1363939 冬、發明説明： 【發明所屬之技術領域】 種時間歷程 ，·本發明係秭於一種指示裝置，特別是關於 指示裝置及其形成方法。 【先前技術】 人們-般認為’只要食品仍在保存期限内，就應該是安 何食用的，但現實並非如此。例如：保存食品的環境溫度過 高、食品長時間直接接觸空氣等，都有可能造成細菌大量繁殖 或食物腐敗’而影響人體健康。為了保護消費者不誤食變質食 品·，眾多企業與學術機構競相投人研魏指示食品是否變質的 新型包紐術’例如：溫度絲n (Time_Temperature indicator’TTI )，其功能在於藉由顏色改變指示產品（例如： 食品）於倉儲、運輸、銷售過程中的溫度和時間變化，它可以 指示產品由製造完成到消費者使用中間過程中的溫度變化和 因溫度變化而引起的質量下_程度，進而保證產品的安全性。 .目前已商業化的商品包含VITSAB*、Life Lines*、3M™、1363939 Winter, invention description: [Technical field to which the invention pertains] The present invention relates to a pointing device, and more particularly to a pointing device and a method of forming the same. [Prior Art] People generally think that as long as the food is still in the shelf life, it should be safe to eat, but this is not the case. For example, if the ambient temperature of the food is too high and the food is in direct contact with the air for a long time, it may cause the bacteria to multiply or the food is corrupted, which may affect human health. In order to protect consumers from eating and changing foods, many companies and academic institutions are competing to invest in the research and development of new types of foods that indicate whether foods have deteriorated. For example, Time_Temperature indicator 'TTI, whose function is to change color. Indicates the temperature and time of the product (eg, food) during storage, transportation, and sales. It can indicate the temperature change of the product from the completion of the manufacturing process to the middle of the consumer's use and the quality caused by the temperature change. In order to ensure the safety of the product. Currently commercialized products include VITSAB*, Life Lines*, 3MTM,
DeltaTrake、OnVu™等，其工作原理有酵素催化、擴散機制 • · (diffusion)、固態聚合反應（solid-state polymerization) 等’常有使用不便、價格昂貴缺點。有鑑於此，仍有必要發展 6 ’年7月少日修正替換頁 .新的時間歷程指示裝置，以符合使用方便、指示準如及降低. 生產成本的需求。 . ♦ 【發明内容】 繁於上述之發明背景中’為了克服傳統技術的缺點，本 發明提供-種新的時_程指示裝置、其配方及其形成方法。 本發明之一特徵在於藉由氧化還原型化合物 .compound)的還原態與氧化磁兩者的色彩不同以指示時間歷 程。本發明藉由時間歷程指示體從還原態經氧化作用至氧化態 過程中色彩的變化並配合背景顏色的選擇，造成時間歷程指示 體在氧化過程中逐漸自背景’層消失的效果，而指示時間歷程。 隨著呈現還原態的氧化還原型化合物接觸環境中氧氣的時間 增加’呈現氧化態的氧化還原型化合物數量也隨之增加，藉此 造成時間歷程指示體色彩的變化效果。 本發明之一實施例提供一種方法以形成時間歷程指示誓 •置。本發·明首先選擇適當的接合劑分佈於時間歷程指示體與背· 景層中以利兩者互相接合’接著透過簡單的塗佈和乾燥程序將 時間歷程指示體製作於背景層上。據此’本發明能符合經濟上 的·效益奐產業上的利用性。 根據以上所述，本發明揭示了一種時間歷程指示裝置， • 咖年7月/卵修正替換頁 匕3基材、一形成於該基材上之背景層，以及一形成於該 背景層上之時間歷程指示體，其中，時間歷程指示體與背景層 透過两分子接合賴由物理或是化學鍵結彼此接合。此外，時 間歷程指示體於一初始態時其顏色不同於背景色而於一最終 .態時其顏色實質相同於背景色，因而能與背景色融為一體而令 肉眼不易分辨，藉此達到該時間歷程指示體自背景層中消失之 效果’以便於指出所欲指示之時驗程的終點。 .【實施方式】 本發明在此所探討的方向為一種時間歷程指示裝置及其 形成方法。為了能徹底地瞭解本發明，將在下列的描述中提出 詳盡的步驟及其組成。顯然地，本發明的施行並未限定於該領 域之技藝者所熟習的特殊細節。另—方面，料周知的組成或 步驟並未描述於細節中，以避免造成本發明不必要之限制。本 發明的較佳貫施例會詳細描述如下，然而除了這些詳細描述之 外’本發魏可以廣泛地施行在其他的實補巾，且本發明的 .範圍不受限定，其以之後的專利範圍為準。 於本說明書中將使用部分技術名詞，其定義如下： 具邊氧性:·透氧度高於lppm ; 不具透氧度性；透氧度等於或低於lppm ;以及 1363939 崎7細修正替換頁 . 無氧環境：環境中氧氣濃度低於lppm。 . 本發明之第一實施例揭露一種時間歷程指示裝置的形成 方法，首先提供一背景層材，，此背景層材料包含一第一高分 子接a劑、一墓底材料(base material)以及一背景層致色材 料(background color rendering material) ’ 其中，基底材 料係為無色且背景層致色材料係表現一背景色。上述之基底材 料可包含下列族群之一者或其任意組合：紙張、塑膠膜、金屬 膜、玻璃、錢金屬的紙張或塑膠膜、金屬氧化物披覆的紙張等。 •上述之弟一高分子接合劑與背景層致色材料將於後詳述。 · 接著’將上述之背景層材料塗佈至一基材上（substrate) 並乾燥之，以於基材上形成一背景層；其中，此背景層係表現 上述之背景色。上述之基材的材料可包含下列族群之一者或其 任意組合·艘紹塑膠膜(aluminum metaHized piasuc)、鑛 鋁紙(aluminum metallized paper)、金屬氧化物披覆的塑膠 膜（metal oxide coated plastic)、金屬氧化物披覆的紙張 (metal oxide coated paper)、玻璃（glass)、金屬膜（metal)、 塑膠膜(plastic),，以及紙張(paper)。 · 其次，提供一時間歷程指示材料，此時間歷程指示材料包 含一溶劑、一氧化還原化合物、一還原劑，以及一第二高分子 接合劑。上述之溶劑可係為親水的溶劑，例如水、醇類，或是 •水與醇類的任意組合。上述之氧化還原化合物在一初始還原態 9 4 7月，爾正替換頁 .時係表現一初始色並在一最終氧化態時係表現一蕞終色其. 中，上述之初始色與上述之背景色不同，而上述之最終色則與 上述乏背景色實質相I此外，上述之還具有—預定組成 並係以一預定ώ例存在於上述之時間歷程指示材料中，以便於 將上述之氧化還原化合物逛原至上述之初始還原態^上述之還 原劑可係為連一亞硫酸納（sodium hydrosulfite)或是連二亞 硫酸鈉（sodium hydrosulfite)與鹼性介質（alkaline medium) 的混合物。 應注意者係為，於本實施例中，上述之背景層致色材料的 選擇係配合上述之氧化還原化合物。於本實施例♦，上述之氧 化還原化合物包含蔥酿(anthraquinone)及其衍生物。此時， • · 背景層致色材料亦應選擇為包含蔥醌(anthraquinone)及其衍 生物。上述之氧化還原化合物亦可為包含具有至少一個取代基 的蔥醌(anthraquinone)，其中，該取代基包含下列族群之一 者或其任意組合：績酸(sulfonic acid)、氫(hydrogen)、烧 基(alkyl)、芳基（aryl)、致基(carboxyl)、酰基(acyl)、烧 氧基(alkoxy)，以及鹵化物(halide)。此時，上述之背景層材 料之選擇亦為包含具有至少一個取代基的蔥酉昆 (anthraquinone)，其中，該取代基包含下列族群之一者或其 任·意組备：確酸（sulfonic acid)、氫（hydrogen)、烧基 (alkyl)、芳基（aryl)、叛基(carboxyl)、酰基(acyl)、烧氧 1.363939 月邮修正替換頁 基(alkoky)，以及鹵化物(halide)。上述之氧化還原化合物與 背景層致色材料的較佳選擇包含下列族群之一者或其任意組 合：·蔥酿（anthraquinone)、蔥酿i -2-礦酸 • · (anthraquinone-2-sulfonic acid)、蔥酉昆-2-石黃酸鈉 (anthraquinone-2-sulfonic sodium salt)、水合；昆_2_續 酸(anthraquinone-2-sulfonic monohydrate)、1-蔥酉昆續酸DeltaTrake, OnVuTM, etc., work on enzyme catalysis, diffusion mechanisms • (diffusion), solid-state polymerization, etc., which are often inconvenient and expensive. In view of this, it is still necessary to develop the 6's July Day Correction Replacement Page. The new time history indicator device is designed to meet the needs of ease of use, indication accuracy and reduction in production costs. ♦ SUMMARY OF THE INVENTION In the context of the above-described invention, in order to overcome the disadvantages of the conventional art, the present invention provides a novel timing indicator device, a formulation thereof and a method of forming the same. One of the features of the present invention is that the time history is indicated by the difference between the reduced state of the redox type compound and the oxidized magnet. The invention changes the color of the time course indicator from the oxidation state to the oxidation state by the time history indicator and cooperates with the selection of the background color, thereby causing the time history indicator to gradually disappear from the background layer during the oxidation process, and indicating the time. course. As the redox-type compound exhibiting a reduced state is exposed to oxygen in an environment, the amount of redox-type compound exhibiting an oxidation state is also increased, thereby causing a change in the color of the time history indicator. One embodiment of the present invention provides a method to form a time history indication oath. The present invention first selects an appropriate bonding agent to be distributed in the time history indicator and the backing layer to facilitate mutual bonding. Then, the time history indicator is formed on the background layer by a simple coating and drying process. According to this, the present invention can meet economical efficiency, industrial utilization, and utilization. In accordance with the above, the present invention discloses a time history indicating device, which includes a July/October Correction Replacement page 3 substrate, a background layer formed on the substrate, and a background layer formed on the substrate layer. A time history indicator, wherein the time history indicator and the background layer are joined to each other by physical or chemical bonding through two molecules. In addition, the time history indicator body has a color different from the background color in an initial state, and the color is substantially the same as the background color in a final state, and thus can be integrated with the background color to make the naked eye difficult to distinguish, thereby achieving the The time history indicates the effect of the body disappearing from the background layer' to indicate the end of the inspection process when the indication is intended. [Embodiment] The direction of the present invention as discussed herein is a time history indicating device and a method of forming the same. In order to thoroughly understand the present invention, detailed steps and compositions thereof will be set forth in the following description. Obviously, the practice of the invention is not limited to the specific details that are apparent to those skilled in the art. In other instances, well-known components or steps are not described in detail to avoid unnecessarily limiting the invention. Preferred embodiments of the present invention will be described in detail below, but in addition to these detailed descriptions, the present invention can be widely applied to other practical wipes, and the scope of the present invention is not limited, and the scope of the following patents Prevail. Some technical terms will be used in this specification, which are defined as follows: Edge oxygen: · Oxygen permeability higher than 1ppm; No oxygen permeability; Oxygen permeability equal to or lower than 1ppm; and 1363939 Saki 7 fine correction replacement page Anaerobic environment: The oxygen concentration in the environment is less than 1ppm. A first embodiment of the present invention discloses a method for forming a time history indicating device. First, a background layer material is provided. The background layer material comprises a first polymer bonding agent, a base material, and a base material. Background color rendering material ' wherein the base material is colorless and the background layer coloring material exhibits a background color. The above-mentioned base material may comprise one of the following groups or any combination thereof: paper, plastic film, metal film, glass, paper or plastic film of money metal, paper coated with metal oxide, and the like. • The above-mentioned brother-polymer binder and background layer-colored material will be described in detail later. Next, the background layer material is applied to a substrate and dried to form a background layer on the substrate; wherein the background layer exhibits the background color described above. The material of the above substrate may comprise one of the following groups or any combination thereof. Aluminum metaHized piasuc, aluminum metallized paper, metal oxide coated plastic ), metal oxide coated paper, glass, metal, plastic, and paper. • Next, a time history indicating material is provided, the time history indicating material comprising a solvent, a redox compound, a reducing agent, and a second polymeric binder. The above solvent may be a hydrophilic solvent such as water, an alcohol, or any combination of water and an alcohol. The above redox compound is in an initial reduced state of 9 4 July, when it is replaced by a page, it exhibits an initial color and in a final oxidation state, it exhibits a final color. In the above, the initial color and the above The background color is different, and the final color is substantially opposite to the above-mentioned background color. In addition, the above-mentioned composition has a predetermined composition and is present in the above-mentioned time history indicating material in a predetermined example to facilitate oxidation of the above. The reducing compound may be a sodium hydrosulfite or a mixture of sodium hydrosulfite and an alkaline medium. It should be noted that in the present embodiment, the above-mentioned background layer coloring material is selected in combination with the above redox compound. In the present embodiment ♦, the above redox compound comprises anthraquinone and a derivative thereof. At this time, • Background layer coloring materials should also be selected to contain anthraquinone and its derivatives. The above redox compound may also be an anthraquinone having at least one substituent, wherein the substituent comprises one of the following groups or any combination thereof: sulfonic acid, hydrogen, and burning An alkyl group, an aryl group, a carboxyl group, an acyl group, an alkoxy group, and a halide. In this case, the background layer material is also selected to include an anthraquinone having at least one substituent, wherein the substituent comprises one of the following groups or a group thereof: sulfonic acid ), hydrogen, alkyl, aryl, carboxyl, acyl, burned oxygen 1.363939 month modified replacement page (alkoky), and halide (halide). A preferred choice of the above redox compound and background layer coloring material comprises one of the following groups or any combination thereof: anthraquinone, onion, -2-mineral acid • (anthraquinone-2-sulfonic acid) ), anthraquinone-2-sulfonic sodium salt, hydration; anthraquinone-2-sulfonic monohydrate, 1-green onion
(1-anthraquinonesulfonic acid) 、 1-蔥醌續酸納 (1-anthraquinonesulfonic sodium salt)、蔥酿i-2, 6—二確酸 (anthraquinone-2, 6-disulfonicacid)、蔥醌-2, 6-二石黃酸二 鈉（anthraquinone-2,6-disulfonic disodium salt)、gj昆 -1，5-·二磺酸（anthraquinone-l，5-disulfonic acid)、慧酿 -1; 5-二磺酸二鈉（anthraquinone-1，5-disulfonic disodium salt) ’以及蔥醌-1，5-二磺酸水合物 (anthraquinone-l，5-disulfonic hydrate)。 接著，將上述之時間歷程指示材料塗佈至背景層上並乾燥 之，以形成一時間歷程指示體於背景層上。所形成之時間歷程 指示體僅佔背景層面積的一部份，且時間歷程指示體與背景層 係藉由上述之第一與第二高分子接合劑透過物理或是化學鍵 結接舍。在此，將時間歷程指示材料塗佈至背景層上的塗佈方 式可係為旋轉塗佈（spin costing)、喷塗佈（sprayc〇ating)、 轉印（printing)、刮刀塗佈（knife c〇ating)，以及浸潰塗佈 11 1363939 100年V月^9修正替换頁 (dip⑽⑽等同時，上述之塗佈與乾燥程序~:— 氧環境中進行。此外，本實施例中，上述之第一與第二高分子 . 接合劑係為水溶性或是可分散於水中。較佳者係為，上述之第 與第二高分子接合劑係各自獨立包含下列族群之—者或其 . 任意組合：聚乙烯醇（Polyvinyl aicohol)、甲基纖維素 (methylcellulose)、羥乙基纖維素 _ (hy—xyethylcellulose)、經丙基纖維去 (hydr〇xypropyiceilulose)、羧曱基纖維素(__咖 1 • cellul^e)，以及聚乙二醇（polyethylene glyc〇1)。 參閱第-圖所示，其係為本發明所提供之時間歷程指示 裝置的工作原理。於時間歷程指示體形成後，時間歷程指示體 •中所含之氧化翁、化合物皆已還原至上述之初始還原態，且後 •續當時間歷程指示體與氧氣分子相遇時，時間歷程指示體與氧 φ &分子進行氧化反應並逐漸自上述之初始還原態轉變為上述 . 之最終氧化態，而時間歷程指示體的顏色亦隨之自上述之初始 色轉變為上述之最終色。當時間歷程指示體達到最終氧化態並 •表現最終色時，由於此最終色與上述之背景色實質相同，使得. 時間歷程指示體融合人背景色中而令肉眼無法分辨，據此而指 出所欲指示之時間歷程的終點。 . 於本㈣之—較佳範例巾，更包含於上述之時_程指. .示體形成後，形成一具透氧性之保護層於上述之背景層上，其 1363939 ⑼年7月細修正替換頁 •中’此保護層包覆時間歷程指示體，且此保護層具有至少一透‘ 明部分以便於從外界觀察時間歷程指示體的顏色變化。此較佳 範例令，形成上述之保護層的程序包含：提供一保護層材料， •. 此保護肩材料包含至少一丙婦酸醋（acrylate)與一起始劑；接 • . ·著’將上述之保護層材料塗佈至背景層上並固化之，以形成上 * 述之保護層於背景層上。上述之固化程序可為熱固化或是光固 ^ 化。此外，上述之塗佈程序與固化程序可於一無氧環境中進行。 上述之保護層可更包含一除氧材料，·此除氧材料係以一 預疋比例存在於保護層材料中，且此除氧材料包含下列族群之 一者或其任意組合：還原金屬（reduced metal )、鞣酸 (tannins)、亞硫酸鹽㈤⑴切）、抗壞血酸(asc〇rbate)、奎 • * . •寧還原態和蔥醌衍生物（reduced form of quinine and .anthraquinone derivative)、光還原羰基化合物 參 （photoreducible carb〇nyl compound)，以及氧化有機化合物 (oxidizable organic compound)。 於本發明之另一較佳範例中，更包含於上述之保護層形成 後’於一無氧環境中利用一不具透氧性之包裝材包覆所形成的. 時間歷程指示裝置。上述之包裝材係用以防止環境中的氧氣與 時間歷程指示裝置接觸，且後續打開此包裝材的同時，時間歷 程·指4置即被啟動。上政包紐陳佳選擇⑽_充填有 农封層（sealing layer)的氣體阻絕膜（gas barrier 13 Γ363939 -- 月/印修正替換頁 ' film)，其中，該氣體阻絕膜的材料包含下列族群之一者或其 ’ 任意組合·金屬f|(metal foil)、金屬氧化物(metal oxide)、 峡（carbon)、氧化石夕（Si〇x)、聚@旨（polyester)、聚酰胺 (的1yamide)、聚氯乙烯(polyvinyl chloride)、聚偏二氣乙 . 烯（P〇1yvinyHdene chloride)、聚萘二甲酸（p〇iyethylene - naphthalate)、聚丙烯腈（polyacrylonitrile)、聚碳酸酯 . (pQlycarb〇nate)、聚轉(PQlyether)、聚酰亞胺(PQiyimide)、 聚砜（polysulfone)、橡膠（rubber)，以.及環氧樹酯（epoxy resin)。另一方面，上述之密封層的材料包含下列族群之一者· 或其任意組合：聚酯（p〇lyester)、聚丙烯(p〇lypr〇pylene)、 聚乙烯醇(polyvinyl alcoh〇1)、聚醋酸乙烯醋（如⑽邮 acetate)、橡膠(rubber)、·環氧樹自旨（印〇χγ resin)，以及聚 乙烯(polyethylene)。 本實施例所揭露之方法係用以形成一時間歷程指示裝 置，以便於藉由時間歷程指示體氧化時_色變化指示時間_ 程。環境中眺氣分子穿過上述之具透·的保護層而到達時 間歷程指示舰進行氧化反應。射，減分子穿過保護声的 速率係取決於保護層㈣的化學域；單辦_進入保護層 内的氧氣分子總4财絲的面積計算得出。因此，在某 段時間内進人保護層的氧I總量受保護層材料與面積大小的 影響，故藉㈣先選擇保護層之材料以及預先計算保護層之面 14 1363939 卜年7 3f正替換頁 積可控制所職_歷軸稍置财絲之㈣ 紐。此外’上述之基材的選擇可係為具透氧性或是不且透氧 性’其中，當基材具透氧性時，氧氣分子將有兩個進入卿 私指不裝置的管道：⑴透過保護層；以及⑵透過基材。此時 亦需預先計算基材之_，並配合基材的化學㈣^ _ 分子穿過紐的速率）以控制自基材處進入時間歷程指示裝置 的氧氣總量。最後再配合上述之自保護層進入時間歷程指示襄 置的氧氣總量，即可精密控制時間歷程指示裝置所可指示之 間歷程長短。 、 另—方面’藉由選擇上述之_劑的化學組成鮮存在 於上述之_難指示材料中的_，可以罐上述之氧化還 .原化合物於上述之初始還職_原程度，此影響氧化還 .錢合物被氧化到上述之最終氧化態（時間歷程指示體消失於 • 冑景層中）的所需時間。此外，上述之保護層中所含之除氧材 .. 料的除氧速率與除氧材料的含量多寡亦可進—步控制實際穿 過保護層而到達時間歷程指示體的氧氣總量。 * 由此可知’本實施例所揭露之方法係用以形‘時間歷 程才曰示裝置，該時間歷程指示裝置所可指示的時間歷程長短受 下列因素_ :⑴由保縣德學組搞決定的倾層透氧 . 速率；（2)由保螘層預設面積所決定的單位時間内進入保護層 之氧氣總量；⑶由基材之化學組成所決定的基材透氧速率； 15 1363939 • I⑷年7月判修正替換頁 - (4)由基材預設面積所決定的單位時間内進入基材之氧氣總. 量，（5)由還原劑之化學組成與還原劑存在於時間歷程指示材 料中之比例所決定的，氧化還原化合物在時間歷程起點時的還 _ .原·程度；以及⑹由除氧材料之化學組成與除氧材料存在於保 ' .護層中之_所蚊的，單位時間内實際通祕護層的氧氣總 - 量。 φ 本發明之第二實施例揭露一種時間歷程指示裝置。參閱第 二A圖所示，時間歷程指示裝置2〇〇包含二基材21〇、一形成 .於該基材210上之背景層220 ’以及-形成於該背景層22〇上. 之時間歷程指示體230。此外’上述之時間歷程指示裝置測 可選擇性包含-具有至少—透明部，分2砸的保護層24〇。應 .注意者係為，圖中所示之時間歷程指示體23〇係為文字圖 .形sign ，然如熟習此領域者所可瞭解，時間歷程指示體 • 230亦可為其他形狀，並不受圖中所示者限制；此外，所形成 ..之時間歷程指示裝置係如第圖所示。上述之基材21〇的選 * 擇係如第一實施例所述者。上述之背景層220係藉由-第-高 ·.分子接合劑、-基底材料以及一背景層致色材料所製成，其. 中’上述之基底材料係為無色且上述之背景層致色材料係表現 貪景色以使得上述之背景層22〇表現該背景色。上述之基底 ，材·料的_擇係如第―實施例巾所述者。上述之時職程指示體 _ 23〇僅覆蓋上述之背景層22〇的一部份，且時間歷程指示體23〇 16 1363939 ' 4.7月的修正替换頁 」 .韻由m化還原化合物、—還原劑以及—第二高分· 子接合綱製成；其中，上述之第二高分子接合劑與上述之第 -高分子接合劑藉由物理或是化學鍵結彼此接合。上述之溶 •.齊！帛间刀子接合劑與第二高分子接合劑的選擇，以及時間 ..難指示體230的製作程序係如第-實施例中所述者。此外， - 上述之時間歷程指示體咖具有-初始態與一最終態，其中， .傷 _歷程指示體230於上述之初始態時表現-初始色並於上 述之最終麟表現-最終色。上述之初始色不·上述之背景 .•色，而上述之最終色則係與上述之背景色實質相同？以使得時 間歷程指示體230於上述之最終態時能與背景色融為一體而 令肉眠不易分辨’藉此達到時間歷程指示體23〇自背景層咖 .中’消失的效果。上述之還原劑具有-預定組成並係以一預定比 例存在於上述之時随程指示㈣巾，以便於將上述之氧化還 參 原化合物還原至上述之初始態。其中，上述之還原劑的選擇係 • 如第一實施例所述者。另外，如同第-實施例，於本實施例中，、 • 上述之背景層致色材料的選擇係配合上述之氧化還原化合 - 物。較隹者係為，本實施例中·氧化還原化合物以及背景層致色 材料的選擇係如第一實施例中所述者。 在所欲指示之時間歷程的起點，時間歷程指示體23〇中所 •含·的減_化合物皆已還.原至上述之初始態，且後續當時= 歷程指示體230與氧氣分子相遇時，時間歷程指示體2加與氣 17 1363939 ' />〇年7月洲修正替換頁 .%为子進打氧化反應並逐漸自上述之初始態轉變為上述之最· ”·、’而時間歷程指不體23〇 _色亦隨之自上述之初始色轉 隻為上述之最終色’當時間歷程指示體咖達到上述之最終態 ..並·表現上述之最終色時，時間歷程指示體23〇融合入上述之背 ，·景色中而使肉眼無法分辨，據以指出時間歷程的終點。 - 如别所述’於本發明之一較佳範例中，上述之時間歷程 心不裝置200更包含一保護層240 ’此保護層240包覆上述之 時間歷程指示體230，且此保護層240具有至少-透明部份 .240A以便於自外界觀察時間▲程指示體23〇的顏色變化。本 範例中’上述之保護層24〇之製作程序係如第一實施例中所述 者。上述之賴層24G之較佳實财絲為包含—除氧材料， .此除氧材料以一預定比例存.在於保護層240的材料中，且該除 氧材料之選擇如第一實施例所述者。 • 本實施例之另一較佳範例更包含一包裳層，此包裝層包 ..®所形紅該_歷雜轉置膽。此包裝層讀佳實施方 式係為包含一不具透氧性的包裝材，其中，此包裝材之選擇係 如第一實施例中所述者。. 本實施例所揭露之時間歷程指示裝置咖係藉由時間歷 程^示體230在氧化過程中的顏色變化指示時間歷程。如同帛 .一實施例’本實施例所揭露之時間歷程指示裝置2〇〇所可指示 .的時間歷程長短受下列因素控制：⑴由保護層24〇之化學租. 1363939(1-anthraquinonesulfonic acid), 1-anthraquinonesulfonic sodium salt, onion, i-2, 6-disulfonic acid, onion-2, 6- Anthraquinone-2,6-disulfonic disodium salt, anthraquinone-l,5-disulfonic acid, broth-1; 5-disulfonic acid Anthraquinone-1, 5-disulfonic disodium salt 'and anthraquinone-l, 5-disulfonic hydrate. Next, the time history indicating material described above is applied to the background layer and dried to form a time history indicator on the background layer. The formed time history indicator body only occupies a part of the background layer area, and the time history indicator and the background layer are physically or chemically bonded by the first and second polymer bonding agents described above. Here, the coating method of applying the time history indicating material to the background layer may be spin costing, spray coating, printing, knife coating (knife c 〇 ating), and impregnation coating 11 1363939 100 years V month ^ 9 correction replacement page (dip (10) (10), etc., while the above coating and drying procedures ~: - oxygen environment. In addition, in this embodiment, the above The first polymer and the second polymer. The binder is water-soluble or dispersible in water. Preferably, the first and second polymer binders each independently comprise the following groups or any combination thereof. : Polyvinyl aicohol, methylcellulose, hydroxyethylcellulose _ (hy-xyethylcellulose), propylcellulose (hydr〇xypropyiceilulose), carboxymethylcellulose (__咖1) • cellul^e), and polyethylene glycol (polyethylene glyc〇1). Referring to the figure, it is the working principle of the time history indicating device provided by the present invention. After the time history indicator is formed, the time History indicator The chemical and the compounds have been reduced to the above-mentioned initial reduced state, and after the time history indicator and oxygen molecules meet, the time history indicator and the oxygen φ & molecule undergo oxidation reaction and gradually from the initial reduction state Converting to the final oxidation state of the above, and the color of the time history indicator is also converted from the initial color to the final color described above. When the time history indicator reaches the final oxidation state and • represents the final color, due to this The color is substantially the same as the background color described above, such that the time history indicator is merged into the background color of the person to make the eye indistinguishable, thereby indicating the end point of the time history to be indicated. In (4), the preferred example towel, Further included in the above-mentioned time _ Cheng refers to. After the formation of the body, an oxygen-permeable protective layer is formed on the above-mentioned background layer, and its 1363939 (9) July fine correction replacement page a time history indicator, and the protective layer has at least one transparent portion to facilitate observation of a color change of the time history indicator from the outside. This preferred example forms the above The protective layer process comprises: providing a protective layer material, • the protective shoulder material comprises at least one acrylate and a starter; and • applying the above protective layer material to the background layer And curing to form a protective layer on the background layer. The curing process described above may be thermal curing or photocuring. In addition, the coating procedure and curing procedure described above may be performed in an anaerobic environment. The protective layer may further comprise an oxygen scavenging material, the oxygen scavenging material is present in the protective layer material in a pre-ratio, and the oxygen scavenging material comprises one of the following groups or any combination thereof: a reducing metal (reduced metal), tannins, sulfite (5) (1) cut, ascorbic acid (asc〇rbate), quinane * * · reduced form of quinine and .anthraquinone derivative, light Reducing photoreducible carb〇nyl compound, and oxidizable organic compound. In another preferred embodiment of the present invention, the time history indicating device is formed by coating a non-oxygenated packaging material in an oxygen-free environment after the protective layer is formed. The above-mentioned packaging material is used to prevent oxygen in the environment from coming into contact with the time history indicating device, and the time history finger 4 is activated at the same time as the packaging material is subsequently opened. Shangzheng Baoxin Chenjia chooses (10)_ gas barrier film filled with a sealing layer (gas barrier 13 Γ 363939 - month/print correction replacement page 'film), wherein the material of the gas barrier film contains the following groups One of them or any combination thereof, metal foil, metal oxide, carbon, oxidized stone (Si〇x), poly@polyester, polyamide 1yamide), polyvinyl chloride, P〇1yvinyHdene chloride, p〇iyethylene-naphthalate, polyacrylonitrile, polycarbonate. (pQlycarb 〇nate), PQlyether, polyimide (PQiyimide), polysulfone, rubber, and epoxy resin. In another aspect, the material of the sealing layer comprises one of the following groups, or any combination thereof: polyester (p〇lyester), polypropylene (p〇lypr〇pylene), polyvinyl alcohol (polyvinyl alcoh〇1), Polyvinyl acetate vinegar (such as (10) acetate), rubber (rubber), epoxy tree gamma resin, and polyethylene. The method disclosed in this embodiment is used to form a time history indicating device, so as to indicate the time _ color change when the body is oxidized by the time history. In the environment, the helium molecules pass through the above-mentioned protective layer and reach the time history indicating that the ship undergoes an oxidation reaction. The rate at which the molecules pass through the protective sound depends on the chemical domain of the protective layer (4); the area of the single chemical enthalpy into the protective layer is calculated. Therefore, the total amount of oxygen I entering the protective layer during a certain period of time is affected by the material and area of the protective layer. Therefore, the material of the protective layer is selected first and the surface of the protective layer is pre-calculated. 14 1363939 The page product can control the position of the _ calendar. In addition, the above-mentioned substrate may be selected to have oxygen permeability or oxygen permeability. Among them, when the substrate has oxygen permeability, the oxygen molecules will have two pipes that enter the device: (1) Through the protective layer; and (2) through the substrate. It is also necessary to pre-calculate the substrate _ and match the chemical (4) of the substrate to the rate at which the molecules pass through the nucleus to control the amount of oxygen entering the time history indicating device from the substrate. Finally, in conjunction with the above-mentioned self-protection layer entering the time history indicating the total amount of oxygen, the length of the course that can be indicated by the time history indicating device can be precisely controlled. And the other aspect 'by selecting the above-mentioned chemical composition of the agent is rarely present in the above-mentioned _ difficult indicator material, and the can be oxidized as described above. The original compound is in the above-mentioned initial reinstatement, which affects oxidation. Also, the time required for the valence to be oxidized to the final oxidation state described above (the time history indicator disappears into the 胄 层 layer). Further, the oxygen scavenging rate of the oxygen scavenging material contained in the protective layer and the content of the oxygen scavenging material may further control the total amount of oxygen which actually passes through the protective layer and reaches the time history indicator. * It can be seen that the method disclosed in the present embodiment is used to shape the time history display device, and the time history indication device can indicate the length of the time course by the following factors: (1) determined by Baoxian Dexue Group The rate of oxygen permeation through the protective layer; (3) the oxygen permeation rate of the substrate determined by the chemical composition of the substrate; 15 1363939 • I(4) was awarded a revised replacement page in July - (4) the total amount of oxygen entering the substrate per unit time determined by the predetermined area of the substrate, (5) the chemical composition of the reducing agent and the presence of the reducing agent in the time course The proportion of the indicating material, the redox compound at the beginning of the time history is also the original degree; and (6) the chemical composition of the oxygen scavenging material and the oxygen scavenging material are present in the protective layer of the mosquito The total amount of oxygen in the actual protective layer per unit time. φ A second embodiment of the present invention discloses a time history indicating device. Referring to FIG. 2A, the time history indicating device 2 includes a second substrate 21, a background layer 220' formed on the substrate 210, and a time course formed on the background layer 22. Indicator body 230. Further, the above-described time history indicating device may optionally include a protective layer 24 having at least a transparent portion and two turns. It should be noted that the time history indicator 23 shown in the figure is a text map. The shape sign, however, as can be understood by those skilled in the art, the time history indicator 230 can also be other shapes, and It is limited by the one shown in the figure; in addition, the time history indicating device formed is as shown in the figure. The selection of the substrate 21〇 described above is as described in the first embodiment. The background layer 220 is made of a -first-high molecular bonding agent, a base material, and a background layer coloring material, wherein the above-mentioned base material is colorless and the above-mentioned background layer is colored. The material exhibits a greedy view such that the background layer 22 above exhibits the background color. The above-mentioned substrate, material and material are selected as described in the first embodiment. The above-mentioned time indicator _ 23 〇 covers only a part of the above-mentioned background layer 22 ,, and the time history indicator 23 〇 16 1363939 ' 4.7 months of correction replacement page 】 rhyme by m-reduction compound, - reduction And a second high-component sub-joint; wherein the second polymer binder and the first polymer binder are bonded to each other by physical or chemical bonding. The above dissolves. The selection of the inter-turn knife cement and the second polymer cement, and the timing of the production of the hard indicator 230 are as described in the first embodiment. In addition, the above-described time history indicates that the body has an initial state and a final state, wherein the injury _ history indicator 230 exhibits an initial color in the initial state described above and the final lining performance-final color described above. The above initial color does not have the above background color, and the final color is substantially the same as the above background color. In order to make the time history indicator 230 integrate with the background color in the final state described above, it is difficult to distinguish the meat sleep, thereby achieving the effect that the time history indicator 23 disappears from the background layer. The above-mentioned reducing agent has a predetermined composition and is present in a predetermined ratio at the above-mentioned time indicating (4) towel in order to reduce the above-mentioned oxidized ortho-compound compound to the above initial state. Wherein, the selection of the above reducing agent is as described in the first embodiment. Further, as in the first embodiment, in the present embodiment, the above-mentioned background layer coloring material is selected in combination with the above-described redox compound. More preferably, the selection of the redox compound and the background layer coloring material in this embodiment is as described in the first embodiment. At the beginning of the time course to be indicated, the subtractive compounds contained in the time history indicator 23〇 have been returned. The original state to the above initial state, and the subsequent time = history indicator 230 meets the oxygen molecule. Time history indicator 2 plus gas 17 1363939 ' /> July 7th revision correction page. % is the sub-oxidation reaction and gradually changes from the above initial state to the above-mentioned "··, ' and time history The color is changed from the initial color to the final color described above. 'When the time history indicates that the body coffee reaches the final state described above. and the final color is expressed, the time history indicator 23 〇 〇 〇 上述 上述 , , , , 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 A protective layer 240' covers the time history indicator 230 described above, and the protective layer 240 has at least a transparent portion 240A to facilitate color change of the time indicator body 23 from the outside. In the above The manufacturing process of the layer 24 is as described in the first embodiment. The preferred solid wire of the layer 24G is an oxygen scavenging material, and the oxygen scavenging material is stored in a predetermined ratio in the protective layer 240. In the material, and the selection of the oxygen scavenging material is as described in the first embodiment. • Another preferred embodiment of the embodiment further comprises a skirt layer, the packaging layer package. The preferred embodiment of the packaging layer comprises a non-oxygenated packaging material, wherein the packaging material is selected as described in the first embodiment. The time disclosed in the embodiment The history indicating device indicates the time history by the time history of the color change of the body 230 during the oxidation process. As in the embodiment, the time history indicating device 2 disclosed in the embodiment can indicate the time. The length of the course is controlled by the following factors: (1) Chemical rent by the protective layer 24〇. 1363939
p年7月的修正替換; 成所決定的保護層24G的透氧速率；⑵由保護層·之預設 面積所決领單位_内進人保護層240的減總量；⑶當 基材210係為具透氣性時’ &基材21()之化學組成所決定的基 材.210的透氧速率；⑷當基材21〇係為具透氣性時，由紐 210之預設面積所決定的單位時間内進入基材21()的氧氣總 量；（5)由上述之還原劑的化學組成與其存在於時間歷程指示Correction replacement in July of the year; the oxygen permeation rate of the protective layer 24G determined by the formation; (2) the total amount of the protective layer of the inner layer of the protection layer by the predetermined area of the protective layer; (3) when the substrate 210 The oxygen permeability rate of the substrate .210 determined by the chemical composition of the & substrate 21 () when gas permeable; (4) when the substrate 21 is gas permeable, the predetermined area of the New 210 Determine the total amount of oxygen entering the substrate 21 () per unit time; (5) the chemical composition of the reducing agent described above and its presence in the time history indication
體230之製備材料中的比例所決定的，上述之氧化還原化合物 在時間歷程起點時的還度；以及⑹由上述之除氧材料的 化學組成與其存在於保護層240之製備材料中的呜例所決定 的，單位時間内實際通過保護層240的氧氣總量。 第.一範例時間Μ程指示裝置形成程序 (a)背景層之製備 使用等比例之水與酒精混合物做為溶劑製備1 濃度 2(U之聚乙烯醇溶液(p〇iyVinyi aic〇h〇i solution)，並準備 〇. 8g含一個結晶水之蒽職二續g复(Anthraquinone-2-sulfonic acid)的鈉鹽（AQS)。將上述各物質混合並攪拌1〇分鐘。 其次，利用一塗佈棒(draw-down rod)將上述溶液塗佈至 一玻璃基材上並形成一厚度為2〇〇jum之薄膜。接著於溫度 環J境中乾燥所形成之薄膜；.待溶劑移除後可得一厚度約為3〇 卿的背景層薄膜。 1.363939 ----------- -. /说年7 W日修正替換頁 .(b)時間歷程指示材料及其轉郎程序(printing) · 本範例中，時間歷程指示材料之較佳化學組成如下：（D - 氧化.還原化合物：含一個結晶水之蒽酿二續酸 (Anthr的uinone_2-sulf〇ni.c acid)的鈉鹽（AQS) ; (2)還原 . 劑：連二亞硫酸鈉（s〇dium hydrosulf ite)(Na2S2〇4)與鹼 (alkali)氩氧化鈉（NaOH)的混合物；（3)溶劑：等比例之水與 . 酒精混合物；以及（4)高分子接合劑：聚乙烯醇（p〇lyvinyl ^ alcohol) (PVA)。詳細組成數據如下表： ’ 表一時間歷程指示 ^~' —— - 組成物質 •化合物之化學組成 含量（g) 鈉鹽(AQS) · · 0.025 連二亞硫酸納（Na<2S2〇4) 0.2 氫氧化鈉（NaOH) (5M water solution) 0.8 聚乙烯醇（PVA) (20 % in water-ethanol mixture) L------[ 3 --------___ 首先，混合上述之各組成物質並於大氣中攪拌約1〇分鐘 以得到一高黏度、暗紅色之時間歷程指示材料溶液。其次，利 用-塗佈棒與_印章(sterol)將此溶液轉印至先前製備之背 20 1363939 細修正替換頁 本層麵上並形成—厚度約.⑽的時間歷程指示體。接 著’使用吹風機(hot _)賴並移除溶劑以制厚度約為15 ⑽的時間歷程指示體。應注意者係為，上述之轉印與乾燥程 序.皆係於一手套箱中進行，其中，該手套箱内係充以惰性氣體 如氮氣或是氬氣’且箱内之氧氣濃度係低Klppm。 (c)保護層之製作 保護層係用以覆蓋背景層以及時間歷程指示體。保護層 材料的基本化學組成係為丙烯酸酯（acry late)以及光起始 劑。詳細化學組成數據如下表： 表二高分子保護層之化學組成 組成构質 . 含量ώ 新戍一酵聚甲基環氧乙烧二丙稀 酸酯（Propoxy 1 a t ed ( 2) neopen ty 1 glycol diacrylate) 3 曱基丙烯酸-2-经乙酯 (2-Hydroxyethyl methacrylate) 3 光起始劑（Irgacure 651) 0.12 首先授拌丙烯酸酯（acirylate)與光起始劑（irgacure 651) 混合物約10分鐘。其次，利用一塗佈棒將上述之溶液塗佈在 21 1363939 正替換頁 先前製作之背景層薄膜與時間歷程指示體上。接著’利用一紫 外光（4-watts UVGL-25 Mineral ight® lamp，又=365 nm) 進行-光聚合程序約2分鐘並得到-厚度約no⑽的薄膜。 應·注意者係為：上述之光聚合程序係於一手套箱中進行其 中’該手套箱内係充以惰性氣體如氮氣或是氬氣，且箱内之氣· 氣濃度係低於1 ppm。 至此，所形成之時間歷程指示裝置已準備完成可執行時 間歷程指示工作。參閱第三圖所示，當時間歷程指示襄置與大 乳中的氧氣好接觸而行氧化時，上述之時舰程指示體的顏 .色^氧化程度增加而逐漸變淡。此過程需時約三天方完成，此 時’時間歷程指示體係為米黃色(beige) ’此顏色與背景層所 表·現者相同，因而達到該時間歷程指示體自該背景層消失的效 果。 第二範例時間歷程指示體之化學組成 本範例將測試時間歷程指示體之化學組成對其顏色及 顏色變化速度的影響。 • (a)強鹼(Alkali)含量 . . 本測試中所採用之時間歷程指示裝置其形成程序係如第 一範和中所述者。本測試將t匕較時間歷程指示體中不同含量之 氫氧化鈉（sodium hydroxide)對時間歷程指示體於開始指示. 22 1363939 -- — -.· 月修正替換頁 '· 時間歷程時的顏色，以及於氧化過程中顏色變化的影響。時間. •歷程指示體測試樣品之化學組成如下：3 g之乙氧基化三羥甲 基丙烧三丙稀酸醋（Ethoxylated(15)trimethylolpropane Tr.iacryiate)、3 g 之曱基丙烯酸-2-经乙酉旨（2-Hydroxyethyl * methacrylate) ’ 以及 0.12 g 之光起始劑（Irgacure651)。此 ， 外’測試樣品之膜厚約為170 μπι。詳細比較結果如表三： 表三Alkali含量對時間歷程指示體初始顏色及顏色變化之影響 時間歷程指示體之化學組成 時間歷 樣品 鈉 鹽 連亞硫酸 氫氧化鈉 聚乙烯醇 程指示 (AQS) 鈉 (NaOH) (PVA)) 體之初 • (g) (NS2S2〇4 )(g) (5M) (g) (20%) (g) 始顏色 2a. 1 0.025 0.2 0.24 3 黃 2a. 2 0.025 0.2 0.4 3 橘 2a. 3 0.025 0.2 0.8 3 紅 2a. 3 0.025 0.2 1.0 3 一_ 一 紅 時間歷程指示體的顏色取決於強鹼(alkali)的含量。當 強鹼(alkali)的含量為零或是微量時，時間歷程指示體係為亮 黃.色（樣品2a. 1)。隨著強鹼(alkau)的含量增加，時間歷程 指示體的顏色各係為橘色（樣品2a. 2)以及暗紅色（樣品2a 3 23 1363939 u许？月啦修正替換頁The ratio of the above-mentioned redox compound at the beginning of the time history determined by the ratio in the material of the body 230; and (6) the example of the chemical composition of the oxygen scavenging material described above and the material of the protective layer 240 Determined, the total amount of oxygen actually passing through the protective layer 240 per unit time. The first example time course indicating device forming procedure (a) The preparation of the background layer is carried out using a mixture of water and alcohol in an equal ratio as a solvent. 1 Concentration 2 (U polyvinyl alcohol solution (p〇iyVinyi aic〇h〇i solution) ), and prepare 〇. 8g of sodium salt (AQS) containing an crystallization water of Anthraquinone-2-sulfonic acid. Mix the above materials and stir for 1 minute. A draw-down rod is applied to a glass substrate to form a film having a thickness of 2 〇〇jum, and then the formed film is dried in a temperature loop J; after the solvent is removed, A background film with a thickness of about 3 〇 Qing is obtained. 1.363939 ----------- -. / The 7 W day correction replacement page. (b) Time history indicator material and its lang program ( Printing) · In this example, the preferred chemical composition of the time history indicator material is as follows: (D - Oxidation. Reduction compound: Sodium containing a crystal water of eucalyptus acid (Anthr's uinone_2-sulf〇ni.c acid) Salt (AQS); (2) Reduction. Agent: sodium sulfite (Na2S2〇4) and alkali (alkali) argon a mixture of sodium (NaOH); (3) solvent: an equal ratio of water and an alcohol mixture; and (4) a polymeric binder: p〇lyvinyl ^ alcohol (PVA). The detailed composition data is as follows: 'Table 1 time history indication ^~' —— - Composition of substance • Chemical composition of compound (g) Sodium salt (AQS) · · 0.025 Sodium dithionite (Na<2S2〇4) 0.2 Sodium hydroxide (NaOH) (5M water solution) 0.8 Polyvinyl alcohol (PVA) (20% in water-ethanol mixture) L------[ 3 --------___ First, mix the above constituent materials and in the atmosphere Stir for about 1 minute to obtain a high viscosity, dark red time history indicating material solution. Secondly, transfer the solution to the previously prepared back with a coating bar and sterol 20 1363939 fine correction replacement page At this level, a time history indicator having a thickness of about (10) is formed. Then, using a hair dryer (hot _) and removing the solvent to make a time history indicator having a thickness of about 15 (10), it should be noted that the above is Transfer and drying procedures are carried out in a glove box, wherein the glove The nitrogen-based gas, or filled with an inert argon 'and the oxygen concentration inside the system, such as a low Klppm. (c) Production of protective layer The protective layer is used to cover the background layer and the time history indicator. The basic chemical composition of the protective layer material is acry late and a photoinitiator. The detailed chemical composition data are as follows: Table 2 Chemical composition of the protective layer of the polymer. Content ώ New 戍 酵 聚 甲基 甲基 Pro ( ( ( ( ( ( ( ( ( ( ( ( ( glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol Diacrylate) 3-Hydroxyethyl methacrylate 3 Photoinitiator (Irgacure 651) 0.12 A mixture of acrylic and photoinitiator (irgacure 651) was first applied for about 10 minutes. Next, the above solution was applied to a background film and a time history indicator previously prepared on the 21 1363939 replacement page using a coating bar. Then, a photopolymerization procedure was carried out for about 2 minutes using an ultraviolet light (4-watts UVGL-25 Mineral ight® lamp, again = 365 nm) to obtain a film having a thickness of about no (10). It should be noted that the above photopolymerization procedure is carried out in a glove box where 'the glove box is filled with an inert gas such as nitrogen or argon, and the gas concentration in the tank is less than 1 ppm. . So far, the formed time history indicating device is ready to complete the executable time history indication work. Referring to the third figure, when the time history indicates that the device is in contact with the oxygen in the milk and is oxidized, the degree of oxidation of the ship indicator is gradually increased. This process takes about three days to complete. At this time, the time history indication system is beige (beige). This color is the same as the background layer, so that the time history indicator disappears from the background layer. The chemical paradigm of the second example time history indicator. This example tests the effect of the chemical composition of the time history indicator on its color and color change rate. • (a) Alkali content. The time history indicating device used in this test is formed as described in the first and second sections. This test will compare the different amounts of sodium hydroxide in the time history indicator to the time history indicator. 22 1363939 -- — -.· Month correction replacement page '· time history color, And the effect of color changes during the oxidation process. Time. • The chemical composition of the test indicator sample is as follows: 3 g of ethoxylated trimethylolpropane acetate (Ethoxylated (15) trimethylolpropane Tr. iacryiate), 3 g of thiol acrylate-2 - 2-Hydroxyethyl * methacrylate ' and 0.12 g of photoinitiator (Irgacure 651). Thus, the outer test sample has a film thickness of about 170 μm. The detailed comparison results are shown in Table 3: Table 3 The effect of Alkali content on the initial color and color change of the time history indicator. Time history of the chemical composition of the indicator. Sodium salt, sodium sulfite, sodium hydroxide, polyvinyl alcohol, alcohol indicating (AQS), sodium (NaOH) (PVA)) At the beginning of the body • (g) (NS2S2〇4)(g) (5M) (g) (20%) (g) Starting color 2a. 1 0.025 0.2 0.24 3 Yellow 2a. 2 0.025 0.2 0.4 3 Orange 2a. 3 0.025 0.2 0.8 3 Red 2a. 3 0.025 0.2 1.0 3 A _ A red time history indicator color depends on the content of the strong base (alkali). When the content of the alkali is zero or a small amount, the time history indicating system is bright yellow. (Sample 2a. 1). As the content of alkau (alkau) increases, the color of the time course indicator is orange (sample 2a. 2) and dark red (sample 2a 3 23 1363939 u
及 2a. 4) 〇 ~ J •參閱第四a圖所示’各測試樣品之顏色淡化時間長短係 受其強鹼(alkali)含量所影響強鹼(alkali)之含量高時會加 快.顏色淡錢度。表三觸出之職樣品巾，樣品^ i持續 ' 表現育色達14天；樣品2a. 2之顏色淡化時間約為7天（以淡 •.化至與背景色實質相同時為終點）；樣品2a. 3約為30小時； 樣品2a· 4約為20小時。以樣品2a. 1為例，其顏色淡化速度 ’ 在各樣品中最慢，然而由於其係由黃色轉變為米黃色（背景 色），故指示時間歷程之效果並不明顯。因此，本發明之較佳 .實施例係使用較高含量的強驗(alkal i)以增加時間歷程指示 體和背景層顏色對比的視覺效果，據此達到較佳的時間歷程指 示效泉。 . _ · • (b)還原劑含量· 本測試中所採用之測試條件與(a)相似，唯測試標的轉換 ^ 為還原劑之含量。其中，時間歷程指示體測試樣品之化學組成 如下：3 S之乙氧基化三羥曱基丙烷三丙烯酸酯 • (Ethoxylated(15)trimethylolpropane Triacrylate) ' 3 g •.之曱基丙烯酸-2-羟乙酯（2-Hydroxyethyl methacrylate)，以 及〇· 12 g之光起始劑（Irgacure 651)。此外，測試樣品之膜 厚約為170 μπι。詳細比較結果如表四： 24And 2a. 4) 〇~ J • Refer to Figure 4 a. The color fade time of each test sample is accelerated by the high alkali content of the alkali. The color is light. Money. Table 3 shows the sample towel that is touched out, the sample ^ i continues to 'yield for 14 days; the color fade time of sample 2a. 2 is about 7 days (to the end when the color is the same as the background color); Sample 2a.3 is approximately 30 hours; sample 2a.4 is approximately 20 hours. Taking sample 2a. 1 as an example, the color desalination rate ' is the slowest in each sample, but since it changes from yellow to beige (background color), the effect of indicating the time history is not obvious. Accordingly, preferred embodiments of the present invention use a higher level of alkal i to increase the visual effect of the time history indicator and background layer color contrast, thereby achieving a better time history indication effect. _ · • (b) Reducing agent content · The test conditions used in this test are similar to (a), except that the conversion of the test target is the content of the reducing agent. Among them, the chemical composition of the time history indicator test sample is as follows: 3 S ethoxylated trihydroxy propyl propane triacrylate • (Ethoxylated (15) trimethylolpropane Triacrylate) ' 3 g •. thiol acrylate 2-hydroxyl 2-Hydroxyethyl methacrylate, and 12· 12 g of photoinitiator (Irgacure 651). In addition, the test sample has a film thickness of about 170 μm. The detailed comparison results are shown in Table 4: 24
參閱第四b騎示，比較結果顯示，《原劑之含量較高 時會&加顏色淡化所需時間（以淡化至與背景色實質相同時為 終點）。 · · 第二範例_雌指示體厚度對其顏色變化的影響 本範例測試兩個厚度分別係為15卿以及40 Mm的時間歷 私才曰示體樣品’耻較時間歷紗示體之厚度對其顏色變化的 影響；其中，所採用之時間歷程指示裝置其製作程序係如第一 範例中所述者。測試樣品之保護層的化學組成如下：等比例之 乙氧基化三經曱基丙烷三丙烯酸酯 (E'thoxylated(i5)trimethylolpr〇pane Triacrylate)與曱基 25 1363939 __ ·-. ,〇泮《/月肫修正替換頁 • 丙烯酸—2-羟乙酯（2-Hydroxyethyl methacrylate)，以及光起 •始劑（Irgacure 651)。保護層之厚度係為no pm。· - 參閱第五圖所示，比較結果顯示’時間歷程指示體厚度為 15μιη之樣品其顏色約於2天後淡化完全（以淡化至與背景色實 • * .' 質相同時為終黠）；時間歷程指示體厚度為40 μπι之樣品其顏 • .色於5天後淡化完全。 • 第四範例保護層化學組成對時間歷程指示體顏色變化的影響 本範例將測試保護層之化學組成對時間歷程指示體顏色 •淡化時間的影響。測試樣品之保護層的化學組成包含有等比例· 之兩種不同的丙烯酸酯（acrylate)，以及2%的光起始劑。此 外，測試樣品之保護層的厚度皆係為170 Mm。本範例中所採 ’ 用之時間歷程指示裝置其形成程序係如第一範例中所述者。詳 H ·細比較結果如下表四以及第六圖所示： 四保護層化學組成對時間歷程指示體顏色變化的影響 樣品 保護層化學組成 . 顏色淡化時間 (•天） 四甘醇二丙烯酸醋（Tetraethylene 4.1 Glycol Diacrylate) / 曱基丙烯酸-2- 3 经 乙酯 （2-Hydroxyethyl 26 1363939 日修正替換頁 methacrylate) 4.2 聚氧乙烯（2)雙酚A二曱基丙烯酸酯 (Ethoxylated (2) Bisphenol A Dimethacrylate )/ 甲基丙稀酸_2-径 乙醋（2-Hydroxyethy 1 methacry late) 14 4.3 二丙缔酸酯（Tricyclodecane dimethanol diacrylate ) / 曱基丙烯 酸-2-轻乙酯（2-Hydroxyethyl methacrylate) · 12 4.4 新戊上醇聚甲基環氧乙烷二丙烯酸酯 (Propoxy1ated(2)neopenty1 glycol diacrylate) /甲基丙烯酸-2-羟乙酯 • · (2-Hydroxyethyl methacrylate) 3 4.5 乙氧基化三羥曱基丙烷三丙烯酸酯 (Ethoxy1ated(15)tr i methy1o1propane Triacrylate) /甲基丙烯酸_2_羟乙酯 (2-Hydroxyethyl methacrylate) ------- 2 -~~~~-~~~~~ 第玉範例保護層厚度對時間歷程指示體顏色變化的影響 本範例將測試保護層之厚度對時間歷程指示體顏色淡化 時間的影響。測試樣品之缺層的化學域包含等比例之乙氧 27 1363939 ⑽年7月洲修正替換頁 基化三羥曱基丙烷三丙烯酸酯 (Ethoxylated(15)triraethylolpropane Triacrylate)與曱 基丙烯酸-2-羟乙酯（2-Hydroxyethyl methacrylate)，以及光 起始劑（Irgacure 651)。測試樣品之保護層的厚度分別係為 170 μπι以及37Ό μπι。本範例中所採用之時間歷程指示裝置其 形成程序係如第一範例中所述者。 參閱第七圖所示，比較結果顯示，厚度為17〇 μπι之樣品 其顏色約於2天後淡化完全（以淡化至與背景色實質相同時為 終點）；厚度為370μπι之樣品其顏色則於3天後淡化完全。 第六範例濕度對時間歷程指示體顏色變化的影響 本範例將測試濕度對時間歷程指示體之顏色變化時間的 影響。測試樣品之保護層的彳匕學組成包含等比例之乙氧基化三 經甲基丙烧三丙烯酸酯 (Ethoxylated( 15)trimethylolpropane Triacrylate)與甲基 丙烯酸-2-羟乙酯（2-Hydroxyethyl methacrylate)，以及光起 始劑（Irgacure 651)。本範例中所採用之時間歷程指示裝置其 形成程序係如第一範例中所述者。所形成之時間歷程指示裝置 被暴露於44%以及76% RH兩種濕度環境中進行比較。 參閱第八圖所示，比較結果顯示，置於不同濕度環境中 之樣品其顏色變化時間相同’並不受濕度影響。 28 1363939 ‘. /〇睥7月/卯修正替換頁 第七範㈣溫度對時間歷程指示_色變化的影響. 本範例將測試溫度對時隱程指示體之顏色淡化時間的 影響。·如第—範例中所形成之_歷程指示㈣樣品被暴露於 0 C以及+25ec兩種溫度環境中進行比較。 參閱第九圖所示，比較結果顯示，較高之環境溫度會加 快時間歷程指示裝置顏色變化速度。置於+25 〇c環境溫度中之 樣品其顏色於3天後淡化完全（以淡化至與背景色實質相同時 為終點）；置於〇°c環境溫度中之樣品其顏色則於14天後淡化 完全。· . 第八範例時間歷程指示體之光敏感性 .本範例將測試照光度對時間歷程指示體之顏色淡化時間 的影響。測试樣品其氧化還原化合物之化學組成如下：〇. 025 g 之鈉鹽（AQS)、0.3 g之連二亞硫酸鈉（Na2S2〇4)、1.2 g之氫 氧化鈉（NaOH) (5M)，以及3g之聚乙烯醇（pva)(20《 solution)。測試樣品之保護層的化學組成包含3 g之二丙稀 酸酯（Tricyclodecane dimetiianol diacrylate)、3 g之甲基 丙烯酸-2-羟乙酯（2-Hydroxyethyl methacrylate)，以及 0.12 g之光起始劑（Irgacure 651)。本範例中所採用之時間歷程指 示裝置其形成程序係如第一範例中所述者。所形成之時間歷程 29 1363939 ___ *·· /d〇^7月咖修正替換頁 指示裝置分別被暴露於黑暗中以及照光環境照度 • (illuminance) : 300 iux 中進行比較。 • 參閱第十圖所示，比較結果顯示，置於不同照光環境中 之樣品其顏色淡化時間相同皆約為4天，並不受照光度影響。 * ， · 在上述本發明之實施例中，本發明藉由時間歷程指示體 •· 從還原態經氧化作用至氧化態過程中色彩的變化並配合背景 顏色的選擇，造成時間歷程指示體在氧化過程中逐漸自背景層 消失的效果，而指示時間歷程。另一方面，本發明提供一種方 .法以形成時間歷程指示裝置。本發明首先選擇適當的接合劑分 佈於時間聽指示體與f景層中㈣兩者互相接合，接著透過 .簡.單的塗佈和乾燥程序將時間歷程指示體製作於背景層上。據 此，本發明能符合經濟上的效益與產業上的利用性。 _顯然地，錢上面實關中_述，本發明可能有許多的修正與 .差異。因此料在其附加賴利要求項之範_加以理解，除了 .j述詳細的描述外’本發明還可以廣泛地在其他的實施例中施 =上述僅為本發明之較佳實施_已，並翻⑽定本發明之 申凊專利細；凡其絲麟本發明_示之精神下所 . 效改變或修飾，均應包含在下述申請專利範圍内。成W 【圖式簡‘單說明】 第—_、本發騎提供之__絲裝置駐作原理· 30 1363939 并W /<f日替換^ 示意圖； 一'-^ 第二圖係根據本發明之第二實施例所建構之時間歷程指 示裝置之結構示意圖 ...帛二圖係择據本發明之第一範例中所揭露之程序卿成 的時間歷程指示裝置其變色情形； * · 細Α ®係根據本發明之第二範例中，強驗(Alkali)含 * 量對咖歷鋪雜顏色變化之f彡響的峨結果； 第四B圖係根據本發明之第二範例中，還原劑含量對時 •.間歷程指示體顏色變化之影響的測試結果； . 第五圖係根據本發明之第三範例中，咖歷程指示體厚 度對莫顏色變化之影響的測試結果； ♦ ♦ . 第六圖係根據本發明之第四範例中’保護層化學組成對時. φ ·間歷程指示體顏色變化之影響的測試結果； 第七圖係根縣個之第五範例巾，賴層厚度對時間歷 . 程指示體顏色變化之影響的測試結果； 止 第八圖係根據本發明之第六範例中，濕度對時間歷程指示 ·.體顏色變化之影響的測試結果； · 曰丁 ‘ .从嶋根據本發明之第七範例巾，溫度對日铜歷軸* • 體顏色變化之影響的測試結果；以及 曰不 31 1363939 /00^7月以曰修正替換頁 第十圖係根據本發明之箄八範例中，照光度對時間歷程指 示體顏色變化之影響的測試結果； 【主要元件符號說明】 200時間歷程指示裝置 210基材 220背景層 230時間歷程指示體 • 240保護層 240A保護層的透明部分 32Referring to the fourth b riding, the comparison results show that the time required for the color to fade in the higher content of the original agent (to fade to the same as the background color) is the end point. · · The second example _ the effect of the thickness of the female indicator on its color change. This example tests the thickness of the two samples with a thickness of 15 qing and 40 Mm, respectively. The effect of the color change; wherein the time history indicating device used is programmed as described in the first example. The chemical composition of the protective layer of the test sample is as follows: equal proportion of ethoxylated tri-propyl propyl propane triacrylate (E'thoxylated (i5) trimethylolpr〇pane Triacrylate) and sulfhydryl 25 1363939 __ ·-. / month 肫 correction replacement page • 2-Hydroxyethyl methacrylate, and Irgacure 651. The thickness of the protective layer is no pm. · - Referring to the fifth figure, the comparison results show that the sample with a time history indicator thickness of 15μηη is completely faded after about 2 days (after the dilution is the same as the background color • * . ' The time history indicator has a thickness of 40 μπι and its color is completely faded after 5 days. • The effect of the fourth example protective layer chemical composition on the color change of the time history indicator. This example will test the effect of the chemical composition of the protective layer on the time history indicator color • fade time. The chemical composition of the protective layer of the test sample contained two different acrylates in equal proportions, and 2% of the photoinitiator. In addition, the thickness of the protective layer of the test sample was 170 Mm. The time history indicating device used in this example is formed as described in the first example. Detailed H · Fine comparison results are shown in Tables 4 and 6 below: Effect of chemical composition of four protective layers on color change of time history indicator. Chemical composition of sample protective layer. Color desalination time (• day) Tetraethylene glycol diacrylate vinegar ( Tetraethylene 4.1 Glycol Diacrylate) / Mercaptoacrylic acid-2- 3 by ethyl ester (2-Hydroxyethyl 26 1363939 modified replacement page methacrylate) 4.2 Polyoxyethylene (2) bisphenol A dimercapto acrylate (Ethoxylated (2) Bisphenol A Dimethacrylate ) / 2-Hydroxyethy 1 methacry late 14 4.3 Tricyclodecane dimethanol diacrylate / 2-Hydroxyethyl methacrylate · 12 4.4 Propoxy1ated (2) neopentyl 1 glycol diacrylate / 2-hydroxyethyl methacrylate • (2-Hydroxyethyl methacrylate) 3 4.5 Ethoxylation Ethoxy1ated(15)tr i methy1o1propane Triacrylate / 2-Hydroxyethyl methacrylate ------- 2 -~~~~~~~ ~~~ The effect of the thickness of the protective layer on the color change of the time history indicator. This example will test the effect of the thickness of the protective layer on the color fade time of the time history indicator. The chemical domain of the defect layer of the test sample contains an equal proportion of ethoxy 27 1363939 (10) July, the correction of the replacement of benzylated trihydroxy decylpropane triacrylate (Ethoxylated (15) triraethylolpropane Triacrylate) and thiol acrylate 2-hydroxyl 2-Hydroxyethyl methacrylate, and a photoinitiator (Irgacure 651). The thickness of the protective layer of the test sample was 170 μm and 37 Ό μπι, respectively. The time history indicating device used in this example is formed as described in the first example. Referring to the seventh figure, the comparison results show that the sample with a thickness of 17 〇μπι is completely faded after about 2 days (the end point is the same as the background color); the color of the sample with a thickness of 370 μm is After 3 days, the dilution is complete. The sixth example of the effect of humidity on the color change of the time history indicator. This example tests the effect of humidity on the color change time of the time history indicator. The chemical composition of the protective layer of the test sample consisted of an equal proportion of Ethoxylated (15) trimethylolpropane Triacrylate and 2-Hydroxyethyl methacrylate. ), as well as a photoinitiator (Irgacure 651). The time history indicating device used in this example is formed as described in the first example. The resulting time history indicating device was exposed to a humidity environment of 44% and 76% RH for comparison. Referring to Figure 8, the comparison shows that samples placed in different humidity environments have the same color change time' and are not affected by humidity. 28 1363939 ‘. /〇睥July/卯Replacement Replacement Page Seventh (IV) Temperature vs. Time History Indicator_Color Change Effect. This example tests the effect of temperature on the color fade time of the time-hidden indicator. • The _process indication (4) formed in the first example is exposed to 0 C and +25 ec for comparison. Referring to Figure 9, the comparison shows that a higher ambient temperature will speed up the time history of the device. The color of the sample placed at +25 〇c ambient temperature fades completely after 3 days (to the end when it is substantially the same as the background color); the color of the sample placed at 〇°c ambient temperature is after 14 days. Desalination is complete. · The eighth example time history indicator light sensitivity. This example will test the effect of illumination on the color fade time of the time history indicator. The chemical composition of the redox compound of the test sample is as follows: 025 025 g of sodium salt (AQS), 0.3 g of sodium dithionite (Na 2 S 2 〇 4), 1.2 g of sodium hydroxide (NaOH) (5 M), and 3 g Polyvinyl alcohol (pva) (20 "solution"). The chemical composition of the protective layer of the test sample contained 3 g of Tricyclodecane dimetiianol diacrylate, 3 g of 2-Hydroxyethyl methacrylate, and 0.12 g of photoinitiator. (Irgacure 651). The time history indicating device used in this example is formed as described in the first example. The time course formed 29 1363939 ___ *·· /d〇^7 month coffee correction replacement page The indicator device is exposed to the dark and illumination ambient illumination respectively (illuminance): 300 iux for comparison. • Referring to the tenth figure, the comparison shows that the samples in different illumination environments have the same color fade time of about 4 days and are not affected by the illumination. *, · In the above embodiment of the present invention, the present invention causes the time history indicator to be oxidized by the time history indicator body, the color change from the reduced state to the oxidation state, and the background color selection. The process of gradually disappearing from the background layer in the process, indicating the time course. In another aspect, the present invention provides a method to form a time history indicating device. The present invention first selects an appropriate bonding agent to be bonded to each other in the time-audit indicator and the f-view layer, and then fabricates the time history indicator on the background layer through a simple coating and drying process. Accordingly, the present invention can meet economic benefits and industrial applicability. _ Obviously, the above is true, the invention may have many corrections and differences. Therefore, it is intended to be understood in the context of its additional reliance requirements, except that the detailed description of the present invention can be widely applied in other embodiments. The above is only a preferred embodiment of the present invention. And (10) stipulates the patent application of the present invention; any modification or modification of the invention under the spirit of the present invention should be included in the scope of the following patent application. W [Simplified diagram of the figure] The first - _, the hair provided by the __ silk device station principle · 30 1363939 and W / < f day replacement ^ schematic; a '-^ second picture is based on this A schematic diagram of the structure of the time history indicating device constructed by the second embodiment of the present invention. The second embodiment is a time history indicating device of the program disclosed in the first example of the present invention. Α® is a 峨 峨 系 系 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据The test result of the effect of the agent content on the change of the color of the indicator body; the fifth figure is the test result of the influence of the thickness of the coffee course indicator on the change of the color in the third example according to the present invention; The sixth figure is a test result of the influence of the chemical composition of the protective layer on the color change of the φ · interval history indicator according to the fourth example of the present invention; the seventh figure is the fifth sample towel of the root county, the thickness of the layer The measurement of the influence of the color change of the time indicator Test result; the eighth figure is a test result of the influence of humidity on the time history indication · body color change in the sixth example of the present invention; · 曰丁'. From the seventh example towel according to the present invention, the temperature Test results for the influence of the Japanese copper calendar*; body color change; and 曰不 31 1363939 /00^7 曰 替换 替换 替换 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十 第十Test result of influence of body color change; [Description of main component symbols] 200 time history indicating device 210 substrate 220 background layer 230 time history indicator body • 240 protective layer 240A transparent layer of protective layer 32