TWI333085B - Robust multilayer magnetic pigments and foils - Google Patents
Robust multilayer magnetic pigments and foils Download PDFInfo
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- TWI333085B TWI333085B TW092137303A TW92137303A TWI333085B TW I333085 B TWI333085 B TW I333085B TW 092137303 A TW092137303 A TW 092137303A TW 92137303 A TW92137303 A TW 92137303A TW I333085 B TWI333085 B TW I333085B
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- Prior art keywords
- layer
- pigment
- magnetic
- dielectric
- color
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- 230000005291 magnetic effect Effects 0.000 title claims description 161
- 239000011888 foil Substances 0.000 title claims description 18
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
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- C09C2200/301—Thickness of the core
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Description
1333085 玖、發明說明: 【發明所屬之技術領域】 本發明大體而言係關於顏料及箔片。^ & 關於具有磁性層且亦可具有可變 j 本七月h 薄片及绪片,以及包含該…=寺徵之堅固多層顏料 物。 4夕層磁性顏料薄片之顏料組合 【先前技術】 吾人已研發出各種顏料、著色劑與箱片,以用於種類廣 泛之應用。例如,已經研發磁性顏料以用於如裝飾性炊且、 製作圖案化表面以及安全袭置等應用。同樣,已經研發了 色移顏科以用於如化妝品、墨水、塗層材料、裝飾物、陶 究製品、汽車塗料、防偽熱衝麼以及用於安全文件與貨敬 之防僞墨水。 ^ 色移顏料、著色劑及落片顯示根據入射光角度變化或隨 觀測者之視角之改變而改變顏色之屬性。可藉由用於形成 薄片或W塗層結構之光學薄膜之適當設計或分子種類 (molecular species)之適當定向,來控制顏料及落片之色移 屬性。可藉由諸如形成薄片及箱片之各層之厚度與每一層 之折射率等參數之改變來達到所要效果。處於不同視角或 入射光角度時所發生之在觀察到的顏色中之變化,是構成 該等層之材料的選擇性吸收與波長相依之干涉效應相組合 之結果。起因於經過多重反射之光波之疊加的干涉效應, 曰成不同角度下觀察到的色移。反射最大值之位置與強 度會視角改變而改變,此係由於材料之各種層中的光路
0\90\903I9.DOC 徑長度差異會改變干涉 處選擇性地增強。 效應 其中干涉效應會在特定波長 途徑以達到該種色移效應。例m、的 夕曰般由多個薄膜層構成)分散於整體介質(諸如塗 料或墨水)1,隨後可將該介質塗敷於-物體之表面。視情 况可U寺薄片外塗敷塗料以達到所要顏色與光學效廣。 另-途徑“可變層來㈣小型金屬切化基板,且隨後 將該封裝之基板分散於整體介質(諸如塗料或墨水)中。此 外,已於基板材料上製得由多個薄膜層構成之箔片。 -種産生多層薄膜結構之方法爲藉由於其上具有—釋放 層之可撓性幅板材料上形成該結構。可藉由形成薄塗層結 構之技術中熟知之方法(如PVD、㈣或類似方法),將各層° 沈積於幅板上。隨後將該多層薄膜結構自幅板材料移除, 以用作薄膜色移薄片,可將該等薄片加入聚合物介質,例 如各種用作墨水或塗料之顏料媒劑。除了色移薄片外,可 向墨水或塗料加入添加劑以獲得所要色移效果。 已自一包括相同基本層之多層帛膜結構形成色移顏料或 落片。其包括一(多個)吸收層、一(多個)介電層及一視情況 使用之反射層,其中該等層之順序可改變。已形成具有一 對稱多層薄膜結構之塗層,例如:吸收體/介電體/反射體/ 介電體/吸收體;或吸收體/介電體/吸收體。亦已形成具有 一非對私多層薄膜結構之塗層,例如:吸收體/介電體/反射 體。 關於磁性顏料,菲利普斯(Phi丨Ups)等人的美國專利第
O:'.90\90319DOC 1333085 4,838,648號(以下稱爲"菲利普斯,648”)揭示了一種薄膜磁 性色移結構,其中可將磁性材料用作一反射層或吸收層。 種所揭示之磁性材料爲鈷鎳合金。菲利普斯1648揭示具有 以下结構之薄片與箔片: 上色覆蓋層(dyed Superstrate)/吸收體/介電體/磁性層/基 板,上色覆盍層/吸收體/介電體/磁性層/介電體/吸收體/上 色覆蓋層;以及黏接劑/磁性層/介電體/吸收體/可釋放之硬 塗層/基板。 施密德(Schmid)等人之歐洲專利公告Ep 686675B1(以下 稱爲施岔德”)中揭示將一磁性層合併入一多層薄片之嘗 试,其描述了在介電層與一中心鋁層之間包括一磁性層的 層狀色移結構’具體結構如下: 氧化物/吸收體/介電體/磁體/A1/磁體/介電體/吸收體/氧 化物β 因此,施岔德使用鋁小板,且隨後用磁性材料塗敷此等 小板。然而,因爲鋁爲第二光亮之金屬(僅次於銀),且因此 任何磁性材料反射⑽tt純,所以上覆之磁性材料使得 顏料之反射屬性降級。另外,施密德以自球磨法生成之鋁 小板著手,而球磨方法在所能達到之層光滑性方面之受到 限制。 因此,需要能夠克服或避免先前薄片及謂片之不足的改 良之磁性顏料薄片及箔片。 【發明内容】 本發明係關於具有磁性屬性之多層顏料薄片及落片。該
〇\9O\903l9D〇C 1333085 等顏料薄片在一磁性核心之相對側面上具有一堆疊層结 構’或者可形成爲〆封裝結構,其中磁性核心周圍具有封 裝層。該堆疊層結構内之磁性核心包括一夾於相對絕缘層 之間的磁性層,而該等相對絕緣層又夾於相對反射層之 間。同樣,該封裝結構内之磁性核心包括一由一絕緣層環 繞之磁性層,而該絕緣層又由一反射層環繞。當曝露於嚴 酷環境下時,顏料薄片内之絕緣層能大體上防止薄片發生 腐钱。 該等顏料薄片與箔片之一些具體實施例處於不同入射光 或仏視角度時會顯示離散色移。該等色移具體實施例顯示 離散色移,從而於入射光或視角之第一角度具有第一顏 色,且於入射光或視角之第二角度具有與該第一顏色不同 之第二顏色。 可將該顏料薄片散置於液體介質(如塗料或墨水)_,以 産生著色劑組合物,以隨後應用於物體或紙張。可將該等 落片層壓至各種物體,或將其形成於一載體基板上。 自以下說明與隨附之申請專利範圍可更加明瞭本發明之 此等以及其它特徵’或可藉由按照以下所陳述之方式實踐 本發明來瞭解本發明之此等以及其它特徵。 【實施方式】 本發明係關於具有磁性層之炙思 _ 層夂夕層顏料薄片及箔片,以及 併入了該等磁性薄片之顏料組合物。該等薄片及箱片可用 於:製作肉眼不可見之安全特徵;爲安全裝置製 二維空間類影像;或將裝飾性特徵加人産品中。㈣多習
O\90\903l9.DOC • i0· 1333085 =磁性薄片不同’本發明之薄片不僅僅是由可磁化 構成,而是包括可磁化與不可磁化材料兩者。例如 安=的顏料^與泊片中,於—磁性層與-反射層之間 ^置有-絕緣層1曝露於嚴酷環境下時,該顏料薄 泊片内之絕緣層能大體上防止薄片及箱片發生腐钱。 产二有與一金屬反射層(如銘)鄰接之磁性層的磁性 取適5溫度與濕度受控之環境。於諸如戶外、高濕度 及i務或鹽洛液之嚴酷環境下,由於該帶較多負電之= 屬(如紹)發生電偶腐#,因此該種磁性顏料會降級。 電偶腐姓(亦稱爲異金屈腐句爲材料在某些條件下盘另 =材料接觸時發生氧化或腐钱的過程。發生電偶腐钱必 、子在二個特定條件。首先’必須存在兩種不同電化學性 ,異金屬。第^,此兩種金屬必須互相接觸以於此兩種金 屬之間提供_導電路徑。第三,亦必須存在—傳導路徑, 其允許金屬離子自帶較多負電之金屬(陽極)移動至帶較多 正電之金屬(陰極)。若此等三個條❹有—個不存在,則不 會發生電偶腐蝕。 為減少具有鄰接異金屬之磁性顏料中之腐蝕,消除上述 三個電偶腐餘條件之一即可。最易於消除之條件爲異金屬 之間的電接觸’其可藉由將極薄之絕緣層放置於異金屬之 間得以消除。以下將更具體說明具有該種絕緣層之各種顏 料及箔片之具體實施例。 於本發明之各種具體實施例中隨著入射光角度或檢視 者之視角變化,該等顔料薄片及羯片之色度與色調也大大
O:\90\903I9DOC -11 - 1333085 偏移。該種光學效應(稱爲角光度(g〇ni〇chr〇maticity)或n色 移")使得所檢視到之顏色隨照明或檢視角度而變化。因 此,該等顏料薄片及落片於入射光或檢視之第一角度顯示 第顏色,且於入射光或檢視之第二角度顯示與該第一顏 色不同之第二顏色。可將該顏料薄片散置於液體介質(如塗 /墨)中以產生各種色移著色劑組合物,以隨後應用 於物體或紙張。可將料W層壓至各種物體或將其形 成於一載體基板上。 大體而言,本發明之色移顏料薄片可在一磁性核心層之 相對側面上具有-對稱堆疊塗層結構,可具有-大多數層 ;X磁I·生層之一側上之不對稱塗層結構,或可由環繞一 磁性核心之-個或更多封裝塗層形成。該等色移薄片及搭 片之塗層結構大體包括:—磁性核心,其包括—磁性或可 磁化層與其它可選擇層;一位於該 層二位於該絕緣層上方之反射層;一位於該反射層= 之介電層;以及一位於該介電層上方之吸收層。此處所使 用之表不各層之間之關係的術語”位於......上f意爲包括 相互鄰接之各層以及不相鄰接之各層。 藉由大體上達到較高之色度與亮度,本發明呈現出對習 知磁I·生顏料的顯著改良。藉由將較暗之磁性材料放入反射 體内’本發明實現了兩個目# ·· υ反射層之反射率得以維 寺以及2)觀測者無法區分不具有磁性材料内部核心之色 移顏料與具有磁性材料核心之此種顏料。例如,並排檢視 兩個經塗敷物體,-個在塗層中具有磁性材料且一個不具
〇A90\903I9D〇C -12 - 1333085 有對於觀測者來說,二者看上去相同。然而,除了色移 效應外’該磁性色移顏料亦提供一轉換安全特徵(c〇ven secumy feature)。由此,使用一磁性偵測系統,即可藉由(例 如)一法拉第轉子偵測器來讀取顏料中之磁性轉換標記。 可藉由將本發明之顏料薄片曝露於外部磁力中,從而定 向某些薄片之平面來使其垂直於包含該等薄片之塗層之表 面,以産生假像或三維類影像效應。未由.磁場定向之顏料 薄片之平面表面通常平行於塗層表面。三維類影像效果係 由粒子之對準排列所致,從而由磁場來定向縱橫比,意即, 顏料薄片之最長部分沿磁場線自對準。在2〇〇1年5月7曰申 請’名爲"藉由使用磁性顏料產生成像塗敷物品之方法 (Methods For Producing Imaged Coated Articles By Using Magnetic Pigments)"之同在申請中的美國專利申請案序號 第09/850,421號進一步詳細描述使用此處所揭示之磁性顏 料形成假像或三維類影像之方法,該案之揭示内容以引用 的方式併入本文。 可使用習知之薄膜沈積技術來形成本發明之色移薄片與 落片’該等技術在形成薄塗層結構之技術領域中已爲人所 熟知。該等薄膜沈積技術之非限制性實例包括物理氣相沈 積(PVD)、化學氣相沈積(cvd)、CVD之電漿增強(PE)變體 (例如PECVD或下游PECVD)、濺鍍、電解沈積以及其它能 導致形成離散均勻薄膜層之類似沈積方法。 可藉由各種製造方法來形成本發明之色移顏料薄片。例 如’可藉由一幅板塗敷製程來形成該等顏料薄片,於該製 〇-\9〇\9〇3I9 D〇C · 13 _ 1333085 種中’藉由習知沈積技術將各層相繼沈積於幅板材料上, 從而形成一薄膜結構,隨後使其破裂並(例如)藉由使用溶劑 來將其自幅板移除,從而形成複數個薄膜薄片。 於另-製造方法中,將至少包括磁性層之一個或多個薄 膜層沈積於-幅板上以形成一薄膜,隨後使其破裂並將其 自幅板移除,從而形成複數個彦頁料預薄片。若冑要,則; 藉由研磨使該等預薄片變成碎片。接著,在隨後的封裝製 程中以剩餘的層塗敷該等預薄片,從而形成複數個 片。 於另-製造方法中,可於隨後的封裝製程中塗敷磁性粒 子,從而形成複數個顏料薄片。當使用封裝製程來形成薄 片> 之外層時,應理解每一相應之封裝層爲一由一種環繞該 薄片結構之材料構成之連續層。 現在參考諸圖,其中相同結構均具有相同參照編號。圖1 描繪根據本發明一具體實施例之反射性磁性薄片 (讀印〇。驗20可爲一大體對稱薄膜結構,其包含—磁 性層22、一位於磁性層22之一主要表面上方之第一絕緣層 25以及一位於磁性層22之一相對第二主要表面上方之第二 絕緣層26。一第一反射層27位於第一絕緣層乃上方,且= 第二反射層28位於第二絕緣層26上方。 藉由將絕緣層插入反射層與磁性層之間,可避免薄片發 生電偶腐蝕。此外,如圖1所示,磁性層位於外反射層之間, 從而避免該等反射層發生光學屬性降級,且薄片仍保 反射率。 、同
0.\90\90319 DOC •14- 1333085 ,可藉由如前所述之幅板塗敷製程形成對應於獅2〇之 涛片,其中,各層相繼沈積於幅板材料上,以形成薄膜結 構’隨後使其碎裂並將其自幅板移除以形成複數個薄片。 或者’可將第一與第二反射層27與28形成爲—鄰接反射層 以虛線展示)之—部分,反射層29大體上環繞先前藉由幅 板塗敷製程形成之磁性層22及絕緣層25與%。
可將RMF 20用作顏料薄片或用作(例如)色移顏料内之上 方塗敷有額外層之—核心區。在色移顏料之情況下維持 反射層之高反射率對於保持顏料之高亮度與色度非常重 要。以下將更詳細討論RMF 20之塗層結構中之每一層。 磁性層22可由任何磁性或可磁化材料構成,例如鎳、鈷、 鐵、釓、铽、鏑、铒及其合金或氧化物。例如,可使用鈷 鎳合金,其中鈷與鎳之重量比分別爲約8〇%與約2〇Q/(^鈷鎳 合金中每種此等金屬的重量比例可增加或減少約1〇%,且
仍能達到所要結果。因此,以重量計該合金中之鈷之含量 可爲約70%至約90%,且以重量計該合金中之錄之含量可爲 約10%至約30%。諸合金之其它實例包括Fe/Si、Ni/Fe(例 如,鎳鐵導磁合金)、Fe/Ni、Fe/Co、Fe/Ni/Mo及其組合物。 亦可使用 SmCo5 ' NdCo5、Sm2Col7、Nd2Fe14B、Sr6Fe203、
TbFerAl-Ni-Co類型之硬磁材料及其組合物,以及jpe3〇4、 NiFe2〇4、MnFe204、CoFe204類型之尖晶石鐵氧體或YIG(釔 鐵石權石)或GdIG(亂鐵石權石)類型之石權石及其組合物。 儘管可使用此廣泛範圍中之磁性材料,但在本發明之一 些具體實施例中較佳爲軟磁體。此處所使用之術語”軟磁體" 0\90\903I9.DOC -15- 指任何表現出鐵磁屬性但曝露於磁力後剩磁大體上爲零之 材料。軟磁體對於-所施加之磁場顯示出决速回應,值磁 場移除後,其磁場特徵非常低(繞頌磁場_=〇 〇5 3〇〇奥斯 特(〇e))或爲零’或者其會保持非常低之磁力線。此外,此 處所使用之術語”硬磁體"(亦稱爲永久磁體)指任何可表現 出鐵磁屬性且曝露於磁化力後具有持久剩磁之材料。鐵磁 材料爲任何磁導率大體上大W且表現出磁滯屬性之材料。 用於形成本發明之薄片與片中之磁性層之磁性材料之 場頌磁力較佳小於約2_〜,且更佳小於約3〇〇〇e。矯頭 磁力指材料被外部磁場消磁之能力。續頌磁力值愈高,移 除磁場後將該材料消磁所需之磁場則愈高。在本發明之— 些具體實施财,所❹之磁性層較佳爲"軟"磁性材料(易 =磁),其與具有較高料磁力之,,硬,,磁性材料(難以消磁) 之換-根據本發明之磁性色移料n顏料或著色劑 =磁力較佳範圍爲約50Oe至約3〇〇〇e。此等襟頌磁力 顏料錄材料。因此’於磁性色移顏料與磁性非色移 用軟磁體之本發明之諸具體實施例係對習知技術 疋改良。於顏料薄片中使用軟 易而不會聚集。 軟磁〖生材枓使付缚片分散更容 σ字磁/·生層22形成爲具有適當之物理厚度,盆 米=約3_奈米,且較佳爲約5〇奈米至約15〇奈求y·、不 電:=2某:26:由任何適合之電絕緣材料構成,例如介 y〆/、二半導體材料。例如, 氧化鋁、条儿 寻、·έ緣層可由氟化鎂、 録或其組合物,以及任何其它適合用於薄膜
O:\90\90319 00C -16 - 1333085 製造過程且具有適當電絕緣屬性之絕緣材料構成。 該等絕緣層具有有效厚度,以藉由切斷顏料薄片之金屬 反射層(下文將討論)與磁性層之間的電路徑,來大體上避免 顏料薄片發生腐姓。例如,該等絕緣層可各自具有至少爲 約10奈米(且較佳爲約20奈米至40奈米)之物理厚度。 · 反射層27與28可由各種反射材料構成。目前之較佳材料 爲一或多種金屬、一或多種金屬合金或其組合物,因爲它 們具有高反射率且易於使用,但亦可使用非金屬反射材 料。用於反射層之適合金屬材料之非限制性實例包括鋁、籲籲 銀、銅、I、鉑、錫、鈦、鈀、鎳、鈷、铑、鈮、鉻、銥 及其組合物或合金。可將反射層24、26形成爲具有適合之 物理厚度,其爲約20奈米至約1000奈米,且較佳爲約兄奈 米至約100奈米。 在薄片20之一替代具體實施例中,可提供非對稱薄膜薄 片,其包括-薄膜堆疊結構,該結構具有與圖i所示之磁性 層22之一側上之相同層。於此具體實施例中,該非對稱薄鲁 片包括磁性層22、覆蓋磁性層22之絕緣層25以及覆蓋絕緣 層25之反射層27。此等層中的每一層都由與上述薄片之 : 相應各層相同之材料構成,並具有與它們相同的厚度。 .· 於另一替代具體實施例_,可視情況添加相對之介電層 以覆蓋薄片20之反射層27與28。此等相對之介電層能增加 薄片20之耐久性、剛性與耐蝕性。或者,可形成二介 電層,以大體上環繞反射層27、28與磁性層22。該(等)介電 層可視情況爲透明或可選擇性地吸收,以賦予顏料薄片之
OA90V903I9DOC -17- 1333085 顔色效果。其後將針對圖2之具體實施例,說明適於該種介 電層之介電材料之實例。 圖2描繪根據本發明另一具體實施例之一基於一 RMF之 磁性色移顏料薄片40。該薄片40爲一大體對稱之多層薄膜 結構’其於一RMF 42之相對側面上具有塗層,該rmf 42 ' 具有五層結構’如圖1中所示之RMF。如圖2所示,第一 . 介電層44與第二介電層46分別位於RMF 42之相對側面上 方-。第一吸收層48與第二吸收層50分別位於各介電層44與 46上方。可自以上所述之圖1之rmf的相同材料形成rmf鲁鲁 42,同時,以下將更詳細說明薄片4〇之介電層與吸收層。 可藉由一如前所述之幅板塗敷製程形成對應於薄片4〇之 薄片,其中將薄片40之各層相繼沈積於幅板材料上以形成 薄膜、構,後使該結構碎裂並將其自該幅板移除以形 成複數個薄片。 介電層44與46充當薄片40之薄膜堆疊結構中之間隔片。 將孩等;|電層形成爲具有有效光學厚度,以賦予干擾色與 所要之色移屬性。該等介電層視情況可爲透明,或可選擇 性吸收,以有助於顏料之顏色效果。該光學厚度爲一衆所 ·· 沾知之光學參數,其定義爲乘積…,其中々爲層之折射率,.· 且d為層之物理厚度。一般而言,吾人用四分之一波光學厚 度(QWOT)來表示層之光學厚度,QW〇T等於4 η(ΐ/λ,其中 λ爲發生一QWOT條件之波長。視所要之色移而定,該等 介電層之光學厚度範圍可爲約4⑽奈米設計波長處的約2 QWOT至約700奈米設計波長處的9 Qw〇T,且較佳爲
CM90\90JI9.DOC -18- 1333085 400-700奈米處的 2_6 QW〇T。 介兩厗τ目女S 視所要顏色特性而定,該等 "包層可具有爲約100奈米至約 米至約㈣奈米)之物理厚度。^(且車父佳爲約贈 將=介電層44與46之適合材料包括具有|,高"折射率(此處 1^爲大於約⑷)之材料,以及具有低折射率(此處 將其界以社65或更低)之材料。每―介電層都由單__材 料或由各種材料组合物及組態形成。例如,該等介㈣可 僅由低折射率材料或僅由高折射率材料、兩種或兩種以上 低折射率材料之混合物或多個子層、兩種或兩種以上高折 射率材料之混合物或多個子層、或低折射率與高折射率材 料之混合物或多奸層組成H該等介電層可部分或 完全由高/低介電光料疊形A,以下將進一步詳細討論。 當一介電層部分地甴一介電光學堆疊形成時,該介電層之 剩餘部分則可由如上所述之單一材料或各種材料組合物與 組態組成。 適用於介電層44舆46之高折射率材料之實例包括:硫化 _ 辞(ZnS)、氧化辞(ZnO)、氧化锆(Zr〇2)、二氧化鈦(Ti〇2)、 金剛石類碳、氧化銦(In2〇3) '氧化銦錫(IT〇)、五氧化二鈕 . (Ta205)、氧化鈽(Ce〇2)、氧化釔(γ2〇3)、氧化銪(Eu2〇3)、 ·· 鐵氧化物(例如四氧化三鐵((Π )diiron(ffi)〇xide)(Fe3〇4)與 二氧化二鐵(Fe2〇3))、氮化給(HfN)、碳化給(HfC) '氧化給 (Hf02)、氧化爛(La203)、氧化鎂(MgO)、氧化敍(Nd203)、 氧化镨(Pr60丨丨)、氧化釤(Sm203) '三氧化二錄(sb2〇3)、一 氧化矽(SiO)、三氧化二砸(Se2〇3)、氧化錫(Sn〇2)、三氧化 0 \90\90319 DOC -19- 1333085 鎢(wo3)、其組合物及類似物。 適用於介電層44與46之低折射率材料之實例包括:二氧 化矽(Si〇2)、氧化鋁(Α12〇3)、金屬氟化物(例如氟化= (MgF2)、氟化鋁(A1F3)、氟化鈽(CeF3)、氟化鑭(LaF3)、鋁 鈉氟化物(例如Na3AlF6,Na5Al3F14)、氟化鈥(NdF3)、氟化釤 (SmF3)、氟化鋇(BaF2)、氟化鈣(CaF2)、氟化鋰(LiF》、其 組合物,或任何其它折射率爲約165或更低之低折射率材 料。例如’可使用有機單體及聚合物作爲低折射率材料, 包括二稀烴化合物或稀烴化合物,如丙稀酸酷(例如,丙烤 酸甲㈤、全氟烯烴、聚四氟乙歸(Tefk)n)、氟化乙烤丙婦 (FEP)、其組合物以及類似物。 應理解:以上所狀若干介電㈣—般以非理想配比形 式存在’其通常需視將該介電材料沈積爲—塗層所用之呈 體方法而mx上所列之化合物名稱表示近似的理想配 比。例如,雖然一氧化石夕與二氧化石夕分別#有i : !與i : 2 之矽:氧之標稱比,但一 會自此等標稱值稍作變化 本發明之範圍内。 特定介電塗層之實際矽:氧之比 °該種非理想配比介電材料亦在 如以上所提及’肖等介電層可由高/低介電光學堆疊形 成’該等堆®具有低折射率(L)與高折射率⑻材料之交替 層。:一介電層由—高/低介電堆疊形成時,角度之色移將 視堆登中之層之组合狀封去工〜 A 折射率而又。適用於介電層之堆疊組 =實例包_、HL、LHL、HLH、HLHL、LHLH5i^ 爲(LHL阳職)Ony),M各種多層(multiple)
OA90\9〇3I9DOC -20- 1333085 或组合。於此等堆疊中,例如 折射率材料之離散層。 LH表示低折射率材料與高 ◦丨个,又订坷平的高/低 介電堆疊。例如,該堆疊可由具有以下梯度折射率之層形 成:由低至高梯度折射率、由高至低梯度折射率、[低至高 至低]n梯度折射率、[高至低至高]n梯度折射率(其中 於一替代具體實施例中,形成 r-HOO)、及其組合與多層4鄰層之折射率之逐漸變化(例 如由低至高折射率與由高至低折射率)産生梯度折射率。還 可在以不同比例沈積或共沈積兩種材料(例如乙與⑴過程 I藉由改變氣體來產生該等層之梯度折射率。各種高/低 光學堆疊可用於增強色移效能,向介電層提供抗反射屬 性,並改變本發明之顏料之可能顏色空間。 η電層44與46可各由相同材料或不同材料構成,且每一 :都可具有相同或不同之光學或物理厚度。應理解:當介 電層由不同材料構成或具有不同厚度時,料薄片於其各 側面上顯示不㈣色’且將薄片混合在顏料或混合物 内所得之混合物將顯示新的顏色,其爲兩種顏色之組合。 ^得顏色係基於來自薄片之兩個側面之兩㈣色的加色理 觸。於繁多的薄片巾,所得顏色爲兩種顏色之加色和其 是由具有不同側面定向朝向觀測者之薄片的隨機分佈引 起。 薄片40之吸收層48與50可由任何具有所要吸收屬性之吸 收材料構成,包括均勻吸收或非均勻吸收電磁光譜之可見 光。Ρ刀的材料。因此,視所要之顏色特性而定,可使用選 〇\90\90319〇〇c •21, 1333085 擇性吸收(非均勻吸收)材料或非選擇性吸收(均勻吸收)材 料。例如,吸收層可由非選擇性吸收金屬材料構成,其沈 積至足厚度,於該厚度,該吸收層至少部分吸收或半透 明。 適D之吸收材料之非限制性實例包括金屬吸收體,例如 鉻、鋁、鎳、銀、銅、鈀、鉑、鈦、釩、鈷、鐵、錫、鎢' 鉬鍺與銳,以及其相應氧化物、硫化物與碳化物。其它 適合之吸收材料包括碳、石墨、矽、鍺、金屬陶瓷、三氧 化二鐵或其它金屬氧化物、混合於介電基質中之金屬以及 其它能夠充當可見光譜中之非選擇性或選擇性吸收體之物 質。可使用以上吸收材料之各種組合物、混合物、化合物 或合金來形成薄片40之吸收層。 以上吸收材料之適合合金之實例包括:鉻鎳鐵合金 (Ni-Cr-Fe)、不銹鋼 '基於鎳之合金(hastall〇y)(例如, Ni-Mo-Fe ; Ni-Mo-Fe-Cr ; Ni-Si-Cu)以及基於鈦之合金,例 如鈦與碳之混合物(Ti/C)、鈦與鎢之混合物(Ti/W)、鈦與鈮 之混合物(Ti/Nb)、鈦與矽之混合物(Ti/Si)及其組合物。 如以上所提及,吸收層亦可由吸收金屬氧化物、金屬硫 化物、金屬奴化物或其組合物構成。例如,一種較佳吸收 硫化物材料爲硫化銀。其它適合吸收層之化合物之其它實 例包括基於鈦之化合物,例如氮化鈦(ΉΝ)、氧氮化欽 (TiNxOy)、碳化鈦(TiC)、碳氮化鈦(TiNxCz)、碳氧氮化鈦 (TiNxOyCz)、矽化鈦(TiSi2)、硼化鈦(TiB2)及其組合物。於 TiNxOy與TiNxOyCz之情況下’較佳情況爲x=0至卜, O\9O\903l9DOC •21 · 1333085 且2:=0至卜其中,1^队(^中\+7=卜且卩队(^(:2中\+财2=1。 對於TiNxCz而言’較佳情況爲x=〇至1且z=〇至},其中 x+z=l。或者,吸收層可由位於Ti基質中之基於鈦之合金構 成’或者可由位於基於鈦之合金之基質中之丁丨構成。 熟習此項技術者應當理解:吸收層亦可自磁性材料形 成’例如銘鎳合金或先前所述之其它磁性材料。如此可藉 由減少所需材料之數目來簡化磁性色移顏料之製造。 將吸收層形成爲具有一定物理厚度,視吸收層材料之光 學常量與所要峰移而定,其範圍爲約3奈米至5〇奈米,且較 佳爲約5奈米至15奈米。該等吸收層可各由相同材料或不同 材料構成,且每一層都可具有相同或不同之物理厚度。 於薄片40之一替代具體實施例中,可提供不對稱色移薄 片,其包括一薄膜堆疊結構,該結構具有與圖2所示之 RMF 42之一侧面上之相同層。因此,該不對稱色移薄片包 括RMF 42、覆蓋RMF 42之介電層44以及覆蓋介電層44之吸 收層48。此等層中的每一層都可由與上述薄片4〇之相應層 相同之材料構成並具有與它們相同的厚度。此外,可藉由 一如上所述之幅板塗敷製程形成不對稱色移薄片,於該方 法中,將各層相繼沈積於幅板材料上以形成一薄膜結構, IW後使該結構碎裂並將其自該幅板移除以形成複數個薄 於另一替代具體實施例中,可形成無吸收層之薄片4〇。 於此具體實_中,相對介電層44與46由如前所述之高/低 ();1電光子堆疊形成。因此,可組態介電層44與46 ,使
O:\90\903I9DOC -23 - 1333085 得薄片40具有塗層結構:(HL)n/RMF/(LH)n 、 (LH)n/RMF/(HL)n、(LHL)n/RMF/(LHL)n、(HLH)n/RMF/(HLH)n 或其它相似組態,其中n=l-1 00,且該等l與H層於設計波長 處爲1個四分之一波長(QW)。 作爲一般規則’若貴金屬表中兩種金屬之原子勢能之代 數差大於+/-0.3伏特’則其間會發生電偶腐蝕。鋁/鎳對之 勢能差爲-1.41伏特,其表示:當將具有一七層設計(例如 CrVMgFVAl/Ni/Al/MgFVCr)之顏料浸入電解溶液或曝露於 潮濕環境中時,存在驅使該顏料中之紹發生電偶腐蝕之驅 動力。該七層設計之顏料對曝露於鹼或其它鹼性溶液中尤 其敏感。爲了減少該種顏料中銘夕^ , ^ L, . 站之腐蝕,可藉由將此處所 之間,來消除這兩種異金屬 料之設計變爲’九層顏料, 述之絕緣層置於異金屬Α1與]ΝΠ 間之電接觸。於此方案中,七層_ 入銘層與磁性層之間,如 如圖2所示,其中將兩個絕緣層插 下所示:
Cr/MgF2/Al/MgF2 20 奈米 /Al/MgF2/Cr 爲便於製造,此具體實施例+ 赞丨生複合物/MgF2 20奈米 製得,氟化鎂爲該顏料之介電 MgF2之絕緣層的顏料要求以γ 層 之兩個絕緣層可由氟化鎂 < —構成組分。製造具有 敷之多層堆疊來重繞聚醋報(崎個額外步驟:以一部分塗 層。在一替代製造方案中,轉由),及沈積該氟化鎂絕緣 蒸發來沈積2。奈米厚之Al2。,,在氧存在下經由銘之反應 、’從而將鋁層與鎂層分隔。 化第一反射層(如鋁)之表 於另一替代製造方案中, 氣 〇 \90\90319 DOC -24、 1333085 面且氧化位於該氧化之反射層上方之磁性層之表面,從 ;X等異金屬之間形成氧化膜。對該製程而言,離子搶 文裝於距離鋁源很近之下游與磁性材料源之上游之間。以 工,使得正自一鋁源沈積至已沈積於第一吸收層上的 第"電層上之第一鋁層經過一氧化區,其中第一鋁層之 表面發生氧化以形成緻密氧化鋁絕緣薄膜。氧壓、離子搶 力率以及聚酯輥之重繞速度均爲用於控制該A丨薄膜厚 度之表塾。於-^ ” /双於下—步驟中,將磁性材料(例如,鎳)沈積於該 巴緣Al2〇3薄膜之上。於氧化區内,一緻密NiO層形成於該 材料之表面上’從而使該磁性層與相繼之第二鋁層絕 緣^Nl0層爲一 P型半導體,其提供了鎳層與第二鋁層之 電門隔於沈積該第二鋁層後,形成了第二介電層(如一氟 .1 Pre)片),隨後形成第二吸收層(如一鉻吸收體),以完 成具有以下設計之光學堆疊: 基板 /Cr/MgF2/Al/Al2〇3/Ni/NiO/Al/MgF2/Cr 子搶方法申之絕緣層之厚度可低於約2〇奈米,因爲相 ㈣藉由熱或反應蒸發所沈積之薄膜,此等層體具有更高 在度。忒製程之優點在於該製程與形成一七層堆疊所使用 很X貞似,〃、有聚酯輕通過塗敷機的數目不同,但該 離子搶製程此産生—堅固之九層設計,其於潮濕環境與電 解溶液中能夠抗腐蝕。 圖3描繪根據本發明之另—具體實施例之—反射磁性封 裝(RME)薄片60。該_薄片仰具有三層塗層結構其令 反射層62大體上賴並封裝絕緣扣,制環繞核心磁性
O:\90\903I9.DOC -25· ^33085 層64。反射層62與磁性層64之間的絕緣層63防止薄片6〇發 生電偶腐蝕。此外,如圖3所示,由於磁性層位於外反射層 内因此反射層之光學屬性不會降級且反射層能保持高反 射率。 REM薄片60可用作顏料粒子,或可用作一其上塗敷有額 外層之核心粒子。反射層62、絕緣層63以及磁性層64可由 與先前所討論之薄片20中之相應層相同之材料構成,且可 具有與它們相同之厚度。 於薄片60之一替代具體實施例中,可視情況添加介電層 來覆盍反射層62,以增加薄片6〇之耐久性、剛性以及㈣ 性。該介電層視情況可爲透明,或可選擇性吸收,以有助 於顏料薄片之顏色效果。 圖4描緣基於針對圖1與圖3所討論之卿或RME薄片之 封裝形式之磁性色移顏料薄片8〇的—替代塗層結構(虛線 表不)“。該薄片80具有—磁性核心區82,其爲一卿或— RME厚片,其可由—大體上環繞磁性核心區^之封裝介带 層Μ外塗敷。吸收層86(其外塗敷介電層84)爲薄片δ〇提供二 :裝。圖4中之薄片8〇之一側上之半球形虛線表 與吸收㈣可形成爲磁性核心_周圍之連續層。 或者,磁性核心區82盥介雷 一 〃、電層了爲一溥膜核心薄片堆疊 之形式,其t可在RMF磁性核 Η E , ^ 之頂表面與底表面(而 不疋至 >、一側之表面) 〇4,日+ )預先形成相對之介電層84a盥
且由吸收層86來封裝該薄膜堆#。亦可將 W 用於在薄片80上形成額外層,例如 裳製私 封盍層(未圖不)。該顏
〇 \90\90319 DOC -26- Ϊ333085 料薄片80表現出離散色移,使得該顏料薄片於入射光或檢 視之第一角度處具有第一顏色’並於入射光或檢視之第二 角度處具有與該第一顏色不同之第二顏色。 於另一替代具體實施例中’可形成無吸收層之薄片8〇。 於此具體實施例中’介電層84由類似於前述介電光學堆最 之鄰接高/低(H/L)介電光學塗層形成。因此,該介電層84 可具有以下塗層結構:(HL)n、(LH)n、(LHL)n、(HLH)n或其 它類似組態,其中n=l-1〇〇,且該等L與η層在一設計波長處 爲 1 QW。 可利用各種習知塗敷方法藉由封裴形成該等介電層與吸 收層。例如,適用於形成介電層之方法包括真空氣相沈積、 溶膠-凝膠水解、在一流化床内之CVD、下游電漿至裝滿粒 子之振盪盤上以及電化學沈積。適用於形成該等吸收層之 方法包括真空氣相沈積以及濺鍍至一粒子機械振盪床上, 如第US 6,241,858 B1號專利中所揭示,該案之以引用之方 式併入本文中。或者,可經由有機金屬化合物之熱解引起 上進行之相關CVD製程,來沈 步研磨,則此等方法會形成一 圍具有介電層與吸收層。在製 薄片時,可利用以上塗敷製程 的分解或可能需在一流化床 積吸收塗層。若不進行進一 封裝磁性核心’在該核心周 造具有多重封裝塗層之顏料 之各種組合。 =可將前述具體實施例之各種修改與組合視爲在本發明 之範圍内。例如,可於以上每一轳音 母具體貫鈀例之周圍形成額 外之介電層、吸收層及/或其它光學塗層,從而産生其它所
O:\90\903I9.DOC -27- 1333085 要光學特性。該等額外涂屏 卜土層此夠向顏料提供其它顏色效果。 此外可於則述每一顏料呈體营# & + ± 、了寸八媸貫苑例之外表面上形成一 光學透明覆蓋塗層以描玄+ 奐同耐久性。例如,圖2虛線描繪位於 吸收層50上方之第一透明覆 堂層5 2,以及一位於吸收層 48上方之第二透明霜芸涂 塗層54。圖4虛線描繪一環繞吸收層 =之光學透明覆蓋塗層9G。該透明覆蓋塗層可由任何能夠 提U4之合適透明材料構成,例如前述高折射率與低折 射率介電材料,以及平人私,l 次祆0物(例如丙烯酸酯及苯乙烯)、玻璃 狀材料(例如矽酸鹽與删夕姑 如 、项7圾塥)或其組合物。可將該透明覆 蓋塗層形成爲具有一滴合夕私饰后也 、田之物理厚度,其爲約5奈米至1〇 祕米且較佳爲約100奈米至約1微米。 在2〇〇1年4月27曰申請、名爲"多層磁性顏料與落片 (Multi layered Magnetic pigments and F〇ils)"之同在申請中 的專利中請案序號第G9/844,261號中揭示額外薄片具體實 施例其可經修改以在—磁性層與_反射層之間包括絕緣 層’該案之揭示内容以引用之方式併入本文中。 可將本發明之顏料薄片散佈於顏料介質中,以産生可應 用於廣泛範圍之物體或紙張的著色劑組合物。添加至介質 之:等:料薄片藉由入射至固化介質之一表面上的輕射産 生預疋光學回應'。該顏料介質較佳包含樹脂或樹脂之混 。物其此藉由熱製程(例如熱交聯、熱固化(thermal s扣丨叫) 或熱/合釗洛發),或藉由光化學交聯來乾燥或硬化。 適口之顏料介質包括各種聚合組合物或有機黏合劑,例 如醇IΜ知、聚酯樹脂、聚氨酯樹脂、乙烯樹脂、環氧樹
O:\90\90319.DOC •28- 1333085 脂、苯乙烯樹脂及其類似物。適合之樹脂之實例包括三兮 氰胺、丙烯酸酯(例如丙烯酸曱酯)、ABS(丙烯腈-丁二烯 苯乙烯)樹脂、基於醇酸樹脂之墨水與塗料調配物及其各種 混合物。該顏料介質亦較佳包括用於樹脂之溶劑,例如有 機溶劑或水。與該等顏料介質組合之薄片會産生著色咧組 合物,可將其直接用作塗料、墨水或可塑之塑膠材料1 可該著色劑組合物用作習知塗料、墨水或塑膠材料之添加
此外,可視情況將該等薄片與各種添加材料(例如習知3 顏料薄片、粒子或不同色調、色度與亮度之染料)摻合,γ 達到所要之顏色特性。例如,可將該等薄片與其它習知^ 干涉類型或非干涉類型顏料混合,以産生一定範圍的其^ 顏色。隨後可將此預摻合組合物散佈於聚合物介質(例如^ 料、墨水、塑膠或其它聚合顏料媒劑)中,以便以習知方^
加以使用。在先前參照之同在申請中的專利案序號負 09/844,261號中揭示合適添加劑材料之實例。 本發明之磁性色移薄片尤其適用於需要高色度與耐久七 著色劑之應用中。藉由於著色劑組合物中使用該等磁性爸 移薄片,可産生高色度耐久塗料或墨水,其中人眼可覺筹 到可變之顔色效果。本發明之色移薄片具有範圍廣泛之爸 移屬性,包括變化之視角下之色度(色純度)之大偏移以及㈢ 有色調(相關色)之大偏移》因此以包含本發明之色移薄片戈 塗料而著色的物體將視視角或物體相對於檢視眼睛之角方 的變化而改變顏色》 〇 \90\90319 DOC -29· 丄 WU85 本發明之顏料薄片可很容易且經濟地用於塗料與墨水 中,該等塗料可應用於各種物體或紙張,如機動車輛:貨 幣與安全文件、家用電器、建築結構、地板、織物、運動 商品 '電子包裝/外殼、產品包裝等等。亦可將該等色移薄 片用於形成著色之塑膠材料、塗料組合物、擠壓物 (extrusion)、靜電塗層 '玻璃與陶究材料。 叙而έ,本發明之箔片具有一非對稱薄膜塗層結構, 其可對應於任何上述關於薄膜堆疊薄片之具體實施例中之 一 RMF之一側上之層結構。可將該等箔片層壓至各種物 體,或使其形成於一載體基板上。亦可將本發明之箔片用 於一熱衝壓組態,其中藉由使用熱激活黏著劑將箔片之薄 膜堆豐自一基板之一釋放層移除,並將其塗敷至一對立表 面(C〇untersurface) 〇可將該黏著劑塗敷於與該基板相對之 一薄片表面上,或以UV激活黏著劑之形式塗敷於該薄片將 附著之表面上。 圖5描繪一形成於基板ι〇2上之色移箔片1〇〇之一塗層結 構,基板102可爲任何合適之材料,如一可撓性pET幅板、 載體基板或其它塑膠材料,箔片1〇〇包括一位於基板1〇2上 方之磁性層104、一位於磁性層1 〇4上方之絕緣層i 〇6、一位 於絕緣層106上方之反射層1〇8,一位於反射層1〇8上方之介 電層110以及一位於介電層u〇上方之吸收層112。磁性層、 絕緣層、反射層、介電層以及吸收層都可由與前述之薄片 20與40中之相應層相同之材料構成,並可具有與它們相同 之厚度。
OA90V90319.00C -30- 1333085 可由一幅板塗敷製程形成箱片100,其具有如先前所述藉 由習知沈積技術相繼沈積於—幅板上之各層,以形成-薄 膜辖片結構。可將該moo形成於—幅板之釋放層上從 而可隨後將該W移除並將其附著至—物體之—表面。亦 可將該 '治片100形成於一巷辦直4c: 成$體基板上,該載體基板可爲-無 釋放層之幅板。 尤字边明覆蓋塗層形成於本發 此外,可 上,以改良对久性。例如,圖5虛線描緣一位於吸收心 上方之透明覆盍塗層114。該透明覆蓋塗層114可由任何』 生保護之適當透明材料構成,例如前述關於本發明之細 具體實施例之透明覆蓋塗声
Xs之材枓,且可具有與該等塗^ 相同之厚度範圍。 在先前參照之同在Φ社士 Μ $ H > 在甲明中的專利案序號第09/844,261號 中揭示了額外笛片复體眚始办丨 ” 貫施例,如此處所述,其可經修改 以在一磁性層與一>5勒思·> μ a 反射層之間包括絕緣層。其它具體實施 例(例如具有成對光學 J疋予了變結構之各種光學物品),可使用本 發明之磁性顏料薄Μ I 2 导月”泊片。在申請案序號第〇9/844,261 遗中揭不該等光學物σ 1. . 一 物0口。在申凊案序號第09/844,261號中亦 揭示磁性顏料與箱片之各種應用。 提供以下實例以說明本發明,且無意於限制本發明之範 圍0 H ^ 1 藉由將薄膜層沈積於一幅板上,從而製造具有相同j MgF^Cr但具有不同厚度之絕緣層之光亮色移顏料薄>
O\90\9O3l9.DOC •31 · 1333085 不同樣w。將該薄膜層剥離以産生尺寸減少至約2〇奈米(單 個薄片之平均尺寸)之薄片。 第一樣本顏料薄片具有—Cr/MgF2/Al/MgF2/Ci^習知五 層設計。第二樣本顏料薄片爲磁性且具有一 CiVMglVAl/Ni/Al/MgFVCr之七層設計。第三樣本顏料薄片 . 爲磁性且具有一 Cr/MgF2/Al/MgF2/Ni/MgF2/Al/MgF2/Cr 之 · 九層設計。位於A1層與Ni層之間之MgFz絕緣層之厚度爲16 奈米。第四樣本顏料薄片與該第三樣本具有相同之九層塗 層設計,除了位於A1層與Ni層之間之MgF2絕緣層之厚度爲籲 23奈来。第五樣本顏料薄片與該第三樣本具有相同之九層 塗層設計,除了位於A1層與Ni層之間之MgFz絕緣層之厚度 爲25奈米。第六樣本顏料薄片爲磁性且具有一 Cr/MgF2/Al/Al203/Ni/Al203/Al/MgF2/Cr之九層設計。位於 A1層與Ni層之間之a12〇3絕緣層之厚度爲20奈米。 實例2 將塗料媒劑與實例1之樣本之基本顏料以9 : 1之比例混合 翁_ 以製造塗料樣本。用刀片將該等塗料樣本分散於聚酯片 上。將乾燥的1"χ3π之經塗敷聚酯塊浸入2wt-%之NaOH水溶 ‘ 液中1 0分鐘。於浸泡測試前後量測每一樣本之顏色。使用 ' 色差AE比較受測試樣本。L*a*b*顏色空間中之色差表示 顏色差異程度而不是方向,並用以下公式來界定。 AE = [(AL*)2 + (Aa*)2 + (Ab*)2]1/2 其中AL*、Aa*、Ab*相應爲L*、a*與b*值之差值。一大ΔΕ 表明顏料薄片中之薄膜層之降級造成一大色差。於此實例 O:\M\90319DOC -32- 1333085 中,該ΔΕ爲曝露於NaOH中所造成之顏色變化。表1列出所 有受測試塗料樣本之色差。 表1
NaOH後之ΔΕ 34.20 54.77 59.93 39.32 31.34 34.00 樣本顏料設計 1 無異金屬之5層堆疊 2 無絕緣層之7層堆疊 3 具有16奈米厚MgF2絕緣層之9層堆疊 4 具有23奈米厚MgF2絕緣層之9層堆疊 5 具有25奈米厚MgF2絕緣層之9層堆疊 6 有20奈米厚Al2〇3絕緣層之9層堆疊 如表1中所顯示,於NaOH浸泡後樣本2與3較之於具有較 厚絕緣層之樣本4-6具有一大得多的AE。樣本4-6顯示出與 不具有異金屬之樣本1相似之色差。 可以其它具體形式來實施本發明,而不脫離其精神或基 本特性。應將所有態樣中之所述具體實施例都視爲僅具說 明性而非限制性。因此,本發明之範圍由隨附申請專利範 圍而非由前述說明來表明。於申請專利範圍之等價物之範 圍與意義内之所有改變均包含在其範圍之内。 【圖式簡單說明】 爲了說明本發明之以上及其它特徵,藉由參照隨附圖示 中所圖解之其特定實施例更具體說明本發明。應瞭解此等 圖示僅描繪本發明之一般實施例,且因此不可將其視爲對 其範圍之限制。藉由使用隨附圖式可額外詳細具體地說明 並解釋本發明,其中: 圖1爲根據本發明一具體實施例之磁性顏料薄片之塗層 結構之示意圖; O:\90\9O3 J9E>OC -JJ - 圖爲根據本發明另一具體實施例之磁性顏料 層結構之示意圖; 塗 圖3爲根據本發明又一具體實施例之磁性顏料 層結構之示意圖; 塗 圖4爲根據本發明之替代具體實施例之磁性顏料薄片之 塗層結構之示意圖;以及 圖5爲根據本發明之磁性箔片之塗層結構之示意圖。 【圖式代表符號說明】 20 反射性磁性薄片 22 , 64 , 104 磁性層 25 , 26 , 63 , 106 絕緣層 27 , 28 , 62 , 108 反射層 29 鄰接反射層 40 磁性色移顏料薄片 42 RMF 44 , 46 , 84 , 84a , 84b , 110 介電層 48 , 50 , 86 , 112 吸收層 52 , 54 , 90 , 114 透明覆蓋塗層 60,80 薄片 82 RMF 或 RME 100 箔片 102 基板 0\90\90319 00C -34·
Claims (1)
1333085 第092137303號專利申請案 中文申請專利範圍替換本(99年5月) 拾、申請專利範圍: 1. 一種磁性顏料薄片,其包括: 一中心磁性層,其具有一第一主要表面 二主要表面以及至少一個側表面; 一第一絕緣層,其位於該磁性層之該第 方; ^ 相對之第 主要表面上 第二絕緣層’其位於該磁性層 方; 之該第二主要表面上 一第一反射層,其位於該第一絕緣層上方·以及 一第二反射層,其位於該第二絕緣層上方; 度 其中該等絕緣層具有可防止該顏料薄片發生腐餘之月 〇 2. 如申請專利範圍第!項之顏料薄片,其中該顏料薄片顯^ -對應於該等反射層之反射率之反射率,並顯示基射 磁性層之相關磁性之磁性特性。 3. 如申請專利範圍^項之顏料薄片,其中該第一盘第二^ 緣層位於各個該第一與第二主要表面上方,但不位於^ 磁性層之該至少一個側表面上。 4. 如申請專利範圍第i項之顏料薄片,其中該第一與第二万 射層形成一鄰接反射層之部分,該鄰接反射層係環 磁性層與該等絕緣層。 5. 如申請專利範圍第丨項之顔料薄片’其中該磁性層包括卓 磁性材料。 6. 如申請專利範圍第i項之顏料薄片,其中該磁性層包括夫 90319-990526.doc 1333085
頑磁力低於約2000 Oe之材料。 7. 如申請專利範圍第1項之顏料薄片,其中該磁性層包括矯 • 頑磁力低於約300 Oe之材料。 8. 如申請專利範圍第1項之顏料薄片,其中該磁性層包括選 自由下列物質組成之群之材料:鐵、鎳、鈷、鐵、釓、 铽、鏑、餌及其合金或氧化物。 9_如申請專利範圍第丨項之顏料薄片,其中該磁性層包括選 自由下列物質組成之群之材料:Fe/Si、Fe/Ni、Fe/Co、 # Fe/Ni/Mo及其組合物。 如申請專利範圍第i項之顏料薄片,其中該磁性層包括硬 磁性材料。 η.如申請專利範圍第!項之顏料薄片,其中該磁性層包括選 自由下列物質組成之群之材料:SmCG5、麗。5、We。】7、 Nc^FewB、TbFe2及其組合物。 12. 如申請專利範圍第i項之顏料薄片,其中該磁性層包括選 自由下㈣質組成之群之材才斗:%〇4、驗2〇4、 MnFe2〇4、CoFe2〇4、YlG、Gdm及其組合物。 13. 如申請專利範圍第1項之顏料薄片’其中該磁性層具有-約20奈米至約3000奈米之物理厚户。 二請專利範圍第1項之顏料薄片%中該等絕緣層包括 介電材料。 ’其中該等絕緣層包括 一種材料:氧化鋁、氟 15.如申請專利範圍第丨項之顏料薄片 選自由下列物質組成之群之至少 化鎂、氧化錄及其組合物。 90319-990526.doc 16_如申請專利範圍第丨 -至少崎米之物理二^片,其中該等絕緣層具有 絡、錶及其組合物 鈮 17·^Γ利範圍第1項之顏料薄片,其中該等反射層包括 “由以下物質組成之群之反射材料:紹、銀銅、金、 鉑、錫、鈦、鈀、鎳、鈷、铑 或合金。 18. 如申請專利範圍第1項之顏料薄片,其中 —約20奈米至約1000奈米之物理厚度。 該等反射層具有 19. —種磁性著色劑組合物,其包括: 一顏料介質;及 散佈於該顏料介質内之複數個顏料薄片,該等顏料薄 片具有-多層結構,其係與申請專利範圍第】項所界定之 該顏料薄片相同。 2〇.如申請專利範圍第19項之著色劑組合物,其中該顏料介 質包括選自由以下物質所組成之群之材料:丙烯酸三聚 氰胺、聚氨酯樹脂、聚酯、乙烯樹脂、丙烯酸酯、甲基 丙烤酸甲醋、ABS樹脂、環氧樹脂、笨乙烯樹脂、基於^ 酸樹脂之墨水與塗料調配物及其混合物。 21. —種磁性顏料薄片,其包括: 一中心磁性層; 一絕緣層,其環繞該磁性層;及 一反射層,其環繞該絕緣層; 其中該絕緣層具有可防止該顏料薄片發生腐钱之厚 度0 90319-990526.doc 之顏料薄片,其中該絕緣層包括 22·如申請專利範圍第21項 介電材料。 23.如申請專利範圍第21 選自由下㈣…片,其中該絕緣層包括 ^ 材枓.氧化鋁、氟化鎂、氧 化鎳及其組合物。 、礼 其中該等絕緣層具 24·如申請專利範圍第21項之顏料薄片, 有一約20奈来至40奈米之物理厚度。 25. —種磁性著色劑組合物,其包括: 一顏料介質;及 散佈於該顏料介質 片具有一多層結構, 之該顏料薄片相同。 内之複數個顏料薄片,該等顏料薄 其係與申請專利範圍第21項所界定 26. —種磁性色移顏料薄片,其包括: 主要表面及一相對之第 一中心磁性層,其具有—第 二主要表面; 一第一絕緣層 方; 其位於該磁性層之該第一主要表面上 -第二絕緣層,其位於該磁性層之該第二主要表面上 一第一反射層,其位於該第一絕緣層上方,· 一第二反射層,其位於該第二絕緣層上方; 一第一介電層,其位於該第一反射層上方; 一第二介電層,其位於該第二反射層上方; 第一吸收層,其位於該第一介電層上方,·及 903I9-990526.doc •4- 1333085 一第二吸收層,其位於該第二介電層上方; 其中該顏料薄片顯示—離耑 , 入射#… 離散色移’使得該顏料薄片於 入射光或檢視之一第一角度處 .a 啕第—顏色,且於入 射光或檢視之一第二角度處 嚷一沾沐 匀 〃、5亥苐—顏色不同之 第一顏色,且該等絕緣層具有 蝕之厚度。 有了防止该顏料薄片發生腐 27.如申請專利範圍第26項 括介電材料。 糾厚片’其中該等絕緣層包 28·=:利範圍第26項之顔料薄片,其中該等絕緣層包 括=由下列物質組成之群之至少一種材料:氧化紹, iL化鎂、氧化錄及其組合物。 2 9.如申請專利範圍第2 6項之纟ρ μ _ 七 士 ㈣W ’其t料絕緣層具 有一約20奈米至約40奈米之物理厚度。 30.如申請專利範圍第26項 願杆/專片,其中該第一盘該第 二介電層包括具有一約爲165咬 次更低之折射率之介電材 料。 其中該介電材料i| 氧化鋁、氟化鎂、 氟化彭、氟化鎖、 其中該第一與第二 31·如申請專利範圍第3〇項之顏料薄片 自由以下物質組成之群:二氧化石夕 氣化鋁、氟化鈽、氟化鑭、敦化鈦 敗化詞、氟化鐘及其組合物。 32. 如申請專利範圍第26項之顏料薄片 介電層包括具有一大於約1:65之折射率之介電材料' 33. 如申請專利範圍第32項之顔料薄片,其中該介電材料 自由以下物質組成之群:硫化鋅、氧化辞、氧化锆、 90319-990526.doc 34. 35. 36. 37. 38. 39. 40. 月/日修正替换i| 氧化鈦、錢石類碳、氧化銦、氧化銦錫、五氧化二组、 氧化鈽、氧化釔、氧化銪、鐵氧化物、氮化姶、碳化铪、 氧化給、氧化鋼、氧化鎂、氧化鉞、氧化镨、氧化彭、 三氧化二銻、一氧化矽、三氧化二硒、氧化錫、三氧化 鶴及其組合物。 如申請專利範圍第26項之顏料薄片,其中該第—與第二 介電層具有相同之光學厚度。 如申請專利範圍第26項之顏料薄片,其中該第一與第二 介電層係由相同材料所構成。 如申請專利範圍第26項之顏料薄片,其中該第—盘第二 介電層包括-具有高折射率材料與低折射率材料 個交替層之介電光學堆疊。 如申請專利範圍第26項之顏料薄片,其中該第一與 吸收層包括均勻吸收電磁光譜之可見光部分之材料、。〜 如申請專利範圍第26項之顏料薄片,其中該第—與第一 吸收層包括非均勻吸收該電磁光譜之該可見光 ; 料。 之枒 如申請專利範圍第26項之顏料薄片,其中該第一與第— 吸收層包括選自由下列物質組成之群之吸收材料:路了 鎳、鋁、銀、銅、鈀、鉑、鈦 '釩、鈷、鐵、錫、鵝、 顧、錢、铌、碳、石墨、石夕、鍺及其化合物 二 合金。 物或 如申請專利範圍第26項之顏料薄片,其中該第一與 吸收層包括選自自下列物質組成之群之吸收材料: 第二 金屬 90319-990526.doc 1333085
氧化物、金屬硫化物、金屬碳化物及其組合物。 41. 42. 43. 44. 45. 46. 47. 如申請專利範圍第26項之顏料薄片,其中該第一與第二 吸收層具有一約3奈米至約50奈米之物理厚度。八 如申請專利範圍第26項之顏料薄片,其中該第一與第二 吸收層具有相同之物理厚度。 如申請專利範圍第26項之顏料薄片’其中該第一與第 吸收層係由相同材料所構成。 如申請專利範圍第26項之顏料薄片,其中該第一與第 反射層形成一鄰接反射層之部分,兮翻拉一 I刀該鄰接反射層環繞該 磁性層與該等絕緣層,該等第—與第二介電層形成—鄰 接介電層之部分’該鄰接介電層環繞該鄰接反射層,且 該等第一與第二吸收層形成一鄰 曰 州接及收層之部分,該鄰 接吸收層環繞該鄰接介電層。 如申請專利範圍第26項之顏料镇 领针溥片,其中該第一與第二 介電層形成一鄰接介電層之部分 、 刀該鄰接介電層環繞該 等反射層、該等絕緣層與該磁 %丨王層,且第一與第二吸收 層形成一鄰接吸收層之部分,兮 該鄰接吸收層環繞該鄰接 介電層。 如申請專利_第26項之顏料薄片,#中該第-與第 吸收層形成一鄰接吸收層之冲 队增艾部分,該鄰接吸收層環繞 等介電層、該等反射層、今望姐 ^ Μ该等絕緣層與該磁性層。 如申請專利範圍第26項之顏料 竹溽片,其進一步包括: 第一透明覆蓋塗層,其位於 匕枯 '这第一吸收層上方;以及 第二透明覆蓋塗層,其位於 久 々、碎第二吸收層上方。 90319-990526.doc 1333085 ;T\ ; 48. 如申請專利範圍第44項之顏料薄片 繞該吸收層之透明覆蓋塗層。 49. 如申請專利範圍第45項之顏料薄片 繞該吸收層之透明覆蓋塗層。 50.如申請專利範圍第46項之顏料薄片 繞該吸收層之透明覆蓋塗層。 51· —種磁性色移顏料組合物,其包括複數個色移顔料薄
片’該等顏料薄片具有一多層結構,其係與申請專利範 圍第26項所界定之該顏料薄片相同。 52. —種磁性色移著色劑組合物,其包括: 一顏料介質;以及 散佈於該顏料介質内之複數個色移顏料薄片,該等顏 料薄片具有一多層結構,其係與申請專利範圍第26項所 界定之該顏料薄片相同。 53. —種色移磁性顏料薄片,其包括:
其進一步包括一環 其進一步包括一環 其進一步包括一環 一中心磁性層; 一絕緣層’其環繞該磁性層; 一反射層,其環繞該絕緣層; 一介電層,其環繞該反射層;及 一吸收層’其環繞該介電層; 其中該絕緣層具有可防止該顏料薄片發生腐蝕之厚 度。 54.如申請專利範圍第53項之顏料薄月,其進一步包括一環 繞該吸收層之透明覆蓋塗層。 90319-990526.doc r ···** »·· · - ·— - I . · . 0 干乂 :A 移顏㈣合物,其包括複數個色移 片,該等顏料薄片具有一多 J 圍第如所W顏料薄片相同/H月專利範 56.種磁性色移著色劑組合物,其包括: 一顏料介質;以及 散佈於該顏料介暂+ > a μ 7m A 貝中之複數個色移顏料薄片,該等M 料薄片具有—吝恳έ士找 ^ 寻顯 層、.°構,其係與_請專利範圍第53項所 界定之該顏色薄片相同。 、 57· —種磁性顏料薄片,其包括: 中。磁性層,其具有一第一主要表面及一相對之第 二主要表面; 第一絕緣層,其包含一位於該磁性層之該第—主要 表面上方之氧化膜; 第一絕緣層,其包含一位於該磁性層之該第二主要 表面上方之氧化膜; 一第一反射層,其包含位於該第一絕緣層上方之鋁; 一第二反射層,其包含位於該第二絕緣層上方之鋁; 一第一介電層,其位於該第一反射層上方; 一第二介電層,其位於該第二反射層上方; 一第一吸收層,其位於該第一介電層上方;及 一第二吸收層,其位於該第二介電層上方; 其中該顏料薄片顯示了一離散色移,使得該顏料薄片 於入射光或檢視之一第一角度處具有一第一顏色,且於 入射光或檢視之一第二角度具有一與該第一顏色不同之 90319-990526.doc -9- 1333085 第二顏色。 ‘ -—一—J :58.如申請專利範圍第57項之顏料薄片,其中該第一與第二 絕緣層包括氧化銘。 .59·如申請專利範圍第57項之顏料薄片,其中該第一與第二 絕緣層包括該磁性層之氧化物。 •队如申請專利範圍第57項之顏料薄片,其中該第一絕緣層 包括氧化紹,且該第二絕緣層包括該磁性層之氧化物。 61_ —種色移干涉結構,其包括: 鲁 一磁性層; 一位於該磁性層上方之絕緣層; 一位於該絕緣層上方之反射層; 一位於該反射層上方之介電層;及 一位於該介電層上方之吸收層; 其中該干涉結構顯示-離散色移,使得該干涉結構於 入射光或檢視之-第-角度處具有—第—顏色,且於入 射光或檢視之一第二角声虔目女 . ^ 乐月度處具有一與該第一顏色不同之 第二顏色,且該絕緣層具有可P 舟令τ防止该干涉結構發生腐蝕 之厚度。 62. 如中請專利範圍第61項之干涉結構,其中該干涉結構爲 一箔片。 63. 如申請專利範圍第62項之干涉結構,其進一步包括一位 於該吸收層上方之透明覆蓋塗層。 64. 如申請專利範圍第62項之干涉結構,其進一步包括—用 於支撐該箔片之基板載體β 90319-990526.doc 10· 1333085 f-P.X 其中該干涉結構爲 65.如申請專利範圍第61項之干涉結構, 一不對稱顏料薄片。 90319-990526.doc -11 -
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2003
- 2003-02-13 US US10/366,638 patent/US7169472B2/en not_active Expired - Lifetime
- 2003-12-19 CN CN2003801097061A patent/CN1748006B/zh not_active Expired - Lifetime
- 2003-12-19 EP EP03778704.1A patent/EP1594926B1/en not_active Expired - Lifetime
- 2003-12-19 EP EP11161479.8A patent/EP2351797B2/en not_active Expired - Lifetime
- 2003-12-19 BR BRPI0318086A patent/BRPI0318086B1/pt not_active IP Right Cessation
- 2003-12-19 CA CA2515587A patent/CA2515587C/en not_active Expired - Lifetime
- 2003-12-19 RU RU2005128514/15A patent/RU2333230C2/ru active
- 2003-12-19 WO PCT/IB2003/006263 patent/WO2004072186A1/en not_active Application Discontinuation
- 2003-12-19 PL PL378361A patent/PL212104B1/pl unknown
- 2003-12-19 AU AU2003285720A patent/AU2003285720A1/en not_active Abandoned
- 2003-12-29 TW TW092137303A patent/TWI333085B/zh not_active IP Right Cessation
-
2006
- 2006-12-13 US US11/610,256 patent/US7285336B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
TW200417759A (en) | 2004-09-16 |
US20070098989A1 (en) | 2007-05-03 |
CA2515587A1 (en) | 2004-08-26 |
AU2003285720A1 (en) | 2004-09-06 |
PL212104B1 (pl) | 2012-08-31 |
BR0318086A (pt) | 2005-12-20 |
PL378361A1 (pl) | 2006-03-20 |
EP2351797B2 (en) | 2021-02-24 |
RU2005128514A (ru) | 2006-01-27 |
EP2351797B1 (en) | 2018-05-02 |
US20040166308A1 (en) | 2004-08-26 |
EP1594926A1 (en) | 2005-11-16 |
CN1748006B (zh) | 2010-05-26 |
CN1748006A (zh) | 2006-03-15 |
CA2515587C (en) | 2011-12-13 |
RU2333230C2 (ru) | 2008-09-10 |
BRPI0318086B1 (pt) | 2017-03-28 |
WO2004072186A1 (en) | 2004-08-26 |
US7285336B2 (en) | 2007-10-23 |
US7169472B2 (en) | 2007-01-30 |
EP1594926B1 (en) | 2019-02-20 |
EP2351797A1 (en) | 2011-08-03 |
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TWI333085B (en) | Robust multilayer magnetic pigments and foils | |
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US6572784B1 (en) | Luminescent pigments and foils with color-shifting properties | |
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