamp in this embodiment, but is not limited thereto. Further, the light source 11 is connected to a computer 19 to be described later, and the computer 19 controls the ΟΝ/OFF of the light source 11. The filter 12 is located in the vicinity of the traveling direction of the light from the light source 11, and the light emitted from the light source 丨1 is, for example, a predetermined ultraviolet region such as UVB and UVA ultraviolet rays having a wavelength of 290 to 400 nm. This is to illuminate the light source in the on-site SpF measurement site. Further, the filter 12 for UVB and UVA ultraviolet rays having a light beam of 29 〇 to 4 〇〇 11111 wavelength is preferably a WG320 filter or a UG11 filter (all manufactured by Schott Co., Ltd.), but is not limited thereto. Use a suitable filter and wave filter in response to the UV area of the 13⁄4. The optical fiber 13 is located in the vicinity of the traveling direction of the light from the filter 12, and can guide the ultraviolet rays transmitted through the filter 12 to the illumination pupil 14. The ultraviolet ray is irradiated by the irradiation cymbal 14, and the irradiation cymbal 14 and the photodetector 18 are fixed at predetermined intervals, and the skin of the sample 15 is applied to the skin of the sample 15 by a predetermined amount and method, and is fixed at a certain distance from the irradiation cymbal 14. The location. When the direction in which the light travels is shown in order, the irradiation of the crucible 14, the sample 15, the skin substitute film 16, the spectroscope 17, and the photodetector 18 are arranged in this order. Further, the above-described configuration to the skin substitute film 16 is based on the in-vivo SPF measurement method prescribed by the international 5 SUN PROTECTION FACTOR (SPF) TEST METHOD, February 2003. In the case of the skin substitute film 16 which is coated with the sample 15 and the skin of the living body which is measured by the SPF in the living body, it is preferably composed of a material which does not absorb ultraviolet rays of 290 to 400 nm, and Non-Patent Document 1 discloses the use of medical tape. A method in which 10 is a skin instead of a film. In the present embodiment, a PMMA (polymethyl phthalic acid) resin sheet (PlexiglasTM, manufactured by Schonberg GmbH & Co. KG) is preferably used, but is not limited thereto. The photodetector 18 splits light in the range of 290 to 400 nm by the spectroscope 17 at intervals of 1 nm, converts each intensity into a voltage, and further converts the output to the computer 19 by a/d 15 conversion. In the ultraviolet protection effect evaluation device 1A, the photodetector 18 detects the light transmitted through the measurement sample 15 and the skin substitute film 16. The computer 19 inputs the spectral intensity of each of 1 nm from the photodetector 18, and performs the following processing to calculate the light irradiation time and the final in vitro SPF 20 predicted value. Further, the computer 19 controls ON/OFF of the light source 11 as described above. In addition, the computer 19 receives the data from the photodetector 18, and processes the data so that the aforementioned data becomes a type that the user can easily understand from the foregoing content, and can display the result on the screen and print the result on the record. Save the result on paper or in a memory medium. Further, the computer 19 can use 11 200819728, for example, a general-purpose personal computer 4, and can perform the functions of the above-described evaluation device 10 by an instruction from an input device or the like from the user. (Example of the functional configuration of the evaluation device) Fig. 2 is a view showing an example of the functional configuration of the ultraviolet protection effect evaluation device 5 of the present embodiment. Referring to Fig. 2, the ultraviolet protection effect evaluation device 1A roughly includes an input mechanism 21, an output mechanism 22, a storage mechanism 23, a spectroscopic transmission spectrum measuring mechanism 24, an irradiation time setting mechanism 25, and a temporal change measuring mechanism 26, which is corrected. Mechanism 27, SPF predictive value discarding mechanism 28; and control mechanism 29. The input mechanism 21 is provided, for example, in the computer 19, and is responsible for inputting various data input from the evaluation start instruction from the user or the like, or outputting the measurement result by the output unit 22. Further, the input means 21 is constituted by a pointing device such as a keyboard or a slipper. Further, the output unit 22 is provided, for example, on the computer 19, and displays and outputs the content input by the input unit 15 or the content executed based on the input content. Further, the output mechanism 22 is constituted by a display, a speaker, or the like. Further, the output unit 22 may have a function of a printer or the like. In the above case, a simple measurement result, a calculation result, or the like can be printed on a printing medium such as paper, and supplied to a user or the like. Further, the storage unit 23 is provided, for example, on the computer 19, and can store the result measured by the spectral transmission spectrum measuring unit 24 or the irradiation time set by the irradiation time setting unit 25 and the measurement by the time change measuring unit 26. As a result, various pieces of information such as the correction information obtained by the correction unit 27 and the result calculated by the SPF predicted value calculation unit 28 are used. Further, the spectroscopic transmission spectrum measuring means 24 can measure the spectral transmission spectrum of the sample 丨 5 by measuring ultraviolet rays of 290 to 400 nm at a distance of 1 nm, for example, by a photodetector i8. That is, the spectroscopic transmission spectrum measuring means 24 performs preliminary measurement for measuring the light irradiation time of the official measurement. Further, the irradiation time setting means 25 as the function of the computer 19, and the light irradiation time can be set based on the spectral transmission spectrum obtained by the preliminary measurement by the above-described spectral transmission spectrum measuring means 24. In addition, the detailed preliminary measurement will be described later. Further, as the function of the computer 19, the temporal change measuring means 26 can measure the temporal change of the spectral transmission spectrum of the measurement sample 15 by irradiating the light of the light irradiation time set by the irradiation time setting means 25. Further, the change over time setting means 26 can measure the temporal change of the spectral transmission spectrum of the measurement sample 15 due to photodegradation. Thereby, the in vitro SPF predicted value reflecting the photodegradation phenomenon of the sample due to the irradiation light can be calculated. Further, the correction mechanism 27 functions as the computer 19, and corrects the change over time in the light transmission spectrum of the sample 15 according to the measurement result obtained by the time measuring means 26. Further, the SPF predictive value calculating means 28 functions as the computer 19, and the final in vitro SPF predicted value of the measured sample can be calculated using the correction result obtained by the correcting means 27. Further, as the function of the computer 19, the control unit 29 can perform control of all the components of the evaluation unit 20. Specifically, for example, the measurement of the spectral transmission spectrum, the setting of the irradiation time, the measurement of the photo-deterioration, the correction of the temporal change in response to the spectral transmission spectrum, and the prediction of the in vitro SPF are performed in accordance with an instruction from the user or the like from the input means 21. Calculate the control of etc. Further, as the function of the computer 19, the control unit 29 can control the On/off 13 200819728 of the light source 11. In addition, the details of the formal measurement will be described later. (Regarding preliminary measurement) Here, as described below, at the time of preliminary measurement, the photodetector 18 measures a spectroscopic spectrum of an ultraviolet region of, for example, 290 to 40 〇 11111 at a predetermined wavelength interval. Further, the predetermined wavelength interval is, for example, 1 nm each or 5 nm each, but is not particularly limited in the present invention. Therefore, in the following description, for example, one is measured per 1 nm. Further, in order to perform measurement in accordance with each of 1 nm, it is necessary to mix the photodetector 18 and the spectroscope 17 in the wavelength region described above, but it is not particularly limited. However, in order to measure the spectral transmission 10 spectrum at each lnm, the wavelength decomposition energy of the spectroscope I7 must be below 1 nm. In the evaluation device and evaluation method for the ultraviolet protection effect, when the spectroscopic transmission spectrum of the sample is measured, the higher the SPF value, the higher the effect of the sample on the ultraviolet absorption, and the smaller the amount of transmitted light. Therefore, in order to accurately predict the spF value for a high SPF sample having an spF value of more than 50, 15 photodetectors excellent in sensitivity to light detection are required. In the past, photodetectors have generally used photodiode arrays, CCDs, etc., but in recent years, due to advances in weak light detection technology, the use of photomultiplier tubes that improve detection sensitivity has also increased, compared to the light diodes hitherto. Arrays and CCd are theoretically very sensitive to detect high sensitivity, but the photo-electric surface of the photomultiplier tube must be selected in response to the 2 〇 wavelength region of the detected light. In the present embodiment, a sample having a high SPF value can be measured by using a photomultiplier tube having excellent sensitivity characteristics in an ultraviolet region of 290 to 400 nm. (Preparation measurement and determination of light irradiation time) In the present embodiment, preliminary measurement of the 200819728 spectral light transmission spectrum of the measurement sample is performed before the formal measurement. The light irradiation time of the official measurement is determined from the spectral transmission spectrum of the sample obtained by the preliminary measurement. The method for determining the above-mentioned light irradiation time starts from the measurement result of the standard present material whose SPF value is known in vivo, and the tentative in vitro SPF prediction value is first calculated. 5 For a complex standard sample in which the SPF value is known in vivo, the spectroscopic transmission spectrum is measured, and the correlation between the spectrum and the known SPF value in the living body is multivariate analysis from the transmitted light intensity at each wavelength. The analysis method is based on the relationship between the calibration curve formed by the point group and the measurement of the spectral transmission spectrum of the sample from the relationship between the value obtained by the multivariate analysis and the SPF value in the living body, and the result is obtained in close proximity to the living body. Temporary in vitro SPF predictors of SPF values. Further, the multivariate analysis of this embodiment is characterized by the PLS (Partial Least Squares) regression analysis using the conventional analysis method. The complex regression analysis method usually used is a method of regression analysis using all the parameters used in the analysis, and in principle can be used for data analysis including a plurality of 15 factors. However, when the variable is described as being more variable than the objective variable, an excessive regression is not performed, and an appropriate regression equation cannot be obtained. On the other hand, the PLS regression analysis used in this embodiment is a method for constructing a prediction model when there are a large number of explanatory variables. In the PLS regression analysis, the prediction is the final goal, and it is very useful when there is no need to limit the number of factors to be measured. For example, it is very useful when used in the data of the spectroscopic spectrum. Fig. 3 is a graph showing the correlation between the known in vivo SPF value and the predicted in vitro spf value in the standard sample of this embodiment. Referring to Fig. 3, Fig. 3 shows the results of predicting the spF value by the above PLS regression analysis on the standard SPF value in vivo. The horizontal axis is the known in vivo SPF value, and the vertical axis is the in vitro spF predicted value. In addition, the in vitro spF predicted value shown on the vertical axis of Fig. 3 is subjected to preliminary measurement and subsequent measurement, and the result of prediction by the light deterioration phenomenon of the sample is considered as shown by the correlation coefficient (R2 = 0.9743). , the accuracy of the prediction of in vitro SPF values is high. The light irradiation time of the sample is used to reproduce the conditions of the SPF measurement site in vivo using the actual living body. The higher the SPF prediction value is, the longer the light irradiation time is, and the proportional to the in vitro SPF prediction value. The relationship is set to 1〇. Therefore, the measurement of the SPF value in the living body is performed based on lMED (Minimal Erythema Dose). Here, 1MED refers to the amount of ultraviolet light required to cause the minimum amount of erythema of the test subject to be tested at the site where the SPF value is measured in vivo. Since the UV light (solar 15 source simulator) used in the on-site SPF value measurement is used, the light quantity and spectral distribution of the light source are normalized, so 1MED is mainly expressed in time units. This is the case where the test site is in the state where the sample is not coated at the SPF measurement site. As mentioned above, although there are differences in individual differences, site differences, age differences, gender differences, and skin pattern differences, in the 20th embodiment, 1MED is assumed to be 5 seconds (0.083 points). ) to within 90 seconds (1.5 points). Due to the above assumptions, the light irradiation time in the formal measurement of the present embodiment is a tentative in vitro SPF predicted value of χ0·08 (min) or more, and less than a tentative in vitro SPF predicted value of χ1·5 (minute). From the viewpoint of reproducibility of data, etc., in the present embodiment, it is preferable to make 1MED in the range of 10 seconds to 60 seconds, and more preferably 16200819728 in the range of 20 seconds to 50 seconds. When the light irradiation time was calculated by the above conversion, when the pre-existing spF predicted value was 5 〇 and 1 MED was 30 seconds (0.5 minutes) at the time of preliminary measurement, light irradiation of 5 〇χ〇 5 = 25 minutes was performed. The calculation of the light irradiation time is performed by the computer 19, and in the final measurement described later, the computer 19 controls the light source 11 to have a predetermined light irradiation time. (Formal measurement and correction of the photodegradation according to the measurement) The official measurement system irradiates ultraviolet light of 290 to 400 nm to the measurement sample ′ and continues the light irradiation time calculated from the result of the preliminary measurement. At 10 o'clock, the temporal change of the spectral transmission spectrum of the measurement sample was measured, and a correction process for measuring the photodegradation change of the sample was performed, and the final in-vivo SPF prediction value was calculated. Here, the measurement of the photodegradation phenomenon of the sample means that the organic ultraviolet ray absorbing agent is subjected to light irradiation to cause anisotropy or the like, and the original ultraviolet ray absorbing ability is lowered. That is, the SPF value of the measurement sample is lowered due to the photodegradation phenomenon (for example, refer to Photodegradation of Sunscreen Chemicals: Solvent Consideration, Cosmetics & Toiletries (1990) 105: 41-44) 〇 even in the in vivo SPF value measurement site Since the light is continuously emitted, the above-described photodegradation phenomenon occurs even in the sample on the skin of the living body. In the evaluation system, it was confirmed that the sample had a change in the transmission spectrum with light irradiation, that is, a phenomenon in which the amount of transmitted light increased. The purpose of reproducing the photodegradation of the sample is to measure the temporal change of the light-transmitted light under the condition of continuous light irradiation, and consider the provisional in vitro SPF predicted value from the preliminary measurement, which is not reflected by the light, and the light degradation caused by the light deterioration. Equivalent to the lower part, and calculate the final in vitro spF prediction with high accuracy. The measurement of the time-dependent change of the spectral transmission spectrum of the measurement sample at the time of the official measurement is performed by controlling the light irradiation time obtained from the preliminary measurement in units of seconds, and can be obtained at any of the other light irradiation times. Spectroscopic transmission spectroscopy data. Specifically, in the processing of the power isochronous machine 19, the condition of the light makeup shooting day can be set in seconds to a few minutes. Further, even if the time-lapse spectral change in the light irradiation for 10 hours is obtained, it may be obtained at any time interval such as a time interval of 1 minute or an equal irradiation time of 10 equal parts. It is preferable to divide the predetermined light irradiation time equally into six or more (including the start of light irradiation at time 0), and to obtain more than 11 spectral data as the pupil data between the ,, The more you can grasp the light degradation of the sample in detail, the more accurate the prediction can be. In order to accurately obtain the light deterioration of the sample when the light is irradiated, the N* does not change the measurement sample and the entire apparatus. It is very important to improve the accuracy of predictions when the same time is completely fixed. 20 «The time-dependent change detection result of the spectroscopic transmission spectrum of the above-mentioned officially-measured sample, 彳千(五) > The crying order is to correct the correction of the photo-degradation change of the sample. The positive treatment was achieved by predicting the in vitro Spf prediction value from the time-averaged spectrum of the light-transmitting light side of the sample in the ultraviolet region of 290 to 400 nm. 18 200819728 As described in the preliminary measurement described above, as long as the spectroscopic transmission spectrum of the sample is determined, the in vitro SPF prediction value can be determined with a certain degree of precision. In other words, in addition to grasping the temporal change of the spectral transmission spectrum of the measured sample photodegradation accompanying the formal measurement, what kind of spectral transmission spectrum is used to determine the in vitro SPF prediction value of the sample, which is very high in the measurement of high precision. Important thing. If the time-division light transmission spectrum data at the start of light irradiation is used, the same value as the tentative in vitro SPF prediction value at the time of preliminary measurement can be obtained. However, this value does not reflect the deterioration of the sample under continuous light irradiation, so it is predicted that the value is higher than the originally predicted SPF value. In addition, when the final spectral transmission spectrum data at the end of the normal measurement time of the light irradiation is used, the spectral data of the light irradiation condition that has been sufficiently changed, that is, the excess light irradiation condition, is predicted, so that the original measurement sample is predicted. The SPF value is also a low SPF value. 15 Due to the above situation, in order to reflect the original time variation distribution, it is better to calculate the total transmitted light amount as the phenomenon of skin exposure at the same time by time integration of the spectral transmission spectrum, and predict the SPF value in vitro. However, in view of the cumbersome calculation processing, in the present embodiment, a calculation method called time-averaged spectrum 20 is introduced for the time-varying spectral transmission spectrum data. When the in-vivo SPF predicted value is calculated using the idea of the time-averaged spectrum, a method for obtaining a final in vitro SPF predictor having a high correlation with the SPF value in vivo can be constructed. The time-averaged spectrum shown here refers to all the data from the spectral data at the beginning of the light irradiation obtained at any number of times, to the last spectrum of the light irradiation time 19 200819728 'The light transmission intensity according to each wavelength Average the processor. Specifically, the final in vitro SPF predictor is a complex standard for determining the SPF value in vivo (4). The spectroscopic transmission spectrum is determined by using the transmitted light intensity at intervals of 5 wavelengths and the known in vivo SPF value. The correlation was analyzed by the PLS regression analysis method, and the final in vitro SPF predicted value was calculated from the calibration curve derived as described above and the result of the time-averaged correction of the spectral transmission spectrum obtained by the formal measurement. By introducing the above calculation method, the final in vitro SPF value can be predicted by the same calculation method from the measurement sample 10 which is easily affected by photodegradation to the measurement sample which is less susceptible to photodegradation. (Flow of Evaluation Method of Ultraviolet Defense Effect) Fig. 4 is a flow chart showing the evaluation method of the ultraviolet protection effect of the present embodiment. 15 For the evaluation method of the above-mentioned ultraviolet protection effect, arrange the following steps. Referring to Fig. 4(a), the flow of preliminary measurement performed before the formal measurement will be described. The light transmission spectrum of the sample in the ultraviolet region of 290 to 400 nm was measured at 1 nm (S101). Using the multivariate regression analysis method, the spectroscopic transmission spectrum of the standard sample with the SPF value in vivo and the correlation of the SPF value in the living body are used to obtain the $# calibration line, and the tentative in vitro spF of the sample is calculated from the spectroscopic transmission spectrum. The predicted value (S102). With respect to the tentative in vitro SPF predicted value [A], the light irradiation time is determined as 20 200819728 in the range of [Α]χ0·08 (minutes) or more and less than [Α]χ1·5 (minutes) (S103). The process of the formal measurement performed after the preliminary measurement will be described with reference to Fig. 4(b). The light is continuously irradiated onto the measurement sample at the time determined by S103, and the spectral transmission spectrum data is obtained for each of 5 arbitrary elapsed time (S151). The obtained time-division spectral transmission spectrum of each of the obtained elapsed time is subjected to time averaging processing to calculate a time-averaged spectrum of the photodegradation of the corrected measurement sample (S152). Using the obtained time-averaged spectrum and the calibration curve obtained in S102, 10, the final in vitro SPF predicted value is calculated (S153). Here, in the above-described embodiment, the process of performing the predetermined measurement before the formal measurement will be described. However, for example, when the actual effect of the same sample as in the past is evaluated by the measurement system, even if the actual effect is not measured, When it is easy to predict from similar prescriptions with actual results (Example 15), when 10% of titanium oxide is predicted to be SPF20 and the same 5% is predicted to be SPF10, 7% of titanium oxide can be predicted as SPF14. When the SPF value in the living body is known from experience, the preliminary measurement may be omitted as needed. That is, in order to perform high-precision prediction, preliminary measurement is important, but it may be omitted in response to various conditions such as shortening of processing time. 20 EXAMPLES This embodiment mode will be described in more detail by way of examples. Further, the following examples show examples in which preliminary measurement is performed. [Example 1] (Measurement conditions) 21 200819728 In the measurement device shown in the above embodiment, the light emitted from the gas light source is transmitted through the WG320 filter and the UG11 to pass through the waves (all manufactured by SCHOTT). , to obtain light of a wavelength of 290 to 400 nm. For the skin substitute film, a PMMA (polymethacrylic acid) resin sheet 5 (PlexiglasTM, manufactured by Schonberg GmbH & Co. KG) was used, and was placed at an irradiation distance of 1 to 2 mm with respect to the light source. At this time, the intensity of UV-B was 2.0 Med/min. The amount of the sample coated on the PMMA resin plate was 75.75 mg/cm2, and after a predetermined amount of the sample, the surface of the PMMA resin plate was coated with a finger for a minute. After coating, the test material was dried at 25 ° C for 15 minutes. Further, at the time of preliminary measurement, light irradiation was performed for 1 MED for 30 seconds. (Sample measurement) Among the above measurement conditions, the sample A in which the SPF value in the living body was unknown was measured. As a result of the preliminary measurement, the tentative in vitro SPF prediction value was 29.8', so the light irradiation time of the official measurement was determined to be 29.8 χ〇·5 = 14·9 minutes (14 15 minutes 54 seconds). At the time of the formal measurement, the above-described continuous irradiation of the light irradiation time is performed. Further, the light irradiation time was divided into five equal parts at 14 minutes and 54 seconds at equal intervals, and spectral data including a total of six points at the start of the light irradiation was obtained. For the above-mentioned 6-point spectral data, the time-averaged spectrum was calculated for each wavelength, and the final in vitro SPF predicted value was 21.9. The aforementioned final in vitro SpF value approximates the SPF value of 22.5% in the living body 20 obtained later. The in vivo SPF values and the tentative and final in vitro SPF prediction values for sample A are shown in Table 1. 22 200819728 Table 1 Determination of tentative in vitro SPF predictions Final in vitro SPF predictions Example 1 29.8 21.9 __-__ Comparative Example 1 A - 24.6 Comparative Example 2 A 40.5 Example 2 70.5 62.4 Comparative Example 3 B A 33.3 Comparative Example 4 - 84.6 Example 3 32.9 32.2 Comparative Example 5 C - 26.0 - Comparative Example 6 - 81.7 31.5 [Example 2]
64.5 關於測定條件，在與實施例1同樣的條件下，餅於、舌_ 5内SPF值為未知的試料B進行測定。預備測定的結果，暫， 活體外SPF預測值為7〇·5，故正式測定之光照射時間決定為 70·5χ0·5=35·25分(35分15秒）。在正式測定時，進行前述光 照射時間的持續照射。又，以等間隔使光照射時間…扣 秒為10等分，取得包含光照射開始時合計為u點之光譜資 10料。對於前述11點之光譜資料，依各波長算出時間平的i 譜，得到最終活體外SPF預測飢4。前述;== 值近似於後來所得之活體内SPF值64·5。對於試料B之活體 内SPF值以及暫定及最終活體外SPF^測值顯示於表i。 [實施例3] 15 關㈣定條件’在與實補1同樣料件下，對於活體 内SPF值為未知的試料C進行败。預傷測定的社果暫定 活體外刪測值為32·9,故正式測定之光照㈣間決定為 32.9x0.5425分叫15秒）。在正式測定時，進行前述光 23 200819728 照射時間的持續照射。又，以等間隔使光照射時間16分15 秒為5等分，取得包含光照射開始時合計為6點之光譜資 料。對於前述6點之光譜資料，依各波長算出時間平均光 譜，得到最終活體外SPF預測值32.2。前述最終活體外spF 5 值近似於後來所得之活體内SPF值31·5。對於試料c之活體 内SPF值以及暫定及最終活體外SPF預測值顯示於表1。 在實施例3中，暫定及最終活體外SPF預測值會近似的 原因，係由於試料C幾乎不受持續照射之光劣化影響的緣 故。試料C之配方中，容易受到光劣化影響的有機系紫外線 10 吸收劑的含量較小，主要係以無機系之氧化鈦或氧化辞等 所構成。 [比較例1至3] 對於上述試料A、Β及C，使用習知方法之專利文獻工 中的實施例2的測定條件進行測定，得到各試料之活體外 15 SPF預測值。在此所得之試料A、B及C的活體外SPF預測值 顯示如表1。 [比較例4至6] 對於上述試料A、B及C，使用為習知方法之非專利文 獻1的方法進行測定，得到各試料之活體外SPF預測值。在 20此所得之試料A、B及C的活體外SPF預測值顯示如表1。 參照表1，在實施例丨至3中，根據本評估方法之最終活 體外SPF預測值與之後所得之活體内SpF值非常相近，結果 i明了切估方法的妥當性。又，根據本評估方法之最終 活體外SPF預測值也較根據專利文獻1及非專利文獻1所揭 24 200819728 示之習知評估方法所得之活體外SPF預測值相近於活體内 SPF值。因此，本評估方法在預測活體内spF值一點上，可 以說較習知方法優異。 根據本實施例，可反映出因照射光而引起的試料光劣 5化現象，並且即使對於顯示出SPF值超過50之高紫外線防禦 效果的试料’也可得到顯示出與活體内SPF值具有高度相關 的活體外SPF預測值。 又，以本測定方法所得之活體外SPF預測值由於與活體 内SPF值之相關很高，因此在具有防曬效果的化妝品開發階 10段，可以簡易、迅速極高精準度的方法測定試料的SPF值。 因此，由於開發成本較廉價，且可在開發階段進行多數試 料的#價，故藉由使用本評估方法，可期待更加速具有高 性能之防曬效果的化妝品等之開發。 此外，也可應用於奈米材料或紫外線吸收劑之開發或 15 評估用途。 以上詳述本發明之較佳實施型態及實施例，但本發明 並不限定於前述特定之實施型態，可在記載於專利申請範 圍之本發明要旨範圍内，進行各種變形、變更。 本國際申請案係根據2 〇 〇 6年1 〇月6日所提出之日本特 20許出願第2006 — 274783號而主張優先權者，本國際申請案 援用2006-274783號的全部内容。 25 200819728 【圖式簡單說明3 第1圖係顯示本實施型態之紫外線防禦效果評估裝置 之概略構成之一例的圖。 第2圖係顯示本實施型態之紫外線防禦效果評估裝置 5 之機能構成之一例的圖。 第3圖係顯示本實施型態之標準試料中之已知活體内 SPF值及所預測之活體外SPF值之相關的圖。 第4(a)、（b)圖係顯示本實施型態之紫外線防禦效果之 評估方法的流程圖。 10 【主要元件符號說明】 10…紫外線防禦效果之評估裝置 11.. .光源 12.. .濾波器 13…光纖 14…照射埠 15···試料 16…皮膚代替膜 17.. .分光器 18…光檢測器 19···電算機 21…輸入機構 22…輸出機構 23…儲存機構 24…分光透射光譜測定機構 25…照射時間設定機構 26.. .經時變化測定機構 27…修構 28.. . SPF預測值算出機構 29.. .控制機構 2664.5 With respect to the measurement conditions, under the same conditions as in Example 1, the sample B in which the SPF value of the cake and the tongue _5 was unknown was measured. As a result of the preliminary measurement, the predicted value of SPF in vitro was 7〇·5, so the light irradiation time of the official measurement was determined to be 70·5χ0·5=35·25 minutes (35 minutes and 15 seconds). At the time of the formal measurement, continuous irradiation of the above-described light irradiation time is performed. Further, the light irradiation time was set to 10 equal parts at equal intervals, and the spectral material including the total of the u point at the start of the light irradiation was obtained. For the spectral data of the above 11 points, the time-flat i-spectrum was calculated for each wavelength, and the final in vitro SPF prediction hunger was obtained. The above; == value approximates the in vivo SPF value of 64.5. The in-vivo SPF values and the tentative and final in vitro SPF values of sample B are shown in Table i. [Example 3] 15 (4) Setting condition ' Under the same material as that of the actual supplement 1, the sample C having an unknown SPF value in the living body was defeated. The pre-injury measurement was tentatively determined to be 32.9, so the officially determined illumination (four) was determined to be 32.9x0.5425 and 15 seconds. At the time of the formal measurement, continuous irradiation of the above-mentioned light 23 200819728 irradiation time was performed. Further, the light irradiation time was divided into five equal parts at 16 minutes and 15 seconds at equal intervals, and spectral data including a total of six points at the start of light irradiation was obtained. For the spectral data of the above 6 points, the time-averaged spectrum was calculated for each wavelength, and the final in vitro SPF predicted value of 32.2 was obtained. The aforementioned final in vitro spF 5 value approximates the in vivo in vivo SPF value of 31.5. The in vivo SPF values and the tentative and final in vitro SPF prediction values for sample c are shown in Table 1. In Example 3, the reason why the tentative and final in vitro SPF prediction values are approximated is because the sample C is hardly affected by the deterioration of light by continuous irradiation. In the formulation of sample C, the content of the organic ultraviolet ray 10 absorbent which is easily affected by photodegradation is small, and it is mainly composed of inorganic titanium oxide or oxidation. [Comparative Examples 1 to 3] The above-mentioned samples A, Β and C were measured using the measurement conditions of Example 2 of the patent document of the conventional method, and the in vitro 15 SPF predicted value of each sample was obtained. The in vitro SPF predicted values of the samples A, B and C obtained herein are shown in Table 1. [Comparative Examples 4 to 6] The above samples A, B and C were measured by the method of Non-Patent Document 1 which is a conventional method, and the in vitro SPF predicted value of each sample was obtained. The in vitro SPF predicted values of the samples A, B and C thus obtained are shown in Table 1. Referring to Table 1, in Examples 丨 to 3, the final in vitro SPF predicted value according to the present evaluation method is very similar to the in vivo SpF value obtained later, and the result shows the validity of the cut-off method. Further, the final in vitro SPF predicted value according to the present evaluation method is also close to the in vivo SPF value compared with the in vitro SPF predicted value obtained by the conventional evaluation method shown in Patent Document 1 and Non-Patent Document 1 No. 24 200819728. Therefore, this evaluation method is superior to the conventional method in predicting the in vivo spF value. According to the present embodiment, the sample light deterioration phenomenon caused by the irradiation light can be reflected, and even for the sample which exhibits an ultraviolet ray-defining effect having an SPF value exceeding 50, it can be obtained to have an SPF value with the living body. Highly correlated in vitro SPF predictions. Moreover, since the in vitro SPF predicted value obtained by the present measurement method has a high correlation with the SPF value in the living body, the SPF of the sample can be measured easily, quickly, and with high precision in the stage 10 of the cosmetic development stage having the sunscreen effect. value. Therefore, since the development cost is relatively low and the price of most of the samples can be carried out at the development stage, development of cosmetics and the like which have a high-performance sunscreen effect can be expected by using this evaluation method. In addition, it can also be applied to the development or 15 evaluation of nano materials or UV absorbers. The preferred embodiments and examples of the present invention are described in detail above, but the present invention is not limited to the specific embodiments described above, and various modifications and changes can be made within the scope of the invention as described in the appended claims. This international application claims the priority according to Japanese Patent Application No. 2006-274783, which was filed on the 6th of January, 1st, 6th, and 6th. This International Application invokes the entire contents of 2006-274783. 25 200819728 [Simple description of the drawings 3] Fig. 1 is a view showing an example of a schematic configuration of an ultraviolet protection effect evaluation device of the present embodiment. Fig. 2 is a view showing an example of the functional configuration of the ultraviolet protection effect evaluation device 5 of the present embodiment. Fig. 3 is a graph showing the correlation between the known in vivo SPF value and the predicted in vitro SPF value in the standard sample of the present embodiment. Fig. 4(a) and (b) are flowcharts showing the evaluation method of the ultraviolet protection effect of the present embodiment. 10 [Description of main component symbols] 10...Evaluation device for ultraviolet protection effect 11.. Light source 12: Filter 13... Optical fiber 14... Irradiation ·15··· Sample 16... Skin instead of film 17. Beam splitter 18 ...photodetector 19···computer 21...input mechanism 22...output mechanism 23...storage mechanism 24...split transmission spectrometry unit 25...irradiation time setting mechanism 26..time change measurement mechanism 27...construction 28. . . SPF predicted value calculation mechanism 29: Control mechanism 26