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TWI582141B - Ｕｖ－反射組成物 - Google Patents

Ｕｖ－反射組成物 Download PDF

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TWI582141B
TWI582141B TW100131882A TW100131882A TWI582141B TW I582141 B TWI582141 B TW I582141B TW 100131882 A TW100131882 A TW 100131882A TW 100131882 A TW100131882 A TW 100131882A TW I582141 B TWI582141 B TW I582141B
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particles
film
polymeric
polymerized
polymer
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TW201224014A (en
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鍾昭仁
艾德委 納爵瑟
愛德華Ｅ 拉福勒
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羅門哈斯公司
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Description

UV-反射組成物
本發明係關於自我聚集(self-associate)以形成UV反射膜之聚合粒子，而此UV反射膜特別適用於保護基材使免於遭受UV光線之破壞作用。
已有揭露將膠體晶體用於反射UV光線。例如，U.S. Pub. No. 2006/0182968揭露一種用於此目的之粒子液體分散液。然而，此方法需要使用染料並藉由透析自分散液移除離子成分。
本發明所解決之問題係提供形成UV-反射膜之聚合粒子。
本發明提供一種組成物，其包括具有：(a)30至300奈米(nm)之平均粒徑；及(b)維氏(Vicker)硬度表100至700公斤力/平方釐米(Kgf/mm2)之硬度的聚合粒子(polymeric particle)；以及，具有Tg(玻璃轉換溫度)不大於80℃之成膜聚合物；其中，該聚合粒子與該成膜聚合物間之折射率差至少為0.04。
本發明進一步關於一種薄膜，其包括具有：(a)30至300 nm之平均粒徑；(b)維氏硬度表100至700 Kgf/mm2之硬度的聚合粒子；以及，具有Tg不大於80℃之連續聚合相；其中，該聚合粒子與該連續聚合相間之折射率差至少為0.04；以及其中，該聚合粒子間之平均距離為35至400 nm。
除非另外說明，百分比係重量百分比(wt%)，而溫度係以℃表示。於20℃以鈉D線(sodium D line，其波長λ=589.29nm)測定折射率(RI)值。聚合粒子包括有機聚合物，較佳為加成聚合物，且較佳係實質上為球狀。以算術平均粒徑測定平均粒徑(或稱平均直徑)。使用Fox方程式自同元聚合物(homopolymer)之Tg值計算Tg值；參看美國物理學會通報(Bulletin of the American Physical Society) 1,3,第123頁(1956)。基於在該階段加入聚合混合物中之單體總量，計算多段(multistage)聚合物之每階段的單體重量百分比。本文中所使用之術語“(甲基)丙烯酸系”意指丙烯酸系或甲基丙烯酸系，而“(甲基)丙烯酸酯”意指丙烯酸酯或甲基丙烯酸酯。術語“(甲基)丙烯醯胺”意指丙烯醯胺(AM)或甲基丙烯醯胺(MAM)。“丙烯酸系單體”包含丙烯酸(AA)、甲基丙烯酸(MAA)、AA與MAA之酯類、伊康酸(IA)、巴豆酸(CA)、丙烯醯胺(AM)、甲基丙烯醯胺(MAM)，及AM與MAM之衍生物，如，烷基(甲基)丙烯醯胺(alkyl(meth)acrylamide)。AA與MAA之酯類包含，但不限於，烷基酯類、羥烷基酯類、磷烷基酯類(phosphoalkyl ester)及硫烷基酯類(sulfoalkyl ester)，如，甲基丙烯酸甲酯(MMA)、甲基丙烯酸乙酯(EMA)、甲基丙烯酸丁酯(BMA)、甲基丙烯酸羥乙酯(HEMA)、丙烯酸羥乙酯(HEA)、甲基丙烯酸羥丙酯(HPMA)、丙烯酸羥丁酯(HBA)、丙烯酸甲酯(MA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)、丙烯酸2-乙基己酯(EHA)及甲基丙烯酸磷烷基酯(如，PEM)。“苯乙烯系(styrenic)單體”包含苯乙烯、α-甲基苯乙烯；2-、3-或4-烷基苯乙烯，包含甲基-及乙基-苯乙烯；二乙烯苯及二乙烯甲苯。
術語“乙烯基單體(vinyl monomer)”意指含有與諸如氮或氧之雜原子連接的碳-碳雙鍵之單體。乙烯基單體之實例包含，但不限於，乙酸乙烯酯、乙烯基甲醯胺、乙烯基乙醯胺、乙烯基吡咯啶酮、乙烯基己內醯胺及長鏈烷酸乙烯酯諸如新癸酸乙烯酯及硬脂酸乙烯酯。
較佳地，該聚合粒子具有維氏硬度表150至600Kgf/mm2之硬度，較佳為200至500Kgf/mm2，較佳為240至400Kgf/mm2。使用具有鑽石頭之標準硬度計測量維氏硬度。自Hv=1.85444(P/d2)測定硬度，其中P為以Kg表示之載荷(load)及d2為以mm2表示之壓痕面積。自具有相同組成之較大粒子測量本發明尺寸範圍內之粒子硬度。使用Shimadzu微壓縮測試機MCT500測定本發明粒子之硬度。
較佳地，該聚合粒子是：(a)具有Tg為75至150℃之粒子；(b)具有至少0.5%交聯劑之聚合殘基之粒子；或者是其組合。當該粒子具有-50℃至75℃之Tg時，較佳該粒子具有至少0.5%交聯劑殘基，較佳至少0.75%，較佳至少1%，較佳至少1.25%，較佳至少1.5%，較佳至少2%，較佳至少3%，較佳至少5%。具有Tg為75至150℃之粒子可含有上述之交聯劑殘基量或可具有更低量之交聯劑殘基。該聚合粒子亦可高度交聯並具有高Tg，例如，藉由聚合二乙烯芳香(divinylaromatic)單體(如，二乙烯苯)所形成之粒子，或是藉由聚合具有大量二乙烯芳香單體(較佳至少30%，較佳至少50%，較佳至少70%，較佳至少80%)與其他單體(較佳為苯乙烯系單體或丙烯酸系單體)所組合之單體混合物所形成之粒子。
較佳地，該聚合粒子具有至少50nm之平均粒徑，較佳至少70nm，較佳至少80nm。較佳地，該聚合粒子具有不大於260nm之平均粒徑，較佳不大於230nm，較佳不大於200nm，較佳不大於170 nm，較佳不大於140nm。較佳地，該聚合粒子具有顯示單模(single mode)之粒徑分佈；較佳地，粒徑分佈之半高寬為5至70nm，較佳為10至30nm。該組成物或薄膜可含有具有不同平均直徑之粒子，限制條件為各個平均直徑之粒子具有如方才所述之粒徑分佈。使用粒徑分析儀測定粒徑分佈。較佳地，該聚合粒子及該成膜聚合物係組合成具有至少50nm平均粒徑之多段聚合粒子之形式，較佳至少70nm，較佳至少90nm，較佳至少110nm，較佳至少140nm。較佳地，該多段聚合粒子具有不大於450nm之平均粒徑，較佳不大於400nm，較佳不大於350nm，較佳不大於300nm，較佳不大於260nm，較佳不大於240nm，較佳不大於220nm，較佳不大於200nm。較佳地，該多段聚合粒子係二段粒子，即，至少70%之粒子具有本文所提之聚合粒子及成膜聚合物之性質，較佳至少80%，較佳至少90%，較佳至少95%。該多段聚合粒子可為具有上述聚合粒子作為核心及該成膜聚合物作為外殼之核殼粒子，或該成膜聚合物可間斷地分佈於聚合粒子之表面。
較佳地，該聚合粒子具有75至150℃之Tg。較佳地，該聚合粒子具有至少80℃之Tg，較佳至少85℃，較佳至少90℃，較佳至少95℃。較佳地，該聚合粒子具有不大於140℃之Tg，較佳不大於130℃，較佳不大於120℃。較佳地，該成膜聚合物或該連續聚合相具有不大於60℃之Tg，較佳不大於50℃，較佳不大於40℃，較佳不大於30℃，較佳不大於20℃，較佳不大於10℃，較佳不大於0℃，較佳不大於-10℃。較佳地，該成膜聚合物或該連續聚合相具有至少-50℃之Tg，較佳至少-40℃，較佳至少-30℃。
說明於本文之折射率差為絕對值。較佳地，該聚合粒子與該成膜聚合物間，或該聚合粒子與該連續聚合相間之折射率差(即，差之絕對值)，至少為0.06，較佳至少0.08，較佳至少0.09，較佳至少0.1，較佳至少0.105。較佳地，該聚合粒子與該成膜聚合物間，或該聚合粒子與該連續聚合相間之折射率差不大於0.2，較佳不大於0.17，較佳不大於0.15。較佳地，該聚合粒子之折射率為1.45至1.75，較佳為1.5至1.67，較佳為1.53至1.65。較佳地，該成膜聚合物或該連續聚合相之折射率為1.4至1.6，較佳為1.4至1.55，較佳為1.42至1.52。較佳地，該聚合粒子之折射率係大於該成膜聚合物或該連續聚合相之折射率。
本發明組成物中，該成膜聚合物對該聚合粒子之重量比較佳為0.8:1至15:1，較佳1:1至10:1，較佳1.2:1至8:1。於薄膜之連續相中，聚合粒子間之平均距離，即，粒子間之中心-中心距離，係40至300nm，較佳50至200nm，較佳70至130nm。
較佳地，該成膜聚合物或該連續聚合相包括至少60%丙烯酸系單體之聚合殘基，較佳至少70%，較佳至少80%，較佳至少90%，較佳至少95%。較佳地，該成膜聚合物或該連續聚合相包括35至70%之(甲基)丙烯酸C4-C12烷基酯之聚合殘基，較佳40至65%，較佳45至65%。較佳地，該(甲基)丙烯酸C4-C12烷基酯係丙烯酸C4-C12烷基酯，較佳為丙烯酸C4-C10烷基酯，較佳為BA及/或EHA。較佳地，該成膜聚合物或該連續聚合相亦包括30至65%之(甲基)丙烯酸C1-C4烷基酯之聚合殘基(較佳為35至60%，較佳為35至55%)，及0至5%酸單體(如，AA、MAA、IA、CA)之聚合殘基，且亦可含有少量乙烯基單體之殘基。較佳地，該(甲基)丙烯酸C1-C4烷基酯係(甲基)丙烯酸C1-C2烷基酯，較佳為MMA及/或EMA。較佳地，該聚合粒子包括至少60%苯乙烯系單體之聚合殘基，較佳至少70%，較佳至少80%，較佳至少90%，較佳至少95%。較佳地，該聚合粒子亦包括0至5%酸單體(如，AA、MAA、IA、CA)之聚合殘基，較佳為0.5至4%AA及/或MAA，且亦可含有少量乙烯基單體之殘基。
交聯劑係具有兩個或更多個乙烯系不飽和基團之單體，或偶合劑(如，矽烷)或離子性交聯劑(如，金屬氧化物)。具有兩個或更多個乙烯系不飽和基團之交聯劑可包含，如，二乙烯芳香化合物，二-、三-及四-(甲基)丙烯酸酯類，二-、三-及四-烯丙基醚類化合物、二-、三-及四-烯丙基酯類化合物及(甲基)丙烯酸烯丙酯。該等單體之較佳實例包含二乙烯苯(DVB)、三羥甲基丙烷二烯丙基醚、四烯丙基季戊四醇、三烯丙基季戊四醇、二烯丙基季戊四醇、苯二甲酸二烯丙酯、順丁烯二酸二烯丙酯、三聚氰酸三烯丙酯、雙酚A二烯丙基醚、烯丙基蔗糖、亞甲基雙丙烯醯胺、三羥甲基丙烷三丙烯酸酯、甲基丙烯酸烯丙酯(ALMA)、二甲基丙烯酸乙二醇酯(EGDMA)、己-1,6-二醇二丙烯酸酯(HDDA)及二甲基丙烯酸丁二醇酯(BGDMA)。較佳地，在該成膜聚合物或該連續聚合相中之交聯劑聚合殘基含量不超過0.2%，較佳不超過0.1%，較佳不超過0.05%，較佳不超過0.02%，較佳不超過0.01%。較佳地，具有Tg為75至150℃之聚合粒子中之交聯劑聚合殘基含量不超過0.5%，較佳不超過0.3%，較佳不超過0.2%，較佳不超過0.1%，較佳不超過0.05%。較佳地，若交聯劑存在，彼等具有100至250之分子量，較佳為110至230，較佳為110至200，較佳為115至160。較佳地，該交聯劑係雙官能性或三官能性，即，彼等係分別為二乙烯系不飽和或三乙烯系不飽和之交聯劑，較佳為雙官能性。
較佳地，本發明組成物係本發明聚合粒子之水性乳液，較佳固體量為35至65%，較佳為40至60%。當該聚合粒子與該成膜聚合物組合於多段粒子中時，較佳為藉由多段乳液聚合作用自適當的單體製造該組成物。較佳為有兩個聚合階段，其中，將不同單體組成物引入該聚合作用，雖然 如本文所示可以更多階段製作該粒子以提供整個組成物。較佳地，該組成物及該薄膜實質上不含色素或固體無機粒子，即，彼等佔少於0.5wt%，較佳少於0.2wt%，較佳少於0.1wt%，較佳少於0.05wt%之含量。
較佳地，係藉由將本發明多段聚合粒子之水性乳液塗佈於固體基材並乾燥該塗層以製造本發明包括聚合粒子之薄膜。較佳地，該基材係玻璃、木材、石材、石膏板(drywall)、皮革、紙、織物、金屬、塑膠、油漆薄膜或於任何上述基材上之其他聚合物塗層，或光學上清透之塑膠(optically clear plastic)，如，聚對苯二甲酸乙二酯(poly(ethyleneterephthalate))；較佳為玻璃或光學上清透之塑膠。較佳地，該濕塗層具有厚度為0.25至30密耳(mil)(0.0064至0.76mm)，較佳為2至30mil(0.05至0.76mm)，較佳為4至20mil(0.1至0.5mm)，較佳為6至12mil(0.15至0.3mm)。咸信聚合粒子係聚集以產生實質上為面心立方體或六方最密堆積排列之核心基質外層以形成連續聚合相。
[實施例]
實施例1
以下列處理步驟製備由苯乙烯、丙烯酸丁酯及甲基丙烯酸構成之多段聚合粒子(1(97苯乙烯/3MAA)/1.5(58BA/41MMA/1MAA))之一實例：將槳式攪拌器、溫度計、氮氣輸入口及回流冷凝器裝配於5公升圓底瓶。於氮氣氛下及攪拌下，將3.01克SIPONATE DS-4(22.5%固體)加入在瓶中加熱至89℃之733.8克去離子水(DI水)中，隨之加入製備自377.31克去離子水、10.88克SIPONATE DS-4(22.5%固體)、581.82克苯乙烯及17.99克MAA之50.83克單體乳液。將溶於13.89克水之0.65克過硫酸銨加入瓶中。溫度達最高點後，將剩下的單體乳液於85℃、以120分鐘的時間、以起初5分鐘速率為其餘115分鐘速率的一半之速率加入鍋中。進料期間，將溶於55.56克水之0.28克過硫酸銨亦加入鍋中。加入單體五分鐘後，以15分鐘的時間將溶於60.19克水之0.23克過硫酸銨加入鍋中，隨之加入416.67克去離子水。鍋冷卻至20℃後，加入於20克去離子水中之1.8克1.0% FeSO4‧7H2O及1.8克1.0% VERSENE，並以90分鐘的期間於鍋中加入溶於45.0克去離子水之3.5克過氧化三級丁基(70%)及溶於45.0克去離子水之2.40克異抗壞血酸製成之溶液。開始加入之兩分鐘後，製備自226克去離子水、14.60克SIPONATE DS-4(22.5%固體)、522克BA、369克MMA及9克MAA之第二種單體乳液亦以7克/分鐘加入。30分鐘後，將速率增加至14克/分鐘，並於另一個30分鐘後進一步增加至17克/分鐘。加入後，將溶於15.0克去離子水之1.6克過氧化三級丁基(70%)及溶於15.0克去離子水之0.90克異抗壞血酸以15分鐘的期間加入鍋中。然後於低於45℃之溫度，以20克之14%氨水中和該乳液聚合物。
實施例：2至4
此等實施例說明於0.16mm聚對苯二甲酸乙二酯基材(MYLAR)上之薄膜塗層之製備。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑，其值列於下面表I。此等實施例說明該自我聚集粒子之光學性質。其組成物列於表I。使用鳥型塗膜器(bird applicator)(3 mil濕性)或DOW條(20mil濕性)壓延該薄膜。經由U-2000型雙光束UV/Vis(紫外線/可見光)分光光譜儀測值前，大部分之經塗佈樣品先在烤箱中經120℃溫度乾燥3分鐘。
實施例：5至8
列於表I之實施例係同樣製備成聚對苯二甲酸乙二酯基材(MYLAR)上之0.16mm塗層。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑，其值列於下面表I。該等實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3mil濕性)或DOW條(20mil濕性)壓延所有的薄膜。將大部分之經塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/Vis穿透率(%T)。
實施例：9至13
列於下面表I之實施例說明同樣製備成聚對苯二甲酸乙二酯基材(MYLAR)上之0.16mm塗層之聚合薄膜。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑，其值列於下面表I。該等實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3 mil濕性)或DOW條(20 mil濕性)壓延所有的薄膜。將大部分之經塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/Vis穿透率。
實施例：14至16
列於表I之薄膜組成物及光學性質係製備自0.16mm PET、聚對苯二甲酸乙二酯基材(MYLAR)上之分散液。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑，其值列於下面表I。該等實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3 mil濕性)或DOW條(20 mil濕性)壓延所有的薄膜。將大部分之經塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/Vis穿透率。
實施例：17
列於表I之薄膜組成物及光學性質係製備自0.16mm PET、聚對苯二甲酸乙二酯基材(MYLAR)上之分散液。以Brookhaven Instruments粒徑分析儀BI-90測量該乳膠之粒徑，其值列於下面表I。該實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3 mil濕性)或DOW條(20 mil濕性)壓延該薄膜。將經塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/Vis穿透率。
實施例：18至19
列於表I之薄膜組成物及光學性質係製備自0.16mm PET、聚對苯二甲酸乙二酯基材(MYLAR)上之膠體乳膠分散液。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑，其值列於下面表I。該等實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3 mil濕性)或DOW條(20 mil濕性)壓延所有的薄膜。將大部分之經塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/Vis穿透率。
實施例：20至22
列於表I之薄膜組成物及光學性質係製備自0.16mm PET、聚對苯二甲酸乙二酯基材(MYLAR)上之膠體乳膠分散液。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑，其值列於下面表I。該等實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3 mil濕性)或DOW條(20 mil濕性)壓延所有的薄膜。將大部分之經塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/Vis穿透率。
實施例：23至25
列於表I之聚合物組成物為膠體乳膠分散液之形式。該分散液係塗佈於0.16mm PET、聚對苯二甲酸乙二酯薄膜(MYLAR)上。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑，其值列於下面表I。該等實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3 mil濕性)或DOW條(20 mil濕性)壓延所有的薄膜。將大部分之經塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/Vis穿透率。
實施例：26至28
列於表I之聚合物組成物為膠體乳膠分散液之形式。該分散液係塗佈於0.16mm PET、聚對苯二甲酸乙二酯薄膜(MYLAR)上。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑，其值列於下面表I。該等實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3 mil濕性)或DOW條(20 mil濕性)壓延所有的薄膜。將大部分之經塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/Vis穿透率。
實施例：29至37
此等實施例說明使用增稠劑，ACRYSOL ASE-60增稠劑，以加強膠體乳膠之黏稠度。如表I所示，將具有或不具有ASE-60增稠劑之乳膠組成物塗佈於0.16mm PET、聚對苯二甲酸乙二酯薄膜(MYLAR)上。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑，其值列於下面表I。該等實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3 mil濕性)或DOW條(20 mil濕性)壓延所有的薄膜。將大部分之經塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/Vis穿透率。
實施例：38至45
列於表I之聚合物組成物為膠體乳膠分散液之形式。該分散液係塗佈於0.16mm PET、聚對苯二甲酸乙二酯薄膜(MYLAR)上。以Brookhaven Instruments粒徑分析儀BI-90測量各種乳膠之粒徑；其值係全部多段粒子。該等實施例說明自我聚集粒子之光學特性。使用鳥型塗膜器(3 mil濕性)或DOW條(20mil濕性)壓延所有的薄膜。將大部分之塗佈樣品在烤箱中經120℃溫度乾燥3分鐘。經由U-2000型雙光束UV/Vis分光光譜儀測量UV/ViS穿透率。預期核心之折射率非常接近聚苯乙烯之折射率及丙烯酸系外層之折射率接近丙烯酸酯聚合物之折射率，即，分別為1.59及1.46-1.49。
實施例：46至57
於此系列之實施例中，將自我聚集粒子之分散液以3 mil(0.076mm)濕性塗佈於玻璃基材上並於55%相對濕度下暴露於紫外線輻射。該測試平板之表面積為以下尺寸：83mm×76mm。以：ASTM D 10003-00(透明塑膠混濁度與光之穿透率之標準測試方法)及ASTM E 313-00(自儀器測量顏色座標計算黃度和白度指數的標準實施規程)評估該等平板。
實施例：58-67
該等實施例說明前文提到之自我聚集粒子(表I)及增稠劑A(ACRYSOL ASE-60增稠劑)之摻合物。將各種增稠之乳膠組成物塗佈於麥拉膜(Mylar film)。該測試片之表面積為以下尺寸：77mm x 56mm。將所有的薄膜塗層在烤箱中經120℃溫度乾燥3分鐘。藉由U-2000型雙光束UV/Vis分光光譜儀以UV/Vis穿透率評估該樣品。
標記“實施例80”之組成物係1份(苯乙烯/MAA=99/1)//9份(BA/MMA/MAA=58/41/01)
實施例：68至73
於此等實施例中，係將182nm自我聚集粒子(實施例2)及98 nm自我聚集粒子(實施例5)及ASE-60增稠劑組合以形成塗佈組成物。將列於表IV之組成物塗佈於玻璃基材上。將使用3-mil鳥型塗膜器壓延於玻璃上之樣品於QUV氣候機中進行1000小時之UV曝曬。該測試平板之表面積為以下尺寸：83mm×76mm。以：ASTM D 10003-00(透明塑膠混濁度與透光率之標準測試方法)及ASTM E 313-00(自儀器測量顏色座標計算黃度和白度指數的標準實施規程)評估該等平板。
實施例：74至79
於此等實施例中，係將182 nm自我聚集粒子(實施例2)及40 nm自我聚集粒子(實施例17)及ASE-60增稠劑組合以形成塗佈組成物。將列於表IV之組成物塗佈於玻璃基材上。將使用3-mil鳥型塗膜器壓延於表面積為83mm×76mm之玻璃基材上之樣品於QUV氣候機中進行1000小時之UV曝曬。以ASTM D 10003-00(透明塑膠混濁度與透光率之標準測試方法)及ASTM E 313-00(自儀器測量顏色座標計算黃度和白度指數的標準實施規程)評估L、a、b值，混濁度數據，YI及透光百分率值。

Claims (10)

  1. 一種組成物，包括具有：(a)30至300nm之平均粒徑；及(b)維氏硬度表100至700Kgf/mm2之硬度的聚合粒子；以及，具有Tg不大於80℃之成膜聚合物；其中，該聚合粒子與該成膜聚合物間之折射率差至少為0.04，且該成膜聚合物對該聚合粒子之重量比為1.2：1至15：1。
  2. 如申請專利範圍第1項所述之組成物，其中，該聚合粒子與該成膜聚合物間之折射率差至少為0.08。
  3. 如申請專利範圍第2項所述之組成物，其中，該平均粒徑為70至260nm。
  4. 如申請專利範圍第3項所述之組成物，其中該聚合粒子包括至少70wt%苯乙烯系單體之聚合殘基，以及該成膜聚合物包括至少70wt%丙烯酸系單體之聚合殘基。
  5. 如申請專利範圍第4項所述之組成物，其中，該聚合粒子與該成膜聚合物間之折射率差至少為0.105。
  6. 一種薄膜，包括具有：(a)30至300nm之平均粒徑；及(b)維氏硬度表100至700Kgf/mm2之硬度的聚合粒子；以及，具有Tg不大於80℃之連續聚合相；其中，該聚合粒子與該連續聚合相間之折射率差至少為0.04；以及其中，該聚合粒子間之平均距離為35至400nm，且該連續聚合相對該聚合粒子之重量比為1.2：1至15：1。
  7. 如申請專利範圍第6項所述之薄膜，其中，該聚合粒子與該連續聚合相間之折射率差至少為0.08，以及該平均粒徑為70至200nm。
  8. 如申請專利範圍第7項所述之薄膜，其中，該聚合粒子間之平均距離為50至200nm。
  9. 如申請專利範圍第8項所述之薄膜，其中，該聚合粒子包括至少70wt%苯乙烯系單體之聚合殘基，以及該連續聚合相包括至少70wt%丙烯酸系單體之聚合殘基。
  10. 如申請專利範圍第9項所述之薄膜，其中，該聚合粒子與該連續聚合相間之折射率差至少為0.11。
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