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TWI316465B - Transparent film wtih uv-shielding and water/oil repellent functions - Google Patents

Transparent film wtih uv-shielding and water/oil repellent functions Download PDF

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Publication number
TWI316465B
TWI316465B TW094143661A TW94143661A TWI316465B TW I316465 B TWI316465 B TW I316465B TW 094143661 A TW094143661 A TW 094143661A TW 94143661 A TW94143661 A TW 94143661A TW I316465 B TWI316465 B TW I316465B
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Taiwan
Prior art keywords
hydrophobic
powder
zinc oxide
ultraviolet light
oil
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TW094143661A
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TW200722286A (en
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Shih Chieh Liao
Chien Te Hsieh
Jin Ming Chen
Jung Jung Kuo
Chia Hao Chang
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Ind Tech Res Inst
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Priority to TW094143661A priority Critical patent/TWI316465B/zh
Priority to US11/444,411 priority patent/US8119230B2/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04Compounds of zinc
    • C09C1/043Zinc oxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/45Aggregated particles or particles with an intergrown morphology
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • Y10T428/2993Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

1316465 九、發明說明: . 【發明所屬之技術領域】 本發明㈣於_種賴結構,制是—種利用具碳氣 私(CHX)或社二射能基之高分子對奈米氧化辞 =體表面改質,形成蔽料光及疏水/油魏之透明鍍膜結 構。 【先前技術】 # 自然界許多植物葉面上因具有獨特微結構及表面化性而展 露其超疏雜,超疏水性表_特徵為水在其上會形成近似球狀 •液滴,例如自然界中的蓮花葉,當水滴在葉面上形成並滾動,可 同時將灰塵帶走’使葉面能保持清潔亮麗,而具有自潔 (self cleaning)功⑨。造成荷葉表面的自潔現象係為蓮花葉的低 表面張力及表面粗糙度。 曰當液體滴在固體表面上時,固體表面和液滴切線的夾角,即 鲁是所謂的接觸角Θ。當氣—固的界面張力(亦即固體表面能)越 大’接觸角就會越小’此時表示固體表面較易被濕潤;當接觸角 為〇度時’表示液體形成水膜而能完全的濕潤固體表面。相反地, 當氣—固的界面張力越低,接觸角就會越大,代表固體表面越不 易被濕潤’·當接觸角為⑽度時,代表紐形成球狀液滴而完全 不能濕潤於固體表面。 另外’當固體具有粗糙表面時,也會使液體在表面上的接觸 角變大。表雜Μ度對沾雛的效應為尺寸低凹的表面可使吸附 6 1316465 氣體原子穩定存在,在宏觀表面上相當於有一層穩定的氣體薄 膜,使液體無法與固體的表面直接接觸,即液體與固體的接觸表 面包含有固體及氣體的混合界面。 現今已有許多製作具有疏水性的塗料或是具有疏水性的表 面的方法,例如美國專利第5,693,236號係提供一種製作具有疏水 ! 生表面之方法,其步驟係包含有:首先,製備針狀材料與可固形 化液體之混合物,將此混合物塗覆在物體表面並固型化液體,接 著形成含有針狀材料及以固型化液體基材之塗層。當基材被侧 速率大於針狀材料被飿刻速率的情況下,藉侧層而在表面形成 針狀材料之凹處與凸出物,最後將此層表面鑛上疏水物質。 一般將具有疏水性塗料塗佈於_表面後,雖可具有防水的 I*生質’但是灰塵沾上m縣面後,液體不能有效率的在固體表面 上滾動來清除灰塵,因此無法有效達到自潔魏。再者,以疏水 i生磁恤蝴賴人體及有 的於Π提供—種絲面能、具有她麵賴、鑛紫外線 的疏水性塗層’其可克服習知技術之缺失。 【發明内容】 使用具本:=:賴,疏水,油功能之透明鍵膜,係 —奈; 狀的粗财卿,__晴歧編幢的^ 1316465 . 鍍膜。 ’ 本發明揭露之第一種具遮蔽紫外光及疏水/油功能之透明鑛 膜’包含有:奈米氧化鋅粉體及由高分子(例如含有碳氟官能基 (CFX)、碳氫官能基(CHx)或以上二種官能基之聚合物)對氧 化辞粉體表面改質而形成的高分子鍍層。 另外,本發明更揭露之第二種具遮蔽紫外光及疏水/油功能之 透明鍍膜’包含有:奈米氧化鋅粉體、透光阻絕層及高分子鍍層。 _ 透光阻絕層係以透光阻絕材(例如二氧化石夕(Si〇2))鑛於奈米氧 化鋅粉體表面而形成,再以高分子(例如含有碳氣官能基(%)、 兔虱目月b基(CHX)或以上二種官能基之聚合物)對透光阻絕層 表面改質,並於透光阻絕層之上形成高分子鍍層。 以下在實加方式中詳細敘述本發明之詳細特徵以及優點,其 内容足以使任何熟習侧技藝者了解本發明之技術内容並據以實 施,且根據本說明書所揭露之内容、申請專利範圍及圖式,任何 鲁熟習相關技藝者可輕易地理解本發明相關之目的及優點。 【實施方式】 " 依據本發明提供的透明鑛膜結構,係利用四足錐狀 (T_〇c〇或棒狀(rod)的奈米氧化鋅粉體1〇來達到吸收及遮 蔽紫外光效果,再透過含有碳氟官能基(%)、碳氫官罐CHx) 或以上二種官能基之高分子對奈米氧化辞粉體ι〇表面進行改 質,以形成具有微細纖毛狀的粗糖表面結構,而且具有遮蔽紫外 光及疏水/油的功能的透明鍍膜結構。 (8) 8 1316465 再者’四足錐狀或棒狀的奈米氧化辞粉體1G的製造方式, 及含有氮氣之氣氛控制下,以非消耗電極式直流電 f (灿繼咖)使之g,復以大 量3氧及氮猶樹t的麵__㈣核 ^制Γ和口之大小时式,形成高速的魏概,再以大 二二Γ 來防止粒子粗化及凝、賴聚’而生成具有纖維鋅礦 (HCPWu^te) (Tetrap〇d) (r〇d) ^ 辞粉體⑴’如中華民__職及2_186中所 -rrr 〇 ^外’於本發锻供的咖舰結射之四足錐㈤亭心 狀的不米氧化鋅粉體1G係由四域面呈六角 氧 化鋅粉體10所構成,參照「第 > 糾的不水乳 太丰备一 笫1A圖」所不,每-支棒狀(rod) 不。r分體1〇直徑大小為10nm至l〇〇nm之間,長度為5〇 nm至1〇〇〇 nm之間。參昭「 " 氧μ β 第 為棒狀(⑽的奈米 4 0中,每一支棒狀(r〇d)奈米氧化辞粉體⑴直徑大 :至100細之間,長度為50⑽至1〇00 nm之間。 著’依據本發明提供的具韻料紐疏水/油功能的 透明鍍臈結構,將藉由以 詳細說明如下實例配合所附圖式,予以 請參閱「第2圖」係為依據本發明提供 且 構。此透_結構魅含有:可吸收及遮 。先’且具有、纖維鋅礦(HCPWumite)結構的四足錐狀 1316465 (Tetmpod)或棒狀(r〇d)的奈米氧化鋅粉體1〇,及以高分子(例 如碳氟官能基(CFx)、碳氫官能基(CHx)或以上二種官能基之 聚合物)對奈米氧化鋅粉體表面改質而形成的高分子鍍層20。 此透月構係為遮蔽紫外光及疏水/油的功能的粗輪表面結 構。 第3圖」係為依據本發明提供之第二具體實施例的 透·_構。此透明顏結構包含有奈米氧化鋅粉體1〇、透 •光阻絕層15及高分子鑛層20。奈米氧化鋅粉體10係以金屬鋅為 原料,且藉由直流電聚技術生成具有纖維鋅礦(HCPWurztite)結 構的四足錐狀(Tetrapod)或棒狀(r〇d)的奈米氧化鋅粉體ι〇。 接著’為了避免細媒效應,在奈米氧化鋅輔丨上 光阻絕材(例如二氧⑽(Si()2))形成透光阻絕層2g,其厚度約 為1 nm至20 nm之間,而形成Zn〇-Si〇2核殼(core-shell)結構 奈米粉體。 • 接下來以氨基對透光阻絕層15表面改質,亦是對Zn0-Si02 核殼(_·_)結構粉體表面改質,改變Zn〇_si〇2核殼 (_金11)結触子的表面,卿是為了進—步增加高分 子對ZnO-Si〇2核殼(core_shell)結構粉體的相容性。 但是’此氨絲面改質轉—定f要,岐以_的高分子 性質來決定是否需以氨基作表面改質。 最後再以具石反氟官能基(CFx)、碳氨官能基(⑶ο或 以上二種官能基之高分子對經氨基改質的透光阻絕層Μ之表面 1316465 進行表面改質而形成高分子鍍層20。 «月參閱「第4圖」係經由場發射電子顯微鏡所拍攝之微觀相 片,係在絲氧轉㈣1G之上鍍上二氧切(⑽2)而形成的 znas1〇2核殼(core_shell)結構奈米粒子此結構的_殼厚度 約為5 nm。 ,經由前述得知,本發明之透明鍵臈結構係利用具碳敦官能基 • (CF士碳氫官能基(CHx)細上二種官能基的高分子對奈米 #氧化鋅粉體K)表面改質;或以具碳氣官能基(cFx)、碳氣官能 基(CHX) _上二種官能基的高分子對表面財透光阻絕層η 的奈米氧化鋅粉體10表面改質,來形具遮蔽紫外光及疏水/油功 能之透明鍍膜結構。 另外’右以不同形狀的奈米氧化鋅粉體分別塗佈於木材基板 上,再以具碳氟官能基(CFx)、碳氫官能基(CHx)或以上二種 官能基的高分子塗佈於粉齡面,職咖顧,_量測此透 馨明鍍膜之靜態接觸角。結果顯示四足錐狀的奈米氧化辞粉體ι〇比 棒狀及球狀的奈米氧化鋅粉體有較佳的疏水/油功能。此外,本發 明提供之透明鍍膜結構係可運用於玻璃、木材、究碑及汽車烤漆 等等。 雖然本發明以前述之實施例揭露如上,然其並非用以限定本 發明。在不脫離本發明之精神和範圍内,所為之更動與潤飾 屬本發明之專利保護範圍。關於本發明所界定之保護範 所附之申請專利範圍。 > ⑧ 11 1316465 【圖式簡單說明】 第^圖係為四足錐形狀之奈米氧化辞 片, 聪的電子顯微鏡照 奈錄化鋅粉體的電子顯微鏡照片; 第2圖係依據本發明之透明鑛膜結構之第—具體實施 例; 第3圖係依據本發明之透明鍍膜結構之第 例;及 第4圖係依據本發明之奈米Zn〇_Si〇2核殼結構粒子的電子 顯微鏡照片。 【主要元件符號說明】 二具體實施 10 15 20 奈米氧化鋅粉體 透光阻絕層 高分子鍵層 ⑧ 12

Claims (1)

1316465 公告本 一‘ 一 十、申請專利範圍: 1. 種'、遮蔽紫外光及疏水/油功能之透明鍍膜結構,包含有: 一氧化鋅粉體;及 η77子鍍層L S好對魏鱗粉齡面改質而 形成。 2.=申明專利範_丨項所述之具祕料光及疏水/油功能之 明鍍膜結構’其中該高分子為—含碳I官能基(叫之 合物。 ΑΚ 々Ta间刀子為一含碳氫官能基(CHX)之繁 合物。 來 範圍第1項所述之具遮蔽紫外光及疏水/油功能之 5如由^ 中該氧化鋅粉體為—奈米氧化鋅粉體。 透‘膜1 _述之具遮㈣外U疏水7油功能之 ^由二其巾職鱗_雜有纖轉礦結構。 透明^膜7圍第1項所述之具遮蔽紫外光及疏水/油功能之 之粉二、、力構’其中該氧化辞粉體為一四足錐狀(tetrap〇d) 項所述之具遮㈣外光及疏水/油功能之 體之脖A 足錐狀之氧化辞粉體之每一支棒狀晶 “、1〇nm至1〇〇邮之間,長度5〇nm至lOOOmn之 間0 ⑧ 13 1316465 略1 _叙具雜料絲财/油功能之 9如申心二其中該氛化辞粉體為一棒狀㈤)之粉體。 .::=ΓΓ項所述之具遮蔽紫外光及疏水/油功能之 透膜、、、°構,其中該棒狀之氧化鋅粉體之每-支棒狀晶體之 .種具遮蔽紫外光及疏水/油功能之透明鍍膜結構,包含有: 一氧化鋅粉體;及 形成=且絕層,由_透先阻絕材鍵於該氧化辞粉趙表面而 1分子顯,由-高分子觸透光阻絕層做表面 形成。 11·如申睛專利範圍第10項所述之具遮蔽紫外光及疏水/油功能之 透明鑛膜結構’更包含有—氨基,係_透光轉層做表面改 質。 Φ 12.如申請專利範圍第10項所述之具遮蔽紫外光及疏水/油功能之 透明鍍膜結構,其中該透光阻絕材為—二氧切(si02),而 开>成一 ZnO-Si〇2核殼(core-shell)結構奈米粉體。 13·如申請專利範圍第12項所述之具遮蔽紫外光及疏水/油功能之 透明鑛膜結構,其中該ZnO-Si〇2核殼結構奈米粉體之殼厚度 為lnm至20nm之間。 14.如申請專利範圍第1〇項所述之具遮蔽紫外光及疏水/油功能之 透明鍍膜結構,其中該高分子為一含碳氟官能基(Cpx)之聚 14 (8) 1316465 合物 申請專_第1G項所述之具遮蔽紫外光及疏水/油功能之 ^鑛膜結構’其中該高分子為—含錢官絲(CHx)之聚 16.t申請專利範圍第1〇項所述之具遮蔽紫外光及疏水/油功能之 17 構,其中該氧化鋅粉體為一奈米氧化辞粉體。 月專利範圍第16項所述之具遮蔽紫外光及疏水/油功能之 18如8申=結構,其中該氧化鋅粉體係具有纖維鋅礦結構。 專利範圍第10項所述之具遮蔽紫外光及疏水/油功能之 之::膜結構’其中該氧化鋅粉體為一四足錐狀(,⑷ 19.=請專利範圍第18項所述之具遮蔽紫外光及疏水/_ 膜結構’其中該叹錐狀之氧化鋅粉體之每—支棒狀晶 之徑為10nm至100nm之間,長度5〇咖至麵細之 間。 2〇. ^請專利範圍第1G項所述之具遮蔽紫外光及疏水/油功能之 21 ? C-d) ^ 〇 ^ 第2〇項所述之具遮蔽紫外光及疏水/油功能之 直^7構’其中該棒狀之氧化鋅粉體之每一支棒狀晶體之 直仏為10 nm至100 nm之間,長度5〇 nm至聰邮之間。 15
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