TWI412454B - 控制太陽光之多層膜 - Google Patents
控制太陽光之多層膜 Download PDFInfo
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- TWI412454B TWI412454B TW95100676A TW95100676A TWI412454B TW I412454 B TWI412454 B TW I412454B TW 95100676 A TW95100676 A TW 95100676A TW 95100676 A TW95100676 A TW 95100676A TW I412454 B TWI412454 B TW I412454B
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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Description
概言之,本發明係關於控制太陽光之多層膜。更特定言之,本發明係關於包括紅外吸收奈米顆粒之控制太陽光的多層膜。
經染色及真空塗佈之塑料膜已施用於窗戶上以降低由陽光引起之熱負荷。為降低熱負荷,需阻擋太陽光譜之可見或紅外部分(即,在介於400奈米至2500奈米或更高範圍內之波長處)的太陽光透射。
經染色膜主要藉助吸收來控制可見光透射並因此減少眩光。然而,經染色膜通常不能阻擋近紅外太陽能,且因此其作為控制太陽光的膜並不十分有效。經染色膜通常亦會因太陽光曝曬而褪色。另外,當用多種染料為膜著色時,該等染料經常會以不同速率褪色,導致在該膜壽命內不期望之顏色改變。
使用經真空沈積之灰色金屬(例如不銹鋼、英高鎳(inconel)、蒙乃爾(monel)、鉻或鎳鉻合金)可製作其他已知窗戶膜。該經沈積之灰色金屬膜可在太陽光譜之可見與紅外部分提供近似相同的透射程度。因而,該等灰色金屬膜在控制太陽光方面較經染色膜有所改良。當灰色金屬膜暴露於光、氧氣及/或濕氣時,其相對穩定,且在彼等其中塗層透光率因氧化而增加之情況下,一般不會檢測到顏色變化。在施用於透明玻璃後,灰色金屬可藉由約等量之太陽光反射與吸收來阻擋光透射。
經真空沈積之層(例如銀、鋁及銅)主要藉由反射控制太陽光輻射且由於高水平之可見光反射,其僅用於少數應用中。藉由某些反射材料(例如銅及銀)可獲得適度的選擇性(即,較紅外光透射率為高之可見光透射率)。
人們需要具有高可見光透射率且實質上阻擋紅外輻射之經改良的控制太陽光之膜。
概言之,本發明係關於控制太陽光之多層膜。更特定言之,本發明係關於包括紅外吸收奈米顆粒之控制太陽光之多層膜。
在一實施例中,揭示一多層膜物件。該多層膜物件包括一具有第一聚合物類型與第二聚合物類型交替層之紅外光反射多層膜,一包括複數個分散於一經固化聚合黏合劑中之金屬氧化物奈米顆粒且厚度介於1至20微米間之紅外光吸收奈米顆粒層。該奈米顆粒層係設置為毗鄰該多層膜。該金屬氧化物奈米顆粒包括氧化錫或經摻雜之氧化錫。
在再一實施例中,一用於阻擋來自紅外光源之紅外光的控制光物件包括一具有第一聚合物類型與第二聚合物類型交替層之紅外光反射多層膜,及一鄰近該多層膜之紅外光吸收奈米顆粒層。該紅外光吸收奈米顆粒層包括複數個分散於一經固化聚合黏合劑中之金屬氧化物奈米顆粒。該金屬氧化物包括氧化錫或經摻雜之氧化錫且該紅外光吸收奈米顆粒層具有介於1至20微米之間之厚度。該紅外光反射多層膜係設置於一紅外光源與該紅外光吸收奈米顆粒層之間。一玻璃基板設置為鄰近該紅外光吸收奈米顆粒層或紅外光反射多層膜。
在另一實施例中,一多層膜物件包括一具有第一聚合物類型與第二聚合物類型交替層之紅外光反射多層膜及一具有複數個分散於一經固化聚合黏合劑中之金屬氧化物奈米顆粒之紅外光吸收奈米顆粒層。該奈米顆粒層設置為鄰近該多層膜並具有介於1至20微米範圍內之厚度。該多層膜具有至少45%之平均可見光透射率,且對於780奈米至2500奈米的光,其具有低於15%之平均紅外光透射率。
本發明之該等及其他態樣可藉由下文詳細描述而更加明瞭。然而,在任何情況下均不應將以上概要內容解釋為對所申請標題物的限制,此標題物僅由隨附申請專利範圍來界定,且該等申請專利範圍可能會在執行過程中加以修改。
據信本發明控制太陽光之多層膜可應用於各種需要控制太陽光之應用中,此等應用包括(例如)建築及運輸應用。在某些實施例中,該控制太陽光之多層膜物件包括置於一紅外反射多層膜上之紅外吸收奈米顆粒層。在其他實施例中,該控制太陽光之多層膜物件包括置於紅外吸收奈米顆粒層與黏著層間之紅外反射多層膜。控制太陽光之膜可黏附於一光學基板(例如玻璃基板)上。該等實例及以下討論之實例提供所揭示控制太陽光之多層膜的適用性之理解,但其不應以限制意義來理解。
術語"聚合物"或"聚合"應理解為包括聚合物、共聚物(例如使用兩種或以上不同單體形成之聚合物)、寡聚物及其組合、以及聚合物、寡聚物或共聚物。除非另有說明,否則包括嵌段共聚物及無規共聚物二者。
除非另有說明,否則,本說明書及申請專利範圍中用於表示部件大小、數量及物理性質之所有數值在所有情況下皆應理解為由術語"大約"來修飾。因此,除非另有說明,否則,上述說明書及隨附申請專利範圍中所闡述之數值參數係近似值,該等近似值可端視彼等熟習此項技術者利用本文所揭示之教示試圖獲得之期望性質而改變。
重量百分比、wt%及諸如此類皆係指該物質重量除以組合物重量並乘以100的物質濃度之同義詞。
術語"鄰近"係指一元件非常接近另一元件且包括元件彼此相互接觸,且進一步包括元件由置於該等元件間的一或多層分開。
列舉由端點界定之數值範圍包括所有包含於該範圍內之數(例如1至5包括1、1.5、2、2.75、3、3.80、4及5)及該範圍內之任一範圍。
除非本文明確指出,否則本說明書及隨附申請專利範圍中所用單數形式"一"及"該"包括複數個對象。因此,舉例而言,當提及一包含"一奈米顆粒層"之組合物時,包括兩個或多個奈米顆粒層。除非本文明確指出,否則,本說明書及隨附申請專利範圍中所用術語"或"通常使用其包括"及/或"在內的意義。
一般而言,本揭示內容闡述包括一置於聚合多層膜上之紅外吸收奈米顆粒層之多層膜。在許多實施例中,一紅外光反射多層膜具有第一聚合物類型與第二聚合物類型之交替層,且紅外光吸收奈米顆粒層鄰近該多層膜。該奈米顆粒層包括複數個金屬氧化物奈米顆粒。在某些實施例中,該多層膜設置為鄰近一光學基板(例如玻璃基板)以形成一控制太陽光之物件。在某些實施例中,該多層膜具有至少45%之平均可見光透射率及對於780奈米至2500奈米光低於15%之平均紅外光透射率。
圖1A至1C、2及3皆係根據實例1至3所製備膜之光透射與反射光譜。
圖4繪示多層光學膜20。該膜包括單獨層22、24。該等層具有不同折射率特性以使某一光在相鄰層間之介面處反射。該等層應足夠薄以使在複數個界面處反射之光經受相長干涉或相消干涉,以使該膜獲得所期望之反射或透射性質。對於設計用來在紫外、可見或近紅外波長處反射光之光學膜而言,每一層通常具有一低於約1微米之光學厚度(即,一物理厚度乘以反射率)。然而,亦可包括較厚層,例如在該膜外表面處之表層或置於該膜內隔離許多層的保護性邊界層。
多層光學膜20之反射與透射性質係各個層(即子層)折射率之函數。每一層之特徵在於至少在該膜內局部位置上平面內折射率nx
、ny
及折射率nz
與膜之厚度軸相關。該等折射率表示當光分別沿相互正交的x-、y-及z-軸偏振時標題材料的折射率(參見圖4)。在實務中,該等折射率受謹慎的材料選擇及加工條件之限制。膜20可藉由以下方法製備:共擠出通常數十或數百層兩種交替聚合物A、B,隨後視情況使該多層擠出物穿過一或多個放大模具,且繼而拉伸或者使該擠出物取向以形成一最終膜。所得膜一般由數十或數百個單獨層組成,該等層之厚度及折射率經調整,以在所期望光譜區域(例如在可見、近紅外及/或紅外)內提供一或多個反射帶。為用適當數量的層達成高反射率,相鄰層對於沿x-軸偏振的光較佳展示至少為0.05的折射率差(△nx
)。在某些實施例中,若兩個正交偏振需要高折射率,則該等相鄰層對於沿y-軸偏振的光亦展示至少為0.05的折射率差(△ny
)。在其他實施例中,折射率差△ny
可小於0.05或0,以產生一通常反射一偏振態之入射光及通常透射一正交偏振態之入射光的多層疊層。
若需要,亦可調整相鄰層間沿z-軸偏振的光之折射率差(△nz
),以達成斜入射光p-偏振分量之期望反射率性質。為便於解釋,在一多層光學膜上任一感興趣的點處,皆認為x-軸在該膜平面內取向,以使△nx
之量值係最大值。因此,△ny
之量值可等於或小於(但不大於)△nx
之量值。而且,選擇以哪一材料層開始計算差△nx
、△ny
、△nz
係藉由要求△nx
為非負值來規定。換言之,形成一介面的兩層間之折射率差係△nj
=n1 j
-n2 j
,其中j=x、y或z且其中該層標號1、2係經選擇以使n1 x n2 x
,即,△nx 0。
為維持入射斜角處p-偏振光的高反射率,可控制各層間z-折射率失配△nz
實質上小於最大平面內折射率差△nx
,以使△nz 0.5*
△nx
。更佳地,△nz 0.25*
△nx
。零或接近零量值之z-折射率錯配可產生層間介面,該等介面之p-偏振光反射率係隨入射角改變之常數或接近常數。此外,可控制z-折射率錯配△nz
以與平面內折射率差△nx
相比具有相反之偏光性,即,△nz
<0。該條件可產生p-偏振光的反射率隨入射角增加而增加之介面,對於s-偏振光亦如此。
多層光學膜已闡述於(例如)美國專利第3,610,724號(Rogers);美國專利第3,711,176號(Alfrey、Jr.等人),"Highly Reflective Thermoplastic Optical Bodies For Infrared,Visible or Ultraviolet Light";美國專利第4,446,305號(Rogers等人);美國專利第4,540,623號(Im等人);美國專利第5,448,404號(Schrenk等人);美國專利第5,882,774號(Jonza等人)"Optical Film";美國專利第6,045,894號(Jonza等人)"Clear to Colored Security Film";美國專利第6,531,230號(Weber等人)"Color Shifting Film";PCT公開案WO 99/39224(Ouderkirk等人)"Infrared Interference Filter";以及美國專利公開案第2001/0022982 A1號(Neavin等人),"Apparatus For Making Multilayer Optical Films",所有該等皆以引用的方式併入本文中。在此等聚合多層光學膜中,聚合物材料主要或僅用於構成該等單個層。此等膜可與高體積製作方法相匹配,且其可製成大的薄片與捲材商品。
可藉由交替聚合物類型層之任何有用組合形成該多層膜。在許多實施例中,至少一個交替聚合物層係雙折射的且經取向。在某些實施例中,該交替聚合物層中之一係雙折射的且經取向而另一交替聚合物層係各向同性的。在一實施例中,該多層光學膜可藉由包括聚對苯二甲酸乙二醇酯(PET)或聚對苯二甲酸乙二醇酯之共聚物(coPET)在內的第一聚合物類型及包括聚(甲基丙烯酸甲酯)(PMMA)或聚(甲基丙烯酸甲酯)之共聚物(coPMMA)在內的第二聚合物類型之交替層來形成。在另一實施例中,該多層光學膜可藉由包括聚對苯二甲酸乙二醇酯之第一聚合物類型與包括聚(甲基丙烯酸甲酯及丙烯酸乙酯)之共聚物之第二聚合物類型之交替層來形成。在另一實施例中,該多層光學膜可藉由包括環己烷二甲醇(PETG)或環己烷二甲醇之共聚物(coPETG)之第一聚合物類型及包括聚萘二甲酸乙二醇酯(PEN)或聚萘二甲酸乙二醇基酯之共聚物(coPEN)之第二聚合物類型之交替層來形成。在另一實施例中,該多層光學膜可藉由包括聚萘二甲酸乙二醇酯或聚萘二甲酸乙二醇酯之共聚物之第一聚合物類型及包括聚(甲基丙烯酸甲酯)或聚(甲基丙烯酸甲酯)之共聚物之第二聚合物類型之交替層來形成。交替聚合物類型層之有用組合揭示於美國專利第6,352,761號中,該案以引用的方式併入本文中。
圖5示意性的繪示了一控制太陽光之多層膜物件100之實施例。膜100包括一具有上述第一聚合物類型與第二聚合物類型之交替層之紅外光反射多層膜110。一紅外光吸收奈米顆粒層120設置為毗鄰多層膜110。一壓敏層130置於多層膜110上。一離型層或光學基板140設置於壓敏黏著層130上。一可選硬塗層150係經設置毗鄰多層膜110。
在許多實施例中,膜100包括一具有上述第一聚合物類型及第二聚合物類型交替層之紅外光反射多層膜110,且紅外光吸收奈米顆粒層120係設置為毗鄰多層膜110。在該等實施例中,紅外光吸收奈米顆粒層120包括分散於一經固化聚合黏合劑中之金屬氧化物。在某些實施例中,此紅外光吸收奈米顆粒層120具有介於1至20微米、或介於1至10微米、或介於1至5微米範圍內之厚度。一壓敏層130設置於多層膜110上。一離型層或光學基板140置於壓敏黏著層130上。在該等實施例中,紅外光吸收奈米顆粒層120亦起硬塗層作用。
圖6示意性繪示一控制太陽光之多層膜物件200之另一實施例。膜200包括一具有上述第一聚合物類型與第二聚合物類型交替層之紅外光反射多層膜210。一紅外光吸收奈米顆粒層220設置為毗鄰多層膜210。一可選中間黏著層270設置於奈米顆粒層220與多層膜210之間。一壓敏層230置於多層膜210上。一離型層或光學基板240置於壓敏黏著層230上。一可選硬塗層250設置為毗鄰多層膜210。一可選中間聚合物層260設置於硬塗層250與中間黏著層270之間。
上述多層膜物件構造提供經改良的控制太陽光之膜物件。在某些實施例中,該多層膜具有至少45%之平均可見光透射率(400至780奈米),且對於780奈米至2500奈米光,其具有低於10%或低於15%之平均紅外光透射率。在某些實施例中,對於所有實質上介於950奈米與2500奈米間之波長而言,該多層膜具有至少60%之平均可見光透射率及20%或以下之紅外光透射率。在某些實施例中,在780至1200奈米之間,該多層膜物件具有50%或以上之平均光反射率,在1400至2500奈米之間,多層膜物件具有50%或以下之平均光透射率。在另一實施例中,該多層膜物件在780與1200奈米間具有80%或更高之平均光反射率且在1400與2500奈米間具有20%或更低之平均光透射率。在又一實施例中,該多層膜物件在780與1200奈米間具有90%或更高之平均光反射率且在1400與2500奈米之間具有5%或更低之平均光透射率。
上述奈米顆粒層可包括複數個金屬氧化物奈米顆粒。一部分列示之金屬氧化物奈米顆粒包括氧化錫、氧化銻、氧化銦及氧化鋅及經摻雜之氧化物。在某些實施例中,該等金屬氧化物奈米顆粒包括氧化錫、氧化銻、氧化銦、經銦摻雜之氧化錫、經銻摻雜之氧化銦錫、氧化銻錫、經銻摻雜之氧化錫或其混合物。在某些實施例中,該等金屬氧化物奈米顆粒包括氧化錫或經摻雜之氧化錫且視情況其進一步包括氧化銻及/或氧化銦。該等奈米顆粒可具任何有用尺寸,例如1至100、或30至100、或30至75奈米。在某些實施例中,該等金屬氧化物奈米顆粒包括分散於一聚合材料中之氧化銻錫或經摻雜之氧化銻錫。該聚合材料可係任何有用之黏合劑材料,例如聚烯烴、聚丙烯酸酯、聚酯、聚碳酸酯、含氟聚合物及諸如此類。
在許多實施例中,該黏合劑係一可起硬塗層作用之經固化聚合材料。可形成紅外光吸收奈米顆粒層之適宜聚合黏合劑包括丙烯酸酯及/或甲基丙烯酸酯單體之熱及/或UV聚合(即,固化)產物。一適宜經固化之黏合劑係以下之熱聚合及/或UV聚合產物:丙烯酸或甲基丙烯酸之經溴化且經烷基取代的苯基酯(例如丙烯酸4,6-二溴-2-第二-丁基苯基酯)、甲基苯乙烯單體、經溴化之環氧二丙烯酸酯、丙烯酸2-苯氧乙基酯及六官能基芳香族丙烯酸胺基甲酸酯寡聚物,如美國專利第6,355,754號中所述,該案以引用的方式併入本文中。儘管多種可能量聚合遠螯單體及寡聚物可用於形成該等聚合黏合劑,但因丙烯酸酯之高反應性,故其較佳。該可固化黏合劑組合物應具有可流動黏度,其應足夠低以使該組合物中不截獲氣泡。反應性稀釋劑可係單官能基或二官能基單體,例如SR-339、SR-256、SR-379、SR-395、SR-440、SR-506、CD-611、SR-212、SR-230、SR-238及SR-247(自Sartomer公司,Exton,PA購得)。典型有用的寡聚物及寡聚摻和物包括CN-120、CN-104、CN-115、CN-116、CN-117、CN-118、CN-119、CN-970A60、CN-972、CN-973A80、CN-975(自Sartomer公司,Exton,PA購得)及Ebecryl 1608、3200、3201、3302、3605、3700、3701、608、RDX-51027、220、9220、4827、4849、6602、6700-20T(自Surface Specialties,Smyrna,GA購得)。另外,一多官能基交聯劑可有助於獲得一持久高交聯密度之複合基質。多官能基單體之實例包括SR-295、SR-444、SR-351、SR-399、SR-355及SR-368(自Sartomer公司,Exton,PA購得)及PETA-K、PET1A及TMPTA-N(自Surface Specialties,Smyrna,GA獲得)。多官能基單體可用作交聯劑以提高自該可聚合組合物之聚合所獲得黏合劑聚合物之玻璃態轉變溫度。
在某些實施例中,用於形成聚合黏合劑之單體組合物可具低於約50℃之熔點。該單體組合物於室溫下可係一液體。用於形成聚合黏合劑之單體組合物可藉由習知自由基聚合方法聚合。起始劑之實例包括有機過氧化物、偶氮化合物、奎寧、硝基化合物、醯鹵類化合物、腙類化合物、巰基化合物類、正吡蝻離子化合物類、咪唑類、氯代三嗪類、安息香、安息香烷基醚類、二酮類、苯酮類及諸如此類。市售光起始劑包括(但不限於)彼等自Ciba Geigy購得者,商品名為DARACUR 1173、DAROCUR 4265、IRGACURE 651、IRGACURE 1800、IRGACURE 369、IRGACURE 1700及IRGACURE 907、IRGACURE 819。較佳者係氧化膦衍生物,例如LUCIRIN TPO,其係2,4,6-三甲基甲醯基二苯基氧化膦(自BASF,Charlotte,N.C.購得)。一光起始劑可以約0.1至10重量百分比或約0.1至5重量百分比之濃度使用。
該可聚合組合物可形成一硬樹脂或硬塗層。術語"硬樹脂"或"硬塗層"係指當根據ASTM D-882-91程序評價時,所得經固化聚合物展示低於50或40或30或20或10或5百分比之斷裂伸長率。在某些實施例中,當根據ASTM D-882-91程序評價時,該硬樹脂聚合物可展示大於100 kpsi(6.89×108
帕斯卡)之拉伸模量。在某些實施例中,當在泰伯磨耗試驗機(Taber abrader)中根據ASTM D 1044-99在500克負荷及經50次循環測試時,該硬樹脂聚合物可展示低於10%或低於5%之霧度值(霧度可使用Haze-Gard Plus(BYK-Gardner,MD)霧度計量測)。
在某些實施例中,該等金屬氧化物奈米顆粒包括分散於聚合物材料中之氧化銦錫或經摻雜之氧化銦錫。奈米顆粒層可具有任何有用厚度,例如自1至10或2至8微米。奈米顆粒層可包括任何有用裝載量或重量%,例如30至90重量%、40至80重量%、或50至80重量%。在若干實施例中,該奈米顆粒層係無傳導性。舉例而言,奈米顆粒組合物係以商品名稱TRB-PASTET M
SM6080(B)、SH7080、SL6060自(例如)Advanced Nano Products有限公司(South Korea)購得者。在另一實施例中,該等金屬氧化物奈米顆粒包括氧化鋅及/或氧化鋁,此等氧化物可自GfE Metalle und Materialien GmbH(Germany)購得。
上述壓敏黏合劑(PSA)層可係任一種使該控制太陽光之多層膜固定於玻璃上之黏合劑。為使該控制太陽光之膜附著於該玻璃,將該控制太陽光之膜之一個表面用壓敏黏合劑(PSA)塗佈,且自PSA移除離型片,然後將該膜施於玻璃。該PSA中可納入紫外吸收添加劑。在許多實施例中,該PSA係一諸如聚丙烯酸酯壓敏黏合劑等光學透明PSA膜。壓敏膠帶協會(Pressure-Sensitive Tape Council)將壓敏黏合劑定義為具有以下性質之材料:(1)強力且持久之黏著性,(2)僅用手指壓力即可黏合,(3)足以保持於黏附體上之能力,(4)足夠的黏接強度,及(5)無需藉由一能源活化。在通常為室溫或更高(即約20℃至約30℃或更高)之組裝溫度下,PSA通常係黏性的。已發現,很好地起PSA作用之材料係經設計及調配展示所需黏彈性之聚合物,該黏彈性在組裝溫度下可導致黏著性、剝離黏著力及剪切保持力之期望平衡。用於製備PSA之最常用聚合物係以天然橡膠-、合成橡膠-(例如苯乙烯/丁二烯共聚物(SBR)及苯乙烯/異戊二烯/苯乙烯(SIS)嵌段共聚物)、聚矽氧彈性體-、聚α-烯烴-及各種(甲基)丙烯酸酯-(例如,丙烯酸酯及甲基丙烯酸酯)為主之聚合物。在該等中,以(甲基)丙烯酸酯為主的聚合物PSA因其光學透明度、性質隨時間之持久性(老化穩定性)及多功能性黏著水平(僅列舉其少數優點),已逐漸成為用於本發明之一類較佳PSA。
上述離型襯墊可由任何有用材料(例如聚合物或紙)形成,且可包括一離型塗層。用於離型塗層之適宜材料包括(但不限於)經設計用以促使離型襯墊自黏合劑釋放之含氟聚合物、丙烯酸類及聚矽氧。
上述光學基板可由任何有用材料形成。在某些實施例中,該基板係由一諸如三乙酸纖維素、聚碳酸酯、聚丙烯酸酯、聚對苯二甲酸伸丙基酯或聚對苯二甲酸乙二醇酯等聚合材料形成。在其他實施例中,該基板係由諸如石英、玻璃、藍寶石、YAG或雲母等無機材料形成。該基板可具有任何有用的厚度。在一實施例中,該基板係汽車或建築玻璃。在某些包括透明玻璃基板作為釉料系統之實施例中,在70%或更高TV I S
處,釉料系統具有0.68或更低、或0.6或更低、或0.55或更低、或0.50或更低之遮蔽係數。
為保護用於窗戶上之控制太陽光之膜,該多層膜之經曝露表面可視情況用一耐刮傷及耐磨硬塗層塗佈。該硬塗層可改良撓性基板加工期間及最終產品使用期間之耐久性。該硬塗層可包括任何有用的材料,例如以二氧化矽為主之硬塗層、矽氧烷硬塗層、三聚氰胺硬塗層、丙烯酸硬塗層及諸如此類。該硬塗層可具有任何有用厚度,例如自1至20微米、或1至10微米,或1至5微米。如上所述,紅外光吸收層亦可起硬塗層作用,或若期望可將一附加硬塗層設置於該紅外光吸收層上。
上述中間黏合劑可由任何有用材料形成。在某些實施例中,該中間黏著層包括如上所述之壓敏黏合劑材料。在某些實施例中,該中間黏著層包括可固化黏合劑,例如上述可熱或UV固化之黏合劑。該中間黏著層可具有任何有用厚度,例如1至100微米、或5至50微米、或10至50微米、或10至30微米。
上述中間聚合層可由任何有用材料形成。在某些實施例中,該中間層包括聚烯烴、聚丙烯酸酯、聚酯、聚碳酸酯、含氟聚合物及諸如此類。在一實施例中,該中間層包括一聚對苯二甲酸乙二醇酯。中間聚合層可具有任何有用厚度,例如5至500微米、或10至100微米、或25至75微米、或25至50微米。
在某些實施例中,本文所述控制太陽光之膜包括紅外光反射顏料層以及紅外光吸收奈米顆粒層或替代紅外光吸收奈米顆粒層。該等紅外光反射顏料可僅替代上述層中之紅外光吸收奈米顆粒。在許多實施例中,該紅外光反射顏料層係設置為毗鄰該多層之層。
該紅外光反射顏料可包括金屬氧化物。該等紅外光反射顏料可具有任何所期望之顏色。有用的紅外光反射顏料闡述於美國專利第6,174,360號及美國專利第6,454,848號中,且其以與本文揭示內容不衝突之程度以引用方式併入本文中。紅外光反射顏料係以商品名稱AB 820(鐵鈷鉻黑尖晶石CAS# 68186-97-0,顏料黑27)、AE 801及AG 235(氧化鐵鉻CAS# 12737-27-8,顏料棕29)自Kawamura Chemical公司(Japan)購得者。
可在一連續平膜生產線上經由一共擠出製程製備一含約446層之多層膜。此多層聚合物膜可自coPEN及PETG(自Eastman Chemicals獲得)製得。該coPEN係用90% PEN及10% PET起始單體聚合而得。一供料塊法(例如由美國專利第3,801,429號所述者)用於產生約223層光學層,各層在整個擠出物之間具有近似線性之層厚度梯度。
藉由一擠出機將coPEN以約132磅/小時之速率且PETG以約160磅/小時之速率遞送至該供料塊。一部分PETG用作擠出物各邊上之保護性邊界層(PBL),總流量約32磅/小時。然後,使材料流通過一放大設計比例約為1.25的不對稱二倍放大器。放大器概念及功能闡述於美國專利第5,094,788號及第5,094,793號中。放大比例定義為主管道中所產生層之平均層厚度除以子管道中層之平均層厚度。此放大比例係經選擇以提供由兩組223層所產生之兩反射帶之少量重疊。每一組223層皆具有由供料塊所產生之近似層厚度特性,其中總厚度比例因數係由該放大器及膜擠出速率決定。該放大器後,以約72磅/小時(總計)添加由第三擠出機供應之表層。然後,使材料流經過一膜模具並到達一水冷鑄輪上。
將該PETG熔體製程設備保持在約500℉,coPEN(光學層及表層二者)熔體製程設備保持在約525℉,且供料塊、放大器、表層熔體流及模具皆保持在約525℉。用於製造此實例膜之供料塊係經設計以在等溫條件下給出最厚層與最薄層比例為1.3:1之線性層厚度分佈。此層輪廓中之誤差用軸向杆狀加熱器輪廓校正,如美國專利第6,827,886號中所述,該案以引用的方式併入本文中。調節鑄輪速度以精確控制最終膜厚度,且藉此精確控制最終帶邊緣位置。
鑄輪上入口水溫係約7℃。一高電壓釘紮系統用於將擠出物壓入鑄輪。釘紮線係約0.17毫米厚且所施加電壓係約6.5千伏。該釘紮線係由一操作員自接觸點處薄片約3至5毫米處手動定位至鑄輪上,以獲得一外觀平滑的鑄造薄片。可藉由習知順序縱向取向器(LO)及拉伸設備使鑄造薄片連續取向。在約270℉下,薄片縱向取向至約3.8之拉伸比。在拉伸器中約15秒內將該膜預熱至約255℉,並在270℉下將膜橫向拉至拉伸比約3.5。在拉伸器烘箱中及約460℉之溫度下將該膜熱固化約30秒鐘。最終膜具有約0.0035英吋之最終厚度。
經銻摻雜之氧化銦錫(A-ITO)顆粒存於甲基溶纖劑(自Advanced Nano Products有限公司,South Korea獲得,商品名稱TRB Paste SM6080)中之超細分散液與甲基乙基酮混合以將分散液中之固體含量自60%降至45%。使用擠出模塗佈製程將該溶液塗佈於上述多層膜上。關於模塗佈技術之完整闡述參見"Modern Coating and Drying Technology"(E.D.Cohen、E.B.Gutoff編輯,VCH Publishers,NY,1992)。擠出物流速設定為330克/分鐘(使用MicromotionT M
流量計(Micro Motion公司,Boulder,CO,USA)量測),薄片速度設定為50英尺/分鐘且塗佈寬度設定為42英吋。在93攝氏度下乾燥塗層以自分散液中去除溶劑,並使用一配備有D型燈泡的Fusion UV燈系統(在80%功率設定值下運作)來固化塗層。此製程獲得具有約0.7克/平方英尺塗層重量的經固化塗層。進一步將A-ITO對置表面上之壓敏黏合劑與一經聚矽氧塗佈之離型襯墊(自CP Films,Martinsville,VA,USA購得)層壓至已乾燥及固化之A-ITO。去除離型襯墊,使用Lambda 19分光光度計(Perkin Elmer,Boston,MA)量測透射與反射光譜。將該等光譜輸入Optics5及Window 5.2程式(自Lawrence Berkeley National Laboratories購得),以分析釉料系統之熱及光學性質。該等程式可自http://windows.lbl.gov/software/
下載。該經塗佈膜之反射與透射光譜展示於圖1a中。藉由將上述膜層壓至3毫米透明玻璃(PPG透明玻璃,NFRC ID:5009,其黏合劑側朝向光源(太陽))所製備的窗玻璃系統之特性展示於表1中。層壓至3毫米玻璃基板後的透射與反射光譜展示於圖1b及1c中。層壓相同膜使A-ITO表面朝向太陽光,並使用相同軟體重新計算該窗玻璃系統。該等結果展示於下表1中。
可自Advanced Nano Products有限公司(South Korea)購得經銻摻雜之氧化銦錫(A-ITO)顆粒存於甲基溶纖劑(以商品名稱TRB Paste SM6080獲得)之超細分散液。使用一381螺旋單元/線性公分(150螺旋單元/線性英吋)之密紋輥並用CAG-150型Yasui Seiki Lab塗佈機(Yasui Seiki公司,Bloomington,Ind.)將該溶液塗佈於0.05毫米PET基板(自Teijin公司,Japan獲得,商品名為HPE50)上。於95℃下在生產線中乾燥該塗層並使用一配備有D型燈泡之Fusion Systems 1600(400 W/in)W固化系統以6.1米/分鐘實施UV固化。該經乾燥塗層具有約3.6微米之厚度。如實例1中所述來量測該膜之光透射與反射光譜並展示於圖2中。藉由將該膜層壓至6毫米PPG透明玻璃所製備之窗玻璃系統展示於表1中。
可自Advanced Nano Products有限公司(South Korea)購得一經銻摻雜之氧化錫(ATO)顆粒存於甲基溶纖劑(以商品名稱TRB Paste SM6060獲得)之超細分散液。使用一381螺旋單元/線性公分(150螺旋單元/線性英吋)之密紋輥並用CAG-150型Yasui Seiki Lab塗佈機(Yasui Seiki公司,Bloomington,Ind.)將該溶液塗佈於0.05毫米PET基板(由Teijin公司,Japan,商品名為HPE50)上。於95℃下在生產線中乾燥該塗層並使用一配備有D型燈泡之Fusion Systems 6000(600 W/in)W固化系統以6.1米/分鐘實施UV固化。該經乾燥塗層具有約3.6微米之厚度。如實例1中所述量測之該膜的光透射與反射光譜展示於圖3中。藉由層壓該膜至6毫米PPG透明玻璃所製備之窗玻璃系統展示於表1中。
使用Meyer刮條塗佈技術用Meyer刮條#5(實例4a)、#8(實例4b)及#14(實例4c)將TRB膏SL6060塗佈於上述多層膜上。於93℃烘箱中乾燥塗層10分鐘,於Fusion UV燈(20 fpm下300 W/in)下固化塗層並量測樣品之透射光譜。將該等光譜輸入Optics5及Window 5.2中。用3毫米透明玻璃製備之窗玻璃系統之光學與熱特性展示於表1中。
可藉由下述物質一起研磨來製備氧化銻錫(Inframat Advanced Materials LLC,CT產品名稱,50N-5190-2)存於一多官能基丙烯酸酯單體混合物中之分散液:30克ATO、7.5克異戊四醇四丙烯酸酯(Sartomer公司,PA,商品名稱SR295)及7.5克1,6-己二醇二丙烯酸酯(Sartomer公司,PA,商品名稱SR238)及1-甲氧基-2-丙醇。將各0.15克的光起始劑Irgacure 819及Irgacure 184(二者皆可自CIBA Specially Chemicals,Basel,Switzerland獲得)添加至上述分散液中,並將其塗佈於上述多層聚合物膜上。塗佈製程係按實例1中所述實施。固化該塗層並根據ASTM D 1044-99於500克負荷及50次循環下在泰伯磨耗試驗機中測試所得經固化塗層。此獲得用Haze-Gard Plus(BYK-Gardner,MD)濁度計量測低於4%之濁度。
不應將本發明視為受限於上述特定實例,而是應理解為本發明涵蓋隨附申請專利範圍中所明確載明的本發明之所有態樣。熟習本發明所針對技術者在閱讀本說明書後可極易明瞭適用於本發明之各種修改、等效製程及各種結構。
20...多層光學膜
22...層
24...層
100...控制太陽光之多層膜物件
110...紅外光反射多層膜
120...紅外光吸收奈米顆粒層
130...壓敏層
140...離型層或光學基板
150...硬塗層
200...控制太陽光之多層膜物件
210...紅外光反射多層膜
220...紅外光吸收奈米顆粒層
230...壓敏黏著層
240...離型層或光學基板
250...硬塗層
260...中間聚合物層
270...中間黏著層
A...聚合物
B...聚合物
結合附圖來考量下文對本發明各實施例之詳細闡述,可更完整地瞭解本發明,其中:圖1A係根據實例1所製備膜之透射與反射光譜,其中黏合劑側朝向光源;圖1B係根據實例1所製備的膜層壓至3毫米透明玻璃之後的透射與反射光譜,其中黏合劑側朝向太陽光;圖1C係根據實例1所製備的膜層壓至3毫米透明玻璃之後的透射與反射光譜,其中黏合劑側遠離太陽光;圖2係根據實例2所製備膜之透射與反射光譜;圖3係根據實例3所製備膜之透射與反射光譜;圖4係一多層膜之透視圖;圖5示意性繪示了一控制太陽光之多層膜物件之實施例;及圖6示意性繪示了控制太陽光之多層膜物件之另一實施例。
可對本發明實施各種改進且其可具有各種替代形式,其具體細節已藉由圖示以實例方式示出並予以詳細說明。然而,應注意,本文並非意欲將本發明限定於所述具體實施例。相反,本發明意欲囊括屬於本發明精神及範疇內的所有修改形式、等效內容及替代內容。
20...多層光學膜
22...層
24...層
A...聚合物
B...聚合物
Claims (23)
- 一種多層膜物件,其包括:一具有第一聚合物類型與第二聚合物類型之交替層的紅外光反射多層膜;及一包括複數個分散於一經固化聚合黏合劑中之金屬氧化物奈米顆粒之紅外光吸收奈米顆粒層,該紅外光吸收奈米顆粒層毗鄰該多層膜且該金屬氧化物包括氧化錫或經摻雜之氧化錫,該紅外光吸收奈米顆粒層具有介於1至20微米範圍內之厚度。
- 如請求項1之多層膜物件,其中該金屬氧化物奈米顆粒包括分散於一經固化聚丙烯酸酯黏合劑中之氧化銻錫、經摻雜之氧化銻錫或經銦摻雜之氧化錫。
- 如請求項1之多層膜物件,其中該金屬氧化物奈米顆粒進一步包括分散於一經固化聚丙烯酸酯黏合劑中之氧化銻或氧化銦。
- 如請求項1之多層膜物件,其中該紅外光吸收奈米顆粒層具有介於1至10微米範圍內之厚度。
- 如請求項1之多層膜物件,其中該奈米顆粒層包含50至80重量%之金屬氧化物奈米顆粒。
- 如請求項1之多層膜物件,其中該第一聚合物類型包括聚對苯二甲酸乙二醇酯或聚對苯二甲酸乙二醇酯之共聚物且該第二聚合物類型包括聚(甲基丙烯酸甲酯)或聚(甲基丙烯酸甲酯)之共聚物。
- 如請求項1之多層膜物件,其中該第一聚合物類型包括環己烷二甲醇或環己烷二甲醇之共聚物且該第二聚合物類型包括聚萘二甲酸乙二醇酯或聚萘二甲酸乙二醇酯之共聚物。
- 如請求項1之多層膜物件,其進一步包括一設置於該多層膜上之壓敏黏著層,該多層膜係設置於該壓敏黏著層與該紅外光吸收奈米顆粒層之間。
- 如請求項8之多層膜物件,其進一步包括一設置於該壓敏黏著層上之離型襯墊,該壓敏黏著層係設置於該離型襯墊與該多層膜之間。
- 如請求項1之多層膜物件,其進一步包括一設置毗鄰該多層膜之紅外光反射顏料層。
- 一種用於阻擋來自紅外光源之紅外光的控制光物件,其包含:一具有第一聚合物類型與第二聚合物類型之交替層之紅外光反射多層膜;一包含複數個分散於一經固化聚合黏合劑中之金屬氧化物奈米顆粒之紅外光吸收奈米顆粒層,該紅外光吸收奈米顆粒層毗鄰該多層膜且該金屬氧化物包括氧化錫或經摻雜之氧化錫,該紅外光吸收奈米顆粒層具有介於1至20微米間之厚度,其中該紅外光反射多層膜設置於一紅外光源與該紅外光吸收奈米顆粒層之間;及一設置為毗鄰該紅外光吸收奈米顆粒層或毗鄰該紅外光反射多層膜之玻璃基板。
- 如請求項11之控制光物件,其中該第一聚合物類型包括聚對苯二甲酸乙二醇酯或聚對苯二甲酸乙二醇酯之共聚物且該第二聚合物類型包括聚(甲基丙烯酸甲酯)或聚(甲基丙烯酸甲酯)之共聚物。
- 如請求項11之控制光物件,其進一步包括一設置於該紅外光反射多層膜與該玻璃基板間之壓敏黏著層。
- 如請求項11之控制光物件,其中該紅外光吸收奈米顆粒層具有介於1至10微米間之厚度。
- 如請求項11之控制光物件,其進一步包括一經設置毗鄰該多層膜之紅外光反射顏料層。
- 一種多層膜物件,其包括:一具有第一聚合物類型與第二聚合物類型交替層之紅外光反射多層膜;一包含複數個分散於一經固化聚合黏合劑中之金屬氧化物奈米顆粒之紅外光吸收奈米顆粒層,該紅外光吸收奈米顆粒層毗鄰該多層膜且該金屬氧化物包括氧化錫或經摻雜之氧化錫,該紅外光吸收奈米顆粒層具有介於1至20微米間之厚度;該多層膜物件具有至少45%之平均可見光透射率且對於780奈米至2500奈米光具有低於15%之平均紅外光透射率。
- 如請求項16之多層膜物件,其中對於所有實質上介於950奈米與2500奈米間之波長而言,該多層膜物件具有至少60%之平均可見光透射率及20%或更低之紅外光透射率。
- 如請求項16之多層膜物件,其中該多層膜物件在780與1200奈米之間具有50%或更高之平均光反射率且在1400與2500奈米之間具有50%或更低之平均光透射率。
- 如請求項16之多層膜物件,其中該多層膜物件在780與1200奈米之間具有80%或更高之平均光反射率且在1400與2500奈米之間具有20%或更低之平均光透射率。
- 如請求項16之多層膜物件,其中該多層膜物件在780與1200奈米之間具有90%或更高之平均光反射率且在1400與2500奈米之間具有5%或更低之平均光透射率。
- 如請求項16之多層膜物件,其進一步包括一設置於該多層膜上之壓敏黏著層,該多層膜係設置於該壓敏黏著層與該奈米顆粒層之間。
- 如請求項16之多層膜物件,其中該紅外光吸收奈米顆粒層具有介於1至10微米間之厚度。
- 如請求項16之多層膜物件,其進一步包括一設置為毗鄰該多層膜之紅外光反射顏料層。
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TWI412454B true TWI412454B (zh) | 2013-10-21 |
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TW95100676A TWI412454B (zh) | 2005-01-07 | 2006-01-06 | 控制太陽光之多層膜 |
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US (1) | US7632568B2 (zh) |
EP (1) | EP1833672B1 (zh) |
JP (1) | JP5464567B2 (zh) |
KR (1) | KR101208299B1 (zh) |
CN (1) | CN101098782B (zh) |
AU (1) | AU2006204122A1 (zh) |
BR (1) | BRPI0606499B1 (zh) |
CA (1) | CA2597901A1 (zh) |
DK (1) | DK1833672T3 (zh) |
MX (1) | MX2007008225A (zh) |
TW (1) | TWI412454B (zh) |
WO (1) | WO2006074168A2 (zh) |
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Also Published As
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EP1833672B1 (en) | 2015-02-25 |
CN101098782A (zh) | 2008-01-02 |
AU2006204122A1 (en) | 2006-07-13 |
BRPI0606499A2 (pt) | 2010-01-26 |
EP1833672A2 (en) | 2007-09-19 |
DK1833672T3 (en) | 2015-05-11 |
MX2007008225A (es) | 2007-09-11 |
CA2597901A1 (en) | 2006-07-13 |
US7632568B2 (en) | 2009-12-15 |
WO2006074168A2 (en) | 2006-07-13 |
KR101208299B1 (ko) | 2012-12-05 |
CN101098782B (zh) | 2015-11-25 |
WO2006074168A3 (en) | 2006-11-02 |
TW200630221A (en) | 2006-09-01 |
KR20070094834A (ko) | 2007-09-21 |
US20060154049A1 (en) | 2006-07-13 |
JP2008528313A (ja) | 2008-07-31 |
BRPI0606499B1 (pt) | 2017-04-18 |
JP5464567B2 (ja) | 2014-04-09 |
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