TWI363062B

TWI363062B - Polymerizable compositions comprising nanoparticles

Info

Publication number: TWI363062B
Application number: TW094120048A
Authority: TW
Inventors: Clinton Lee Jones; David Bradley Olson; Emily Suzanne Goenner; Brant Ulrick Kolb; John Thomas Brady
Original assignee: 3M Innovative Properties Co
Priority date: 2004-06-17
Filing date: 2005-06-16
Publication date: 2012-05-01
Also published as: TW200611917A; KR101245946B1; TW200612158A; JP2014178689A; KR20070032997A; JP2012078852A; TWI372916B

Description

1363062 九、發明說明：【發明所屬之技術領域】本發明係關於包含奈米粒子之可聚合組合物其特別適用於增亮膜。 ' 【先前技術】某些微複製光學產品（例如闡述於美國專利第5，175,〇3〇號及第5，183,597號中者）通常稱為"增亮膜”。在許多電子產品中使用增亮膜，以增強背光平板顯示器（例如—液晶顯示 ^ 器（LCD) ’包括彼等在電致發光面板、膝上型電腦顯示器、 • 文字處理器、桌上型監視器、電視、視訊攝影機及自動和航空顯示器中所使用者）之亮度。增亮膜理想地展現特定的光學及物理特性，包括與所產生之亮度增益（即’，，增益"）有關之增亮膜之折射率。經改良之亮度容許電子產品藉助更低功率照亮顯示器來更有效地運行，藉此降低功率消耗，使其各組件承受一低的熱負荷，並延長產品壽命。 # 已可由經固化或經聚合之高折射率單體製備增亮膜，例如美國專利第5,908,874號、第5,932,626號、第6，107,364 號 '第6,280,063號、第6,355,754號及歐洲專利第1 014113 號及WO 03/076528中所闡述。儘管吾人已知各種適於製造增亮膜之可聚合組合物，但業界發現使用替代組合物較有利。【發明内容】在一具體實施例中，闡述一具有一增亮經聚合結構之增 102543.doc 1363062 亮膜，其包括含下述物質之可聚合組合物之反應產物： a)至少約15重量％之一或多種選自下述之第一單體： i)一包含具有下述結構之主要部分之單體：1363062 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polymerizable composition comprising nanoparticles which is particularly suitable for use in a brightness enhancing film. [Prior Art] Certain microreplicated optical products (such as those described in U.S. Patent Nos. 5,175, 〇 3 及 and 5, 183, 597) are commonly referred to as "brightening films." used in many electronic products. Brightening film to enhance backlit flat panel displays (eg, liquid crystal display (LCD)' including their own in electroluminescent panels, laptop displays, • word processors, desktop monitors, televisions, video cameras And the brightness of the user in automatic and aeronautical displays. The brightness enhancement film ideally exhibits specific optical and physical properties, including the refractive index of the brightness enhancing film associated with the resulting brightness gain (ie, ', gain'). The improved brightness allows electronic products to operate more efficiently with lower power illuminating displays, thereby reducing power consumption, subjecting each component to a low thermal load and extending product life. A brightening film is prepared by polymerizing a high refractive index monomer, for example, U.S. Patent Nos. 5,908,874, 5,932,626, 6,107,364, 6,280,063, 6,355,754, and Europe. It is described in U.S. Patent No. 1,014,113 and WO 03/076528. Although various polymerizable compositions suitable for the manufacture of brightness enhancing films are known, the industry has found it advantageous to use alternative compositions. [SUMMARY OF THE INVENTION] In the present invention, a bright film having a brightening polymerized structure is disclosed, which comprises a reaction product of a polymerizable composition comprising: a) at least about 15% by weight of one or more selected from the group consisting of The first monomer: i) a monomer comprising a major portion having the following structure:

⑴ 其中R1獨立地係氫或甲基， R2獨立地係Η或Br， Z 獨立地係-C(CH3)2-、-CH2-、-C(O)-、-S-、-S(O)-或 _S(0)2_，及 Q獨立地係O或S ; ii)一包含具有下述結構之主要部分之單體：(1) wherein R1 is independently hydrogen or methyl, R2 is independently Η or Br, and Z is independently -C(CH3)2-, -CH2-, -C(O)-, -S-, -S(O )- or _S(0)2_, and Q is independently O or S; ii) a monomer comprising a major portion having the following structure:

(II) 其中R1獨立地係氫或曱基， R2獨立地係Η或Br， 102543.doc 1363062 、-C(O)-、-S-、-S(〇)-或 Z獨立地係-C(CH3)2-、-CH2--S(0)2-，儿 L係一獨立地選自直鏈及具支鏈^/丨2烷基之連接基團，其中碳鏈視情況經一或多個氧基團取代及/或碳原子視情況經一或多個羥基取代；及i)與ii)之混合物； b) 至少約10重量％之無機奈米粒子；及 c) 視情況一包含至少兩個（甲基）丙烯酸酯官能基之交聯劑。 • 在另一具體實施例中，闡述一具有一增亮經聚合結構之：增亮膜，其包括含下述之可聚合組合物之反應產物： .a)至少約15重量％之一或多種（甲基）丙烯酸化之芳族環氧樹脂寡聚物； b)至少約10重量。/。之無機奈米粒子；及 Ο視情況一包含至少兩個（甲基）丙烯酸酯官能基之交聯劑。在另一具體實施例中，闡述一具有一增亮經聚合結構之增免膜’其包括含-有機組份及至少1〇重量％無機奈米粒 ♦子之實質上無溶劑可聚合組合物之反應產物，該有機組份包3 —或多種乙烯系不飽和單體。該有機組份於卞下具一低於1000 cps之黏度。該有機組份可包含至少一具有超過 450克/莫耳之數目平均分子量之募聚乙烯系不飽和單體。 ^再-具體實施例中’闡述—具有—增亮經聚合結構之〜冗膜’其包括含—有機組份及至少1〇重量％無機奈米粒子之實質上無溶劑可聚合組合物之反應產物，該有機組份匕3或多種乙烯系不飽和單體，其中該有機組份具有至 102543.doc 1363062 少1 5 4之折射率。無機粒子之量通常低於約60重量經表面改質。無機奈米粒子通常包含奈米粒子較佳 :=物:録、氧化銘、氧化錫、其混合金屬氧化物門二。：a粒子之初級粒徑可介於5奈米至75奈米間、"於H)奈米至30奈„、介於5奈米幻5奈米間。該第一單體較佳由四漠雙紛A二縮水甘油喊與（甲基）丙烯酸之反應產物組成。該等可聚合組合物進—步包含至少 -第二高折射率單體(即，不同於該第一單體)。該可聚合組合物較佳不含甲基丙烯酸酯官能基單體。在其他具體實施射，本發明係關於—包含增亮膜及一第二光學膜或光導之物件，纟中該增亮膜與該第二光學膜或光導接觸。該第二光學膜可包括—轉向膜、—擴散器、一吸收偏光器、一反射偏光器或一保護覆蓋膜。本文所述可聚合組合物亦可有利地用於其他光學或微結構物件。【實施方式】如在本發明闡述内容中所使用：折射率"（"index of refraction” 或"refractive index")意指一材料（例如一單體）之絕對折射率，其應理解為在自由空間中之電磁輻射速度與在該材料中之輻射速度之比值。折射率可使用習知方法量測，且通常於可見光區使用一阿貝折射儀（Abbe refractometer)(例如，由 Fisher Instruments 〇f Pittsburgh, PA購得）量測。通常應瞭解，所量測之折射率可 102543.doc -10- 1363062 視儀器而有某種程度的改變β "(曱基）丙稀酸醋"意指丙稀酸醋及甲基丙稀酸醋化合物二者。可聚合組合物"意指包括含至少一可聚合單體之有機組伤及可選無機奈米粒子之整個組合物。 "有機組份"意指除無機奈米粒子外的所有組合物組份。對於其中可聚合組合物不含無機奈米粒子之具體實施例而言’有機組份等同於可聚合組合物。本文所定義之術語"奈米粒子，，意指直徑小於約1〇〇奈米之粒子（初級粒子或經締合的初級粒子）。 ’’經表面改質之膠狀奈米粒子，•意指每—皆具有一經改質表面之奈米粒子，以使奈米粒子可提供一穩定分散相。，，聚集作用"意指彼此間以化學方式結合之初級粒子間之強結合。很難使聚集體分解成更小粒子。 ”團聚作用，，意指藉由電荷或極性結合在一起並可分解成更小實體之初級粒子間之弱結合作用。 ”初級粒徑"意指單個（非聚集體、非團聚體）粒子之平均直徑。增亮膜通常增強一照明裝置之同轴亮度（本文中意指，,亮度）°增亮膜可係透光之微結構膜？該微結構表面形貌係複數個位於膜表面上之棱鏡，以便該等膜可用於通過反射及折射使光變向。棱鏡之高度通常介於約丨至約乃微米之間。當用於-光學顯示器（例如在膝上型電腦、手錄等中所用者）時，該微結構光學膜可藉由將自該顯示器逃逸之光限 102543.doc 1363062 制在與通過該光學顯示器成叼釉線呈期望角度之一對平板内而增強光學顯示益之亮度。結果，原本離開顯示器超出可谷許範圍之光將折回. 顦不器，在該顯示器處光線之一部分可"再循環"並以容許光自顯示器逃逸之角度折回微結、:再循環报有益，此乃因其能降低向顯示器提供所期望亮度水平所必須之功率消耗。(II) wherein R1 is independently hydrogen or fluorenyl, R2 is independently hydrazine or Br, 102543.doc 1363062, -C(O)-, -S-, -S(〇)- or Z is independently -C (CH3)2-, -CH2--S(0)2-, the L-series are independently selected from the group consisting of a straight chain and a branched ^/丨2 alkyl group, wherein the carbon chain is optionally Substituting a plurality of oxygen groups and/or a carbon atom, optionally substituted with one or more hydroxyl groups; and a mixture of i) and ii); b) at least about 10% by weight of inorganic nanoparticles; and c) optionally comprising A crosslinker of at least two (meth) acrylate functional groups. • In another embodiment, a brightness enhancing film comprising a brightening film comprising a reaction product comprising the polymerizable composition described below: .a) at least about 15% by weight of one or more (Meth)acrylated aromatic epoxy resin oligomer; b) at least about 10 weight. /. Inorganic nanoparticles; and, in the case of distraction, a crosslinking agent comprising at least two (meth) acrylate functional groups. In another embodiment, a substantially solvent-free polymerizable composition having a brightness-enhancing polymeric structure-enhancing film comprising an organic component and at least 1% by weight inorganic nanoparticle is illustrated. The reaction product, the organic component comprising 3 - or more ethylenically unsaturated monomers. The organic component has a viscosity below 1000 cps under the armpit. The organic component may comprise at least one polyethylene-based unsaturated monomer having a number average molecular weight of more than 450 grams per mole. ^ </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> <RTIgt; </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> The product, the organic component, has 3 or more ethylenically unsaturated monomers, wherein the organic component has a refractive index of less than 105543.doc 1363062 and less than 154. The amount of inorganic particles is typically less than about 60 weights by surface modification. Inorganic nanoparticles generally contain nanoparticles preferably: = material: recorded, oxidized, tin oxide, mixed metal oxide gate II. : The primary particle size of the a particle may be between 5 nm and 75 nm, and between [H) and 30 nm, between 5 nm and 5 nm. The first monomer is preferably The composition of the reaction product of the (meth)acrylic acid is combined with the (meth)acrylic acid. The polymerizable composition further comprises at least a second high refractive index monomer (ie, different from the first monomer). Preferably, the polymerizable composition is free of methacrylate functional monomers. In other embodiments, the present invention relates to an article comprising a brightness enhancing film and a second optical film or light guide. The film is in contact with the second optical film or light guide. The second optical film may comprise a turning film, a diffuser, an absorbing polarizer, a reflective polarizer or a protective cover film. The polymerizable composition described herein may also Advantageously used in other optical or microstructured articles. [Embodiment] As used in the context of the present invention: Refractive index ""index of refraction" or "refractive index" means a material (e.g. The absolute refractive index of a monomer, which should be understood as free space The ratio of the speed of electromagnetic radiation in the radiation speed of the material. The refractive index can be measured using conventional methods and is typically measured in the visible region using an Abbe refractometer (e.g., available from Fisher Instruments 〇f Pittsburgh, PA). It should be generally understood that the measured refractive index can be 102543.doc -10- 1363062 depending on the instrument and has some degree of change β "(曱基)acrylic vinegar" means acrylic acid vinegar and methyl propyl acrylate Both dilute vinegar compounds. The polymerizable composition " is meant to include the entire composition of the organic group containing at least one polymerizable monomer and optional inorganic nanoparticles. "Organic component" means all composition components except inorganic nanoparticle. For the specific embodiment in which the polymerizable composition is free of inorganic nanoparticles, the 'organic component' is equivalent to the polymerizable composition. The term "nanoparticles" as defined herein, means particles having a diameter of less than about 1 nanometer (primary particles or associated primary particles). The surface-modified colloidal nanoparticles, which means that each has a modified surface of the nanoparticles, so that the nanoparticles provide a stable dispersed phase. , "aggregation effect" means a strong bond between the primary particles chemically combined with each other. It is difficult to break up aggregates into smaller particles. "Agglomeration," means a weak bond between primary particles that are combined by charge or polarity and can be broken down into smaller entities. "Primary particle size" means a single (non-aggregate, non-agglomerated) particle. The average diameter. The brightness enhancing film generally enhances the in-line brightness of a lighting device (in this context, brightness). The brightness enhancing film can be a light transmissive microstructure film. The microstructure surface topography is a plurality of prisms on the surface of the film so that the films can be used to redirect light by reflection and refraction. The height of the prism is typically between about 丨 and about a micron. When used in an optical display (such as in a laptop, hand recording, etc.), the microstructured optical film can be fabricated and passed through the optical display by illuminating the optical limit 102543.doc 1363062 from the display. The enamel line is one of the desired angles to the inside of the plate to enhance the brightness of the optical display. As a result, the light that originally left the display beyond the allowable range will be folded back. No part of the light at the display can be "recycled" and fold back to the microjunction at an angle that allows the light to escape from the display: This is beneficial because it reduces the power consumption necessary to provide the desired level of brightness to the display.

增亮膜包括具有一由對稱的尖與槽構成之規律重複圖案的具有微結構之物件。其他槽圖案之實例包括下述圖案，其中尖及槽不對％ ’且其中大小、取向或尖與槽間之距離皆不均自。增亮膜t實例闡述於Ll^A之美國專利第 5,175,〇3〇號反Lu之美國專利第5，183 597號中。參看圖卜增亮膜30可包含一底層2及一光學層4。光學層 4包含-規則的直角棱鏡線性陣列，該等棱鏡標記為棱鏡 6、8、12及14»每一棱鏡（例如，棱鏡6)具一第一小面職 -第二小面11 °棱鏡6、8、12及14在底層2上形成，底層2 具-棱鏡可於其上形成之第一表面18及一實質上扁平或平坦並與第-表面18對置之第二表面2〇。直角棱鏡意指頂角α 經常係約90。。然而，該角度可介於7〇。至12〇。間及可介於8〇。至100。之間。此外，頂角可係尖的、圓的、扁平的或戴平的。棱鏡小面不必相同，且棱鏡相對於彼此呈傾斜狀。光學物件之總厚度24與棱鏡高度22間之相互關係可改變。然而，理想情形通常係使用相對更薄的具有輪廓分明的棱鏡小面之光學層。棱鏡高度22與總厚度24之典型比例通常介於25/125至2/125之間。 102543.doc •12· 增亮膜之底層具有適於在光學產品（即，設計用於控制光流動之產品）中使用之性質及组成。許多材料可用作一底層材料’其限制條料該材料足夠光學透明，且其結構足夠堅固可組裝成一特定光學產品或可在一特定光學產品内使用較佳選擇對溫度及老化具足夠耐受性之底層材料，以使光學產品之性能不會隨時間流逝而受到損害。對於任何光學產品，底層材料之特定化學組成及厚度可取決於待構造之特定光學產品之要求。即，其中尤其包括平衡對強度、透明度、而ί高溫性、表面能量、對光學層之附著性之需求。底層厚度經常係至少約0.025毫米（mm)，且更經常係至少約〇.25毫米。此外，底層通常具不超過約复毫米之厚度。有用的底層材料包括乙酸丁酸纖維素、乙酸丙酸纖維素、三乙酸纖維素、聚醚砜、聚曱基丙烯酸罕酯、聚胺基甲酸醋、聚S旨、聚碳酸酯、聚氯乙烯、間規聚苯乙烯、聚奈一甲酸乙一 g旨、基於萘二羧酸之共聚物或混合物及玻璃。底層材料視情況可包含該等材料之混合物或組合物。舉例而言，底層可係多層的或可包含一懸浮或分散於一連續相中之分散相。底層材料之實例包括聚對苯二甲酸乙二酯（PET)及聚碳酸酯。有用的pET膜之實例包括相片級聚對苯一曱酸乙二醋（PET)及由 DuPont Films of Wilmington,The brightness enhancing film comprises a microstructured article having a regular repeating pattern of symmetrical tips and grooves. Examples of other groove patterns include patterns in which the tips and grooves are not right and the size, orientation or distance between the tips and the grooves are not uniform. An example of a brightness enhancing film is described in U.S. Patent No. 5,175, the entire disclosure of which is incorporated herein by reference. Referring to the Tub brightness enhancement film 30, a bottom layer 2 and an optical layer 4 may be included. The optical layer 4 comprises a linear array of regular rectangular prisms, the prisms being labeled prisms 6, 8, 12 and 14»each prism (for example, prism 6) having a first small face-second facet 11° prism 6, 8, 12 and 14 are formed on the bottom layer 2, the bottom layer 2 having a first surface 18 formed thereon and a second surface 2 substantially flat or flat opposite the first surface 18. Right angle prism means that the apex angle α is often about 90. . However, the angle can be between 7 inches. To 12 baht. Between and can be between 8 〇. To 100. between. In addition, the apex angle can be sharp, round, flat or flat. The prism facets need not be identical and the prisms are inclined relative to each other. The relationship between the total thickness 24 of the optical object and the prism height 22 can vary. However, the ideal situation is usually to use a relatively thinner optical layer with well-defined prism facets. A typical ratio of prism height 22 to total thickness 24 is typically between 25/125 and 2/125. 102543.doc •12· The underlayer of the brightness enhancing film has properties and composition suitable for use in optical products (ie, products designed to control the flow of light). Many materials can be used as an underlying material' which limits the material to be sufficiently optically transparent and structurally strong enough to be assembled into a specific optical product or to be sufficiently resistant to temperature and aging in a particular optical product. The underlying material so that the performance of the optical product does not suffer over time. For any optical product, the specific chemical composition and thickness of the underlying material may depend on the requirements of the particular optical product to be constructed. That is, it includes, inter alia, the need for balance of strength, transparency, ί high temperature, surface energy, and adhesion to an optical layer. The thickness of the bottom layer is often at least about 0.025 millimeters (mm), and more often at least about 〇25 mm. In addition, the bottom layer typically has a thickness of no more than about a few millimeters. Useful underlayer materials include cellulose acetate butyrate, cellulose acetate propionate, cellulose triacetate, polyether sulfone, polyglycol acrylate, polyurethane urethane, polystyrene, polycarbonate, polyvinyl chloride. , syndiotactic polystyrene, polyethylene naphthoate, copolymer or mixture based on naphthalene dicarboxylic acid and glass. The underlying material may optionally comprise a mixture or composition of such materials. For example, the bottom layer can be multi-layered or can comprise a dispersed phase suspended or dispersed in a continuous phase. Examples of the underlayer material include polyethylene terephthalate (PET) and polycarbonate. Examples of useful pET films include photo-grade poly(p-phenylene phthalate) (PET) and by DuPont Films of Wilmington,

Delaware購得之 PET，商品名” MeHnex"。底層材料可具有光學活性，且其可用作一偏光材料。已知許多底層材料可用作偏光材料。舉例而言，通過一膜之 102543.doc 1363062 偏光可藉由在一選擇性吸收通過的光之膜材料中加入二向色偏光器達成。偏光亦可藉由加入無機材料（例如，經排列之雲母片）或藉由一分散於連續膜内之不連續相（例如分散 H續膜内之光調製液晶之小滴）達成。作為替代方法，一膜可由不同材料之微細層製備。舉例而言，藉由採用拉伸膜、使用電場或磁場及塗佈技術等方法，可使該膜内之偏光材料排列成一偏光取向。偏光膜之實例包括彼等闡述於美國專利第5,825,543號及 φ第5,783，12〇號中者。該等偏光膜與增亮膜之組合使用已聞述於美國專利第6，ln，696號巾1光膜之另—實例聞述於美國專利第5,882,774號中。多層偏光膜由3M公司，以· ρ_， MN出售，商品名DBEF(雙增亮膜（Duai Bdghtness’PET purchased under the trade name "MeHnex". The underlayer material can be optically active and can be used as a polarizing material. Many underlayer materials are known to be used as polarizing materials. For example, through a film 102543.doc 1363062 Polarization can be achieved by adding a dichroic polarizer to a film material that selectively absorbs light. Polarization can also be accomplished by the addition of inorganic materials (eg, aligned mica flakes) or by dispersion of a continuous film. The discontinuous phase within (for example, a droplet of light-modulating liquid crystal dispersed in the H-continuation film) is achieved. Alternatively, a film may be prepared from a fine layer of a different material. For example, by using a stretched film, using an electric field or The polarizing film in the film may be arranged in a polarizing orientation by a method such as a magnetic field and a coating technique. Examples of the polarizing film include those disclosed in U.S. Patent No. 5,825,543 and U.S. Patent No. 5,783,12. In combination with a brightness enhancing film, another example of a film which has been described in U.S. Patent No. 6, ln, 696, is disclosed in U.S. Patent No. 5,882,774. The multilayer polarizing film is manufactured by 3M Company. Sold by · ρ_, MN, trade name DBEF (Duai Bdghtness’

Enhancement Film))。在增亮膜中使用此等多層偏光光學膜已闡述於美國專利第5,828,488號中。其他偏光與非偏光膜亦可用作本發明增亮膜之底層，例冑述於美國專利第5’612,82G號及第5,486,949號中者。本發明係關於用於光學物件且特定而言用於增亮膜光學 f之可聚合樹脂組合物。增亮物件或其他微結構物件包括 I經聚合結構，該經聚合結構包含有機組份反應產物且視 y兄包含複數個奈米粒子。經聚合結構可係由一底層及一 :*層構成之光于凡件或光學產品。該底層及光學層可由相同或不同聚合材料製備。一對:大多數產品應用，該可聚合樹脂组合物包含一具有之折射率之第一單體；而轉向膜之可聚合樹脂 102543.doc •14- 1363062 組合物可具有低至1.44之折射率。在可見光譜中之高透光度通常亦較佳。本發明之組合物較佳可藉由在光起始劑存在下用紫外或可見光照射而聚合。在一具體實施例中，本發明係關於一含一第一單體之可聚合組合物，該第一單體包含一具下述通用結構式I或主·要部分：Enhancement Film)). The use of such multilayer polarizing optical films in brightness enhancing films is described in U.S. Patent No. 5,828,488. Other polarizing and non-polarizing films can also be used as the underlying layer of the brightness enhancing film of the present invention, as exemplified in U.S. Patent Nos. 5,612,82, and 5,486,949. The present invention relates to polymerizable resin compositions for optical articles and in particular for brightness enhancing film optics f. The brightness enhancing article or other microstructured article comprises a polymeric structure comprising an organic component reaction product and comprising a plurality of nanoparticles. The polymerized structure can be composed of a bottom layer and a :* layer to light the parts or optical products. The bottom layer and optical layer can be made from the same or different polymeric materials. A pair: for most product applications, the polymerizable resin composition comprises a first monomer having a refractive index; and the polymerizable resin of the turning film 102543.doc • 14-1363062 The composition may have a refractive index as low as 1.44 . High transmittance in the visible spectrum is generally preferred. The composition of the present invention is preferably polymerized by irradiation with ultraviolet or visible light in the presence of a photoinitiator. In one embodiment, the invention is directed to a polymerizable composition comprising a first monomer comprising a general structural formula I or a main portion:

(II) 在結構式I及II中之每一個中，每一 R1獨立地係氫或曱基。每一 R2獨立地係氫或溴。每一 ζ獨立地係-C(CH3)2-、-CH2-、 -C(O)-、-S-、-S(O)-或-S(0)2- ’ 且每一 Q獨立地係〇或 s。 R1基團通常皆相同。R2基團通常彼此亦相同。在結構式ιι 中’ L係一連接基團。L可獨立地包含一具支鏈或直鏈C2_Ci2 102543.doc -15· 1363062 统基。烧基之碳鏈視情況可經一或多個氧基團取代。此外，烧基之碳原子視情況可經一或多個羥基取代。舉例而言，L 可係-CH2CH(OH)CH2·。連接基團通常皆相同。該烷基較佳包含不超過8個碳原子且更佳包含不超過6個碳原子。亦可使用I與II之混合物。該第一單體可合成或購買。本文所用之主要部分意指含有剛才所述特定結構之至少6〇至7〇重量％之單體。通常應瞭解，其他反應產物經常亦可作為此等單體合成之副產物 | 存在》該第一單體較佳係四溴雙酚A二縮水甘油醚與丙烯酸之反應產物。該第一單體可自UCB &司，Smyrna，GA獲得，商品名"RDX-51027”。該材料包含由2_丙烯酸（1_甲基亞乙基）雙[(2,6-二溴-4，1-伸苯基）氧基（2_羥基_3，丨·丙二基）]酯構成之主要部分。儘管，亦可適當應用此等第一單體之混合物，但為便於製造，較佳使用盡可能少的不同單體，且仍可獲得具適當 •增益之增亮膜。為滿足該目的，增亮膜較佳係由該等第一單體中唯種之反應產物（且特定而言四溴雙酚八二縮水甘油醚與丙烯酸之反應產物）組成。 CN115"及在另一具體實施例中，該可聚合組合物包含至少一（甲基） ^酸化之芳族環氧樹脂寡聚物。各種（甲基）丙烯酸化之芳，氧樹脂寡聚物市而有售。舉例而言，（甲基）丙稀酸化之方族被氧樹脂（闡述為經改質之環氧丙烯酸酯）可自 Exton，PA獲得，商品名”CNU8"、 102543.doc 16 1363062 ’’CN112C60'，。（甲基）丙烯酸化之芳族環氧樹脂寡聚物（闊述為一環氧丙烯酸酯寡聚物）可自Sartomer獲得，商σ名 "CN2204'此外，一（曱基）丙烯酸化之芳族環氧樹脂I聚物（闡述為摻混有40%三羥甲基丙烷三丙烯酸酯之環氧線型盼駿丙烯酸酯樹脂）可自Sart〇mer獲得，商品名 "CN112C60"。在某些具體實施例中，該芳族環氧丙烯酸酯係衍生自雙酚A，例如Π之雙酚Αβ然而，在其他具體實施例中，芳族 _環氧丙烯酸g旨可衍生自—不同於雙紛Α之單體。該有機組份可包含芳族環氧丙烯酸酯、至少一交聯劑、至少一反應性稀釋劑及至少一其他乙烯系不飽和單體。另一選擇為，該可聚合組合物之有機組份可僅包括芳族環氧丙烯酸酯及交聯劑或芳族環氧丙烯酸酯及反應性稀釋劑，此等中之每一個皆包括光起始劑。若在可聚合組合物中使用芳族環氧丙烯酸酯，則該芳族環氧丙烯酸酯係單官能基的，其限制條件為該可聚合組合物包括至少一含至少兩個乙稀系不飽和可聚〇基團之成份。該芳族環氧丙烯酸酯可具有三個或多個（甲基）丙烯酸酯基團。該芳族環氧（甲基）丙烯酸酯可經鹵化’通常具有1·56以上之折射率。在其他態樣中，該芳族環氧（甲基）丙稀酸酯可具有低於丨56之折射率。於65t：下，該方族環氧（甲基）丙烯酸酯可具有2150 cps以上之黏度。可用低於3 0重量％之芳族環氧（甲基）丙烯酸酯，例如與一反應，稀釋劑組合使用。在其他具體實施例中，於价下，〇芳族裱氧（，基）丙烯酸酯可具有低於cps之黏度，且 102543.doc 1363062 可使用30重量％以上之芳不必使用稀釋劑。在有機組份中族環氧（甲基）丙烯酸酯。該第-單體及/或芳族環氧（甲基）丙稀酸醋較佳以 15重量%(例如’2〇重量。〜。重量％、35重量％'40重量%約 45重量％及5〇重量％及介於其間之任何幻存在於可聚合物中。該第—單體及/或芳族環氧（甲基）丙稀酸S旨之;通常不超過約60重量％。除該第-單體及/或芳族環氧（甲基）丙稀酸醋外，本發明 _之可聚合組合物視情況可包括至少一種且較佳僅包括一種交聯劑。多官能基單體可用作交聯劑，以提高由可聚合組合物之聚合所產生聚合物之玻璃轉變溫度。玻璃轉變溫度可藉由此項技術中習知之方法量測，例如示差掃描熱量測定法(DSC)、調節式DSC或動態機械分析。該聚合組合物較佳經充分交聯，以提供一大於451之玻璃轉變溫度。該交聯劑包含至少兩個（甲基）丙烯酸酯官能基。由於甲基丙烯酸酯基團之反應性往往較丙烯酸酯基團弱，故該交 _聯劑較佳包含三或多個丙烯酸酯基團。舉例而言，合適的交聯劑包括己二醇丙烯酸酯（HDDA)、異戊四醇三（甲基）丙烯酸酷、異戊四醇四（曱基）丙烯酸酯、三羥甲基丙烷三（甲基丙烯酸醋）、二異戊四醇五（甲基）丙烯酸酯、二異戊四醇六（曱基）丙烯酸酯、乙氧基化三羥甲基丙烷三（曱基）丙烯酸醋、甘油二（甲基）丙烯酸酯、丙氧基化異戊四醇三（甲基）丙浠酸自旨及二三羥曱基丙烷四（曱基）丙烯酸酯。可使用任何一種交聯劑或彼等之組合。 102543.doc -18 - 1363062 交聯劑較佳以至少約2重量％之量存在於該可聚合組合物中。交聯劑之量通常不超過約25重量％。交聯劑可以介於約5重量至約丨5重量％間之任何量存在。交聯劑較佳包括己二醇二丙烯酸酯（HDDA)、異戊四醇三 (甲基）丙烯酸酯、異戊四醇四（甲基）丙烯酸酯、二聚異戊四醇五（甲基）丙烯酸酯、三羥甲基丙烷三（曱基）丙烯酸酯、二二經甲基丙院四（曱基）丙烯酸酯及其混合物。交聯劑更佳不含曱基丙烯酸酯官能基。異戊四酵三丙烯酸酯（peta)及二 # 聚異戊四醇五丙烯酸酯可自Sartomer公司，Exton，PA購得’商品名分別係"SR444"及"SR399LV";自〇saka〇rganic(II) In each of Structural Formulas I and II, each R1 is independently hydrogen or fluorenyl. Each R2 is independently hydrogen or bromine. Each ζ independently is -C(CH3)2-, -CH2-, -C(O)-, -S-, -S(O)- or -S(0)2-' and each Q is independently System or s. The R1 groups are usually the same. The R2 groups are usually also identical to each other. In the structural formula, 'L is a linking group. L may independently comprise a branched or linear C2_Ci2 102543.doc -15· 1363062 system. The carbon chain of the alkyl group may be substituted with one or more oxygen groups as appropriate. Further, the carbon atom of the alkyl group may be substituted with one or more hydroxyl groups as the case may be. For example, L can be -CH2CH(OH)CH2. The linking groups are usually the same. The alkyl group preferably contains no more than 8 carbon atoms and more preferably no more than 6 carbon atoms. Mixtures of I and II can also be used. The first monomer can be synthesized or purchased. A major portion as used herein means a monomer containing at least 6 to 7 wt% of the specific structure just described. It is generally understood that other reaction products are often also used as by-products of the synthesis of such monomers. The presence of the first monomer is preferably the reaction product of tetrabromobisphenol A diglycidyl ether with acrylic acid. The first monomer is available from UCB & Division, Smyrna, GA under the trade name "RDX-51027". The material comprises 2-acrylic (1-methylethylidene) bis[(2,6-di) The main component of the bromo-4,1-phenylphenyloxy group (2-hydroxyl-3,anthracenediyl)] ester. Although a mixture of these first monomers can be suitably used, it is convenient. Manufacture, preferably using as few different monomers as possible, and still obtaining a brightness enhancing film with appropriate gain. To satisfy this purpose, the brightness enhancing film is preferably the only reaction product of the first monomers. (and in particular the reaction product of tetrabromobisphenol octahydroglycidyl ether and acrylic acid). CN115" and in another embodiment, the polymerizable composition comprises at least one (methyl) acidified aromatic Epoxy Resin Oligomers. Various (meth)acrylated aryl, oxy resin oligos are commercially available. For example, the (meth) acrylated family is oxygenated (described as modified) Epoxy acrylate) available from Exton, PA under the trade designation "CNU8", 102543.doc 16 1363062 ''CN112C60',(Meth)acrylated aromatic epoxy resin oligomers (herein referred to as epoxy acrylate oligomers) are available from Sartomer, quotient "CN2204', in addition, one (fluorenyl) acrylated An aromatic epoxy resin I polymer (described as an epoxy line type styrene acrylate resin blended with 40% trimethylolpropane triacrylate) is available from Sart〇mer under the trade name "CN112C60". In certain embodiments, the aromatic epoxy acrylate is derived from bisphenol A, such as bisphenol quinone beta. However, in other embodiments, the aromatic epoxidized acrylate is derived from - different The only ones in the double. The organic component may comprise an aromatic epoxy acrylate, at least one crosslinking agent, at least one reactive diluent, and at least one other ethylenically unsaturated monomer. Alternatively, the organic component of the polymerizable composition may comprise only aromatic epoxy acrylates and crosslinkers or aromatic epoxy acrylates and reactive diluents, each of which includes light. Starting agent. If an aromatic epoxy acrylate is used in the polymerizable composition, the aromatic epoxy acrylate is monofunctional, with the proviso that the polymerizable composition comprises at least one comprising at least two ethylenically unsaturated A component that can be agglomerated. The aromatic epoxy acrylate may have three or more (meth) acrylate groups. The aromatic epoxy (meth) acrylate may be halogenated' generally having a refractive index of 1.56 or more. In other aspects, the aromatic epoxy (meth) acrylate may have a refractive index lower than 丨56. At 65t:, the aromatic epoxy (meth) acrylate can have a viscosity of 2150 cps or more. Less than 30% by weight of an aromatic epoxy (meth) acrylate can be used, for example, in combination with a reaction, a diluent. In other embodiments, the fluorene aromatic oxime (,) acrylate may have a viscosity below cps, and 102543.doc 1363062 may use more than 30% by weight of the aryl without the use of a diluent. In the organic component, a group of epoxy (meth) acrylates. The first monomer and/or aromatic epoxy (meth) acrylate vinegar is preferably 15% by weight (for example, '2 〇 weight. 〜.% by weight, 35% by weight' 40% by weight and about 45% by weight and 5 % by weight and any intervening between them in the polymerizable polymer. The first monomer and / or aromatic epoxy (meth) acrylic acid S; usually not more than about 60% by weight. In addition to the first monomeric and/or aromatic epoxy (meth) acrylate vinegar, the polymerizable composition of the present invention may optionally comprise at least one and preferably only one crosslinking agent. The body can be used as a crosslinking agent to increase the glass transition temperature of the polymer produced by the polymerization of the polymerizable composition. The glass transition temperature can be measured by methods known in the art, such as differential scanning calorimetry (DSC). The modified DSC or dynamic mechanical analysis. The polymeric composition is preferably sufficiently crosslinked to provide a glass transition temperature greater than 451. The crosslinking agent comprises at least two (meth) acrylate functional groups. The acrylate group is often less reactive than the acrylate group, so the cross-linking agent Preferably, three or more acrylate groups are included. For example, suitable crosslinking agents include hexanediol acrylate (HDDA), pentaerythritol tris(meth) acrylate, and isopentaerythritol tetrakis Acrylate, trimethylolpropane tris(methacrylic acid vinegar), diisopentaerythritol penta (meth) acrylate, diisopentaerythritol hexa(meth) acrylate, ethoxylated trishydroxyl Propane tris(indenyl)acrylic acid vinegar, glycerol di(meth)acrylate, propoxylated pentaerythritol tris(methyl)propionic acid and ditrihydroxyhydrin propane tetra(indenyl)acrylic acid Any one of the crosslinking agents or a combination thereof may be used. 102543.doc -18 - 1363062 The crosslinking agent is preferably present in the polymerizable composition in an amount of at least about 2% by weight. Not more than about 25% by weight. The crosslinking agent may be present in any amount between about 5 and about 5% by weight. The crosslinking agent preferably comprises hexanediol diacrylate (HDDA), isovalerol tris ( Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dimeric pentaerythritol penta (methyl) Acrylate, trimethylolpropane tris(decyl) acrylate, dimethicone, tetrapropyl (meth) acrylate, and mixtures thereof. The crosslinker is more preferably free of mercapto acrylate functional groups. Four yeast triacrylate (peta) and two # polyisopreneol pentaacrylate can be purchased from Sartomer, Exton, PA, 'product name respectively' "SR444" &"SR399LV"; from 〇saka〇rganic

Chemical有限實業 ’ Osaka, Japan購得，商品名"Viscoat #300 ，自Toagosei有限公司，T〇ky0，japan購得，商品名 "Aronix M-305";及自 Eternal Chemical有限公司，Ka〇hsiung， Taiwan購得’商品名"Etermer 235"。三羥甲基丙烷三丙烯酸酯（TMPTA)及二三羥甲基丙烷四丙烯酸酯（二_TMpTA)自Chemical limited industry 'Osaka, Japan purchased, trade name " Viscoat #300, purchased from Toagosei Co., Ltd., T〇ky0, japan, trade name "Aronix M-305"; and from Eternal Chemical Co., Ltd., Ka〇 Hsiung, Taiwan purchased 'commodity name' "Etermer 235". Trimethylolpropane triacrylate (TMPTA) and ditrimethylolpropane tetraacrylate (di-TMpTA)

Sart〇mer 公司購得，商品名"SR351"及"SR355"。TMPTA 亦 •可自T〇ag〇Sei有限公司獲得，商品名"Aronix M_3〇9"。此外，乙氧基化二羥甲基丙烷三丙烯酸酯及乙氧基化異戊四醇三丙烯酸醋可自Sart()mei•購得，商品名分別係"似54"及 "SR494” ° 對於其中使用具足夠的可聚合反應性基團之表面經改質之奈来粒子之具體實施例而言，不必使用—交聯劑。舉例而言，！〇重量％之丙稀酸苯氧基乙基g旨可與該第一單體及至少H)重量。/。表面經改質之奈米粒子聯合(例如，實例【之彼 102543.doc -19- 丄363062 等）。該（等）(例如，第一芳族環氧（甲基）丙烯酸酯）單體及可選交聯劑與可選反應性稀釋劑通常包含（甲基）丙婦酸醋官能基。在較佳具體實施例中，該可聚合組合物僅包含丙稀酸賴官能基，且藉此實質上不含甲基丙烯酸醋官能基。 #本文所述之可聚合組合物包含（例如表面經改質之）無機 p化物粒子。此等粒子之粒徑經選擇以避免顯著的可見光放射。s想情形係使用—多種無機氧化物粒+類型之混合 :以優化-光學或材料特性並降低總組合物成本。由：：奈米粒子及有機樹脂所形成之複合聚合物易於達成單獨用常規有機樹脂所不能獲得之耐久性。加入無機奈米粒子可改進藉此所形成物件（例如，增亮膜）之耐久性。剛才所述之可聚合組合物係用於提供實f上無溶劑之可聚合組合物之較佳組合物，該可聚合組合物包含無機奈米粒^及-有機組份，其中該有機組份具低黏度，例二於 180卞下，黏度低於1000 cps » 、 ”曰貫質上無溶劑”意指料聚合組合物具有低於5重量％、4 重量％、3重量％、2重量％、i重量％及〇5重量％之（例如，有機）溶劑。溶劑濃度可藉由習知方法量測’例如氣相法。低於0.5重量％之溶劑濃度較佳。該有機組份可係一固體或包含一固體組份，1 為該可聚合組合物之溶點低於塗佈溫度。室；/、艮制條件份可係一液體。 ’皿下該有機組该有機組份之各組份較佳經選擇，以忧磙有機組份具一 I02543.doc •20- 1363062 低黏度。通常，有機組份之黏度實質上低於先前所使用組合物之有機組份。該有機組份之黏度低於1000 cps，且通常低於900 cps。在塗佈溫度下，該有機組份之黏度可低於8〇〇 cps，低於450 cps，低於600 cps或低於500 cps。本文所用黏度使用動態應力流變儀（剪切速度高達1〇〇〇秒-1)，用25毫米平行板量測。此外，在塗佈溫度下，該有機組份之黏度通常係至少10 cps ’更通常係至少50 cps，尤基通常係至少 100 cps ’且最通常係至少2〇〇 cps 〇Sart〇mer acquired the trade name "SR351" and "SR355". TMPTA is also available from T〇ag〇Sei Co., Ltd. under the trade name "Aronix M_3〇9". In addition, ethoxylated dimethylolpropane triacrylate and ethoxylated pentaerythritol triacrylate vinegar are available from Sart () mei, under the trade names "like 54" and "SR494" ° For a specific embodiment in which a surface-modified nanoparticle having sufficient polymerizable reactive groups is used, it is not necessary to use a crosslinking agent. For example, 〇% by weight of acrylic acid phenoxy The base ethyl group is intended to be combined with the first monomer and at least H) by weight of the surface modified nanoparticle (for example, the example [the one of 102543.doc -19- 丄 363062, etc.). (for example, the first aromatic epoxy (meth) acrylate) monomer and optional crosslinker and optional reactive diluent typically comprise a (meth) propyl acetoacetate functional group. In one embodiment, the polymerizable composition comprises only the acrylate lyophile group, and thereby substantially free of methacrylate acrylate functionality. # The polymerizable composition described herein comprises (eg, surface modified) inorganic P-particles. The particle size of these particles is chosen to avoid significant visible radiation. The situation is the use of a mixture of multiple inorganic oxide particles + types: to optimize - optical or material properties and reduce the cost of the total composition. From:: Composite polymers formed from nanoparticles and organic resins are easy to achieve with conventional organic resins alone Durability not obtained. The addition of inorganic nanoparticles can improve the durability of the article (e.g., brightness enhancing film) formed thereby. The polymerizable composition just described is used to provide solventless polymerizable on real f. A preferred composition of the composition, the polymerizable composition comprising an inorganic nanoparticle and an organic component, wherein the organic component has a low viscosity, and the second component has a viscosity of less than 1000 cps under 180 » », "Soluble-free" means that the polymeric composition has less than 5% by weight, 4% by weight, 3% by weight, 2% by weight, i% by weight, and 5% by weight of (for example, an organic) solvent. It is measured by a conventional method, for example, a gas phase method. A solvent concentration of less than 0.5% by weight is preferred. The organic component may be a solid or comprise a solid component, and 1 is a melting point of the polymerizable composition. Coating temperature The chamber can be a liquid. The components of the organic component of the organic group are preferably selected to worry about the organic component having a low viscosity of I02543.doc • 20-1363062. Typically, the viscosity of the organic component is substantially lower than the organic component of the previously used composition. The viscosity of the organic component is less than 1000 cps and is typically less than 900 cps. At the coating temperature, the organic component Viscosity can be less than 8 〇〇 cps, less than 450 cps, less than 600 cps or less than 500 cps. The viscosity used in this paper uses a dynamic stress rheometer (shear speed of up to 1 -1 -1) with 25 mm Parallel plate measurements. Further, at the coating temperature, the viscosity of the organic component is typically at least 10 cps' more typically at least 50 cps, and the Ukki is typically at least 100 cps' and most typically at least 2 cps 〇

塗佈溫度通常介於室溫（即，25eC)至180°F(82°C)之間。塗佈溫度可低於170下（77。(：），低於16〇。1?(71。(：），低於15〇 F (66 C )，低於 140卞（60。(：），低於 130°F (54°C )或低於 120 F (49 C)。該有機組份可係一固體或包含一固體組份，其限制條件為熔點低於塗佈溫度。室溫下有機組份可係一液體。The coating temperature is typically between room temperature (ie, 25 eC) to 180 °F (82 °C). The coating temperature can be less than 170 (77. (:), less than 16〇.1? (71. (:), less than 15〇F (66 C), less than 140卞 (60. (:), Below 130 °F (54 ° C) or below 120 F (49 C). The organic component may be a solid or contain a solid component, the restriction is that the melting point is lower than the coating temperature. The component can be a liquid.

對大多數產品應用而言，該有機組份及可聚合組合物具一至少1.47之折射率；而一轉向膜之可聚合樹脂組合物可具一低至1.44之折射率。該有機組份或可聚合組合物之折射率可係至少 H M9、15〇、i 51、i 52、i」3、154、 ’56 1·57' 1·58、1·59或1.60。包括奈来粒子之可 ^ 3、且〇物可具一面至^70(例如至少1.61、1.62、1.63、丄65 1.66、1.67、1.68或1.69)之折射率。可見光譜中之高透光度通常亦較佳。因此’剛才所述可聚合組合物亦係用於提供-實質上益物之較佳組合物，該可聚合組合物包不米粒子及—^ _ Λ, Λ „ 或夕種乙烯系不飽和單體之有機組份， 102543.doc -21 · 1363062 其中該有機組份具有高折射率，即至少1.54之折射率。具有低黏度及/或高折射率有機組份之可聚合組合物亦可由其他乙烯系不飽和單體製備。該有機組份可包含一（甲基）丙烯酸化之胺基甲酸酯寡聚物、（甲基）丙烯酸化之聚酯寡聚物、（曱基）丙烯酸化之酚系寡聚物、（甲基）丙烯酸化之丙烯酸寡聚物及其混合物。然而，在某些具體實施例中，該有機組份不含胺基曱酸酯鍵。該有機組份可包含至少一具有大於450克/莫耳數目平均分子量之寡聚乙烯系不飽和單體，其通常與一反應性稀釋劑及/或交聯劑組合。合適的寡聚（甲基）丙烯酸化之芳族環氧樹脂寡聚物可自 Sartomer購得，商品名"CN104"、"CN116"、"CN120，，、 "CN121” 及"CN136";自 Cognis 購得，商品名"Photomer 3016";及自 UCB 購得，商品名 ”3200"、"3201"、”3211”及 "3212"。合適的胺基甲酸酯（甲基）丙烯酸酯可自Sartomer購得，商 Φ 品名"CN965”、”CN968n、"CN981”、”CN 983”、"CN 984”、 "CN972” 及”CN978” ；自 Cognis 購得，商品名"Photomer 6210"、"Photomer 6217"、"Photomer 6230"、"Photomer 6623"、"Photomer 6891”及"Photomer 6892” ；及自 UCB購得，商品名"Ebecryl 1290”、"Ebecryl 2001"及”Ebecryl 4842"。合適的聚酯（甲基）丙烯酸酯可自Sartomer賭得，商品名，’CN292·，；自 Cognis購得，商品名"Photomer 5010”、 "Photomer 5429”、"Photomer 5430”、"Photomer 5432"、 102543.doc -22- 1363062 ”Photomer 5662”、"Photomer 5806”及"Photomer 5920";及自 UCB購得，商品名"Ebecryl 80"、"Ebecryl 81"、"Ebecryl 83"、"Ebecryl 450"、"Ebecryl 524"、"Ebecryl 525"、"Ebecryl 585"、"Ebecryl 588"、"Ebecryl 810"及"Ebecryl 2047"。合適的盼系（甲基）丙稀酸酯可自Sartomer購得，商品名 "SR601"及’’SR602";自 Cognis購得，商品名"Photomer 4025" 及"Photomer 4028”。合適的（曱基）丙烯酸化之丙烯酸寡聚物亦可購得或可藉由此項技術尹習知之方法製備。在本文所述之每一具體實施例中，該可聚合樹脂組合物視情況但較佳包含至多約35重量％(例如，介於1至35間之整數）之反應性稀釋劑’以降低可聚合樹脂組合物之黏度，並改進可加工性。反應性稀釋劑係單乙烯系不飽和單體，例如（甲基）丙烯酸酯或經N-單取代或經Ν,Ν-二取代之（甲基）丙烯醢胺’特別是丙烯醯胺。該等反應性稀釋劑包括义烷基丙烯醯胺及Ν，Ν-二烷基丙烯醯胺，特別是彼等含有Ci 4 烧基者。實例係N-異丙基丙烯醯胺、N_第三_ 丁基丙烯醯胺、N，N-二甲基丙烯醯胺、N，N_二乙基丙烯醯胺、N_乙稀基°比略咬酮及N-乙烯基己内醯胺。較佳稀釋劑可具一超過1.50(例如，超過1.55)之折射率。此等反應性稀釋劑可經.化或未經自化（例如，未經溴化）。合適的單體通常具—不超過（含）450克/莫耳之數目平均分子量。舉例而。’合適的反應性稀釋劑包括（曱基）丙烤酸笨氧 102543.doc •23- 1363062 基乙基酯；（曱基）丙烯酸苯氧基_2_甲基乙基酯；（甲基）丙烯酸苯氧基乙氧基乙基酯、（甲基）丙烯酸3-羥基-2-羥基丙基雖；（甲基）丙烯酸苄酯、（甲基）丙烯酸4-(1-甲基-1-苯乙基）苯氧基乙基酯；丙烯酸苯硫基乙基酯；丙烯酸2-萘硫基乙基輯；丙烯酸1·萘硫基乙基酯；丙烯酸2,4,6-三溴苯氧基乙基醋；丙烯酸2,4·二溴苯氧基乙基酯；丙烯酸2·溴苯氧基乙基酷；丙烯酸1·萘氡基乙基酯；丙烯酸2-萘氧基乙基酯；丙稀酸苯氧基2-甲基乙基酯；丙烯酸苯氧基乙氧基乙基酯； • 丙稀酸3_苯氧基-2-羥丙基酯；丙烯酸2-苯基苯氧基乙基醋；丙烯酸4-苯基苯氧基乙基酯；丙烯酸2,4-二溴-6-第二丁基苯基酯；丙烯酸2,4-二溴-6-異丙基苯基酯；丙烯酸苄基輯；丙烯酸苯基酯；丙烯酸2,4,6-三溴苯基酯。亦可應用其他高折射率單體，例如丙稀酸五溴苄基酯及丙烯酸五溴笨基酯。為便於製造，僅加入一種稀釋劑較佳。一較佳稀釋劑係 (甲基）丙烯酸苯氧基乙基酯；且特定而言，丙烯酸笨氧基乙 _ 基酯（PEA)。丙烯酸苯氧基乙基酯有不止一個市售來源，包括可自 Sart〇mer購得，商品名"SR339";自 EternalChemical 有限公司購得，商品名，，Etermer 21〇” ；及自T〇ag〇sei有限公司購得，商品名"TO-1166"。丙烯酸苄基酯可自AlfaAeser 公司，Ward Hill，ΜΑ購得。此等可選單體可以至少約5重量％之量存在於可聚合組合物中。該（等）可選單體通常總計不超過該可聚合組合物之約50重量％。某些具體實施例之可選高折射率單體之總量 102543.doc •24- 1363062 介於約30重量％至約45重量％之間（包括介於30至45間之整數）。，可選高折射率單體可經鹵化（即，經溴化）。一高折射率 .* 可選單體之實例係（甲基）丙烯酸2,4,6-三溴苯氧基乙基酯，自 Daiichi K〇gy〇 Seiyaku有限公司（Kyoto, japan)購得，商品名"BR-31" » 合適的聚合方法包括此項技術中所習知之溶液聚合、懸浮液聚合、乳液聚合及本體聚合。合適的方法包括在游離 # 基起始劑存在下加熱及在光起始劑存在下用電磁輻射（例如各外光或可見光）照射。在可聚合組合物合成中經常使用抑制劑’以阻止合成、運輸及儲存期間樹脂之過早聚合。合適的抑制劑包括50至1000 ppm水平之對苯二酚、4_甲氧基笨酚及受阻胺氮氧化物抑制劑。如熟習此項技術者所熟知，可使用其他種類及/或數量之抑制劑。本發明之組合物視情況包含至少一光起始劑。單個光起始劑或其摻合物可用於本發明之增亮膜中。通常，光起始 ® 劑係至少部分可溶的（例如，在樹脂之處理溫度下），且在聚合後實質上係無色的。光起始劑可係有色的（例如，黃色）， • 其限制條件為光起始劑在曝露於UV光源後變得基本無色。 '· 合適的光起始劑包括氧化單醯基膦及氧化雙醯基膦。市 * 售氧化單或雙醯基膦光起始劑包括2,4,6-三甲基苯甲醯基一苯基氧膦，自BASF (Charlotte，NC)購得，商品名"Lucirin τρο";亞膦酸乙基_2,4,6_三曱基苯甲醯基苯基酯，亦自 BASF購得，商品名"Lucirin TP0-L” ；及雙（2,4,6-三甲基苯 102543.doc •25· 1363062 甲酿基）-苯基氧膦，自Ciba Specialty Chemicals購得，商品名"Irgacure 819，'。其他合適的光起始劑包括2-羥基-2-曱基 -1-本基-丙-1-酮，自 Ciba Specialty Chemicals講得，商品名 "Darocur 1173";及其他自 Ciba Specialty Chemicals購得之光起始劑’商品名"Darocur 4265"、"Irgacure 651"、"Irgacure 1800"、"lrgacure 369"、"Irgacure 1700"及"Irgacure 907，.。For most product applications, the organic component and the polymerizable composition have a refractive index of at least 1.47; and the polymerizable resin composition of a turning film can have a refractive index as low as 1.44. The organic component or polymerizable composition may have a refractive index of at least H M9, 15 〇, i 51, i 52, i"3, 154, '56 1·57' 1.58, 1.59 or 1.60. Including the Nai's particles can be 3, and the object can have a refractive index of one side to ^70 (for example, at least 1.61, 1.62, 1.63, 丄65 1.66, 1.67, 1.68 or 1.69). High transmittance in the visible spectrum is generally preferred. Thus, the polymerizable composition just described is also used to provide a preferred composition of the substantially beneficial material, which comprises non-rice particles and -^ _ Λ, Λ „ or oxime vinyl unsaturated tablets. The organic component of the body, 102543.doc -21 · 1363062 wherein the organic component has a high refractive index, that is, a refractive index of at least 1.54. The polymerizable composition having a low viscosity and/or high refractive index organic component may also be used. Preparation of ethylenically unsaturated monomers. The organic component may comprise a (meth)acrylated urethane oligomer, a (meth)acrylated polyester oligomer, (mercapto) acrylated a phenolic oligomer, a (meth)acrylated acrylic oligomer, and mixtures thereof. However, in certain embodiments, the organic component does not contain an amine phthalate linkage. An oligoethylenically unsaturated monomer comprising at least one number average molecular weight greater than 450 grams per mole, usually in combination with a reactive diluent and/or crosslinker. Suitable oligo(meth)acrylated Aromatic epoxy resin oligomers available from Sartomer The trade names "CN104", "CN116", "CN120,,, "CN121" and "CN136"; purchased from Cognis, trade name "Photomer 3016"; and purchased from UCB, the goods The names "3200", "3201", "3211" and "3212". Suitable urethane (meth) acrylates are available from Sartomer, quotient "CN965", "CN968n, &quot ;CN981", "CN 983", "CN 984", "CN972" and "CN978"; purchased from Cognis, trade name "Photomer 6210", "Photomer 6217", "Photomer 6230", &quot Photomer 6623","Photomer 6891" and "Photomer 6892"; and purchased from UBC, trade name "Ebecryl 1290", "Ebecryl 2001" and "Ebecryl 4842". Suitable polyester (meth) acrylates are available from Sartomer under the trade name 'CN292·, available from Cognis, trade name "Photomer 5010", "Photomer 5429", "Photomer 5430", &quot Photomer 5432", 102543.doc -22- 1363062 "Photomer 5662", "Photomer 5806" and "Photomer 5920"; and purchased from UBC, trade name "Ebecryl 80", "Ebecryl 81", &quot Ebecryl 83", "Ebecryl 456", "Ebecryl 525", "Ebecryl 585", "Ebecryl 588", "Ebecryl 810" and "Ebecryl 2047". Suitable forward (meth) acrylates are commercially available from Sartomer under the trade designations "SR601" and ''SR602"; available from Cognis under the trade name "Photomer 4025" and "Photomer 4028" The (fluorenyl) acrylated acrylic oligomers are also commercially available or can be prepared by the methods known in the art. In each of the specific embodiments described herein, the polymerizable resin composition is optionally It is preferred to include up to about 35% by weight (e.g., an integer between 1 and 35) of a reactive diluent ' to lower the viscosity of the polymerizable resin composition and to improve processability. The reactive diluent is a monoethylene system. Unsaturated monomers, such as (meth) acrylates or N-monosubstituted or fluorene, fluorene-disubstituted (meth) acrylamides, especially acrylamide. These reactive diluents include n-alkylene Acrylamide and hydrazine, hydrazine-dialkyl acrylamide, especially those containing Ci 4 alkyl. Examples are N-isopropyl acrylamide, N_third butyl decyl amide, N , N-dimethyl methacrylate, N, N-diethyl acrylamide, N-ethylene ° is slightly ketone and N-vinyl caprolactam. Preferred diluents may have a refractive index of more than 1.50 (for example, more than 1.55). These reactive diluents may or may not be self-chemically modified ( For example, without bromination. Suitable monomers usually have - no more than (including) a number average molecular weight of 450 g / mol. For example, 'suitable reactive diluents include (nonyl) propane acid 102543.doc •23- 1363062 ethyl ethyl ester; (fluorenyl) phenoxy-2-methylethyl acrylate; phenoxyethoxyethyl (meth)acrylate, (meth)acrylic acid 3 -hydroxy-2-hydroxypropyl; benzyl (meth)acrylate, 4-(1-methyl-1-phenylethyl)phenoxyethyl (meth)acrylate; phenylthioethyl acrylate Ester; 2-naphthylthioethyl acrylate; 1·naphthylthioethyl acrylate; 2,4,6-tribromophenoxyethyl acrylate; 2,4·dibromophenoxyethyl acrylate Ester; 2,bromophenoxyethyl acrylate; 1·naphthylethyl acrylate; 2-naphthyloxyethyl acrylate; phenoxy 2-methylethyl acrylate; phenoxy acrylate Ethyloxy Ethyl ester; • 3_phenoxy-2-hydroxypropyl acrylate; 2-phenylphenoxyethyl acrylate; 4-phenylphenoxyethyl acrylate; 2,4-acrylic acid Dibromo-6-t-butylphenyl ester; 2,4-dibromo-6-isopropylphenyl acrylate; benzyl acrylate; phenyl acrylate; 2,4,6-tribromobenzene acrylate Other high refractive index monomers such as pentabromobenzyl acrylate and pentabromyl acrylate may also be used. For ease of manufacture, it is preferred to add only one diluent. Phenyloxyethyl acrylate; and in particular, phenoxyethyl acrylate (PEA). Phenoxyethyl acrylate is available from more than one commercial source, including those available from Sart〇mer under the trade name "SR339"; available from Eternal Chemical Co., Ltd., trade name, Etermer 21〇; and from T〇 Ag〇sei Co., Ltd., trade name "TO-1166". Benzyl acrylate is commercially available from Alfa Aeser, Ward Hill, Inc. These optional monomers may be present in the polymerizable amount in an amount of at least about 5% by weight. In the composition, the (optional) optional monomers generally do not exceed about 50% by weight of the polymerizable composition. The total amount of optional high refractive index monomers of some embodiments is 102543.doc • 24-1363062 Between about 30% by weight and about 45% by weight (including an integer between 30 and 45). The optional high refractive index monomer can be halogenated (ie, brominated). A high refractive index.* An example of a monomer selected is 2,4,6-tribromophenoxyethyl (meth)acrylate available from Daiichi K〇gy〇Seiyaku Co., Ltd. (Kyoto, japan) under the trade name "BR-31" » Suitable polymerization methods include solution polymerization as is known in the art, Suspension polymerization, emulsion polymerization and bulk polymerization. Suitable methods include heating in the presence of a free #based initiator and irradiation with electromagnetic radiation (for example, external or visible light) in the presence of a photoinitiator. Inhibitors are often used in the synthesis to prevent premature polymerization of the resin during synthesis, transport and storage. Suitable inhibitors include hydroquinone, 4-methoxy phenol and hindered amine NOx at levels of 50 to 1000 ppm. Inhibitors. Other types and/or amounts of inhibitors may be used as is well known to those skilled in the art. The compositions of the present invention optionally comprise at least one photoinitiator. A single photoinitiator or blend thereof may be used. In the brightness enhancing film of the present invention, typically, the photoinitiator is at least partially soluble (e.g., at the processing temperature of the resin) and is substantially colorless after polymerization. The photoinitiator can be colored. (eg, yellow), • The limitation is that the photoinitiator becomes substantially colorless after exposure to a UV source. '· Suitable photoinitiators include oxidized monophosphorylphosphine and bisphosphonium oxide. Sales oxidation Or bis-decylphosphine photoinitiators include 2,4,6-trimethylbenzimidyl-phenylphosphine oxide, available from BASF (Charlotte, NC) under the trade name "Lucirin τρο"; phosphinic acid Ethyl 2,4,6-tridecyl benzhydryl phenyl ester, also available from BASF under the trade name "Lucirin TP0-L"; and bis(2,4,6-trimethylbenzene 102543 .doc •25· 1363062, a phenylphosphine oxide, available from Ciba Specialty Chemicals under the trade name "Irgacure 819, '. Other suitable photoinitiators include 2-hydroxy-2-mercapto-1-propenyl-propan-1-one, available from Ciba Specialty Chemicals under the trade name "Darocur 1173"; and others from Ciba Specialty Chemicals. The light starter 'product name' is Darocur 4265", "Irgacure 651", "Irgacure 1800", "lrgacure 369", "Irgacure 1700" and "Irgacure 907,.

光起始劑可以介於約〇. i至約10重量％間之濃度使用。光起始劑更佳以介於約0.5至約5重量％間之濃度使用。超過5 重量°/。通常不利，此乃因其有導致增亮臈變黃之傾向。如可熟習此項技術者決定，亦可適當應用其他光起始劑。表面活性劑，例如氟表面活性劑及以聚矽氧為主之表面活性劑視情況可包括在該可聚合組合物中以降低表面張力’增進潤濕’使塗層更光滑及塗層缺陷更少等。在較佳低於5分鐘之時標中，該可聚合組合物係可以能量The photoinitiator can be used at a concentration of between about 0.1% and about 10% by weight. The photoinitiator is more preferably used at a concentration of between about 0.5 and about 5 wt%. More than 5 weights /. It is usually unfavorable because it has a tendency to cause brightening and yellowing. Other photoinitiators may also be suitably employed as determined by those skilled in the art. Surfactants, such as fluorosurfactants and polyoxyxides-based surfactants, may optionally be included in the polymerizable composition to reduce surface tension & 'improve wetting' to make the coating smoother and coating defects more And less. The polymerizable composition can be energized in a time scale preferably less than 5 minutes.

固化的，例如對於一具75微米厚度之增亮臈而言。該可聚合組合物較佳經充分交聯以提供一通常大於45t之玻璃轉變溫度。玻璃轉變溫度可藉由任何此項技術中習知之方法量測’例如示差掃描熱量測定法（DSC)、冑節式dsc或動態機械分析》可聚合組合物可藉由常規游離基聚合法聚合。儘官可有用地使用缺少可聚合表面改質之無機奈米: 子’但無機奈米粒子較佳經表面改f，以使奈⑽子可有機組份聚合。表面經改質之（例如，膠狀）奈米粒子可以: 效增強物件或光學元件耐久性及/或折射率之量存在於‘ 聚合結構中。本文所述表面經改f之膠狀奈米粒子可〜 I02543.doc -26 - 1363062 種所期望之特性，包括（例如）奈米粒子與樹脂系統相容，以使奈米粒子在樹脂系統内形成穩定的分散相，表面改質可提供奈米粒子與樹脂系統之反應性，以使複合物更耐久，向樹脂系統令添加表面經適當改質之奈米粒子可使得對未固化組合物黏度影響較小。表面改質劑之組合可用於控制組合物之未固化與固化特性。表面經適當改質之奈米粒子可改良光學元件之光學及物理特性，例如，改良樹脂機械強度，使黏度變化最小化，同時增加樹脂系統中固體體積用量，及維持光學透明度，同時增加樹脂系統中之固體體積用量。表面經改質之膠狀奈米粒子可係具超過〗奈米且小於1〇〇奈米之初級粒徑或締合粒徑之氧化物粒子。奈米粒子較佳係未經締合。彼等之量測基於穿透式電子顯微術（TEM)。奈米粒子可包括金屬氧化物，例如氧化鋁、氧化錫、氧化銻' 二氧切、氧化錯、二氧化鈦、其混合物或其混合氧化物。表面經改質之膠狀奈米粒子實質上可完全凝聚。軋化矽之完全凝聚奈丨…丨、料丁一煆兵有乃％以上(較佳60%^上，且更佳7〇%以上）之結晶度（以經分離金屬氧化曰^。里'則）。舉例而言’結晶度可高達約86%或更高。結 :度可由X-射線繞射技術量測。經凝聚結晶㈠列如，氧化錯）具有—高折射率’而非晶形奈米粒子通常具有較 102543.doc -27- 1363062 至60重量％間或介於ι〇至4〇重量％之量存在於耐用物件或光學元件中。在本發明材料中所使用之二氧化矽可自Nalc〇Cured, for example, for a 75 μm thick brightening enamel. Preferably, the polymerizable composition is sufficiently crosslinked to provide a glass transition temperature generally greater than 45t. The glass transition temperature can be measured by any method known in the art, e.g., differential scanning calorimetry (DSC), sputum dsc or dynamic mechanical analysis. The polymerizable composition can be polymerized by conventional free radical polymerization. It is useful to use an inorganic nanoparticle which lacks a polymerizable surface modification: the sub-', but the inorganic nanoparticle is preferably surface-modified to polymerize the naphthalene (10) organic component. Surface modified (e.g., gelatinous) nanoparticles can be present in the 'polymeric structure in an amount that enhances the durability and/or refractive index of the article or optical component. The gelatinous nanoparticles described herein have been modified to have the desired properties, including, for example, nanoparticle compatible with the resin system to allow the nanoparticles to be in the resin system. Forming a stable dispersed phase, the surface modification can provide the reactivity of the nano particles with the resin system to make the composite more durable, and adding the surface to the resin system to properly modify the nanoparticle can make the viscosity of the uncured composition Less affected. A combination of surface modifying agents can be used to control the uncured and cured characteristics of the composition. Nano-particles with appropriately modified surfaces can improve the optical and physical properties of optical components, for example, improve the mechanical strength of the resin, minimize viscosity changes, increase the volume of solids in the resin system, and maintain optical transparency while increasing the resin system. The amount of solids used in the volume. The surface-modified colloidal nanoparticles may be oxide particles having a primary particle size or an association particle size of more than 1 nanometer and less than 1 nanometer. Preferably, the nanoparticles are unassociated. Their measurements are based on transmission electron microscopy (TEM). The nanoparticles may comprise a metal oxide such as alumina, tin oxide, cerium oxide dioxo prior to oxidation, titanium dioxide, mixtures thereof or mixed oxides thereof. The surface-modified colloidal nanoparticles are substantially completely agglomerated. The complete condensed nep of the rolled ruthenium 丨丨, 料煆煆煆乃乃乃乃乃乃 % % % 结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶结晶then). For example, the degree of crystallinity can be as high as about 86% or higher. Junction: The degree can be measured by X-ray diffraction technique. The agglomerated crystals (a) are, for example, oxidized, have a high refractive index and the amorphous nanoparticles generally have an amount between 102,543.doc -27 to 1363062 to 60% by weight or between ι and 4% by weight. For durable objects or optical components. The cerium oxide used in the material of the present invention may be derived from Nalc®

Chemical公司，Naperville，IL購得，商品名"NalcoCollodial Silicas"，例如產品 1040、1042、1050、1060、2327及 2329。舉例而言，合適的發煙二氧化矽包括自DeGussa AG，（Hanau， Germany)購得之產品，商品名"Aerosil series OX-50"及產品編號-130、-150及-200。發煙二氧化矽亦可自Cabot公司， Tuscola，I 購得，商品名"cab-0-SPERSE 2095” ' φ '’CAB_〇-spERSE A105"及"CAB-O-SIL M5"。氧化錯奈米粒子可具有介於5至5〇奈米間或5至15奈米間或10奈米之粒徑》氧化錯奈米粒子可以介於10至70重量％間或30至60重量％間之量存在於耐用物件或光學元件中。在本發明之組合物及物件中所使用之氧化鍅可自Nale〇 Chemical公司獲得’商品名"Nalc〇〇〇ss〇〇8"，及自 Buhler AG Uzwil，Switzerland獲得，商品名"Buhler zirconia z_w〇 sol。亦可製備氧化錯奈米粒子，例如在年η月曰申籲請之美國專利申請案第11/027426號及美國專利第 6,376,590號中所述。一氧化鈦、氧化銻、氧化鋁、氧化錫及/或混合金屬氧化物不米粒子可具有介於5至5〇奈米間或介於5至15奈米間或 10奈米之粒徑或締合粒徑。二氧化鈦、氧化銻、氧化鋁、氧化錫及/或混合金屬氧化物可以介於10至70重量％間或30 至6〇重量％間之量存在於耐用物件或光學元件中。在本發明材料中所使用之混合金屬氧化物可自CaMysts & 102543.doc •28- 1363062Chemical Company, Naperville, IL, trade name "NalcoCollodial Silicas", such as products 1040, 1042, 1050, 1060, 2327 and 2329. For example, suitable fumed cerium oxide includes products available from DeGussa AG, (Hanau, Germany) under the trade name "Aerosil series OX-50" and product numbers -130, -150 and -200. Fumed cerium oxide is also available from Cabot Corporation, Tuscola, I under the trade name "cab-0-SPERSE 2095" ' φ ''CAB_〇-spERSE A105" and "CAB-O-SIL M5". The oxidized nano-particles may have a particle size of between 5 and 5 nanometers or between 5 and 15 nanometers or 10 nanometers. The oxidized nano-particles may be between 10 and 70% by weight or between 30 and 60 weights. The amount between % is present in a durable article or optical component. The cerium oxide used in the compositions and articles of the present invention is available from Nale(R) Chemical Company as 'commercial name" Nalc〇〇〇ss® 8", and Obtained by Buhler AG Uzwil, Switzerland under the trade name "Buhler zirconia z_w〇sol. It is also possible to prepare oxidized nano-particles, for example, in U.S. Patent Application Serial No. 11/027,426, and U.S. Patent No. 6,376,590. The titanium oxide, cerium oxide, aluminum oxide, tin oxide and/or mixed metal oxide non-rice particles may have a range of between 5 and 5 nanometers or between 5 and 15 nanometers or 10 nanometers. Particle size or association particle size. Titanium dioxide, cerium oxide, aluminum oxide, tin oxide and / The mixed metal oxide may be present in the durable article or optical component in an amount between 10 and 70% by weight or between 30 and 6% by weight. The mixed metal oxide used in the material of the present invention may be from CaMysts & 102543 .doc •28- 1363062

Chemical Industries公司，Kawasaki, Japan購得，商品名 "Optolake 3"。表面處理奈米粒徑之粒子可在聚合物樹脂中提供一穩定分散相。表面處理較佳可穩定奈米粒子，以使粒子能在可聚合樹脂中充分分散，並產生一實質均一之組合物。此外’ 奈米粒子表面之至少一部分上可用一表面處理劑改質，以在固化期間使經穩定粒子可與可聚合樹脂共聚合或發生反應。本發明之奈米粒子較佳用一表面處理劑處理。一般而言，一表面處理劑具有一將附著至粒子表面（共價、離子方式或通過強物理吸附）之第一端及在固化期間使粒子與樹脂相容及/或可與樹脂反應之第二端。表面處理劑之實例包括醇、胺、羧酸、磺酸、膦酸、矽烷及鈦酸鹽。較佳類型之處理劑可部分由金屬氧化物表面之化學性質決定。矽烷適用於二氧化矽；且其他表面處理劑適用於矽質填充劑。對於金屬氧化物（例如氧化锆）而言，矽烷及羧酸較佳。表面改質可在與單體混合的同時或混合後實施。在矽烷之狀況下，在納入樹脂中前，使矽烷與粒子或奈米粒子表面反應較佳。所需表面改質劑之量取決於數種因素，例如粒徑、粒子類型、改質劑分子量及改質劑類型。一般而言，約一單層之改質劑附著至粒子表面較佳。所需附著步驟或反應條件亦取決於所用表面改質劑。對於矽烷而言，較佳係在酸性或鹼性條件下高溫表面處理約1至24小時。表面處理劑 (例如羧酸）不需要高溫或長時間處理。 102543.doc •29· 1363062 適於組合物之表面處理劑之代表性具體實施例包括例如以下化合物：異辛基三甲氧基·矽烷、N (3三乙氧基甲矽烷基丙基）胺基甲酸甲氧基乙氧基乙氧基乙基酯、N_(3三乙氧基曱矽烷基丙基）胺基曱酸甲氧基乙氧基乙氧基乙基酯、 3-(甲基丙烯醯氧基）丙基三甲氧基矽烷、3丙烯醯氧基丙基二甲氧基矽烷、3-(甲基丙烯醯氧基）丙基三乙氧基矽烷、 3-(甲基丙烯醯氧基）丙基甲基二曱氧基矽烷、3 (丙烯醯氧基丙基）甲基二甲氧基矽烷、3·(曱基丙烯醯氧基）丙基二甲 • 基乙氧基矽烷、甲基丙烯醯氧基）丙基二曱基乙氧基矽烷、乙烯基二甲基乙氧基矽烷、苯基三甲氧基矽烷、正辛基二甲氧矽烷、十二烷基三甲氧基矽烷、十八烷基三甲氧基矽烷、丙基三曱氧基矽烷、己基三甲氧基矽烷、乙烯基甲基二乙醯氡基矽烷、乙烯基甲基二乙氧基矽烷、乙烯基三乙酿氧基珍烧、乙烯基三乙氧基矽烷、乙烯基.三異丙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三苯氧基矽烷、乙烯基三-第三·丁氧基矽烷 '乙烯基三·異丁氧基矽烷、乙烯 ® 基二異丙烯氡基矽烷、乙烯基三（2-甲氧基乙氧基）矽烷、苯乙烯基乙基三甲氧基矽烷、巯基丙基三甲氧基矽烷、3縮水甘油氧基丙基三甲氧基矽烷、丙烯酸、甲基丙烯酸、油酸、硬脂酸、十二烷酸、2_[2_(2_曱氧基乙氧基）乙氧基]乙酸（MEEAA)、丙烯酸-β_羧乙基酯、2·(2·甲氧基乙氧基）乙酸、曱氧基苯基乙酸及其混合物。此外，已發現一專賣的石夕烧表面改質劑特別適合’其自〇SI Specialties，cronipton South Charleston，WV購得，商品名"SilqUestA123〇"。 102543.doc 30- 丄允3062 踢狀分散相中粒子之表面改質可以各種方式達成。該過程包括無機分散相與表面改質劑之混合物。視情況此時可添加-共溶劑，例如卜甲氧基·2_丙醇、乙醇、異丙醇、乙、％ ν,ν-一曱基乙醯胺及丨_曱基-2_啦咯烷酮。共溶劑可増強表面改質劑及經表面改f粒子之溶解I包含無機溶膠及表面改質劑之混合物隨後在室溫或高溫下藉助或不藉助混口發生反應。在一較佳方法中混合物可於約Μ。。下反應約24小時’產生表面經改f之溶膠。在對金屬氧化物進行表面改質之較佳方法中，金屬氧化物之表面.處理較佳涉及使酸性分子吸附至粒子表φ。重金屬氧化物之表面改質可於室溫下進行。Chemical Industries, Kawasaki, Japan, trade name "Optolake 3". The surface treated nanoparticles of nanoparticle size provide a stable dispersed phase in the polymer resin. The surface treatment preferably stabilizes the nanoparticles so that the particles are sufficiently dispersed in the polymerizable resin to produce a substantially uniform composition. Further, at least a portion of the surface of the nanoparticle can be modified with a surface treatment agent to allow the stabilized particles to copolymerize or react with the polymerizable resin during curing. The nanoparticles of the present invention are preferably treated with a surface treating agent. In general, a surface treatment agent has a first end that will adhere to the surface of the particle (covalently, ionicly or by strong physical adsorption) and the particles are compatible with the resin during curing and/or can react with the resin. Two ends. Examples of the surface treating agent include alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, decanes, and titanates. A preferred type of treating agent can be determined in part by the chemical nature of the metal oxide surface. Decane is suitable for cerium oxide; and other surface treatment agents are suitable for enamel fillers. For metal oxides such as zirconia, decane and carboxylic acid are preferred. Surface modification can be carried out while mixing with or after mixing with the monomers. In the case of decane, it is preferred to react the decane with the surface of the particles or nanoparticles before being incorporated into the resin. The amount of surface modifying agent required will depend on several factors such as particle size, particle type, modifier molecular weight, and modifier type. In general, it is preferred that about a single layer of modifier is attached to the surface of the particles. The desired attachment step or reaction conditions will also depend on the surface modifier used. For decane, it is preferred to subject to high temperature surface treatment under acidic or basic conditions for about 1 to 24 hours. The surface treatment agent (e.g., carboxylic acid) does not require high temperature or long time treatment. 102543.doc • 29· 1363062 Representative specific examples of surface treatment agents suitable for the composition include, for example, the following compounds: isooctyltrimethoxy-decane, N(3triethoxycarbamidopropyl)amine Methoxyethoxyethoxyethyl formate, methoxyethoxyethoxyethyl N-(3triethoxydecylpropyl)amine decanoate, 3-(methacryl)醯 oxy) propyl trimethoxy decane, 3 propylene methoxy propyl dimethoxy decane, 3-(methacryloxy) propyl triethoxy decane, 3- (methacryl oxime) Propylmethyl decyloxydecane, 3 (propylene methoxypropyl) methyl dimethoxy decane, 3 · (mercapto propylene methoxy) propyl dimethyl ethoxy decane, Methyl propylene oxime) propyl decyl ethoxy decane, vinyl dimethyl ethoxy decane, phenyl trimethoxy decane, n-octyl dimethoxy decane, dodecyl trimethoxy decane , octadecyltrimethoxydecane, propyltrimethoxy decane, hexyltrimethoxydecane, vinylmethyldiethoxydecane, vinylmethyldiethoxy矽, vinyl triethyl ethoxylated, vinyl triethoxy decane, vinyl. triisopropoxy decane, vinyl trimethoxy decane, vinyl triphenyl oxane, vinyl tri- Tris-butoxy decane 'vinyl tri-isobutoxy decane, ethylene ketone diisopropenyl decyl decane, vinyl tris(2-methoxyethoxy) decane, styrylethyl trimethoxy Decane, mercaptopropyltrimethoxydecane, 3 glycidoxypropyltrimethoxydecane, acrylic acid, methacrylic acid, oleic acid, stearic acid, dodecanoic acid, 2_[2_(2_曱oxy B Oxy)ethoxy]acetic acid (MEEAA), acrylic acid-β-carboxyethyl ester, 2·(2·methoxyethoxy)acetic acid, decyloxyphenylacetic acid, and mixtures thereof. In addition, it has been found that a monolithic stone shovel surface modifier is particularly suitable for 'sales from SI Specialties, cronipton South Charleston, WV, trade name "SilqUestA123〇". 102543.doc 30- 丄 306 The surface modification of the particles in the kick-like dispersed phase can be achieved in a variety of ways. The process includes a mixture of an inorganic dispersed phase and a surface modifying agent. Depending on the situation, a co-solvent such as methoxy- 2-propanol, ethanol, isopropanol, B, % ν, ν-mercaptoacetamide and 丨曱 -2 -2 -2 -2 Alkanone. The co-solvent may be a strong surface modifying agent and the dissolution of the surface-modified particles I. The mixture comprising the inorganic sol and the surface modifying agent is then reacted at room temperature or elevated temperature with or without a mixing port. In a preferred method the mixture can be in the range of about Μ. . The reaction was carried out for about 24 hours to produce a sol having a surface modified. In a preferred method of surface modification of a metal oxide, the surface treatment of the metal oxide preferably involves adsorption of acidic molecules to the particle table φ. Surface modification of heavy metal oxides can be carried out at room temperature.

Zr〇2與矽烷之表面改質可於酸性條件或鹼性條件下達成。在一較佳情況下，矽烷較佳於酸性條件下加熱一適當時間。在該時間内，分散相與氨水（或其他鹼）組合。該方法容許自Zr〇2表面移除酸抗衡離子，同時又能與矽烷反應。在一較佳方法中，使沉澱粒子自分散相並自液相分離。然後可以各種方法將表面經改質之粒子納入可固化樹脂中》—方面，較佳使用一溶劑交換操作，藉此向表面經改質之溶膠中添加該樹脂，隨後藉由蒸發移除水及共溶劑（若使用），藉此使粒子分散於聚合樹脂中。蒸發步驟可（例如）藉由蒸餾、旋轉蒸發或烘箱乾燥達成。另一方面，表面經改質之粒子可萃取至一不與水混溶之溶劑中’隨後進行溶劑交換（若需要）。另一選擇為，用於在可聚合樹脂中納入表面經改質奈米 102543.doc •31 - 1363062 粒子之另一方法包括將經改質粒子乾燥成-粉末’隨後添加粒子於其尹分散之樹腊材料。該方法令之乾燥步驟可藉由習知適於該系統之方法達成，例如㈣乾燥或喷霧乾燥。可使用表面改質劑之組合，其中至少一試劑具有一盥可固化樹脂共聚合之官能基。表面改質劑之組合物導致一更低黏度。舉例而言，該聚合基團係乙婦系不餘和基圓或一經受開環聚合反應之環狀宫能基。舉例而言，一乙稀系不餘和聚合基團可係—丙_^基丙稀酸自旨或乙稀基。一經受開環聚合反應之@ w 夂應之核狀呂能基通常含有-雜原子(例 =、硫或氮），且較㈣包含氧原子之Η環，例如環氧化物。一表面改質劑之較佳組合包括至少—具有能與可固月曰(之有機組份)共聚合之官能基之表面改質劑，及一不同於 :第一改質劑之第二改質劑。該第二改質劑視情況與可聚 t =物之有機組份共聚合。該第二改質劑可具有-低折 =率（Γ低於丨.52或低於丨.50)。該第二改質劑較佳係一包 4¾氧烧之改質劑，視情況其可與可聚合組組份共聚合。 ’機如Lu及LU等人所述，一具有微結構之物件（例如可由包含下述步驟之方法製備:⑷製備—可聚合組厶 (即，本發明之可聚合組合物)；(b)以剛夠填充一主表面* 腔！:量在負微結構化模製主表面上沉積該可聚合μ合^ (C)精由在預成型基材及主表面間移動可聚合組人來填充空腔，其中預成型基材及…0之粒 τ至少一個具有撓 102543.doc •32- 1363062 性；及（d)固化該組合物。主表面係金屬的（例如鎳鍍鎳銅或黃銅）或係在聚合條件下很穩定之熱塑性材料，且其較佳具有一容許自主表面完全移除經聚合材料之表面能。基底膜之一或多個表面視情況可塗有底漆或經別的方式處理以促進光學層與基底之附著。為達改進增益之目的，在顯示器中有效地使用本發明之增亮膜。一例示性背光液晶顯示器之示意圖一般於圖2中之 110處指出β在實際顯示器中，所繪示之各組件經常與增亮 • 膜接觸。本發明之增亮膜通常係位於光導118與液晶顯示器面板114之間。液晶顯示器面板一般在兩表面上皆包括一吸收偏光器。故，此吸收偏光器係毗鄰本發明之增亮膜放置。背光液晶顯示器亦可包括一光源116(例如，一螢光燈）及一白光反射器120(其亦用於朝向液晶顯示器面板反射光）。增亮膜111準直由光導118所發出之光，藉此增加液晶顯示器面板114之亮度，增加之亮度使液晶赫器面板能產生一更清晰的圖像，並容許光源116之功率降低以產生一擧所選亮度。背光液晶顯示器可用於參考標記符121所代表諸如電腦顯示器（膝上型顯示器及電腦監視器）、電視、錄影裝置、移動通信裝置、手持式裝置（即，行動電話、個人數位助理（PDA))、汽車及航空儀錶顯示器及諸如此類之設備中。顯不器可進-步包括位於增亮膜與液晶顯示器面板114 間之另-光學膜112。舉例而言，該另—光學膜可包括一擴散β、一反射偏光器或一第二增亮膜。如此項技術中所習知’其他光學膜可置於光學膜112與液晶顯示器面板114之 102543.doc •33· 1363062 間或置於增亮膜11丨與光導118之間。此外，一轉向膜可位於光導與光學膜之間。另一選擇為，增亮膜可係一轉向膜。一轉向膜通常包括形成於一輸入表面上之棱鏡結構，且該輸入表面係础鄰光導放置。以（與輸出表面通常呈小於30。之掠射角離開光導之光線遇到棱鏡結構。光線由該棱鏡結構之一第一表面折射’並由該棱鏡結構之第二表面反射光線’以便藉由轉向棱鏡或膜將光線導向所期望之方向（例如’實質上平行於顯示器之視轴偏光膜之實例包括彼等闡述於美國專利第5,825,543號及第5,783’120號中者。該等儋光膜與一增亮膜之組合使用已閣述於美國專利第6，ln，696號中。偏光膜之另一實例闡述於美國專利第5,882,774號中。市售之此等膜之一實例係由 3M公司以 DBEF (雙增亮膜（Dual Brightness Enhancement Film))為商品名出售之多層膜。多層偏光光學膜已闡述於 (幻如）美國專利第5,828,488號中。轉向膜通常包括形成於 '表面上之棱鏡結構，且該輸入表面係ott鄰光導放置。以與輸出表面通常呈小於30〇之掠射角離開光導之光線遇到棱鏡結構。《線由該棱鏡結構之一第一表面折射，並由該棱鏡結構之—第二表面反射，以便藉由轉向膜將光線導向，期望之方向（例如，實質上平行於顯示器視軸）。若加入該等附力口光學臈作為增亮膜之觸，則底層之厚度可明顯厚於先前所述者。本文所述可聚合組合物對於其他光學材料（例如，具有微結構之光學物件（例如，膜）)較為有利性光學材料包 102543.doc •34- 光學透鏡，例如菲彡圼耳广折射率膜，例如微二)透鏡;光學膜，例如高平垣膜，多層1例如全内反射膜，或增亮膜，、夕層膜，回射板；光學光纖或管道· 如適於製造雷玻辟… 尤纖次會道，撓性模具(例、電漿顯不器面板之障壁凸緣）及其# & & 折射率可聚合組合物製造光學產：二=他材料。由高第㈤，物號中。…產-聞述於(例如)美國專利本：明之優點進一步由下述實例聞述，但實例中所列兴之特疋材料與其數量以及其他條件與細節不應理解當地限制本發明。除非另右不適 ^除非另有說明，否則本文中所有百分奸及比率皆係以重量計。實例測試方法 I增益測試方法在一自 Photo Research公司，chatsw〇nh，CA所獲得之 Specti*aSCanTM PR-650分光色彩計上量測增益，即一光學材料與一標準材料相比之透光強度差。對於下述所形成之每一實例，該方法之結果報告於下述"結果"部分。為量測單板增益（即"ss")，切割開膜樣品並將其置於一使用F〇ster DCRII光源經由一光管道照明之特氟隆（Ten〇n)光室上，以使棱鏡之槽平行於特氟隆光室之前表面。對於交又板增益 (即"XSH) ’將由相同材料構成之第二板置於該第一板下並經取向’以使該第二板之槽垂直於該特氟隆光室之前表面。在三組實驗中，使用一具有一由棱鏡側邊之斜度所界定之90°頂角之主工具，將可聚合樹脂組合物製備成增亮膜。 102543.doc -35- 在第一組實驗中，相鄰頂角間之平均距離約係50微卡且棱鏡頂點之頂角係圓的。在第二組實驗中，相鄰頂角間之平均距離約係5〇微米，且棱鏡頂點之頂角係尖的。在第三組實驗中，相鄰頂角間之平均距離約係24微米，且棱鏡頂點之頂角係尖的。對於實驗1(對照1，樣品il3)及實驗3(對照3 ’樣品5)’將可聚合樹脂組合物加熱至約5 之溫度，並以一足以產生一連續膜之體積倒於主工具上。推動主工具及可聚合樹脂使其穿過一塗佈棒器件，以在第一組實驗中產生厚約25微米之可聚合樹脂及在第三組實驗中產生厚約13微米之可聚合樹脂。塗佈後’將一pET膜層壓於可聚合樹脂上。然後將主工具、可聚合樹脂及PET膜置於可uv固化之機器中，並曝露於3〇〇〇毫焦耳/平方公分下。固化後，自主工具剝離經聚合樹脂及ΡΕΤ〇於類似實例1和3所述之製程條件下達成實驗2 ’但以一連續模式實施實驗2。在第一組實驗中’增亮膜由可聚合樹脂組合物1至3及一對照（即表I之對照1)製備。在第二組實驗中，增亮膜由可聚合樹脂組合物4及一對照（即表〗之對照2)製備。在第三組實驗中’增亮膜由可聚合樹脂組合物5及一對照（即表I之對照 3)製備。對於每一組實驗’對照由125重量。/〇之pea、37.5 重置％2BR-31、30重量。/〇之rdx_51〇27、20重量％自 UCB A司所獲知之父聯劑（商品名，ΈΒ-9220”）、1 PPh Darocur 1173及〇·3重量％之表面活性劑（自3M公司獲得，商品名 "FC-430")組成。下表I列出在s亥等實例中使用之第一單體之數量、單官能 102543.doc •36· 1363062The surface modification of Zr〇2 and decane can be achieved under acidic or basic conditions. In a preferred embodiment, the decane is preferably heated under acidic conditions for a suitable period of time. During this time, the dispersed phase is combined with aqueous ammonia (or other base). This method allows the removal of acid counterions from the Zr〇2 surface while reacting with decane. In a preferred method, the precipitated particles are self-dispersed and separated from the liquid phase. The surface-modified particles can then be incorporated into the curable resin in various ways, preferably using a solvent exchange operation whereby the resin is added to the surface modified sol, followed by removal of water by evaporation and A co-solvent (if used) whereby the particles are dispersed in the polymeric resin. The evaporation step can be achieved, for example, by distillation, rotary evaporation or oven drying. Alternatively, the surface modified particles can be extracted into a solvent that is immiscible with water' followed by solvent exchange (if desired). Alternatively, another method for incorporating surface modified nanoparticle 102543.doc • 31 - 1363062 particles into a polymerizable resin comprises drying the modified particles into a powder followed by the addition of particles to their Yin dispersion. Tree wax material. The method allows the drying step to be accomplished by conventional methods suitable for the system, such as (d) drying or spray drying. A combination of surface modifiers may be used, wherein at least one of the reagents has a functional group copolymerized with a curable resin. The composition of the surface modifying agent results in a lower viscosity. For example, the polymeric group is an oxime and a base or a cyclic ensemble which undergoes ring opening polymerization. For example, the ethylidene group and the polymerizable group may be a propyl group or a vinyl group. The nucleus of the nucleus of the @w 经受经受经受通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常通常A preferred combination of a surface modifying agent includes at least a surface modifying agent having a functional group copolymerizable with the organic component of the stagnate, and a second modification other than: the first modifying agent Quality agent. The second modifier is optionally copolymerized with the organic component of the polymerizable material. The second modifier may have a low fold rate (Γ below 丨.52 or below 丨.50). Preferably, the second modifier is a buffer of oxygenate which, if desired, can be copolymerized with the polymerizable component. 'Machine such as Lu and LU et al., a microstructured article (for example, may be prepared by a process comprising the steps of: (4) preparing - a polymerizable group (ie, a polymerizable composition of the invention); (b) Just enough to fill a major surface* cavity!: deposit the polymerizable μ on the negative microstructured molding main surface. (C) Fine is filled by moving the polymerizable group between the preformed substrate and the main surface. a cavity in which at least one of the preformed substrate and the particles τ has a flexibility of 102543.doc • 32-1363062; and (d) the composition is cured. The main surface is metal (for example, nickel-plated copper or brass) Or a thermoplastic material that is stable under the polymerization conditions, and which preferably has a surface energy that allows the autonomous surface to completely remove the polymeric material. One or more of the surface of the base film may be primed or coated as appropriate. The method is to promote the adhesion of the optical layer to the substrate. The brightness enhancing film of the present invention is effectively used in the display for the purpose of improving the gain. A schematic diagram of an exemplary backlit liquid crystal display is generally indicated at 110 in FIG. In the actual display, the groups shown The film is often in contact with the brightening film. The brightness enhancing film of the present invention is typically positioned between the light guide 118 and the liquid crystal display panel 114. The liquid crystal display panel typically includes an absorption polarizer on both surfaces. Therefore, the absorption polarizer is Adjacent to the brightness enhancement film of the present invention, the backlight liquid crystal display may further include a light source 116 (for example, a fluorescent lamp) and a white light reflector 120 (which is also used to reflect light toward the liquid crystal display panel). The light emitted by the light guide 118 is increased, thereby increasing the brightness of the liquid crystal display panel 114. The increased brightness enables the liquid crystal panel to produce a clearer image and allows the power of the light source 116 to be reduced to produce a selected brightness. The backlit liquid crystal display can be used for reference indicators 121 such as computer monitors (laptop monitors and computer monitors), televisions, video devices, mobile communication devices, handheld devices (ie, mobile phones, personal digital assistants (PDAs). ), automotive and aerospace instrument displays, and the like. The display can be step-by-step including the brightness enhancement film and the LCD panel. An additional -optical film 112. For example, the additional optical film may comprise a diffusing beta, a reflective polarizer or a second brightness enhancing film. As is known in the art, other optical films may be placed The optical film 112 is disposed between 102543.doc • 33· 1363062 of the liquid crystal display panel 114 or between the brightness enhancement film 11A and the light guide 118. Further, a turning film may be located between the light guide and the optical film. Alternatively, The brightness enhancing film can be a turning film. A turning film typically includes a prismatic structure formed on an input surface, and the input surface is placed adjacent to the light guide to leave the light guide (with a grazing angle of less than 30. The light encounters a prismatic structure. Light is refracted by a first surface of the prism structure and reflects light from a second surface of the prism structure to direct light to a desired direction by turning a prism or film (eg, 'substantially Examples of the viewing-axis polarizing film that is parallel to the display include those described in U.S. Patent Nos. 5,825,543 and 5,783'120. The use of such a matte film in combination with a brightness enhancing film is described in U.S. Patent No. 6,ln,696. Another example of a polarizing film is described in U.S. Patent No. 5,882,774. An example of such a film commercially available is a multilayer film sold by 3M Company under the trade name DBEF (Dual Brightness Enhancement Film). Multilayer polarizing optical films are described in U.S. Patent No. 5,828,488. The turning film typically includes a prism structure formed on the 'surface, and the input surface is ott adjacent to the light guide. The light exiting the light guide at a grazing angle that is typically less than 30 输出 from the output surface encounters a prismatic structure. The line is refracted by a first surface of the prism structure and reflected by the second surface of the prism structure to direct light through the turning film in a desired direction (e.g., substantially parallel to the viewing axis of the display). If the optical port of the attachment port is added as a touch of the brightness enhancement film, the thickness of the bottom layer can be significantly thicker than previously described. The polymerizable compositions described herein are advantageous for other optical materials (eg, optical articles (eg, films) having microstructures). Optical material packages 102543.doc • 34- optical lenses, such as phenanthrene wide refractive index films , for example, micro-second) lenses; optical films, such as high-grade enamel films, multilayers 1 such as total internal reflection films, or brightness enhancement films, slab films, retroreflective plates; optical fibers or pipes • suitable for manufacturing thunderbolt... In particular, the flexible mold (for example, the barrier flange of the plasma display panel) and its # && refractive index polymerizable composition for optical production: two = other materials. By the high (5), the item number. The product is described in, for example, the U.S. Patent. The advantages of the present invention are further exemplified by the following examples, but the exemplified materials and the amounts thereof, as well as other conditions and details, are not to be construed as limiting the invention. Unless otherwise disagreeable ^ Unless otherwise stated, all percentages and ratios herein are by weight. Example Test Method I Gain Test Method The gain is measured on a Specti*aSCanTM PR-650 spectrophotometer obtained from Photo Research, Chatsw〇nh, CA, which is the difference in light transmission between an optical material and a standard material. . For each of the examples formed below, the results of the method are reported in the "Results" section below. To measure the board gain (ie "ss"), cut the open film sample and place it on a Tef〇n light chamber illuminated by a light pipe using a F〇ster DCRII source. The groove of the prism is parallel to the front surface of the Teflon light chamber. For the cross-plate gain (i.e., "XSH)', a second plate of the same material is placed under the first plate and oriented' such that the grooves of the second plate are perpendicular to the front surface of the Teflon light chamber. In three sets of experiments, the polymerizable resin composition was prepared as a brightness enhancing film using a master tool having a 90° apex angle defined by the slope of the sides of the prism. 102543.doc -35- In the first set of experiments, the average distance between adjacent apex angles was approximately 50 microcals and the apex angle of the apex of the prism was rounded. In the second set of experiments, the average distance between adjacent apex angles was about 5 〇 microns, and the apex angle of the prism apex was sharp. In the third set of experiments, the average distance between adjacent apex angles was approximately 24 microns, and the apex angle of the prism apex was pointed. The polymerizable resin composition was heated to a temperature of about 5 for Experiment 1 (Control 1, Sample il3) and Experiment 3 (Control 3 'Sample 5)' and poured onto the main tool in a volume sufficient to produce a continuous film. The master tool and polymerizable resin were pushed through a coating bar device to produce a polymerizable resin having a thickness of about 25 microns in the first set of experiments and a polymerizable resin having a thickness of about 13 microns in the third set of experiments. After coating, a pET film was laminated on a polymerizable resin. The main tool, polymerizable resin and PET film were then placed in a uv-curable machine and exposed to 3 〇〇〇mJ/cm 2 . After curing, the autoclave was stripped of the polymerized resin and the crucible under the process conditions similar to those described in Examples 1 and 3 to achieve Experiment 2' but Experiment 2 was carried out in a continuous mode. In the first set of experiments, the brightness enhancement film was prepared from polymerizable resin compositions 1 to 3 and a control (i.e., Control 1 of Table I). In a second set of experiments, a brightness enhancing film was prepared from a polymerizable resin composition 4 and a control (i.e., Control 2 of the Table). In the third set of experiments, the brightness enhancing film was prepared from the polymerizable resin composition 5 and a control (i.e., Control 3 of Table I). For each set of experiments 'controls were 125 weights. /〇pea, 37.5 Reset %2BR-31, 30 weight. /〇之rdx_51〇27,20% by weight of the parental agent (trade name, ΈΒ-9220), 1 PPh Darocur 1173 and 〇·3 wt% of surfactants obtained from UCB A Division (obtained from 3M Company, Composed of the trade name "FC-430"). Table I below lists the amount of the first monomer used in the shai and other examples, monofunctional 102543.doc •36· 1363062

基稀釋劑（即，丙烯酸苯氧基乙基酯（PEA))、交聯劑（即， PETA)、無機奈米粒子、光起始劑（Lucirin TPO-L)之種類及數量。該等實例中所使用之第一單體包含至少約6〇至7〇重量％之2-丙烯酸、（1-曱基亞乙基）雙[(2,6_二溴_41伸苯基）氧基（2-羥基-3,1-丙二基）]酯》 ___ 表I 可聚合樹_ 脂组合物光起始劑 1 pph 重量％ PEA 重量％第一單體重量％ PETA 表面改質劑重量％其他 SS 增益 XS 增插對照1 1.666 實例1 TPO-L 9.7 29 9.7 5.7 46重量％ 20奈米Si02 1.552 實例2 TPO-L 11.5 34.4 11.5 4.7 38重量％ 20奈米Si02 1.557 實例3 TPO-L 12.8 24.5 12.8 4 32重量％ 20奈米Si02 1.570 對照2 1.707 2.500 實例4 TPO-L 9.2 27.5 9.2 15 39% Nalco 氧化锆 1.717 2.535 對照3 1.721 2.488 實例5 TPO-L 8.6 25.7 8.6 9.1 48% Buhler 氧化鉛 1.838 2.496 實例6 1.881 2.687 *成份參見實例。 Φ 實例1 將Nalco 2327(400克）加至1夸脫罐中。準備甲氧基_2_ 丙醇（450克）、甲基丙烯酸3-(三甲氧基甲矽烷基）丙基酯（由 Sigma-Aldrich, Milwaukee, WI 購得，商品名"Silane Α174’’（18·95 克）、Silquest Α1230(12·74 克）及一由 Ciba Specialty Chemical 公司，Tarrytown，NY 購得（商品名 "Prostab 5 198")之受阻胺氮氧化物抑制劑於水中之5%溶液 (0.2克），並邊攪拌邊將其添加至一膠狀二氧化矽分散液（由 102543.doc -37- 1363062The type and amount of the base diluent (i.e., phenoxyethyl acrylate (PEA)), crosslinker (i.e., PETA), inorganic nanoparticles, and photoinitiator (Lucirin TPO-L). The first monomer used in the examples comprises at least about 6 to 7 wt% of 2-acrylic acid, (1-mercaptoethylidene) bis[(2,6-dibromo-41 stretch phenyl) Oxy(2-hydroxy-3,1-propanediyl)]ester ___ Table I Polymerizable tree _ Lipid composition Photoinitiator 1 pph Weight % PEA Weight % First monomer weight % PETA Surface modifier Weight % Other SS Gain XS Addition Control 1 1.666 Example 1 TPO-L 9.7 29 9.7 5.7 46% by weight 20 nm Si02 1.552 Example 2 TPO-L 11.5 34.4 11.5 4.7 38% by weight 20 nm Si02 1.557 Example 3 TPO-L 12.8 24.5 12.8 4 32% by weight 20 nm Si02 1.570 Control 2 1.707 2.500 Example 4 TPO-L 9.2 27.5 9.2 15 39% Nalco Zirconia 1.917 2.535 Control 3 1.721 2.488 Example 5 TPO-L 8.6 25.7 8.6 9.1 48% Buhler Lead Oxide 1.838 2.496 Example 6 1.881 2.687 *Ingredients see examples. Φ Example 1 Nalco 2327 (400 grams) was added to a 1 quart can. Prepare methoxy-2-propanol (450 g), 3-(trimethoxyformamido)propyl methacrylate (available from Sigma-Aldrich, Milwaukee, WI, trade name "Silane Α174'' ( 18·95 g), Silquest® 1230 (12·74 g) and a hindered amine nitrogen oxide inhibitor (trade name "Prostab 5 198") purchased by Ciba Specialty Chemical Company, Tarrytown, NY, 5% in water Solution (0.2 g) and add it to a colloidal ceria dispersion with stirring (from 102543.doc -37-1363062)

Ondeo-Nalco公司，Naperville，IL購得，商品名"Nalco 2327") 中。密封罐，並將其加熱至80°C 16·5小時。此可產生一經改質二氧化矽之透明、低黏度分散液。將上述經改質溶膠（442.23克）、20/60/20 SR444/第一單體 /ΡΕΑ(82.25 克）及一 Prostab 5198 於水中之 5〇/。溶液（0.65 克）加至一 1公升圓底燒瓶（長頸）中。藉由旋轉蒸發移除水及醇類。由TGA量測，調配物含有46.04重量％之Si02。折射率係1.512。添加1重量％之TP0-L。 > 實例2 使來自實例1之含Si〇2之樹脂（10克）與20/60/20 SR444/第一單體/PEA(2.12克）混合，得到38重量％含8丨02之樹脂。添加1重量％2TPO-L。實例3 使來自實例1之包含Si02之樹脂（10克）與20/60/20 SR444/ 第一單體/PEA(4.3 8克）混合，得到32重量％含8丨02之樹脂。添加1重量％2TP0-L。 _ 實例4 製備經矽烷改質之氧化鍅奈米粒子分散液：將Nalco OOSS008氧化鍅溶膠（372.56克）及自Sigma-Aldrich購得之 2-[2-(2-甲氧基乙氧基）乙氧基]乙酸（MEEAA)(23.16克）加至一 1公升圓底燒瓶中。藉由旋轉蒸發移除水及乙酸。藉此所獲得之粉末重新分散於127.58克D.I.水中並將其加至一 2公升燒瓶中’邊攪拌邊向該燒杯中添加400克1-甲氧基-2-丙醇、36.62克八-174'24.61克8叫1^1八-1230及0.4克卩1*(^&5 102543.doc • 38 · 1363062 5198於水中之5%溶液。於室溫下攪拌該混合物30分鐘，然後將其倒入1公升（夸脫）罐中，密封並加熱至90°C 3.0小時。移取出罐之内容物並藉由旋轉蒸發濃縮至40% Zr02。將去離子水（15 65克）及5 1克濃氨水（29% NH3)加至一 4公升燒杯中。邊攪拌邊向該燒杯中缓慢添加經濃縮之分散液（295 克）。藉由真空過濾分離如此所獲得之白色沉澱，並用另外的D.I·水洗滌。使潮濕固體分散於1·甲氧基-2-丙醇（370克）中。所得經矽烷改質之氧化锆分散液含有20.2%之固體。齡將上述經改質之Zr02分散液（540克）、20/60/20 PEA/第一單體/SR444(90.4克）及一 Prostab 5198於水中之5%溶液 (0.72克）加至一 1公升圓底燒瓶中。藉由旋轉蒸發移除水及醇類。由丁〇八量測，所得調配物含有38.60%之乙1*〇2，並且具有1.587之折射率。實例5 製備經矽烷改質之氧化鍅奈米粒子分散液：將Buhler氧化鉛7-'\^〇溶膠（401.5克）（自81111161八〇1；2'^1,8\^26士1^ • 購得）加至一 1夸脫罐中，邊攪拌邊向罐中添加450克1-曱氧基-2-丙醇、28.5克矽烷八174、19.16克8叫1^1八-123 0及0.5 克Prostab 5 198於水中之5%溶液。於室溫下攪拌該混合物3〇分鐘，然後將其密封並加熱至9〇。〇 3 ·〇小時。移取出罐之内容物並藉由旋轉蒸發濃縮至約40% Zr02。將去離子水（707.8 克）及24,2克濃氨水（29% NH3)加至一 4公升燒杯中。邊攪拌邊向该燒杯中緩慢添加經濃縮之分散液（346·8克卜藉由真空過濾分離如此所獲得之白色沉澱，並用另外的D丄水洗 102543.doc •39- 1363062 滌。使潮濕固體分散於1-甲氧基·2-丙醇中。所得經矽烷改質之氧化錯分散液含有20.58%之固體。將上述經改質之Zr02分散液（225.2克）、20/60/20 ΡΕΑ/第單體/SR444(30.9克）及一 prostab 5 198於水中之5%溶液 (0.24克）加至一 i公升圓底燒瓶中。藉由旋轉蒸發移除水及醇類°由丁0八量測’所得調配物含有47.85%之21*02，並且具有1.615之折射率。添加1重量％之丁卩〇·]^。實例6 _ 根據2004年12月30日提出申請之美國專利申請案第 11/027426號製備一 Zr〇2溶膠，獲得一具有45 78%固體之溶膠。根據下述Zr02測試方法測試Zr02 : 光子相關光譜（PCS) 使用一 Malvern Series 4700 粒徑分析儀（自 Malvern Instruments公司，Southborough，ΜΑ購得）藉由光子相關光 6普（PCS)測定體積-平均粒徑。使用一由唧筒所施加之壓力使稀釋氧化錯溶膠樣品通過一 0.2微米過遽器過濾至一玻 •璃比色槽中，接著蓋上蓋子。在開始數據採集前，讓樣品至之溫度平衡至25°C。所提供之軟體用於以9〇度之角度實施C0NTIN分析。C0NTIN係一廣泛使用的用於分析一般逆變換問題之數學法，其進一步闡述於s w. Pr〇vencher， (：〇11^扎？!^.(：〇111|111111.，27,229 (1982)中。分析使用24個數據庫（data bin)實施。在計算中使用下述數值：等於1333 之水之折射率，等於〇.89〇厘泊之水之黏度及等於丨9之氧化锆粒子之折射率。 102543.doc -40- 1363062 基於PCS數據’計算兩種粒徑量測值。以奈米所報主之強度-平均粒徑等於對應於散射光強度分佈之平均值之粒徑。散射光強度與粒子直徑之六次方成比例。亦以奈米報告之體積-平均粒徑係源自由散射光強度分佈計算所得之體積刀佈，其at及氧化錯粒子折射率及分散介質（即，水）折射率二者。體積-平均粒徑等於對應於體積分佈之平均值之粒徑。強度-平均粒徑除以體積-平均粒徑可提供一指示粒徑分 | 佈之比率。微晶結構及粗徑（XRD分析）使用一瑪堪研缽及研杵藉由手工研磨可降低一經乾燥氧化锆樣品之粒徑。藉由刮刀將大量樣品施加於—已黏附有一段雙重塗佈帶之顯微鏡玻片上。藉由用刮刀刀片將樣品壓到塗佈帶上將樣品擠壓至塗佈帶之黏合劑中。藉由用刮刀刀片之邊緣刮擦樣品區域可移除過量樣品，使一薄層粒子黏附至黏合劑上。藉由將顯微鏡玻片有力地敲擊在一硬 • 表面上可在到擦後移除鬆散黏附之材料《以一類似方式，製備金剛砂（Linde 1.0微米氧化鋁拋光粉，批號c〇62，Uni⑽Ondeo-Nalco, available from Naperville, IL, under the trade name "Nalco 2327". The can was sealed and heated to 80 ° C for 16.5 hours. This produces a clear, low viscosity dispersion of modified cerium oxide. The above modified sol (442.23 g), 20/60/20 SR444/first monomer/rhodium (82.25 g) and a Prostab 5198 were added in water at 5 Torr. The solution (0.65 g) was added to a 1 liter round bottom flask (long neck). Water and alcohol are removed by rotary evaporation. The formulation contained 46.04% by weight of SiO 2 as measured by TGA. The refractive index is 1.512. 1% by weight of TP0-L was added. > Example 2 A resin containing Si 2 (10 g) from Example 1 was mixed with 20/60/20 SR444/first monomer/PEA (2.12 g) to obtain 38% by weight of a resin containing 8丨02. Add 1% by weight of 2TPO-L. Example 3 A SiO2-containing resin (10 g) from Example 1 was mixed with 20/60/20 SR444/first monomer/PEA (4.38 g) to obtain 32% by weight of a resin containing 8丨02. Add 1% by weight of 2TP0-L. _ Example 4 Preparation of decane-modified cerium oxide nanoparticle dispersion: Nalco OOSS008 cerium oxide sol (372.56 g) and 2-[2-(2-methoxyethoxy) available from Sigma-Aldrich Ethoxy]acetic acid (MEEAA) (23.16 g) was added to a 1 liter round bottom flask. Water and acetic acid were removed by rotary evaporation. The powder thus obtained was redispersed in 127.58 g of DI water and added to a 2 liter flask. To the beaker, 400 g of 1-methoxy-2-propanol and 36.62 g of octa-174 were added while stirring. '24.61g 8 is called 1^1-8-1230 and 0.4g 卩1*(^&5 102543.doc • 38 · 1363062 5198 5% solution in water. Stir the mixture for 30 minutes at room temperature, then place it Pour into a 1 liter (quart) jar, seal and heat to 90 ° C for 3.0 hours. Remove the contents of the jar and concentrate to 40% Zr02 by rotary evaporation. Deionized water (15 65 g) and 5 1 Concentrated ammonia (29% NH3) was added to a 4 liter beaker. The concentrated dispersion (295 g) was slowly added to the beaker while stirring. The white precipitate thus obtained was separated by vacuum filtration and used with additional DI·water washing. The moist solid was dispersed in 1·methoxy-2-propanol (370 g). The obtained decane-modified zirconium oxide dispersion contained 20.2% solids. The above-mentioned modified Zr02 Dispersion (540 g), 20/60/20 PEA/first monomer/SR444 (90.4 g) and a 5% solution of Prostab 5198 in water (0.72 g) It was added to a 1 liter round bottom flask. Water and alcohol were removed by rotary evaporation. The resulting formulation contained 38.60% of B 1*〇2 and had a refractive index of 1.587. Preparation of decane-modified cerium oxide nanoparticle dispersion: Buhler lead oxide 7-'\^〇 sol (401.5 g) (from 81111161 八〇1; 2'^1,8\^26士1^ • purchase Add) to a 1 quart jar, add 450 g of 1-decyloxy-2-propanol, 28.5 g of decane eight 174, 19.16 g of 8 to 1 18-123 0 and 0.5 while stirring. Gram 5% solution of Prostab 5 198 in water. Stir the mixture for 3 minutes at room temperature, then seal and heat to 9 Torr. 〇3 · 〇 hours. Remove the contents of the can and concentrate by rotary evaporation. Up to about 40% Zr02. Add deionized water (707.8 grams) and 24,2 grams of concentrated ammonia (29% NH3) to a 4 liter beaker. Add the concentrated dispersion slowly to the beaker while stirring. • 8 g of the white precipitate thus obtained was separated by vacuum filtration, and washed with another D丄 water 102543.doc • 39-1363062. Disperse the wet solid in 1-methoxy· In 2-propanol, the obtained decane-modified oxidative dispersion contains 20.58% solids. The above modified Zr02 dispersion (225.2 g), 20/60/20 ΡΕΑ/cell/SR444 (30.9) g) and a prostab 5 198 solution in water (0.24 g) was added to a one liter round bottom flask. The water and the alcohol were removed by rotary evaporation. The resulting formulation contained 47.85% of 21*02 and had a refractive index of 1.615. Add 1% by weight of 卩〇··^. Example 6 _ A Zr〇2 sol was prepared according to U.S. Patent Application Serial No. 11/027,426, filed on December 30, 2004, to obtain a solvate having 45 78% solids. Zr02 was tested according to the Zr02 test method described below: Photon Correlation Spectroscopy (PCS) Volume-averaged by photon correlation light (PCS) using a Malvern Series 4700 particle size analyzer (available from Malvern Instruments, Southborough, USA) Particle size. The diluted oxidized sol sample was filtered through a 0.2 micron filter into a glass cuvette using a pressure applied by a cartridge followed by a lid. Allow the sample to equilibrate to 25 °C before starting data collection. The software provided was used to perform C0NTIN analysis at a 9 degree angle. C0NTIN is a widely used mathematical method for analyzing general inverse transformation problems, which is further described in s w. Pr〇vencher, (:〇11^扎?!^.(:〇111|111111.,27,229 (1982) The analysis was performed using 24 data bins. The following values were used in the calculation: the refractive index of water equal to 1333, the viscosity of water equal to 〇.89〇PCT and the refraction of zirconia particles equal to 丨9. 102543.doc -40- 1363062 Calculate two particle size measurements based on PCS data. The intensity-average particle size reported by the nanometer is equal to the particle size corresponding to the average of the scattered light intensity distribution. The intensity is proportional to the sixth power of the particle diameter. The volumetric knives calculated from the volume-average particle size of the free-scattered light intensity distribution reported by the nanometer, the at and the refractive index of the oxidized particle and the dispersion medium (ie, Water) Both refractive indices. The volume-average particle size is equal to the particle size corresponding to the average of the volume distribution. The intensity-average particle size divided by the volume-average particle size provides a ratio of the indicated particle size to the cloth. Structure and diameter (XRD analysis) Grinding and grinding can reduce the particle size of a dried zirconia sample by hand grinding. A large number of samples are applied by a doctor blade to a microscope slide that has been adhered to a double coated belt. The sample is pressed by a doctor blade. The sample is extruded onto the coating tape into the adhesive of the coating tape. By scraping the sample area with the edge of the doctor blade, the excess sample can be removed to adhere a thin layer of particles to the adhesive. The slide is strongly tapped on a hard surface to remove loosely adhering material after rubbing. Prepare Emery in a similar manner (Linde 1.0 micron alumina polishing powder, lot number c〇62, Uni(10)

Carbide, Indianapolis, IN)並將其用於校準繞射儀之儀器增寬。 S 使用一具有反射幾何配置、銅Κα輻射及散射輻射之正比偵測器記錄模式之Philips垂直繞射儀獲得又_射線繞射掃描。繞射儀裝備有可變的入射光束狹縫、固定的繞射光束狹縫及石墨繞射光束單色光鏡。使用一〇〇4度步長及8秒停 102543.doc •41- 1363062 留時間自25至55度2Θ實施波長掃描。使用45千伏及乃毫安之X-射線發生器。可於數個個別金剛砂底座之三個不同區域上實施金剛砂標準品之數據採集。在薄層樣品底座之三個不同區域上採集數據。藉由與國際繞射數據中心（International Center如 Diffracti〇n Data，ICDD)粉末繞射數據庫（組 147, icdd， Newton Square，PA)中所包含之標準繞射圖案比較雾定所觀測至之繞射峰並將其賦於立方/四方（C/T)或單斜氧化 • 鍅晶型。立方相之（111)峰及四方相之（101)峰無法分開，故該兩相一起報告。每一氧化锆晶型之數量以相對基礎計算，且指定具有最強繞射峰之氧化锆晶型之相對強度值為 100。其餘氧化锆結晶之最強線係相對於最密集線標示，且獲得介於1至100間之數值。藉由曲線擬合量測由金剛砂導致之所觀測繞射最大值之峰寬。平均金剛砂峰寬與金剛砂峰位置（2Θ)間之相互關係藉由以下測定，即將一多項式擬合至該等數據，以獲得一 •用於評價在金剛砂測試範圍内任何峰位置處儀器寬度之連續函數。藉由曲線擬合觀測繞射峰量測所觀測到的由氧化鍅所致之繞射最大值之峰寬。下述峰寬可根據所存在之氧 .化鍅相評估：立方/四方（c/τ) : (111) 單斜（Μ) : (-111)及（111) 在所有情況下，皆使用一計及Κα1與Κα2波長分量之Pears〇n VII峰型模型及線性背景模型。已發現寬度係以度為單位之 102543.doc -42- 1363062 半峰全幅值（FWHM)。曲線擬合藉助jAde繞射軟體套組之月b力達成。評估同一薄層樣品底座所獲得之三個獨立數據採集之樣品峰寬。藉由内插金剛砂儀器校準儀器寬度校正樣品峰之儀器增寬，並將經校正之峰寬轉換成弧度單位。使用Scherrer方程式計算初級晶體粒徑。微晶粒徑（D)= Κλ/β (cos Θ) 在Scherrer方程式中，Carbide, Indianapolis, IN) and used it to calibrate the instrumentation of the diffractometer. S A ray diffraction scan is obtained using a Philips vertical diffractometer with a reflective geometry, copper Κ alpha radiation and scattered radiation proportional detector recording mode. The diffractometer is equipped with a variable incident beam slit, a fixed diffracted beam slit, and a graphite diffracted beam monochromator. Use a 4 degree step and 8 seconds to stop 102543.doc • 41- 1363062 Leave the time to scan from 25 to 55 degrees 2Θ. An X-ray generator of 45 kV and mA is used. Data collection of corundum standards can be performed in three different areas of several individual corundum bases. Data was collected on three different areas of the thin sample base. Compare the observed haze with the standard diffraction pattern contained in the International Diffracti Data Center (ICDD) Powder Diffraction Database (Group 147, icdd, Newton Square, PA) Shoot the peak and assign it to the cubic/tetragonal (C/T) or monoclinic oxidation • twin form. The (111) peak of the cubic phase and the (101) peak of the tetragonal phase cannot be separated, so the two phases are reported together. The number of each zirconia crystal form is calculated on a relative basis, and the relative intensity value of the zirconia crystal form having the strongest diffraction peak is specified to be 100. The strongest line of the remaining zirconia crystals is indicated relative to the densest line and obtains values between 1 and 100. The peak width of the observed diffraction maximum caused by silicon carbide was measured by curve fitting. The correlation between the average diamond peak width and the diamond peak position (2Θ) is determined by fitting a polynomial to the data to obtain a continuous evaluation of the width of the instrument at any peak position within the corundum test range. function. The peak width of the diffraction maximum due to yttrium oxide observed by the diffraction peak measurement was observed by curve fitting. The following peak widths can be evaluated based on the oxygen present and the enthalpy phase: Cubic/Quadruple (c/τ): (111) Monoclinic (Μ): (-111) and (111) In all cases, one is used. The Pears〇n VII peak model and the linear background model of Κα1 and Κα2 wavelength components are considered. The width has been found to be in the range of 102,543.doc -42 - 1363062 full width at half maximum (FWHM). The curve fit is achieved by means of the jAde diffraction software set's monthly b force. Evaluate the sample peak widths of the three independent data acquisitions obtained from the same thin sample base. The instrument width is corrected by interpolating the diamond instrument to calibrate the width of the sample peak and the corrected peak width is converted to radians. The primary crystal grain size was calculated using the Scherrer equation. Microcrystalline particle size (D) = Κλ/β (cos Θ) In the Scherrer equation,

K=形狀因數（此處係0 9); λ=波長（1.540598 Α); β =在校正儀器增寬後計算得出之峰寬（用弧度表示卜 [計算得出之蜂FWHM_儀器寬度](轉換成弧度），其中 FWHM係半峰全幅值；且 Θ = Κ峰位置（散射角）。 1 1)峰之三次量測值之平立方/四方微晶粒徑量測為使用（1 均值。K = form factor (here is 0 9); λ = wavelength (1.540598 Α); β = peak width calculated after the calibration instrument is widened (in radians) [calculated bee FWHM_instrument width] (converted to radians), where FWHM is the full-width of the half-peak; and Θ = the peak position (scattering angle). 1 1) The measurement of the flat cubic/tetragonal crystallite size of the three measurements of the peak is used (1 mean .

立方/四方平均微晶粒徑= [D( 1 1 1 )* « i+D( 1 1 單斜微晶粒徑量測為使用i (1 1 1)峰之三次量測值之平均單斜平均微晶粒徑= 1)^2+D(l 1 1)^3]/3 1 1)峰之二次量測值及使用值。 +Cubic/tetragonal average crystallite size = [D( 1 1 1 )* « i+D ( 1 1 monoclinic crystallite size is measured as the average monoclinic average of the three measurements using the i (1 1 1) peak Crystallite size = 1)^2+D(l 1 1)^3]/3 1 1) The second measurement of the peak and the value of use. +

[D(-l 1 1)^,+D(-1 1 \)^2+Ό{_χ γ ^ 面 D(1 1 1)**,+D(1 1 l)6tt2+D(1 J 1} ^ 面計算立方/四方（C/T)及科相（M)之加權平均:]。 102543.doc -43· 1363062 加權平均值=[(% C/T)(C/T粒徑）+ (% M)(M粒徑）]/100 在此方程式中， % C/T=由Zr02粒子之立方及四方微晶含量所提供之百分結晶度； c/τ粒徑=立方及四方微晶之粒徑； % M=由Zr〇2粒子之單斜微晶含量所提供之百分結晶度；且 Μ粒徑=單斜微晶之粒徑。 φ 分散指數分散指數等於由PCS量測之體積-平均粒徑除以由XRD量測之加權平均微晶粒徑。固體之重量百分比藉由於120°C下乾燥一重3至6克之樣品30分鐘，測定固體之重量百分比。可使用下述方程式由濕樣品重量（即，乾燥前之重量，重量a )及乾樣品重量（即，乾燥後之重量，重量乾）計算固體之百分比。 # 重量％固體= 100(重量乾）/重量在結果如下：強度-平均粒徑(奈米）體積-平均粒徑(奈米）強度-平均：體積-平均比率 Zr02溶膠 42.1 17.5 2.41 Μ強度 Μ粒徑 (奈米） C/T 強度 c/τ粒徑 (奈米） % C/T XRD平均粒徑 (奈米）分散指數 Zr02 溶膠 9 6.5 100 8.0 92 7.9 2.21 102543.doc -44- 1363062 將ZΓO2溶膠（50.00克）、MEEAA(2.22克）、BCEA(1.06克）、 i -甲氧基-2-丙醇（75克）及一 50/50 PEA/RDX之混合物（17.60 克）加至一圓底燒瓶中，並藉由旋轉蒸發移除醇類及水。含心〇2之樹脂係49.59%之2|*〇2，並具有一 1.639之折射率。向上述混合物t添加0.5 pph之TPO-L。此可製備成一根據實驗2之增亮膜，不同之處為棱鏡類似於由3M公司以商品名"Vikuiti BEF III 90/50 Film"出售之增免膜之棱鏡在沿其長度方向上高度有變化。結果報告於表【中。由端點所列舉之數值範圍包括所有包含在該範圍内之數值（例如 ’ 1至 5 包括 1、1.5、2 ' 2.75、3、3.80、4及 5)。本文所引用之專利、專利文件及出版物之整個揭示内容皆以引用的方式併入本文中，其併入程度如同每一皆逐個地併入本文中。熟習此項技術者將明瞭對本發明所作之各種改質及改變，此並不背離本發明之範圍及主旨。應瞭解，本發明不欲不適當地受到本文所列例示性具體實施例及實例之限制，且此等實例及具體實施例僅以實例方式呈現，本發明範圍僅欲受到如下於本文中列出之申請專利範圍之限制。【圖式簡單說明】圖1係本發明之具有微結構之例示性光學產品之透視圖。圖2係一包括本發明增亮膜之例示性背光液晶顯示器之示意圖。【主要元件符號說明】 102543.doc •45· 1363062[D(-l 1 1)^, +D(-1 1 \)^2+Ό{_χ γ ^ Face D(1 1 1)**, +D(1 1 l)6tt2+D(1 J 1 } ^ Calculate the weighted average of cubic/quadruple (C/T) and phase (M):] 102543.doc -43· 1363062 Weighted average = [(% C/T) (C/T particle size) + (% M) (M particle size)] / 100 In this equation, % C / T = percent crystallinity provided by the cubic and tetragonal crystallite content of Zr02 particles; c / τ particle size = cubic and tetragonal Particle size; % M = percent crystallinity provided by the monoclinic crystallite content of Zr〇2 particles; and Μ particle size = particle size of monoclinic crystallites. φ Dispersion index dispersion index equal to PCS measurement The volume-average particle size is divided by the weighted average crystallite size as measured by XRD. The weight percent of solids is determined by drying a weight of 3 to 6 grams of sample at 120 ° C for 30 minutes. The equation calculates the percentage of solids from the wet sample weight (ie, weight before drying, weight a) and dry sample weight (ie, weight after drying, dry weight) #重量%固体 = 100 (weight dry) / weight in results As follows: Strength - Average Particle Size (Nano) Volume - Average Diameter (nano) Strength-Average: Volume-average ratio Zr02 Sol 42.1 17.5 2.41 Μ Strength Μ Particle size (nano) C/T Strength c/τ particle size (nano) % C/T XRD average particle size (Nai m) Dispersion index Zr02 Sol 9 6.5 100 8.0 92 7.9 2.21 102543.doc -44- 1363062 ZΓO2 sol (50.00 g), MEEAA (2.22 g), BCEA (1.06 g), i-methoxy-2-propanol A mixture of (75 g) and a 50/50 PEA/RDX (17.60 g) was added to a round bottom flask and the alcohol and water were removed by rotary evaporation. The resin containing the heart 2 was 49.59% 2 | 〇2, and having a refractive index of 1.639. Add 0.5 pph of TPO-L to the above mixture t. This can be prepared as a brightness enhancing film according to Experiment 2, except that the prism is similar to the trade name by 3M Company. Vikuiti BEF III 90/50 Film"The prisms of the reinforced film that are sold vary in height along its length. The results are reported in the table. The range of values recited by the endpoints includes all values included in the range ( For example, '1 to 5 includes 1, 1.5, 2 ' 2.75, 3, 3.80, 4, and 5). The patents cited in this article, Lee entire disclosure of documents and publications of tailor incorporated by reference herein in their entirety to the same extent as are each individually and references contained therein. Various modifications and changes of the present invention will be apparent to those skilled in the art without departing from the scope and scope of the invention. It is to be understood that the invention is not intended to be limited by the exemplified embodiments and examples set forth herein, and that the examples and specific examples are presented by way of example only. The scope of the patent application is limited. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a perspective view of an exemplary optical product having microstructures of the present invention. Figure 2 is a schematic illustration of an exemplary backlit liquid crystal display including a brightness enhancing film of the present invention. [Key component symbol description] 102543.doc •45· 1363062

2 4 6 8 10 11 12 14 18 20 22 24 30 110 111 112 114 116 118 120 121 底層光學層棱鏡棱鏡第一小面第二小面棱鏡棱鏡第一表面第二表面棱鏡南度光學物件之總厚度增亮膜背光液晶顯不益增亮膜光學膜液晶顯示器面板光源光導全反射器諸如電腦顯示器（膝上型顯示器及電腦監視器）、電視、錄影裝置、移動通信裝置、手持式裝置（即，行動電話、個人數位助理（PDA))、汽車及航空儀錶顯示器等設備 102543.doc -46-2 4 6 8 10 11 12 14 18 20 22 24 30 110 111 112 114 116 118 120 121 bottom layer optical layer prism prism first facet second facet prism prism first surface second surface prism south optical object total thickness Brightening film backlight LCD display unfavorable brightness enhancement film optical film liquid crystal display panel light source light guide total reflector such as computer display (laptop display and computer monitor), television, video device, mobile communication device, handheld device (ie, Mobile phones, personal digital assistants (PDAs), automotive and aerospace display devices, etc. 102543.doc -46-

Claims

1303002第09412加48號專利申請案 ^ 中文申請專利範圍替換本(97年6月）十、申請專利範圍： 1. 一種具有一經聚合結構之增亮膜，其包含一或多種選自由下列組成之群之第一單體之反應產物： i) 一包含一具有下述結構式之主要部分之單體：1303002 Patent Application No. 09512 and No. 48 ^ Chinese Patent Application Substitution (June 1997) X. Patent Application Range: 1. A brightness enhancing film having a polymerized structure comprising one or more selected from the group consisting of The reaction product of the first monomer of the group: i) a monomer comprising a major portion of the formula:

其中R1獨立地係氫或甲基， R2獨立地係氫或溴， Q獨立地係0或S，及 Ζ獨立地係-C(CH3)2_、-CH2-、-C(0)-、-S-、-s(o)· 或-S(0)2·， ii) 一包含具下述結構式之主要部分之單體：Wherein R1 is independently hydrogen or methyl, R2 is independently hydrogen or bromine, Q is independently 0 or S, and Ζ is independently -C(CH3)2_, -CH2-, -C(0)-, - S-, -s(o)· or -S(0)2·, ii) A monomer comprising a major portion of the following structural formula:

其中R1獨立地係氫或曱基， R2獨立地係氫或溴， Q獨立地係0或S， 102543-970616.doc Z獨立地係-C(CH3)2-、-CH2-、-C(0)-、-s-、-s(o)-或-S(0)2-，及 L係一獨立地選自直鏈或具支鏈c2_Ci2烷基之連接基團’其中該碳鏈視情況經一或多個氧基團取代及 /或該等碳原子視情況經一或多個羥基取代；及i與ii之混合物； b) 至少約1〇重量％之含氧化锆之無機奈米粒子； c) 至少一交聯劑、乙烯系不飽和稀釋劑或其混合物；其中該增亮膜具有至少1.717之增益。 2 j 3如叫求項1之增亮膜，其中該組合物包含光起始劑。如μ求項1之増亮膜，其中該經聚合結構包含3〇至6〇重量 %之氧化锆。如°月求項1之増亮膜，其中該等無機奈米粒子係經表面改求項1之增免膜，其中該等無機奈米粒子包含二氧化 ::氧化敘、氧化銻、氧化銘、氧化錫、其軋化物或其混合物。嘴 6. 8. 9. 如請求項1夕楊-& ^ 米至75 ,曰焭膜，其中該初級粒子之粒徑係介於5夺介於10奈米至30奈米之間或介於5奈米如請求項I 3»以> * 之增焭膜，其中該第一單俨縮水甘油Μ* A 早體係由四溴雙酚八二冰崎與（甲基）丙如請求項㈣之反應產物組成。如請求項i θ冗膜’其中該交聯劑於室溫下係液體。之増亮膜，其中該交聯劑係多官能基（甲基）汚 102543-9706l6.doc 1363062 烯酸胺基曱酸酯交聯劑。 10.如請求項1之增亮膜，其中該交聯劑係選自由下列組成之群：己二醇二丙烯酸酯、異戊四醇三（曱基）丙烯酸酯、異戊四醇四（曱基）丙烯酸酯、三羥曱基丙烷三（甲基）丙烯酸酯、二三羥甲基丙烷四（甲基）丙烯酸酯、二異戊四醇五（甲基）丙烯酸酯、己二醇二丙烯酸酯及其混合物。 11·如叫求項1之增焭膜，其進—步包含至少一單官能基乙烯系不飽和稀釋劑。Wherein R1 is independently hydrogen or fluorenyl, R2 is independently hydrogen or bromine, Q is independently 0 or S, 102543-970616.doc Z is independently -C(CH3)2-, -CH2-, -C( 0) -, -s-, -s(o)- or -S(0)2-, and L is a linking group independently selected from a linear or branched c2_Ci2 alkyl group, wherein the carbon chain is Substituting one or more oxygen groups and/or the carbon atoms are optionally substituted with one or more hydroxyl groups; and a mixture of i and ii; b) at least about 1% by weight of inorganic boron oxide containing zirconia a particle; c) at least one crosslinking agent, an ethylenically unsaturated diluent or a mixture thereof; wherein the brightness enhancing film has a gain of at least 1.718. 2 j 3 The brightness enhancing film of claim 1, wherein the composition comprises a photoinitiator. A bright film of the item 1, wherein the polymerized structure comprises from 3 to 6 % by weight of zirconium oxide. For example, the bright film of the item 1 of the month, wherein the inorganic nanoparticles are modified by the surface modification item 1, wherein the inorganic nanoparticles comprise dioxide:: oxidized sulphur, cerium oxide, oxidized Tin oxide, its rolled product or a mixture thereof. Mouth 6. 8. 9. As requested in Item 1 杨 Yang-& ^ m to 75, aponeurosis, wherein the primary particle size is between 5 and 10 nm or between At 5 nm, as claimed in item I 3» by & * , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , (d) The composition of the reaction product. As the request item i θ is a film, wherein the crosslinking agent is a liquid at room temperature. The bright film, wherein the crosslinking agent is a polyfunctional (methyl) contamination 102543-9706l6.doc 1363062 an enoyl phthalate crosslinker. 10. The brightness enhancing film of claim 1, wherein the crosslinking agent is selected from the group consisting of hexanediol diacrylate, pentaerythritol tris(decyl) acrylate, and isopentaerythritol tetrakis(曱). Acrylate, trishydroxypropyl propane tri(meth) acrylate, ditrimethylolpropane tetra(meth) acrylate, diisopentaerythritol penta (meth) acrylate, hexane diol diacrylate Esters and mixtures thereof. 11. The ruthenium film of claim 1 further comprising at least one monofunctional ethylenically unsaturated diluent.

12.如請求項10之增亮膜，其中該稀釋劑於室溫下係液體。 13· T請求項丨丨之增亮膜，其中該稀釋劑包含（甲基）丙烯酸苯氧基乙基醋、（甲基）丙稀酸节基顆、N_乙稀基D比洛㈣及 N-乙烯基己内醯胺。 14，如请求項η之增亮膜，兑中兮接碰七丨& a a几肤 "T 〇亥稀釋劑包含經N—取代或經 Ν，Ν-二取代之（甲基）丙稀醯胺。12. The brightness enhancing film of claim 10, wherein the diluent is a liquid at room temperature. 13. The brightening film of the T request item, wherein the diluent comprises phenoxyethyl ketone (meth) acrylate, (meth) acrylate acid group, N-ethylene D pir (IV) and N-vinyl caprolactam. 14. For the brightening film of claim η, the 兮兮丨丨丨 amp amp amp a 稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂稀释剂Guanamine.

15.如請求们之增亮臈’ #中該可聚合組合物不含甲基丙烯酸酯官能基單體。 16.如請求項丨之增亮膜，其中該膜係_視情況包含具〇 5請微米半徑之圓形頂角之轉向膜。 17·:種包含如請求項1之增亮臈及-與該增亮膜接觸之第二光學臈之物件。 18.如請求項17之物件，向膜、一擴散器、一護覆蓋膜之群。其中該第二光學膜係選自包含一轉吸收偏光器、一反射偏光器及一保 19.如請求項1 8之物件其中該第二光學膜包含一棱鏡結構。 102543-970616.doc 2 0 ——_ g -有一經聚合結構之增亮臈，其包括含有下列之可 * 聚合級合物之反應產物： a)至少約15重量％之一或多種（曱基）丙烯酸化之芳族環 . 氧樹脂寡聚物； ^ . b)至少約1 0重量％之無機奈米粒子；及 c)視情況一交聯劑。 21_如凊求項1之增亮膜，其中該結構包含複數個具有圓形頂角之脊，而該等圓形頂角具有介於4至丨5微米之間之半 Φ 徑。 22· —種增亮膜，其包含：一包含一實質上無溶劑可聚合組合物之反應產物之增亮經聚合結構，該可聚合組合物包含一包含一或多種乙稀系不飽和單體之有機組份，其中該有機組份於180卞下具有一低於1〇〇〇 cpS之黏度；及至少3 0重量％之無機奈米粒子。 23. 如請求項22之增亮膜’其中該有機組份於1 6〇卞下具有一鲁低於1000 cPs之黏度，於l4〇°F下具有一低於1〇〇〇 cps之黏度，於120°F下具有一低於l〇〇〇CpS之黏度，於i2〇°F下具有一低於800 cps之黏度或於12〇卞下具有一低於6〇〇 cps 之黏度。 24. 如請求項22之增亮膜，其中該有機組份包含至少一（甲基）丙烯酸化之胺基曱酸酯寡聚物、（曱基）丙烯酸化之聚酯寡聚物、（曱基）丙稀酸化之盼系寡聚物、（甲基）丙烯酸化之丙烯酸募聚物 '(曱基）丙烯酸化之環氧樹脂（曱基）丙烯酸 102543-970616.doc -4- 丄允3062 _及其混合物。 25.如請求項22之增亮膜，其中該有機組份包含至少一具有至夕450克/莫耳之數目平均分子量之寡聚乙稀系不飽和單體。 26·—種增亮膜，其包含： ▲包含-實質上無溶劑可聚合組合物之反應產物之增亮經聚合結構，該可聚合組合物包含15. The bright polymerizable composition of the present invention does not contain a methacrylate functional monomer. 16. A brightness enhancing film as claimed in claim 1, wherein the film system comprises, as the case may be, a turning film having a circular apex angle of 微米5 micron radius. 17·: An object comprising a brightening element as claimed in claim 1 and a second optical element in contact with the brightness enhancing film. 18. The article of claim 17, wherein the film, a diffuser, and a cover film are grouped. Wherein the second optical film is selected from the group consisting of a transflective polarizer, a reflective polarizer, and an article 19. The article of claim 18 wherein the second optical film comprises a prismatic structure. 102543-970616.doc 2 0 —— _ g - a brightening enthalpy of a polymeric structure comprising a reaction product comprising the following polymeric intermediates: a) at least about 15% by weight of one or more (fluorenyl) An acrylated aromatic ring. an oxy-resin oligomer; ^. b) at least about 10% by weight of inorganic nanoparticles; and c) optionally a crosslinking agent. 21) The brightness enhancing film of claim 1, wherein the structure comprises a plurality of ridges having a rounded apex angle, and the rounded apex angles have a half Φ diameter of between 4 and 丨5 microns. 22. A brightness enhancing film comprising: a brightness enhancing polymerized structure comprising a reaction product of a substantially solvent-free polymerizable composition, the polymerizable composition comprising one or more ethylenically unsaturated monomers An organic component, wherein the organic component has a viscosity of less than 1 〇〇〇 cpS at 180 Torr; and at least 30% by weight of inorganic nanoparticles. 23. The brightness enhancing film of claim 22, wherein the organic component has a viscosity of less than 1000 cPs at 16 Torr and a viscosity of less than 1 〇〇〇 cps at 14 °F. It has a viscosity lower than 10 CpS at 120 °F, a viscosity lower than 800 cps at i2 〇 °F or a viscosity lower than 6 〇〇 cps at 12 〇卞. 24. The brightness enhancing film of claim 22, wherein the organic component comprises at least one (meth) acrylated amino phthalate oligomer, (mercapto) acrylated polyester oligo, (曱Acrylating oligopolymer, (meth) acrylated acrylic acid polymer [(mercapto) acrylated epoxy resin (fluorenyl) acrylic acid 102543-970616.doc -4- 丄 306 _ and its mixture. 25. The brightness enhancing film of claim 22, wherein the organic component comprises at least one oligoethylenically unsaturated monomer having a number average molecular weight of 450 grams per mole. 26. A brightness enhancing film comprising: ▲ a brightened polymerized structure comprising a reaction product of a substantially solvent-free polymerizable composition, the polymerizable composition comprising

包3 —或多種乙烯系不飽和單體之有機組份，其尹該有機組份具有至少丨.54之折射率；及至少1〇重量％之實質上可完全凝聚之無機奈米粒子。 .如請求項26之增亮膜，其令該可聚合組合物具有至少147 之折射率、至少L52之折射率、至少155之折射率或至少 1.60之折射率。請求項1-16及20-25中仕一項之增亮膜，其中該氧化锆如實質上可完全凝聚 29.如請求項22_27中任一項 9儿膘，其中該經聚合結構包含30至60重量％之氧化鍅。 3〇.如請求項22-27中任一項之增亮膜，丨中該有機組份包含或多種選自下列組成之群之第—單體：〇 -包含-具有下述^式之主要 R2\ /R2 干肋·An organic component comprising 3 or more ethylenically unsaturated monomers, wherein the organic component has a refractive index of at least 丨54; and at least 1% by weight of substantially completely condensable inorganic nanoparticles. A brightness enhancing film according to claim 26 which has a polymerizable composition having a refractive index of at least 147, a refractive index of at least L52, a refractive index of at least 155, or a refractive index of at least 1.60. The brightness enhancing film of any one of claims 1-16 and 20-25, wherein the zirconia is substantially completely condensable. 29. The ninth aspect of claim 22, wherein the polymerized structure comprises 30 to 60% by weight of cerium oxide. The brightness enhancing film according to any one of claims 22 to 27, wherein the organic component comprises or a plurality of monomers selected from the group consisting of: 〇-containing - having the following R2\ /R2 dry ribs ·

102543-9706I6.doc ⑽3062 其中R1獨立地係氫或曱基， R2獨立地係氯或漠， Q獨立地係Ο或S，及 Z獨立地係-C(CH3)2-、_ch2·、-c(0)-、-S-、-S(〇) 或-S(0)2-; u) —包含一具有下述結構式之主要部分之單體： _102543-9706I6.doc (10)3062 wherein R1 is independently hydrogen or fluorenyl, R2 is independently chlorine or desert, Q is independently Ο or S, and Z is independently -C(CH3)2-, _ch2., -c (0)-, -S-, -S(〇) or -S(0)2-; u) - contains a monomer having the main part of the following structural formula: _

其中R1獨立地係氫或曱基， R2獨立地係氫或溴， Q獨立地係Ο或S， z獨立地係-C(CH3)2-、_CH2-、-c(0)-、-S-、-s(〇)_ 或-S(〇)2-，及 L係一獨立地選自直鏈或具支鏈C2_Ci2烷基之連接基團，其中該碳鏈視情況經一或多個氧基團取代及 /或該等碳原子視情況經一或多個羥基取代；及i與i i之混合物。 31. 32. 種包含如請求項30之反應產物之光學物件。月求項3 1之光學物件，其中該材料係一視情況具有一微結構表面之膜。 102543-970616.doc • 6 - 1363062 33.如請求項32之光學物件，其中該微結構表面包含方角結構或適於製造一電漿顯示器面板之障壁凸緣之結構。Wherein R1 is independently hydrogen or fluorenyl, R2 is independently hydrogen or bromine, Q is independently Ο or S, z is independently -C(CH3)2-, _CH2-, -c(0)-, -S -, -s(〇)_ or -S(〇)2-, and L is a linking group independently selected from a linear or branched C2_Ci2 alkyl group, wherein the carbon chain is optionally one or more The oxygen group is substituted and/or the carbon atoms are optionally substituted with one or more hydroxyl groups; and a mixture of i and ii. 31. An optical article comprising the reaction product of claim 30. The optical article of item 3, wherein the material has a film of a microstructured surface as the case may be. The optical article of claim 32, wherein the microstructured surface comprises a square corner structure or a structure suitable for fabricating a barrier flange of a plasma display panel.

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