201235095 六、發明說明： 【明所屬技系奸領】 發明領域 本發明關於一種機能性膠態二氧化矽溶液的製造方法 及紫外線硬化型硬塗覆用樹脂組成物與其硬化物，係用以 於聚碳酸is等光學薄膜及塑膠零件表面形成鉛筆硬度、耐 磨耗性、低捲曲性、密合性及經濟性優異之保護皮膜。 L先前技術;1 發明背景 聚碳酸醋、聚甲基丙烯酸甲酯、聚苯乙稀、聚醋及三 醋酸纖維素等光學薄膜及塑膠零件，為防止生產時處理造 成損傷或防止使用者使用造成損傷，而進行於單面或兩面 設置表面保護用之硬塗覆層。 此硬塗覆層一般使用各種活性能量線硬化樹脂及熱硬 化性樹脂，膜厚為卜汕口⑺範圍。但是，當設置硬塗覆層時’ 將發生鉛筆硬度不足、密合性不良及薄膜捲曲，而需要改善。 曰本特開昭號公報（專利文獻1}與日本特3開 2009-102503公報(專利文獻2)中，揭示將水分散性膠態二氧 化矽表面以甲基丙烯醯氧矽烷處理過之粒子與丙烯酸酯之 組成物做為光硬化型塗佈劑使用。此塗佈劑之特徵在於— 由將二氧化矽粒子表面以特定有機矽烷及特定條件處理: 而改善塗佈劑之性能。 ^但是，此種塗佈劑未必能充分滿足需要。即為改，保 護皮膜之硬度，有必要提高硬化後皮膜之交聯密度，= 201235095 高皮膜之硬度，料隨硬化㈣之_與捲曲增大而有 硬度與低捲曲性之間難以取得平衡之問題。 日本特開2GG9-91448?虎公報(專利文獻3)中，將水分散 性勝態二氧切表面以甲基丙_氧料表面處理過之二 氧化石夕與新戊四醇三丙_s旨做為主成份，而於皮膜硬度 與低捲曲性可見-定程度之改善，但仍期望更加改善。 一方面，特開平7_109355號公報（專利文獻4)中，將溶 劑分散性膠態二氧化⑦表面以甲基丙烯酿氧雜表面處理 過之二氧化矽與丙烯酸酯單體做為主成份而改善皮膜硬度 等，但以高價之溶劑分散性膠態二氧化矽做為起始材料製 得之最終製品亦為高價，不利於經濟面。 先行技術文獻 專利文獻 專利文獻1日本特開昭57-131214號公報 專利文獻2日本特開2009-102503號公報 專利文獻3日本特開2009-91448號公報 專利文獻4日本特開平7-109355號公報 C發明内容；3 發明概要 習知技術中’藉由多使用多官能性丙烯酸酯單體，或 添加表面以特定有機矽烷處理之膠態二氧化矽而提高表面 硬度，但多產生硬化收縮問題，特別當多使用多官能性丙 烯酸酯單體時。 為解決如此收縮之問題，可考慮將丙烯酸酯單體樹脂 201235095 構造本身全部以柔軟成份取代而減少收縮，但硬度將極端 降低，而有不適用於光學用薄膜及塑膠零件之表面保護硬 塗覆劑之問題。 又即使增加表面處理之膠態二氧化矽量，亦無法達到 充分之表面硬度改善，而確認有皮膜脆弱與密合性降低之 情形。 因此，維持硬度之同時減少硬化收縮基本上為困難，而 需要使硬度與低硬化收縮並立，且密合性優異之硬塗覆劑。 本發明係鑑於前述課題而成，其目的為提供一種用於 硬塗覆用樹脂組成物之機能性膠態二氧化矽溶液製造方法 及使用前述方法所製得機能性膠態二氧化矽溶液之硬塗覆 用樹脂組成物’該硬塗覆用樹脂組成物於光學薄膜或塑膠 零件表面上形成硬塗覆層時，鉛筆硬度、耐擦傷性、薄膜 捲曲、密合性及經濟性皆有改善。 本發明者為解決前述習知技術之問題，提供硬度與低硬 化收縮並立，耐擦傷性、密合性及經濟性優異之紫外線硬化 型硬塗覆劑而積極探討之結果，發現使用藉由下列組成及製 程所合成出具有-定範圍粒徑之機能性膠態二氧化石夕溶液 做為紫外線硬化型硬塗覆義極為有效m本發明。 即本發明為-«能轉態二氧切溶液的製造方 法，該機能性雜二氧切溶㈣平均_為卜3()抓，且 水解反應前後之二氧切平均粒徑差為15倍以内者； 本製造方法係使(a)平均粒徑i〜3 〇nm且氮離子濃度 (PH)6以下之水分散性膠態二氧化石夕；二氧化石夕為重量 5 201235095 份；（B)含甲基丙烯醯基之烧氧矽炫；2〇〜3〇重量份；及(C) 電容率10以上之極性溶媒；50~500重量份； 在(D)自由基聚合禁止劑；o.ooiq重量份之存在下進行 水解反應後， 使用（E)l-甲氧基-2-丙醇藉由共沸脫水溶媒取代，而製 得機能性膠態二氧化石夕溶液。 以及’一種紫外線硬化型硬塗覆用樹脂組成物’係含 有該機能性膠態二氧化石夕溶液、丙烯酸酯樹脂及/或胺酯丙 稀酸酯樹脂及光聚合起始劑，且相對於整體固體成份’源 自該機能性膠態二氧化石夕溶液之固體成份為5〇%以上。 以及，一種光學薄膜或塑膠零件，具有厚度丨〜如卜瓜之 硬塗覆層’該硬塗覆層係藉由塗佈該紫外線硬化型硬塗覆 用樹脂組成物後，行紫外線照射硬化而形成者。 藉由本發明’於光學薄膜及塑膠零件上形成硬塗覆層 時’可較低價提供財擦傷性、密合性及薄膜捲曲改善之硬 塗覆用樹脂組成物。201235095 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a functional colloidal cerium oxide solution and a resin composition for ultraviolet curing hard coating and a cured product thereof, which are used for The optical film and plastic parts such as polycarbonate are formed into a protective film with excellent pencil hardness, abrasion resistance, low curling property, adhesion and economy. L prior art; 1 invention background optical film and plastic parts such as polycarbonate, polymethyl methacrylate, polystyrene, polyester and cellulose triacetate, in order to prevent damage during production or prevent user use Damage, and a hard coating layer for surface protection on one or both sides. As the hard coat layer, various active energy ray-hardening resins and heat-hardening resins are generally used, and the film thickness is in the range of burr (7). However, when the hard coat layer is provided, the pencil hardness is insufficient, the adhesion is poor, and the film is curled, and improvement is required. In the Japanese Patent Publication No. 2009-102503 (Patent Document 2), the surface of the water-dispersible colloidal ceria is treated with methacryloxane. The composition of the acrylate is used as a photocurable coating agent. The coating agent is characterized in that the surface of the cerium oxide particles is treated with a specific organic decane and specific conditions to improve the performance of the coating agent. Such a coating agent may not be sufficient to meet the needs. That is, to change the hardness of the film, it is necessary to increase the cross-linking density of the film after hardening, = 201235095 high film hardness, the material with hardening (four) _ and curl increase There is a problem that it is difficult to balance between hardness and low curling property. In Japanese Patent Laid-Open No. 2GG9-91448, Tiger Gazette (Patent Document 3), the surface of the water-dispersible dioxo prior is treated with methyl propyl hydride. The sulphur dioxide and pentaerythritol tripropyl _ s are intended to be the main component, and the hardness and low curling property of the film are improved to a certain extent, but it is still expected to be improved. On the one hand, Japanese Patent Laid-Open No. Hei 7-109355 ( Patent Document 4), Solvent-dispersed colloidal oxidized cerium oxide on the surface of methacrylate-doped cerium oxide and acrylate monomer as the main component to improve the hardness of the film, but with high-priced solvent-dispersible colloidal cerium oxide The final product produced as a starting material is also expensive, and it is not advantageous for the economical. Patent Document 1 Patent Publication No. JP-A-57-131214. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Treatment of colloidal cerium oxide to increase surface hardness, but often causes hardening shrinkage problems, especially when multi-functional acrylate monomers are used. To solve the problem of shrinkage, consider the acrylate monomer resin 201235095 construction itself All are replaced by soft ingredients to reduce shrinkage, but the hardness will be extremely reduced, and it is not suitable for the surface protection of optical films and plastic parts. The problem of hard coating agent. Even if the amount of colloidal cerium oxide added to the surface treatment is increased, sufficient surface hardness improvement cannot be achieved, and it is confirmed that the film is weak and the adhesion is lowered. Therefore, the hardness is reduced while being reduced. Hardening shrinkage is basically difficult, and it is necessary to form a hard coating agent which is excellent in adhesion and low hardening shrinkage, and has excellent adhesion. The present invention has been made in view of the above problems, and an object thereof is to provide a resin composition for hard coating. Method for producing functional colloidal cerium oxide solution and hard coating resin composition for functionalized colloidal cerium oxide solution obtained by the above method 'The hard coating resin composition for optical film or plastic part When a hard coat layer is formed on the surface, pencil hardness, scratch resistance, film curl, adhesion, and economy are all improved. In order to solve the problems of the prior art described above, the present inventors have actively studied the results of the ultraviolet curing type hard coating agent which is excellent in hardness, low-hardening shrinkage, scratch resistance, adhesion, and economy, and found that the use is as follows. The composition and the process for synthesizing the functional colloidal silica dioxide solution having a predetermined range of particle diameters are extremely effective as the ultraviolet curing type hard coating. That is, the present invention is a method for producing a «transferable dioxo-cut solution, wherein the functional hetero-dioxo-dissolving (four) average is _3(), and the difference in the average particle size of the dioxo prior to the hydrolysis reaction is 15 times. The method of the present invention is to (a) a water-dispersible colloidal silica dioxide having an average particle diameter of i 〜3 〇 nm and a nitrogen ion concentration (pH) of 6 or less; and a weight of 5 201235095 parts by weight; B) a methacrylic acid-containing oxime oxime; 2 〇 to 3 〇 by weight; and (C) a polar solvent having a permittivity of 10 or more; 50 to 500 parts by weight; in (D) a radical polymerization inhibiting agent; After the hydrolysis reaction was carried out in the presence of o.ooiq in parts by weight, (E) 1-methoxy-2-propanol was substituted with an azeotropic dehydration solvent to prepare a functional colloidal silica dioxide solution. And 'a resin composition for ultraviolet curing type hard coating' contains the functional colloidal silica dioxide solution, an acrylate resin and/or an amino ester acrylate resin, and a photopolymerization initiator, and The overall solid content 'from the functional colloidal silica dioxide solution has a solid content of more than 5%. And an optical film or a plastic part having a thickness of 丨~such as a hard coating layer of a diced granule. The hard coating layer is cured by ultraviolet irradiation by applying the ultraviolet ray hardening resin composition. Former. According to the present invention, when a hard coat layer is formed on an optical film or a plastic part, a resin composition for hard coating which provides improved scratch resistance, adhesion, and film curl can be provided at a low price.
C實施方式;J 發明之詳細說明 以下詳細說明本發明。 用於本發明之(A)成份為平均粒徑1〜3〇nm，氫離子濃度 (pH)6以下之水分散性膠態二氧化矽。 一般而言膠態二氧化矽微粒子係將平均粒徑 之無水矽酸超微粒子以水或有機溶媒分散者。 用於膠態二氧化矽之分散媒有水、曱醇、乙醇、異丙 6 201235095 醇、正丙醇、異丁醇、正丁 醇系溶劑、乙赛路 基鲷、甲基異丁基_、 丙烯醆醋、 醇等醇系溶劑、乙二醇等多價 蘇、丁赛路蘇等多價醇衍生物、尹基乙 丙酮醇等醇系溶劑、2-羥基己義 一 2-羥基丙基丙烯酸酯及四氫糠基丙烯酸酯等卵 體類其中從經濟面來看宜為水分散型又，從水解反 处驟面來看特別宜為氫離子濃度(p聯以下 之水分散十生 悲一氧化石夕。 應 膠 3亥等膠態二氧化石夕宜為以習知方法製造，二氧化石夕成 伤大致宜為5〜40%左右濃度。 平均粒徑為1〜3〇nm，宜為1〇〜3〇nm，較宜為丨5〜3〇nm， 更宜為18〜25nm。粒徑未滿lnm者為高價，又反應步驟中易 發生凝膠化。又粒徑超過3〇11〇1者，將降低硬化皮膜之透明 性。膠態二氧化矽可顯著改善硬化皮膜之耐擦傷性，且於 賦予抗捲曲性為有效。 本發明最終將膠態二氧化矽中之水分最終以共沸脫水 行溶媒取代，因此從經濟面來看膠態二氧化矽中宜為高一 氧化矽濃度，由於可提高前述濃度，平岣粒徑最適為 18〜25nm左右。 二氡化矽成 本發明中，平均粒徑宜為18~25nm範園， 份宜為30〜40°/。範圍。C. DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below. The component (A) used in the present invention is a water-dispersible colloidal cerium oxide having an average particle diameter of 1 to 3 〇 nm and a hydrogen ion concentration (pH) of 6 or less. In general, colloidal cerium oxide microparticles disperse anhydrous citric acid ultrafine particles having an average particle diameter in water or an organic solvent. The dispersing medium used for colloidal ceria is water, decyl alcohol, ethanol, isopropyl 6 201235095 alcohol, n-propanol, isobutanol, n-butanol solvent, ethyl sulfonate, methyl isobutyl _, An alcohol solvent such as acryl vinegar or alcohol; a polyvalent alcohol derivative such as polyvalent sulphate or butyl sulphate such as ethylene glycol; an alcohol solvent such as Yin Ke et al., 2-hydroxyhexyl mono-2-hydroxypropyl acrylate; The ovoids such as tetrahydrofurfuryl acrylate should be water-dispersed from the economical point of view, and it is particularly preferable to be a hydrogen ion concentration from the side of the hydrolysis reaction. In the evening, it should be made by a conventional method, such as gelatin 3 hai, etc., and the concentration of the dioxide is about 5 to 40%. The average particle size is 1~3〇nm, preferably 1 〇~3〇nm, preferably 丨5~3〇nm, more preferably 18~25nm. The particle size is less than 1nm, and the gelation is easy to occur in the reaction step. The particle size is more than 3〇11〇 In one case, the transparency of the hardened film will be lowered. Colloidal cerium oxide can significantly improve the scratch resistance of the hardened film, and imparts curl resistance to The present invention finally replaces the water in the colloidal cerium oxide with a solvent of azeotropic dehydration, so that it is economically preferable to have a high cerium oxide concentration in the colloidal cerium oxide, since the concentration can be increased, The particle size of the crucible is preferably about 18 to 25 nm. In the invention of the diterpene, the average particle diameter is preferably 18 to 25 nm, and the fraction is preferably 30 to 40 °.
量，將於酸性水溶液下藉由水解與膠態二氡化矽化學結 合，可顯著改善硬化皮膜之耐擦傷性。 如此等矽烷有3_甲基丙烯醯氡基丙基三甲乳矽烷、2_ 201235095 甲基丙稀醯氧基乙基三甲氧魏' 3_甲基丙稀醯氧基丙基 二乙氧㈣'2·甲基丙烯醯氧基乙基三乙氧料及^甲基丙 稀醯氧基丙基Ψ基二甲氧魏#，從容易取狀觀點來看 宜為3-甲基丙稀酿氧基丙基三甲氧石夕院。 又，摻混量有必要相對於(A)成份之有效成份量（二氧化 矽成份）100重量份為20〜3〇重量份。 未滿20重量份則膠態二氧化矽表面處理未能充分進 行’其結果無法得耻分耐磨耗性。又，水解狀脫水步驟 中膠態二氧化魏子將發生凝集4多於3()重量份則製得之 機能性膠態二氧化矽溶液粒徑變化增大，調製紫外線硬化型 硬塗覆組成物時，將無法表現充分硬度與耐擦傷性。又，水 解時過剩之(B)成份將形成寡聚合物，對鉛筆硬度與耐磨耗性 造成影響。再者於薄膜基材塗佈時捲曲將增大。 (C) 成份係為使(A)成份與(B)成份水解時相溶性提高而 換混。 電容率10以上之極性溶媒有1-丁醇、2-丁醇、曱醇、乙 醇及赛路蘇等，從(A)成份與(B)成份水解反應前後之相溶 性、對膠態二氧化矽粒徑之影響以及共沸脫水效率等面來 看，宜為異丙醇及/或1-甲氧_2·丙醇。從相溶性與水解反應 後之溶劑除去效率面來看宜為50〜500重量份，特別宜為 70〜150重量份。 (D) 成份於⑷成份與(B)成份水解反應時共存，可抑制 甲基丙烯醯基聚合而使產率提昇° 自由基聚合禁止劑無特別限定，一般用作自由基聚合 201235095 防止劑之物質皆可使用。 具體來講，可列舉氳醌、甲氧氫醌、苯醌及對三級丁 基兒命紛等酿糸聚合禁止劑；2,6-二-三級丁基盼、2,4-二_ 二級丁基紛、2-二級丁基-4,6-二曱基紛、2,6-二-三級丁基_4_ 甲基酿及2,4,6-二-二級丁基紛等院基盼系聚合禁止劑；烧基 化二苯胺、N，N’-二苯-對伸苯二胺、硫代二苯胺、4_羥基 -2,2,6,6-四曱基哌啶、4-苯甲醯氧基_2,2,6,6-四甲基哌啶、 1，4-二羥基-2,2,6,6-四曱基哌啶及丨_羥基_4_苯甲醯氧基 -2,2,6,6-四甲基哌啶等胺系聚合禁止劑；二甲基二硫胺曱酸 銅、二乙基二硫胺甲酸銅及二丁基二硫胺甲酸銅等二硫胺 曱酸銅糸聚合禁止劑，2,2,6,6-四甲基u辰〇定_ι_氧、4-經基 -2,2,6,6-四曱基旅咬-1-氧、4-苯甲醯氧基_2,2,6,6-四曱基旅 。定-1-氧及4-經基-2,2,6,6-四甲基η底。定_ι_氧之酯類等μ氧系 聚合禁止劑等。 其中適宜之自由基聚合禁止劑可列舉如醌系聚合禁止 劑、胺系聚合禁止劑、二硫胺曱酸銅系聚合禁止劑及1_氧 系聚合禁止劑。 特別適宜之自由基聚合禁止劑可列舉如氫醌、曱氧氫 醌、苯醌、對三級丁基兒茶酚、硫代二苯胺、烷基化二苯 胺、二丁基二硫胺甲酸銅、2,2,6,6-四曱基哌啶小氧、4·經 基-2,2,6,6-四曱基哌啶-卜氧及4·羥基_2,2,6,6_四曱基派咬 -1-氧之酯類等。摻混量從水解反應時自由基聚合反應之抑 制效果，以及硬塗覆組成物調製時硬塗覆組成物對於紫外 線之反應性來看，宜為〇.001〜1重量份，特別宜為0.01〜0.1 9 201235095 重量份。 (E)成份使用於水解反應後，從系統中將水與副生成物 等蒸鶴除去時。 習知將1，6·己二醇二丙烯酸酯或三伸丙二醇二丙稀酸 酯等具有低黏度之丙烯酸酯摻混，而進行水或副生成物等 之蒸餾除去，或使用異丁醇、甲苯' IpA(異丙醇）或DMF(二 曱基曱醯胺）等溶媒進行脫水或共沸脫水。當使用該等材料 進行脫水時，最終製得之機能性膠態二氧化矽溶液中二氧 化石夕粒徑將增大，結果可見調製硬塗覆用樹脂組成物時， 錯筆硬度、耐磨耗性及低捲曲性等將有所影響。 又’當摻混具有低黏度之丙烯酸酯時，所製得機能性 膠態—氧化石夕已含有特定丙稀酸酯，因此最終調製之硬塗 覆組成物特性將受限，無法做為具有汎用性之機能性膠態 二氧化矽母料運用而使其價值受限。 又’該等具有低黏度之丙烯酸酯皆為2官能性，將其摻 成之組成不符本發明高硬度及耐擦傷性之目的。 一方面，當使用1-甲氧基-2-丙醇時，水解前後機能性 膠態二氧化矽溶液中二氧化矽粒徑幾乎無變化。又，脫水 時共'弗比率高，因此脫水效率高生產性優。 又’由於與機能性膠態二氧化矽之相溶性優秀，可高 /農度濃縮而無黏度•搖變性上昇。又，由於完全不含丙烯 酸酿等，可做為汎用性高之母料運用。 再者1-曱氧基-2-丙醇對於易受聚碳酸酯等有機溶劑侵 蝕衫響之塑膠基材不造成影響，因此適用於薄膜與各種塑 10 201235095 #混量若為共沸脫水之必 氧化>5夕安定分散之量，則 膠用硬塗覆樹脂組成物。另外， 要量，再者為可使機能性膠態二 無特別限定。 製造本機自_態二氧切溶液，叫賴AHC) 成份於⑼成份存在下水解。此時條件無_限制，一㈣ ?_(:，車交宜以回流溫度2小時以上為適當。 接著第2步驟使用（Ε)成份共彿脫水，製得機能性膠態 氧化石夕溶液。㈣脫水條件無特難定，但宜於減壓下 溶液溫度不達到50°C以上進行共彿脫水 另外，於無損本發明特性之範圍内，可摻混石夕烧偶合 劑、調平劑、丙烯咖旨或胺酿丙#酸酿及稀釋溶劑等添加劑。 本發明中，如前述，藉由控制含f基丙_基之_ 石夕烧摻混量’同時選擇使用1·甲氧基_2_丙醇做為共沸脫水 用，可製造水解反應别後一氧化矽平均粒徑差為15倍以内 之機能性膠態二氧化矽溶液。 使用本機能性膠態二氧化矽溶液調製紫外線硬化型硬 塗覆用樹脂組成物時，摻混丙烯酸酯樹脂或胺酯丙烯酸酯 樹脂作為黏合劑成份，換混光聚合起始劑，因應需要摻混 稀釋溶媒及調平劑等而製得’但為製得本質上高硬度之紫 外線硬化型硬塗覆用樹脂組成物，做為黏合劑成份，宜以3 官能以上之多官能型丙烯酸酯或胺酯丙烯酸酯為主使用。 又’從硬度、财擦傷性及低捲曲性之面來看，有必要 調製紫外線硬化型硬塗覆用樹脂組成物，使來自於機能性 膠態二氧化矽溶液之固體成份（有效成份)相對於全體固體 11 201235095 成份(有效成份)為50%以上，_宜為6Q%以上。 若為滿足前述條件之組成物，便可得本發明所期效 果，而具體組成，機能性膠態二氧化♦溶液；宜相對於二 氧化石夕成f/j 100重5:份’丙;旨樹脂及/或胺醋丙稀酸酉旨 树月曰40〜100重1_伤，光聚合起始劑4〜16重量份，總溶媒成 份為200〜1000重量份。 用於本發明之丙炼酸酿樹脂、胺醋丙稀酸醋樹脂、光 聚合起始航_溶媒，若為習知用於紫外線硬化型硬塗 覆用柄J曰組成物者，則無特別限制，丙烯酸酯樹脂可列舉 二新戊四醇六丙烯酸酯、新戊四醇五丙烯酸酯、二新戊四 醇五丙烯酸酯、新戊四醇四丙烯酸酯及二新戊四醇四丙烯 酸酯等。 又，胺酯丙烯酸酯樹脂可列舉JSR(股)製胺酯丙烯酸酯 「紫光UV-i 7_」、「紫光υν·63〇〇Β」、「紫光υν·764〇Β」、 dAIcel-CYTEC社製Ebecryl 129〇及共榮社化學製 「UA-306H」等。 光聚合起始劑’習知-般可取得者皆可使用，特別為 確保可見光領域之透明性，UV吸收之最大波長峰值宜為 400nm以下。 該等聚合起始劑，可使用苯乙啦之丨_經基環己基_ 苯基酮、2,2-二曱氧基-1，2-二苯小乙酮、2_經基_2_甲基小 苯基-1-丙酮、2-甲基-1·[4-(甲基硫）苯基]_2_嗎啉基_丨-丙 酮、2·苯甲基_2-二甲基胺·ι_(4-嗎琳基苯基•丁嗣及氧化 鱗系之2,4,6-三甲基苯曱醯基-二苯基_氧化膦，再者亦可使 12 201235095 用二笨基酮與聚合促進劑之乙基-4-二曱基胺笨曱酸酿及2_ 乙基己基-4-二曱基胺苯甲酸酯等組合。 稀釋溶媒可使用1-曱氧基-2-丙醇等醇系溶媒、曱基乙 基酮、甲基異丁基酮等酮系溶劑、醋酸乙酯及醋酸丁醋等 醋系溶媒等習知一般可取得者，可為單獨亦可為混合溶媒 系使用。 又’本硬塗覆用樹脂組成物，宜於使用前以過渡器渡 過。過濾器材質宜為PTFE及聚丙稀等，不易受丙烯酸化合 物侵蝕者，濾過時過濾徑〇_2〜10微米左右者容易取得而為 適宜。尤其將過濾徑分為2階段，於初期通過2〜10微米，後 期通過0,2〜1微米者，藉此可有效率除去膠態二氧化矽之凝 集物與來自丙烯酸樹脂之凝膠物，以及從大氣混入之塵 埃’最終將可保持皮膜外觀良好。 前述紫外線硬化型硬塗覆組成物可藉由滾輪、繞線 棒、刮刀、流動塗膜、喷塗及刷塗等塗佈於光學薄膜或塑 膠零件基材表面，以市販之光照射裝置照射紫外線使其硬 化。紫外線光源若為產生紫外線之光源則可無限制使用。 例如，可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、 超高壓水銀燈、碳弧燈、金屬鹵素燈、氙燈及融合燈等。 照射條件依各種燈而異，當使用融合燈(H閥）時，於紫 外線UV-B之波長領域照射光量宜為50~1000mJ/cm2左右。 於紫外線硬化型硬塗覆組成物塗佈乾燥中或其後照射紫外 線為佳，照射時間宜為0.5秒〜5分，從紫外線硬化性樹脂之 硬化效率或作業效率觀點來看較宜為3秒〜2分。 13 201235095 本發明中紫外線硬化型硬塗覆劑之形成厚度為, 宜為5〜15μπι。若膜厚減少，光硬化時氧氣所造成聚合阻礙之 影響增大，將需要於氮氣等不活性氣體下之硬化系統。又膜 厚:¾極度增大，則有硬化收縮中基材變形增大之缺陷。 貫施例 以下列舉本發明實施例，但本發明不限定於以下實施 例。又實施例中，份表示重量份。 評估方法如下所述。 (平均粒徑） 以BECKMAN COULTER社製亞微米粒度分佈測定裝 置 Coulter N4 Plus測定。 (鉛筆硬度） 於形成硬化皮膜之薄膜表面，根據JISK56〇〇_5_4之試 驗法進行。唯，於23eC50%RH之條件下調整狀態16小時以 上後，以荷重lkg，同一硬度級之鉛筆進行5次試驗，藉由 目視調查壓痕類別，以各硬度級之無塑性變形與凝集破壞 次數/試驗次數作評估。 (耐擦傷性）The amount can be chemically combined with colloidal bismuth telluride by hydrolysis in an acidic aqueous solution to significantly improve the scratch resistance of the hardened film. Such decane has 3_methacryl propyl propyl trimethyl decane, 2_ 201235095 methacryloxyethyl trimethoxy wei ' 3 _ methyl propyl methoxy propyl di ethoxy ( 4 ) '2 ·Methyl propylene oxiranyl ethyl triethoxy hydride and ^ methyl propyl methoxy propyl fluorenyl dimethoxy wei #, from the point of view of easy to take it should be 3-methyl propylene oxide Base trimethoxide court. Further, the blending amount is required to be 20 to 3 parts by weight based on 100 parts by weight of the active ingredient (component of cerium oxide) of the component (A). When the amount is less than 20 parts by weight, the surface treatment of the colloidal cerium oxide is not sufficiently performed. As a result, the scratch resistance is not obtained. Further, in the hydrolyzed dehydration step, the colloidal dioxins will be agglomerated by 4 more than 3 parts by weight, and the functionalized colloidal ceria solution having a larger particle size change is prepared, and the ultraviolet curing hard coating composition is prepared. When it is used, it will not be able to exhibit sufficient hardness and scratch resistance. In addition, the excess (B) component during the hydrolysis will form an oligopolymer, which will affect the hardness and wear resistance of the pencil. Furthermore, the curl will increase when the film substrate is coated. (C) The composition is such that the compatibility between the component (A) and the component (B) is improved and the mixing is improved. The polar solvent having a permittivity of 10 or more is 1-butanol, 2-butanol, decyl alcohol, ethanol, celecoxib, etc., compatibility between (A) component and (B) component before and after hydrolysis reaction, and colloidal oxidation The influence of the particle size of the crucible and the azeotropic dehydration efficiency are preferably isopropanol and/or 1-methoxy-2-propanol. The solvent removal efficiency after the compatibility and the hydrolysis reaction is preferably from 50 to 500 parts by weight, particularly preferably from 70 to 150 parts by weight. (D) The component coexists in the hydrolysis reaction of the component (4) and the component (B), and inhibits the polymerization of the methacrylinyl group to increase the yield. The radical polymerization inhibiting agent is not particularly limited, and is generally used as a radical polymerization agent 201235095. All substances can be used. Specifically, it can be exemplified by ruthenium, methoxyhydroquinone, benzoquinone, and a third-stage butyl sulfonate polymerization inhibitor; 2,6-di-tri-butyl butyl, 2,4-di _ Dibutyl butyl, 2-second butyl-4,6-dimercapto, 2,6-di-tertiary butyl-4-methyl and 2,4,6-di-secondyl butyl Polypropylene, N,N'-diphenyl-p-phenylenediamine, thiodiphenylamine, 4-hydroxy-2,2,6,6-tetradecyl Piperidine, 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetradecylpiperidine and oxime_hydroxyl_ Amine polymerization inhibitors such as 4_benzimidyl-2,2,6,6-tetramethylpiperidine; copper dimethyldithioate citrate, copper diethyldithiocarbamate and dibutyl Inhibitor of copper disulfide bismuth citrate, such as copper dithiocarbamate, 2,2,6,6-tetramethyl-u-chenidine _ι_oxygen, 4-yl-based-2,2,6,6- Four-base brigade bite-1-oxygen, 4-benzylideneoxy-2,2,6,6-tetradecyl brigade. 1-Hydroxy- and 4-yl-based-2,2,6,6-tetramethyl-7. An oxygen-based polymerization inhibitor such as an ester of oxygen is used. Among them, a suitable radical polymerization inhibiting agent may, for example, be an anthraquinone polymerization inhibitor, an amine polymerization inhibitor, a copper dithioacetate polymerization inhibitor, or a 1-oxygen polymerization inhibitor. Particularly suitable radical polymerization inhibitors include, for example, hydroquinone, anthrahydroquinone, benzoquinone, p-tert-butylcatechol, thiodiphenylamine, alkylated diphenylamine, and dibutyldithiocarbamate copper. , 2,2,6,6-tetradecylpiperidine small oxygen, 4·transyl-2,2,6,6-tetradecylpiperidine-bu-oxygen and 4·hydroxy-2,2,6,6 _ 四曱基派咬-1-Oxygen esters and the like. The blending amount is from the inhibition effect of the radical polymerization reaction in the hydrolysis reaction, and the reactivity of the hard coating composition to the ultraviolet ray when the hard coating composition is prepared is preferably 0.001 to 1 part by weight, particularly preferably 0.01. ~0.1 9 201235095 parts by weight. The component (E) is used after the hydrolysis reaction, and the water and the by-products are removed from the system by steaming the crane. It is known to blend a low-viscosity acrylate such as 1,6·hexanediol diacrylate or tri-propylene glycol diacrylate to distillate water or by-products, or use isobutanol. A solvent such as toluene' IpA (isopropyl alcohol) or DMF (dimercaptoguanamine) is subjected to dehydration or azeotropic dehydration. When the materials are used for dehydration, the particle size of the dioxide in the functional colloidal cerium oxide solution finally obtained will increase, and as a result, when the resin composition for hard coating is prepared, the hardness and wear resistance of the pen are wrong. Consumption and low curling will have an impact. 'When blending acrylates with low viscosity, the functional colloidal-oxidized oxides already contain specific acrylates, so the characteristics of the final hard coating composition will be limited and cannot be The utility of the functionally functional colloidal cerium oxide masterbatch is limited in its value. Further, these low-viscosity acrylates are all bifunctional, and the composition thereof is incompatible with the object of high hardness and scratch resistance of the present invention. On the one hand, when 1-methoxy-2-propanol is used, there is almost no change in the particle size of cerium oxide in the functional colloidal cerium oxide solution before and after hydrolysis. In addition, the dehydration rate is high, so the dehydration efficiency is high and the productivity is excellent. In addition, due to its excellent compatibility with functional colloidal cerium oxide, it can be concentrated at high/agronomic level without viscosity and increased in shaking. In addition, since it is completely free of acrylic acid, it can be used as a masterbatch with high general availability. Furthermore, 1-nonyloxy-2-propanol has no effect on plastic substrates which are susceptible to attack by organic solvents such as polycarbonate, and therefore is suitable for use in films and various plastics 10 201235095 #混量 if azeotropic dehydration The amount of dispersion must be oxidized and the resin composition is hard coated with the resin. In addition, the amount is required, and the other is that the functional colloidal state is not particularly limited. Manufacture of the local self-oxidation solution, called AHC) The component is hydrolyzed in the presence of (9) component. At this time, there is no _ limit, one (four) _ (:, the car should be reflux temperature for more than 2 hours is appropriate. Then the second step using (Ε) ingredients for dehydration, the functional colloidal oxidized oxide solution. (4) Dehydration conditions are not particularly difficult, but it is preferred to carry out dehydration of the solution at a temperature below 50 ° C under reduced pressure. In addition, within the scope of non-destructive characteristics of the present invention, a mixture of stone smelting coupler and leveling agent may be blended. In the present invention, as described above, by controlling the amount of the f-containing propyl group-based _ _ _ _ _ _ _ _ _ _ _ _ _ _ 2_Propanol is used as azeotropic dehydration to produce a functional colloidal cerium oxide solution with a mean particle size difference of less than 15 times after the hydrolysis reaction. Use this functional colloidal cerium oxide solution to modulate ultraviolet rays. In the case of a hard resin composition for hard coating, an acrylate resin or an amine ester acrylate resin is blended as a binder component, and a photopolymerization initiator is blended, and a diluent solvent and a leveling agent are blended as needed. However, in order to obtain an ultraviolet curing type which is inherently high in hardness The resin composition for coating is used as a binder component, and it is preferable to use a polyfunctional acrylate or amine ester acrylate having three or more functional groups. Further, from the viewpoints of hardness, scraping property and low curling property, It is necessary to prepare a resin composition for ultraviolet hardening type hard coating so that the solid component (active ingredient) derived from the functional colloidal cerium oxide solution is 50% or more with respect to the entire solid 11 201235095 component (active ingredient), _ It is 6Q% or more. If the composition satisfies the above conditions, the desired effect of the present invention can be obtained, and the specific composition, the functional colloidal oxidizing ♦ solution; should be relative to the sulphur dioxide, the f/j 100 weight 5 : Parts 'C; the resin and / or amine acetoacetate 酉 树 曰 曰 40~100 weight 1_ injury, photopolymerization initiator 4~16 parts by weight, total solvent component is 200~1000 parts by weight. The acrylic acid smelting resin, the amine acetoacetic acid vinegar resin, and the photopolymerization starting solvent-solvent of the present invention are not particularly limited as long as they are conventionally used for the ultraviolet curing type hard coating stalk J 曰 composition. The acrylate resin may be dipentaerythritol hexaacrylate. Pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, etc. Further, the amine ester acrylate resin may be an amine produced by JSR. Ester acrylates "Purple UV-i 7_", "Purple υν·63〇〇Β", "Purple υν·764〇Β", Ebecryl 129〇 by dAIcel-CYTEC, and "UA-306H" by Kyoeisha Chemical Co., Ltd. Photopolymerization initiators can be used as well as conventionally available, especially to ensure transparency in the visible light field, and the maximum wavelength peak of UV absorption should be 400 nm or less. These polymerization initiators can be used.丨 _ _ Cyclohexyl phenyl ketone, 2,2-didecyloxy-1,2-diphenyl ketone, 2 _ base 2 - methyl small phenyl-1-propanone, 2- Methyl-1·[4-(methylthio)phenyl]_2_morpholinyl-indole-acetone, 2·benzyl-2-dimethylamine·ι_(4-morphinylphenyl·butyl嗣 and oxidized squamous 2,4,6-trimethylphenyl fluorenyl-diphenyl phosphine oxide, and further can be used to make 12 201235095 diphenyl ketone with polymerization accelerator ethyl-4- bis Mercaptoamine alum acid and 2_ethylhexyl-4-didecylamine benzoate Ester composition. As the solvent to be diluted, an alcohol-based solvent such as 1-nonoxy-2-propanol, a ketone solvent such as mercaptoethyl ketone or methyl isobutyl ketone, or an vinegar-based solvent such as ethyl acetate or butyl acetate may be used. Generally available, it can be used alone or in a mixed solvent system. Further, the resin composition for hard coating is preferably used as a transitioner before use. The material of the filter should be PTFE or polypropylene, and it is not easily eroded by the acrylate compound. It is suitable for the filter diameter 〇_2~10 μm when it is filtered. In particular, the filter diameter is divided into two stages, which are passed through 2 to 10 μm at an initial stage and 0, 2 to 1 μm at a later stage, whereby the agglomerate of the colloidal ceria and the gel from the acrylic resin can be efficiently removed. And the dust that mixes in from the atmosphere will eventually keep the film looking good. The ultraviolet curable hard coating composition can be applied to the surface of an optical film or a plastic component substrate by a roller, a wire bar, a doctor blade, a flow coating film, a spray coating, a brush coating, or the like, and irradiated with ultraviolet light by a commercially available light irradiation device. Make it harden. The ultraviolet light source can be used without limitation if it is a light source that generates ultraviolet light. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, and a fused lamp can be used. The irradiation conditions vary depending on the various lamps. When a fused lamp (H valve) is used, the amount of light to be irradiated in the wavelength range of the ultraviolet ray UV-B is preferably about 50 to 1000 mJ/cm 2 . It is preferable to apply ultraviolet rays to the ultraviolet curable hard coat composition after application or drying, and the irradiation time is preferably 0.5 second to 5 minutes, and is preferably 3 seconds from the viewpoint of curing efficiency or work efficiency of the ultraviolet curable resin. ~2 minutes. 13 201235095 The thickness of the ultraviolet curable hard coating agent in the present invention is preferably 5 to 15 μm. If the film thickness is reduced, the influence of polymerization inhibition by oxygen upon photohardening increases, and a hardening system under an inert gas such as nitrogen gas is required. Further, the film thickness: 3⁄4 is extremely increased, and there is a defect that the deformation of the substrate increases during hardening shrinkage. BEST MODE FOR CARRYING OUT THE INVENTION Examples of the present invention are listed below, but the present invention is not limited to the following examples. In still another embodiment, parts represent parts by weight. The evaluation method is as follows. (Average particle diameter) Measured by a Coulter N4 Plus submicron particle size distribution measuring apparatus manufactured by BECKMAN COULTER. (Pencil hardness) The surface of the film on which the hardened film was formed was carried out in accordance with the test method of JIS K56〇〇_5_4. However, after adjusting the state for more than 16 hours under the condition of 23eC50%RH, 5 tests were carried out with a pencil of the same hardness level of lkg, and the indentation type was visually investigated to determine the number of non-plastic deformation and agglutination damage of each hardness level. / The number of trials is evaluated. (scratch resistance)
Jis K 7204及JIS K 71〇5記載之丁化打磨耗試驗，以磨耗 輪CS10F ,單輪250g荷重使用2輪，500回轉時之霧度(Haze) 減去初期霧度來評估磨耗性。該值低則对磨耗性優。 (捲曲性） 將試料切出lOOmmxlOOmm見方大小之樣本，於23t 50%RH之條件下狀態調節16小時以上後，測定樣本4隅浮起 201235095 距離求平均值。 (密合性） 於形成硬化皮膜之薄膜表面，依據jISK 5600-5-6之試 驗法I作方格狀之十字切痕，進行25mm寬之賽璐凡膠布剝 離試驗。密合性之評估以殘留方格數/全方格數表示。 合成例1 將異丙醇（IPA)430份，日產化學工業（股）製Snowtex 0-40(水分散性膠態二氧化矽；二氧化矽成份4〇% , 口凡約3， 粒 ^16·7ηηι)1340 伤 ’ Momentive Performance MaterialsThe chirping abrasion test described in Jis K 7204 and JIS K 71〇5 evaluates the wear resistance by using the wear wheel CS10F, a single wheel 250g load for two rounds, and a haze at 500 turns minus the initial haze. This value is low and is excellent in wear resistance. (Curling property) The sample was cut out to a sample of 100 mm×100 mm square, and the state was adjusted for 16 hours or more under conditions of 23 t 50% RH, and then the sample 4 隅 floated and the distance was averaged at 201235095. (Adhesion) On the surface of the film on which the hardened film was formed, a 25 mm wide celluloid peeling test was carried out in accordance with the test method I of JISK 5600-5-6 as a checkered cross cut. The evaluation of the adhesion is expressed by the number of residual squares/full squares. Synthesis Example 1 430 parts of isopropyl alcohol (IPA), Snowtex 0-40 made of Nissan Chemical Industry Co., Ltd. (water-dispersible colloidal cerium oxide; cerium oxide component 4% by weight, mouth about 3, granules ^16 ·7ηηι)1340 injury' Momentive Performance Materials
Japan(同）製TSL8370(3·甲基丙浠醯氧基丙基三曱氧矽 烷）140份，4-羥基-2,2,6,6-四曱基哌啶_丨_氧自由基〇 35份之 混合物加熱，於約82。(：攪拌回流3小時。 冷卻後，添加1-甲氧基_2-丙醇(PGM)5〇〇份，減壓除去 異丙醇與副生成之甲醇。再將丨_甲氧基·2_丙醇85〇份分作數 -入添加，藉由共沸減壓除去水，至不揮發成份為6〇%。又， 不揮發成份以15GC/3G分之條件測定。最終製作不揮發成份 60%之機能性膠態二氧切之i _甲氧基·2丙醇溶液(Fcs_丄）。 合成例2 將合成例1使用之異丙醇43〇份替代為1曱氧基-2·丙醇 830份’ X ’減壓除去時使用之卜曱氧基_2_丙醇總量從135〇 份改為62〇份(減歸去f醇等與藉由共沸減驗去水時， 使用之比率與合成例1相同。以下亦同樣），以與合成例！同 樣之合成步驟’最·終製作不揮發成份60%之機能性膠態二 氧化石夕之1·曱氧基-2-丙醇溶液(FCS_2)。 15 201235095 合成例3 冷卻後’添加1-曱氧基-2-丙醇500份之際，同時添加新 戊四醇二丙稀酸S旨275份，又，減壓除去時使用之ι_曱氧基 -2-丙醇總量1350份改為1530份，以與合成例1同樣之步驟， 最終製作不揮發成份60%之機能性膠態二氧化石夕之丨_曱氧 基-2-丙醇溶液(FCS-3)。 合成例4 將異丙醇430份’曰產化學工業（股(水 分散性膠態二氧化矽；二氧化矽成份4〇%，pH約3，粒徑 16.7nm)1340份，Momentive Performance Materials Japan(同） 製TSL8370(3-甲基丙烯醯氧基丙基三甲氧矽烧）14〇份，4_ 羥基-2,2,6,6-四甲基哌啶_ι·氧自由基〇 35份之混合物加 熱’於約82°C攪拌回流3小時。 冷卻後，添加1，6-己二醇二丙烯酸酯(HDDA)357份，減 壓除去異丙醇、副生成之甲醇以及水，調整不揮發成份為 9 8 %以上。最終製作不揮發成份9 8以上之機能性膠態二氧 化矽溶液(FCS-4 ;内機能性二氧化矽成份約6〇%)。 合成例5 將異丙醇430份’日產化學工業（股)製Sn〇wtex 〇_4〇(水 分散性膠態二氧化矽；二氧化矽成份4〇。/。，pn約3，粒徑 16.7nm)1340伤 ’ Momentive Performance Materials Japan(同） 製TSL8370(3-曱基丙烯醯氧基丙基三曱氧矽烷）14〇份，4_ 羥基-2,2,6,6-四甲基哌0定·卜氧自由基〇 35份之混合物加 熱，於約82°C攪拌回流3小時。 16 201235095 冷卻後，添加異丁醇(IBA)500份，減壓除去異丙醇與副 生成之甲醇。再將異丁醇1720份分作數次添加，最終製作不 揮發成份60%之機能性膠態二氧化妙之異丁醇溶液(fc§ 5) 合成例6 將TSL8370掺混量從140份增量為240份，以與合成例i 同樣之合成步驟’最終製作不揮發成份60%之機能性膠態 二氧化矽之1-甲氧基_2·丙醇溶液(FCS-6)。 實施例1〜4 以得到表1記載之紫外線硬化型硬塗覆組成物，調製合 成例1〜3製得之機能性膠態二氧化矽溶液、新戊四醇三丙稀 酸酯（PETA)、JSR(股）製胺酯丙烯酸酯（UA ;紫光 UV_7640B)、BASF JAPAN(股）製IRGACURE184(光聚合起 始劑）及1-甲氧基-2-丙醇等後’進行加壓過濾製得硬塗覆 液。又，表中單位為重量份。 如此製得之硬塗覆液，以塗佈棒塗佈機於188μ厚之易 接著PET薄膜(TORAY(股）製LUMIRROR U34)塗佈為厚度 10μ’於90°C熟成1分後，使用FUSION社製F450T-10，H閥， 200mJ/cm2(以UV-A)之紫外線照射條件照射4次形成硬塗覆 皮膜。評估結果示於表1。 比較例1〜4 與實施例1〜4同樣地，以得到表1記載之紫外線硬化型 硬塗覆組成物，調製合成例4〜6製得之機能性膠態二氧化矽 溶液、新戊四醇三丙烯酸酯、JSR(股）製胺酯丙烯酸酯（紫光 UV-764〇B)、BASF JAPAN(股）製IRGACURE184(光聚合起 17 201235095 始劑）及1-曱氧基-2-丙醇等。又，比較例1添加FCS-1調製為 表1之組成。以與實驗例1〜4同樣方法形成硬塗覆皮膜。評 估結果示於表1。 18 201235095 比較例4 1 FCS-6 1 00 (N S 1 1_7 倍 1 | PGM 1 Ο] 00 m § 70/30 »〇 5 寸 25/25 v〇 比較例3 FCS-6 00 (N Ο ν〇 丨1.7倍 | PGM 1 PETA 〇〇 r—H 5 cn § 70/30 in ΓΟ O 25/25 o (N 比較例2 FCS-5 00 m Ο νο g |標準 a PETA 00 ro § 70/30 (N 〇 25/25 m 比較例1 FCS-4 Os Ο νο 標準 1 HDDA PETA 〇〇 ro 70/30 JO 〇 JO o OO m 25/25 寸 實施例4 FCS-3 τ—Η Ο νο g 標準 PGM PETA (FCS合成時） CN 寸 00 r—< Pi m § 70/30 in JO 00 25/25 m 實施例3 FCS-2 § 1 PGM |標準| | PGM 丨 PETA 00 $ ro § 70/30 in 00 1-H 25/25 寸 實施例2 FCS-1 CN ο ν〇 |標準1 [PGM | 00 P； ro 70/30 in in ON r-H 25/25 m 實施例1 FCS-1 |標準| PGM PETA 〇1 oo m S 70/30 ^T) 00 25/25 寸 機能性膠態二氧化矽溶液 平均粒徑(nm) 機能性膠態二氧化矽溶液固體成份％ FCS處方 水解溶媒 TSL8370 共沸/稀釋溶媒 丙烯酸酯/胺酯丙烯酸酯 機能性膠態二氧化梦機能性二氧化梦成份 新戊四醇三丙烯酸酯 1，6-己二醇二丙烯酸酯 紫光 UV-7640B 1稀釋溶媒 PGM < s IRGACURE184 總固體成份％ FCS固體成份％/丙烯酸酯(胺酯丙烯酸酯)％ 鉛筆硬度 2H 寸 耐擦傷性 Haze值 密合性 捲曲(mm) 越Μ & 黏合劑 错每Μ 皮膜特性 19 201235095 如表1所示，藉由如合成例1〜3控制含曱基丙烯醯基之 烷氧矽烷摻混量，同時選擇使用1-曱氧基-2-丙醇為共沸脫 水用，將可製造水解反應前後二氧化矽平均粒徑差為1.5倍 以内之機能性膠態二氧化矽溶液。相對於此，以1，6-己二醇 二丙烯酸酯（HDDA)或異丁醇(IBA)做為共沸脫水用之合成 例4及5，與含甲基丙烯醯基之烷氧矽烷摻混量過多之合成 例6，只能得到平均粒徑大者。 而使用本發明機能性膠態二氧化矽溶液之實施例1〜4， 製得鉛筆硬度、耐擦傷性、捲曲性及密合性優秀之皮膜。 C圖式簡單說明：！ (無） 【主要元件符號說明】 (無） 20Japan (same) TSL8370 (3·methylpropoxypropyltrioxane) 140 parts, 4-hydroxy-2,2,6,6-tetradecylpiperidine 丨-oxyl radical 〇 A mixture of 35 parts was heated at about 82. (: stirring under reflux for 3 hours. After cooling, 5 parts of 1-methoxy-2-propanol (PGM) was added, and isopropanol and by-produced methanol were removed under reduced pressure. _Propanol 85 parts are counted as a number-in addition, water is removed by azeotropic decompression to a non-volatile content of 6%. Further, the non-volatile content is determined by 15GC/3G. The final non-volatile content is determined. 60% functional colloidal dioxygenated i-methoxy-2-propanol solution (Fcs_丄). Synthesis Example 2 43 parts of isopropanol used in Synthesis Example 1 was replaced by 1曱oxy-2 · 830 parts of propanol 'X' used in the removal of reduced pressure, the total amount of oxime oxy-2-propanol used was changed from 135 〇 to 62 〇 (reduced by de-alcohol, etc. and dehydrated by azeotropy) In the case of using the same ratio as in Synthesis Example 1, the same synthetic procedure as in the synthesis example is used to produce a 60% functional non-volatile component of the non-volatile component. -2-propanol solution (FCS_2). 15 201235095 Synthesis Example 3 After cooling, when adding 500 parts of 1-nonoxy-2-propanol, 275 parts of neopentyl alcohol dipropionic acid were added simultaneously. Ι_曱 used when removing under reduced pressure The total amount of base 2-propanol was changed from 1350 to 1530 parts, and the same procedure as in Synthesis Example 1 was carried out to finally prepare a functional non-volatile component of 60% of functional colloidal silica dioxide 丨 丨 曱 曱 -2- -2- 丙Alcohol solution (FCS-3). Synthesis Example 4 430 parts of isopropanol's chemical industry (water-dispersible colloidal cerium oxide; cerium oxide component 4%, pH about 3, particle size 16.7 nm 1340 parts, Momentive Performance Materials Japan (same) TSL8370 (3-methacryloxypropyltrimethoxypyrene) 14 parts, 4_hydroxy-2,2,6,6-tetramethylpiperidine A mixture of 35 parts of oxygen free radicals was heated and stirred at about 82 ° C for 3 hours. After cooling, 357 parts of 1,6-hexanediol diacrylate (HDDA) was added, and isopropanol was removed under reduced pressure. Methanol and water are produced, and the non-volatile content is adjusted to be more than 98%. Finally, a functional colloidal cerium oxide solution (FCS-4; internal functional cerium oxide component of about 6〇%) having a nonvolatile content of 98 or more is produced. Synthesis Example 5 430 parts of isopropyl alcohol: Sn 〇 tex tex 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 水 水 水 水 水 tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex tex Diameter 16.7nm) 1340 injury' Momentive Performance Materials Japan (same) TSL8370 (3-mercapto propylene oxypropyl trioxane) 14 parts, 4_ hydroxy-2,2,6,6-tetramethyl A mixture of 35 parts of oxazolidine oxime was heated and stirred at reflux at about 82 ° C for 3 hours. 16 201235095 After cooling, 500 parts of isobutanol (IBA) was added, and isopropanol and by-produced methanol were removed under reduced pressure. Then, 1720 parts of isobutanol was added in several portions to finally prepare a functionalized colloidal dioxygen isobutanol solution (fc § 5) having a nonvolatile content of 60%. Synthesis Example 6 The TSL8370 blending amount was increased from 140 parts. The amount was 240 parts, and the same synthetic procedure as in Synthesis Example i was used to finally prepare a solution of functionalized colloidal cerium oxide in a 1-methoxy-2-propanol (FCS-6) having a nonvolatile content of 60%. Examples 1 to 4 The ultraviolet curable hard coat compositions described in Table 1 were obtained, and the functional colloidal ceria solution prepared by Synthesis Examples 1 to 3 and neopentyl alcohol triacrylate (PETA) were prepared. , JSR (share) amine ester acrylate (UA; violet UV_7640B), BASF JAPAN (stock) IRGACURE 184 (photopolymerization initiator) and 1-methoxy-2-propanol, etc. A hard coating liquid is obtained. Further, the units in the table are parts by weight. The hard coating liquid thus obtained was coated with a 188 μ thick easy-to-adhere PET film (LUMYROR U34 manufactured by TORAY Co., Ltd.) to a thickness of 10 μ' and cooked at 90 ° C for 1 minute, using FUSION. The F450T-10, H valve, and 200 mJ/cm2 (UV-A) were irradiated four times to form a hard coat film. The evaluation results are shown in Table 1. Comparative Examples 1 to 4 In the same manner as in Examples 1 to 4, the ultraviolet curable hard coat compositions described in Table 1 were obtained, and the functional colloidal cerium oxide solutions prepared in Synthesis Examples 4 to 6 were prepared. Alcohol triacrylate, JSR (shared) amine ester acrylate (violet UV-764〇B), BASF JAPAN (produced by IRGACURE 184 (photopolymerization from 17 201235095 starting agent) and 1-decyloxy-2-propanol Wait. Further, Comparative Example 1 was prepared by adding FCS-1 to the composition of Table 1. A hard coat film was formed in the same manner as Experimental Examples 1 to 4. The evaluation results are shown in Table 1. 18 201235095 Comparative Example 4 1 FCS-6 1 00 (NS 1 1_7 times 1 | PGM 1 Ο) 00 m § 70/30 »〇5 inch 25/25 v〇Comparative Example 3 FCS-6 00 (N Ο ν〇丨1.7 times | PGM 1 PETA 〇〇r—H 5 cn § 70/30 in ΓΟ O 25/25 o (N Comparative Example 2 FCS-5 00 m Ο νο g |Standard a PETA 00 ro § 70/30 (N 〇 25/25 m Comparative Example 1 FCS-4 Os Ο νο Standard 1 HDDA PETA 〇〇ro 70/30 JO 〇JO o OO m 25/25 inch Example 4 FCS-3 τ—Η Ο νο g Standard PGM PETA (FCS When synthesized) CN inch00 r—< Pi m § 70/30 in JO 00 25/25 m Example 3 FCS-2 § 1 PGM | Standard | | PGM 丨PETA 00 $ ro § 70/30 in 00 1- H 25/25 inch Example 2 FCS-1 CN ο ν〇|Standard 1 [PGM | 00 P; ro 70/30 in in ON rH 25/25 m Example 1 FCS-1 |Standard | PGM PETA 〇1 oo m S 70/30 ^T) 00 25/25 inch functional colloidal cerium oxide solution average particle size (nm) functional colloidal cerium oxide solution solid content % FCS prescription hydrolysis solvent TSL8370 azeotrope / dilute solvent acrylate /amine ester acrylate functional colloidal dioxane Dreaming Functional Dioxide Dream Ingredients Neopentyl Alcohol Triacrylate 1,6-Hexane Diester Violet UV-7640B 1Diluent Solvent PGM < s IRGACURE184 Total Solids Ingredient FCS Solid Ingredient % / Acrylate (Amine Ester acrylate)% pencil hardness 2H inch scratch resistance Haze value adhesion curl (mm) Μ & adhesive agent error Μ film characteristics 19 201235095 As shown in Table 1, by controlling as in Synthesis Examples 1 to 3 The alkoxy decane blending amount of mercapto acrylonitrile is also selected to be azeotropic dehydration using 1-nonoxy-2-propanol, and the average particle size difference of ceria before and after the hydrolysis reaction can be made within 1.5 times. Functional colloidal cerium oxide solution. In contrast, 1,6-hexanediol diacrylate (HDDA) or isobutanol (IBA) was used as the azeotropic dehydration synthesis examples 4 and 5, and the methacryloyl group-containing alkoxysilane was added. In Synthesis Example 6 in which the amount of the mixture was too large, only the average particle diameter was large. Further, in Examples 1 to 4 using the functional colloidal cerium oxide solution of the present invention, a film excellent in pencil hardness, scratch resistance, curling property and adhesion was obtained. Simple description of C::! (none) [Explanation of main component symbols] (none) 20