捌、新型說明： 【新型所屬之技術領域】 本創作係關於一種光學薄膜，特別是關於—種位於平面顯示 器或多層高性能光學薄膜最外層之抗眩薄膜。 【先前技術】 目前應用於平面顯示器最外層，例如液晶平面顯示器的偏光 板外層TAC (二醋酸纖維素）上’先塗佈一層硬度膜，硬度膜上施 加雷射小孔，除了增加硬度膜表面粗縫硬度外，還能使外來反射 光強度於反射面均勻散開，增加消光（haze)的防眩功能。 大日本印刷（Di Nippon printing) US 6, 217, 176B1 光透明 樹脂中，加入兩種以上光透明微粒，光透明微粒彼此之間的反射 係數（refractive index)差異值或與樹脂的反應係數差異值在 0· 03至0· 2區間。樹脂反射係數為1· 49至1· 53區間，透明微粒 反射係數為1· 53至1· 57和1· 58至1· 62區間。透明微粒由可分 散有機微粒或無機微粒所組成，微粒直徑範圍為1 Am至5//m區 間。新型 Description of the new type: [Technical field to which the new type belongs] This creation is about an optical film, especially an anti-glare film located on the outermost layer of a flat panel display or a multilayer high-performance optical film. [Previous technology] Currently applied to the outermost layer of a flat-panel display, such as TAC (cellulose diacetate) on the outer layer of a polarizing plate of a liquid-crystal flat-panel display. First, a layer of hardness film is applied. In addition to the thick seam hardness, the intensity of external reflected light can be spread evenly on the reflecting surface, and the anti-glare function of matting (haze) is increased. Di Nippon printing US 6, 217, 176B1 Adding two or more kinds of light-transparent particles to light-transparent resin, the difference between the reflection index (refractive index) of the light-transparent particles or the difference between the reaction coefficient and the resin Between 0.03 and 0.2. The reflection coefficient of the resin ranges from 1.49 to 1.53, and the reflection coefficient of the transparent particles ranges from 1.53 to 1.57 and 1.58 to 1.62. The transparent particles are composed of dispersible organic particles or inorganic particles, and the particle diameter ranges from 1 Am to 5 // m.
Parkhurst & Wendel LLP 專利公佈·· US2002/0150722A1 光透 明樹脂中加入非聚附性（non—aggl〇merative)光透明微粒，微粒 彼此之間或與光透明樹脂的反射係數差異值為〇. 〇5至〇· 15區 間’微粒直徑範為1· 〇 Am至5. 0//m區間。 【新型内容】 本創作主要目的，係在提供一種光學薄膜，使其具有光學抗 眩和機械強度之功能。 本創作另一目的，係在提供一種光學薄膜，擴大其無機氧化 物之反射率使用範圍，涵蓋更多不同的無機氧化物應用。 本創作又-目的，係在提供-種光㈣膜，獻無機氧化物 微粒直徑的使用範圍。 本創作又一目的，係在提供一種光學薄膜，以增加其抗眩膜 的明暗對比，以提供抗眩薄臈更佳的明暗對比強度和抗眩功能。' 為達到上述目的，本創作提出一種光學抗眩薄膜，包括：一 透明基板；以及，一抗眩化合物塗佈在透明基板上，而抗眩化人 物組成’包括在可被UV光硬化的透明樹脂溶液中，添加一種以1 以無機氧化物微粒為主體，外圍包覆有機壓克力單體矽醇趟偶 劑製成的有機-無姐紐粒，域氧化物錄細在如η^σ 200nm區間，無機氧化物折射率範圍為145 至 化物彼此之_反射率差異_為Q. Q1至75區間°°，1，無機氧 物混成微粒直徑範圍為300nm至1 區間。 …、機氧化 當更瞭 底下藉料細制巾_的方財和_詳加說明 解本創作之目的、技_容、_及其崎叙功效。 【實施方式】 M252022 光學抗眩薄膜係塗佈於多層鑛膜最外層，提供下列功能（i)# 筆硬度>3H，（ii)耐刮性（abrasion resistance)大於 以上， 荷重lkg尖端物體’來回試驗十次以上，表面無損傷，（iiDhaze > 10%，外部之反射強光在表面均勻被散開，（iv)抗閃爍性，消除 内部光通過時，螢幕所產生不穩定，閃爍影像(v)維持高明暗 (contrast)對比。 已經有多篇專利文獻利用光源内部之微粒散射（scattering) 特性，達到光學抗眩功能，例如大日本印刷和Parkhurst & Wendel φ LLP etc，他們利用一種以上的可分散性透明有機微粒，或透明無 機微粒，摻雜加進透明有機樹脂鍍液中，經過uv烘烤製程後製得。 所摻加的透明有機微粒，或無機微粒，為商業用已硬化 (sintering)處理過的微粒，微粒直徑範圍在丨至之間。 為了達到有效抗眩功能，各微粒彼此之間的反射係數差異值，或 微粒與有機樹脂的反射係數差異值被限制在0· 〇3至〇· 2區間。一 般通用的壓克力有機樹脂反射率範圍在149至153之間，因此 · 有機微粒或無機微粒的反射係數被在丨· 53至丨· 57和1· 58至1 如果光透觀粒的反射係數差異值小於G. Q3，_光微粒 散散所造成抗眩效果不彰，如果光透明微粒的反射係數差異值大 於〇.2〇 ’光透明微粒很可能會形絲點，鍍膜塗佈後將形成霧狀 缺陷。 · 本創作係於光透明壓克力樹脂奈米微粒溶液中，加進一觀 . 7 f明無機-有機混成微粒。無機'有機現成微粒由無機氧化物微 外表議 粒’例如TiO.2· 2)，混成微粒的直徑不可設計過大，以免鑛膜 後形成霧狀雜。如果使収鱗較小的無機氧化倾粒例如 =3(n=l. 65) ’ Si〇2(㈣· 42)，混成微粒的直徑範圍，會有較寬廣 叹叶空間。目刖市售之AG(抗眩）膜所使用的化學鍍液，大都包含 由金屬賴化合物，經由水解反應製得。無機氧化物折射率範圍 為1.45至2. 20區間，無機氧化物直徑範圍為2Qnm至驗m區間 無機氧化物彼此之_反射率差異範圍在g. qi至q· 75區間益 機、有機混合微粒直徑範圍為_nm至丨_區間混成微粒的反射 率軌圍在1· 5G至1. 8G區間。如果採用反射率高的無機氧化物微 固含量61%至_以上之商業用無機微粒，微粒直徑分佈在_ 至3/zm最為通用，無機微粒佔ag化學鍍液成本的絕大部份。本 創作的AG化學鍍液組成，無機微粒固含量僅佔1〇%至6〇%區間， 大部份均分佈於10%至20%區間，所使用的無機氧化微粒種類也較 寬廣，AG膜的塗佈厚度更薄，對於降低化學鍍液成本有著很大的 市場競爭力。詳細的混成微粒製程敘述如下： (A )金屬醇鹽氧化物R；iM(OR2)4 n在醇/酮/醚系列溶劑中水解 反應製得，如方程式（1)所示 R:M(〇r2)4 n」^MxOy Eqn· (1) 其中，x=l or 2 ; y=2 or 3 ; R1，R2可相同，為氫或α〜(：4烷基，n 為0〜3整數’ Μ代表鈦、石夕、錯、石西铪金屬。審慎控制水含量摩爾 (mole)數，比為金屬醇鹽摩爾數之1至3倍，反應的曲值控制 在1. 0至3. 0區間。 (B )包覆反應，（A )反應水解後所形成之無機氧化物結構、鬆 政’加入光 t 〇 早體 MA (inethy 1 aery 1 ate)、MAA (me thy 1 aery 1 i c acid)或矽醇鹽偶合劑來包覆無機氧化物微粒形成有機—無機混成 微粒，如方程式（2)所示Parkhurst & Wendel LLP Patent Publication · US2002 / 0150722A1 Non-agglomerative light-transparent particles are added to the light-transparent resin, and the reflection coefficient difference between the particles or the light-transparent resin is 〇. 〇 The range of 5 to 0. 15 'particle diameter ranges from 1.0 to 5.0 // m. [New content] The main purpose of this creation is to provide an optical film with optical anti-glare and mechanical strength. Another purpose of this creation is to provide an optical film that expands the range of reflectance of inorganic oxides to cover more different applications of inorganic oxides. The purpose of this creation is to provide a kind of photoluminescence film, which can be used for the diameter of inorganic oxide particles. Another purpose of this creation is to provide an optical film to increase the light-dark contrast of its anti-glare film to provide better anti-glare contrast strength and anti-glare function. 'In order to achieve the above purpose, the present invention proposes an optical anti-glare film including: a transparent substrate; and, an anti-glare compound is coated on the transparent substrate, and the anti-glare character composition is included in the transparent which can be hardened by UV light In the resin solution, an organic-non-nucleus particle made of an inorganic oxide particle as the main body and coated with an organic acrylic monomer silanol coupling agent is added. The domain oxide is recorded as η ^ σ In the 200nm range, the refractive index of the inorganic oxide ranges from 145 to the difference in reflectivity between the compounds. It is Q. Q1 to 75 °°, 1, the diameter of the inorganic oxide mixed particles ranges from 300nm to 1. …, Organic oxidation, when it ’s more important, let ’s borrow the fine towels _ Fang Cai and _ to explain in detail the purpose, skills, and its effectiveness of this creation. [Embodiment] M252022 Optical anti-glare film is coated on the outermost layer of a multi-layer mineral film and provides the following functions: (i) # Pen hardness > 3H, (ii) Abrasion resistance is greater than the above, and the load is 1 kg for a pointed object. Tested back and forth more than ten times, the surface is not damaged, (iiDhaze > 10%, the externally reflected strong light is evenly spread on the surface, (iv) anti-flicker, eliminating the instability and flickering image produced by the screen when the internal light passes through ( v) Maintain high contrast. Many patent documents have used the scattering characteristics of light sources inside the light source to achieve optical anti-glare functions, such as Dainippon Printing and Parkhurst & Wendel φ LLP etc., they use more than one type The dispersible transparent organic particles or transparent inorganic particles are doped and added to the transparent organic resin plating solution and prepared after UV baking process. The added transparent organic particles or inorganic particles are hardened for commercial use. (sintering) processed particles, the particle diameter range is between 丨 to. In order to achieve an effective anti-glare function, the difference in reflection coefficient between each particle, The difference between the reflection coefficient of fine particles and organic resin is limited to the range of 0.03 to 0.2. Generally, the reflectance range of acrylic organic resin is generally between 149 and 153. Therefore, the reflection coefficient of organic fine particles or inorganic fine particles If the difference between the reflection coefficient of the light-transmitting particles is less than G. Q3, the number of reflection coefficients is less than G. Q3, the anti-glare effect caused by the scattering of light particles is not good, and the reflection coefficient of light-transparent particles The difference value is greater than 0.20 '. Light-transparent particles are likely to form filaments, and mist-like defects will be formed after coating. · This creation is based on the light-transparent acrylic resin nanoparticle solution, added to the view. 7 f Ming inorganic-organic mixed particles. Inorganic 'organic ready-made particles are composed of inorganic oxide micro-appearance particles', such as TiO. 2 · 2), the diameter of the mixed particles should not be designed to be too large, so as to avoid the formation of haze after the mineral film. If the scale of the inorganic oxidized particles is small, for example, = 3 (n = 1.65) ′ SiO 2 (㈣ · 42), the diameter range of the mixed particles will have a wide sigh space. Most of the electroless plating solutions used in Meguro's commercially available AG (anti-glare) films are prepared by hydrolysis of metal compounds. The refractive index range of inorganic oxides is in the range of 1.45 to 2.20, and the diameter of inorganic oxides is in the range of 2Qnm to m. The difference in reflectance between inorganic oxides is in the range of g.qi to q · 75. The range of the reflectance of the mixed particles in the range of _nm to 丨 _ is in the range of 1.5G to 1.8G. Commercial inorganic fine particles with a high reflectivity of inorganic oxides with a solid content of 61% to _ or more are used. The particle diameter distribution of _ to 3 / zm is the most common. Inorganic particles make up the majority of the cost of the ag electroless plating solution. The composition of the AG chemical plating solution created by this invention, the solid content of inorganic particles only occupies the range of 10% to 60%, and most of them are distributed in the range of 10% to 20%. The type of inorganic oxide particles used is also wide. AG film The coating thickness is thinner, which has great market competitiveness for reducing the cost of the electroless plating solution. The detailed mixed particle manufacturing process is described as follows: (A) Metal alkoxide oxide R; iM (OR2) 4 n is prepared by hydrolysis reaction in alcohol / ketone / ether series solvents, as shown in equation (1) R: M (〇 r2) 4 n ″ ^ MxOy Eqn · (1) where x = l or 2; y = 2 or 3; R1 and R2 may be the same, and are hydrogen or α ~ (: 4 alkyl, n is an integer of 0 ~ 3 ' Μ represents titanium, Shi Xi, Wuji, Shixiyan metal. Carefully control the number of moles of water content (mole), the ratio is 1 to 3 times the number of moles of metal alkoxide, the curvature of the reaction is controlled to 1.0 to 3.0 (B) Encapsulation reaction, (A) Inorganic oxide structure formed after reaction hydrolysis, Songzheng 'added light t 〇 early body MA (inethy 1 aery 1 ate), MAA (me thy 1 aery 1 ic acid ) Or silicon alkoxide coupling agent to coat inorganic oxide particles to form organic-inorganic hybrid particles, as shown in equation (2)
矽醇鹽偶劑之通用化學結構式為R〖Si(0R'n，其中Rl可為氫、苯 基、環氧基、壓克力基、烯基、酮基、氨基包含烷基，R2為 甲基或乙基’ η為0〜3之整數，以η為1最通用，說明如下： (1 來含丙烯醯基化合物，例如 MPTS(CH2C(CH3)COOC3H6SI(OCH3)3) (2 ) R1 含環氧基化合物，例如 AMPTS (H2COCHCH2〇GH6Si(OCH3)3) (3 ) R1 含胺基化合物，例如 AEApTS(MC2H4NHC3H6Si(〇CH3)3) 包覆後之無機-有機氧化物混成微粒最終直徑控制在3〇〇nm至i # 10之間，混合微粒反射率控制在1· 50至丨· 85之間，包覆製程須保 也鍍膜後不起霧不龜裂。所添加光聚合單體矽醇鹽偶合劑的重量 佔無機氧化物重量比之5%至_之間。無機氧化微粒的來源，也 可藉市售商業官道取得，不過，市售之無機氧化微粒大都數已經 歷更化製程’剩餘可作用的官能基不同，純粹當做孔隙填補，增 加硬度使帛。翻之無機祕微粒直錄圍控齡編至施m 1間。如果尚麵部份官可參與水難誠倾壓克力基之 聚合反應’無機氧化微粒直徑範圍宜控制在20咖至20_之間。 ⑻光透賴克力樹脂溶液，_由壓克力單體（_)或 光1合預聚物（ohgamer)所組成。紋料體為賴預聚物的 一種，包含一個至六個丙烯醯官能基（-C=C-C00-)系列化合物， 例如SR285 ’ SR306 ’ TPGDA，SR454和SR444等。光聚合性單體具 有透明，分散性佳，和易與⑽硬化起始劑反應的優點。光聚合性 單體與光聚合性縣物，切醇鹽偶合獅反料差異健制在〇 至〇· 03之間。光聚合性單體或預聚物之微粒直徑控制在12nm以 下，不致影響與有機—無機混成微粒的散射功能。整體而言，光透 月树月曰固含里佔溶凝膠鍍液固含量之4〇%至，無機氧化微粒固 含量佔溶凝膠鑛賴含量之舰至_，抗眩薄膜的塗佈厚度約為 有機-無機混成微粒平均直徑的1至5倍。 接下來說明如何增加抗眩膜的抗閃爍性和提昇明暗對比，在 抗眩膜鑛液巾添加適量染色（dye)㈣或獅系職f，使抗眩 薄膜透光雜 70%至__，以獲得最㈣暗雌和抗閃爍 性，無機-有機氧化物混成微粒添加進光透明壓克力樹脂溶液，除 了 了以增加光學鍍膜的抗閃爍性外和haze消光性功能外，還可以 整加光學抗眩膜之機械強度功能，例如鉛筆表面硬度（>3H)，耐 到性和抗化學腐蝕功能。抗眩硬度膜塗佈使用的基材，係選自三 M252022 酷酸纖維素（TAC)，聚甲基丙烯酸甲脂（PMMA),聚乙烯對苯二曱 脂（PET)，聚碳酸脂（pC)和 N〇rb〇rene (NB)。 參閱第一圖所示，應用於平面顯示器外部抗眩薄膜1〇中，在 TAC或PEC基板11上，塗佈包含一種以上有機—無機混成微粒15 之有機透明樹脂12所形成的高分子混合溶液，有機-無機混成微 粒15的直徑範圍定義為3〇〇nm至km區間，有機-無機混成微粒 15由一種以上的無機氧化物微粒13外圍各自包覆一有機單體或 石夕醇鹽偶合劑所形成，無機氧化物微粒的直徑範圍介於2〇咖至 300nm區間。 例1:光學抗眩膜製作 抗眩硬度膜的溶膠塗佈液重量百分比組成包括1成份 SiCOGHa)4，2 成份 Ti(0C4Ha)4，1 成份 MAA，2 成份 MPTS，10 成份 乙醇，12成份水溶液和微量UV起始劑Irgacure 1700，4成份 TPGDA ’ 2成份SR444，1成份SR256，Ph值控制在酸性溶液中，經 UV以500mj和80 C熱供烤15分鐘，製成抗眩硬度膜。 例2:光學抗眩膜製作 抗眩硬度膜的溶膠塗钸液重量百分比組成包括2成份 SiCOGHa)4，1 成份 ZrCOGHa)4，1 成份 MAA，2 成份 MPS，8 成份乙 醇，4成份MIBK，12成份水溶液，6成份TPGDA，3成份SR454， 和微量UV起始劑Irgacure 1700，Ph值控制在酸性溶液中，經UV 以500mj和80°C熱烘烤20分鐘，製成抗眩硬度膜。 11 M252022 以上所述者，為本創作之塗佈溶液組成說明，並非用來限定 本創作之實絲目。故驗本鑛範贿述之結構，特徵及精神 所為之均等變化祕綱應包括於本創狀專利申請範圍内。The general chemical structural formula of the silicon alkoxide coupler is R [Si (0R'n, where R1 can be hydrogen, phenyl, epoxy, acrylic, alkenyl, keto, and amino groups include alkyl groups, and R2 is Methyl or ethyl 'η is an integer from 0 to 3, and η is the most common, which is explained as follows: (1 to contain acryl fluorenyl compounds, such as MPTS (CH2C (CH3) COOC3H6SI (OCH3) 3) (2) R1 Epoxy-containing compounds, such as AMPTS (H2COCHCH2〇GH6Si (OCH3) 3) (3) R1 Amine-containing compounds, such as AEApTS (MC2H4NHC3H6Si (〇CH3) 3) coated inorganic-organic oxide mixed particles to control the final diameter of the particles Between 300nm and i # 10, the reflectivity of the mixed particles is controlled between 1.50 and 丨 · 85, and the coating process must ensure that the coating is not fogged and cracked. The photopolymerizable monomer silicon is added. The weight of the alkoxide coupling agent accounts for 5% to _ of the weight ratio of the inorganic oxide. The source of the inorganic oxidized particles can also be obtained through commercially available commercial channels. However, most of the commercially available inorganic oxidized particles have undergone changes. In the process, the remaining functional groups are different, and it is purely used as pore filling, which increases the hardness and makes it 帛. The age ranges from 1 to 10 m. If some officials can participate in the polymerization reaction of acrylic acid based on acrylic acid, the diameter range of inorganic oxide particles should be controlled between 20 and 20 mm. ⑻Light transparent acrylic resin solution, _ Is composed of acrylic monomer (_) or photo 1 prepolymer (ohgamer). The texture is a kind of prepolymer, which contains one to six acrylic fluorene functional groups (-C = C-C00 -) Series of compounds, such as SR285 'SR306' TPGDA, SR454 and SR444, etc. Photopolymerizable monomers have the advantages of transparency, good dispersibility, and easy reaction with the hardening initiator. Photopolymerizable monomers and photopolymerization The difference between the prefecture and the alkoxide-coupled lion reaction is between 0 and 03. The particle diameter of the photopolymerizable monomer or prepolymer is controlled below 12nm, which will not affect the scattering function of organic-inorganic hybrid particles. On the whole, the solid content of the transparent moon accounts for 40% of the solid content of the solution gel plating solution, the solid content of the inorganic oxide particles accounts for the content of the soluble gel mineral solution, and the coating of the anti-glare film. The thickness of the cloth is about 1 to 5 times the average diameter of the organic-inorganic hybrid particles. How to increase the anti-glare film's anti-flicker property and enhance the contrast between light and dark, add an appropriate amount of dye (dye) or lion series f to the anti-glare film mineral towel, and make the anti-glare film transmit 70% to __ to get the most雌 Dark female and anti-flicker, mixed inorganic-organic oxide particles into light transparent acrylic resin solution, in addition to increasing the anti-flicker of the optical coating and the haze extinction function, it can also add optical anti-glare The mechanical strength functions of the film, such as pencil surface hardness (> 3H), resistance and chemical resistance. The base material for anti-glare hardness film coating is selected from three M252022 cellulose acid (TAC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polycarbonate (pC) ) And Norborne (NB). Referring to the first figure, it is applied to an external anti-glare film 10 for a flat display, and a polymer mixed solution formed of an organic transparent resin 12 containing more than one type of organic-inorganic mixed particles 15 is coated on a TAC or PEC substrate 11 The diameter range of the organic-inorganic hybrid microparticles 15 is defined as 300 nm to km. The organic-inorganic hybrid microparticles 15 are each covered by one or more inorganic oxide microparticles 13 with an organic monomer or stone alkoxide coupling agent. The diameter of the formed inorganic oxide particles ranges from 20 to 300 nm. Example 1: Optical anti-glare film The weight percentage composition of the sol coating solution for making anti-glare hardness film includes 1 component SiCOGHa) 4, 2 component Ti (0C4Ha) 4, 1 component MAA, 2 component MPTS, 10 component ethanol, 12 component aqueous solution And trace UV starter Irgacure 1700, 4-component TPGDA '2-component SR444, 1-component SR256, Ph value is controlled in acid solution, and heated at 500mj and 80 C for 15 minutes under UV to make an anti-glare hardness film. Example 2: Optical anti-glare film The weight percentage composition of the sol coating solution for making anti-glare hardness film includes 2 components SiCOGHa) 4, 1 component ZrCOGHa) 4, 1 component MAA, 2 component MPS, 8 component ethanol, 4 component MIBK, 12 Aqueous solution, 6-component TPGDA, 3-component SR454, and trace UV initiator Irgacure 1700, Ph value is controlled in acidic solution, and then heat-baked at 500mj and 80 ° C for 20 minutes under UV to make anti-glare hardness film. 11 M252022 The above is a description of the composition of the coating solution for this creation and is not intended to limit the real order of the creation. Therefore, the basic changes of the structure, characteristics and spirits of the authors should be included in the scope of this patent application.
【圖式簡單說明】 圖式說明： 第一 構。 圖為本創作應用於平面顯示器或多層高性絲學抗眩薄膜結[Schematic description] Schematic description: First structure. The picture shows the creative application of flat display or multilayer high-performance silk anti-glare film junction
圖說說明： 基板 無機氧化物微粒 10 抗眩薄膜 12 透明樹脂 有機-無機混成微教Description of the illustrations: Substrate Inorganic oxide particles 10 Anti-glare film 12 Transparent resin Organic-inorganic hybrid micro-education
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