TW200948871A

TW200948871A - Silica coating for enhanced hydrophilicity/transmittivity

Info

Publication number: TW200948871A
Application number: TW97118076A
Authority: TW
Inventors: Naiyong Jing; Roxanne A Boehmer; Xue-Hua Chen; Zhi-Gang Yu; Ying Zhang; Dang Xie; Bangwei Xi
Original assignee: 3M Innovative Properties Co
Priority date: 2008-05-16
Filing date: 2008-05-16
Publication date: 2009-12-01
Also published as: TWI441854B

Abstract

This invention provides a spreaded product, which is a substrated covered via a layer of the nano silicon dioxide particles. The layer has a uniform thickness and is binded lastingly to the substrate. Vin the layer, the surface of the substrate becomes less reflective and/or has a stronger water affinity.

Description

200948871 九、發明說明：【發明所屬之技術領域】 . 本發_於—種二氧切（si〇2)奈餘子塗層，特別關於 -種在其上帶有奈棘子二氧切塗層的製品，例如光學襄置或 ' 圖形媒體，和用於製備這樣的製品之方法。【先前技術】 ❹ 錄應用都需要具魏觸展水的表面之m目此防止在製品的表社形成賴。例如，在有霧或細環境巾使用的透明师，例如溫㈣窗戶，應當避免形成反射光的水滴，其會降低光透射。在這些材料上的水鋪展表面有助於保持其透明性並使不希望的斑紋形成最小化。對於使用反光膜的交通標認，也需要水鋪展性質。反光膜具有大夏入射光返酬光源的能力。黏著雨滴和/或露水會損害光透〇射進入反光膜並由其反射出。水影響光透群的主要形式是形絲水。因為露水主要出現 •在反細μ树的賴，它尤其·題。#則、珠㈣水滴之形、式存在於交通標誌上時’露水會破壞入射和反射光的光路。這會、使路過的行車者非常難以識別標誌、上的資訊。相反地，當露水在反光交通觀的表面上平穩鋪展成咖層時，麟上的資訊就較易識別因為形成之薄的平滑水層不會明顯把入射和反射的光路誤導到报強的程度。 X鋪展表面塗層、特別是二氧化石夕基塗層的問題是膠體二氧 200948871 化石夕和膠體二氧切_表面化學、反應化學和溶祕學的高度複雜。例如，儘管進行了深入的研究，但離子與二氧化石夕表面的相互作用還不能完全瞭解（參見Iler，，,The⑸响办〇f趾叫·· John Wdey，1979 P.656)。儘管有這樣_難，但依照下述的本發 '明’提供了—種耐久性提高的二氧切基水鋪展膜。【發明内容】 ❹ 有鑑於上述課題，本發明之目的為提供一種塗料組合物，其包括合有平均-次粒度為4G奈米（nm)或更小的一氧化梦奈米粒子的为政體和pKa<3.5的酸，以及一種用於塗覆基體的方法，其包括用塗料組合物塗覆基體並乾燥塗層。為達上述目的，依據本發明之一種包含基體、特別是聚合基體的塗層製品，基體在其上具有二氧化石夕奈米粒子塗層。塗層包〇括平均一次粒度40奈米或更小的凝聚之二氧化矽奈米粒子的連續塗層。塗層之厚度是實質上均勻的，且持久黏合在基體上。、塗層對各種基體的黏合都非常好，特別是對聚合物基體，並且可以為這樣的基體提供出色的平均鏡面反射率降低，例如至少 2°/〇。當基體是透明時，塗層可以提供為400〜700奈米波長範圍内的法向入射光比透射通過未塗層的相同材料之基體的透射率提高’其中較佳為提高至少2%，且直至多達10〇/〇或更高。此處所用之「透明的」是指在選定部分的可見光譜（約400〜70()奈米波長）中，入射光透射至少85%。對UV區和近IR區的透明度也可以提 200948871 高。對於任意選定波長的光，對應減反射層也將具有最佳之厚产塗層可崎-步為基體提供親水表面，特別咖於為疏^聚合物基體提供親水表面。塗層也可以提供防霧性質，並為总到電堆積的聚合物膜和片材提供抗靜電性質。$，塗層較佳物材料，例如膜和ϋ材提㈣磨損性’由此提高其操作性能^ 由这些酸化的奈米粒子組合物產生之塗層可以進一步為表面例如玻璃和聚對苯二甲酸乙二_旨（财）：&體提供防水域械耐久的親水表面:，和在各種溫度和高濕度條件下良好的防霧性質。此外’塗層可以提絲制，並表現料洗去除錢污染物，包括食物和機油、麵、灰塵和污垢，因騎層之奈米孔結構傾向於防止低聚合的聚合分子之滲透。、承上所述’因依據本發顿方法不需要用於在基體上塗覆的洛劑或界面活賴，因此危害更小’並且不會為空氣增添揮發性有機化合物（VOC)。其他優點包減層更㈣、雜體的黏合更好、塗層之耐久性更好、減反射性更高和透射率提高，且在污染物可以沖洗掉之情況下提供易於清潔的表面。【實施方式】以下將參照相關圖式，說明依據本發明較佳實施例之一種用於提间親水性/透射率的二氧化石夕塗層，其中相同的元件將以相同的元件符號加以說明。一種用於塗覆基體的方法’包括用包含pKa (托〇) $3.5、較 8 200948871 佳為pKa<2.5、最佳為pKa小於〗的酸和平均一次粒度為4〇奈米或更小之二氧切奈綠子的溶雜覆基體，以及乾燥塗層。出乎意料的是，這些二氧化雜料組合物，#酸化時，能夠不用有我溶劑或界面活性_直接塗覆在疏水有機和無機基體上。这些無機奈米粒子水分散體在疏水表面例如聚對苯二甲酸乙二醇醋或聚碳酸g旨（PC)上的潤濕性質是分散體的pH值和此酸的pKa之函數。當用氯化氫（HC1)將其酸化到pH==2〜3，甚至在-些實施方式巾pH直至5時，塗料組合物可塗覆麵水有機基體上。相反，塗料組合物在中性或驗性pH值時會在有機基體上團結成珠。 ❹ 不希望被理論所限制，我們認為二氧化石夕奈米粒子的凝聚體是通過由酸催化的魏絲好切鱗基在奈餘子表面讀結形成的’這些凝《娜了在疏水有機表面上的可塗覆性，因為這些基團容易被疏水表面所鍵結、吸附或其他方式耐久地附著。儘管描述了奈米粒子二氧化石夕分散體之含水有機溶劑基塗層，但這獅水和有機溶狀混合物通常會發生蒸發速率不同，導致液相的組成連續變化，其又會改變塗皙. 〇，、 J丨土貝，導致均勻性但陷較差和雜。儘管界面滩财財赌分龍的難性質，的塗層其會干擾粒子間和介面間的基體黏合，經常產生不均勻和=缺對這些酸化分散體溶液的光散射測定表明，這些二氧化米粒子確實容綠聚，提供C在塗覆和乾燥後）二氣切奈^ 200948871 子的二維纽網狀結構，在其f各奈綠子看上缺臨近粒子穩固地結合在1。顯微⑼揭示這種結合是购二氣^ 粒子之關「頸部聯結」，其是在矽彻存在⑽蝴— 烷鍵中的催化作用。令人驚奇的是，當pH值在酸化的分散體呈現出穩定性。光散射測定 ^奈米或4奈米二氧化石夕奈米粒子倾=2〜3和在1〇wt%濃 a ’在超過—周或甚至超過—個月之後健朗樣的尺寸樣的酸化之二氧化料餘子分健有望奴低的分散體濃度^ 在甚至更長時間内保持穩定。 2〜4之範圍内時，顯示，這些凝聚之酸化200948871 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a bismuth dioxate (si〇2) nanocapsule coating, in particular, to a species with a scorpion scorpion dioxygen coating A layered article, such as an optical device or 'graphic medium, and a method for making such an article. [Prior Art] The application of the surface of the water is required to prevent the formation of the products in the product. For example, a transparencyist using a fog or fine environmental towel, such as a warm (four) window, should avoid the formation of water droplets that reflect light, which can reduce light transmission. The water spreading surface on these materials helps to maintain its transparency and minimize undesirable streaking. For traffic marking using reflective films, water spreading properties are also required. The reflective film has the ability to return light from a large summer. Adhesive raindrops and/or dew can damage the light and penetrate into the reflective film and reflect it out. The main form of water-affecting light-transmitting groups is the shape of silk water. Because dew mainly appears in the anti-fine μ tree, it is especially problematic. #则,珠 (4) The shape of the water droplets, when the pattern exists on the traffic sign, the dew will destroy the light path of the incident and reflected light. This will make it very difficult for passers-by to identify the signs and information. Conversely, when the dew spreads smoothly into a coffee layer on the surface of the reflective traffic concept, the information on the lining is easier to identify because the thin, smooth water layer formed does not significantly mislead the incident and reflected optical paths to the level of the newspaper. . The problem with X-spreading surface coatings, especially for sillimanite-based coatings, is the high degree of complexity of colloidal dioxogens in the chemical and reactional chemistry. For example, despite intensive research, the interaction of ions with the surface of the dioxide is not fully understood (see Iler,,, The (5) is called tough, John Wdey, 1979 P.656). Despite this, it is difficult to provide a dioxic water-spreading film having improved durability in accordance with the present invention. SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a coating composition comprising a oxidized Moonlight particle having an average-minor particle size of 4G nanometers (nm) or less. An acid of pKa < 3.5, and a method for coating a substrate comprising coating a substrate with a coating composition and drying the coating. To achieve the above object, a coated article comprising a substrate, in particular a polymeric matrix, having a coating of a cerium oxide nanoparticle thereon is provided in accordance with the invention. The coating comprises a continuous coating of condensed cerium oxide nanoparticles having an average primary particle size of 40 nm or less. The thickness of the coating is substantially uniform and adheres permanently to the substrate. The adhesion of the coating to the various substrates is very good, especially for polymer matrices, and can provide excellent average specular reflectance reduction for such matrices, for example at least 2°/〇. When the substrate is transparent, the coating can provide an increase in transmittance of the normal incident light in the wavelength range of 400 to 700 nm than in the substrate of the same material transmitted through the uncoated layer, wherein preferably at least 2% is improved, and Up to 10 〇 / 〇 or higher. As used herein, "transparent" means that the incident light is transmitted at least 85% in the visible spectrum of the selected portion (about 400 to 70 (nm wavelength). The transparency of the UV zone and the near IR zone can also be raised to 200948871. For any selected wavelength of light, the corresponding anti-reflective layer will also have an optimally thick coating that provides a hydrophilic surface for the substrate, particularly to provide a hydrophilic surface for the polymer matrix. The coating also provides anti-fog properties and provides antistatic properties to the polymer film and sheet that are fully charged. $, coating preferred materials, such as film and coffin, (4) abrasion resistance' thereby improving its handling properties ^ coatings produced from these acidified nanoparticle compositions may further be surfaces such as glass and poly-p-phenylene Formic acid ethane _ _ (Finance): & body provides a durable waterproof surface of the waterproof domain: and good anti-fog properties under various temperatures and high humidity conditions. In addition, the coating can be silk-finished and exhibits a wash-off of money contaminants, including food and oil, noodles, dust and dirt, as the nanoporous structure of the riding layer tends to prevent penetration of oligomerized polymeric molecules. According to the above-mentioned method, the agent or interface used for coating on the substrate does not need to be used, so the hazard is smaller, and no volatile organic compound (VOC) is added to the air. Other advantages include a reduced layer (4), better adhesion of the hybrid, better durability of the coating, higher anti-reflectivity and increased transmittance, and an easy-to-clean surface where the contaminants can be rinsed off. [Embodiment] Hereinafter, a corrosive oxide coating for intertwining hydrophilicity/transmittance according to a preferred embodiment of the present invention will be described with reference to the related drawings, wherein the same elements will be described with the same reference numerals. . A method for coating a substrate 'comprises an acid comprising a pKa (tortorium) of $3.5, a ratio of 8 200948871, preferably a pKa < 2.5, preferably a pKa less than, and an average primary particle size of 4 nanometers or less. A hetero-coated matrix of oxygen chopped greens, and a dried coating. Unexpectedly, these dioxo-compound compositions, when acidified, can be applied directly to hydrophobic organic and inorganic substrates without my solvent or interfacial activity. The wetting properties of these aqueous inorganic nanoparticle dispersions on hydrophobic surfaces such as polyethylene terephthalate or polycarbonate (PC) are a function of the pH of the dispersion and the pKa of the acid. When acidified to pH == 2 to 3 with hydrogen chloride (HC1), even when the pH of the embodiments is up to 5, the coating composition can be applied to the surface water organic substrate. Conversely, the coating composition will agglomerate on the organic substrate at neutral or inspective pH. ❹ Do not wish to be bound by theory, we believe that the condensate of the cerium oxide nanoparticles is formed by the acid-catalyzed weiss squaring on the surface of the Naizi. The coatability on the surface, because these groups are easily bonded, adsorbed or otherwise adhered to the hydrophobic surface. Although the aqueous organic solvent-based coating of the nanoparticle dioxide dioxide dispersion is described, the lion water and the organic solvent mixture usually have different evaporation rates, resulting in a continuous change in the composition of the liquid phase, which in turn changes the coating. 〇, , J丨土贝, resulting in uniformity but poor and mixed. Despite the difficult nature of the interface, the coating will interfere with the matrix bonding between the particles and the interface, often producing unevenness and = lack of light scattering measurements of these acidified dispersion solutions indicate that these dioxide meters The particles do contain green pigmentation, providing a two-dimensional network structure of C-cutting Nai 200948871 after coating and drying, and the lack of adjacent particles in the f-negative greens is firmly bound to 1. Microscopy (9) reveals that this combination is the "neck junction" of the two gas particles, which is the catalytic effect in the (10) butterfly-alkane bond. Surprisingly, the pH appears to be stable in the acidified dispersion. Light scattering measurement ^Nano or 4 nm of smectite smectite particles tilt = 2 to 3 and at 1 〇 wt% rich a ' after more than - weeks or even more than - months after the healthy sample size acidification The concentration of the dispersion of the sulphur dioxide remaining in the hopeful slave is stable for a longer period of time. When the range of 2 to 4 is displayed, the acidification of these condensations is shown.

在此組合物巾賴的二氧切奈餘子是亞微米尺寸之二氧化石夕奈絲子在水或在水/有機斜祖合物巾的分健， ^粒徑為40奈米或更小，射較料2Q奈米或更小更佳為1〇 ^米或更小。其平均粒度可錢用穿透式電子麵鏡（tem)測定。二氧切奈米粒子，其愤佳為未經過表面改性的二氧化石夕奈未粒子。更小之奈米粒子，20奈米或更小的那些，·在酸化時，通常不需要添加劑例如四絲基魏、界面活_或錢㈣就能提供更好的塗層。此外’奈絲子的tb表面積騎具有大於約15〇平方公尺/克’其愤佳為大於平方公尺/克，更佳為大於400平方公尺/克的比表面積。奈綠子較佳為具有窄粒度分佈，即多分散性為2.0或更小，其中較佳為15或更小。如果需要， 10 200948871 可以添加較大的二氧化矽粒子’其含量不能減損組合物在選定基體上的可塗覆性，且不會降低透射率和/或親水性。在含水介質中的無機二氧化矽溶膠是現有技術中公知的，並可商業得到。在水或水-醇溶液中的二氧化矽溶膠可以商品名如 LUDOX (由 E.I. duPont de Nemours 和 Co.，Inc.，Wilmington，Del. USA 製備）、NYACOL(可獲自 Nyacol Co” Ashland，MA)或NALCO (由 Ondea Nalco Chemical Co.，Oak Brook, 111. USA 製備)商業得到。一種有用的二氧化矽溶膠是NALCO 2326，可作為平均粒度為5奈米’pH為10.5且固體含量為15 wt.%的二氧化石夕溶勝得到。其他可商業得到的二氧化矽奈米粒子包括可購自NALCO Chemical Co.的「NALC0 1115」和「NALC〇 113〇」、可購自 Re_The dioxodine residue of the composition of the composition is a submicron-sized smectite of the ceramsite in water or in a water/organic oblique auxiliaries. The particle size is 40 nm or more. Small, shot 2Q nanometer or smaller is better than 1〇^m or smaller. The average particle size can be measured using a transmissive electronic mirror (TEM). The dioxetane particles, which are excellent in anger, are non-surface-modified cerium oxide. Smaller nanoparticles, those of 20 nm or less, do not require additives such as tetrafilament, interface or money to provide a better coating when acidified. In addition, the tb surface area ride of the 'Nessite has a specific surface area greater than about 15 square meters per gram, more preferably greater than square meters per gram, more preferably greater than 400 square meters per gram. The nepheline is preferably a narrow particle size distribution, i.e., polydispersity is 2.0 or less, and preferably 15 or less. If desired, 10 200948871 may add larger cerium oxide particles' in an amount that does not detract from the coatability of the composition on the selected substrate without reducing transmission and/or hydrophilicity. Inorganic ceria sols in aqueous media are well known in the art and are commercially available. The cerium oxide sol in water or water-alcohol solution can be traded under the trade name LUDOX (manufactured by EI duPont de Nemours and Co., Inc., Wilmington, Del. USA), NYACOL (available from Nyacol Co) Ashland, MA. Or NALCO (prepared by Ondea Nalco Chemical Co., Oak Brook, 111. USA). A useful cerium oxide sol is NALCO 2326, which has an average particle size of 5 nm 'pH of 10.5 and a solids content of 15 The wt.% of the dioxide is well obtained. Other commercially available cerium oxide nanoparticles include "NALC0 1115" and "NALC 〇 113 可" available from NALCO Chemical Co., available from Re_

Corp.的「Remasol SP30」和可購自£丄Du p〇nt如价咖邮c〇，^ 的「LUDOXSM」。Corp.'s "Remasol SP30" and "LUDOXSM" are available from £丄Du p〇nt for free.

也可以使用不含水的二氧切轉（也稱作二氧化料機溶膠>’其是二氧化雜膠分散體，其中液相為有機溶劑或含水有機溶劑。在本發明时射，選擇二氧切轉使得其液她乳液相容，並且其液相通常是水絲水的有機溶劑穩定之二氧切奈絲子應當麵麵溶_如㈣卿^前首先賊化。在酸化之前進行稀釋可能產生差或不均勻岭層十穩定之二氧化石夕奈米粒子通常可以任何順序稀釋和酸化。戈如果需要，可以添加較大的二氧化石夕粒子，其含透射率值和/或嘯生質。這些另外的二氧化矽粒子通;具:大: 200948871 40〜100奈米，其中較佳為50〜100奈米的平均一次粒度，並且相對於小於40奈米的一氧化珍奈米粒子之重量，以〇.2: 99.8〜99 8 : 0.2的比例使用。較大的粒子較佳以1 : 9〜9 : 1之比例使用。通 • 常二氧化石夕粒子（即<40奈米和較大的二氧化石夕粒子之總和）在組 • 合物中的總重量為〇.1〜4〇 wt.%，其中較佳為树％，最佳為 2〜7 wt.% 〇塗料組合物包含pKa (H2〇) $3.5，其中較佳為pKa<2.5，最 ❹ 佳為PKa小於1的酸。有用的酸包括有機酸和無機酸，其實例可以為草酸、檸檬酸、H2S〇3、H3PO4、CF3C02H、HC1、HBr、HI、 HBr03、丽〇3、hC104、H2S04、CH3S03H、CF3S03H、CF3C02H 和 CH3S〇2〇H。最佳的酸包括 Ha、hn〇3、h2S04 和 h3po4。在一些實細*方式中，需要提供有機酸和無機酸的混合物。在一些實施方式中，可以使用包含pKa$3.5 (較佳為pKa<2.5，最佳為pKa _ 小於1)的酸和少量pKa>〇之其他酸的酸混合物。已經發現pKa>4 的弱酸’例如乙酸’不能提供具有所需透射度、可清潔性和/或耐久性性質的均勻塗層。特別地’含有弱酸例如乙酸之塗料組合物通常在基體的表面上團結成珠。塗料組合物通常包含足量的酸，以提供小於5的pH，其中較佳為小於4的PH，最佳為小於3的pH。在一些實施方式中，已經發現在將pH降低到小於5之後，可以將塗料組合物之pH調節到Ρίί 5〜6。這樣可以塗覆對pH更敏感的基體。四烧氧基偶聯劑例如四乙氧基矽烷（TE〇s)，和低聚形式例 12 200948871 罐:錢(例如聚(二乙氧基嫩))，二:切奈米粒子之間的結合。塗料組合物中包括的偶聯2 ’以防止破壞塗層的減反射性或防霧性質。偶聯劑的 Γ:二確定，其取決於偶聯劑的特性、分子量和折射率。偶㈣，如果存在，通常以二氧化石夕奈米粒子漠度的0 ::广，更佳以二氧化伽子的約丨〜15It is also possible to use a non-aqueous dioxygen (also referred to as a dioxide machine sol > 'which is a dioxide dispersion in which the liquid phase is an organic solvent or an aqueous organic solvent. In the present invention, the second is selected Oxygen chopping makes the liquid her emulsion compatible, and the liquid phase is usually the organic solvent stable of the water-line water. The dioxetane should be surface-soluble. For example, (4) before the first ^ thief. Dilute before acidification It is possible to produce a poor or inhomogeneous ridge layer of ten-doped oxidized cerium nanoparticles which can be diluted and acidified in any order. If desired, larger cerium oxide particles can be added, which contain transmittance values and/or whistle. Biomass. These additional cerium oxide particles pass; have: large: 200948871 40~100 nm, of which an average primary particle size of 50 to 100 nm is preferred, and compared to less than 40 nm of oxidized Jane The weight of the particles is used in a ratio of 〇.2: 99.8 to 99 8 : 0.2. The larger particles are preferably used in a ratio of 1: 9 to 9: 1. The normal arsenic dioxide particles (ie < 40 The sum of nano and larger dioxide dioxide particles in the group) The total weight in the composition is 〇1 to 4 〇 wt.%, wherein preferably the tree %, preferably 2 to 7 wt.%, the 〇 coating composition contains pKa (H2 〇) $3.5, of which pKa< 2.5, most preferably an acid having a PKa of less than 1. Useful acids include organic acids and inorganic acids, examples of which may be oxalic acid, citric acid, H2S〇3, H3PO4, CF3C02H, HC1, HBr, HI, HBr03, 丽〇 3, hC104, H2S04, CH3S03H, CF3S03H, CF3C02H and CH3S〇2〇H. The best acids include Ha, hn〇3, h2S04 and h3po4. In some real* methods, it is necessary to provide a mixture of organic and inorganic acids. In some embodiments, an acid mixture comprising an acid having a pKa of 3.5 (preferably pKa < 2.5, optimally pKa _ less than 1) and a small amount of pKa > other acids may be used. A weak acid of pKa > 4 has been found. For example, acetic acid 'does not provide a uniform coating with the desired transmission, cleanability and/or durability properties. In particular, coating compositions containing weak acids such as acetic acid typically unite into beads on the surface of the substrate. Coating compositions are typically Contains a sufficient amount of acid to provide a pH of less than 5, of which It is a pH of less than 4, preferably a pH of less than 3. In some embodiments, it has been found that after lowering the pH to less than 5, the pH of the coating composition can be adjusted to Ρίί 5~6. pH more sensitive substrate. Four alkoxy coupling agents such as tetraethoxy decane (TE〇s), and oligomeric form Example 12 200948871 Cans: money (eg poly(diethoxy)), two: cut The combination of nanoparticles. The coupling 2' included in the coating composition to prevent damage to the coating's anti-reflective or anti-fog properties. The enthalpy of the coupling agent is determined by two depending on the characteristics, molecular weight and refractive index of the coupling agent. Even (four), if present, usually with a gradient of 0:::,,,,,,,,,,,,,,,,,,,,,

本A開中的製品是帶有二氧切奈麵子妙體的連結構之基體。奈練子，射紐為具有4G奈絲更小的平均— 次粒度。其平均粒度可赌用穿透式電子酿鏡败。此處所用的術語「連續」是指在霜網狀結構塗覆的區_，幾乎沒有中斷和間隙地覆蓋基體的表面。娜「驗結構」是指連接起形成多孔三糊狀結構的奈綠子之料體和凝聚體。術語「一次粒度」是指未㈣之二氧切單鍊子的平均錢。圖1顯示了來自實施例78之本發明的塗層製品。由其可見，單體二氧化㈣錄子與相鄰的二氧化料米粒子相連接。塗層疋均勻的。相反’圖2顯示了在驗性pH值中含有乙醇之塗層，此塗層是不均勻的，單體粒子與相鄰粒子不相連接。術語「多孔」是指奈米粒子形成連續塗層時，二氧化矽奈米粒子之間存在的空隙。對於單層塗層，已知為了使在空氣中透過光學透明之基體的光透射最大化和基體反射最小化，塗層的折射率應當盡可能接近等於基體之折射率的平方根，塗層的厚度應當 13 200948871 是入射光之光波長的四分之_ 〇/4)。塗層中的空隙提供了在二氧化石夕奈米粒子之間之多個亞波長間隙，其中折射率（rj)突铁從空氣的折料㈤，改變為金魏化物粒子的折群（例如對於二氧化石夕RK44)。通過調節空隙率，可以產生具有非常接近基體的折射率之平方根_算折射率之塗層（如制專利號 4风333 (Lange等）中所示，引入此處作為參考）。通過使用具有最佳折射率的歸’在料於人射光的光波長之四分之一的塗層厚度時，财塗層基_光其透射百分特以最大化，反射得以最小化。其中較佳地，當乾操時，網狀結構具有約25〜45體積百分比，更佳為約30〜40體積百分比的孔隙率。在一些實施方式中，孔隙率可能更高。孔隙率可以依照已公佈的方法由塗層之折射率計算，例如W. L. Bragg，a. b. Pippard，Acta咖灿嗯叩㈣第6 卷’第865頁（1953)，引入此處作為參考。使用二氧化石夕奈米粒子，這種孔_提供了具有以〜^的折射率之塗層，其中較隹為1.25〜1.36的折射率之塗層，約等於聚酯、聚碳酸酯和聚甲基丙烯酸曱s旨基體的折射率之平方根。例如，折射率為L25〜i 36 的多孔二氧化矽奈米粒子塗層當以1000〜2〇〇〇A的厚度塗覆在聚對苯二甲酸乙二醇醋基體（RI=1.⑷上時’能夠提供高度減反射的表面。塗層厚度可以更高，高至幾微米或密耳（mils)厚，這取決於應彳列如為了易於清潔去除不需要的微粒而不是減反射。當塗層厚度提高時，可以預見其機械性質可能改進。 14 200948871 在-些實施方式中’本發明的製品包括基體，其實質上可以是任意結構，透_到不透_，聚合物、玻璃、H該屬的， •具有平坦、料讀_微，且在其上職凝集的三氧化石夕奈綠子之連軸狀結構。#塗層施加到透明基體切實現光透射。率提高時’在至少400〜700奈米之間的波長範圍之廣度上取決 =層的基體’塗層製品較佳域生法向人射光的透射率總平均 ❹提问至7 2/〇且直至南達10%或更高。在進入光譜的紫外和/或紅外部分之波長下也可以觀察到透射率的提高。當在550奈米測疋時’知加到域射基體的至少—面上為佳，塗料組合物將基體的透射百分比提南至少5% ,較佳為1〇%。除了對用其塗覆的基體提供減反射性之外，本發明的塗料組合物逛為基體提供親水性’有利於狀防雜#。在接觸對製品上的直接重複人為吹氣之後和/在將製品保持在「蒸汽」喷嘴上之 ❹後如果塗層的基體抵抗小冷凝水滴之形成，其密度足以顯著降低塗層基體透明度、使得其不能充分看透，那麼認為塗層是防霧的gp使在塗層基體上形成均句水膜或少量大水滴，但只要塗層，土體的透明度/又有顯著降低使得其不易看透，仍可以認為塗料組口物疋P方霧的。在很多情況下，在基體接觸「蒸汽」喷嘴之後，不G顯著降低基體之透明度的水膜仍會保留。在復夕種情况下，如果製品產生光散射或眩光或在製品表面上开乂成務，而導致其模糊之趨勢可以降低的話，那麼光學透明之製°°的仏值將會提高。例如，防護性眼鏡（護目鏡、面罩、頭盔 15 200948871 等^鏡片、建築玻璃窗、裝_破璃框、機動車輛窗戶和撞風罩都:以造成干擾和破·眩光的方式散射光。使料樣之製品也曰又到在h表面上㊉成水蒸㈣的有害影響。縣的是，在較佳的實施方式中’本發明的塗層製品具有傑出之防霧性質，同時還另外具有大於90⑽55〇奈米光雜率。 ❹ 聚合基體可以包括聚合片、職模糖料。在—些實施方式中，其中需要提高透射率’基體是透明的。術語「透明」是指透過至少85%的可見光譜（約·〜奈米波長）中之入射光。透明基體可以是彩色或無色的。在其他實施方式中，其t需要提高親水性，基體起初可以是疏水的。可以通過多種塗覆丨法將組合物施加到各種各樣的基體上。此處所用的「親水性」僅用於表示熱塑性聚合物層的表面性質，即其被水〉谷液潤濕，並不表示層是否吸收水溶液。因此，無 0 5金層對水溶液是不可滲透的還是可滲透的，熱塑性聚合物層都可以表示為親水的。在其上水或含水溶液之液滴表現出小於5〇。的靜恶水接觸角之表面被稱作是「親水的」。疏水基體具有5〇。或更大的水接觸角。此處所述之塗層可以將基體的親水性提高至少1〇。， * 其中較佳為提高至少20。。本發明之塗料組合物可以施加的基體，其中較佳為對可見光是透明或半透明的。其中較佳的基體由以下製成：聚酯（例如聚對苯二曱酸乙二醇酯、聚對苯二甲酸丁二醇酯）、聚碳酸酯、聚稀丙基二乙二醇碳酸酯、聚丙烯酸酯例如聚甲基丙烯酸甲酯、聚苯 16 200948871 乙烯、聚颯、聚蝴、號環氧聚合物、與聚二胺的環氧加成物、聚二硫盼、聚乙烯共聚物、氟化表面、纖維素醋例如乙酸醋和丁 _、玻璃、喊、有機和無機複合表面等，包括其共混物和層壓物。 ❹ ❹ 通常基體是材料的膜、#、域長方塊之形式，可以是製品的-部分，製品例如制、賴_t、裝飾性麵框、機動: 輛窗戶和觀罩’和防護性眼鏡，例如手術面罩和麵屏。可選如果需要，麵可以健蓋製品的—部分，例如僅賴面罩中轉睛直接相鄰的部分。基體可以是平坦的、f曲的或有形狀的。待塗層的製品可輯過吹塑、麟、擠出或注塑製備。〜用本發明之減反射、防霧組合物塗覆的製品，例如一次性手办面罩和面罩，其中較佳為儲存在降低魏暴露和防止污染的獨 =吏用包裝中，續止_师降低。可域使_製品在不用 1，較佳以與保護和完全㈣產品不會暴露於環境的包裝結合使 ^於構成包裝的㈣應當由無污染轉構成。已經發現某些㈣會導致防雜㈣部分或完全鼓。辭沒雜何理論限八旦目u為包含增塑劑、催化劑和其他—旦絲會揮發的低刀里物質之材料會被吸收到塗層中並導致防霧性質的降低。及且本發明提供了防護性眼鏡，例如手術面罩和麵屏，以，、減反射性和防霧性質的鏡片、窗戶和擔風罩。為具i其Γ實施方式中，基體不必須是透明的。已經發現組合物為基體例如用赠圖和標牌之柔_膜提供了容易清潔的表面。 200948871 柔㈣膜可以由聚醋例#聚對苯二甲酸乙二醋或聚稀煙例如聚两烯（PP)製成，聚乙烯（PE)和聚氣乙烯（PVC)是特別佳的。可以使用常規成膜技術，例如將基體樹脂擠出成膜和可選將擠出 V 的膜單軸或雙軸取向，來將基體形成臈。使用例如化學處理、電 * 暈處理例如空氣或氮氣電暈、等離子體、火焰或光化輕射，可以處理基體以提局基體和硬塗層之間的黏合性。如果需要，也可以在基體和塗料組合物之間施加可選的連接層以提高層間黏合性。也可以使用上述處理方法處理基體的另一側，以提高基體和黏人劑之間的黏合性。如本領域已知的那樣，基體可以帶有圖案，例如單詞或符號。在一些貝施方式中，塗料組合物提供了改進的可清潔性且提供了堅實之耐磨層，保護基體和下面的_顯示不受例如劃痕、磨損和溶縱朗造成的損害。「可清潔的」是指_組合物在固 ❹化後’提供耐油和耐汗性，以幫助塗層製品不受暴露於污染物例如油或外來的汗物之污染。塗料組合物也可以使硬塗層如果被弄癖時更容I清潔m要在水巾鮮沖洗以去除污染物。 . 為了餘合物從含水祕巾均勻塗覆顺水紐上，增加基體的表面此和/或降低塗料組合物之表面張力會是適合的。通過在 k覆之别使用電暈放電或火焰處理方法氧化基體表面，可以提高 2月b ° ^些方法還可以改進塗層與基體雜合。其他能夠提高 *之表面此的方法包括使用底塗層，例如聚偏二氣乙烯的薄塗層。志| -Γ ^ 有，可以通過添加低級醇（c〗〜c8)降低塗料組合 18 200948871 卜、/ °然而，在—些情況下，為了對所需性質提高塗層 '、1·生和為了雜製品由水驗或水醇溶液得到的均句塗層，添加潤濕劑可能有益，其通常是界面活性劑.。此處所㈣術語「界硫_」是指铜—分子中包含親水 (極I·生）和疏水（雜性）區域的分子，其能夠降健料溶液之表面張力。有用的界面活性劑可以包括US6,040,053 (Scholz等）公開的那些，通過參考引入此處。對於一氧化石夕奈米粒子的通常濃度（例如相對於總塗料組合物為約0·2〜15 wt.%)，大多數界面活性劑含量小於塗料組合物約〇·1 wt.%，其中較佳為約〇.〇〇3〜〇.〇5 ,以保持塗層的減反射性質。應當指出對於一些界面活性劑，在超過實現防霧性質需要的濃度下，會得到多斑點之塗層。當為了提咼所形成的塗層之均勻性而添加時，塗料組合物中的陰離子界面活性劑是為佳。有用的陰離子界面活性劑包括但不限於具有包含下述分子結構的那些：（1)至少一個疏水部分，例如約Q〜約Qo的院基、院芳基和/或稀基，（2)至少一個陰離子基團’例如硫酸根、續酸根、填酸根、聚氧化乙烯硫酸根、聚氧化乙烯磺酸根、聚氧化乙烯磷酸根等，和/或（3)這樣的陰離子基團的鹽，其中鹽包括驗金屬鹽、銨鹽、叔氨基鹽等。有用的陰離子界面活性劑的代表性商品實例包括月桂基疏酸鈉，以商品 TEXAP0N L-100 獲自 Henkel he.，Wilmington, Del. ’ 或以商品 POLYSTEP B-3 獲自 Stepan Chemical Co” Northfield，111.;月桂醚硫 19 200948871 酸納，以商品 POLYSTEP B-12 獲自 Stepan Chemical Co·，Northfield, 111.;月桂基硫酸銨，以商品STANDAPOL A獲自Henkel Inc.， Wilmington，Del.;和十二烷基苯磺酸鈉，以商品SIPONATE DS-10 • 獲自 Rhone-Poulenc, Inc.，Cranberry, N.J.。 . 在塗料組合物不包含界面活性劑或在需要改進塗層均句性的情況下，添加另一種潤濕劑可能是有益的，包括不會賦予耐久之防霧性質的那些，以便確保製品來自水或水醇溶液的均勻塗層。〇 .曰有用之满屬劑的實例包括聚乙氧基化的烧基醇（例如可從iciThe product of this A is a matrix with a structure of a dioxetane face. Naizheng, the shot is a smaller average-sub-grain size with 4G nanowires. Its average particle size can be squandered with a penetrating electronic brewing mirror. As used herein, the term "continuous" means the area covered by the frost network structure, covering the surface of the substrate with almost no interruptions and gaps. Na "test structure" refers to a body and agglomerates of nemed greens that form a porous three-paste structure. The term "one-time particle size" refers to the average amount of the undioed single chain of the (four). Figure 1 shows a coated article of the invention from Example 78. It can be seen that the monomeric (4) recording is linked to the adjacent rice dioxide particles. The coating is uniform. Conversely, Figure 2 shows a coating containing ethanol at an illustrative pH. The coating is not uniform and the monomer particles are not connected to adjacent particles. The term "porous" refers to a void existing between the cerium oxide nanoparticles when the nanoparticles are formed into a continuous coating. For single layer coatings, it is known that in order to maximize the transmission of light through the optically transparent substrate in air and to minimize substrate reflection, the refractive index of the coating should be as close as possible to the square root of the refractive index of the substrate, the thickness of the coating. It should be 13 200948871 is the quarter of the wavelength of the incident light _ 〇 / 4). The voids in the coating provide a plurality of sub-wavelength gaps between the SiO2 particles, wherein the refractive index (rj) spurs change from the air (f) to the group of gold-based particles (eg For the oxidized stone eve RK44). By adjusting the void ratio, it is possible to produce a coating having a square root-refractive index of refractive index very close to the substrate (as shown in the patent No. 4 333 (Lange et al.), incorporated herein by reference). By using a coating thickness having a refractive index of one quarter of the wavelength of light emitted by human light having the optimum refractive index, the transmittance of the coating layer is maximized and the reflection is minimized. Preferably, the mesh structure has a porosity of about 25 to 45 volume percent, more preferably about 30 to 40 volume percent, when dry. In some embodiments, the porosity may be higher. Porosity can be calculated from the refractive index of the coating in accordance with published methods, for example, W. L. Bragg, a. b. Pippard, Acta, et al., Vol. 6, pp. 865 (1953), which is incorporated herein by reference. Using a cerium oxide nanoparticle, the pore _ provides a coating having a refractive index of 〜, wherein a coating having a refractive index of 1.25 to 1.36 is approximately equal to polyester, polycarbonate, and poly. The yttrium methacrylate is the square root of the refractive index of the matrix. For example, a porous cerium oxide nanoparticle coating having a refractive index of L25 to i 36 is coated on a polyethylene terephthalate substrate (RI = 1. (4) at a thickness of 1000 Å to 2 Å. Time 'can provide a highly anti-reflective surface. The thickness of the coating can be higher, up to a few microns or mils thick, depending on the array, such as for easy cleaning to remove unwanted particles rather than anti-reflection. When the thickness of the coating is increased, it is foreseen that its mechanical properties may be improved. 14 200948871 In some embodiments, the article of the invention comprises a matrix which may be of virtually any structure, transparent, polymer, glass, H. The genus, • has a flat, material read _ micro, and the axillary structure of the smectite smectite green smectite. # Coating applied to the transparent substrate cut to achieve light transmission. In the breadth of the wavelength range between at least 400 and 700 nm, depending on the thickness of the layer of the substrate, the coated article is better than the total average transmittance of the human light, and the question is to 7 2/〇 and up to 10% in the south. Or higher. Waves entering the ultraviolet and/or infrared portion of the spectrum The increase in transmittance can also be observed in the long period. When the 550 nm is measured, it is better to add at least the surface of the matrix, and the coating composition increases the transmission percentage of the substrate by at least 5%. In addition to providing anti-reflective properties to the substrate coated therewith, the coating composition of the present invention provides hydrophilicity to the substrate to facilitate the prevention of the appearance of the product. After the gas and/or after the article is held on the "steam" nozzle, if the substrate of the coating resists the formation of small condensed water droplets, the density of which is sufficient to significantly reduce the transparency of the coating matrix, such that it is not sufficiently see through, then the coating is considered The anti-fog gp forms a uniform water film or a small amount of large water droplets on the coating substrate, but as long as the coating, the transparency of the soil is significantly reduced, making it difficult to see through, it can still be considered that the coating group is 疋P square fog. In many cases, after the substrate is in contact with the "steam" nozzle, the water film that does not significantly reduce the transparency of the substrate will remain. In the case of the eve, if the product produces light scattering or glare or on the product table If the trend of ambiguity is reduced, the ambiguity of the optically transparent system will be improved. For example, protective glasses (goggles, masks, helmets 15 200948871, etc.) Glass windows, _ _ glass frame, motor vehicle windows and hoods: scatter light in a way that causes interference and glare. The product of the sample is also detrimental to the steam on the surface of the h (four) The effect is that, in a preferred embodiment, the coated article of the present invention has excellent anti-fog properties while additionally having a photon ratio of more than 90 (10) 55 Å. 聚合 The polymeric matrix may include a polymeric sheet, a functional sugar. In some embodiments, where the transmittance needs to be increased, the substrate is transparent. The term "transparent" refers to the transmission of incident light in at least 85% of the visible spectrum (about ~ nanometer wavelength). The transparent substrate can be colored or colorless. In other embodiments, the t needs to increase hydrophilicity and the matrix may initially be hydrophobic. The composition can be applied to a wide variety of substrates by a variety of coating methods. As used herein, "hydrophilic" is used merely to indicate the surface properties of a thermoplastic polymer layer, i.e., it is wetted by water & gluten, and does not indicate whether the layer absorbs an aqueous solution. Thus, the gold layer is impermeable or permeable to the aqueous solution, and the thermoplastic polymer layer can be expressed as hydrophilic. The droplets in the water or aqueous solution thereof exhibit less than 5 Å. The surface of the contact angle of the static water is called "hydrophilic". The hydrophobic matrix has 5 Å. Or a larger water contact angle. The coatings described herein can increase the hydrophilicity of the matrix by at least 1 Torr. , * Which is preferably increased by at least 20. . The coating composition of the present invention can be applied to a substrate wherein it is preferably transparent or translucent to visible light. Among the preferred substrates are made of polyester (e.g., polyethylene terephthalate, polybutylene terephthalate), polycarbonate, poly(propylene carbonate) carbonate. Polyacrylate such as polymethyl methacrylate, polyphenyl 16 200948871 ethylene, polyfluorene, poly butterfly, epoxy polymer, epoxy adduct with polydiamine, polydithioethylene, polyethylene copolymer Fluorinated surfaces, cellulosic vinegars such as acetic acid and vinegar, glass, shouts, organic and inorganic composite surfaces, and the like, including blends and laminates thereof. ❹ ❹ Usually the substrate is in the form of a film of material, #, a long square, which can be a part of a product, such as a product, a lai, a decorative frame, a maneuver: a window and a hood, and protective spectacles. For example, surgical masks and face screens. Optionally, the face can be used to cover the part of the article, for example, only the portion of the mask that is directly adjacent to the eye. The substrate can be flat, f-curved or shaped. The article to be coated can be prepared by blow molding, lining, extrusion or injection molding. - articles coated with the anti-reflection and anti-fog composition of the present invention, such as disposable hand masks and face masks, wherein it is preferably stored in a package for reducing exposure and preventing contamination, and continuing to reduce. The _ product can be used in the absence of 1, preferably in combination with the packaging that protects and completely (4) the product is not exposed to the environment, so that (4) constituting the package should be composed of non-contaminated conversion. It has been found that some (four) can lead to the prevention of (46) partial or complete drumming. There is no limit to the theory. The material of the low-knife material, which contains plasticizers, catalysts, and other materials, will be absorbed into the coating and cause a decrease in anti-fog properties. And the present invention provides protective spectacles such as surgical masks and face shields, lenses for anti-reflective and anti-fogging properties, windows and windshields. In the embodiment, the substrate does not have to be transparent. It has been found that the composition provides a surface that is easy to clean, such as a soft film of a gift and a sign. 200948871 The soft (four) film can be made of polyacetate example #polyethylene terephthalate or poly-smoke such as polydiene (PP), and polyethylene (PE) and polyethylene (PVC) are particularly preferred. The substrate can be formed into a crucible using conventional film forming techniques, such as extruding a matrix resin into a film and optionally uniaxially or biaxially orienting the film of the extruded V. The substrate can be treated to improve the adhesion between the substrate and the hard coat layer using, for example, chemical treatment, electro-halation treatment such as air or nitrogen corona, plasma, flame or actinic light. If desired, an optional tie layer can also be applied between the substrate and the coating composition to improve interlayer adhesion. It is also possible to treat the other side of the substrate by the above treatment method to improve the adhesion between the substrate and the adhesive. The substrate can be provided with a pattern, such as a word or symbol, as is known in the art. In some Besch modes, the coating composition provides improved cleanability and provides a solid abrasion resistant layer that protects the substrate and underside from damage such as scratches, abrasion and dissolution. "Cleanable" means that the composition provides oil and sweat resistance after solidification to help protect the coated article from exposure to contaminants such as oil or foreign sweat. The coating composition can also be used to make the hard coat more clean if it is smashed. It may be desirable to increase the surface of the substrate and/or reduce the surface tension of the coating composition in order for the remainder to be uniformly coated onto the water from the aqueous skin. By oxidizing the surface of the substrate by corona discharge or flame treatment at the k-coating, it is possible to increase the thickness of the substrate by a factor of 2 b. These methods can also improve the hybridization of the coating with the substrate. Other methods that improve the surface of this include the use of an undercoat such as a thin coating of polyvinylidene dioxide.志| -Γ ^ Yes, it is possible to reduce the coating composition by adding a lower alcohol (c) ~ c8) 2009, 2009, 871, / ° However, in some cases, in order to improve the coating on the desired properties ', 1 · raw and A uniform coating obtained from a water test or a hydroalcoholic solution. It may be beneficial to add a wetting agent, which is usually a surfactant. (4) The term "intermediate sulfur" refers to a molecule containing a hydrophilic (polar I.) and hydrophobic (hetero) region in a copper-molecule, which is capable of lowering the surface tension of a solution. Useful surfactants can include those disclosed in U.S. Patent No. 6,040,053 (Scholz et al.) incorporated herein by reference. For a typical concentration of nitric oxide ceram nanoparticles (e.g., about 0.2 to 15 wt.% relative to the total coating composition), most of the surfactant is less than about 1 wt.% of the coating composition, wherein It is preferably about 〇〇.〇〇3~〇.〇5 to maintain the anti-reflective properties of the coating. It should be noted that for some surfactants, a more spotted coating will be obtained at concentrations above that required to achieve anti-fog properties. Anionic surfactants in the coating composition are preferred when added for the purpose of improving the uniformity of the coating formed. Useful anionic surfactants include, but are not limited to, those having a molecular structure comprising: (1) at least one hydrophobic moiety, such as a hospital base, a aryl group and/or a dilute group of from about Q to about Qo, and (2) at least An anionic group such as a sulfate, a sulphate, a sulphate, a polyethylene oxide sulphate, a polyoxyethylene sulfonate, a polyoxyethylene phosphate, etc., and/or a salt of such an anionic group, wherein the salt Including metal salts, ammonium salts, tertiary amino salts and the like. Representative commercial examples of useful anionic surfactants include sodium lauryl sulfate, available from Henkel He., Wilmington, Del. 'in commercial TEXAP0N L-100 or from Stepan Chemical Co" Northfield under the trade POLYSTEP B-3. 111.; lauryl ether sulfur 19 200948871 soda, available from Stepan Chemical Co., Northfield, 111.; ammonium lauryl sulfate, available from Henkel Inc., Wilmington, Del.; Sodium dodecylbenzene sulfonate, available from Rhone-Poulenc, Inc., Cranberry, NJ, under the trade name SIPAATE DS-10. . . . in coating compositions that do not contain surfactants or where it is desirable to improve the uniformity of the coating. It may be beneficial to add another wetting agent, including those that do not impart durable anti-fogging properties, in order to ensure that the article is derived from a uniform coating of water or hydroalcoholic solution. Examples of useful useful agents include Polyethoxylated alkyl alcohol (for example from ici

Americas，Inc 商業獲得的「Brjj™ 30」和「Brjj™ 35」，和可從 Union Carbide Chemical and Plastics Co.商業獲得的「Tergitol™ TMN-6™Americas, Inc. commercially acquired "BrjjTM 30" and "BrjjTM 35", and "TergitolTM TMN-6TM" commercially available from Union Carbide Chemical and Plastics Co.

Specialty Surfactant」）、聚乙氧基化烷基酚（例如來自Uni〇n CarbideSpecialty Surfactant"), polyethoxylated alkylphenols (eg from Uni〇n Carbide)

Chemicals and Plastics Co.的「TritonTMX-100」和來自 BASFC〇rp 的「Ic_lTMNP-70」）和聚乙二醇/聚丙二醇嵌段共聚物（可作為 ❹ 「Testromc™ 1502嵌段共聚物界面活性劑」、「Testr〇nicTM 9〇8傲段共㈣界面活性劑」和「piur〇nic™F38嵌段共聚物界面活性劑」商業獲自BASF, Corp.)。當然，任何添加的潤濕劑必須包括不會 .相害塗層之減反射性和防雜質的水準。通常潤__量小於，料組合物的約0.1 wt.%，其中較佳為根據二氧化料米粒子之含 f ’在塗料組合物的約_3〜0.05 wt.%之間。可以將塗層製品在尺中冲洗或/叉/包來去除過量之界面活性劑或潤濕劑。、且σ物其中較佳為使用常規技術塗覆在製品上，例如棒塗、塗簾塗輪轉凹版塗覆、喷塗或浸塗技術。較佳的方式包括 20 200948871 棒塗和魅，錢刀塗細釋厚度。為了確保膜的均勻潤濕’會轉在塗覆之前使用電暈放電献焰處理方法氧化表面。其倾触綠减喊財杜域縣偏二氣乙烯。聚本發明之塗層，其巾較佳以均⑽平均厚度施加，並變化^ 於約2〇〇 A’更佳為小於觸A，以避免塗層中可見的干擾色變化。最適的平均乾塗層厚度取決於具體之塗料組合物，但根據使用擴"TritonTM X-100" from Chemicals and Plastics Co. and "Ic_lTMNP-70" from BASFC〇rp) and polyethylene/polypropylene glycol block copolymer (available as Test "TestromcTM 1502 block copolymer surfactant" "Testr〇nicTM 9〇8 Pride (4) Surfactant" and "piur〇nicTM F38 Block Copolymer Surfactant" are commercially available from BASF, Corp.). Of course, any added wetting agent must include no anti-reflective and anti-impurity levels of the phase-damaging coating. Typically, the amount of wetting is less than about 0.1 wt.% of the composition of the composition, preferably between about _3 and 0.05 wt.% of the coating composition based on the f' of the rice dioxide particles. The coated article can be rinsed or/forked/packed in a ruler to remove excess surfactant or wetting agent. And the sigma is preferably applied to the article using conventional techniques, such as bar coating, curtain coating gravure coating, spray coating or dip coating techniques. The preferred method includes 20 200948871 stick coating and charm, and the money knife is applied to the thickness. In order to ensure uniform wetting of the film, the surface is oxidized using a corona discharge flame treatment method prior to coating. It touched the green and shouted the Du Duo County. In the coating of the present invention, the towel is preferably applied in an average thickness of (10) and varies by about 2 Å A', more preferably less than A, to avoid visible interference color changes in the coating. The optimum average dry coating thickness depends on the specific coating composition, but

Gaertner Scientific Coip Model No. L115C 定，通常塗層的平均厚度為5〇〇〜測A，其中較佳為75〇〜2_ 更佳為麵〜謂A。在棚之上和之下塗層的減反射性質會明顯減弱。然而’應當指出’儘管平均塗層厚度，其中較佳為均勾的，但實際之塗層厚度從塗層上的一個特定點到另個可以顯著變化。這種厚度的變化，#與視覺敏感的區域相關聯時，對塗層之寬頻減反射性質，實際上是有益的。本發明之塗層，其中較佳為塗覆在基體的兩面上。或者，本發明之塗層可以塗覆在基體的一面上。基體的相反面可以不塗覆，或用常規界面活性劑或聚合防霧組合物例如美國專利號 2,803,552、3,075,228、3,819,522、4,467,073 或 4,944,294 中所公開的那些（均通過參考引入此處）塗覆，或用減反射組合物例如美國專利號4,816,333中公開的減反射組合物或者j. D Mass〇在 Evaluation of Scratch Resistant and Anti-reflective Coatings for Plastic Lenses，」（同上）中多層塗層塗覆，兩者都通過參考引入此 21 200948871 處。較佳地，防霧塗層表面應當朝向較高濕度之方向，例如在面罩上具有防霧塗層的—面應#朝向佩戴者。相反面可以具有透明彈性和/或堅拿刃的塗層以對抗粒子磨損，和/或風吹碎裂。 . 「經塗覆’製品通常在2〇〜靴的溫度下在環流爐中乾燥。 .可以迴_性氣體。可賤—步提高溫度以加快乾_程，但必須加以小灿避免對基_财。在將紐組合物施加到基體上 0並乾燥之後，塗層較佳為包含約60〜95脱％ (更佳為約70〜92 wt.% )的二氧化石夕奈米粒子（通常為凝聚的），約〇. i〜烈机％ (更佳為約10〜25 wt.%)的四垸氧基石夕烧和可選約〇〜5机％ (更佳為約0.5〜2 wt.〇/0)的界面活性劑，和最多約5败％ (較佳為〇二〜2 wt.%)的潤濕劑。當將本發明的塗料組合物施加到基體上以提供減反射性質時’通過提高塗層基體之光透射率，降低了眩光。較佳地，當與》未塗層的基體相比時，塗層基體表現出在MO毫米（腿）處（例如’在此波長處人眼顯示光_視覺的峰回應），法向入射光透射率提冋至少3個百分點和多達1〇個百分點或更高。透射百分率取決於射角矛光的波長，使用通為「Haze an(jLuminous Transmittance ofGaertner Scientific Coip Model No. L115C, usually the average thickness of the coating is 5 〇〇 ~ measured A, of which preferably 75 〇 ~ 2 _ better face ~ said A. The antireflective properties of the coating above and below the shed are significantly reduced. However, it should be noted that despite the average coating thickness, which is preferably hooked, the actual coating thickness can vary significantly from one particular point on the coating to the other. This change in thickness, when associated with a visually sensitive area, is actually beneficial for the broadband anti-reflective properties of the coating. The coating of the present invention is preferably coated on both sides of the substrate. Alternatively, the coating of the present invention can be applied to one side of the substrate. The opposite side of the substrate may be uncoated, or coated with conventional surfactants or polymeric anti-fogging compositions such as those disclosed in U.S. Patent Nos. 2,803,552, 3,075,228, 3,819,522, 4,467,073, or 4,944,294, each incorporated herein by reference. Or a multi-layer coating in an anti-reflective composition such as the anti-reflective composition disclosed in U.S. Patent No. 4,816,333 or j. D Mass(R) in Evaluation of Scratch Resistant and Anti-reflective Coatings for Plastic Lenses, (supra), All of them are introduced by reference to this 21 200948871. Preferably, the surface of the anti-fog coating should be oriented in the direction of higher humidity, e.g., the surface of the anti-fog coating on the mask should face the wearer. The opposite side may have a coating of transparent elasticity and/or a gripping edge to resist particle wear, and/or wind blown. "Coated" products are usually dried in a circulating oven at a temperature of 2 〇 ~ boots. Can be returned to the _ sex gas. Can be 贱 - step to increase the temperature to speed up the dry process, but must be added to avoid the base _ After applying the composition to the substrate and drying, the coating preferably comprises about 60 to 95% by weight (more preferably about 70 to 92% by weight) of the cerium oxide nanoparticles (usually For condensed), about 〇. i~ 机% (more preferably about 10~25 wt.%) of tetradecyl oxy-stone and optionally about 〇~5 machine% (more preferably about 0.5~2 wt 〇/0) of a surfactant, and up to about 5% by weight (preferably 2 to 2 wt.%) of a wetting agent. When the coating composition of the present invention is applied to a substrate to provide anti-reflective properties Tempering reduces glare by increasing the light transmission of the coated substrate. Preferably, when compared to an uncoated substrate, the coated substrate exhibits at MO millimeters (legs) (eg 'at this wavelength The human eye shows the light_visual peak response), and the normal incident light transmittance is improved by at least 3 percentage points and as much as 1% or more. The percentage of transmission depends on the shot. Spear wavelength of light, through the use of "Haze an (jLuminous Transmittance of

Transparent Plastics」的 ASTJV[測試方法 D 1003-92 來確定，其通過參考引入此處。較佳地，使用55〇奈米光，當與未塗層的基體比較’塗層基體表現出透射百分率提高大於，更佳為大於 ’取佳為大於8%。當所需之用途涉及明顯的「離軸」（即非法向入射）觀看或不希望的反射時，特別是在反射接近或超過觀測 22 200948871 中的物體亮度之情況下，可以得到更大的可視性。如上所討論的本發明之塗料組合物翻驗㈣表面提供了防霧和減反射师。通過塗層對抗形成容㈣顯降缝層某體的透明度之水滴的傾向性，證明了防霧性質。來自例如人體呼吸的水蒸汽容料水膜之形式在塗層基體上凝結，而不是作為水滴。這麵⑽不會㈣降低基體崎晰度或透明度。Transparent Plastics" ASTJV [Test Method D 1003-92 to determine, which is incorporated herein by reference. Preferably, 55 nanometers of light is used, and the coated substrate exhibits a percent increase in transmission greater than, more preferably greater than, greater than 8% when compared to an uncoated substrate. Greater visibility can be obtained when the desired use involves significant "off-axis" (ie, illegal incident) viewing or unwanted reflections, especially if the reflection approaches or exceeds the brightness of the object in observation 22 200948871 Sex. The coating composition of the present invention as discussed above is provided with an anti-fog and anti-reflector. The anti-fog property is demonstrated by the tendency of the coating to resist the formation of water droplets of the transparency of the body of the body layer. The form of the water vapour water film from, for example, human respiration, condenses on the coating substrate rather than as water droplets. This side (10) does not (4) reduce the base roughness or transparency.

在很多實施方式中’本發明之塗料組合物都是耐儲存的，例如其不會凝膠’變料透明，或麵著劣化。此外，在报多實施方式中’使用此處所賴測試方法，塗層製品是财久的和耐磨損的。實施例材料二氧化石夕奈米粒子分散體為Nalco 1115tm (4奈米）、2326tm (5 奈米）、1〇3〇tm ( 13 奈米）、1〇5〇tm (20 奈米）、2327™ (20 奈米）、45 奈米和 93 奈米，獲自 Nalco Company，Naperville, IL。四乙氧基矽烷（TEOS，99.9% )獲自 Alfa Aesar，Ward Hill，ΜΑ。聚對苯二甲酸乙二醇酯膜獲自E. L Dupont de Nem〇urs， Wilmington，DE，商品名「Melinex 618」，具有5.0密耳的厚度和底塗之表面。聚碳酸酯膜以商品 LEXAN 8010 (〇.381-mm)、8010SHC (1.0-mm)和 QQ92 獲自 GE Advanced Materials Specialty Film and Sheet，Pittsfield，MA。 23 200948871In many embodiments, the coating compositions of the present invention are shelf-stable, e.g., they do not gel, the coating is transparent, or the surface is degraded. In addition, in the multi-implementation mode, the coated article is durable and wear resistant using the test method herein. EXAMPLES Materials The dispersion of the cerium oxide nanoparticles was Nalco 1115 tm (4 nm), 2326 tm (5 nm), 1 〇 3 〇 tm (13 nm), 1 〇 5 〇 tm (20 nm), 2327TM (20 nm), 45 nm and 93 nm, available from Nalco Company, Naperville, IL. Tetraethoxydecane (TEOS, 99.9%) was obtained from Alfa Aesar, Ward Hill, ΜΑ. The polyethylene terephthalate film was obtained from E. L Dupont de Nem〇urs, Wilmington, DE under the trade designation "Melinex 618" having a thickness of 5.0 mils and a primed surface. The polycarbonate film was obtained from GE Advanced Materials Specialty Film and Sheet, Pittsfield, MA, under the trade names LEXAN 8010 (〇.381-mm), 8010SHC (1.0-mm) and QQ92. 23 200948871

ByneUlOl™是聚乙烯共聚物，獲自 e_L DuPont deNemours & Co., Wilmington, Del °ByneUlOlTM is a polyethylene copolymer available from e_L DuPont deNemours & Co., Wilmington, Del °

Pellathene 2363TM 是聚醚基聚氨酯，獲自 Dow Chemical, ' Midland, MI。 ’ 聚氣乙烯膜是 3M( TM ) Scotchcal™ Luster Overlaminate 8519, 1.25 密耳，獲自 3M Company, St. Paul，MN。以全氟聚醚（PFPE)塗布的聚碳酸酯（實施例84)是指在其上具有全氟聚醚塗層的聚碳酸酯基體，依照11/828566 (jQun等，通過參考引入此處）的實施例1製備，使用包含〇 5wt%由製備2 得到之全氟聚醚的SHC-1200的溶液作為面塗。. 樣品製備：用去料水將二氧切奈綠子分親（實侧巾所示之尺寸）稀釋到5wt.〇/。’用濃HCL水溶液酸化到所述的阳值（通常〇為2·3)。對於-些實施例，用四乙氧基石夕烧或有機溶劑以表中所述之比例與酸化的二氧化石夕奈米粒子分散體（5被％)相混合。仙連賴⑴Geked eGate〇絲啊棒，幻密耳間 •隙和5机％二氧化⑦分散體（總二氧切重量）塗覆所述之基體，提供厚度在湖〜200奈米翻_乾塗層。將紐樣品加熱到8〇〜100°C、5〜10分鐘，以實現乾燥。透射率使用Varian Caiy 5E分光光度計，在靡的相對濕度下進行透射和反射測試。使用範圍為奈米〜5微米㈣的恤⑽亭 24 200948871Pellathene 2363TM is a polyether based polyurethane available from Dow Chemical, ' Midland, MI. The polyethylene gas film was 3M(TM) ScotchcalTM Luster Overlaminate 8519, 1.25 mils, available from 3M Company, St. Paul, MN. Polyfluoropolyether (PFPE) coated polycarbonate (Example 84) refers to a polycarbonate matrix having a perfluoropolyether coating thereon, in accordance with 11/828566 (jQun et al., incorporated herein by reference) For the preparation of Example 1, a solution containing 5% by weight of SHC-1200 of the perfluoropolyether obtained in Preparation 2 was used as the top coat. Sample preparation: Dilute the dioxetine greens (dimensions shown on the side towels) to 5 wt. 〇/ with dewatered water. ' Acidified to a positive value (usually 2 2·3) with a concentrated aqueous solution of HCL. For some of the examples, the acidified cerium oxide nanoparticles dispersion (5% by weight) was mixed with tetraethoxy cerium or an organic solvent at the ratios indicated in the table. Xian Lian Lai (1) Geked eGate 〇啊 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , coating. The sample is heated to 8 〇 to 100 ° C for 5 to 10 minutes to achieve drying. Transmittance Transmission and reflection tests were carried out at a relative humidity of helium using a Varian Caiy 5E spectrophotometer. Use a shirt with a range of nanometers ~ 5 microns (four) (10) Pavilion 24 200948871

Ilia，Dimensi⑽ 5000 原子力顯微鏡（AFM)⑽挪 Instm_ts， Santa Barbara) ’收集原子力顯微鏡高度像和相位像。對聚對苯二甲酸乙二醇酯或玻璃上的塗層進行多角度橢圓偏振光譜儀 (M2000) >則®。在70。的入射角處進行3〇〇〜9〇〇奈米的測量。 . 在範圍内測定膜厚度，在555奈米處測定折射率值。接觸角測量使用通過獲自 MllllP〇re Corporation (Billerica，MA)的過濾體系過濾之原樣去離子水，在得自ASTPr〇ducts (腦红㈣皿）的產品編號VCA-2500XE之視頻接觸角分析儀上，對乾燥的塗層樣品進灯靜悲水接觸角測量。報導之數值是在液滴的右侧和左侧上測：§：的至少二個液滴之測量平均值，示於表中。對於靜態測量，液滴體積為IjjJL。防霧測試 ❹通過對朝向不含酒精的評估者之呼吸吹氣的塗層侧的即時外表變化來評估防霧性質。防霧性質評級如下： 5 =優秀 4=良好 • 3 =差耐久性測試 L過如實知例中所示’用乾和濕的KimwipeTM紙巾用力擦拭 k層表面來5平估機械耐久性。在表格中報導的數值表示可見地去塗層戶斤而之御^次數。使用光透射來確㈣層是否保留或除去。 25 200948871 容易清潔測試將髒柴油、植物油或肥皂施加在塗層表面上—段時間（2八梦到過夜）。然後，對污染區域進行水沖洗直至髒油或植物油完全去 -除。在應用的流速設定為每分鐘750毫升（750mL/min)時，記錄 * 消耗的時間。通常’水沖洗時間在1分鐘内。然後重複4〜5個、'主潔迴圈。通過清潔速度（時間）和在表面上的殘餘油來評估可清潔性。通過用濕Kimwipe™紙巾用力擦拭塗層表面來評價易清潔 ® 表面的機械耐久性。在以下對比例和實施例1-5中，用所示之5 wt.o/o奈米粒子一氧化矽組合物在pH 2〜3和1密耳（〜25微米）的塗層厚度备覆經電暈處理之聚對苯二曱酸乙二醇酯基體，在8〇〜1〇(rc乾燥5〜 10分鐘。使用前述測試方法測試塗層樣品的機械耐久性和透射率 k咼。結果示於表1。為了比較的目的，也測試了使用93奈米一 ❹氧化石夕的樣品。從測試結果中總結出：較小之粒度表現出提高的财久性。表1 ------- 實施例 ~~—----- 二氧化矽奈米粒子分散體機械耐久性 #擦拔—乾/濕 -------- 550奈米的△透射率（％) 對比例1 -------- 93奈米 1/1 --- 5.5 1 45奈米 1/1 4.5 2 ------ 加奈米 2/2 —---- 5.3 3 ------- 5奈米 11/>30 ~~-- 4.2 4 1 : 1比例混合的. 45奈米/20奈米 1/1 -~___ 4.7 ~~~~- "-----— 26 200948871 5 1 : 1比例混合的45奈米/5 ~~-- 6/>15 Ρ-—_ - 奈米 4.5 灿下實施例6〜8中，如前塗覆並甲酸乙二醇醋基體。在基體上不易塗覆45奈米或更大粒度的姑酸化分散體表2 實施例二氧化矽奈米粒子分散體 --~~-- 機械耐久性 550奈米的△透射 - 率（％) _ __4.5 4.5 6 5奈米粒子 --濕 ----—— 6/>9Π 7 1 : 1比例混合的 45奈米/20奈米 ~~--- 1/1 8 1 : 1比例混合的 45奈米/5奈米 --------— 4/>1〇 4.4 —------ 在以下實施例9〜20中’騎示之5桃％奈絲子二氧化石夕組合物在pH 2〜3和1密耳（〜％微米）的塗層厚度下，塗覆經電暈處理之賴苯二甲酸乙二_旨，在UG〜i2(rc乾燥％〇 K)分鐘。-些實_進—步包含所示比例細乙氧基魏。如前測試塗層樣品。從測試結果中總結出：添加四乙氧基石夕烧提高了塗層之财久性。表3 實施例 9 一氧化石夕奈米粒子分散體 1ΩΓ)0乂 z s太止夫，卜.卜機械財久性 -察拭—乾/濕 550 10 —/〇呼j常不贫术粒子 90% 45奈米奈米粒子， 10%TEOS 1/1 4/4 11 70% 45奈米奈米粒子， 30% TEOS 7/200 12 50% 45奈米奈米粒子， 12/200 1 13 50% TEOS 20奈米奈来齟子 ___2/2 ： 5.2 U 5.0 4.9 5.3 奈米的率（％) 27 200948871 14 90% 20奈米奈米粒子， 10%TEOS 6/200 4.7 15 70% 20奈米奈米粒子， 30%TEOS 10/200 22~~ 16 50% 20奈米奈米粒子， 50% TEOS 15/200 2.5 17 100% 5奈米奈米粒子 5/30 4.2 18 90% 5奈米奈米粒子， 10%TEOS 8/200 4.7 19 70% 5奈米奈米粒子， 30% TEOS 12/200 4.4 20 50% 5奈米奈米粒子， 50% TEOS 18/200 5.0' 在以下實施例21〜28中，用所示之5 wt.%混合奈米粒子二氧〇化矽組合物，在pH 2〜3和1密耳（〜25微米）的塗層厚度下，塗覆經電暈處理之聚對苯二曱酸乙二醇酯基體，在110〜12(TC乾燥5〜10分鐘。一些實施例進一步包含所示比例的四乙氧基矽烷。如前測試塗層樣品。從測試結果總結出：四乙氧基矽烷提高了混合粒子系統之耐久性。表4 ------- 實施例 ------ —氧化梦奈米粒子分散體機械财久性 550奈米的A透 ---—^ ----- #擦拭一乾/濕射率（％) 21 50% 45奈米， _____20奈米奈米粒子 1/1 5.3 22 45% 20奈米 45%45奈米奈米粒子， ___ 10% TEOS 6/60 5.9 23 35% 20奈米 35%45奈米奈米粒子， 30% TEOS 12/200 4.5 24 25% 20奈米 25% 45奈米奈米粒子， 50% TEOS 15/200 2.5 25 50% 45奈米， __奈米奈米粒子 5/15 4.2 28 200948871 26 45% 5奈米 45% 45奈米奈米粒子， 10%TEOS 6/200 6.2 27 35% 5奈米· 35% 45奈米奈米粒子， 30% TEOS 9/200 4.6 28 25% 5奈米 25%45奈米奈米粒子， 50% TEOS 13/200 3.1 在以下實施例29〜32中，用所示之5 wt.%奈米粒子二氧化石夕 ❹ 組合物’在pH 2〜3和1密耳（〜25微米）的塗層厚度下，塗覆未經處理之聚對苯二甲酸乙二醇酯基體，在11〇〜12〇。〇乾燥5〜 10分鐘。組合物進一步包含所示比例的四乙氧基石夕烧。如前測試塗層樣品。從測試結總結出：四乙氧基矽烷提高了塗層在未經處理之聚對笨二甲酸乙二醇醋上的财久性。表5Ilia, Dimensi (10) 5000 Atomic Force Microscopy (AFM) (10) Move Instm_ts, Santa Barbara) 'Collect the height and phase images of the atomic force microscope. Multi-angle ellipsometry (M2000) for polyethylene terephthalate or glass coatings. At 70. The measurement of the angle of incidence is 3 〇〇 ~ 9 〇〇 nanometer. The film thickness was measured in the range, and the refractive index value was measured at 555 nm. The contact angle measurement was performed using the deionized water filtered through a filtration system obtained from MllllP〇re Corporation (Billerica, MA), and the video contact angle analyzer of the product number VCA-2500XE obtained from ASTPr〇ducts (brain red (four) dish). Above, the dry coating sample was measured for the light and sad water contact angle. The reported values are measured on the right and left side of the drop: the measured average of at least two drops of §: are shown in the table. For static measurements, the drop volume is IjjJL. Anti-fog test 防 The anti-fog property was evaluated by an immediate appearance change on the coated side of the breath-blowing toward the non-alcoholic evaluator. The anti-fog property rating is as follows: 5 = Excellent 4 = Good • 3 = Poor Durability Test L. As shown in the example of the truth, wipe the k-layer surface with a dry and wet KimwipeTM paper towel to evaluate the mechanical durability. The values reported in the table indicate the number of times that the coating is visibly removed. Light transmission is used to determine if the (four) layer is retained or removed. 25 200948871 Easy cleaning test Apply dirty diesel, vegetable oil or soap to the surface of the coating – for a period of time (2 nights to overnight). Then, rinse the contaminated area until the dirty oil or vegetable oil is completely removed. When the applied flow rate is set to 750 ml per minute (750 mL/min), the time consumed for * is recorded. Usually the 'water rinse time is within 1 minute. Then repeat 4~5, 'main clean loops. The cleanability was evaluated by the cleaning speed (time) and residual oil on the surface. The mechanical durability of the Easy Clean ® surface was evaluated by wiping the surface of the coating with a wet KimwipeTM paper towel. In the following comparative examples and Examples 1-5, the 5 wt.o/o nanoparticle niobium oxide composition shown was applied at a coating thickness of pH 2 to 3 and 1 mil (~25 μm). The corona-treated polyethylene terephthalate substrate was dried at 8 Torr to 1 Torr (rc dried for 5 to 10 minutes. The mechanical durability and transmittance of the coated samples were tested using the aforementioned test methods. It is shown in Table 1. For the purpose of comparison, a sample using 93 nm of strontium oxide was also tested. It is concluded from the test results that the smaller particle size shows an increase in the longevity. Table 1 ---- --- Example ~~------ 二二粒子粒子粒子粒子粒子机械机械机械机械机械机械机械机械机械机械机械 — — — — 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 Proportion 1 -------- 93 nm 1/1 --- 5.5 1 45 nm 1/1 4.5 2 ------ Cana 2/2 —---- 5.3 3 --- ---- 5nm 11/>30 ~~-- 4.2 4 1 : 1 ratio mixed. 45nm / 20nm 1/1 -~___ 4.7 ~~~~- "---- -— 26 200948871 5 1 : 1 ratio mixed 45 nm/5 ~~-- 6/>15 Ρ--_ - nm 4.5 Can be applied as in Example 6~8, as before and coated with formic acid Glycol acetate matrix. It is difficult to coat a sub-acidified dispersion of 45 nm or larger on the substrate. Table 2 Example bismuth dioxide nanoparticle dispersion--~~-- △ transmission of mechanical durability of 550 nm - Rate (%) _ __4.5 4.5 6 5 Nanoparticles - Wet----- 6/>9Π 7 1 : 1 ratio of 45 nm / 20 nm ~~--- 1/ 1 8 1 : 1 ratio of 45 nm / 5 nm ------- - 4 / > 1 〇 4.4 ------- In the following Examples 9 to 20, 'riding the display 5 Peach Nyros sulphur dioxide dioxide composition coated with corona treated lysine at pH 2~3 and 1 mil (~% micron) coating thickness, in UG ~i2 (rc dry % 〇K) minutes. - Some real _ advance - step contains the proportion of fine ethoxy wei. As before the test coating sample. From the test results concluded: the addition of tetraethoxy zebra The longevity of the coating. Table 3 Example 9 Oxidized smectite particle dispersion 1 Ω Γ) 0乂zs too cough, Bu. Mechanical long-term - inspection wipe - dry / wet 550 10 - / 〇呼j often not poor particles 90% 45 nanometer nanoparticles, 10% TEOS 1/1 4/4 11 70 % 45 nanometer nanoparticles, 30% TEOS 7/200 12 50% 45 nanometer nanoparticles, 12/200 1 13 50% TEOS 20 nanonai scorpion ___2/2 : 5.2 U 5.0 4.9 5.3 Nai Rate of rice (%) 27 200948871 14 90% 20 nanometer nanoparticles, 10% TEOS 6/200 4.7 15 70% 20 nanometer nanoparticles, 30% TEOS 10/200 22~~ 16 50% 20 nm Nanoparticles, 50% TEOS 15/200 2.5 17 100% 5 nanometer nanoparticles 5/30 4.2 18 90% 5 nanometer nanoparticles, 10% TEOS 8/200 4.7 19 70% 5 nanometer nanoparticles , 30% TEOS 12/200 4.4 20 50% 5 nanometer nanoparticles, 50% TEOS 18/200 5.0' In the following Examples 21 to 28, the nanoparticle dioxin was mixed with 5 wt.% as shown. The bismuth composition is coated with a corona-treated polyethylene terephthalate substrate at a coating thickness of pH 2 to 3 and 1 mil (~25 μm) at 110 to 12 (TC). Dry for 5 to 10 minutes. Some embodiments further comprise the tetraethoxydecane in the ratios indicated. Test the coating sample as before. From the test results, it was concluded that tetraethoxy decane improved the durability of the mixed particle system. Table 4 ------- Example ------ - Oxidized Monname Particle Dispersion Mechanical Long-lasting 550 nm A-----^ ----- #擦一干/湿Rate (%) 21 50% 45 nm, _____20 nanometer nanoparticles 1/1 5.3 22 45% 20 nm 45% 45 nm nanoparticles, ___ 10% TEOS 6/60 5.9 23 35% 20 Nai Rice 35% 45 nanometer nanoparticles, 30% TEOS 12/200 4.5 24 25% 20 nm 25% 45 nanometer nanoparticles, 50% TEOS 15/200 2.5 25 50% 45 nm, __Nylon Nanoparticles 5/15 4.2 28 200948871 26 45% 5 nanometers 45% 45 nanometer nanoparticles, 10% TEOS 6/200 6.2 27 35% 5 nanometers · 35% 45 nanometer nanoparticles, 30% TEOS 9/200 4.6 28 25% 5 nanometers 25%45 nanometer nanoparticles, 50% TEOS 13/200 3.1 In the following Examples 29 to 32, the 5 wt.% nanoparticle dioxide is shown.组合 The composition 'coated with an untreated polyethylene terephthalate substrate at a coating thickness of pH 2 to 3 and 1 mil (~25 μm), at 11 Torr to 12 Torr. Dry for 5 to 10 minutes. The composition further comprises tetraethoxylated sinter in the indicated proportions. Test the coating sample as before. From the test results, it was concluded that tetraethoxy decane improved the long-term durability of the coating on the untreated poly(p-ethylene glycolate). table 5

實施例二氧化矽奈米粒子分散體機械对久性 #擦栻一乾/濕 550奈米的△透射率（％) 29 100% 5奈米奈米粒子 6/>30 3.5 30 90% 5奈米奈米粒手， 7/200 5.0 . 10% TEOS 31 .70% 5奈米奈米粒子， 10/200 4.0 30% TEOS 32 50% 5奈米奈米粒子， 18/200 3.5 1--------—.. 50% TEOS 在以下實施例33〜40中，用所示之5 wt.〇/0混合奈米粒子二氧化石夕組合物（含不同尺寸的混合物），在pH2〜3和1密耳（〜25 U米）的塗層厚度下，塗覆未經處理之聚對苯二甲酸乙二醇酯基 29 200948871 體，在80〜100°C乾燥5〜10分鐘。組合物進一步包含— 四乙氧基矽烷。如前測試塗層樣品。從測試結果中總鈇出例的氧基矽烷提高了混合粒子組合物在未經處理之聚對苯二甲酸乙^ 醇酯上的塗層耐久性。表6 實施例二氧化矽奈米粒子分散體機械耐久性在用乾Kimwipe強摩擦X次和用濕 Kimwipe強摩擦y 次後塗層剝落(χ/νΊ 550奈米的Α透射率（％) 33 50%45奈米奈米粒子， 50% 20奈米奈米粒子 1/1 4.5 34 45% 20奈米奈米粒子， 45%45奈米奈米粒子， 10%TEOS 4/12 5.1 35 35% 20奈米奈米粒子， 35% 45奈米奈米粒子， 30% TEOS 8/200 4.8 36 25% 20奈米奈米粒子， 25% 45奈米奈米粒子， 50% TEOS 12/200 3.1 37 50% 45奈米奈米粒子， 50% 5奈米奈米粒子 2/4 4.4 38 45% 5奈米奈米粒子， 45% 45奈米奈米粒子， 10% TEOS 4/150 6.2 39 35% 5奈米奈米粒子， 35% 45奈米奈米粒子， 30% TEOS 7/200 3.7 30 200948871 ❹Example 二二矽粒子粒子粒子粒子粒子机械机械 # # # # 栻 / / / / / / / / 550 550 550 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 29 Minami grain hand, 7/200 5.0 . 10% TEOS 31 .70% 5 nanometer nanoparticles, 10/200 4.0 30% TEOS 32 50% 5 nanometer nanoparticles, 18/200 3.5 1---- -----.. 50% TEOS In the following Examples 33 to 40, the 5 wt. 〇/0 mixed nanoparticle SiO2 composition (containing mixtures of different sizes) was used at pH 2~ Apply 3 to 1 mil (~25 U m) of coating thickness to the untreated polyethylene terephthalate group 29 200948871 and dry at 80 to 100 ° C for 5 to 10 minutes. The composition further comprises -tetraethoxydecane. Test the coating sample as before. The total oxirane from the test results improved the coating durability of the mixed particle composition on the untreated polyethylene terephthalate. Table 6 Example Mechanical Deterioration of Antimony Oxide Nanoparticle Dispersion After strong rubbing with dry Kimwipe X times and strong rubbing with wet Kimwipe for y times, the coating peeled off (χ/νΊ 550 nm Α transmittance (%) 33 50% 45 nanometer nanoparticles, 50% 20 nanometer nanoparticles 1/1 4.5 34 45% 20 nanometer nanoparticles, 45% 45 nanometer nanoparticles, 10% TEOS 4/12 5.1 35 35% 20 nanometer nanoparticles, 35% 45 nanometer nanoparticles, 30% TEOS 8/200 4.8 36 25% 20 nanometer nanoparticles, 25% 45 nanometer nanoparticles, 50% TEOS 12/200 3.1 37 50% 45 nanometer nanoparticles, 50% 5 nanometer nanoparticles 2/4 4.4 38 45% 5 nanometer nanoparticles, 45% 45 nanometer nanoparticles, 10% TEOS 4/150 6.2 39 35% 5 nanometer nanoparticles, 35% 45 nanometer nanoparticles, 30% TEOS 7/200 3.7 30 200948871 ❹

25%5奈米奈米教子 25% 45奈米奈米粒子 TEOS 10/200 3.5 在以下實施^— --丨---J 化矽組合物，在ρίί 2〜3和〗户不之1 2 3 4辦.％混合奈米粒子二氧塗覆未經處理之聚對苯二25微米）的塗層厚度下，〜10八## > 次乙—醇酯基體，在80〜loot乾焊5 10刀鐘。實施例對比了水。乾知5 Kimwipe測試機械耐久性〇卷古和乙醇分散體的性能。僅用濕的性能。乙醇未經酸化時’對比例顯示了差表725% 5 nanometer teachers 25% 45 nanometer nanoparticles TEOS 10/200 3.5 In the following implementation ^—-丨---J 矽 composition, in ρίί 2~3 and 〗〖Family 1 2 3 4 do.% mixed nanoparticle dioxygen coated untreated poly-p-phenylene 25 micron) coating thickness, ~10 八## > sub-ethyl alcohol ester matrix, dry soldering at 80~loot 5 10 knives. The examples compare water. Dry knowledge 5 Kimwipe tested the mechanical durability of the performance of the ancient and ethanol dispersions. Use only wet performance. When ethanol was not acidified, the ratio showed a difference. Table 7

42 5奈米二氧化石夕奈米粒子， 5奈米二氧化石夕奈米粒子 5奈米二氧化石夕奈米粒子，42 5 nanometer sulphur dioxide ceramsite particles, 5 nanometer sulphur dioxide cerium nanoparticles 5 nanometer sulphur dioxide ceramsite particles,

對比例2 對比:在、絲子作錢性分龍塗覆。_將朗性能餘 31 1 〜3秘她_，絲謝_分散體的 _塗層之則再次调即到ΡΗ5〜5的分散體相比較。如表8中 2 所不^各分健具有5〜.％奈綠子。基體是未鱗理之聚對苯 3 -甲酸乙二醇g旨。將提供視覺均勻塗層的分散體命名為「可塗 4 覆」。團成珠和/或提供視覺不均勻塗層的塗料命名為「起珠」。也 5 提仏了具有混合尺寸的奈米粒子乳液之實關。這些實施例證實 200948871 對可塗覆性和經過再調節pH保持可塗覆性的影響。表8 實施例二氧化矽奈米粒子分散體最初pH 酸化pH 再調節pH 塗覆性能對比例3 4奈米奈米粒子 10 n/a n/a 起珠 43 4奈米 10 1-3 n/a 可塗覆 44 4奈米 10 1-3 5-6 可塗覆對比例4 5奈米 10 / / 、起珠 45 5奈米 10 1-3 n/a 可塗覆 46 5奈米 10 1-3 5-6 可塗覆對比例5 20奈米 10 n/a n/a 起珠 47 20奈米 10 1-3 n/a 可塗覆 48 20奈米 10 1-3 5-6 可塗覆對比例6 45奈米 10 n/a n/a 起珠 49 45奈米 10 1-3 n/a 起珠 50 1 : 1的4奈米/45 奈米 10 1-3 n/a 可塗覆 51 1 : 9的4奈米/45 奈米 10 1-3 n/a 可塗覆 52 1 : 1的5奈米/45 奈米 10 1-3 n/a 可塗覆 53 1 : 9的5奈米/45 奈米 10 1-3 n/a 可塗覆 54 1 : 1的4奈米/93 奈米 10 1-3 n/a 可塗覆 32 200948871 55 1 : 9的4奈米/93 奈米 10 1-3 n/a 可塗覆 56 1 : 1的5奈米/93 奈米 10 1-3 n/a 可塗覆 57 1 : 9的5奈米/93 奈米，1 10 1-3 n/a 可塗覆在實施例58〜63和對比例7〜8中，用所示之5 wt.%奈米粒子二氧化矽組合物，在所示之pH、1密耳（〜25微米）的塗層厚度下，塗覆未經處理之聚對苯二曱酸乙二醇酯基體，在110〜120 °C乾燥5〜10分鐘。實施例59、60、62和63以98 : 2的二氧化石夕’界面活性劑之比，包含幻jone—Poulenc，lnc的界面活性劑 SIPONATEtmDS-10。報導了靜態水接觸角、透射率和防霧性能。這些實施例顯示了 pH對可塗覆性和對塗層性質之影響。表9 實施例二氧化矽奈米粒子分散體 pH 塗層品質水接觸角 ---- _ 550奈米的 Δ透射率 (%) ------- 2.10 防霧性能對比例7 4 奈米，70 : 30 重量比的水/醇 10 ---—— 2-3 非常差，很多缺陷和針孔 18.4 3 58 4奈米，水 .非常好 10.0 4.95 4 —-— 5 59 — — 98:2的4奈米 /DS-10，水 2-3 L一非常好 ---- 5.2 4.90 60 95:5的4奈米 / DS-10，水 2-3 非常好. 5.4 ------ 4.90 5 l 33 200948871 對比例8 5 奈米，30 : 70 重量比的水/醇 10 ---- 非常差，很多缺陷和針孔 14.5 2.30 3 61 --------- 5奈米，水 2-3 非常好 9.2 5.02 4 62 98 :2的5奈米 2-3 非常好 5.3 4.98 5 /DS-10，水 63 95:5的5奈米 2-3 非常好 4.6 4.90 5 /DS-10，水溶 --~--— 液 ❹ 在以下實施例64〜82和對比例9〜14中，用所示之5 wt.%奈米粒子二氧化矽組合物，在所示之pH、1密耳（〜25微米）的塗層厚度下’塗覆未經處理之聚對苯二曱酸乙二醇酯基體，在110 〜120 C乾燥5〜1〇分鐘。報導了水前進和後退接觸角。在實施例 84中’基體是具有全氟聚醚塗層的聚碳酸醋，依照11/828566(Klum 等’通過參考引入此處）的實施例1製備，使用包含0.5 wt.%的製備2得到的全氟聚醚之SHC-1200的溶液作為面塗。在實施例85 〇中’基體是以商品ByndTM銷售的酸酐改性之聚乙烯聚.合物，可購自 E. I. DuPont de Nemours & Co.，Wilmington，Del.。穩定表示在至 . 少2個月内沒有凝膠。這些實施例證實，分散體穩定性和可塗覆 - 性與pH和粒度有關。表10 實施例二氧化矽奈米基體 pH 接觸角分散體溶液塗覆 —--- _粒子分散體前進/後退（°) 的保存期性能對比例 9 --- 僅去離子水 PET 7 74.0/63.0 n/a 起珠農纪列10 5奈米 ί 5 10.5 72.1/61.5 穩定可塗覆 34 200948871 64 5奈米 “ 2 72.5/21.9 穩定可塗覆 65 5奈米 “ 3 70.7/23.7 7天後凝膠可塗覆 66 5奈米 “ 4 71.9/20.0 5天後凝膠可塗覆 67 5奈米 5 72.1/19.0 6天後凝膠可塗覆對比例11 4奈米 “ 9.5 72.2/55.5 穩定起珠 68 4奈米 “ 2 75.0/21.5 穩定可塗覆 69 4奈米 “ 3 24小時後凝膠可塗覆 70 4奈米 “ 4 75.1/27.6 2天後凝膠可塗覆 71 4奈米 “ 5 74.2/22.6 24小時後凝膠可塗覆 72 13奈米 “ 2 80.4/21.2 穩定可塗覆 73 13奈米 “ 3 79.8/22.1 穩定可塗覆 74 13奈米 “ 4 80.9/40.1 穩定起珠 75 13奈米 “ 5 81.1/55.7 穩定起珠 76 13奈米 “ 6 79.8/57.3 穩定起珠對比例12 20奈米 “ 9.5 77.9/54.4 穩定起珠 78 20奈来 “ 2 79.6/19.4 穩定可塗覆 79 20奈米 “ 3 穩定可塗覆 80 20奈米 “ 4 80.5/25.5 穩定可塗覆對比例13 20奈米 “ 5 79.2/44.6 穩定起珠對比例14 20奈米 “ 6 79.9/55.9 穩定起珠 81 5奈米聚石厌酸酯 2 88.1/31.1 穩定可塗覆 82 5奈米聚氨 m 2 104.8/24.2 穩定可塗覆 83 5奈米 PVC 2 70.2/23.2 穩定可塗覆 84 5奈米 PFP E塗布的 PC 2 109.2/24.3 穩定可塗覆 85 5奈米 Byn el 2 80.2/30.3 穩定可塗覆Contrast Example 2 Contrast: In the silk, the silk is coated with money. _ will be the performance of the remaining 31 1 ~ 3 secret her _, silk thank _ dispersion of the _ coating is then adjusted to the ΡΗ 5 ~ 5 dispersion compared. As shown in Table 8, 2 does not have 5~.% Naizi. The matrix is an unscaled poly(p-phenylene terephthalate) glycol. The dispersion providing a visually uniform coating was named "coatable". The paint that is formed into beads and/or provides a visually uneven coating is named "beading". Also 5 raised the practicality of nanoparticle emulsions with mixed sizes. These examples demonstrate the effect of 200948871 on coatability and re-adjustable pH to maintain coatability. Table 8 Example bismuth dioxide nanoparticle dispersion Initial pH Acidification pH Re-adjustment pH Coating performance Comparative Example 3 4 nm Nanoparticles 10 n/an/a Beads 43 4 nm 10 1-3 n/a Can be coated 44 4 nm 10 1-3 5-6 can be coated in contrast ratio 4 5 nm 10 / /, bead 45 5 nm 10 1-3 n / a can be coated 46 5 nm 10 1- 3 5-6 coatable comparative example 5 20 nm 10 n/an/a bead 47 20 nm 10 1-3 n/a coatable 48 20 nm 10 1-3 5-6 coatable pair Ratio 6 45 nm 10 n/an/a Beads 49 45 nm 10 1-3 n/a Beads 50 1 : 1 4 nm / 45 nm 10 1-3 n/a Can be coated 51 1 : 9 4 nm / 45 nm 10 1-3 n / a can be coated 52 1 : 1 5 nm / 45 nm 10 1-3 n / a can be coated 53 1 : 9 of 5 nm /45 nm 10 1-3 n/a can be coated with 54 1 : 1 4 nm / 93 nm 10 1-3 n / a can be coated 32 200948871 55 1 : 9 4 nm / 93 nm 10 1-3 n/a can be coated with 56 1 : 1 of 5 nm / 93 nm 10 1-3 n / a can be coated with 57 1 : 5 of 5 nm / 93 nm, 1 10 1-3 n/a can be coated in Examples 58 to 63 and Comparative Examples 7 to 8, and is oxidized with the 5 wt.% nanoparticles shown. The composition is coated with an untreated polyethylene terephthalate base at a pH of 1 mil (~25 microns) coating thickness and dried at 110~120 °C. 10 minutes. Examples 59, 60, 62 and 63 contained a surfactant of SIPONATEtmDS-10 in the ratio of 98:2 of the dioxide dioxide surfactant. Static water contact angle, transmittance, and anti-fog performance are reported. These examples show the effect of pH on coatability and on coating properties. Table 9 Example bismuth dioxide nanoparticle dispersion pH coating quality water contact angle---- _ 550 nm Δ transmittance (%) ------- 2.10 anti-fog performance comparison ratio 7 4 Meter, 70: 30 by weight water/alcohol 10 --- -- 2-3 Very poor, many defects and pinholes 18.4 3 58 4 nm, water. Very good 10.0 4.95 4 —-— 5 59 — — 98 : 2 4 nm / DS-10, water 2-3 L is very good --- 5.2 4.90 60 95: 5 4 nm / DS-10, water 2-3 very good. 5.4 ---- -- 4.90 5 l 33 200948871 Comparative Example 8 5 nm, 30: 70 by weight water/alcohol 10 ---- Very poor, many defects and pinholes 14.5 2.30 3 61 --------- 5 Nano, water 2-3 very good 9.2 5.02 4 62 98 : 2 5 nm 2-3 very good 5.3 4.98 5 / DS-10, water 63 95: 5 5 nm 2-3 Very good 4.6 4.90 5 /DS-10, water-soluble ~---- liquid helium In the following Examples 64 to 82 and Comparative Examples 9 to 14, the 5 wt.% nanoparticle ceria composition shown is used, as shown Coating untreated polyethylene terephthalate based on pH, 1 mil (~25 microns) coating thickness , Dried at 110 ~120 C 5~1〇 minutes. Water advancement and receding contact angles are reported. In Example 84, the matrix was a polycarbonate having a perfluoropolyether coating, prepared in accordance with Example 1 of 11/828566 (Klum et al., incorporated herein by reference), using Preparation 2 containing 0.5 wt.%. A solution of perfluoropolyether SHC-1200 was applied as a top coat. In Example 85, the substrate was an anhydride-modified polyethylene polymer sold under the trade name BYndTM, available from E. I. DuPont de Nemours & Co., Wilmington, Del. Stable indicates that there is no gel within 2 months. These examples demonstrate that dispersion stability and coatability are related to pH and particle size. Table 10 Example cerium oxide nanobase pH contact angle dispersion solution coating ----- _ particle dispersion forward/backward (°) shelf life performance comparative example 9 --- only deionized water PET 7 74.0 / 63.0 n/a 珠农农纪10 5 nm ί 5 10.5 72.1/61.5 stable coatable 34 200948871 64 5 nm "2 72.5/21.9 stable coatable 65 5 nm" 3 70.7/23.7 7 days later The gel can be coated with 66 5 nm "4 71.9/20.0 5 days after the gel can be coated 67 5 nm 5 72.1/19.0 6 days after the gel can be coated with a contrast ratio of 11 4 nm" 9.5 72.2/55.5 Stable Beads 68 4 nm "2 75.0/21.5 Stable coated 69 4 nm" 3 24 hours after gel coating 70 4 nm "4 75.1/27.6 2 days after gel coating 71 4 nm " 5 74.2/22.6 After 24 hours the gel can be coated 72 13 nm" 2 80.4/21.2 Stable coated 73 13 nm "3 79.8/22.1 Stable coated 74 13 nm" 4 80.9/40.1 Stabilized Beads 75 13 nm "5 81.1/55.7 Stabilizing Beads 76 13 nm" 6 79.8/57.3 Stabilizing Beads Comparative 12 20 nm "9.5 77.9/54.4 Stabilization 78 20 Nailai "2 79.6/19.4 Stable coated 79 20 nm" 3 Stable coatable 80 20 nm "4 80.5/25.5 Stable coatable comparison 13 20 nm" 5 79.2/44.6 Stabilized beads Comparative Example 14 20 nm "6 79.9/55.9 Stabilized Bead 81 5 nm Poly Stone Oxate 2 88.1/31.1 Stable Coatable 82 5 Nano Polymethane m 2 104.8/24.2 Stable Coatable 83 5 nm PVC 2 70.2/23.2 Stable coated 84 5 nm PFP E coated PC 2 109.2/24.3 Stable coated 85 5 nm Byn el 2 80.2/30.3 Stable coated

在以下實施例86〜89中，用所示之5 wt.%奈米粒子二氧化矽 35 200948871In the following Examples 86 to 89, 5 wt.% of nanoparticle ceria was used as shown. 35 200948871

組合物，在pH2〜3、1密耳（〜止、 ^ L 寸、25微未）的塗層厚度下，塗覆未經處理之料苯二甲酸乙二關基體，在⑽〜12叱乾燥5〜ι〇分鐘。測定初始透料，_錄品受到顧巾的⑽*擦拭「濕擦」以測定耐久性，再次測定透醉。另外細試了防霧性質。在實施例87和89中，添加了 DS_1Q界面活性劑。進—步通過在贼和95减度下老化至少Η天來評細雜。實_顯示界面The composition is coated with an untreated phthalic acid phthalate substrate at a coating thickness of pH 2 to 3, 1 mil (1 deg, ^ L inch, 25 micro Å), and dried at (10) to 12 Torr. 5 ~ ι〇 minutes. The initial permeate was measured, and the recording was subjected to (10)* wiping "wet rubbing" to measure the durability, and the drench was again measured. In addition, the anti-fog properties were carefully tested. In Examples 87 and 89, a DS_1Q surfactant was added. Step-by-step evaluation is done by aging at least Η days under thieves and 95 reductions. Real_display interface

活性麵塗層性能沒有㈣财並且改進了防霧性能。表11 -------- 實施例二氧化矽奈米粒子分散體初始透射率％最終透射率％防霧’在50°C和95%濕 86 4奈米 —----- ---------- 度下老化 91.87 91.70 最初防霧好，但在.22小 B#蚀ail视女费 87 95 : 5比例的 4 奈米/DS-I0 91.56 91.40 J Ί夂佩名務在11〜20天後防霧優秀 88 5奈米 91.87 91.70 ----—-- 最初防霧好，但在22小時後略傲古渡 89 _ 95 : 5比例的 5 奈米/DS-10 91.56 91.40 在1】〜20天後防霧優秀在以下實施例90〜93和對比例15〜16中，用所示之5机％奈米粒子二氧化砍組合物，在所示之阳值、和〗密耳（〜b奈米）的塗層厚度下’塗覆莞碑，在no〜i2(rc乾燥5〜10分鐘。通過浸入棘（SQap seum)中並鎌财流成功沖洗掉皂沫來進行皂床容易去除的沖洗清潔。通·濕紙巾或交替用乾紙巾擦拭來評價塗層耐久性；用測量光透射來測定塗層是保留還是已除去。如果出現針孔或者如果干擾色強烈且不均勻，則塗層品質差。 36 200948871 表12 實施例二氧化矽奈米粒子分散體類型 pH 塗層品質皂沫容易去除 "Ί--· 機械对久性巾（#擦） ΟΠ 4奈米，水溶液 2-3 y\) 非常好殘留皂沫 ISO 對比例15 95 : 5比例的4 奈米/DS-10，水溶液 10 差 ----— 40 91 95 : 5比例的4 奈米/DS-10，水溶液 2-3 非常好非常乾淨 120 耐久性提高 92 95 : 5的5奈米/ DS-I0，水溶液 2-3 非常好非常乾淨 100 對比例16 95 : 5的5奈米/ DS-10，水溶液 10 均勻性差 J八J 土'同 30 93 5奈米，水溶液 2-3 非常好殘留皂沫 —-» 120 在以下實施例94和對比例17中，用所示之5站.％奈米粒子The performance of the active topcoat is not (4) and the anti-fog performance is improved. Table 11 -------- Example bismuth dioxide nanoparticle dispersion initial transmittance % final transmittance % anti-fog 'at 50 ° C and 95% wet 86 4 nm -------- --------- Degree of aging 91.87 91.70 Initial anti-fog is good, but in .22 small B# Eclipse ail as female fee 87 95 : 5 ratio of 4 nm / DS-I0 91.56 91.40 J Ί夂佩名After 11 to 20 days, the anti-fog is excellent 88 5 nm 91.87 91.70 ------- The initial anti-fog is good, but after 22 hours slightly aogudu 89 _ 95: 5 ratio of 5 nm / DS-10 91.56 91.40 Excellent antifogging after 1 to 20 days In the following Examples 90 to 93 and Comparative Examples 15 to 16, the composition was shown by the 5 machine % nanoparticle dioxide chopping, as shown in the positive value, and 〗密密 (~b nm) under the coating thickness 'coating the monument, in no~i2 (rc drying 5~10 minutes. By immersing in the spine (SQap seum) and smashing the liquid to successfully rinse off the soap Perform rinsing and cleaning of the soap bed easily. Wipe the wetness of the wet wipes or alternately with a dry paper towel to evaluate the durability of the coating; measure the light transmission to determine whether the coating is retained or removed. If pinholes appear or if the interference color is strong And uneven, the coating quality is poor. 36 200948871 Table 12 Example bismuth dioxide nanoparticle dispersion type pH coating quality soap easy to remove " Ί -- mechanical long-term towel (# rub) ΟΠ 4 Nano, aqueous solution 2-3 y\) Very good residual soap ISO ISO 15 95 : 5 ratio of 4 nm / DS-10, aqueous solution 10 difference ---- 40 90 95 : 5 ratio of 4 nm /DS-10, Aqueous solution 2-3 Very good very clean 120 Durability increased 92 95 : 5 5 nm / DS-I0, Aqueous solution 2-3 Very good very clean 100 Comparative example 16 95 : 5 5 nm / DS-10, aqueous solution 10 uniformity difference J VIII J soil 'with 30 93 5 nm, aqueous solution 2-3 very good residual soap foam -» 120 In the following Example 94 and Comparative Example 17, with 5 stations shown .% nanoparticle

二氧化矽組合物，在所示之pH、1密耳（〜25微米）的塗層厚度下，塗覆未經處理之聚苯二甲酸乙二醇酯基體，在11〇〜12〇t：乾燥5〜10分鐘。通過將幾個油滴施加到塗層樣品上並然後用 75〇mL/min的窄水流成功沖轉油絲進行容絲油的沖洗清潔。通過賴紙巾或交_乾紙巾擦拭來評層耐久性；用測量光透射來測定塗層是保留還是除去。表13 PH —--» 食物油的容易去除 ----— — 辦柴油的容易去除 2-3 ------ 〜_完全去除完全去除 n/a "—-—1 -_ 保留保留實施例二氧化矽奈米粒子分散體類型 94 5奈米對比例17 無 37 200948871 在圖3目5中，㈣了塗層製品的透射施例1中，使《對笨基體製備。在圖3中，樣品如下： - A聚對苯二甲酸乙二_旨膜，作為對照 • B pH為2之5奈米二氧化石夕的5 wt.%水分散體 C pH為2之5奈米二氧化石夕的5加.％乙醇分散體 D pH為1〇之5奈米二氧化石夕的5 wt.%乙醇分散體 Ο 如圖3中可見，樣an B和C與未塗層的聚對笨二甲酸乙二醇醋樣品Α相比，表現出尚得多的透射率。在驗性pH值下塗層之樣品P沒有表現出樣品B和C任一個在350〜600奈米波長處的提高。在圖4中，樣品如下： A聚對苯二曱酸乙二醇酯膜，作為對照 E pH為2之5奈米/45奈米混合物（1〇 : 90)的5机％水分 © 散體 F pH為2之5奈米/45奈米混合物（1〇 : 90)的5 wt.%乙醇 - 分散體 . g pH為2之5奈米/90奈米混合物（10 : 90)的5机％水分散體The cerium oxide composition is coated with an untreated polyethylene terephthalate matrix at a pH of 1 mil (~25 micrometers) as indicated, at 11 Torr to 12 Torr: Dry for 5 to 10 minutes. The rinse of the rotor oil was carried out by applying several oil droplets to the coating sample and then successfully rotating the oil filament with a narrow water flow of 75 〇 mL/min. The durability of the layer was evaluated by wiping with a paper towel or a dry paper towel; the light transmission was measured to determine whether the coating was retained or removed. Table 13 PH —-»Easy removal of food oil ----- Easy to remove diesel 2-3 ------ ~_ Complete removal completely remove n/a "---1 -_ Reserved Retaining Example of Cerium Oxide Nanoparticle Dispersion Type 94 5 nm Comparative Example 17 No 37 200948871 In Fig. 3, (4) Transmissive Example 1 of a coated article, "Prepared for a stupid substrate." In Figure 3, the sample is as follows: - A polyethylene terephthalate film, as a control • B pH 2 of 5 nm dioxide, 5 wt.% aqueous dispersion C pH 2 of 5 5 wt.% ethanol dispersion of 5 g.% ethanol dispersion of nanometer sulphur dioxide in the evening. 5 wt.% ethanol dispersion Ο of 5 nm of sulphur dioxide. As shown in Fig. 3, samples of an B and C are uncoated. The layer of poly(p-diacetate) glycol vinegar sample showed much better transmission than the sample. Sample P of the coating at an illustrative pH did not exhibit an increase in either of samples B and C at a wavelength of 350 to 600 nm. In Figure 4, the sample is as follows: A polyethylene terephthalate film, as a control E pH of 2 5 nm / 45 nm mixture (1 〇: 90) 5 machine % moisture © bulk F 5 wt.% ethanol-dispersion of pH 5 to 5 nm/45 nm mixture (1〇: 90). 5 pH of 5 nm/90 nm mixture (10: 90) Aqueous dispersion

HpH為2之5奈米/90奈米混合物（10 : 90)的5 wt.%乙醇分散體5 wt.% ethanol dispersion with a HpH of 2 to 5 nm/90 nm mixture (10: 90)

IpH為1〇之5奈米/90奈米混合物（10 : 90)的5 wt·%乙醇 38 200948871 分散體 J pH為2之90奈米的5賊％乙醇分散體 KpH為H)之90奈米的5wt%乙醇分紐 L pH為2之45奈米的5賊％乙醇分散體在圖5中，樣品如下： A聚對苯二甲酸乙二_旨膜，作為對照IpH is 1 〇 5 nm / 90 nm mixture (10 : 90) of 5 wt·% ethanol 38 200948871 Dispersion J pH 2 of 90 nm 5 thief % ethanol dispersion KpH is H) 90 奈5 wt% ethanol of rice, L pH 5 of 45 nm, 5 thief % ethanol dispersion in Figure 5, the sample is as follows: A polyethylene terephthalate film, as a control

MpH為2之4奈米/45奈米混合物（50/50重量比）的5 wt.% 水分散體，單面塗覆 NPH為2之4奈来的5破％水分散體，單面塗覆〇阳為2之4奈米/45奈米混合物（50/50重量比）的5wt·% 水分散體，雙面塗覆 P PH為2之4奈米的5破％水分散體，雙面塗覆由樣品Μ和Q、或N和p的對比可以看出，通過雙面塗覆該〇基體膜，可以大大提高基體之透射率。以上所述僅為舉例性，而非為限制性者。任何未脫離本發明之精神與範疇，而對其進行之笙4^ . .專效t改或變更，均應包含於後附 ^ 之申請專利範圍中。【圖式簡單說明】圖1為實施例78中製備的製品 · II 2 牙遗式电子顯微鏡照片為對比例12的製品之穿透式電子顯微齡片；及圖3〜圖5是本發明的製品之透射率圖。 39 200948871 【主要元件符號說明】無 ❹ ❹ 40MpH is a 4 wt.% aqueous dispersion of 4 4 nm/45 nm mixture (50/50 by weight), one side coated with a 5 wt% aqueous dispersion of NPH 2 4, one side coated Fuyang is a 5 wt.% aqueous dispersion of 2 4 nm/45 nm mixture (50/50 by weight), double coated with 5 % water dispersion of P 4 of 4 4 nm, double The surface coating can be seen from the comparison of the sample Μ and Q, or N and p, by double-coated the ruthenium base film, the transmittance of the substrate can be greatly improved. The above is intended to be illustrative only and not limiting. Any changes or modifications to the spirit and scope of the present invention are intended to be included in the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a product prepared in Example 78. The II 2 tooth electron micrograph is a transmissive electron micrograph of the product of Comparative Example 12; and FIGS. 3 to 5 are the present invention. Transmittance map of the product. 39 200948871 [Explanation of main component symbols] None ❹ ❹ 40

Claims

200948871 十、申請專利範圍： 1、一種為基體提供塗層的方法，該方法包括使基體與塗料組合物接觸，並乾燥以提供二氧化矽奈米粒子塗層，該塗料組合物包 : 含： . a)平均粒徑為40奈米或更小的二氧化矽奈米粒子的水分散體，其pH小於5 ;以及 b) pKa<3.5 的酸。 2、如申請專利範圍f 1項所述之方法’其中該二氧化石夕奈米粒子在塗料組合物中的濃度為0.1〜20 wt 〇/〇。 3、如申請專利範圍第1項所述之方法，其中該基體是靜態水接觸角大於5(Γ的疏水基體。 4、如申請專利範圍第！項所述之方法，其中該二氧化石夕奈米粒子的水分散體還包含平均粒徑大於4〇奈米的二氧化矽奈米粒子。〇 5、如申請專利範圍第1項所述之方法，其中該酸選自草酸、檸檬酸、H3P〇4、HC1、HBr、HI、ΗΒι·〇3、ΗΝ〇3、HCl〇4、H2S04、 CH3S03H、CF3S03H、CF3C02H 和 CH3S020H 〇 .6、如申請專利範圍第1項所述之方法’其中該二氧化石夕奈米粒子具有20奈米或更小的平均粒徑。 7、如申請專利範圍第1項所述之方法，其中該二氧切奈米粒子具有10奈米或更小的平均粒徑。 8、如申請專利範圍第1項所述之方法，其中該塗料組合物進一步包含四烷氧基矽烷。 41 200948871 9 Ή___ 1項所述之方法，其中該塗料組合物包含： a) 0·5〜99wt.%的水； 2〇 Wt%的平均粒徑為40奈来或更小的二氧化石夕奈米；粒子； c) 〇〜20 wt·%的平均粒徑為5()奈米或更大的二氧化梦奈米粒子，其中b)和c)的總和為〇」〜2〇 wt〇/〇 ; d) 含1足以將阳降低到小於5的PKa<3.5的酸；以及丨於—氧化％奈米粒子的量，的四烧氧基石夕炫0 10、如中凊專利範圍第i項所述之方法，其中該基體在塗覆後具有小於50°的靜態水接觸角。 Π、如申物_第〗項所述之方法，其中該塗料組合物的pH 小於3。包括以下步驟··添加足小於5，然後添加足量 12、如申請專利範圍第】項所述之方法，量的酸以將該塗料組合物的pH調節到的域以將pH調節到5〜6的範圍内。 13 14 、一種如㈣專利範圍第1項所述之方法製備的親水性製品。、-種被塗㈣製品’包括顧和其上的塗層，該塗層為平均粒徑為40奈米或更小的二氧姆奈錄子的凝聚體，該凝聚體包括二氧_奈料好的三維纽植結構如巾請專利範園第，並且該二氧切奈米粒子與相_二氧切奈米粒子結合。 42 200948871 15如申喷專利範圍第14項所述之被塗覆的製品，具有小於的水接觸角。 16如申凊專利範圍第14項所述之被塗覆的製品，其中該塗層的；厚度為約500〜2500 A。 * 17、如申請專利範圍第14項所述之被塗覆的製品，其中該基體是透明的。 18、如申請專利範圍第17項所述之被塗覆的製品，與未被塗 Ο 萝復的基體相比，在400〜700奈米波長範圍内的法向入射光的透射得以提高。 19、如申請專利範圍第18項所述之被塗覆的製品，其中該平均透射率提高了至少2%。 20、如申請專利範圍第14項所述之被塗覆的製品，其中該塗層的折射率在約1_2〜1.4的折射率之間。 ❹ 1如申睛專利範圍第14項所述之被塗覆的製品，其中該塗層包括： a. 60〜95 wt·%的凝聚的二氧化石夕奈米粒子， : b.約〇·1〜2〇wt.%的四烷氧基石夕烧， c. 可％地約0〜5wt·%的界面活性劑；以及 d. 0〜約5 wt.%的潤濕劑。 22、—種塗料組合物，包含： a) 0.5〜99 wt.%的水， b ) 〇.丨〜2〇桃％的平均粒徑為4〇奈求或更小的二氧化石夕奈米 43 200948871 粒子， c) 0〜20 wt.%的平均粒徑大於50奈米的二氧化矽奈米粒子，其中b)和c)的總和為0.1〜20wt.% ; d) 含量足以將pH降低到小於5的pKa<3.5的酸；以及 e) 相對於二氧化石夕奈米粒子的量，0〜20 wt.%的四烧氧基石夕烷。 ❹ ❹ 44200948871 X. Patent Application Range: 1. A method for providing a coating for a substrate, the method comprising contacting a substrate with a coating composition and drying to provide a coating of cerium oxide nanoparticles, the coating composition comprising: a) an aqueous dispersion of cerium oxide nanoparticles having an average particle diameter of 40 nm or less having a pH of less than 5; and b) an acid having a pKa < 3.5. 2. The method of claim 1, wherein the concentration of the cerium oxide nanoparticles in the coating composition is from 0.1 to 20 wt 〇 / 〇. 3. The method of claim 1, wherein the substrate has a static water contact angle greater than 5 (a hydrophobic matrix of yttrium. 4. The method of claim 2, wherein the sulphur dioxide The aqueous dispersion of the nanoparticle further comprises a cerium oxide nanoparticle having an average particle diameter of more than 4 Å. The method of claim 1, wherein the acid is selected from the group consisting of oxalic acid, citric acid, H3P〇4, HC1, HBr, HI, ΗΒι·〇3, ΗΝ〇3, HCl〇4, H2S04, CH3S03H, CF3S03H, CF3C02H, and CH3S020H 〇.6, as described in claim 1, wherein The cerium dioxide particles have an average particle diameter of 20 nm or less. 7. The method of claim 1, wherein the dicepreon particles have an average of 10 nm or less. 8. The method of claim 1, wherein the coating composition further comprises a tetraalkoxy decane. The method of claim 1, wherein the coating composition comprises: a) 0·5~99wt.% of water; 2〇Wt% average a diameter of 40 nm or less of SiO2; particles; c) 〇~20 wt·% of Monoxide particles having an average particle size of 5 () nm or more, wherein b) And the sum of c) is 〇"~2〇wt〇/〇; d) contains 1 acid sufficient to reduce the yang to less than 5 PKa <3.5; and 丨 — - oxidize the amount of nanoparticle, the four burned oxygen The method of claim 1, wherein the substrate has a static water contact angle of less than 50° after coating. The method of claim 1, wherein the coating composition has a pH of less than 3. Including the following steps: adding a foot of less than 5, and then adding a sufficient amount of 12, as described in the scope of the patent application, the amount of acid to adjust the pH of the coating composition to the domain to adjust the pH to 5~ Within the scope of 6. 13 14. A hydrophilic article prepared by the method of (4) the scope of claim 1. - The coated (four) article 'includes a coating thereon, the coating being an agglomerate of a dioxonite having an average particle diameter of 40 nm or less, the agglomerate comprising dioxane The good three-dimensional implant structure is as disclosed in the patent, and the dioxon nanoparticles are combined with the phase-dioxon nanoparticles. 42 200948871 15 The coated article of claim 14, which has a water contact angle of less than that. The coated article of claim 14, wherein the coating has a thickness of about 500 to 2500 Å. * The coated article of claim 14, wherein the substrate is transparent. 18. The coated article of claim 17, wherein the transmission of normal incident light in the wavelength range of 400 to 700 nm is improved as compared to the substrate which is not coated with the dill. 19. The coated article of claim 18, wherein the average transmittance is increased by at least 2%. The coated article of claim 14, wherein the coating has a refractive index between about 1 and 2 to 1.4. The coated article of claim 14, wherein the coating comprises: a. 60 to 95 wt.% of condensed dioxide cerium nanoparticles, : b. about 〇· 1 to 2 〇 wt.% of tetraalkoxylate, c. may be about 0 to 5 wt.% of the surfactant; and d. 0 to about 5 wt.% of the wetting agent. 22. A coating composition comprising: a) 0.5 to 99 wt.% water, b) 〇.丨~2〇Peach% has an average particle size of 4 〇 or less or less. 43 200948871 particles, c) 0 to 20 wt.% of cerium oxide nanoparticles having an average particle diameter of more than 50 nm, wherein the sum of b) and c) is 0.1 to 20 wt.%; d) the content is sufficient to lower the pH To an acid of pKa <3.5; less than 5; and e) 0 to 20 wt.% of tetra-oxygenated alkane relative to the amount of cerium oxide nanoparticles. ❹ ❹ 44