201200963 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種組成物，特別是指一種可固化組 成物。本發明另有關於一種利用該組成物之具有透明保護 層之製件的製備方法。 【先前技術】 傳統之電子影像顯示裝置中的圖像顯示介面，以及於 一基材（例如塑膠或玻璃等材質之基板）上具有裝飾用或功能 性圖樣（pattern)[例如銦錫氧化物（indiurn tin 〇xide，IT〇)線路 或其他導電物質之線路圖樣]等之部件，極易於後續再加工 之程序中受刮傷及磨損，亦隨之增加了製程中的耗損與生 產的成本。為了克服上述之缺點，業界需要研發一可在具 有圖樣的基材表面形成一耐擦傷性（wear resisUnce)的塗層 ，且更具有抗反射（anti-reflection)、抗眩（anti_glare)，甚至 是抗指紋（anti-finger)等性能的組成物，以避免部件上的圖 樣因加工造成擦傷。 台灣專利公告號1298078揭示一種硬塗層之形成成分， 其係含有具有脂環構造的（甲基）丙烯酸酯、分子内具有2個 以上聚合性不飽和基和丨個以上芳基的化合物並添加具 有聚合性不飽和基的有機化合物結合於矽石微粒子而形^ 的化合物，以組成該形成成分。而含有該硬塗層形成成分 之一塗佈液則可藉由塗佈在一基材薄膜的至少一面上，再 經由電離輻射線使其硬化以形成一硬塗層，其中，該硬塗 層中含有20〜60重量％的石夕；ε，且其折射率為153以上” 3 201200963 該發明主要是藉由所含之具有聚合性不飽和基的有機化人 物結合於石夕錢粒子而形成的化合物，以使得所形成之i 塗層中3有同3里（20〜6〇wt%)的石夕石，並賦予該硬塗膜在 向溫、尚溫高濕時有抑制捲曲的效果。 月J述專利案中，因為無機微粒是以外加方式添加至待 聚合之組成物中，因此在操作時有嚴重之無機微粒凝聚問 題，且製得的塗屬中無機微粒常分散性不佳。另外，必須 添加问含量之無機粒子，才能達到企求之機械及光學性質 在塗層製備過程及最終產品中面臨無機微粒分散問題的 技術亦見於其他專利申請案，譬如tw〇9〇1〇9187及 TW092123516。 中國專利公開號CN101475774所揭示之塗層用固化性 樹脂組合物中，則是於一含有具有反應官能基團c的黏合劑 成分C之固化反應性基質中，添加具有不同粒徑範圍以及 不同之表面親疏水性質的無機微粒A與B，其中，該無機 微粒A的表面具有與該官能基團c具有交聯反應性的反應 官能基團a。將該塗層用固化性樹脂組合物塗佈在透明基材 膜上’經乾無、固化之後’形成不損害透明度且对擦傷之 具有凹凸形狀的硬塗層，在此案中，同樣有操作時無機微 粒凝聚以及後續無機微粒在塗層中分散不佳的問題。 另外’歐洲專利公告號EP1327670揭示·一硬塗組成物 ，其含有0.1 ~50重量份之由乙烯基單體所形成之聚合物、 50~5000重量份之親水性有機溶劑（hydrophilic organic solvent) ’以及100重量份之由矽烷化合物（siiane 201200963 corn’d)經部分縮合而成的具彳ου構之寡聚物。 ^於6亥具彳RmSiX4m結構之寡聚物並非呈現粒子型態，使 得此塗層不具備目前顯示裝置需求之光學性質（譬如抗眩）， 且相對於該由乙稀基單體所形成之聚合物而言，寡聚物& 硬塗組成物中之含量極高。 口此需要進一步研發一可在具有圖樣的基材表 面形成—耐擦傷性的保護層的組成物，且需研發―可使無201200963 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a composition, and more particularly to a curable composition. The invention further relates to a process for the preparation of a part having a transparent protective layer using the composition. [Prior Art] An image display interface in a conventional electronic image display device, and a decorative or functional pattern on a substrate (for example, a substrate made of plastic or glass) [for example, indium tin oxide ( Indiurn tin 〇xide, IT〇) circuit components such as lines or other conductive materials are extremely susceptible to scratching and abrasion in subsequent reprocessing procedures, which in turn increases the cost of production and production. In order to overcome the above disadvantages, the industry needs to develop a coating that can form a wear resisunce on the surface of a patterned substrate, and is more anti-reflection, anti-glare, or even Anti-finger and other properties of the composition to avoid scratches on the part of the part due to processing. Taiwan Patent Publication No. 1298078 discloses a forming component of a hard coat layer containing a (meth) acrylate having an alicyclic structure, a compound having two or more polymerizable unsaturated groups in the molecule, and more than one aryl group, and adding The organic compound having a polymerizable unsaturated group is bonded to the fine particles of the vermiculite particles to constitute the forming component. The coating liquid containing the hard coat forming component can be formed by coating on at least one side of a substrate film and hardening it by ionizing radiation to form a hard coat layer, wherein the hard coat layer is formed. Containing 20 to 60% by weight of Shi Xi; ε, and its refractive index is 153 or more” 3 201200963 The invention is mainly formed by combining an organic character having a polymerizable unsaturated group with a stone particle. a compound such that 3 of the formed i coating has the same 3 (20 to 6 〇 wt%) of the stone, and imparts the effect of suppressing curl to the hard coating at high temperature and humidity. In the case of the patent, since the inorganic fine particles are added to the composition to be polymerized in an externally added manner, there is a problem of severe inorganic particle agglomeration during the operation, and the inorganic particles in the obtained coating are often poorly dispersed. In addition, it is necessary to add the inorganic particles of the content to achieve the desired mechanical and optical properties. The technology of the inorganic particles in the coating preparation process and the final product is also found in other patent applications, such as tw〇9〇1〇9187. And TW09212351 6. The curable resin composition for coating disclosed in Chinese Patent Publication No. CN101475774 is added to a curing reactive matrix containing a binder component C having a reactive functional group c, and has a different particle size range and Inorganic fine particles A and B having different surface hydrophobicity properties, wherein the surface of the inorganic fine particles A has a reactive functional group a having crosslinking reactivity with the functional group c. The curable resin composition for the coating layer Coating on a transparent substrate film 'after drying, after curing' to form a hard coat layer which does not impair transparency and has a concave-convex shape for scratching, in this case, there is also agglomeration of inorganic particles during operation and subsequent inorganic particles are coated In addition, the problem of poor dispersion in the layer is disclosed in the 'European Patent Publication No. EP1327670. A hard coating composition containing 0.1 to 50 parts by weight of a polymer formed of a vinyl monomer, and 50 to 5000 parts by weight of hydrophilicity. A hydrophilic organic solvent' and 100 parts by weight of an oligomer having a partial condensation of a decane compound (siiane 201200963 corn'd). The oligo of the RmSiX4m structure is not in the form of particles, so that the coating does not have the optical properties (such as anti-glare) required by the current display device, and the polymer formed from the ethylene-based monomer In general, the content of the oligomer & hard coating composition is extremely high. Therefore, it is necessary to further develop a composition which can form a scratch-resistant protective layer on the surface of the patterned substrate, and needs to be developed. no
機微粒均句地分散於塗層之固化基質的製備方法’以使得 所形成之保護層同時具備極佳之耐擦傷性、高透光率及抗 眩等光學特性。 【發明内容】 於疋，本發明之第一目的，即在提供一種可固化組成 物，其包含一光可固化反應基質、一可水解縮合之組份及一 光聚合起始齊,j。 6亥光可固化反應基質包括至少一含有1至ό個末端（甲 基）丙烯酸酯基之單體、該單體之預聚物、該單體之寡聚物 ’或其等之一組合。在本文中，該（甲基）丙烯酸酯 [(meth)acrylate]表示丙烯酸酯（acryiate)及/或曱基丙烯酸酯 (methacrylate)，而（甲基）丙烯酸酯基[(meth)acryl〇xy]又被稱 為（甲基）丙烯醯氧基。 該可水解縮合之組份包括一矽醇鹽（silic〇n alk〇xide)& 一可使該石夕醇鹽進行水解縮合之含水溶液。其中，該石夕醇鹽 具有如下所示之化學式（I):The method for preparing the solid particles of the machine particles uniformly dispersed in the coating layer is such that the formed protective layer has excellent optical properties such as excellent scratch resistance, high light transmittance and anti-glare. SUMMARY OF THE INVENTION In the present invention, a first object of the present invention is to provide a curable composition comprising a photocurable reaction substrate, a hydrolyzable condensation component, and a photopolymerization initiation unit. The 6-light curable reaction substrate comprises at least one monomer having 1 to a terminal (meth) acrylate group, a prepolymer of the monomer, an oligomer of the monomer, or a combination thereof. Herein, the (meth)acrylate means (acryiate) and/or methacrylate, and (meth)acrylate group [(meth)acryl〇xy] Also known as (meth) propylene oxime. The hydrolyzable condensable component comprises a silicium alk〇xide & an aqueous solution which hydrolytically condenses the alkoxide. Wherein, the alkaloid salt has the chemical formula (I) shown below:
Si(OR1)(OR2)(〇R3)(R4) (I) 5 201200963 式（I)中，R丨、112及R3分別是（：丨至C4的烷基，以及R4 是甲氧基、乙氧基、丙氧基、C!至C15的直鏈型院基，或 至C!5的含至少一末端稀鍵型不飽和基（ethyienic unsaturated group)的基團。較佳地，該C2至（：丨5的含至少一 末端烯鍵型不飽和基的基團是C4至C15烯丙基胺基烷基 [(allylamino)alkyl]、<：2至Cls的烯鍵型不飽和基團位於末端 的稀基，或C5至C1S的（甲基）丙烯酸酯基烷基 [(meth)acryloxyalkyl]。 以該光可固化反應基質之重量計，該石夕醇鹽之含量是 介於0.1至15wt%之間。當該矽醇鹽之含量低於〇 lwt%時 ，最終製得之保護層將無法提供足夠之硬度及抗眩性質，當 該矽醇鹽之含量高於15wt%時，最終製得之保護層會有相 分離及透光率不良之問題。 前述本發明可固化組成物經水解縮合及光聚合反應所 製得之透明保護層，經掃瞄式電子顯微鏡（SEM)觀察，其内 部分散有多個粒徑介於5nm至1〇〇nm之奈米微粒，且經熱 重分析儀（TGA)於咖Μ試後，該等微粒經加熱分解後所 得無機灰份之含量是佔該透明保護層總重之Q切。至 ο 本發明之第 目的，疋提供一種具有透明保護層之製 件的製備方法，其包含以下步驟：提供—如上所述之可固化 組成物；使該可固化組成物中之可水解縮合之組份進行水解 2合反應，並在該水解縮合反應持續進行中且部分形成奈米 微粒後再與該反應基質及光聚合起始劑混合成一反應液，接 201200963 著將該反應液施加至-基材上⑽成—濕膜、接著藉由乾燥 形成一乾膜，並使該乾膜進行光聚合反應而形成一透明保護 層’以獲得-具有透明保護層之製件’其中該透明保護層包 含-由該反應基質聚合而得之固化基質，及多個分散於該固 化基質中、以三度空μ Si_〇_Si網狀結構為主且表面具有 Si-OH或-Si-R_4之奈米微粒。 本案申請人鑑於前述各專利案中外加無機微粒時有分 散性不佳、操作困難，且用量需較高才能達到需求之機械 及光學性質的問題，因此摒除現有將已 外加至待聚合之單趙或預聚物中的作法，而採用類= On sltU)反應的方法來製備保護層，也就是，本發明具有透 明保護層之製件的製備方法的特點在於：該可水解縮合之 組份在與待聚合的反應基f (及光聚合起始劑）混合前後，以 及混合後形成之反應液在㈣至基材上時，都處於持續進 行水解縮合（或俗稱轉·㈣（sq1训)反應之狀態，混合前 後進行水解縮合產生之奈米微粒的表面具有ΜΗ或H ’因此最終製得之保護層中微粒能均句分散於固化基質，4 也因此，本發明組成物及製備方法令，僅需使用較少量之 矽醇鹽就能獲得需求之物理與光學性質。 本發明之功效在於：該組成物令是使用尚未形成夺米 微粒的可水解縮合組份，因此在利用本發明組成物來製備 ㈣護層之製件時’是先使該可水解縮合之組份進行水解 縮合反應’在水解縮合反應持續進行十且部分形成奈米微 粒後’再使水解縮合反應料自分散料反應基#(及光乾] 7 201200963 合起始劑）中，因此在奈米微粒完全生成及光聚合固化反應 後，可以獲得一具有多個均勻分散之奈米微粒、具有耐摩 擦性、高透光率以及抗眩效果的透明保護層，因此，本發 明製備方法大幅改進了傳統技術上使用外加之奈米微粒來 製備塗層時所存在的分散問題，故確實能達到本發明之功 效。 【實施方式】 除了以上所述之各基本要件，以下將再就本發明之二 目的，提供其他技術上之建議與說明。 較佳地，該至少一含有1至6個末端（甲基）丙烯酸酯基 之單體是擇自於（甲基）丙稀酸乙酯[ethyl (meth)acrylate]、（ 甲基）丙晞酸乙基己基6旨[ethylhexyl (meth)acrylate]、己二醇 (曱基）丙稀酸醋[hexanediol (meth)acrylate]、三丙二醇二（甲 基）丙婦酸 S旨[tripropylene glycol di(meth)acrylate]、二甘醇 二（甲基）丙稀酸醋[diethylene glycol di(meth)acrylate]、1,6-己二醇二（甲基）丙稀酸醋[1,6-hexanediol di(meth)acrylate]、 新戊二醇二（甲基）丙稀酸酯[ne〇Pemtyi giyc〇1 di(meth)acrylate]、聚乙二醇二丙烯酸酯[polyethylene glycol diacrylate]、三甘醇二丙烯酸酯[triethylene g〗yco1 diacrylate] 、乙二醇二丙稀酸酯[ethylene glycol diacrylate]、聚丙二醇 二丙烯酸酯[p〇iy(Propyiene glyco1) diacrylate]、聚醚二丙烯 酸酯[polyether diacrylate]、二丙二醇二丙稀酸酿 [dipropylene glycol diacrylate]、雙酚 A 型環氧二丙烯酸酯[ bisphenol A glycer〇late (1 glycerol/ phen〇1) diacrylate]、雙 201200963 酴 F 型環氧二丙烯酸酯[bisphenol F glycerolate (1 glycerol/ phenol) diacrylate (簡稱 Bis-F ) ]、1，4-丁 二醇二（甲基）丙稀 酸 S旨[l,4_butanediol di(meth)acrylate]、1，9_壬二醇二（曱基）Si(OR1)(OR2)(〇R3)(R4) (I) 5 201200963 In the formula (I), R丨, 112 and R3 are respectively (: an alkyl group of 丨 to C4, and R4 is a methoxy group, B a oxy group, a propoxy group, a linear group of C! to C15, or a group having at least one terminal ethyienic unsaturated group of C!5. Preferably, the C2 is (The group containing at least one terminal ethylenically unsaturated group of oxime 5 is a C4 to C15 allylaminoalkyl group, <:2 to Cls ethylenically unsaturated group a dilute group at the end, or a (meth) acrylate oxyalkyl group of C5 to C1S. The content of the alkoxide is from 0.1 to the weight of the photocurable reaction substrate. Between 15wt%. When the content of the bismuth alkoxide is less than 〇lwt%, the final protective layer will not provide sufficient hardness and anti-glare properties, and when the sterol salt content is higher than 15% by weight, the final The protective layer obtained has the problems of phase separation and poor light transmittance. The transparent protective layer obtained by the hydrolysis condensation and photopolymerization of the curable composition of the present invention is scanned and displayed electronically. SEM observation shows that a plurality of nano-sized particles with a particle diameter of 5 nm to 1 〇〇 nm are dispersed therein, and after being subjected to a thermogravimetric analyzer (TGA), the particles are heated and decomposed. The content of the inorganic ash is a Q cut which accounts for the total weight of the transparent protective layer. To the first object of the present invention, a method for preparing a part having a transparent protective layer comprises the following steps: providing - as described above a curable composition; subjecting the hydrolyzable condensable component of the curable composition to a hydrolysis 2 reaction, and continuing to carry out the hydrolysis condensation reaction and partially forming the nanoparticle particles, and then reacting with the reaction substrate and photopolymerization The starting agent is mixed into a reaction liquid, and the reaction liquid is applied to the substrate (10) to form a wet film, followed by drying to form a dry film, and the dry film is photopolymerized to form a transparent protective layer. Obtaining a workpiece having a transparent protective layer, wherein the transparent protective layer comprises a solidified matrix obtained by polymerizing the reaction substrate, and a plurality of dispersed in the solidified matrix, and having a three-dimensional space of Si_〇_Si Main structure The surface of the present invention has Si-OH or -Si-R_4 nano-particles. In view of the above-mentioned patents, the applicants have poor dispersibility, difficult operation, and high dosage to achieve the mechanical and optical properties required. The problem, therefore, eliminating the existing practice of adding to the single Zhao or prepolymer to be polymerized, and using the method of the reaction of the type = On sltU) to prepare the protective layer, that is, the article having the transparent protective layer of the present invention The preparation method is characterized in that the hydrolyzable condensation component is before and after mixing with the reactive group f (and photopolymerization initiator) to be polymerized, and the reaction liquid formed after mixing is at (iv) to the substrate. The state of the hydrolysis condensation (or the so-called (4) (sq1 training) reaction is continued, and the surface of the nanoparticle produced by the hydrolysis condensation before and after the mixing has ΜΗ or H ', so that the particles in the protective layer finally obtained can be uniformly dispersed in the cured layer. Substrate, 4 Thus, the compositions and methods of the present invention allow for the physical and optical properties desired to be obtained using only a relatively small amount of decyl alkoxide. The effect of the present invention is that the composition is such that a hydrolyzable condensed component which has not yet formed the rice granules is used, and therefore, when the composition of the present invention is used to prepare the article of the (four) sheath, the group which is first hydrolyzable The hydrolysis condensation reaction is carried out 'after the hydrolysis condensation reaction is continued for ten and part of the nanoparticle is formed, and then the hydrolysis condensation reaction material is self-dispersing reaction group # (and light-drying) 7 201200963 and the initiator), and thus After the rice particles are completely formed and photopolymerized and cured, a transparent protective layer having a plurality of uniformly dispersed nano particles, having abrasion resistance, high light transmittance and anti-glare effect can be obtained, and thus the preparation method of the present invention is greatly improved. The problem of dispersion which is conventionally used when extra nano particles are used to prepare a coating layer can indeed achieve the effects of the present invention. [Embodiment] In addition to the above-mentioned basic elements, other technical suggestions and explanations will be provided below for the second object of the present invention. Preferably, the at least one monomer having 1 to 6 terminal (meth) acrylate groups is selected from ethyl (meth) acrylate and (methyl) propyl acrylate. Acid ethylhexyl 6 means [ethylhexyl (meth)acrylate], hexanediol (meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(methyl)propanate S (tripropylene glycol di) Meth)acrylate], diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid vinegar [1,6-hexanediol di (meth)acrylate], neopentyl glycol di(meth)acrylate [ne〇Pemtyi giyc〇1 di(meth)acrylate], polyethylene glycol diacrylate, triethylene glycol Acrylate [triethylene g] yco1 diacrylate], ethylene glycol diacrylate, polypropylene glycol diacrylate [p〇iy (Propyiene glyco1) diacrylate], polyether diacrylate] Dipropylene glycol diacrylate, bisphenol A glycerol 〇late (1 glycerol/ phen〇1) diacrylate], double 201200963 bisphenol F glycerolate (1 glycerol/ phenol) diacrylate (abbreviated as Bis-F), 1,4-butanediol II (Methyl)acrylic acid S is intended to be [l,4_butanediol di(meth)acrylate], 1,9-nonanediol di(indenyl)
丙稀酸醋[l，9-nonanediol di(meth)acrylate]、三經甲基丙烧 二（曱基）丙烯酸酯[trimethylolpropane di(meth)acrylate]、三 環葵院二甲醇二（甲基）丙稀酸酯[tricyclodecane dimethylol di(meth)acrylate]、季戊四醇二（曱基）丙稀酸醋單硬酸醋 [pentaerythrityl tetrastearate diacrylate]、異氰尿酸二丙稀酸 酉旨[isocyanurate diacrylate]、三經曱基丙烧三（曱基）丙稀 酸酯[trimethylolpropane tri(meth)acrylate]、三經甲基乙烧 三（甲基）丙烯酸醋[trimethylolethane tri(meth)acrylate]、甘 油三（甲基）丙烯酸醋[glycerol tri(meth)acrylate、季戊四醇 三（曱基）丙烯酸酉旨[pentaerythritol tri(meth)acrylate]、季戊 四醇四（甲基）丙烯酸 δ旨[pentaerythritol tetra(meth)acrylate] 、二季戍四醇五（甲基）丙烯酸醋[dipentaerythritol penta (meth)acrylate]、二季戊四醇六（甲基）丙稀酸酉旨 [dipentaerythritolhexa(meth)acrylate]，或其等之一組合。 更佳地，該至少一含有1至6個末端（甲基）丙烯酸酯基 之單體是三羥甲基丙烷三（甲基）丙烯酸酯和雙酚F型環氧 二丙烯酸酯的組合 '三羥甲基丙烷三（甲基）丙烯酸酯和雙酚 A型環氧二丙烯酸酯之組合，或三羥甲基丙烷三（曱基）丙 烯酸酯、雙酚F型環氧二丙烯酸酯和雙酚A型環氧二丙烯 酸醋的組合。Acetate [l,9-nonanediol di(meth)acrylate], trimethylolpropane di(meth)acrylate, tricyclogalan dimethanol di(meth)acrylate Tricyclodecane dimethylol di(meth)acrylate, pentaerythritol diacetate vinegar [pentaerythrityl tetrastearate diacrylate], isocyanurate diacrylate, isocyanurate diacrylate Trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol trimethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate Acrylic vinegar [glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate], pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, diquaternol Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or a combination thereof. More preferably, the at least one monomer having 1 to 6 terminal (meth) acrylate groups is a combination of trimethylolpropane tri(meth) acrylate and bisphenol F epoxy diacrylate. a combination of methylolpropane tri(meth)acrylate and bisphenol A epoxy diacrylate, or trimethylolpropane tris(decyl)acrylate, bisphenol F epoxy diacrylate and bisphenol A combination of type A epoxy diacrylate.
在本發明之一具體例中’該至少一含有1至6個末蟀L 9 201200963 曱基）丙烯酸酯基之單體是三羥曱基丙烷三丙烯酸酯[ trimethylolpropane triacrylate (簡稱 TMPTA)]和雙盼 F 型 環氧二丙烯酸酯的組合。 較佳地，該矽醇鹽是擇自於曱基三甲氧基矽烷 [methyltrimethoxysilane]、 曱基三乙氧基石夕烧 [methyltriethoxysilane(簡稱TEOS)]、乙烯基三曱氧基石夕烧 [vinyltrimethoxysilane]、 三乙氧基乙烯基石夕烧 [Triethoxy vinyl si lane]、 乙烯基三異丙氧基石夕炫* [tri(isopropoxy)vinylsilane]、三（1,1-二曱基乙氧基）乙稀基石夕 烧[tris(tert-butoxy)vinylsilane]、3-(甲基丙烯酿氧基）丙基三 甲氧基石夕烧[3-methacryloxypropyltrimethoxysilane]、甲基丙 烯醯氧 基甲基 三乙氧 基矽烷 [methacryloxymethyltriethoxysilane]、3-(N-烯丙基胺基）丙基 三曱氧基石夕炫[3-(N-allylamino)propyltrimethoxysilane]，或 其等之一組合。 前述列舉適用於本發明之矽醇鹽種類中具有末端烯鍵 型不飽和基團者，也就是式⑴中R4是<：2至C15的含至少一 末端烯鍵型不飽和基的基團所代表的矽醇鹽，譬如乙烯基三 曱氧基矽烷等，不僅可進行水解縮合反應，在後續光聚合反 應中，其所具有之末端烯鍵型不飽和基團還可與前述單體之 末端（甲基）丙烯酸酯基進行聚合，而使得最終固化所得保護 層具有更佳之奈米微粒之分散性，及更佳之物理特性。 更佳地，該矽醇鹽是甲基三甲氧基矽烷、甲基三乙氧 基矽烷，或其等之一組合。在本發明之一具體例中，該矽醇 10 201200963 鹽是曱基三乙氧基石夕院。 較佳地’以該光可固化反應基質之重量計，該矽醇鹽 之含量是介於0.1至l〇wt%之間。 更佳地’以該光可固化反應基質之重量計，該矽酵鹽 之含量是介於0.1至3wt%之間。 較佳地’該可水解縮合之組份之含水溶液是水，或水 與一第一溶劑之組合。更佳地，該含水溶液是水與一第一溶 劑之組合。In one embodiment of the present invention, the at least one monomer having 1 to 6 terminal fluorene-based groups is trimethylolpropane triacrylate (TMPTA) and double Hope for a combination of F-type epoxy diacrylate. Preferably, the oxime salt is selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane (TEOS), vinyltrimethoxysilane, Triethoxy vinyl si lane, vinyl triisopropoxy hydride* [tri(isopropoxy)vinylsilane], tris(1,1-didecylethoxy)ethene [tris(tert-butoxy)vinylsilane], 3-(methacryloxypropyltrimethoxysilane), methacryloxymethyltriethoxysilane , 3-(N-allylamino)propyltrimethoxysilane, or a combination thereof. The foregoing list is applicable to the group having a terminal ethylenically unsaturated group in the oxime salt type of the present invention, that is, a group having at least one terminal ethylenically unsaturated group in the formula (1) wherein R4 is <:2 to C15. The oxime salt represented by the oxime, such as vinyl trimethoxy decane, can be subjected to hydrolysis condensation reaction, and in the subsequent photopolymerization reaction, the terminal ethylenically unsaturated group having the terminal group can also be combined with the aforementioned monomer. The terminal (meth) acrylate group is polymerized, so that the protective layer obtained by final curing has better dispersibility of nano particles, and better physical properties. More preferably, the oxime salt is methyltrimethoxydecane, methyltriethoxydecane, or a combination thereof. In a specific embodiment of the present invention, the sterol 10 201200963 salt is a decyl triethoxy stone court. Preferably, the content of the sterol salt is between 0.1 and 1% by weight based on the weight of the photocurable reaction substrate. More preferably, the content of the fermented salt is between 0.1 and 3 wt% based on the weight of the photocurable reaction substrate. Preferably, the aqueous solution of the hydrolyzable condensable component is water or a combination of water and a first solvent. More preferably, the aqueous solution is a combination of water and a first solvent.
較佳地’該第一溶劑是拜自於醇類：甲醇[methanol]、 乙醇[ethanol]、異丙醇[isopropyl alcohol (簡稱 IPA) ]、丁 醇[butanol]、異丁醇[2-methylpropyl alcohol];酮類：丙 _ [acetone]、曱基乙基嗣[methyl ethyl ketone]、曱基異 丁基酮 [4-methylpentan-2-one]、環己酿I [cyclohexanone]等，或其等 之一組合；醋類：甲酸甲醋[methyl formate]、乙酸甲醋[ethyl formate]、乙酸乙醋[ethyl acetate]、乙酸丁醋，或其等之一 組合；含氮化合物：硝基曱烧[nitromethane]、N -曱基°比0各酮 [N-methyl-2-pyrrolidone] 、Ν,Ν-二曱基曱醯胺[N，N-dimethylformamide]等，或其等之一組合；醚類：四氫咬喃 [tetrahydrofuran (簡稱 THF)]、二氧戊環[dioxolane]、二異 丙基醚[isopropyl ether]，或其等之一組合；鹵统類：二氯甲 院[methylene chloride]、氣仿[chloroform]、三氯乙烧 [trichloroethane]、四氣乙烧[tetrachloroethane]，或其等之一 組合；及二甲基亞领L [dimethyl sulfoxide]。 更佳地，該第一溶劑是異丙醇、乙酸甲酯、乙酸乙靡1Preferably, the first solvent is derived from alcohols: methanol, ethanol, isopropyl alcohol (IPA), butanol, 2-methylpropyl Ketone: acetone, methyl ethyl ketone, 4-methylpentan-2-one, cyclohexanone, etc., or the like One combination; vinegar: methyl formate, ethyl formate, ethyl acetate, butyl acetate, or a combination thereof; nitrogen-containing compound: nitroguanidine [nitromethane], N-fluorenyl ratio 0 ketone [N-methyl-2-pyrrolidone], hydrazine, fluorenyl-nonyl hydrazide [N, N-dimethylformamide], etc., or a combination thereof; ether Class: tetrahydrofuran (THF), dioxolane, isopropyl ether, or a combination thereof; halogen: methylene chloride ], chloroform, trichloroethane, tetrachloroethane, or a combination thereof; and dimethyl sulfoxide L [dimethyl Sulfoxide]. More preferably, the first solvent is isopropanol, methyl acetate, ethyl acetate 1
L J 11 201200963 、乙酸丁酯、甲基乙基酮，或其等之一組合。在本發明之一 具體例中，該含水溶液是水及異丙醇之組合。 較佳地，本發明之組成物還包含一第二溶劑，其是用 於在本發明組成物被利用來製備保護層時，為操作方便， 先使該反應基質及光聚合起始劑能溶解於其中，之後再與 可水解縮合之組份混合。該第二溶劑之定義與第一溶劑相 同，且二者可為相同或不同。在本發明之各具體例中，該 第一溶劑與第二溶劑都是異丙醇。 該第一與第二溶劑之目的在於使各成份分散均勻及調 整黏度，該等溶劑含量隨著施加於該基材方式不同而改變 。該等溶劑的種類不以此上述為限，只要是能使各成份溶 解並進行反應者皆可。 較佳地，以本發明組成物之總重計，該第一溶劑與第 二溶劑含量總和為3 ~ 90 wt%，更佳地為15〜40 wt%。 較佳地，該光聚合起始劑是擇自於苯乙酮類[1-phenylethanone]、二苯曱酮類[benzophenone]、硫化四甲基 秋蘭姆[bis(dimethylthiocarbamyl) sulfide]、苯偶姻類[ benzoin)、苯偶姻甲醚類[benzoin methyl ether]、嗟吩酮類 、苯基乙基酮類、二苯甲醯類、醯基氧化膦類、1-羥基-環 己基-苯基-酮[1-hydroxy cyclohexyl phenyl ketone (簡稱 CIBA 184) ]、α-胺基烷基苯酮類（WCIBA-907、CIBA- 3 6 9 )，或其等之一組合，但必須隨光源不同而選擇地搭配 。在本發明之一具體例中，該光聚合起始劑為CIBA-184。 較佳地，以該光可固化反應基質之重量計，該光聚合 12 201200963 起始劑之含量是介於之間。更佳地，該光聚合起 始劑之含量是介於4至10wt%之間。 較佳地，該可固化組成物還包含防靜電劑、防炫劑， 流平劑、敏化劑或促進劑等各種添加劑。 本發明具有透明保護層之製件的製備方法，包含以下步驟 :提供一如前述本發明之可固化組成物；使該可固化組成物中 之可水解縮合之組份進行水解縮合反應，並在該水解縮合反應 持續進行中且部分形成奈米微粒後再與該反應基 質及光聚合起 始劑混合成一反應液，接著將該反應液施加至一基材上以形成 濕膜、接著藉由乾燥形成一乾膜，並使該乾膜進行光聚合反 應而形成一透明保護層，以獲得一具有透明保護層之製件，其 中該透明保護層包含-由該反應基f聚合而得之固化基質，及 多個分散於該固化基質中、以三度空M si_〇_si網狀結構為主 且表面具有Si-OH或-Si-R_4之奈米微粒。 較佳地，該基材包含一透明底材，及一位於該底材上 之圖樣、導電膜或其等之一組合。 較佳地，該透明底材是擇自於玻璃 '透明塑膠膜、聚 甲基丙烯酉变曱醋（PMMA)板、聚石炭酸醋（pc)板或其等之一組 合。但該透明底材不以上述為限。 較佳地，該圖樣是擇自於裝飾用圖樣、功能性之圖樣 或其等之一組合。該功能性之圖樣包含導電線路之圖樣。 更佳地，該圖樣是ITO 4其他導電物f之線路。在本 發明之一具體例中，該圖樣是IT0線路。 較佳地，本發明之該製備方法是包含以下細部步驟：^ 13 201200963 (a) 提供一如如前述本發明之可固化組成物； (b) 使該可固化組成物中之反應基質與光聚合起始劑予以 混合成一第一預備組成物； (c) 使該可固化組成物中之可水解縮合之組份進行水解縮 合反應，而形成一第二預備液； (d) 將該持續進行水解縮合反應且部分形成奈米微粒之第 二預備液與該第一預備組成物予以混合成一反應液； (e) 將該持續進行水解縮合反應且部分形成奈米微粒之反 應液施加至該基材之表面上，以形成一濕膜： (f) 將該濕膜予以乾燥，而獲得一乾膜；及 (g) 對該乾膜料-光照處理以進行聚合反應，*製得一 具有該透明保護層之製件。 較佳地，該步驟(b)還包含使用一如前述之第二溶劑來 冷解反應基f與光聚合起始劑，而使該第—預備組成物還包 含第二溶劑。 由於水解縮合反應之溶膠-凝膠法常受到下列因子影響 :PH值、％〇/醇鹽比值、偶合劑濃度、反應物濃度、溶劑 、催化劑及溫度。較佳地，兮+跡γ、 較佳地忒步驟（c)之水解縮合反應是使 用酸或驗催化劑來調控為阳值是介於Μ之間更佳是# 為約2。且較佳地，該步驟⑷之水解縮合反應是於2〇·贼 溫度間進行，更佳地是於室溫下進行。 該步驟（d)之混合無特別之限制 ,.m 阪剩條件，但因為本發明中 使用之矽醇鹽之含量相對是較低的， 吾夕功A 因此知作時’先取較大 量之夕醇鹽並配製成較大量體 第—預備液，之後再由其 14 201200963 中取少量來與第一預備組成物混合，將有利於較精確地控制 . 矽醇鹽用量。 較佳地，該步驟（e)中施加至該基材的方式是選自於旋 塗法、浸塗法、喷霧法、棒塗法、輥塗法或網版印刷法。該 基材上反應液的塗敷量，是根據反應液的固含量不同而異。 孝乂佳地’於乾燥後之塗敷量為1〜5〇 g/m2，更佳地，為 5〜30 g/m2，最佳地，為5〜20 g/m2。 . 較佳地，該步驟⑴之乾燥是擇自於減壓乾燥、加熱乾 • 燥或其等之一組合。乾燥溫度隨溶劑種類不同而不同，較佳 地’該乾燥溫度為室溫〜80。(：溫度下進行。較佳地，乾燥時 間為20秒〜5分鐘。 較佳地，該步驟（g)之光照處理是使用紫外線、電子束 或電離放射線或其等之一組合。更佳地，該光照處理是使用 紫外線（UV)。較佳地’該紫外線是擇自於超高壓水銀灯、 南壓水銀灯、低壓水銀灯、碳弧、或金屬齒化物灯所發出。 較佳地’該紫外線波長是365 nm ，其累積曝光能量約 _ 40〜5500 mJ/cm2 左右。 較佳地，透明保護層的厚度（通過接觸式膜厚計測定整 製件之厚度’减去該透明底材及圖樣之厚度來求得）為丨〜％ μηι，更佳地’為5〜30 μιη。最佳地，為5-20 μηι。 本發明將就以下實施例及比較例來做進一步說明，但 應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為 本發明實施之限制。 <實施例1 > 15 201200963 ι·使用可固化組成物製備具有透明保護層之製件 令10克的雙酚F型環氧二丙烯酸酯（簡稱Bis-F)，及 10毫升的異丙醇均勻混合後，再加入10克三羥甲基丙烷三 丙烯酸酯（簡稱TMPTA)及〇.8克的1-羥基-環己基-苯基-酮（簡稱CIBA -184)均勻攪拌，而獲得一第一預備組成物， 其中TMPTA與Bis-F的重量比例為1。將13克的曱基三 乙氧基矽烷（簡稱TEOS)與定量的超純水（h20與TEOS的 莫爾比例為2 : 1 )混合於2.29克的異丙醇中，再以微量鹽 酸調整溶液的pH值，使得pH值為2，並於室溫下授拌30 分鐘以進行水解縮合反應，可獲得一第二預備液。取少量第 二預備液與第一預備組成物相互混合（相對於TMPTA及 Bis-F的總重，所取的第二預備液量是使teos重量百分率 為0.1 %)’並均勻攪拌1小時，持續進行水解縮合反應並形 成一反應液。 接著將該持續進行水解縮合反應的反應液直接塗佈於 一在具有ITO線路圖樣的基材面上，其濕膜厚度為1〇 9 μιη並將該濕膜置於烘箱中，於溫度為8〇()(：下進行乾燥3 刀鐘，得乾膜厚度為7 μπι。將含該薄膜之製件以耐熱膠帶 黏貼於電木板上，置於紫外線光聚合設備之輸送帶上以8 M/min的速度，經波長為365 nmi照度為2〇〇 j/cm2的紫外 線進行光聚合反應’進而得到具有透明保護層之製件。 Π.物性測試 依據以下方法及儀器對實施例丨製得之具有透明保護 層之製件進行各項物性測試，所得結果如下表丨及表2所示 16 201200963 ⑴霧度：霧度計（Haze Meter);型號為NDH-2000;購自 於 NipponDenshoku Industries。 (ii) 透過率：霧度計（Haze Meter);型號為NDH-2000;購 自於 NipponDenshoku Industries 〇 (iii) 透過（光）率（在特定550nm波長下）：紫外光可見光 光譜儀（UV/Vis spectrometer);型號為 Lambada 35UV/Vis spectrometer ;購自於 PerkinElmer。 (iv) 硬度：使用JIS K5400測式方法。硬度等級：3H > 2H > H> F > HB。 (v) 附著性：使用JIS K5600測式方法。附著性等級：0 >1 > 2 >3 > 4 > 5 ° (vi) 耐擦傷性：使用耐磨耗測試機進行測試，其型號為 Model 339且購自於錦亮（台灣）。將耐磨耗測試機設置於 水平狀態，並將待測之具有透明保護層之製件置於該耐磨 耗測試機之固定台上，使用固定夾固定該製件，將# 〇〇〇〇 的鋼絲絨架於研磨舉桿上，調整該研磨舉桿讓該鋼絲絨接 觸該製件，並於該研磨舉桿上方放置100g砝碼，設定該 研磨舉桿來回次數為往返10次並調整轉速即可執行測試 。於進行該測試前先量測該製件之霧度（H,)，且於該測試 後再次量測該製件之霧度（H2)，將該測試後的霧度（H2)減 去測試前的霧度（H0得到之數值（△ HAZE)即表示耐擦傷性 ，△ HAZE的數值愈小代表耐擦傷性愈佳。 <比較例1 > [ s 17 201200963 因為一般具有表層裝飾或功能性圖樣之基材上的圖樣 很容易受到所施加之外力而被破壞，所以此種具有表層裝 飾或功能性圖樣之基材並無法用來進行前述耐擦傷性測試 ，所以比較例1直接使用購自日本TOYOBO且型號為 A4100的PET透明保護膜進行測試。 <比較例2 > 比較例2是以與實施例1相同方式進行，不同的地方 在於：TMPTA與Bis-F的重量比例、CIBA 184及TEOS的 用量。比較例2之成份的用量及種類、操作條件及物性測 0 試結果如下表1及表2所示。 〈實施例2〜15 > 實施例2至15是以與實施例1相同方式進行，不同的 地方在於：TMPTA與Bis-F的重量比例、CIBA 184及 TMOS的用量。各個實施例之成份的用量及種類、操作條件 及物性測試結果如下表1及表2所示。在表1中，該 TMPTA與Bis-F是以相對重量比例表示；該TEOS之含量 是以相對於該TMPTA與Bis-F之重量總和之重量百分比表 · 示；該CIBA-184之含量則以相對於該TMPTA與Bis-F之 重量總和之重量百分比表示；該微粒含量是藉由假設溶膠-凝膠反應完全下經由計算所獲得的。 18 201200963 表1L J 11 201200963 , butyl acetate, methyl ethyl ketone, or a combination thereof. In one embodiment of the invention, the aqueous solution is a combination of water and isopropanol. Preferably, the composition of the present invention further comprises a second solvent, which is used for preparing the protective layer when the composition of the present invention is used for preparing a protective layer, and is capable of dissolving the reaction substrate and the photopolymerization initiator first. Therein, it is then mixed with the hydrolytically condensable component. The second solvent is defined the same as the first solvent, and both may be the same or different. In each of the specific examples of the invention, the first solvent and the second solvent are both isopropanol. The purpose of the first and second solvents is to uniformly disperse the components and adjust the viscosity, and the solvent contents vary depending on the manner of application to the substrate. The type of the solvent is not limited to the above, as long as the components can be dissolved and reacted. Preferably, the total content of the first solvent and the second solvent is from 3 to 90% by weight, more preferably from 15 to 40% by weight, based on the total weight of the composition of the present invention. Preferably, the photopolymerization initiator is selected from the group consisting of [1-phenylethanone], benzophenone, bis(dimethylthiocarbamyl sulfide), benzophenone [benzoin], benzoin methyl ether, benzophenone, phenylethyl ketone, benzophenone, fluorenylphosphine oxide, 1-hydroxy-cyclohexyl-benzene a combination of 1-hydroxy cyclohexyl phenyl ketone (CIBA 184), α-aminoalkyl phenone (WCIBA-907, CIBA-369), or a combination thereof, but must be different from the light source And choose to match. In one embodiment of the invention, the photopolymerization initiator is CIBA-184. Preferably, the photopolymerization 12 201200963 initiator is present in an amount between the weight of the photocurable reaction substrate. More preferably, the photopolymerization initiator is present in an amount between 4 and 10% by weight. Preferably, the curable composition further contains various additives such as an antistatic agent, an antifoaming agent, a leveling agent, a sensitizer or an accelerator. The method for preparing a product having a transparent protective layer comprises the steps of: providing a curable composition of the present invention as described above; subjecting the hydrolyzable condensable component of the curable composition to a hydrolysis condensation reaction, and The hydrolysis condensation reaction is continued and a part of the nanoparticle is formed, and then mixed with the reaction substrate and the photopolymerization initiator to form a reaction liquid, and then the reaction solution is applied to a substrate to form a wet film, followed by drying. Forming a dry film, and subjecting the dry film to photopolymerization to form a transparent protective layer to obtain a workpiece having a transparent protective layer, wherein the transparent protective layer comprises a solidified matrix obtained by polymerization of the reactive group f, And a plurality of nano particles dispersed in the solidified matrix and having a three-dimensional M Si_〇_si network structure and having Si-OH or -Si-R_4 on the surface. Preferably, the substrate comprises a transparent substrate, and a pattern on the substrate, a conductive film or a combination thereof. Preferably, the transparent substrate is selected from the group consisting of a glass transparent plastic film, a polymethyl methacrylate vinegar (PMMA) plate, a polycarbonic acid vinegar (PC) plate, or the like. However, the transparent substrate is not limited to the above. Preferably, the pattern is selected from a decorative pattern, a functional pattern, or a combination thereof. The functional pattern contains a pattern of conductive traces. More preferably, the pattern is the line of other conductive material f of ITO 4. In one embodiment of the invention, the pattern is an IT0 line. Preferably, the preparation method of the present invention comprises the following detailed steps: ^ 13 201200963 (a) providing a curable composition as in the foregoing invention; (b) reacting the reaction substrate and light in the curable composition The polymerization initiator is mixed into a first preliminary composition; (c) subjecting the hydrolyzable condensable component of the curable composition to a hydrolysis and condensation reaction to form a second preliminary liquid; (d) continuing the reaction a second preliminary liquid which hydrolyzes and condenses and partially forms nanoparticles is mixed with the first preliminary composition to form a reaction liquid; (e) a reaction liquid which continuously undergoes hydrolysis condensation reaction and partially forms nanoparticles is applied to the base a surface of the material to form a wet film: (f) drying the wet film to obtain a dry film; and (g) treating the dry film-light treatment to carry out a polymerization reaction, * producing a transparent film Protective parts. Preferably, the step (b) further comprises: using a second solvent as described above to cold-react the reactive group f and the photopolymerization initiator, and the first preliminary composition further comprises a second solvent. The sol-gel process due to the hydrolysis condensation reaction is often affected by the following factors: pH, % 〇 / alkoxide ratio, coupler concentration, reactant concentration, solvent, catalyst and temperature. Preferably, the hydrazine + trace γ, preferably the hydrolytic condensation reaction of the step (c) is controlled by an acid or a catalyst to have a positive value of between Μ and more preferably about #2. Preferably, the hydrolysis condensation reaction of the step (4) is carried out at a temperature of 2 Torr., more preferably at room temperature. The mixing of the step (d) is not particularly limited, and the content of the samarium salt is relatively low, but since the content of the cerium alkoxide used in the present invention is relatively low, the kiln A is therefore known as the first The alkoxide is formulated into a larger amount of the first preparation liquid, and then a small amount of it is mixed with the first preliminary composition from 14 201200963, which is advantageous for more precise control of the amount of the decyl alkoxide. Preferably, the method of applying to the substrate in the step (e) is selected from the group consisting of spin coating, dip coating, spray coating, bar coating, roll coating or screen printing. The amount of the reaction liquid applied to the substrate varies depending on the solid content of the reaction liquid. The application amount of filial piety is 1 to 5 g/m 2 , more preferably 5 to 30 g/m 2 , and most preferably 5 to 20 g/m 2 . Preferably, the drying of the step (1) is selected from the group consisting of drying under reduced pressure, drying by heating, or the like. The drying temperature varies depending on the kind of the solvent, and preferably the drying temperature is room temperature to 80. Preferably, the drying time is from 20 seconds to 5 minutes. Preferably, the light treatment of the step (g) is a combination of ultraviolet rays, electron beams or ionizing radiation or the like. More preferably The illumination treatment uses ultraviolet (UV). Preferably, the ultraviolet light is selected from an ultrahigh pressure mercury lamp, a south pressure mercury lamp, a low pressure mercury lamp, a carbon arc, or a metal toothed lamp. Preferably, the ultraviolet wavelength It is 365 nm and its cumulative exposure energy is about _40~5500 mJ/cm2. Preferably, the thickness of the transparent protective layer (measuring the thickness of the finished part by a contact film thickness meter) minus the transparent substrate and the pattern The thickness is determined to be 丨%%ηηι, more preferably '5~30 μιηη. optimally, 5-20 μηι. The present invention will be further illustrated by the following examples and comparative examples, but it should be understood This embodiment is for illustrative purposes only, and should not be construed as limiting the implementation of the invention. <Example 1 > 15 201200963 ι·Preparation of a workpiece having a transparent protective layer using a curable composition 10 Gram bisphenol F epoxy After acrylate (abbreviated as Bis-F) and 10 ml of isopropyl alcohol were uniformly mixed, 10 g of trimethylolpropane triacrylate (TMPTA) and 88 g of 1-hydroxy-cyclohexyl-benzene were added. The base-ketone (CIBA-184 for short) is uniformly stirred to obtain a first preliminary composition, wherein the weight ratio of TMPTA to Bis-F is 1. 13 grams of mercaptotriethoxydecane (TEOS) and quantification The ultrapure water (the molar ratio of h20 to TEOS is 2:1) is mixed in 2.29 g of isopropanol, and the pH of the solution is adjusted with a trace amount of hydrochloric acid to make the pH 2, and the mixture is stirred at room temperature. A second preparation liquid is obtained by performing a hydrolysis condensation reaction for 30 minutes. A small amount of the second preliminary liquid is mixed with the first preliminary composition (the total amount of the second preparation liquid is taken relative to the total weight of TMPTA and Bis-F). The weight percentage of teos is 0.1%)' and uniformly stirred for 1 hour, and the hydrolysis condensation reaction is continued to form a reaction liquid. Then, the reaction liquid which is continuously subjected to the hydrolysis condensation reaction is directly applied to a substrate having an ITO circuit pattern. On the surface of the material, the wet film thickness is 1〇9 μιη and the wet film is placed In the box, the temperature is 8 〇 () (: drying for 3 knives, the dry film thickness is 7 μπι. The workpiece containing the film is adhered to the electric board with heat-resistant tape, placed in the ultraviolet photopolymerization equipment. The photopolymerization reaction was carried out on a conveyor belt at a speed of 8 M/min at a wavelength of 365 nmi with an illuminance of 2 〇〇j/cm 2 to obtain a transparent protective layer. 物. Physical properties were tested according to the following methods and instruments. The physical properties of the articles having the transparent protective layer prepared in the examples were tested. The results obtained are shown in Table 丨 and Table 2 below. 201200963 (1) Haze Meter: Haze Meter; Model NDH-2000; Purchased from Nippon Denshoku Industries. (ii) Transmittance: Haze Meter; model NDH-2000; purchased from Nippon Denshoku Industries 〇 (iii) Transmitted (light) rate (at a specific wavelength of 550 nm): UV-visible spectrometer (UV/Vis) Spectrometer); model number is Lambada 35 UV/Vis spectrometer; purchased from PerkinElmer. (iv) Hardness: The JIS K5400 method was used. Hardness rating: 3H > 2H >H> F > HB. (v) Adhesion: The JIS K5600 method was used. Adhesion rating: 0 >1 > 2 >3 > 4 > 5 ° (vi) Scratch resistance: Tested with a wear tester, model Model 339 and purchased from Jinliang (Taiwan ). The wear tester is set to a horizontal state, and the workpiece with a transparent protective layer to be tested is placed on the fixed table of the wear tester, and the workpiece is fixed by using a fixing clip, and ## The steel wool frame is arranged on the grinding rod, the grinding rod is adjusted to make the steel wool contact the workpiece, and a weight of 100 g is placed above the grinding rod, and the number of round trips of the grinding rod is set to 10 times and the speed is adjusted. You can perform the test. The haze (H,) of the part is measured before the test, and the haze (H2) of the part is measured again after the test, and the haze (H2) after the test is subtracted from the test. The former haze (the value obtained by H0 (△ HAZE) indicates the scratch resistance, and the smaller the value of △ HAZE, the better the scratch resistance. <Comparative Example 1 > [ s 17 201200963 Because it generally has a surface decoration or function The pattern on the substrate of the pattern is easily destroyed by the applied external force, so the substrate having the surface decoration or the functional pattern cannot be used for the aforementioned scratch resistance test, so the comparative example 1 is used directly. Tested from PET transparent protective film of TOYOBO model No. A4100 in Japan. <Comparative Example 2 > Comparative Example 2 was carried out in the same manner as in Example 1, except that the weight ratio of TMPTA to Bis-F, CIBA The amount of 184 and TEOS used. The amount and type of the components of Comparative Example 2, the operating conditions and the physical properties of the test results are shown in Tables 1 and 2 below. <Examples 2 to 15 > Examples 2 to 15 were implemented Example 1 is carried out in the same way, the difference is that The weight ratio of TMPTA to Bis-F, the amount of CIBA 184 and TMOS. The dosage and type, operating conditions and physical property test results of the respective examples are shown in Tables 1 and 2. As shown in Table 1, the TMPTA and Bis -F is expressed in terms of relative weight; the TEOS content is expressed as a percentage by weight of the total weight of the TMPTA and Bis-F; the content of the CIBA-184 is relative to the TMPTA and Bis-F The weight percentage of the sum of the weights is expressed; the particle content is obtained by assuming that the sol-gel reaction is completely calculated. 18 201200963 Table 1
TMPTA ：Bis-F TEOS (wt%) CIBA-184 (wt %) 微粒 (wt%) 霧度 (%) 透過率 (%) 透過率 (%) (550nm) 比較例 1 0 0 0 0 1.295 93.05 97.85 比較例 2 3:1 0 4 0 1.32 91.54 92.16 實施例 1 1:1 0.1 4 0.15 1.325 91.05 94.63 實施例 2 8 1.395 91.07 94.43 實施例 3 10 1.315 91.04 94.20 實施例 4 1.2 ： 1 0.1 4 0.15 1.37 91.415 94.915 實施例 5 1.5 ： 1 1.34 91.395 95.605 實施例 6 1.8 ： 1 1.38 92.55 97.325 實施例 7 2:1 1.41 91.435 95.415 實施例 8 3:1 1.37 91.625 95.965 實施例 9 3:1 1 4 1.4 1.36 91.32 90.14 實施例 10 2 3.0 1.40 91.48 93.28 實施例 11 3 4.5 1.42 91.44 96.56 實施例 12 3:1 3 6 4.5 1.43 91.58 93.50 實施例 13 8 4.5 1.45 91.44 93.50 實施例 14 10 4.5 1.47 91.33 93.25 實施例 15 3:1 15 4 12.5 1.62 90.5 90.86 19 201200963 表2 塗佈 厚度 (μιη) 耐擦傷性 附著性 (等級） 硬度 (等級） 測試前霧 度（Η,) (%) 測試後霧 度（η2) (%) △ HAZE (H2-HO (%) 比較例 1 0 0 F 1.8 21.23 19.43 比較例 2 7 0 2Η 1.32 9.94 8.62 實施例 1 2Η 1.325 6.69 5.365 實施例 2 2Η 1.395 2.47 1.075 實施例 3 2Η 1.315 2.12 0.805 實施例 4 2Η 1.35 2.45 1.10 實施例 5 2Η 1.32 2.41 1.09 實施例 6 2Η 1.36 2.38 1.02 實施例 7 3Η 1.39 2.31 0.92 實施例 8 7 0 3Η 1.35 2.36 1.01 實施例 9 4Η 1.36 1.74 0.38 實施例 10 3Η 1.40 3.98 2.58 實施例 11 3Η 1.42 3.77 2.35 實施例 12 2Η 1.43 3.55 2.12 實施例 13 2Η 1.45 3.60 2.15 實施例 14 2Η 1.47 3.62 2.15 實施例 15 4Η 1.62 1.94 0.32 20 201200963 由表1及表2之結果可知，實施例丨〜〗5之具有透明保 護層之製件具有h315〜丨.62%的霧度、90.5〜92.55%的透過 率、90.14〜97.325%的透過（光）率（在波長55〇11111下）、皆為〇 之附著性等級、2H〜4H等級的硬度以及Q 32〜5 365%的耐擦 傷性。將實施例9及比較例2相比較可以發現，添加TE〇s 並使最終保護層具有奈米微粒可增強該透明保護層的硬度 及耐擦傷性，且其透過率及霧度只有微小的差異，此也顯 不該等微粒是均勻分散在該透明保護層巾，故此發明完全 符合業界需求，尤其適用於具有裝飾用或功能性圖案之基 材上形成一具有透明保護層之製件。 综合上述可知，該發明之可固化組成物及利用該可固 化組成物之具有透明保護層之製件的製備方法，是利用該 可水解縮合之組份在與待聚合的反應基質（及光聚合起始劑） 混合前後，以及混合後形成之反應液在塗佈至基材上時， 都處於持續進行溶膠-凝膠反應之狀態，也就是水解縮合反 應持續進行下且部分形成奈米微粒之反應液是與待聚合的 反應基質充分混合後，再使奈米微粒繼續生成及進行最後 的光聚σ反應’因此最終製得之保護層中奈米微粒是能均 W t & SMb基質的’也因& ’本發明組成物及製備方法 中僅而使用較少I之石夕_鹽就能獲得需求之物理與光學 性質，亦即最終保護層中微粒的含量僅有〇1彻％，就具 有極佳之而ί擦傷性、硬度、光學及抗眩性質，故確實能達 到本發明之功效。 准以上所述者，僅為本發明之較佳實施例而已，當不1TMPTA : Bis-F TEOS (wt%) CIBA-184 (wt %) Particulate (wt%) Haze (%) Transmittance (%) Transmittance (%) (550nm) Comparative Example 1 0 0 0 0 1.295 93.05 97.85 Comparative Example 2 3:1 0 4 0 1.32 91.54 92.16 Example 1 1:1 0.1 4 0.15 1.325 91.05 94.63 Example 2 8 1.395 91.07 94.43 Example 3 10 1.315 91.04 94.20 Example 4 1.2 : 1 0.1 4 0.15 1.37 91.415 94.915 Example 5 1.5 : 1 1.34 91.395 95.605 Example 6 1.8 : 1 1.38 92.55 97.325 Example 7 2:1 1.41 91.435 95.415 Example 8 3:1 1.37 91.625 95.965 Example 9 3:1 1 4 1.4 1.36 91.32 90.14 Example 10 2 3.0 1.40 91.48 93.28 Example 11 3 4.5 1.42 91.44 96.56 Example 12 3:1 3 6 4.5 1.43 91.58 93.50 Example 13 8 4.5 1.45 91.44 93.50 Example 14 10 4.5 1.47 91.33 93.25 Example 15 3:1 15 4 12.5 1.62 90.5 90.86 19 201200963 Table 2 Coating thickness (μιη) Scratch resistance (grade) Hardness (grade) Haze before test (Η,) (%) Haze after test (η2) (%) △ HAZE ( H2-HO (%) Comparative Example 1 0 0 F 1.8 21.23 19.43 Comparative Example 2 7 0 2Η 1.32 9.94 8.62 Example 1 2Η 1.325 6.69 5.365 Example 2 2Η 1.395 2.47 1.075 Example 3 2Η 1.315 2.12 0.805 Example 4 2Η 1.35 2.45 1.10 Example 5 2Η 1.32 2.41 1.09 Example 6 2Η 1.36 2.38 1.02 Example 7 3Η 1.39 2.31 0.92 Example 8 7 0 3Η 1.35 2.36 1.01 Example 9 4Η 1.36 1.74 0.38 Example 10 3Η 1.40 3.98 2.58 Example 11 3Η 1.42 3.77 2.35 Example 12 2Η 1.43 3.55 2.12 Example 13 2Η 1.45 3.60 2.15 Implementation Example 14 2Η 1.47 3.62 2.15 Example 15 4Η 1.62 1.94 0.32 20 201200963 It can be seen from the results of Table 1 and Table 2 that the article having the transparent protective layer of Example 丨~5 has a haze of h315~丨.62%, 90.5 to 92.55% transmittance, 90.14 to 97.325% transmission (light) rate (at a wavelength of 55〇11111), adhesion grade of 〇, hardness of 2H to 4H grade, and resistance of Q 32~5 365% Scratch. Comparing Example 9 with Comparative Example 2, it was found that adding TE〇s and having the final protective layer with nanoparticles can enhance the hardness and scratch resistance of the transparent protective layer, and the transmittance and haze have only a slight difference. Therefore, it is also obvious that the particles are uniformly dispersed in the transparent protective layer towel, so the invention fully meets the needs of the industry, and is particularly suitable for forming a workpiece having a transparent protective layer on a substrate having a decorative or functional pattern. In summary, the curable composition of the present invention and the preparation method of the article having the transparent protective layer using the curable composition are prepared by using the hydrolyzable condensation component in the reaction substrate to be polymerized (and photopolymerization). The initiator before and after the mixing, and the reaction solution formed after the mixing, are applied to the substrate in a state of continuous sol-gel reaction, that is, the hydrolysis condensation reaction is continued and the nanoparticle is partially formed. After the reaction solution is thoroughly mixed with the reaction substrate to be polymerized, the nanoparticle particles are continuously formed and the final photopolymerization σ reaction is carried out. Thus, the nanoparticles in the protective layer finally obtained are capable of W t & SMb matrix. 'Also & 'In the composition and preparation method of the present invention, only the use of less I, the salt and the salt can obtain the physical and optical properties of the demand, that is, the content of the particles in the final protective layer is only 彻1% It has excellent ί abrasion, hardness, optical and anti-glare properties, so it can indeed achieve the efficacy of the present invention. The above is only the preferred embodiment of the present invention, when not
ί- Ο J 21 201200963 能 範 屬 以此限定本發明實施之範圍，即大凡依本發明中請 圍及發明說明内容所作之簡單的等效變化與° 本發明專利涵蓋之範圍内。 / 11，皆仍 圖式簡單說明】無 【主要元件符號說明】無 22。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 / 11, are still simple description of the schema] None [Main component symbol description] None 22