201013601 -九、發明說明： 【發明所屬之技術領域】 本發明係有關一種彩色半色調網點夜光裝置、其製法及其 發光方法，尤指一種以夜光材料與透明油墨調製成發光油墨， 將其塗佈在基材（如金屬片）上，再利用彩色半色調網點印刷 技術將彩色圖案印刷在該發光油墨上，以顯示其鮮盤色彩及夜 光效果之技術。 ❹【先前技術】 自古以來，能夠於暗處發光的物體，總是能夠吸引人的目 光。而隨著現今科技的快速發展與光學研究的日益深入，相關 的發光材料與技術漸趨成熟與廣泛應用》發光材料從一般的電 致發光、顯示和照明材料發展為由高能射線、陰極射線、光、 聲、熱以及化學、生物和機械能等所激發的材料，廣泛應用於 超薄電視、液晶顯示和精密感應器等高科技領域的關鍵材料（如 參考文獻【1】），遍及人們生活的每個角落，而其中長餘暉發光 材料也是近來廣為研究發展的發光材料之一。長餘暉發光材料 是一種光致發光材料，其能經由光的照射來吸收與儲存激發 能，在停止激發後能把儲存的能量以可見光的形式逐漸、持續 地發射出來，時間可達幾小時甚至幾十小時，是一種蓄光型發201013601 - IX, invention description: [Technical field of invention] The present invention relates to a color halftone dot-light luminous device, a preparation method thereof and a light-emitting method thereof, and more particularly to a luminous ink prepared by using a luminous material and a transparent ink, and coating the same A technique in which a cloth is printed on a substrate (such as a metal sheet) and a color pattern is printed on the luminescent ink by a color halftone dot printing technique to display the color of the fresh disk and the luminous effect. ❹[Prior Art] Since ancient times, objects that can emit light in the dark have always attracted people's attention. With the rapid development of today's technology and the deepening of optical research, related luminescent materials and technologies are becoming more mature and widely used. The luminescent materials have evolved from general electroluminescence, display and illumination materials to high-energy rays and cathode rays. Materials inspired by light, sound, heat, and chemical, biological, and mechanical energy are widely used in high-tech fields such as ultra-thin TVs, liquid crystal displays, and precision sensors (eg, reference [1]). Each corner, and the long-lasting luminescent material is also one of the recently developed luminescent materials. The long-lasting luminescent material is a photoluminescent material that absorbs and stores the excitation energy through the irradiation of light, and can gradually and continuously emit the stored energy in the form of visible light after stopping the excitation for a period of several hours or even For several tens of hours, it is a light storage type
度高、發光時間長等優點（如參考文獻【2】），極具環保性。因 此長餘暉發光材料被廣泛應用於：電子電器、商業場所、民用 通訊、電力、石油、 公安、消防、交通、 設施、軍事設施、救難裝備、工藝美術、 化工、紡織、建築、建材、礦山、機械、 201013601 醫院、旅遊、 么路、鐵路、地鐵、船舶、港口、航空、郵電、 廣告等社會各個領域（如參考文獻【3】）。 i 口 m ^生活中，鐵片製品的應用相當廣泛，如指示標諸、 頭鐵製禮盒、車輛排氣管等皆是。本發明人嘗試藉由 ^餘軍發，材料與印刷油墨的配製，將發光油墨與鐵片作結 合，以期讓鐵片呈現出彩色夜光的效果，來增加鐵片製品的新 功能性、商業性甚至於㈣效果或軍事用途。 Ο 一目别夜光產品报多，如用在陶变、塑膠、玻璃、纺織布、 Λ ’、牌貼、我等。本案所用的夜光原料為从^ 來自大 陸與市面上很多夜光產品的原料相同。不同的是本發明專注 於製程的研究以用於彩色印刷，也就是不止要求良好的夜光， 還須顯示彩色網㈣_效果。目前有關夜光產品的開發以美 國日本以及大陸為全世界的重鎮。本發明的產品較目前市面 上既有的夜光產品有明確的優勢’將會對夜光產品的應用帶來 更為廣泛的空間。 ❹ ^著長餘暉發光材料研究的日m，所發展出材料的亮 度與品質也有报大的進步。然而長餘暉發光材料並不能作為最 終產品’關與其他材料配合加王再製造才能應祕日常生活 中。因此近年來’許多相關應用技術也逐漸發展出來。 目前在夜光印刷方面，既有的產品似乎集中在簡易的標示 牌。製程就是先將圖案印上，再將長餘暉微米粒子攙入透明漆 中並印在基材上的淺色部份區域，將其當成色彩與夜光的來源。 也因著長餘暉材料的顏色有限（比如沒有接近印鐵所常用 的CMYK四主色，甚至連純白色也還未開發出來），材料的粒徑 偏大（約5〜200 ym)難以直接用市面上現成的半色調網印設^ 201013601 -印製，所以無法適用於全彩的網點印刷，以致於難製作出精美 的全彩夜光圖。以熱為能源者更是未見有類似的產品。 目前可找到最接近的產品為門牌的印刷，其製作方式為在 PVC (或金屬品）上塗上一般的漆料後，於預留的地方再塗上欲 顯示夜光的字（中國專利字號CN99104693.5)，因此所顯示出來 的字大都是單色。如附件一所示的三個成品。 本案因涉及要採用彩色半色調網點印刷的特殊須求，而目 前使用的夜光材料的特性與印鐵不相容（因厚度的關係）。現今 ❾夜光漆在市面上使用很興旺時，唯獨欠缺全彩網印（不僅限於 金屬品）的應用。本發明人也是嘗試數年才突破相容性的問題。 目前市面上的夜光產品所用的基材大都不同於本案，其製 程、漆料、製作方式、運用的機具都不同，如常用的陶瓷類、 玻璃、織物、塑膠等’其各自有特殊的優勢。至於現今市面上 既有的夜光平面印刷產品很容易被本發明所取代。因本發明的 技術可製作出精美的全彩夜光圖。本發明產品不但可承襲既有 ◎產品的吸取紫外線或可見光後產生長餘暉的夜光功能，也可因 著熱源（氣熱或水熱）同樣也可產生長餘暉的夜光功能。加上本 案疋利用半色調的網點印刷，在色彩的艷麗與精緻上遠超過市 面上類似的平面產品。 現有市面上夜光產品只是利用夜光材料本身的餘輝與顏色 ，現在基材上的一部份區域，大都以實色印刷方式為主，也就 疋在顏色的表現上較為單調。加上其夜光漆只是塗在整個面的 一部份而已，因此整體的發光亮度會因所佔面積多寡而打折扣。 本案的產品為利用微米材的長餘暉當成亮度的來源塗佈在 整片基材（或金屬）’在其上加上彩色半色調網點圖以顯示出鮮 201013601 盤的色彩。本案不但在圖形的亮度、細腻、精美、或是全彩方 面都遠勝過既有的產品，對於微米材以及基材的保護性更佳， 而且本案的夜光漆是塗在整個面上，所以可發崎亮的光。 本^因有豐虽的全彩夜光顏色，可衍生的技術或產品很 多。申吻人也印證此產品不一定要靠紫外線或可見光才能蓄 能，利用熱或是冰也可有蓄能或減能的效果。若加入不同顏色 的微米漆會是-個值得開發探討的路。所以本案應可衍生很多 的技術與應用產品。 ® 參考文獻 【1】薑偉捸，長餘暉發光材料的進展，材料導報，第21卷， 第8期，第106-115頁，2007年8月。 【2】陳育山，長餘暉與奈米結構硫氧化釔螢光體之合成與其發 光特性之研究，交通大學應用化學研究所碩士論文，2〇〇2 年6月。 【3】蔡宜壽’發光纖維的製造與應用，絲織園地，第44期， 2003年4月。 ❹【4】康岌釋，奈米油墨在製罐印刷上的研究，逢甲大學環境資 訊科技研究所碩士論文，2006年6月。 【5】蔡宜壽’奈米發光與應用，演說講義，2〇〇3年。 【6】肖志國、羅昔賢，蓄光型發光材料及其製品，第二版，化 學工業出版社，2005年03月。 【7】洪勤懷’奈米發光油墨在鐵皮印刷上的研究，逢曱大學土 木工程學系碩士論文，2008年1月。 【發明内容】 8 201013601 本發明之目的’在於提供一種當有明顯的光源時，會讓人 看到由彩色半色調網點印刷技術所印製成之彩色圖案；經一般 的光源或熱源的刺激-小段時間後，當處在暗處時，夜光材料 所發出的光源透過半色調網點印刷形成彩色夜光圖案。 為達成上述功效，本發明所採用之技術手段係包括：本發 明利用夜光材料當成亮度（非顏色）的來源，將夜光材料與透 明油墨調製成發光油墨，並利用網版印刷技術將發光油墨塗饰 在基材上（或金屬片），再利用彩色半色調網點印刷技術將彩色 〇圖案印刷在該發光油墨上，以顯示出其鮮制色彩。 【實施方式】 I ·本發明的基本特徵及特色 本發明將具有長餘暉特性的石夕_鹽u^4:£M2+zy+) _ 米材料加到彩色半色調網點印刷。除可保持印鐵 盤、細腻與精敏的半色調網點圖外，在夜光上也能有相當程度 的夜光全彩圖案效果。對於產生夜光的能量來源除可經由紫外 ❹線或可見光外，也可在熱源的刺激後發出長餘輝夜光。當以金 屬為基材時，產品的外型可以很容易加工成多樣化。田 本發明將夜光材料置於基材上（如金屬或其 再印上彩色半色調網點。當有明顯的光源時，如白天面^^)讓 人看到由彩色半色調網點印刷成之彩色圖案。然經由一般的 源（最好是紫外線）或是熱源的刺激一段時間後， = 時夜光材料就會發生作用。底漆上的夜光微来粒子二 源透過半色調網點印刷成的透明彩色圖案後，會讓人看到全彩 201013601 本發明以金屬（亦可用其它的基材）為對象，讓產品會發 出半色調的彩色夜光以增加產品的應用以及功能。以發光油墨 中的夜光材料為光源，以半色調網點印刷成之彩色圖案為色 源，此造成在夜光中顯現細腻、精敏的全彩圖文。夜光材料需 要先蓄光後才能有長餘暉的效果，但因本案的基材是金屬，本 發明人發現熱源也可以讓夜光材料蓄光（冷源有相反的效果）， 由此更可擴大本發明的應用範圍。 為達成上述的構想，本發明人歷經數年的研究後，終於成 ®功的製作出成品。因目前使用的長餘暉發光材料以梦鋁酸鹽的 微米材料（以说:况+办3+)最被看好，本發明用此材料主。然這 種材料的粒徑太大（60~150μιη)，須群聚才會發出較亮的光以及 維持較久的餘輝。本發明因而將發光材的印刷與半色調的彩色 印刷分開，也就是在顯示夜光時，前者負責發光，後者負責顏 色。在一般亮度（如白天）的環境下不會影響彩色印刷所顯示 的圖文。 ❹本發明的製程為先將基材（如金屬片、pVC、木質或玻璃片） 先塗上一層底漆層（一般用白色）或印上一層螢光漆，之上再 塗掺有矽鋁酸鹽的微米材料的透明油墨，此層須特別注意所造 成的厚度與微米材濃度的問題，一般的應用希望保持在200"m 左右（約微米材的粒徑的兩倍）。此種印刷也會面臨汽泡以及平 整度的問題。接著就進行一般的彩色半色調網印的工作，此時 選用的印刷油墨必須是彩色透明才可。 Π.本發明之原理 i.發光原理 長餘暉發光材料主要是由作為主體的化合物（基質）和糁 201013601 入特定的少量雜質離子（激活劑）組成’為改善發光材料的光 學性能’又再添加另一種雜質離子作為敏化劑。這些雜質離子 會取代部分基質晶體原有格位上的離子，造成基質晶格的缺 陷，從而產生能夠補捉激發電子的陷阱，陷阱越深餘輝時間越 長。激活劑是發光中心，其受到外界能量的激發而產生發光的 現象。而敏化劑的加入，則是為了有效地吸收激發能量，並藉 由敏化劑將能量傳遞給激活劑以達到能量效率化。以鋁酸鹽 SrAHEu，Dy3+發光材料為例，Eu2+為材料中的發光中心，而 Dy3+離子則為陷阱中心，能有效地捕獲並儲存被激發的電子，而 產生了時間長達2000分鐘的餘輝特性。 當發光材料受到能量激發時，會產生電子一電洞對 (electron-hole pair)’其中絕大部分的電子、電洞很快結 合，並放出該材料之特性光譜。另外少部分的電子與電洞被困 於材料杉的缺陷（defects)或陷牌中心（trappingcenter) :、w由於這些陷牌中心束缚能量低，激發能量停止照射後，在 ❹至躯的熱活化下即足以緩慢地脫困，而脫困的電子與電洞再次 t並以光的形式釋放能量，即為餘輝現象。囷1所示為發光材 料受激發後，電子、電洞_與電子躍遷的情形，其順序分別 為：（a)激發、（b)電子陷阱、（c)電子脫困、（d)和（g)電 同復合、(e)電洞陷阱、⑴電洞脫困、(h)直接複合 吾赫：i面來講，即物質中之電子吸收激發能量，並將能 ，=為位能之型態儲存。在不經過震動的情況下，以鶴射方 ft合過程回到基態時，釋放能量而發光。位能之改變，則 °所不之位能與配位座標關係圖。（點位置為基態，當受到 .11 201013601 受激發（excitation)後跳至B位置之能階，而到C時穩定，如 果要回到D點基態時，便會開始發光（emission)。 ii.奈米長餘暉發光材料 本發明所使用之長餘暉發光材料其顆粒大小（不超過 ΙΟΟμπι)遠大於奈米的範_，因此有人認為此種材料並不能稱為 奈米’而稱之為微米。奈米科技實際上並無統一的定義，一般 說法係指物質在奈米尺寸下呈現出有別於巨觀尺度下的物理、 化學或生物特性與現象。所謂奈米科技便是運用這方面的知 ❹識’在奈米尺寸等級的微小世界中操作、控制原子或分子組合 成新的奈米尺度結構（奈米材料）’以便展現新的機能與特性。 以此為基礎’設計、製作或組裝成新的材料、器具或系統，使 之產生全新功能，並加以利用的技術總稱。長餘暉發光材料的 發光現象是來自於晶格上離子的替換，並且長餘禪初期的製作 方式也是奈米材_常用的製作方式。因此長餘暉發光材料也是 以控制分子組成而製作的，其亦可稱為奈米材料。 皿·本發明製造方法 本發明發光油墨的印刷部分，是分兩步驟處理。以下就針 對這兩種印刷方法做基本的說明。 i.網版印刷 網版印刷又稱透孔法（Porous)或油印法（stencn )，將 油墨加在一張有細孔網幕的網版，利用刮刀的刮壓動作，讓油 墨穿過細孔印到置於網下的紙張或物品上，不需印刷的部位則 在網版外以人工或機械製成負片躐版加以保護。網版印刷是一 種多用途的印刷’可在紙張以外的材料，例如衣服、莞碑、茶 具、電器、大型看板、電路版、計算機、電腦及高科技相關產 12 201013601 品等’從事少量、多樣的印刷，也成為現在高科技電子行業不 可或缺的一門技術。附件二上圖即為本發明網版印刷所使用的 70目網版與刮刀。 ii·網點印刷 網點印刷在印刷過程中，圖像都是由網點的疏密來進行調 整表現的。而透過基本色網點的混合與重疊，來表現出多彩與 豐虽的顏色。目前在印刷技術中所使用的網點主要有兩種不同 的類型·調幅網點與調頻網點。 調幅網點是目前使用最為廣泛的一種網點。其網點密度是 固疋的’透過調整網點的大小來表現顏色的深淺與不同色調。 在印刷中’主要須考慮網點大小、網點形狀、網點角度與網線 精度等因素。附件二下圖所示為不同網點大小所呈現出的效 果’其中的數值部份代表油墨的覆蓋率。本發明的彩色圖形部 份便是採用此方式。 調頻網點是90年代以後新發展出來的一種網印方式，其與 ❹調幅網點不同之處在於’調頻網點的網點大小是固定的，藉由 控制網點的密集程度來呈現不同色彩與色調。亮調部分網點較 疏· ’暗調部分則較密集。本發明的底漆部份採用此方式。 IV.本發明之實驗例 為了加強發光油墨印刷後的發光亮度，並希望達到彩色夜 光的效果’本發明在實驗例之印刷的方法上，先在基材塗上一 層白色不透明漆，然後將透明發光油墨以網版印刷做為基底， 再於其上將彩色油墨以網點印刷覆蓋的兩步驟複合式印刷，其 詳細的實驗流程如后所述。 13 201013601 本發明實驗例利用網版印刷與網點印刷兩步驟的印刷方 式，將透明發光油墨與彩色油墨在鐵片上作結合，以期達到夜 光提升及全彩色夜光的效果。藉由照度的量測率定，找出時間 對發光油墨亮度的影響曲線，與探討發光油墨的耐水性和溫度 對其的影響性。為此，本發明對發光油墨進行了以下的實2广 i·本發明之發光油墨複合式印刷實驗例 本實驗例不考慮厚度問題’以大幅提高發光亮度為前提， ❹採用網版與網點印刷配合的兩階段複合式印刷技術來進行。在 考量發光效果的情況下，本實驗以印有白色油墨的鐵片為底， 先以網版印刷的方式在鐵皮印上一層發光油墨，再於發光油墨 層上以網點印刷印上彩色油墨，藉由網版印刷的粒子高密隼度 與網點印刷彩色油墨的半透明性，來達到高亮度發光與彩色夜 光的效果。本實驗材料設備如表1。 表1發光油里複合式印刷實驗材料設備一κ表 實驗使用材料與設備 簡介 如墨 曰商松井化學公司所生產之透明油里。 長餘暉發光材料 由台商介觀量子公司所提供之 SrAl必:Eu'Dy1 2 3*黃綠色發光材料· 高速攪拌機 用以攬拌發光油墨。 3〇〇目篩網與分篩機 " — 用以過濾發光材料· ~ 数位式厚度計（最小量測刻度0.001mm) 用以量測發光油墨印刷厚度 超近景攝影系統（放大倍數140x) 用以觀察發光材料之粒子分布 本發明之發光油墨複合式印蒯管驗例步驟如下： 1 先將長餘暉發光材料用150目篩進行過篩，本實驗均使 用以過150目篩之發光材料來調配。 2 以重量百分比 10%、20%、30%、40%、50%、60% 的比例分別量取過篩發光材料與透明油墨之所需用量，配製成 發光油墨。 3 將配製完成的六種比例發光油墨與印有白色油墨底漆 201013601 的鐵片以70目網版進行網版印刷。附件三上左圖與下左圖所示 分別為20%與50%發光油墨於亮處的網版印刷成果，附件三上 右圖與下右圖分別為其於暗處的發光效果。 (4) 將印有一層發光油墨的鐵片再進行彩色油墨層的印 刷。附件四上圖與下圖所示分別為20%與50%發光油墨於亮處 的彩色圖案印刷成品，附件五上圖與下圖分別為其於暗處的發 光效果。 (5) 觀察印刷鐵片的發光效果並分別以超近景攝影系統與 ®厚度計觀察發光材料粒子分布與量測成品厚度。 發光油墨複合式印刷實驗結果與討論： 由附件五下圖印刷成品的發光現象可以看出，本實驗例所 採用的複合式印刷方法相較於僅用網點印刷的方法，在發光成 效上，可說是呈現出不同的效果，不僅發光亮度大幅提升，亦 逹到了彩色夜光的效果。以下就針對本實驗成品的外觀、發光 效能與發光粒子分佈這幾部分來做探討。 〇 首先在發光效能部分，由附件五上圖與下圖比較可以看 出’隨著發光油墨濃度的提升，不僅發光亮度增加，在彩色效 果與層次方面也會有較明顯的表現。由附件六中上方之發光材 料粉末與下方60%印刷成品的發光亮度比較可以看出，60%印 刷成品在亮度的表現上，已有相當不錯的效果。 在外觀部分，由附件三上左圖與下左圖比較可以看出，隨 著發光油墨濃度的提升，網版印刷層的顏色也隨著變深，而過 深的發光材料黃綠色，將會影響到彩色圖形所要呈現出的原 色’如附件四下圖所示。雖然高濃度的發光油墨能在暗處呈現 201013601 圖案，在亮處的色彩吏件原本設計以白色為底漆的彩色 :==用照度的量測，來找出各濃度配比的發光 b 了作為日後應用上的參考依據。 在=粒子分布部分，由附件三上右圖與下右 象可以比較出，20%的印刷樣 布 ： ❹=而嶋度的提升，粒子分布趨於密集，其== _ 錄时·^上圖針目分弱濃度戰與60脚 口口白色縣的近照圖。由這兩張圖比較可以看出，㈣成 品其發光粒子分布明顯比1〇%成品密集很多，甚至還有粒子堆 叠的現象’而&也就是高濃度印刷成品其亮度較高的主要原 因發光粒子的尚密集度不僅亮度較高，其粒子彼此間發光的 ❹相互激發’更能延長發光餘輝的時間。若將本實驗例複合式印 刷10%成品的近照圖（如附件七上圖）與附件七下圖僅網點印 刷70%的近照圖作比較，可以明顯看出，在相同放大倍率下， 兩者單彳立表面積上發光粒子的分布數量是差異很大的，而這也 是複合式印刷方法在亮度上能大幅提升的原因。 此外，藉由數位式厚度計的量測可以得到各印刷層與不同 濃度印刷下的厚度，量測儀器如附件八上圖所示，各層厚度量 測結果整理成表2。由表2中可以看出，隨著發光油墨濃度的增 加，其網版印刷層的厚度也隨著增加，這也更可表現出高濃度 201013601 發光油墨其發光粒子的堆疊現象與亮度較高的原因。由圖 3(a)、3(b)分別為本發明複合式印刷成品與一般網點印刷成品的 縱剖面示意圖中，更可以看出兩種不同印刷方法其發光粒子分 布厚度的差異。本發明成品包括一金屬片（10)做為基材，至少 一層混合包含有夜光材料及透明油墨的發光油墨（20)，其以網 版印刷技術印在該金屬片（10)上；及一彩色油墨層（30)，其以 彩色半色調網點印刷技術印在該發光油墨層（20)上。 表2各材料印刷層的厚度表 «料層 大約厚度（mm> 鐵片 0.220 白色底漆層 0.040 10%發光油墨網版印刷層 0.055 20%發光油墨網版印刷屠 0.060 30»發光油墨網版印刷層 0,065 40%發光油墨網版印刷層 0.070 50%發光油墨網版印刷層 0.090 60%發光油墨網版印刷層 0.110 彩色圖案網黏印刷層 <0.001 本發明時間對發光油墨亮度之影響性測試： 發光油墨隨著配比濃度的不同，有著不同的發光亮度，而 發光亮度也會隨著時間變動而有遞減的趨勢，故本實驗將藉由 照度計的量測，來觀察發光油墨亮度隨時間遞減的趨勢，並透 Ο過與發光材料亮度的比對，來探討各配比濃度的發光效能與特 性’藉以作為日後發光油墨在應用上的參考依據。本實驗材料 设備如表3。 $ 3胃間對發光油墨亮度之影響性實驗材料設備一覽表 寅驗使用材料與設備 «介 長餘嗶發光材料 由台商介観置子公司所提供之SrAh〇；TI^^ 黄綠色發光材料。 y 發光油畕網版印刷樣品 濃度分別爲10%、20%…60%等六種1 κ光油墨彩色印is丨丨昧a 澳度分別爲10%、20%…60%等六種-------- 照度計 - 最小童測軍位爲O.Ollux · ~~— 撤《光额 亮度爲1601ux ---~ 本發明時間對發光油墨亮度之影響性的測試步驟如下： ⑴將長餘暉發光材料以亮度1601ux的光源激發3〇分鐘 17 201013601 -再以照度計分別量測其停止激發後o.l分鐘、0.5分鐘、1分鐘、 2分鐘、5分鐘、10分鐘、15分鐘、20分鐘與30分鐘之亮度， 其中當亮度遞減至O.Ollux，即停止記錄。 (2) 分別改用5分鐘、10分鐘、15分鐘、60分鐘、90分 鐘與120分鐘的激發時間，重複步驟（1)。 (3) 分別以 10%、20%、30%、40%、50%與 60%之發光 油墨網版印刷樣品取代長餘暉發光材料，重複步驟（1)。 (4) 分別以 10%、20%、30%、40%、50%與 60%之發光 ❹油墨彩色印刷成品取代長餘暉發光材料，重複步驟（1)。此步 驟之亮度量測位置如附件九中紅色圓圈之範圍。 本發明時間對發光油墨亮度之影響性實驗結果與討論如 下： 本實驗所使用之照度計，如附件八下圖所示，最小刻度為 O.Ollux，lux(勒克斯）為照度單位，其定義為入射光通量（lumen) 與被照面（iri)之比值，其中光通量為由光源發射並被人眼感 知之所有輻射能。而即使亮度在〇 〇Uux時，在黑暗處仍可清 楚觀查到其發光現象。因儀器刻度所限，本實驗之照度量測數 據，僅至o.oilux。一般對夜光的定義上採用〇 〇〇〇321ux為可 見光的低限。 本實驗之研究成果主要可以從發光材料、發光油墨網版印 刷，品、與發光油墨彩色印刷成品等三方面的亮度量測結果來 做討論’並透過與發光材料亮度的比對，來做各印刷層的發光 效能做探討。 、首先在發光材料部分，由圖4餘輝亮度之時間衰減曲線可 以看出在不同的時間激發下，其亮度的衰減趨勢可說是相當 • 18 201013601 近似的’這可說明本實驗所使用之發光材料有一定的性質穩定 f生此外，由哀減曲線可以看出，發光材料亮度的衰減在餘輝 時間前5分鐘較為急遽，5分鐘之後則漸趨平緩，而不同激發 時間所造成的亮度差距也是在前5分鐘較為明顯。由圖中亦可 發現，激發時間的增長對發光亮度的提升也有很明顯的影響， 而激發時間超過30分鐘後，其亮度的衰減曲線則相當接近，故 可推測本實驗所使用之發光材料，在l601ux光源的激發下，其 亮度飽和所需的激發時間為30分鐘。這也與參考文獻【6】中 ❹提到的，在2001ux光源的激發下，亮度飽和所需的激發時間為 30分鐘相當接近。此現象亦可由圖5不同量測時間下，激發時 間與餘輝焭度的關係圖可以看出’激發時間在分鐘以上，各 量測時間所得到之餘輝亮度趨於穩定，相對地，在激發時間小 於30分鐘的情況下，由於發光材料能量的吸收未達飽和，故所 測得的餘輝亮度則變化較大》此外，由圖6本實驗發光材料與 參考文獻【5】中相同發光材料之相對照度趨勢圖可以看出，兩 種材料在亮度遞減的趨勢上是非常接近的，這也顯示本實驗使 ®用之照度計有一定的準確度。 在發光油墨網版印刷樣品部分，濃度配比10%之初始激發 亮度小於O.Ollux，故無法量測。圖7〜11所示為60%〜20%五種 配比濃度’分別在30分鐘、60分鐘、90分鐘與120分鐘激發 時間下，其餘輝亮度對量測時間的衰減趨勢圖。由圖7與圖8 可以看出，60%與50%發光油墨樣品在四種激發時間下，其衰 減曲線是相當接近的，故可知在16〇lux的光源下，其達飽和亮 度所需的激發時間為30分鐘。相對地’ 20%〜40%由於亮度較 小’加上照度計的精度有限，故會有較大的誤差，看仍可看出 201013601 -其達飽和亮度所需的激發時間亦約為3〇分鐘。 圖12所7F為60%〜20%五種濃度配比與發光材料對照的相 對亮度衰減趨勢圖，激發時間為3〇分鐘，由圖中可以看出，％ %和㈣的衰減趨勢與發紐料十分㈣，這說明此兩種農度 配比的發光油墨，仍保有相當不錯的發光材料特性。而4〇%以 下的二種配比發光油墨，則有量測上的誤差存在。 本實驗將不同濃度配比於各時間點所測得之亮度與發光材 料測得之7C度的比值作為發光效能。圖13所示為6〇%〜2〇%五 〇種濃度配比與發光材料對照的發光效能曲線圖，由圖中曲線可 以看出，發光效迠有隨著時間而遞減的現象，不同濃度配比的 效能差異在餘輝時間前5分鐘較為明顯。而由準確度較高的濃 度50%與60%之效能曲線可以看出，量測時間前兩分鐘的亮度 效能起伏變化較為平穩，且濃度20%僅能測得前兩分鐘之亮 度，故本實驗各濃度配比的發光效能即以量測時間2分鐘以 前’四個時間測點的發光效能平均值來做為依據，整理成表5。 表5光源1601ux激發時間30分鐘各濃度前兩分鐘之發光效能表 濃度配比 平均發光效能 _ _ 20% 4.2¾ 30% —1,1% ~ --- 40% ' ' 14.7% 50% 35.2% 60% 46.1¾ 發光油墨彩色印刷成品部分，在量測位置的選擇上，主要 是想觀察彩色油墨對發光效能的影響，而彩色油墨處的發光亮 度除了受其底下發光油墨層的影響之外，亦與周遭不同顏色的 亮度有關，故選取此處既有彩色油墨覆蓋，周圍又有較高發光 亮度的色系來做模擬。而經由量測其餘輝亮度發現，僅有濃度 配比40%、50%與60%之初始激發亮度大於O.Ollux，其中40 %之初始亮度僅為0.061ux，其餘濃度配比則無法量測。圖14 20 201013601 所不刀別為50%和60%其網版印刷與彩色印刷之亮度衰減趨 勢圖由圖中可以看出，經過彩色印刷其亮度明顯降低很多， 但其衰減趨勢仍是相當接近的。此外，也可看出不同濃度配比 與印刷步料餘輝亮度的f彡響，在餘輝時間前5分鐘較為明 顯。若同樣地取餘輝時間前兩分鐘的平均發光效能，可得到彩 色印刷5G%與6G%其發光效能分別為4 5%與8 4%，相較於網 版印刷的發光效能可發現，再經過彩色網點印刷的步驟，會使 發光效能再降低80%以上，不過這會因彩色印刷圖案的不同而 〇有所改變。 本發明之發光油墨耐水性測試 根據參考文獻【6】，發光材料的耐水性較差，在水中會慢 慢地分解，使發光性能下降。因此本實驗將透過發光油墨網版 印刷樣品浸水後亮度的量測，探討發光油墨之耐水性，來了解 油墨對發光材料的包覆情形。另外也對本實驗所用之發光材料 遇水後的變化作觀察。 ❹本發明發光油墨耐水性測試步驟如下： (1) 將長餘暉發光材料加入裝有水的透明容器中，均勻混 合後’靜置兩天觀察其現象。 (2) 分別將20%、30%、40%、50%與60%之發光油墨網 版印刷樣品浸置於水中兩天後取出，以16〇lux光源激發3〇分 鐘後再以照度計量測其亮度變化，並與未浸泡水之樣品亮度作 比較。 支 發明發光油墨耐水性眚驗結果奧討論： 長餘暉發光材料經過兩天的浸泡之後，發現在沉澱的發光 材料上方與水面接觸的地方，出現一層白色物質，如附件十上 21 201013601 圖所示。初步推測可能為發光材料製造過程中摻入的雜質，或 者是發光材料與水作用分解出的物質。於是利用白色物質密度 較低的特性’將其與發光材料分離出來，並再次加水於發光材 料中，重複這兩個步驟，附件十下圖所示為分離出之白色物質。 結果發現’多次與白色物質分離後之發光材料，再經過水的浸 泡後，仍會產生新的一層白色物質，故可進一步確定此白色物 質為發光材料水解的產物，而這也就是發光材料效能會降低的 原因。 〇 發光油墨方面，在經過兩天的浸泡之後發現，其亮度並沒 有出現明顯的改變，如圖15所示，可以看出發光材料含量較高 的50%與60%樣品，其亮度衰減曲線與未浸水之樣品相近，這 也顯示油墨對發光材料有著良好的包覆性，使發光油墨有著良 好的耐水性。 主發明溫度對發光油黑皋唐之彩響性測試 根據觀察，發光油墨對突然增高的溫度會有亮度提升的現 Ο象，而急遽的降溫則會使亮度驟減，故可知溫度對發光油墨有 一定的影響性。本實驗將藉由長時間的高溫，來探討發光油墨 的耐熱性。 本發明溫度對發光油墨亮度之影響性測試步驟如下： (1)將濃度配比50%與60%之網版印刷樣品置入溫度保持 為85°C的熱水中，靜置60分鐘，取出後擦乾，以1601ux光源 激發30分鐘，量測其亮度。 (2)將測得的亮度資料與未加熱之樣品資料做比較，並續* 圖討論。 22 201013601 • 本發明溫度對發光油墨亮度之影響性竇驗結果輿討論： 發光油墨樣品在經過60分鐘的加熱後，其外觀顏色上有變 暗的現象’附件十一上圖與下圖所示分別為50%樣品加熱前後 的顏色。而在亮度量測結果的比較上發現，經過加熱之樣品， 其發光效能有變低的現象，圖16所示為濃度50%與60%樣品 加熱前後亮度衰減曲線的對照圖，可以看出經過實驗加熱後， 各量測時間的餘輝亮度皆有降低的現象。而在彩色網點印刷的 步驟中’會經過160°C烘烤數分鐘的手續，這也是降低彩色印 ®刷發光效能的影響因素之一。經由本實驗可知，長時間的高溫 狀態將會降低發光油墨的發光效能。 根據實驗結杲本發明發現下列四點： (1) 在不添加稀釋劑的情況下，以隔水加熱法，發光材料與 透明油墨的濃度配比上限約為70%。 (2) 透明發光油墨採用網版與網點兩步驟複合式印刷法，可 在鐵片上呈現出明顯的彩色夜光效果。 ❹ （3)透明發光油墨仍保有相當不錯的發光材料特性，其亮度 的衰減趨勢在餘輝時間前5分鐘最為急遽，之後則漸趨平緩。 而不同激發時間、配比濃度與印刷步驟對亮度的影響性也是餘 輝時間前5分鐘較為明顯。 (4)透，發光油墨在耐候性方面’雖然有良好的耐水性，但 在長時間高溫的條件下，會有發光效能降低的現象。 本發明採用的複合式印刷方法已得到了不錯的成效。但在 發光亮度與效能方面，一種可行的實施方式係添加稀釋劑（或 軟化劑），藉由蒸發性稀釋㈣拌合卫作性的作用，來增加發光 23 201013601 -油墨的統濃度，_亮度提升的效果。其次，若採用混凝土 的觀念’在目前在發光油墨中，加入粒徑較小的發光粉末，也 可用來填補大粒徑發絲子_空隙，達到亮度的提升，但須 注意的是，過小粒徑的發光材料，其亮度也會相對降低。而大 小粒徑發光材料的不同排列搭配印刷，也可藉由其發光亮度的 差異，來達到發光時的特殊效果。此外，也可藉由搭配不同色 系的發光材料’利用其發出的各種色光，來增加彩色夜光的效 果，其中，硫化物體系發光材料的顏色豐富，便是可以使用的 © —種材料。 本發明透過實驗發現溫度對發光油墨的亮度效能有很大的 影響蜂’這方面可藉由定溫系統，如烘箱，來更加了解發光油 墨在溫度方面的影響機制，增加發光油墨應用上的參考依據。 VI.結論 由上述之說明可歸納本發明具有下列之優點： 1 ·本發明成品除了具無毒、環保、節能等特性外；它具 〇有很多的獨特性’因此可應用的產品範圍應可持績的闊大，如 熱的應用、以及精美彩色半色調網點印刷等就有很大的空間。 2 .消防安全··可提供當有災害發生而人工光源失效時本 產品可以提供逃生所需微光供指示標誌、逃生路線、或消防設 備等標示。 3·本發明成品不但可提供較一般市面上微光產品有更良 好的微光效果，而且可用金屬品上全彩的顏色特性發揮出更好 的特效。 4 ·防偽機制：由於目前具夜光全彩（半色調網點印刷）印 24 201013601 •鐵的產品尚未出現。縱使有人可以製造出來，其半色調網點印 刷、製程、以及漆料的調配等都會造成不同的效果，因此容易 辨識出產品的差異。 5 ·夜光產品：如禮品，現代藝術畫及照片（附件十二） 等。因著全彩（半色調網點印刷）夜光效果可創造出細膩的夜光 圖形與顏色。另在標示牌（如路標、門牌、道路攔竿標線、汽機 車車牌等）的使用上在很多國家已用法規規定必須具備。本發明 使這些產品的圖文變得更精緻。 Ο 6·在野外測量時’若使用具夜光能力的標竿將對測量有 好處，尤其是須長期測量時候很有用。 7 ·熱效應：如摩拖車引擎防熱罩（附件十三）、汽車引擎 室、高壓電塔等有熱源之處、熱水瓶的外殼及電器用品等，本 發明裝置結合於前述物品之熱源處，可藉著長餘暉夜光材料將 熱轉化成夜光的能量來源。此構想目前沒有其它相似的產品。 8 ♦熱指示計：因著熱源所發出夜光的亮度，本產品可以 作為熱度的指標、或是警告標誌。市面上沒有類似的產品。 ❽ 9 .省Hb裝製·當停止人工光源，於關燈後有些地方可利用 夜光而達省能。而且此產品具環保性，耐用性也很好。有熱源 時就可以保證夜光的持續存在。 以上所述，僅為本發明之一些可行實施例，並非用以限定 本發明之專利範園，凡舉依據下列申請專利範圍所述之内容、 特徵以及其精神而為之其他變化的等效實施，皆應包含於本發 明之專利範圍内。本發明所具體界定於申請專利範圍之結構特 徵，未見於同類物品，且具實用性與進步性，已符合發明專利 要件，爰依法具文提出申請，謹請鈞局依法核予專利。 • ,25 201013601 '【圖式簡單說明】 圖1為解說發光材料甲電子、電洞陷阱與電子躍遷的情形圖； 圖2為解說長餘暉發光之位能與配位座標關係圖； 圖3(a)為本發明複合式印刷成品縱剖面示音圖； 圖3(b)為本發明網點印刷成品縱剖面示意圖； 圖4為本發明不同激發時間下餘輝亮度隨時間之衰減趨勢圖； 圖5為本發明不同量測時間下激發時間對餘輝亮度之影響圖； 圖6為本發明實驗例與文獻發光材料之相對照度趨勢圖； ❹圖7為本發明濃度60%餘輝亮度對量測時間的衰減趨勢圖； 圖8為本發明濃度50%餘輝亮度對量測時間的衰減趨勢圖； 圖9為本發明濃度40%餘輝亮度對量測時間的衰減趨勢圖； 圖10為本發明濃度30%餘輝亮度對量測時間的衰減趨勢圖； 圖11為本發明濃度20%餘輝亮度對量測時間的衰減趨勢圖； 圖12為本發明各濃度配比與發光材料對照的相對亮度衰減趨 勢圖； ❹圖13為本發明各濃度配比與發光材料對照的發光效能曲線圖； 圖14為本發明不同印刷步驟餘輝亮度對量測時間的衰減趨勢 圖； 圖15為本發明浸水與否對照之餘輝亮度衰減趨勢圖； 圖16為本發明加熱前後之餘輝亮度衰減對照圖； 附件一：市面上夜光印鐵的三個成品照片； 附件二：上圖為本發明網版印刷所使用的網版與刮刀照片，下 圖為不同網點大小所呈現出的效果較圖； 附件三：上左圖為2〇%透明發光油墨網版印刷樣品於亮處，下 左圖為50%透明發光油墨網版印刷樣品於亮處，上右圖為2〇0/〇 26 201013601 透明發光油墨網版印刷樣品於暗處，下右圖為5〇%透明發光油 墨網版印刷樣品於暗處； 附件四.上圖為20%透明發光油墨彩色印刷成品於亮處，下圖 為50%透明發光油墨彩色印刷成品於亮處； 附件五·上圖為20%透明發光油墨彩色印刷成品於暗處，下圖 為50°/〇透明發光油墨彩色印刷成品於暗處； 附件六：為發光材料粉末與6〇%印刷成品之發光亮度比較圖。 附件七·上圖為10%發光油墨複合式印刷成品放大近照，中圖 ❹為（50%發光油墨複合式印刷成品放大近照，下圖為7〇%發光油 墨彩三層網點印刷成品放大近照； 附件八.上圖為本發明量測使用之數位式厚度計，下圖為為本 發明量測使用之照度計； 附件九：為發光油墨彩色印刷成品之亮度量測位置照片； 附件十：上圖為發光材料水解現象照片，下圖為濃度5〇%樣品 加熱後照片，下圖分離出之白色物質照片；及 附件十一：上圖為濃度50%樣品加熱前照片，下圖為濃度50 ® %樣品加熱後照片。 附件十二：上圖為本發明所作彩色圖片，下圖為其夜光圖片。 附件十三：上圖為本發明所作摩拖車排汽管的塗漆，下圖為其 夜光效果。 【主要元件符號說明】 (10)金屬片 (20)發光油墨 (30)彩色油墨層 27The advantages of high degree and long illumination time (such as reference [2]) are extremely environmentally friendly. Therefore, Changhui luminescent materials are widely used in: electronic appliances, commercial places, civil communications, electricity, petroleum, public security, fire, transportation, facilities, military facilities, rescue equipment, arts and crafts, chemicals, textiles, construction, building materials, mining, Machinery, 201013601 Hospitals, tourism, roads, railways, subways, ships, ports, aviation, post and telecommunications, advertising and other fields of society (such as reference [3]). i mouth m ^ life, the application of iron sheet products is quite extensive, such as indicator labels, head iron gift boxes, vehicle exhaust pipes, etc. The inventors attempted to combine the luminescent ink with the iron sheet by the preparation of materials, printing materials and printing inks, in order to make the iron sheet exhibit the effect of color luminous, thereby increasing the new functionality and commerciality of the iron sheet product. Even (iv) effects or military uses. Ο There are many products for luminous products, such as ceramics, plastics, glass, woven fabrics, ’ ’, stickers, and so on. The raw materials used in this case are the same as those from many lunar products on the market. The difference is that the present invention focuses on process research for color printing, that is, not only requires good night light, but also displays a color network (4) effect. At present, the development of luminous products is based on the United States, Japan and the mainland as the world's major cities. The product of the present invention has a clear advantage over the existing luminous products currently available on the market', which will bring a wider space for the application of luminous products. ❹ ^ With the research of the long-glow luminescent materials, the brightness and quality of the materials developed have also been greatly improved. However, the long-lasting luminescent material can't be used as the final product. Therefore, in recent years, many related application technologies have gradually developed. At present, in terms of luminous printing, existing products seem to focus on simple signage. The process is to first print the pattern, then the long afterglow micron particles into the transparent paint and printed on the light part of the substrate, as a source of color and luminous. Also because of the limited color of the long-lasting materials (such as the CMYK four main colors not commonly used in printing iron, even pure white has not been developed), the material particle size is too large (about 5~200 ym) difficult to use directly in the market The ready-made halftone screen printing ^ 201013601 - printed, so it can not be applied to full-color dot printing, so that it is difficult to produce a beautiful full-color luminous map. Those who use heat as an energy source have not seen similar products. At present, the closest product can be found in the printing of the house. It is made by applying the general paint on the PVC (or metal) and then painting the words to display the luminous light in the reserved place (Chinese Patent No. CN99104693. 5), so the words displayed are mostly monochrome. Three finished products as shown in Annex 1. This case involves special requirements for color halftone dot printing, and the properties of the currently used luminescent materials are incompatible with the printed iron (due to thickness). Nowadays, when the use of enamel paint is very prosperous in the market, it is lacking in the application of full-color screen printing (not limited to metal products). The inventors have also tried to break through the compatibility problem for several years. At present, the substrates used in the luminous products on the market are mostly different from the present case. The processes, paints, production methods, and tools used are different, such as commonly used ceramics, glass, fabrics, plastics, etc., each of which has special advantages. As for the existing luminous flat printing products available on the market today, it is easily replaced by the present invention. The fine full-color night light map can be produced by the technique of the present invention. The product of the invention can not only inherit the luminous function of the product which absorbs ultraviolet light or visible light, but also produces a long-lasting luminous function due to the heat source (gas heat or water heat). In addition, the use of halftone dot printing in this case far exceeds similar flat products on the market in terms of color beauty and sophistication. The existing luminous products on the market only use the afterglow and color of the luminous materials themselves. Now, most of the areas on the substrate are mainly printed in solid color, which is more monotonous in the performance of the color. In addition, its luminous paint is only applied to a part of the whole surface, so the overall brightness of the light will be compromised by the amount of area. The product of this case is coated with a long afterglow of micron material as a source of brightness on a whole substrate (or metal) with a color halftone dot pattern added to show the color of the fresh 201013601 disk. This case is not only better than the existing products in terms of brightness, exquisiteness, exquisiteness or full color, but also better protection for micro-materials and substrates, and the luminous paint of this case is applied on the whole surface. So you can make a bright light. This is because of the full color of the luminous color, there are many technologies or products that can be derived. Shen Kiss also confirmed that this product does not have to rely on ultraviolet light or visible light to store energy. The use of heat or ice can also have the effect of energy storage or energy reduction. If you add micron paint of different colors, it will be a road worth exploring. Therefore, this case should be able to derive a lot of technology and application products. ® References [1] Jiang Weijun, The Progress of Long Afterglow Luminescent Materials, Materials Review, Vol. 21, No. 8, pp. 106-115, August 2007. [2] Chen Yushan, Chang Yuhui and the synthesis of sulphur oxysulfide phosphors and their luminescent properties. Master's thesis of Institute of Applied Chemistry, Jiaotong University, June 2nd. [3] Cai Yishou's manufacture and application of luminescent fiber, Silkland, No. 44, April 2003. ❹【4】Kang Yuxi, research on nano-ink in can printing, Master's thesis of Fengjia University Environmental Information Technology Institute, June 2006. [5] Cai Yishou's nano-luminescence and application, speeches, 2, 3 years. [6] Xiao Zhiguo, Luo Xixian, Light-storing luminescent materials and their products, Second Edition, Chemical Industry Press, March 2005. [7] Hong Qinhuai's research on nano-lighting ink on iron printing, Master's thesis of Department of Civil Engineering, Fengyi University, January 2008. SUMMARY OF THE INVENTION 8 201013601 The object of the present invention is to provide a color pattern printed by a color halftone dot printing technique when there is a distinct light source; stimulation by a general light source or heat source - After a short period of time, when in a dark place, the light source emitted by the luminous material is printed through halftone dots to form a colored luminous pattern. In order to achieve the above effects, the technical means adopted by the present invention include: the invention utilizes a luminous material as a source of brightness (non-color), modulates a luminous material and a transparent ink into a luminescent ink, and coats the luminescent ink by screen printing technology. It is embossed on a substrate (or a metal sheet), and a color enamel pattern is printed on the luminescent ink by a color halftone dot printing technique to display its fresh color. [Embodiment] I. Basic Features and Features of the Invention The present invention adds a zea-salt salt of a long afterglow characteristic to a color halftone dot print. In addition to maintaining a semi-tone dot pattern of printed iron plates, delicate and sensitive, there is also a considerable degree of full-color luminous effect on the night light. For the energy source that produces night light, in addition to ultraviolet rays or visible light, it can also emit long afterglow glow after stimulation by the heat source. When metal is used as the substrate, the appearance of the product can be easily processed into a variety. Tian Ben invention puts the luminous material on the substrate (such as metal or reprinted with colored halftone dots. When there is a clear light source, such as daytime ^^), people can see the color printed by colored halftone dots. pattern. However, after a period of stimulation by a general source (preferably ultraviolet) or a heat source, the luminous material will act. The luminous light on the primer is micro-particles. The transparent color pattern printed by the half-tone dots will make people see the full color. 201013601 The invention is made of metal (other substrates can also be used), so that the product will emit half. The color of the night light to increase the application and function of the product. The luminous material in the luminescent ink is used as the light source, and the color pattern printed by the halftone dot is used as the color source, which results in a delicate and sensitive full-color graphic in the luminous light. The luminous material needs to be stored first to have the effect of long afterglow, but since the substrate of the present invention is metal, the inventors have found that the heat source can also store the luminous material (the opposite effect of the cold source), thereby further expanding the present invention. Application range. In order to achieve the above concept, after several years of research, the inventors finally made a finished product. Since the long-lasting luminescent material currently used is most favored with the micro-material of the dream aluminate (say: + + 3 +), the present invention uses this material as the main material. However, the particle size of this material is too large (60~150μιη), it must be clustered to emit brighter light and maintain a longer afterglow. The invention thus separates the printing of the luminescent material from the halftone color printing, i.e., when displaying night light, the former is responsible for illuminating and the latter is responsible for color. In the general brightness (such as daylight) environment does not affect the graphics displayed by color printing. The process of the present invention first coats a substrate (such as a metal sheet, pVC, wood or glass sheet) with a primer layer (usually white) or a layer of fluorescent paint, and is coated with yttrium aluminum. The transparent ink of the micron material of the acid salt, this layer must pay special attention to the thickness and the concentration of the micron material. The general application is expected to be maintained at about 200"m (about twice the particle size of the micron material). This type of printing also faces problems with bubbles and flatness. Then, the general color halftone screen printing work is performed, and the printing ink selected at this time must be color transparent. Π. Principles of the Invention i. Principle of Luminescence The long-lasting luminescent material is mainly composed of a compound (matrix) as a host and 糁201013601 into a specific small amount of impurity ions (activator) to improve the optical properties of the luminescent material. Another impurity ion acts as a sensitizer. These impurity ions will replace the ions in the original lattice of some of the matrix crystals, causing the lattice of the matrix to be trapped, resulting in traps that can capture the excited electrons. The deeper the trap, the longer the afterglow. The activator is a luminescent center that is excited by external energy to produce luminescence. The sensitizer is added to effectively absorb the excitation energy, and the sensitizer transfers energy to the activator to achieve energy efficiency. Taking aluminate SrAHEu and Dy3+ luminescent materials as an example, Eu2+ is the luminescence center in the material, while Dy3+ ion is the trap center, which can effectively capture and store the excited electrons, and produce the afterglow of 2000 minutes. characteristic. When the luminescent material is excited by energy, an electron-hole pair is formed, in which most of the electrons and holes are quickly combined, and the characteristic spectrum of the material is released. In addition, a small number of electrons and holes are trapped in the defect or trapping center of the material fir: w, because of the low energy of the trapping center, the thermal activation of the body after the excitation energy stops the irradiation. The next is enough to slowly get out of trouble, and the electrons and holes that are out of sleep are again t and release energy in the form of light, which is the afterglow phenomenon.囷1 shows the case of electrons, holes, and electronic transitions after the luminescent materials are excited. The order is: (a) excitation, (b) electron trap, (c) electron depletion, (d), and (g). ) electric composite, (e) hole trap, (1) hole escape, (h) direct composite Wuhe: i surface, that is, the electrons in the material absorb the excitation energy, and will be able to = the type of potential energy Store. When the motion is returned to the ground state without the vibration, the energy is released and the light is emitted. If the potential energy changes, then the position of the position can be related to the coordinate coordinate. (The position of the point is the ground state, and when it is excited by .11 201013601, it jumps to the energy level of position B, and is stable when it reaches C. If it is to return to the ground state of point D, it will start to emit (emission). Nano-long-lasting luminescent material The long-lasting luminescent material used in the present invention has a particle size (not exceeding ΙΟΟμπι) which is much larger than that of nanometers. Therefore, it is considered that such a material cannot be called nanometer and is called micron. There is actually no uniform definition of rice technology. The general term refers to the physical, chemical or biological properties and phenomena that differ from the macroscopic scale in nanometer size. The so-called nanotechnology is the use of this knowledge. Knowing 'operating in a tiny world of nanometer-scale, controlling the combination of atoms or molecules into a new nanoscale structure (nanomaterial)' to reveal new functions and characteristics. Based on this, 'design, manufacture or assemble The general term for a new material, appliance, or system that produces new functions and uses them. The luminescence of long-lasting luminescent materials comes from the replacement of ions on the lattice, and Moreover, the production method of the early period of Changyu Chan is also a commonly used production method of nanomaterials. Therefore, the long-lasting luminescent material is also made by controlling the molecular composition, and it can also be called a nano material. The invention is also a method for producing the invention. The printing part of the ink is processed in two steps. The following is a basic description of the two printing methods. i. Screen printing screen printing, also known as Porous or stencn, stencn In a screen with a fine mesh screen, the scraping action of the scraper is used to print the ink through the fine holes to the paper or articles placed under the net. The parts that do not need to be printed are manually or mechanically outside the screen. It is made into a negative film to protect it. Screen printing is a multi-purpose printing material that can be used outside the paper, such as clothes, wine, tea sets, electrical appliances, large billboards, circuit boards, computers, computers and high-tech related products. 201013601 Products and so on 'small and diverse printing, has become an indispensable technology in the high-tech electronics industry. The above figure is the 70 mesh used in the screen printing of the present invention. Version and scraper ii·Dot printing dot printing In the printing process, the images are adjusted by the density of the dots, and the color and color of the dots are displayed through the mixing and overlapping of the basic color dots. At present, there are two different types of dots used in printing technology, such as AM and FM. The AM is the most widely used dot. Its dot density is solid and the color is adjusted by adjusting the size of the dots. The depth and different shades. In printing, the main factors of dot size, dot shape, dot angle and mesh accuracy should be considered. The figure below shows the effect of different dot sizes. The coverage of the ink. The color pattern part of the present invention adopts this method. The frequency modulation network dot is a newly developed screen printing method after the 1990s, and the difference from the ❹ amplitude modulation network point is that the dot size of the FM frequency point is fixed. Different colors and tones are displayed by controlling the density of the dots. Some of the bright spots are more dense. The darker part is denser. The primer portion of the present invention is in this manner. IV. Experimental Example of the Invention In order to enhance the brightness of the luminescent ink after printing, and to achieve the effect of color luminous light, the present invention applies a white opaque lacquer to the substrate in the printing method of the experimental example, and then transparent. The luminescent ink is screen-printed as a substrate, and the two-step composite printing of the color ink is covered by dot printing, and the detailed experimental procedure is as follows. 13 201013601 The experimental example of the present invention combines a transparent luminescent ink and a color ink on an iron sheet by a two-step printing method of screen printing and dot printing, in order to achieve the effect of luminous enhancement and full-color luminous. By measuring the illuminance, the influence of time on the brightness of the luminescent ink is found, and the influence of the water resistance and temperature of the luminescent ink on it is discussed. Therefore, the present invention has the following aspects of the luminescent ink: a luminescent ink composite printing experiment example of the present invention. This experimental example does not consider the thickness problem, which is based on the premise of greatly improving the illuminating brightness, and adopts screen printing and dot printing. A two-stage composite printing technique is used in conjunction with the process. In the case of considering the illuminating effect, this experiment uses the iron sheet printed with white ink as the bottom, first prints a layer of luminescent ink on the iron sheet by screen printing, and then prints the color ink on the luminescent ink layer by dot printing. The high-intensity luminescence and the color luminous effect are achieved by the high-density density of the screen printing and the translucency of the dot-printing color ink. The equipment of this experimental material is shown in Table 1. Table 1 Luminous oil in the composite printing experimental materials equipment κ table experimental materials and equipment used in the introduction of the ink in the transparent oil produced by the company. Long afterglow luminescent material SrAl must be provided by Taiwanese Mesoscopic Quantum Co., Ltd.: Eu'Dy1 2 3* yellow-green luminescent material · High-speed mixer Used to mix luminescent ink. 3 mesh screen and siever" — for filtering luminescent materials · ~ Digital thickness gauge (minimum measurement scale 0.001mm) for measuring illuminating ink printing thickness ultra-close-range photography system (magnification 140x) To observe the particle distribution of the luminescent material, the steps of the luminescent ink composite printing tube of the present invention are as follows: 1 First, the long afterglow luminescent material is sieved with a 150 mesh sieve, and the experiment uses a luminescent material with a 150 mesh sieve. Provisioning. 2 The required amount of the sieve luminescent material and the transparent ink is separately measured in a ratio of 10%, 20%, 30%, 40%, 50%, and 60% by weight to prepare a luminescent ink. 3 The six proportions of the luminescent inks prepared with the white ink primer 201013601 were screen-printed with a 70-mesh screen. On the left and right left side of Annex III, the screen printing results of 20% and 50% luminescent inks are respectively displayed in bright places. The right and lower right pictures in Annex 3 respectively show their illuminating effects in the dark. (4) The iron sheet printed with a layer of luminescent ink is printed on the color ink layer. The upper part of the attached figure and the figure below show the color pattern printing of 20% and 50% of the luminescent ink in the bright place respectively. The upper picture and the lower picture of the annex 5 respectively show the illuminating effect in the dark place. (5) Observe the illuminating effect of the printed iron piece and observe the distribution of the luminescent material particles and measure the thickness of the finished product with the ultra-close-range photographic system and the thickness gauge. The results and discussion of the composite printing experiment of luminescent ink: It can be seen from the luminescence phenomenon of the finished product printed in the attached figure below. The composite printing method used in this experimental example is better than the printing method using only dot printing. It is said that it shows different effects, not only the brightness of the light is greatly improved, but also the effect of colored luminous. The following is a discussion of the appearance, luminescence efficacy and luminescent particle distribution of the finished product. 〇 First of all, in the luminous performance part, it can be seen from the comparison of the above figure and the following figure. As the concentration of the luminescent ink increases, not only the illuminance is increased, but also the color effect and level are more obvious. It can be seen from the comparison of the illuminating brightness of the luminescent material powder in the upper part of the sixth and the 60% printed product below, 60% of the printed products have a very good effect on the brightness performance. In the appearance part, it can be seen from the left and left pictures of Annex III that as the concentration of the luminescent ink increases, the color of the screen printing layer also becomes darker, and the too deep luminescent material is yellow-green. It affects the primary color to be presented in color graphics as shown in the figure below in Annex 4. Although the high-concentration luminescent ink can present the 201013601 pattern in the dark, the color element in the bright place is originally designed with white-primed color: == illuminance measurement to find the luminous b of each concentration ratio. As a reference for future applications. In the = particle distribution part, it can be compared with the right image and the lower right image in Annex 3, 20% of the printed sample: ❹ = and the increase of the enthalpy, the particle distribution tends to be dense, and its == _ recording time ^ The figure is divided into a close-up picture of the weak concentration warfare and the 60-foot mouth white county. It can be seen from the comparison of these two figures that (4) the finished product has a luminescent particle distribution that is significantly denser than the 1%% finished product, and even has the phenomenon of particle stacking 'and' is the main reason for the high brightness of high-concentration printed products. The intensity of the particles is not only high in brightness, but also the mutual excitation of the particles illuminating each other's time to extend the afterglow of the light. If we compare the close-up image of the 10% finished product of this experimental example (such as the above figure in Annex VII) with the close-up image of only 70% of the dot printing in the attached figure below, it can be clearly seen that at the same magnification, The number of luminescent particles distributed on the surface area of the two is very different, and this is the reason why the composite printing method can greatly increase the brightness. In addition, the thickness of each printed layer and different density printing can be obtained by the measurement of the digital thickness meter. The measuring instrument is shown in the figure above in the attached figure, and the thickness measurement results of each layer are compiled into Table 2. It can be seen from Table 2 that as the concentration of the luminescent ink increases, the thickness of the screen printing layer also increases, which also shows the high concentration of the 201013601 luminescent ink, the stacking phenomenon of the luminescent particles and the higher brightness. the reason. 3(a) and 3(b) are schematic longitudinal cross-sectional views of the composite printed product and the general dot printed product of the present invention, respectively, and the difference in the distribution thickness of the luminescent particles of the two different printing methods can be seen. The finished product comprises a metal sheet (10) as a substrate, and at least one layer is mixed with a luminescent ink (20) comprising a luminescent material and a transparent ink, which is printed on the metal sheet (10) by screen printing technology; A color ink layer (30) is printed on the luminescent ink layer (20) by a color halftone dot printing technique. Table 2 Thickness of printed layer of each material «Abgregate thickness of material layer (mm> Iron sheet 0.220 White primer layer 0.040 10% Luminous ink screen printing layer 0.055 20% Luminous ink screen printing butcher 0.060 30» Luminous ink screen printing Layer 0,065 40% luminescent ink screen printing layer 0.070 50% luminescent ink screen printing layer 0.090 60% luminescent ink screen printing layer 0.110 color pattern NET adhesive printing layer <0.001 The influence of the time of the invention on the brightness of the luminescent ink: The luminescent ink has different illuminating brightness depending on the concentration of the luminescent ink, and the illuminating brightness also tends to decrease with time, so the experiment will Through the measurement of the illuminometer, the tendency of the brightness of the luminescent ink to decrease with time is observed, and the comparison with the brightness of the luminescent material is used to investigate the luminescence efficiency and characteristics of each concentration concentration, which is used as a future luminescent ink. The reference on the basis. The experimental materials are shown in Table 3. $ 3 Stomach's influence on the brightness of luminescent inks Experimental equipment list 寅 使用 使用 使用 使用 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI y illuminating oil 畕 screen printing sample concentration of 10%, 20% ... 60% and other six kinds of 1 κ light ink color printing is 丨丨昧a Australia degrees are 10%, 20% ... 60% and other six -- ------ Illuminance meter - The minimum child test position is O.Ollux · ~~- Withdrawal of the light amount of brightness is 1601ux ---~ The test procedure for the influence of the time of the invention on the brightness of the luminescent ink is as follows: (1) The long-lasting luminescent material is excited by a light source with a brightness of 1601 ux for 3 〇 17 17 2010 13601 - and then measured by illuminance meter, respectively, after stopping the excitation, ol minutes, 0.5 minutes, 1 minute, 2 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes With a brightness of 30 minutes, where the brightness is decremented to O.Ollux, the recording is stopped. (2) Repeat steps (1) for 5 minutes, 10 minutes, 15 minutes, 60 minutes, 90 minutes and 120 minutes respectively. (3) Replace the long-lasting luminescent material with 10%, 20%, 30%, 40%, 50%, and 60% of the luminescent ink screen printing samples, and repeat step (1). (4) Replace the long-lasting luminescent material with 10%, 20%, 30%, 40%, 50%, and 60% of the luminescent ink color printing products, and repeat step (1). The brightness measurement position of this step is as shown in the red circle in Annex IX. The experimental results and discussion of the influence of the time of the invention on the brightness of the luminescent ink are as follows: The illuminance meter used in this experiment, as shown in the figure below in Annex 8, the minimum scale is O.Ollux, lux (lux) is the unit of illumination, which is defined as The ratio of the incident luminous flux (lumen) to the illuminated surface (iri), where the luminous flux is all of the radiant energy emitted by the source and perceived by the human eye. Even when the brightness is 〇 〇Uux, the luminescence can be clearly observed in the dark. Due to the limitation of the instrument scale, the measurement data of this experiment is only to o.oilux. In general, the definition of luminous is based on 低 〇〇〇 321ux as the lower limit of visible light. The research results of this experiment can mainly be discussed from the brightness measurement results of luminescent materials, luminescent ink screen printing, products, and color printing products of luminescent inks, and through the comparison with the brightness of luminescent materials. The luminous efficacy of the printed layer is discussed. First, in the luminescent material part, from the time decay curve of the afterglow brightness of Fig. 4, it can be seen that the attenuation trend of brightness under different time excitation can be said to be equivalent. 18 201013601 Approximate 'This can be used in this experiment. The luminescent material has certain properties and is stable. In addition, it can be seen from the sag curve that the attenuation of the illuminating material is more urgent 5 minutes before the afterglow time, and gradually becomes smoother after 5 minutes, and the brightness caused by different excitation times. The gap is also more pronounced in the first 5 minutes. It can also be seen from the figure that the increase of the excitation time also has a significant effect on the improvement of the brightness of the luminescence. After the excitation time exceeds 30 minutes, the attenuation curve of the brightness is quite close, so the luminescent material used in the experiment can be inferred. Under the excitation of the l601ux source, the excitation time required for saturation of the luminance was 30 minutes. This is also related to the reference in [6], where the excitation time required for brightness saturation is quite close to 30 minutes under the excitation of the 2001 ux source. This phenomenon can also be seen from the relationship between excitation time and afterglow intensity under different measurement time in Fig. 5. It can be seen that the 'excitation time is above the minute, and the afterglow brightness obtained by each measurement time tends to be stable. When the excitation time is less than 30 minutes, since the absorption of the energy of the luminescent material is not saturated, the measured afterglow brightness changes greatly. In addition, the experimental luminescent material of Fig. 6 is the same as that in the reference [5]. It can be seen from the comparison trend of the materials that the two materials are very close to the trend of decreasing brightness, which also shows that the experiment makes the illuminometer used by the о a certain degree of accuracy. In the luminescent printing screen printing sample portion, the initial excitation brightness of the concentration ratio of 10% is less than O.Ollux, so it cannot be measured. Figures 7 to 11 show the attenuation trends of the remaining luminances for the measurement time at 30 minutes, 60 minutes, 90 minutes, and 120 minutes of excitation time, respectively, at 60% to 20% of the five concentration concentrations. It can be seen from Fig. 7 and Fig. 8 that the attenuation curves of the 60% and 50% luminescent ink samples are quite close under the four excitation times, so it is known that under the 16 lux light source, the saturation brightness is required. The excitation time is 30 minutes. Relatively '20%~40% due to the small brightness' plus the accuracy of the illuminometer is limited, so there will be a large error, it can be seen that 201013601 - its excitation time required to reach saturation brightness is also about 3〇 minute. Figure 7F shows the relative brightness decay trend of the five concentration ratios of 60%~20% compared with the luminescent materials. The excitation time is 3〇 minutes. It can be seen from the figure that the decay trend of %% and (4) is related to the growth trend. The material is very (4), which shows that the two kinds of agricultural color ratio of the luminescent ink still retains quite good luminescent material characteristics. And the ratio of the two kinds of luminescent inks below 4% is measured. In this experiment, the ratio of the brightness measured at each time point to the measured 7C degree of the luminescent material was used as the luminescence efficiency. Figure 13 is a graph showing the luminous efficacy of the concentration ratio of 6〇%~2〇% of the five quinones and the luminescent material. It can be seen from the curve in the figure that the luminescence effect has a decreasing phenomenon with time, different concentrations. The difference in potency was more pronounced 5 minutes before the afterglow time. From the performance curves of 50% and 60% with higher accuracy, it can be seen that the brightness fluctuations of the first two minutes before the measurement time are relatively stable, and the concentration of 20% can only measure the brightness of the first two minutes. The luminous efficacy of each concentration ratio of the experiment was calculated based on the average of the luminous efficacy of the four time measuring points 2 minutes before the measurement time, and was compiled into Table 5. Table 5 Light source 1601ux excitation time 30 minutes luminous concentration of the first two minutes of each concentration concentration ratio average luminous efficacy _ _ 20% 4.23⁄4 30% —1,1% ~ --- 40% ' ' 14.7% 50% 35.2% 60% 46.13⁄4 luminescent ink color printing finished part, in the selection of measurement position, mainly want to observe the effect of color ink on luminous performance, and the illuminating brightness at the color ink is affected by the underlying luminescent ink layer. It is also related to the brightness of different colors around, so it is selected to have both color ink coverage and a color with high brightness around it for simulation. By measuring the rest of the brightness, it is found that only 40%, 50% and 60% of the initial excitation brightness is greater than O.Ollux, 40% of which is only 0.061ux, and the remaining concentration ratio cannot be measured. . Figure 14 20 201013601 is not 50% and 60% of its screen printing and color printing brightness attenuation trend chart can be seen from the figure, after color printing, its brightness is significantly reduced, but its attenuation trend is still quite close of. In addition, it can be seen that the ratio of different concentrations and the afterglow brightness of the printing step are more pronounced, 5 minutes before the afterglow time. If the average luminous efficacy of the two minutes before the afterglow time is taken in the same way, the luminous performance of the color printing 5G% and 6G% can be 45% and 8%, respectively, which can be found compared with the luminous efficacy of the screen printing. After the color dot printing step, the luminous efficiency is further reduced by more than 80%, but this will change due to the difference in color printing patterns. The water resistance test of the luminescent ink of the present invention According to the reference [6], the luminescent material has poor water resistance and is slowly decomposed in water to lower the luminescent property. Therefore, this experiment will measure the brightness of the luminescent ink after immersing the water through the luminescent ink screen to understand the coating of the luminescent material. In addition, the changes in the luminescent materials used in this experiment after water contact were observed. The test procedure for the water resistance of the luminescent ink of the present invention is as follows: (1) The long-lasting luminescent material is added to a transparent container filled with water, and uniformly mixed, and the phenomenon is observed after standing for two days. (2) 20%, 30%, 40%, 50% and 60% of the luminescent ink screen printing samples were respectively immersed in water for two days, and then taken out with a 16 lux light source for 3 〇 minutes and then measured by illuminance. The change in brightness is measured and compared to the brightness of the sample that is not soaked in water. After the two-day soaking, the long afterglow luminescent material was found to be in contact with the water surface above the precipitated luminescent material, and a layer of white matter appeared, as shown in Figure 10 201013601 . It is presumed that it may be an impurity incorporated in the manufacturing process of the luminescent material, or a substance which is decomposed by the luminescent material and water. The white matter is then separated from the luminescent material by the characteristic of the lower density of the white matter, and water is added again to the luminescent material. These two steps are repeated, and the white matter separated is shown in the figure below. It was found that the luminescent material separated from the white matter repeatedly, after being soaked in water, still produces a new layer of white matter, so it can be further confirmed that the white substance is the product of hydrolysis of the luminescent material, and this is the luminescent material. The reason why performance will decrease. In terms of 〇 luminescent ink, after two days of immersion, the brightness did not change significantly. As shown in Figure 15, it can be seen that the 50% and 60% samples with higher luminescent materials have a brightness decay curve. The samples that are not immersed in water are similar, which also shows that the ink has good coating property to the luminescent material, so that the luminescent ink has good water resistance. According to the observation, the temperature of the luminescent ink will increase the brightness of the sudden increase of the temperature of the luminescent ink, and the rapid cooling will reduce the brightness, so it is known that the temperature has a certain amount of luminescent ink. The impact. This experiment will investigate the heat resistance of luminescent inks by prolonged high temperatures. The test procedure of the influence of the temperature of the invention on the brightness of the luminescent ink is as follows: (1) The screen printing sample with the concentration ratio of 50% and 60% is placed in hot water maintained at a temperature of 85 ° C, allowed to stand for 60 minutes, and taken out. After drying, it was excited by a 1601 ux light source for 30 minutes, and its brightness was measured. (2) Compare the measured brightness data with the unheated sample data and continue to discuss the figure. 22 201013601 • The effect of the temperature of the invention on the brightness of the luminescent ink sinus test results 舆 Discussion: After the 60-minute heating of the luminescent ink sample, the appearance of the color has a darkening phenomenon. The color before and after heating is 50% of the sample. On the comparison of the brightness measurement results, it is found that the luminescence efficiency of the sample after heating is low. Figure 16 shows the comparison of the brightness decay curves before and after heating of the 50% and 60% samples. After the experiment was heated, the afterglow brightness of each measurement time was reduced. In the step of color dot printing, 'the process of baking at 160 ° C for several minutes is one of the factors that reduce the luminous efficacy of the color printing brush. It can be seen from this experiment that a long-term high temperature state will lower the luminous efficacy of the luminescent ink. According to the experimental results, the following four points were found: (1) In the case of no water addition, the upper limit of the concentration ratio of the luminescent material to the transparent ink is about 70% by the water-heating method. (2) The transparent luminescent ink adopts a two-step composite printing method of screen and dot, which can display an obvious color luminous effect on the iron sheet. ❹ (3) The transparent luminescent ink still retains quite good luminescent material characteristics, and its brightness decay trend is most urgent 5 minutes before the afterglow time, and then gradually becomes gentle. The effect of different excitation time, ratio and concentration on the brightness of the printing step is also obvious 5 minutes before the afterglow time. (4) Transparency, although the luminescent ink has good water resistance in terms of weather resistance, it has a phenomenon that the luminous efficiency is lowered under conditions of high temperature for a long period of time. The composite printing method adopted by the invention has achieved good results. However, in terms of illuminance and efficacy, a feasible embodiment is to add a diluent (or softener) to increase the luminescence by evaporative dilution (4) mixing action, 2010-13601 - ink concentration, _ brightness The effect of the upgrade. Secondly, if the concept of concrete is used, in the current luminescent ink, the addition of a luminescent powder with a smaller particle size can also be used to fill the large-diameter hair _ void to achieve an increase in brightness, but it should be noted that the granules are too small. The luminescent material of the diameter will also have a relatively low brightness. The different arrangement and size of the large-size luminescent materials can also achieve the special effect of illuminating by the difference in illuminance. In addition, it is also possible to increase the effect of color luminous light by using various luminescent materials emitted by different luminescent materials. Among them, the luminescent material of the sulphide system is rich in color, and can be used as a material. The invention finds through experiments that the temperature has a great influence on the brightness performance of the luminescent ink. This aspect can be understood by a constant temperature system, such as an oven, to understand the influence mechanism of the luminescent ink in temperature, and to increase the reference of the luminescent ink application. in accordance with. VI. Conclusions From the above description, it can be summarized that the present invention has the following advantages: 1. The finished product of the present invention has the characteristics of being non-toxic, environmentally friendly, and energy-saving; it has many unique characteristics, so the range of products that can be applied should be sustainable. There is a lot of room for performance, such as hot applications and fine color halftone dot printing. 2. Fire Safety··This product can provide indications such as low light for escape signs, escape routes, or fire fighting equipment when there is a disaster and the artificial light source fails. 3. The finished product of the invention not only provides better dimming effect than the general market low-light products, but also can exert better special effects by using the full-color color characteristics of the metal products. 4 · Anti-counterfeiting mechanism: Due to the current full-color (halftone dot printing) printing 24 201013601 • Iron products have not yet appeared. Even if someone can make it, the halftone dot printing, the process, and the blending of the paint will have different effects, so it is easy to identify the difference in the product. 5 · Luminous products: such as gifts, modern art paintings and photos (Annex 12). The full-color (halftone dot print) luminous effect creates a delicate luminous pattern and color. In addition, the use of signage (such as road signs, house numbers, road markings, steam locomotive license plates, etc.) has been required in many countries. The present invention makes the graphics of these products more refined. Ο 6· When measuring in the field ‘If you use the indicator with luminous ability, it will be good for measurement, especially when it is necessary to measure for a long time. 7 · Thermal effect: such as motorcycle trailer heat shield (Annex 13), automobile engine room, high-voltage electric tower and other places with heat source, hot water bottle shell and electrical appliances, etc., the device of the present invention is combined with the heat source of the aforementioned article, The energy of the night light is transformed by the long-lasting luminous material. There are currently no other similar products in this concept. 8 ♦Hot indicator: This product can be used as an indicator of heat or a warning sign due to the brightness of the night light emitted by the heat source. There are no similar products on the market. ❽ 9. Provincial Hb installation · When the artificial light source is stopped, some places can use the night light to save energy after turning off the light. And this product is environmentally friendly and durable. When there is a heat source, the night light can be guaranteed. The above is only some of the possible embodiments of the present invention, and is not intended to limit the scope of the patents of the present invention, and equivalent implementations of other changes in accordance with the contents, features and spirit of the following claims. All should be included in the scope of the patent of the present invention. The invention is specifically defined in the structural features of the scope of application for patents, is not found in the same kind of articles, and has practicality and progress. It has already met the requirements for invention patents, and has applied for it according to law. I would like to ask the bureau to approve patents according to law. • , 25 201013601 ' [Simple diagram of the diagram] Figure 1 is a diagram illustrating the situation of electron-emitting electrons, hole traps and electronic transitions of luminescent materials; Figure 2 is a diagram illustrating the relationship between potential energy and coordination coordinates of long-lasting luminescence; a) is a longitudinal sectional view of the composite printed product of the present invention; FIG. 3(b) is a longitudinal sectional view of the finished product of the dot printing of the present invention; FIG. 4 is a graph showing the attenuation trend of the afterglow brightness with time at different excitation times according to the present invention; 5 is a graph showing the influence of the excitation time on the afterglow brightness under different measurement times of the present invention; FIG. 6 is a trend diagram of the comparison between the experimental example and the document luminescent material of the present invention; FIG. 7 is a concentration of 60% afterglow brightness of the present invention. Fig. 8 is a graph showing the attenuation trend of the 50% afterglow brightness versus the measurement time according to the present invention; Fig. 9 is a graph showing the attenuation trend of the 40% afterglow brightness to the measurement time according to the present invention; FIG. 11 is a graph showing the attenuation trend of the 20% afterglow brightness of the present invention on the measurement time; FIG. 12 is a comparison diagram of the attenuation ratio of the 20% afterglow brightness to the measurement time of the present invention; Relative brightness decay trend Figure 13 is a graph showing the luminous efficacy of the contrast ratios of the present invention in comparison with the luminescent materials; Figure 14 is a graph showing the attenuation trend of the afterglow luminance versus the measurement time for different printing steps of the present invention; Comparison of the afterglow brightness decay trend graph; Figure 16 is a comparison of the afterglow brightness decay before and after heating of the present invention; Annex 1: three finished photographs of the luminous ink on the market; Annex 2: The above figure is used for screen printing of the present invention The screen and the scraper photo, the following figure shows the effect of different dot sizes; Annex 3: The upper left image shows the 2〇% transparent illuminating ink screen printing sample in the bright place, and the lower left picture shows the 50% transparent luminescent ink. The screen printing sample is in the bright place, the upper right picture is 2〇0/〇26 201013601 The transparent luminous ink screen printing sample is in the dark, and the lower right picture is the 5〇% transparent luminous ink screen printing sample in the dark; Annex IV The picture above shows 20% transparent luminescent ink color printing finished in bright place, the following picture shows 50% transparent luminescent ink color printing finished in bright place; Annex V. Above picture shows 20% transparent luminescent ink color printing finished in the dark, under The picture shows the 50 ° / 〇 transparent luminescent ink color printing finished in the dark; Annex 6: is the comparison of the illuminance brightness of the luminescent material powder and 6 〇 % printed products. Attachment VII. The above picture shows a magnified close-up of 10% luminescent ink composite printing finished product. The middle picture shows ( (50% luminescent ink composite printing finished product magnified recent photo, the following picture shows 7〇% luminescent ink color three-layer dot printing finished product magnification The above picture is the digital thickness meter used in the measurement of the present invention. The following figure is the illuminance meter used for the measurement of the present invention; Annex IX: the photometric position photo of the color printing finished product of the luminescent ink; X: The above picture is a photo of the hydrolysis phenomenon of the luminescent material. The following picture shows the photo of the sample after heating at a concentration of 5〇%, and the photo of the white substance separated by the following figure; and Annex XI: The above picture shows the photo of the sample before heating at 50% concentration. Photograph of the sample after heating for a concentration of 50 ® %. Attachment 12: The above picture is a color picture of the present invention, and the picture below is a picture of it. Annex 13: The above picture shows the painting of the trailer exhaust pipe of the present invention. The picture shows its luminous effect. [Main component symbol description] (10) Metal sheet (20) Luminous ink (30) Color ink layer 27