TW201235369A

TW201235369A - Fluorine-containing highly branched polymer and photo-cationic polymerizable composition containing the polymer

Info

Publication number: TW201235369A
Application number: TW100144302A
Authority: TW
Inventors: Tomoko Misaki; Masayuki Haraguchi; Motonobu Matsuyama; Masaaki Ozawa
Original assignee: Nissan Chemical Ind Ltd
Priority date: 2010-12-01
Filing date: 2011-12-01
Publication date: 2012-09-01
Also published as: JPWO2012074064A1; WO2012074064A1; JP5920590B2; TWI555760B

Abstract

To provide a surface modifier capable of being fixed in a cured product and enabling simple surface modification without the loss of conventional characteristics, such as transparency, of the cured products of photo-cationically polymerizable resins, and a photo-cationically polymerizable composition containing the surface modifier. A fluorine-containing hyperbranched polymer, a surface modifier for a photo-cationically polymerizable resin comprising the hyperbranched polymer, a photo-cationically polymerizable resin composition and a cured product obtained therefrom, said hyperbranched polymer being obtained by polymerizing monomer (A), monomer (B), and monomer (C) in the presence of polymerization initiator (D), said polymer initiator (D) being present in an amount of 5-200 mol% relative to the number of moles of said monomer (A). Monomer (A) has at least two radically polymerizable double bonds per molecule, monomer (B) has a fluoroalkyl group and at least one radically polymerizable double bond per molecule, and monomer (C) has at least one radically polymerizable double bond and at least one photo-cationically polymerizable group selected from the group comprising a cycloaliphatic epoxy group and an oxetanyl group per molecule.

Description

201235369 六、發明說明：【發明所屬之技術領域】本發明係有關含有光陽離子聚合性基之含氟高分支聚合物、添加該高分支聚合物之光陽離子聚合性組成物，及 ' 由該光陽離子聚合性組成物所得之經表面改質之硬化物。【先前技術】聚合物（高分子）材料近來逐漸被使用於各種領域。伴隨著因應各自之領域，而使基質用之聚合物之性狀，與其表面及界面之特性成爲重點。例如，藉由表面改質劑使用表面能量較低之氟系化合物，期待可提升撥水撥油性、防污性、非黏合性、剝離性、離模性、滑動性、耐摩耗性、防反射特性、耐藥品性等之有關控制表面、界面之特性，而有各種提案。該等材料之一的以環氧樹脂爲首之光陽離子聚合性樹脂爲，藉由照射紫外線等之光線使聚合性官能基發生聚合反應而三次元交換之樹脂。該光陽離子聚合性樹脂可於無溶劑下硬化，另外聚合時不受氧之影響，因此可於空氣存在下硬化。又，硬化所需之能量較低，因此可稱爲適用於產業面、環境面雙方之樹脂。又，該硬化物具有優良之接著性、耐藥品性、耐熱性及富有電絕緣性，而被使用於塗料、電器絕緣體、接著劑等各種領域。另外因具有高透明度之特徵，故多數被使用 201235369 於以發光二極管爲首之光電子用透明絕緣封裝劑等要求高透明性之光學領域。該等光陽離子聚合性樹脂之表面改質方法如所揭示，將同一分子內含有氟烷基與環氧基等之硬化反應基之酚醛清漆樹脂，加入胺基甲酸酯丙烯酸酯樹脂或環氧樹脂等之光陽離子聚合性樹脂中，而將防污性賦予其硬化物之表面之方法（專利文獻1)。又如所揭示，以丙烯酸-環氧樹脂爲材料之光學用途之熱硬化性單體樹脂透鏡，包覆氟系高分子膜單層膜之方法（專利文獻2)。另外已知的聚合物之表面改質方法之一如，將分支聚合物加入由線狀聚合物所形成之基質聚合物，而於基質聚合物表面濃縮該分支聚合物之方法（專利文獻3)。先前技術文獻專利文獻專利女獻1 :國際公開第2008/ 1 4668 1號報告專利文獻2 :特開20 1 0-2243 1 5號公報專利文獻3 :國際公開第2007/049608號報告【發明內容】發明所欲解決之課題如上述曾有各種使用含氟聚合物的光陽離子聚合性樹脂之表面改質之提案，但例如專利文獻1中’未曾記載光陽離子聚合性樹脂硬化物之重要特徵的透明性。又’專利 -6- 201235369 文獻2之方法中，形成基材之樹脂於硬化後需另外進行表面包覆，故步驟煩雜不利於工業上。即’需求不喪失透明性等之光陽離子聚合性樹脂硬化物之原有特徵下，於硬化物中可固定化，且可簡便表面改質之表面改質劑，及含有其之光陽離子聚合性組成物。解決課題之方法爲了解決上述課題經本發明者們專心檢討後發現，採用藉由高分支聚合物導入氟烷基及導入脂環式環氧基及環氧丙烷基所得之含氟高分支聚合物作爲光陽離子聚合性樹脂之表面改質劑，不僅相對於有機溶劑具有優良之溶解性 ’且相對於基質樹脂之光陽離子聚合性樹脂具有優良之混合、分散性，於基質樹脂中不會發生凝聚，可得表面改質性優良之具有高透明性之硬化物，而完成本發明。即，本發明爲，第1觀點係有關一種含氟高分支聚合物’其爲使分子內具有2個以上之自由基聚合性雙鍵之單體A’與分子內具有氟烷基及至少丨個之自由基聚合性雙鍵之單體B，與分子內具有由脂環式環氧基及環氧丙烷基所成群中所選出之至少1個光陽離子聚合性基及至少1個自由基聚合性雙鍵之單體C，於相對於該單體A之莫耳數爲5至200莫耳％量之聚合起始劑〇的存在下聚合所得。第2觀點係有關第1觀點所記載之含氟高分支聚合物，其中前述單體A爲，具有乙烯基或（甲基）丙烯酸基中任何一方或雙方之化合物。 201235369 第3觀點係有關第2觀點所記載之含氟高分支聚合物，其中前述單體A爲，二乙烯基化合物或二（甲基）丙烯酸酯化合物。第4觀點係有關第3觀點所記載之含氟高分支聚合物，其中前述單體A爲脂環式二（甲基）丙烯酸酯。第5觀點係有關第4觀點所記載之含氟高分支聚合物，其中前述單體A爲三環癸烷二甲醇二（甲基）丙烯酸酯。第6觀點係有關第1觀點所記載之含氟高分支聚合物 ’其中相對於前述單體A係使用5至3 00莫耳％量之前述單體B所得。第7觀點係有關第6觀點所記載之含氟高分支聚合物 ’其中前述單體B爲，具有乙烯基或（甲基）丙烯酸基中任何一方或雙方之化合物。第8觀點係有關第7觀點所記載之含氟高分支聚合物 ’其中前述單體B爲下述式[1]所表示之化合物，201235369 6. Technical Field of the Invention The present invention relates to a fluorine-containing highly branched polymer containing a photocationic polymerizable group, a photocationic polymerizable composition to which the high branched polymer is added, and 'from the light A surface-modified hardened material obtained from a cationically polymerizable composition. [Prior Art] Polymer (polymer) materials have recently been used in various fields. Accompanied by the properties of the polymer used in the matrix in response to their respective fields, the characteristics of the surface and interface are important. For example, a fluorine-based compound having a low surface energy is used as a surface modifier, and it is expected to improve water repellency, antifouling property, non-adhesiveness, peelability, mold release property, slidability, abrasion resistance, and antireflection. There are various proposals regarding the characteristics of the control surface and the interface, such as characteristics and chemical resistance. A photocationic polymer resin such as an epoxy resin, which is one of the materials, is a resin which is exchanged three-dimensionally by polymerizing a polymerizable functional group by irradiation with light such as ultraviolet rays. The photocationic polymerizable resin can be cured in the absence of a solvent, and is not affected by oxygen during the polymerization, so that it can be cured in the presence of air. Further, since the energy required for hardening is low, it can be referred to as a resin suitable for both the industrial surface and the environmental surface. Further, the cured product has excellent adhesion, chemical resistance, heat resistance and electrical insulating properties, and is used in various fields such as paints, electrical insulators, and adhesives. In addition, because of its high transparency, it is used in the field of optics requiring high transparency, such as transparent insulating encapsulants for optoelectronics, such as LEDs. The surface modification method of the photocationic polymerizable resin is as disclosed, and a novolak resin containing a hardening reactive group such as a fluoroalkyl group and an epoxy group in the same molecule is added to the urethane acrylate resin or epoxy. In the photocationic polymerizable resin such as a resin, the antifouling property is imparted to the surface of the cured product (Patent Document 1). Further, as disclosed, a method of coating a fluorine-based polymer film single-layer film with a thermosetting monomer resin lens for optical use of an acrylic-epoxy resin is disclosed (Patent Document 2). Another known method for surface modification of a polymer is a method in which a branched polymer is added to a matrix polymer formed of a linear polymer and a branched polymer is concentrated on a surface of a matrix polymer (Patent Document 3). . [Patent Document 1] International Publication No. 2008/1 4668 No. 1 Report Patent Document 2: JP-A 20 1 0-2243 1 5 Patent Document 3: International Publication No. 2007/049608 Report [Summary of the Invention OBJECTS OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The surface modification of the photocationic polymerizable resin using a fluoropolymer has been proposed as described above. For example, Patent Document 1 discloses that the important features of the photocationically polymerizable resin cured product are not described. Transparency. Further, in the method of Patent No. -6-201235369, the resin forming the substrate needs to be additionally coated after hardening, so that the steps are troublesome and unfavorable to the industry. In other words, a surface modifier which can be immobilized in a cured product and which can be easily surface-modified, and a photocationic polymerizable property thereof, which is capable of being immobilized in a cured product without losing the transparency of the photocationic polymerizable resin. Composition. Solution to Problem In order to solve the above problems, the inventors of the present invention conducted a review and found that a fluorine-containing high-branched polymer obtained by introducing a fluoroalkyl group into a highly branched polymer and introducing an alicyclic epoxy group and an oxypropylene group is used. The surface modifier of the photocationic polymerizable resin has excellent solubility and solubility with respect to the organic resin, and has excellent mixing and dispersibility with respect to the photocationic polymerizable resin of the matrix resin, and does not cause aggregation in the matrix resin. The present invention can be completed by obtaining a cured product having high surface transparency and having high transparency. In other words, the present invention relates to a fluorine-containing highly branched polymer which is a monomer A' having two or more radical polymerizable double bonds in a molecule and a fluoroalkyl group in the molecule and at least fluorene. a monomer B having a radically polymerizable double bond, and at least one photocationic polymerizable group selected from the group consisting of an alicyclic epoxy group and an oxypropylene group, and at least one radical The monomer C of the polymerizable double bond is obtained by polymerization in the presence of a polymerization initiator 〇 in an amount of 5 to 200 mol% relative to the monomer A. The second aspect is the fluorine-containing highly branched polymer according to the first aspect, wherein the monomer A is a compound having one or both of a vinyl group and a (meth)acryl group. The present invention relates to a fluorine-containing highly branched polymer according to the second aspect, wherein the monomer A is a divinyl compound or a di(meth)acrylate compound. The fourth aspect is the fluorine-containing highly branched polymer according to the third aspect, wherein the monomer A is an alicyclic di(meth)acrylate. The fifth aspect is the fluorine-containing highly branched polymer according to the fourth aspect, wherein the monomer A is tricyclodecane dimethanol di(meth)acrylate. The sixth aspect is the fluorine-containing highly branched polymer described in the first aspect, wherein the monomer B is used in an amount of from 5 to 300% by mole based on the monomer A. The seventh aspect is the fluorine-containing highly branched polymer described in the sixth aspect, wherein the monomer B is a compound having one or both of a vinyl group and a (meth)acryl group. The eighth aspect is the fluorine-containing highly branched polymer described in the seventh aspect, wherein the monomer B is a compound represented by the following formula [1].

(式中’R表示氫原子或甲基，R2表示可被羥基取代之碳原子數2至 12之氟烷基）第9觀點係有關第8觀點所記載之含氟高分支聚合物其中前述單體B爲下述式U]所表示之化合物， 201235369(wherein R represents a hydrogen atom or a methyl group, and R2 represents a fluoroalkyl group having 2 to 12 carbon atoms which may be substituted by a hydroxyl group). The ninth aspect is the fluorine-containing highly branched polymer according to the eighth aspect, wherein the aforementioned single The body B is a compound represented by the following formula U], 201235369

:CH2)m 一 (CF2)n-CF2—X (式中，R1表示與前述式Π]之定義相同，X表示氫原子或氟原子，m表示1或2’ η表示〇至5之整數）。第10觀點係有關第1觀點所記載之含氟高分支聚合物，其中相對於前述單體Α係使用10至300莫耳％量之前述單體C所得。第1 1觀點係有關第1 0觀點所記載之含氟高分支聚合物，其中前述單體C爲，具有乙烯基或（甲基）丙烯酸基中任何一方或雙方之化合物。第1 2觀點係有關第1 1觀點所記載之含氟高分支聚合物，其中前述單體C爲下述式[3]所表示之化合物，:CH2)m -(CF2)n-CF2-X (wherein R1 represents the same as defined above), X represents a hydrogen atom or a fluorine atom, and m represents 1 or 2' η represents an integer from 〇 to 5) . The fluorinated high-branched polymer according to the first aspect, wherein the monomer C is used in an amount of 10 to 300 mol% based on the monomer oxime. The present invention relates to a fluorine-containing high-branched polymer according to the first aspect, wherein the monomer C is a compound having either or both of a vinyl group and a (meth)acryl group. The fluorine-containing high-branched polymer according to the above aspect, wherein the monomer C is a compound represented by the following formula [3],

(式中，R3表示氫原子或甲基，L表示單鍵，或可含有醚鍵或酯鍵之碳原子數1至6之伸烷基）。第1 3觀點係有關第丨！觀點所記載之含氟高分支聚合物，其中前述單體C爲下述式[4]所表示之化合物，(wherein R3 represents a hydrogen atom or a methyl group, and L represents a single bond or an alkylene group having 1 to 6 carbon atoms which may have an ether bond or an ester bond). The 1st point of view is related to Dijon! The fluorine-containing high-branched polymer described in the above aspect, wherein the monomer C is a compound represented by the following formula [4].

201235369 【化4】【4] (式中，R4表示氫原子或甲基，R5表示氫原子或 1至6之烷基，L表示單鍵或可含有醚鍵或酯鍵數1至6之伸烷基）。第14觀點係有關第1觀點至第13觀點中任記載之含氟高分支聚合物，其中前述聚合起始劑系聚合起始劑。第1 5觀點係有關第1 4觀點所記載之含氟高物’其中前述聚合起始劑D爲二甲基1，1’-偶氮烷羧酸酯）。第1 6觀點係有關第1 4觀點所記載之含氟高物’其中另藉由相對於前述單體A之莫耳數共！ 3 00莫耳％量之下述式[5]所表示之單體e共所得【化5】 [5] (式中’ R6表示氫原子或甲基，R7表示碳原子數烷基或碳原子數3至30之脂環基）。胃1 7觀點係有關一種光陽離子聚合性樹脂質劑’其爲由第1觀點至第1 6觀點中任何一項 -10- ;碳原子數 [之碳原子何一項所 D爲偶氮分支聚合雙（1-環己分支聚合聚合5至 6至30之之表面改所記載之 201235369 含氟高分支聚合物所形成。第1 8觀點係有關一種光陽離子聚合性樹脂組成物，其爲含有（a)第1觀點至第1 6觀點中任何一項所記載之含氟高分支聚合物，及（b)光陽離子聚合性樹脂預聚物。第1 9觀點係有關第丨8觀點所記載之樹脂組成物，其中相對於前述（b)預聚物之質量含有0.001至20質量％之目U述（a)含氟高分支聚合物。第20觀點係有關第丨9觀點所記載之樹脂組成物，其中前述（b)預聚物爲至少具有！個脂環式環氧基之化合物。第2 1觀點係有關第丨8觀點所記載之樹脂組成物，其中另含有（c)光酸發生劑。第22觀點係有關第2 1觀點所記載之樹脂組成物，其中相對於前述（b)預聚物之質量含有〇.〇5至30質量％之前述（c)光酸發生劑。第23觀點係有關一種硬化物，其爲藉由第1 8觀點至第22觀點中任何一項所記載之樹脂組成物所得。第24觀點係有關一種含氟高分支聚合物之製造方法，其特徵爲，使分子內具有2個以上之自由基聚合性雙鍵之單體A，與分子內具有氟烷基及至少1個自由基聚合性雙鍵之單體B，與分子內具有由脂環式環氧基及環氧丙烷基所成群中所選出之至少1個之光陽離子聚合性基及至少 1個之自由基聚合性雙鍵之單體C，於相對於該單體A之莫耳數爲5至200莫耳％量之聚合起始劑D的存在下聚合 201235369 發明效果本發明之含氟高分支聚合物因積極導入分支之構造，故比較線狀高分子可減少分子間糾葛，表現微粒子性舉動，且相對於有機溶劑之溶解性及相對於樹脂之分散性較高。因此光陽離子聚合性樹脂組成物等添加本發明之含氟高分支聚合物，製作硬化物時，微粒子狀之該高分支聚合物易移動於界面（硬化物表面）上，而易將剝離性、撥水撥油性、防污性等之活性賦予樹脂表面。又，本發明之含氟高分支聚合物係藉由分子內具有光陽離子聚合性基，而選擇基質樹脂用之光陽離子聚合性樹脂時，於該樹脂硬化時可固定化，故賦予樹脂表面之活性可固定化》且本發明之含氟高分支聚合物可提高與基質樹脂之混合、分散性，於樹脂中不會發生凝聚等可混合、分散，故可製造透明性優良之硬化性。因此光陽離子聚合性組成物添加少量本發明之含氟高分支聚合物時，可簡便且長期將光陽離子聚合性樹脂硬化物表面改質，及形成透明性優良之硬化物。實施發明之形態 <含氟高分支聚合物> 本發明之含氟高分支聚合物爲，藉由使分子內具有2 個以上之自由基聚合性雙鍵之單體A，與分子內具有氟烷基及具有至少1個自由基聚合性雙鍵之單體B，與分子內 •12- 201235369 具有由脂環式環氧基及環氧丙烷基所成群中所選出之至少 1個光陽離子聚合性基及至少1個自由基聚合性雙鍵之單體C’與所希望之後述之單體E，於相對於該單體A之莫耳數爲5至200莫耳％量之聚合起始劑D的存在下聚合所得之聚合物。又，本發明之含氟高分支聚合物爲所謂的起始劑斷片組合型含氟高分支聚合物，故其末端具有聚合所使用之聚合起始劑D之斷片。 [單體A] 本發明中分子內具有2個以上之自由基聚合性雙鍵之單體A較佳爲，具有乙烯基或（甲基）丙烯酸基中任何一方或雙方，特佳爲二乙烯基化合物或二（甲基）丙烯酸酯化合物。又，本發明之（甲基）丙烯酸酯化合物係指丙烯酸酯化合物與甲基丙烯酸酯化合物雙方。例如（甲基）丙烯酸爲丙烯酸及甲基丙烯酸。該類單體A如，下述（人〇至（A7)所表示之有機化合物 (A 1)乙烯基系烴： (A 1-1)脂肪族乙烯基系烴類：異戊二烯、丁二烯、3-甲基-1，2·丁二烯、2,3-二甲基-1，3·丁二烯、1，2-聚丁二烯、戊二烯、己二烯、辛二烯等 (Α 1-2)脂環式乙烯基系烴：環戊二烯、環己二烯、環辛二烯、降冰片二烯等 -13- 201235369 (A1-3)芳香族乙烯基系烴：二乙烯基苯、二乙烯基甲苯、二乙烯基二甲苯、三乙烯基苯、二乙烯基聯苯、二乙烯基萘、二乙烯基芴、二乙烯基咔唑、二乙烯基吡啶等 (Α2)乙烯酯、烯丙酯、乙烯醚、烯丙醚、乙烯酮： (Α2-1)乙烯酯：己二酸二乙烯酯、馬來酸二乙烯酯、酞酸二乙烯酯 '間苯二酸二乙烯酯、衣康酸二乙烯酯、乙烯基 (甲基）丙稀酸酯等 (Α2-2)烯丙酯：馬來酸二烯丙酯、酞酸二烯丙酯、間苯二酸二烯丙酯、己二酸二烯丙酯、烯丙基（甲基）丙烯酸酯等 (Α2-3)乙烯醚：二乙烯醚、二乙二醇二乙烯醚、三乙二醇二乙烯醚等 (Α2-4)烯丙醚：二烯丙醚、二烯丙氧基乙烷、三烯丙氧基乙烷、四烯丙氧基乙烷、四烯丙氧基丙烷、四烯丙氧基丁烷、四甲基丙烯氧基乙烷等 (Α2-5)乙烯酮：二乙烯酮、二烯丙酮等 (Α3)(甲基）丙烯酸酯：乙二醇二（甲基）丙烯酸酯 '三乙二醇二（甲基）丙烯酸酯、丙二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸醋、三羥甲基丙烷三（甲基）丙烯酸酯、雙三羥甲基丙烷四（甲基 )丙烯酸酯、丙三醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、垸氧基鈦三（甲基）丙烯酸酯、丨，6_己二醇二（甲基）丙烯酸酯、2-甲基·1，8-辛二醇二（甲基）丙稀酸酯、19_ -14- 201235369 壬二醇二（甲基）丙烯酸酯、l，l〇 -癸二醇二（甲基）丙烯酸醋、三環[5_2.1.02,6]癸烷二甲醇二（甲基）丙烯酸酯、二己二醇二（甲基）丙烯酸酯、2-羥基-1-丙烯醯氧基-3-甲基丙烯醯氧基丙烷、2·羥基-1，3-二（甲基）丙烯醯氧基丙烷、9，卜雙 [4-(2-(甲基）丙烯醯氧基乙氧基）苯基]芴、十—烯氧基乙二醇二（甲基）丙烯酸酯、雙[4-(甲基）丙烯醯基硫苯基]硫化物、雙[2-(甲基）丙烯醯基硫乙基]硫化物、13 —金剛二醇二（甲基）丙烯酸酯、1，3-金剛烷二甲醇二（甲基）丙烯酸酯等 (A4)具有聚烷二醇鏈之乙烯基系化合物：聚乙二醇（分子量300)二（甲基）丙烯酸酯、聚丙二醇（分子量500)二（甲基）丙烯酸酯等 (A5)含氮乙烯基系化合物：二烯丙基胺、二烯丙基三聚異氰酸酯、二烯丙基氰尿酸酯、伸甲基雙（甲基）丙烯醯胺、雙馬來醯亞胺等 (A6)含矽乙烯基系化合物：二甲基二乙烯基矽烷、二乙烯基甲基苯基矽烷、二苯基二乙烯基矽烷、1，3-二乙烯基-1,1,3,3-四甲基二矽氮烷、1，3-二乙烯基-1，1,3,3-四苯基二矽氮烷、二乙氧基二乙烯基矽烷等 (A7)含氟乙烯基系化合物·· -15- 201235369 1,4-二乙烯基全氟丁烷、1，4-二乙烯基八氟丁烷、1，6-二乙烯基全氟己烷、1，6-二乙烯基十二氟己烷、1，8-二乙烯基全氟辛烷、1，8-二乙烯基十六氟辛烷等該等較佳爲，上述（A 1-3)群之芳香族乙烯基系烴化合物、（A2)群之乙烯酯、烯丙酯、乙烯醚、烯丙醚及乙烯酮、（A3)群之（甲基）丙烯酸酯、（A4)群之具有聚烷二醇鏈之乙烯基系化合物，及（A5)群之含氮乙烯系化合物。特別是，（A 1-3)群所屬之二乙烯基苯、（A2)群所屬之酞酸二烯丙酯、（A3)群所屬之乙二醇二（甲基）丙烯酸酯、1，3-金剛烷二甲醇二（甲基）丙烯酸酯、三環[5.2.1_02’6]癸烷二甲醇二（甲基）丙烯酸酯及（A5)群所屬之伸甲基雙（甲基）丙烯酸酯。其中又以二乙烯基苯、乙二醇二（甲基）丙烯酸酯及三環 [5.2.1.02’6]癸烷二甲醇二（甲基）丙烯酸酯爲佳，特佳爲三環[5·2·1·02’6]癸烷二甲醇二（甲基）丙烯酸酯。 [單體Β] 本發明中分子內具有氟烷基及至少1個自由基聚合性雙鍵之單體Β較佳爲，具有乙烯基或（甲基）丙烯酸基中任何一方或雙方，特別是前述式[1]所表示之化合物，更佳爲式[2]所表示之化合物。該類單體Β如，2,2,2-三氟乙基（甲基）丙烯酸酯， 2,2,3,3,3-五氟丙基（甲基）丙烯酸酯，2-(全氟丁基）乙基（甲基）丙烯酸酯、2-(全氟己基）乙基（甲基）丙烯酸酯、2-(全氟辛基）乙基（甲基）丙烯酸酯、2-(全氟癸基）乙基（甲基）丙烯 -16 - 201235369 酸酯、2-(全氟-3 -甲基丁基）乙基（甲基）丙烯酸酯、2-(全氟-5-甲基己基）乙基（甲基）丙烯酸酯、2-(全氟-7-甲基辛基 )乙基（甲基）丙烯酸酯、1H,1H，3H-四氟丙基（甲基）丙烯酸酯、1H，1H,5H-八氟戊基（甲基）丙烯酸酯、1H,1H，7H-十二氟庚基（甲基）丙烯酸酯、1H，1H,9H-十六氟壬基（甲基）丙烯酸酯、1H-1-(三氟甲基）三氟乙基（甲基）丙烯酸酯、 1H，1H，3H-六氟丁基（甲基）丙烯酸酯、3-全氟丁基-2-羥基丙基（甲基）丙烯酸酯、3-全氟己基-2-羥基丙基（甲基）丙烯酸酯、3-全氟辛基-2-羥基丙基（甲基）丙烯酸酯、3-(全氟-3·甲基丁基）-2-羥基丙基（甲基）丙烯酸酯、3-(全氟-5-甲基己基）-2-羥基丙基（甲基）丙烯酸酯及3_(全氟-7_甲基辛基）_ 2-羥基丙基（甲基）丙烯酸酯等。本發明中’單體B之使用量就反應性及來自氟烷基之表面改質效果之觀點，相對於前述單體A之使用莫耳數較佳爲使用5至3 0 0莫耳％，特別是i 〇至i 5 〇莫耳％，更佳爲20至1〇〇莫耳％之量。201235369 [In the formula, R4 represents a hydrogen atom or a methyl group, R5 represents a hydrogen atom or an alkyl group of 1 to 6, and L represents a single bond or may have an ether bond or an ester bond number of 1 to 6. alkyl). The fluorine-containing high-branched polymer according to any one of the first aspect, wherein the polymerization initiator is a polymerization initiator. The fifteenth aspect is the fluorine-containing high material described in the above aspect, wherein the polymerization initiator D is a dimethyl 1,1'-azo alkanecarboxylate. The 16th point of view is related to the fluorine-containing high substance described in the 1st 4th aspect, which is additionally made up of the number of moles relative to the aforementioned monomer A! A total of 300% of the monomer is represented by the following formula [5]: [5] [5] (wherein R6 represents a hydrogen atom or a methyl group, and R7 represents an alkyl group or a carbon atom of a carbon atom; A number of 3 to 30 alicyclic groups). The stomach 17 is related to a photocationic polymerizable resin agent' which is any one of the first to the 16th viewpoints; - 10 carbon atoms, which one is D, an azo branch. Polymerized bis(1-cyclohexyl branch polymerization polymerization 5 to 6 to 30, which is formed by the surface modification of 201235369 fluorine-containing high-branched polymer. The 18th aspect relates to a photocationic polymer resin composition which contains (a) The fluorine-containing highly branched polymer described in any one of the first aspect to the first aspect, and (b) the photocationic polymerizable resin prepolymer. The ninth aspect is related to the eighth aspect. The resin composition containing 0.001 to 20% by mass of the (a) fluorine-containing highly branched polymer with respect to the mass of the prepolymer (b). The 20th viewpoint is the resin described in the ninth aspect. In the composition, the (b) prepolymer is a compound having at least one alicyclic epoxy group. The second aspect is a resin composition according to the eighth aspect, which further contains (c) a photoacid. The agent 22 is the resin group described in the 2nd aspect. And the (c) photoacid generator of the above-mentioned (b) prepolymer having a mass of 5 to 30% by mass relative to the mass of the prepolymer (b). The 23rd aspect relates to a cured product which is based on the 1st 8th viewpoint The resin composition described in any one of the twenty-fourth aspects. The twenty-fourth aspect relates to a method for producing a fluorine-containing highly branched polymer, which comprises having two or more radical polymerizable double bonds in a molecule. a monomer A, a monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule, and a molecule selected from the group consisting of an alicyclic epoxy group and an oxypropylene group. a monomer C having at least one photocationic polymerizable group and at least one radical polymerizable double bond, and a polymerization initiator D in an amount of 5 to 200 mol% relative to the molar amount of the monomer A Polymerization in the presence of 201235369 Effect of the Invention The fluorine-containing high-branched polymer of the present invention has a structure in which a branch is actively introduced, so that the linear polymer can be reduced in molecular entanglement, exhibiting microparticle behavior, and solubility with respect to an organic solvent and relative High dispersibility in the resin. Therefore, light When the fluorinated high-branched polymer of the present invention is added to an ionic polymerizable resin composition or the like, and the cured product is produced, the high-branched polymer in the form of fine particles is easily moved on the interface (hardened surface), and the peeling property and the water are easily removed. The activity of the oil-repellent property, the anti-fouling property, and the like is applied to the surface of the resin. Further, the fluorine-containing high-branched polymer of the present invention is a photocationic polymerizable resin for a matrix resin when a photocationic polymerizable group is contained in the molecule. When the resin is cured, the resin can be immobilized, and the activity of the surface of the resin can be immobilized. The fluorine-containing high-branched polymer of the present invention can improve the mixing and dispersibility with the matrix resin, and can be mixed without causing aggregation in the resin. Dispersed, it can produce hardenability with excellent transparency. Therefore, when a small amount of the fluorine-containing highly branched polymer of the present invention is added to the photocationic polymerizable composition, the surface of the photocationically polymerizable resin cured material can be easily and long-termly modified, and a cured product excellent in transparency can be formed. MODE FOR CARRYING OUT THE INVENTION <Fluorine-containing high-branched polymer> The fluorine-containing high-branched polymer of the present invention has a monomer A having two or more radical polymerizable double bonds in its molecule, and has intramolecular a fluoroalkyl group and a monomer B having at least one radical polymerizable double bond, and at least one light selected from the group consisting of an alicyclic epoxy group and an oxypropylene group in the molecule. Polymerization of a cationically polymerizable group and a monomer C' having at least one radical polymerizable double bond and a monomer E to be described later in an amount of 5 to 200 mol% relative to the molar amount of the monomer A The resulting polymer is polymerized in the presence of initiator D. Further, the fluorine-containing highly branched polymer of the present invention is a so-called starter fragment-combination type fluorine-containing high-branched polymer, and therefore has a fragment of a polymerization initiator D used for polymerization at its end. [Monomer A] The monomer A having two or more radically polymerizable double bonds in the molecule in the present invention preferably has either or both of a vinyl group or a (meth)acryl group, and particularly preferably diethylene. a base compound or a di(meth)acrylate compound. Further, the (meth) acrylate compound of the present invention means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic acid is acrylic acid and methacrylic acid. Such a monomer A is, for example, an organic compound represented by (A7) (A1), a vinyl hydrocarbon: (A 1-1) an aliphatic vinyl hydrocarbon: isoprene, butyl Diene, 3-methyl-1,2.butadiene, 2,3-dimethyl-1,3.butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octane Diene (Α 1-2) alicyclic vinyl hydrocarbon: cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc.-13- 201235369 (A1-3) Aromatic vinyl Hydrocarbons: divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylanthracene, divinylcarbazole, divinylpyridine Etc. (Α2) vinyl ester, allyl ester, vinyl ether, allyl ether, ketene: (Α2-1) vinyl ester: divinyl adipate, divinyl maleate, divinyl phthalate Divinyl phthalate, divinyl itaconate, vinyl (meth) acrylate, etc. (Α2-2) allyl ester: diallyl maleate, diallyl citrate, between Diallyl phthalate, diallyl adipate, allyl (meth) acrylate Etc. (Α2-3) Vinyl ether: divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc. (Α2-4) Allyl ether: diallyl ether, diallyloxyethane , triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethylpropenyloxyethane, etc. (Α2-5) ketene: two (Α3) (meth) acrylate such as ketene or diene acetone: ethylene glycol di(meth)acrylate 'triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, new Pentandiol di(meth)acrylic acid vinegar, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol Tetrakis(meth)acrylate, titanyl tris(meth)acrylate, anthracene, 6-hexanediol di(meth)acrylate, 2-methyl·1,8-octanediol di(a) Base) acrylate, 19_ -14- 201235369 decanediol di(meth) acrylate, l,l 〇-nonanediol di(meth)acrylic acid vinegar, tricyclo[5_2.1.02,6]decane Dimethanol II Acrylate, dihexyl glycol di(meth)acrylate, 2-hydroxy-1-propenyloxy-3-methylpropenyloxypropane, 2·hydroxy-1,3-di(methyl) a propylene methoxypropane, 9, bis[4-(2-(methyl) propylene oxyethoxy) phenyl] fluorene, deca- oxy ethoxy di(meth) acrylate, Bis[4-(methyl)propenylthiophenyl]sulfide, bis[2-(methyl)propenylthioethyl]sulfide, 13-adamantanediol di(meth)acrylate, 1 , 3-adamantane dimethanol di(meth)acrylate, etc. (A4) a vinyl compound having a polyalkylene glycol chain: polyethylene glycol (molecular weight 300) di(meth)acrylate, polypropylene glycol (molecular weight 500) Di(meth)acrylate or the like (A5) nitrogen-containing vinyl compound: diallylamine, diallyl isocyanurate, diallyl cyanurate, methyl bis(methyl) Acrylamide, bismaleimide, etc. (A6) fluorene-containing vinyl compound: dimethyldivinyl decane, divinylmethylphenyl decane, diphenyl divinyl decane, 1, 3 -divinyl -1,1,3,3-tetramethyldiazepine, 1,3-divinyl-1,1,3,3-tetraphenyldiazepine, diethoxydivinyldecane, etc. (A7) Fluorine-containing vinyl compound·· -15- 201235369 1,4-divinyl perfluorobutane, 1,4-divinyloctafluorobutane, 1,6-divinyl perfluorohexane 1,6-divinyldodecafluorohexane, 1,8-divinyl perfluorooctane, 1,8-divinylhexadecyloctane, etc., preferably, the above (A 1- 3) Group of aromatic vinyl hydrocarbon compounds, (A2) group of vinyl ester, allyl ester, vinyl ether, allyl ether and ketene, (A3) group of (meth) acrylate, (A4) group A vinyl compound having a polyalkylene glycol chain and a nitrogen-containing vinyl compound of the group (A5). In particular, divinylbenzene to which the (A 1-3) group belongs, diallyl citrate to which the (A2) group belongs, ethylene glycol di(meth)acrylate to which the (A3) group belongs, 1, 3 -adamantane dimethanol di(meth)acrylate, tricyclo[5.2.1_02'6]decane dimethanol di(meth)acrylate and methyl bis(meth)acrylate of (A5) group . Among them, divinylbenzene, ethylene glycol di(meth)acrylate and tricyclo[5.2.1.02'6]decane dimethanol di(meth)acrylate are preferred, especially tricyclic [5· 2·1·02'6] decane dimethanol di(meth) acrylate. [Monomer] The monomer fluorene having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule in the present invention preferably has either or both of a vinyl group or a (meth)acryl group, and particularly The compound represented by the above formula [1] is more preferably a compound represented by the formula [2]. Such monomers are, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2-(perfluoro Butyl)ethyl (meth) acrylate, 2-(perfluorohexyl)ethyl (meth) acrylate, 2-(perfluorooctyl)ethyl (meth) acrylate, 2-(perfluoro Ethyl)ethyl(meth)acryl-16 - 201235369 acid ester, 2-(perfluoro-3-methylbutyl)ethyl (meth) acrylate, 2-(perfluoro-5-methylhexyl) Ethyl (meth) acrylate, 2-(perfluoro-7-methyloctyl)ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H ,1H,5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorodecyl (meth) acrylate Ester, 1H-1-(trifluoromethyl)trifluoroethyl(meth)acrylate, 1H,1H,3H-hexafluorobutyl(meth)acrylate, 3-perfluorobutyl-2-hydroxyl Propyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (methyl) propyl Acid ester, 3-(perfluoro-3·methylbutyl)-2-hydroxypropyl (meth) acrylate, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl (methyl) ) acrylate and 3_(perfluoro-7-methyloctyl)-2-hydroxypropyl (meth) acrylate, and the like. In the present invention, the amount of the monomer B used is preferably from 5 to 30,000 mol% with respect to the use of the monomer A in terms of reactivity and surface modification effect from the fluoroalkyl group. In particular, i 〇 to i 5 〇 mol%, more preferably 20 to 1 〇〇 mol%.

[單體CJ 本發明中分子內具有由脂環式環氧基及環氧丙烷基所成群中所選出之至少丨個光陽離子聚合性基及至少1個自由基聚合性雙鍵之單體C較佳爲’具有乙烯基或（甲基）丙烯酸基中任何一方或雙方，特佳爲前述式[3]所表示之化合物或式[4]所表示之化合物。該類單體C如’具有光陽離子聚合性基用之2,3-環氧 201235369 環戊基、3,4·環氧環己基、3,4-環氧-1-羥基環己基、3,4-環氧-6_甲基環己基等之脂環式環氧基；3·環氧丙烷基、3-甲基-3-環氧丙烷基、3-乙基-3-環氧丙烷基等之環氧丙烷基等之化合物。特別是前述式[3]所表示之化合物如，2,3-環氧環戊基甲基（甲基）丙烯酸酯、3,4·環氧環己基（甲基）丙烯酸酯、 3,4·環氧環己甲基（甲基）丙烯酸酯、2-(3,4-環氧環己基）乙基（甲基）丙烯酸酯、2-(3,4-環氧環己基）-2-羥基乙基（甲基）丙烯酸酯等》又前述式[4]所表示之化合物如，（3_甲基環氧丙烷- 3-基）甲基（甲基）丙烯酸酯、（3-乙基環氧丙烷-3-基）（甲基）丙烯酸酯、（環氧丙烷-3-基）甲基（甲基）丙烯酸酯、（3-乙基環氧丙烷-3-基）甲基（甲基）丙烯酸酯等》本發明中’單體C之使用量就反應性及相對於光陽離子硬化性樹脂之分散性之觀點，相對於前述單體A之使用莫耳數較佳爲使用10至300莫耳％，特別是20至200莫耳％，更佳爲3 0至1 5 0莫耳％之量。 [聚合起始劑D ] 本發明之聚合起始劑D較佳爲使用偶氮系聚合起始劑。偶氮系聚合起始劑如’下述（1)至（6)所示之化合物。 (1)偶氮腈化合物： 2,2’-偶氮雙異丁腈、2,2，-偶氮雙（2-甲基丁腈）、2,2，_偶氮 -18- 201235369 雙（2,4-二甲基戊腈）、1，1，-偶氮雙（1_環己烷腈）、2,2’-偶氮雙（4 -甲氧基-2,4 -二甲基戊腈）、2-(胺基甲醯偶氮）異丁腈等； (2) 偶氮醯胺化合物： 2,2，-偶氮雙{2-甲基-N-[l，l-雙（經基甲基）_2_經基乙基]丙醯胺}、2,2，-偶氮雙{2-甲基-N-[2-(l-經基丁基）]丙酶胺}、 2,2’-偶氮雙[2 -甲基-N-(2-羥基乙基）丙醯胺]、2,2’_偶氣雙 [N-(2-丙烯基）-2-甲基丙醯胺]、2,2’-偶氮雙（N-丁基-2-甲基丙醯胺）、2,2’-偶氮雙（N-環己基-2-甲基丙醯胺）等； (3) 環狀偶氮脒化合物： 2,2’-偶氮雙[2-(2 -咪唑啉-2-基）丙烷]二氫氯物、2，2’-偶氮雙[2-(2-咪唑啉-2-基）丙烷]二硫酸鹽二水合物、2,2’-偶氮雙[2-[1-(2-羥基乙基）-2-咪唑啉-2-基]丙烷]二氫氯化物、 2,2’-偶氮雙[2-(2-咪唑啉-2-基）丙烷]、2,2’-偶氮雙（1-亞胺基-1-吡咯基-2-甲基丙烷）二氫氯化物等； (4) 偶氮脒化合物： 2,2’-偶氮雙（2-甲基丙脒）二氫氯化物、2,2’-偶氮雙[N-(2-羧基乙基）-2-甲基丙脒]四水合物等； (5) 其他： 2，2’-偶氮雙異丁酸二甲酯、4,4’-偶氮雙（4-氰基戊酸）、 -19- 201235369 2,2’-偶氮雙（2,4,4-三甲基戊烷）、1，1’-偶氮雙（1-乙醯氧基- 1- 苯基乙烷）、二甲基1,1’·偶氮雙（1-環己烷羧酸酯）、 4,4’·偶氮雙（4-氰基戊酸）等。 (6)含有氟烷基之偶氮系聚合起始劑： 4,4’-偶氮雙（4-氰基戊酸2-(全氟甲基）乙酯）、4,4’-偶氮雙 (4-氰基戊酸2-(全氟丁基）乙酯）、4,4’-偶氮雙（4-氰基戊酸 2- (全氟己基）乙酯）等。上述偶氮系聚合起始劑中，就相對於光陽離子硬化性樹脂之分散性之觀點較佳爲，2,2’·偶氮雙（2-甲基丁腈）、 2,2’-偶氮雙異丁酸二甲酯或二甲基1，1’-偶氮雙（1-環己烷羧酸酯），特佳爲二甲基1,1’-偶氮雙（1·環己烷羧酸酯）。前述聚合起始劑D爲，相對於前述單體A之莫耳數使用5至200莫耳％之量，較佳爲使用20至200莫耳％，更佳爲20至100莫耳％之量。 [單體E] 本發明之含氟高分支聚合物中，除了前述單體A、單體B及單體C，可含有單體E之前述式[5]所表示之化合物，即，分子內具有碳原子數6至30之烷基或碳原子數3 至30之脂環基及（甲基）丙烯酸基之單體。藉由含有單體e ，可將優良之離模性等之表面改質性賦予由含有本發明之含氟高分支聚合物之樹脂組成物所得之塗膜。前述碳原子數6至30之烷基如，己基、乙基己基、 -20- 201235369 3，5,5 -三甲基己基、庚基、辛基、2 -辛基、異辛基、壬基、癸基、異辛基、十一烷基、月桂基、十三烷基、十四烷基、棕櫚醯基、硬脂醯基、異硬脂醯基、二十烷基、二十二烷基、二十四烷基、二十六烷基、二十八烷基、三十烷基等。其中，烷基之碳原子數就表面改質效果之觀點，較佳爲10至30，更佳爲16至24。前述碳原子數3至30之脂環基如，環丙基、環丁基、環戊基、環己基、4-tert-丁基環己基、異冰片基、降冰片烯基、基、金剛烷基、三環[5.2.1.02’6]癸基等。其中就表面改質效果之觀點，較佳爲碳原子數3至14 之脂環基，更佳爲碳原子數6至12之脂環基。該類單體E如，己基（甲基）丙烯酸酯、乙基己基（甲基 )丙烯酸酯、3，5,5-三甲基己基（甲基）丙烯酸酯、庚基（甲基 )丙烯酸酯、辛基（甲基）丙烯酸酯、2-辛基（甲基）丙烯酸酯、異辛基（甲基）丙烯酸酯、壬基（甲基）丙烯酸酯、癸基（甲基）丙烯酸酯' 異癸基（甲基）丙烯酸酯、十一烷基（甲基）丙烯酸酯、月桂基（甲基）丙烯酸酯、十三烷基（甲基）丙烯酸酯' 棕櫚基（甲基）丙烯酸酯、硬脂醯（甲基）丙烯酸酯、異硬脂醯（甲基）丙烯酸酯、二十二烷基（甲基）丙烯酸酯、環丙基（甲基）丙烯酸酯、環丁基（甲基）丙烯酸酯、環戊基（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、4-tert-丁基環己基 (甲基）丙烯酸酯、異冰片基（甲基）丙烯酸酯、降冰片烯（甲基）丙烯酸酯、基（甲基）丙烯酸酯、金剛烷基（甲基）丙烯 -21 - 201235369 酸酯、三環[5.2.1.02’6]癸烷（甲基）丙烯酸酯等。該等單體 E可單獨使用，或2種以上倂用。本發明中’單體E之使用量就反應性及表面改質效果之觀點，較佳爲相對於前述單體A之使用莫耳數使用5至 3 00莫耳％，特別是10至150莫耳％之量。 <含氟高分支聚合物之製造方法> 本發明之含氟高分支聚合物係由，使前述單體A、單體B、單體C及所希望之單體E，於相對於該單體A爲一定量之聚合起始劑D的存在下聚合所得，該聚合方法可爲已知之方法，例如溶液聚合、分散聚合、沈澱聚合及塊狀聚合等，其中較佳爲溶液聚合或沈激聚合。特別是控制分子量之方法，又以藉由有機溶劑中之溶液聚合實施反應爲佳。又，含氟高分支聚合物之製造方法也爲本發明之對象〇此時所使用之有機溶劑如，苯、甲苯、二甲苯、乙基苯、萘滿等之芳香族烴系溶劑；η-己烷、η-庚烷、礦油精、環己烷等之脂肪族或脂環式烴系溶劑；氯甲烷、溴甲烷、碘甲烷、伸甲基二氯化物、氯仿、四氯化碳、三氯乙烯、全氯乙烯、原二氯苯等之鹵系溶劑；乙酸乙酯、乙酸丁酯、甲氧基丁基乙酸酯、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丙二醇單甲基醚乙酸酯等之酯系或酯醚系溶劑：二乙基醚、四氫呋喃、1,4-二噁烷、甲基溶纖劑、乙基溶 -22- 201235369 纖劑、丁基溶纖劑、丙二醇單甲基醚等之醚系溶劑；丙酮、甲基乙基酮、甲基異丁基酮、二-η -丁基酮、環己酮等之酮系溶劑；甲醇、乙醇、η-丙醇、異丙醇、η-丁醇、異丁醇、tert-丁醇、2-乙基己醇、苄醇、乙二醇等之醇系溶劑 ;N，N -二甲基甲醯胺、N，N -二甲基乙酿胺等之醯胺系溶劑 :二甲基亞颯等之亞颯系溶劑；N -甲基-2 -吡咯烷酮等之雜環式化合物系溶劑，及該等之2種以上之混合溶劑。該等之中較佳爲芳香族烴系溶劑、鹵系溶劑、酯系溶劑、醚系溶劑、酮系溶劑、醇系溶劑、醯胺系溶劑等，特佳爲苯、甲苯、二甲苯、原二氯苯、乙酸乙酯、乙酸丁酯、丙二醇單甲基醚乙酸酯、丙二醇單甲基醚、四氫呋喃、 1，4-二噁烷、甲基乙基酮、甲基異丁基酮、甲醇、乙醇、 η-丙醇、異丙醇、η-丁醇、異丁醇、tert-丁醇、N，N-二甲基甲醯胺、Ν,Ν-二甲基乙醯胺、N-甲基-2-吡咯烷酮等。於有機溶劑之存在下進行本發明之聚合反應時，相對於前述單體Α之1質量份的前述有機溶劑之質量，一般爲 5至120質量份，較佳爲10至110質量份》聚合反應係於常壓、加壓密閉下，或減壓下進行，就裝置及操作之簡便性較佳於常壓下進行。又，較佳於N2 等之不活性氣體環境下進行。聚合溫度可爲反應混合物之沸點以下之任意溫度，但就聚合效率與調節分子量之觀點，較佳爲50°C以上200。(：以下，又以80°C以上150°C以下爲佳，更佳爲80°C以上 i30°C以下。 -23- 201235369 反應時間會因反應溫度，及單體A、單體B、單體c 、單體E及聚合起始劑D之種類與比例、聚合溶劑種等而變動，無法一槪而定，但較佳爲30分鐘以上720分鐘以下更佳爲40分鐘以上540分鐘以下。聚合反應結束後，以任意之方法回收所得之含氟高分支聚合物，必要時進行洗淨等之後處理。由反應溶液回收高分子之方法如，再沈澱等之方法。本發明之含氟高分支聚合物藉由凝膠滲透色譜法以聚苯乙烯換算測得之重量平均分子量（Mw)爲1，〇〇〇至400,000，較佳爲 2,000 至 200,000。 <表面改質劑及光陽離子聚合性樹脂組成物> 本發明之含氟高分支聚合物適用爲光陽離子聚合性樹脂之表面改質劑，該表面改質劑也爲本發明之對象。又，本發明係有關含有前述之（a)含氟高分支聚合物，及（b)光陽離子聚合性樹脂預聚物之光陽離子聚合性樹脂組成物。 [(b)光陽離子聚合性樹脂預聚物] 上述（b)光陽離子聚合性樹脂預聚物可爲，分子內具有 —個以上，較佳爲2至10個之光陽離子聚合性之部分的化合物無特別限制。又，本發明之預聚物含義爲，非所謂高分子物質之化合物，但非僅爲狹義之單體化合物（單體），也包含二聚物' 三聚物、低聚物及反應性高分子》 -24- 201235369 上述具有光陽離子聚合性之部位之化合物如，具葙環氧基及環氧丙烷環等之環狀醚構造、乙烯醚構造及乙烯基硫醚構造等之化合物。該等化合物之中較佳爲，具有至少1個脂環式環氧基之化合物，例如具有至少1個環氧環己烷環 '環氧環戊烷環等之化合物。該類（b)光陽離子聚合性樹脂預聚物如，雙（2,3-環氧環戊基）醚、1,2-雙（2,3-環氧環戊氧基）乙烷、3,4-環氧-6-甲基環己基3’，4’-環氧-6-甲基環己烷羧酸酯、二（3,4·環氧環己基甲基）己二醇酯、二（3,4-環氧-6-甲基環己基甲基）己二醇酯、伸乙基雙（3，4-環氧環己烷羧酸酯）、乙二醇二 (3，4-環氧環己基甲基）醚、乙烯基環己烯二氧化物、二環戊二烯二環氧化物、2-(3,4-環氧環己基-5,5-螺-3,4-環氧）環己烷-1，3-二噁烷、2,2，-雙（3,4-環氧環己基）丙烷、3,4-環氧環己基甲基3’，4，·環氧環己烷羧酸酯、1,2:8,9-二環氧檸檬烯、環氧化丁烷四羧酸四（3-環己烯基甲基）修飾ε-己內酯、3-乙基-3-羥基甲基環氧丙烷、3-(甲基）烯丙氧基甲基-3-乙基環氧丙烷、（3-乙基-3-環氧丙烷基甲氧基）甲基苯、4-氟-[1_(3_乙基_3_環氧丙烷基甲氧基）甲基]苯、4_甲氟基-Π-(3-乙基-3-環氧丙烷基甲氧基）甲基]苯、[丨-㈠-乙基_ 3_環氧丙烷基甲氧基）乙基]苯基醚、異丁氧基甲基（3 _乙基-3-環氧丙烷基甲基）醚、異冰片氧基乙基（3_乙基_3_環氧丙烷基甲基）醚、異冰片基（3 -乙基-3 -環氧丙烷基甲基）醚、2 -乙基己基（3 -乙基-3-環氧丙烷基甲基）醚、乙基二乙二 -25- 201235369 醇（3-乙基-3-環氧丙烷基甲基）醚、二環戊二烯（3-乙基·3-環氧丙烷基甲基）醚、二環戊烯氧基乙基（3_乙基-3-環氧丙烷基甲基）醚、二環戊烯基（3-乙基-3-環氧丙烷基甲基）醚、四氫糠基（3 -乙基-3 -環氧丙烷基甲基）醚、四溴苯基（3 -乙基-3-環氧丙烷基甲基）醚、2-四溴苯氧基乙基（3·乙基-3-環氧丙烷基甲基）醚、三溴苯基（3-乙基-3-環氧丙烷基甲基）醚、2-三溴苯氧基乙基（3-乙基-3-環氧丙烷基甲基）醚、2-羥基乙基（3-乙基-3-環氧丙烷基甲基）醚、2-羥基丙基（3-乙基-3-環氧丙烷基甲基）醚、丁氧基乙基（3-乙基-3·環氧丙烷基甲基）醚、五氯苯基（3-乙基-3-環氧丙烷基甲基）醚、五溴苯基（3-乙基-3-環氧丙烷基甲基）醚、冰片基（3-乙基-3· 環氧丙烷基甲基）醚、三環氧甲烷、3，3·二甲基環氧丙烷、 3，3-二氯甲基環氧丙烷、3,3-[1,4-伸苯基雙（環氧甲烷伸甲基）]雙（3-乙基環氧丙烷）、3-乙基-3-羥基甲基環氧丙烷、雙[U-乙基（3-環氧丙烷）甲基）]醚等。本發明之光陽離子聚合性樹脂組成物中，（a)含氟高分支聚合物及（b)光陽離子聚合性樹脂預聚物之添加量如下所述。即，相對於（b)預聚物之質量，（a)含氟高分支聚合物較佳爲0 · 0 0 1質量％至2 0質量％，特別是0.0 0 5質量％至 15質量％，更佳爲〇.〇1質量％至1〇質量％。 [(c)光酸發生劑] 本發明之光陽離子聚合性樹脂組成物爲，另含有（c)光酸發生劑所得。 -26- 201235369 上述（C)光酸發生劑可爲，藉由照射光可直接或間接發生酸之物無特別限定，例如磺酸化合物及其他之磺酸衍生物、二偶氮甲烷化合物、鑰鹽化合物、磺醯亞胺化合物、二楓系化合物、硝基卡基化合物、苯偶因對甲苯磺酸鹽化合物、鐵芳烴化合物、含有鹵系之三化合物、乙醯苯衍生物化合物及含有氰基之肟磺酸鹽化合物等。本發明適用先前已知或先前所使用之任何光酸發生劑，無特別限定。 (C)成分之光酸發生劑可一種單獨使用，或二種以上組合使用。光酸發生劑之具體例如下所述。該等化合物爲極多數適用之光酸發生劑中之一例，當然非限定爲該等。 -27- 201235369 【化61[Monomer CJ In the present invention, a monomer having at least one photocationic polymerizable group and at least one radical polymerizable double bond selected from the group consisting of an alicyclic epoxy group and an oxypropylene group in the molecule; C is preferably 'having either or both of a vinyl group or a (meth)acryl group, and particularly preferably a compound represented by the above formula [3] or a compound represented by the formula [4]. Such monomers C are as follows: 2,3-epoxy 201235369 cyclopentyl, 3,4·epoxycyclohexyl, 3,4-epoxy-1-hydroxycyclohexyl, 3, having a photocationic polymerizable group. 4-epoxy-6-methylcyclohexyl alicyclic epoxy group; 3· propylene oxide group, 3-methyl-3-epoxypropane group, 3-ethyl-3-epoxypropane group A compound such as an oxypropylene group. In particular, the compound represented by the above formula [3] is, for example, 2,3-epoxycyclopentylmethyl (meth) acrylate, 3,4 epoxycyclohexyl (meth) acrylate, 3, 4· Epoxycyclohexylmethyl (meth) acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth) acrylate, 2-(3,4-epoxycyclohexyl)-2-hydroxyl Ethyl (meth) acrylate, etc. Further, a compound represented by the above formula [4], for example, (3-methyl propylene oxide-3-yl)methyl (meth) acrylate, (3-ethyl ring) Oxypropan-3-yl)(meth)acrylate, (propylene oxide-3-yl)methyl(meth)acrylate, (3-ethylepoxypropan-3-yl)methyl (methyl) Acrylate or the like. In the present invention, the amount of the monomer C used is preferably from 10 to 300 in terms of the reactivity and the dispersibility with respect to the photocationic curable resin with respect to the monomer A. Molar%, especially 20 to 200 mol%, more preferably 30 to 150 mol%. [Polymerization Initiator D] The polymerization initiator D of the present invention is preferably an azo polymerization initiator. The azo polymerization initiator is a compound represented by the following (1) to (6). (1) Azoonitrile compound: 2,2'-azobisisobutyronitrile, 2,2,-azobis(2-methylbutyronitrile), 2,2,_azo-18- 201235369 double ( 2,4-Dimethylvaleronitrile), 1,1,-azobis(1_cyclohexanecarbonitrile), 2,2'-azobis(4-methoxy-2,4-dimethyl Valeronitrile), 2-(aminoformamidine azo)isobutyronitrile, etc.; (2) Azoguanamine compound: 2,2,-azobis{2-methyl-N-[l,l-double (transmethyl)_2_transethylethyl]propanamine}, 2,2,-azobis{2-methyl-N-[2-(l-butylidene)]propanamide} , 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide], 2,2'-diox bis[N-(2-propenyl)-2-methyl Propionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropanamide (3) Cyclic azo compound: 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis [ 2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2- Propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane Alkane], 2,2'-azobis(1-imino-1-pyrrolyl-2-methylpropane) dihydrochloride, etc.; (4) azo hydrazine compound: 2,2'-azo Bis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate; (5) Others: 2,2'-dimethyl azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), -19- 201235369 2,2'-azobis (2,4,4 -trimethylpentane), 1,1'-azobis(1-ethenyloxy-1-phenylethane), dimethyl 1,1'-azobis(1-cyclohexanecarboxylate Acid ester), 4,4'-azobis(4-cyanovaleric acid), and the like. (6) Azo-based polymerization initiator containing a fluoroalkyl group: 4,4'-azobis(2-cyanomethyl)ethyl 4-cyanopentanoate, 4,4'-azo Bis(4-(perfluorobutyl)ethyl 4-cyanopentanoate), 4,4'-azobis(2-(perfluorohexyl)ethyl 4-cyanopentanoate), and the like. Among the above azo-based polymerization initiators, 2,2'-azobis(2-methylbutyronitrile) and 2,2'-couple are preferred from the viewpoint of dispersibility with respect to the photocationic curable resin. Dimethyl bis-isobutyrate or dimethyl 1,1'-azobis(1-cyclohexanecarboxylate), particularly preferably dimethyl 1,1'-azobis (1·cyclohexyl) Alkyl carboxylate). The polymerization initiator D is used in an amount of 5 to 200 mol%, preferably 20 to 200 mol%, more preferably 20 to 100 mol%, based on the mole number of the monomer A. . [Monomer E] The fluorine-containing highly branched polymer of the present invention may contain, in addition to the above-mentioned monomer A, monomer B and monomer C, a compound represented by the above formula [5] of monomer E, that is, intramolecular A monomer having an alkyl group having 6 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms and a (meth)acrylic group. By containing the monomer e, surface modification property such as excellent mold release property can be imparted to the coating film obtained from the resin composition containing the fluorine-containing highly branched polymer of the present invention. The aforementioned alkyl group having 6 to 30 carbon atoms is, for example, hexyl, ethylhexyl, -20-201235369 3,5,5-trimethylhexyl, heptyl, octyl, 2-octyl, isooctyl, fluorenyl , mercapto, isooctyl, undecyl, lauryl, tridecyl, tetradecyl, palmitoyl, stearyl, isostearyl, eicosyl, docosane Base, tetracosyl, dihexadecyl, octadecyl, tridecyl and the like. Among them, the number of carbon atoms of the alkyl group is preferably from 10 to 30, more preferably from 16 to 24, from the viewpoint of surface modification. The aforementioned alicyclic group having 3 to 30 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, isobornyl, norbornenyl, yl, adamantane Base, three rings [5.2.1.02'6] thiol and the like. Among them, from the viewpoint of surface modification effect, an alicyclic group having 3 to 14 carbon atoms is preferred, and an alicyclic group having 6 to 12 carbon atoms is more preferred. Such monomers E are, for example, hexyl (meth) acrylate, ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, heptyl (meth) acrylate , octyl (meth) acrylate, 2-octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate ' Mercapto (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate 'palmityl (meth) acrylate, hard Lipid (meth) acrylate, isostearyl oxime (meth) acrylate, behenyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate Ester, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornene ( Methyl) acrylate, methacrylate, adamantyl (meth) propylene-21 - 201235369 Ester, tricyclo [5.2.1.02'6] decane (meth) acrylate. These monomers E may be used singly or in combination of two or more. In the present invention, the use amount of the monomer E is preferably from 5 to 300% by mole, particularly from 10 to 150 moles, per mole of the use of the monomer A in terms of reactivity and surface modification effect. The amount of ear %. <Production Method of Fluorinated High-branched Polymer> The fluorine-containing high-branched polymer of the present invention is obtained by using the monomer A, the monomer B, the monomer C, and the desired monomer E The monomer A is obtained by polymerization in the presence of a certain amount of the polymerization initiator D. The polymerization method may be a known method such as solution polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, etc., among which solution polymerization or sedimentation is preferred. Stimulate polymerization. In particular, the method of controlling the molecular weight is preferably carried out by solution polymerization in an organic solvent. Further, the method for producing a fluorine-containing highly branched polymer is also the object of the present invention. The organic solvent used at this time is an aromatic hydrocarbon solvent such as benzene, toluene, xylene, ethylbenzene or tetralin; An aliphatic or alicyclic hydrocarbon solvent such as hexane, η-heptane, mineral spirits or cyclohexane; methyl chloride, methyl bromide, methyl iodide, methyl dichloride, chloroform, carbon tetrachloride, three a halogenated solvent such as vinyl chloride, perchloroethylene or dichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate Esters or ester ether solvents such as ester, propylene glycol monomethyl ether acetate, etc.: diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl solution-22-201235369 An ether solvent such as butyl cellosolve or propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone or cyclohexanone; methanol; An alcohol solvent such as ethanol, η-propanol, isopropanol, η-butanol, isobutanol, tert-butanol, 2-ethylhexanol, benzyl alcohol or ethylene glycol; N, N - a guanamine solvent such as dimethylformamide or N,N-dimethylethenamine: an hydrazine solvent such as dimethyl hydrazine; and a heterocyclic ring such as N-methyl-2-pyrrolidone The compound is a solvent, and a mixed solvent of two or more of these. Among these, an aromatic hydrocarbon solvent, a halogen solvent, an ester solvent, an ether solvent, a ketone solvent, an alcohol solvent, a guanamine solvent, or the like is preferable, and benzene, toluene, xylene, and the like are particularly preferable. Dichlorobenzene, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Methanol, ethanol, η-propanol, isopropanol, η-butanol, isobutanol, tert-butanol, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, N -methyl-2-pyrrolidone and the like. When the polymerization reaction of the present invention is carried out in the presence of an organic solvent, the mass of the organic solvent is usually from 5 to 120 parts by mass, preferably from 10 to 110 parts by mass, based on 1 part by mass of the mass of the monomer. It is carried out under normal pressure, pressure tightness, or under reduced pressure, and the simplicity of the apparatus and operation is preferably carried out under normal pressure. Further, it is preferably carried out in an inert gas atmosphere such as N2. The polymerization temperature may be any temperature below the boiling point of the reaction mixture, but from the viewpoint of polymerization efficiency and molecular weight adjustment, it is preferably 50 ° C or more. (: The following is preferably 80 ° C or more and 150 ° C or less, more preferably 80 ° C or more and i30 ° C or less. -23- 201235369 Reaction time will be due to reaction temperature, and monomer A, monomer B, single The type and ratio of the body c, the monomer E and the polymerization initiator D, and the type of the polymerization solvent may vary depending on the type, and it is preferably 30 minutes or more and 720 minutes or less, more preferably 40 minutes or more and 540 minutes or less. After the completion of the polymerization reaction, the obtained fluorine-containing high-branched polymer is recovered by any method, and if necessary, it is washed and the like, and the method of recovering the polymer from the reaction solution, for example, reprecipitation or the like. The branched polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography in terms of polystyrene of 1, 〇〇〇 to 400,000, preferably 2,000 to 200,000. < Surface modifier and photocationic polymerization Resin Composition> The fluorine-containing highly branched polymer of the present invention is suitably used as a surface modifier of a photocationic polymerizable resin, and the surface modifier is also an object of the present invention. Further, the present invention relates to the above ( a) Fluorinated high-branched polymerization And (b) a photocationic polymerizable resin composition of the photocationic polymerizable resin prepolymer. [(b) Photocationic polymerizable resin prepolymer] The (b) photocationic polymerizable resin prepolymer may be The compound having one or more, preferably 2 to 10, photocationic polymerizable moieties in the molecule is not particularly limited. Further, the prepolymer of the present invention means a compound which is not a so-called high molecular substance, but not only a monomer compound (monomer) in a narrow sense also contains a dimer 'trimer, oligomer, and reactive polymer>> -24-201235369 The above compound having a photocationic polymerizable moiety, such as an anthracene epoxy group And a compound such as a cyclic ether structure such as a propylene oxide ring, a vinyl ether structure or a vinyl sulfide structure. Among these compounds, a compound having at least one alicyclic epoxy group, for example, at least a compound such as an epoxycyclohexane ring, an epoxycyclopentane ring, etc. (b) a photocationic polymerizable resin prepolymer such as bis(2,3-epoxycyclopentyl)ether, 1, 2-bis(2,3-epoxycyclopentyloxy)ethane, 3,4-epoxy- 6-Methylcyclohexyl 3',4'-epoxy-6-methylcyclohexanecarboxylate, bis(3,4.epoxycyclohexylmethyl)hexanediol, bis(3,4- Epoxy-6-methylcyclohexylmethyl)hexanediol, ethyl bis(3,4-epoxycyclohexanecarboxylate), ethylene glycol bis(3,4-epoxycyclohexyl Ether, vinyl cyclohexene dioxide, dicyclopentadiene diepoxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Alkano-1,3-dioxane, 2,2,-bis(3,4-epoxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl 3',4,·epoxycyclohexanecarboxylate Acid ester, 1,2:8,9-diepoxy limonene, epoxidized butane tetracarboxylic acid tetrakis(3-cyclohexenylmethyl) modified ε-caprolactone, 3-ethyl-3-hydroxyl Propylene oxide, 3-(methyl)allyloxymethyl-3-ethyl propylene oxide, (3-ethyl-3-epoxypropenylmethoxy)methylbenzene, 4-fluoro- [1_(3_Ethyl_3_epoxypropenylmethoxy)methyl]benzene, 4-methylfluoro-indole-(3-ethyl-3-epoxypropenylmethoxy)methyl] Benzene, [丨-(i)-ethyl_3_epoxypropenylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3 _ B -3-Epoxypropanemethyl)ether, isobornyloxyethyl (3-ethyl-3-cyclopropenylmethyl)ether, isobornyl (3-ethyl-3-epoxypropanyl) Methyl)ether, 2-ethylhexyl(3-ethyl-3-epoxypropanemethyl)ether, ethyldiethylenedi-25- 201235369 alcohol (3-ethyl-3-epoxypropane group A) Ether, dicyclopentadiene (3-ethyl·3-epoxypropanemethyl)ether, dicyclopentenyloxyethyl (3-ethyl-3-epoxypropanemethyl)ether , dicyclopentenyl (3-ethyl-3-epoxypropanemethyl)ether, tetrahydroindenyl (3-ethyl-3-epoxypropanemethyl)ether, tetrabromophenyl (3 -ethyl-3-epoxypropanemethyl)ether, 2-tetrabromophenoxyethyl (3·ethyl-3-epoxypropanemethyl)ether, tribromophenyl (3-ethyl -3-Ethoxypropenylmethyl)ether, 2-tribromophenoxyethyl (3-ethyl-3-epoxypropanemethyl)ether, 2-hydroxyethyl (3-ethyl-3) -Epoxypropanemethyl)ether, 2-hydroxypropyl(3-ethyl-3-epoxypropanemethyl)ether, butoxyethyl (3-ethyl-3. propylene oxide) Ether, pentachlorophenyl (3-ethyl-3- Propylene oxide methyl)ether, pentabromophenyl (3-ethyl-3-epoxypropanemethyl)ether, borneol (3-ethyl-3. propylene oxide methyl) ether, three Methylene oxide, 3,3·dimethyl propylene oxide, 3,3-dichloromethyl propylene oxide, 3,3-[1,4-phenylene bis(ethylene oxide methyl) methyl (3-ethyl propylene oxide), 3-ethyl-3-hydroxymethyl propylene oxide, bis [U-ethyl (3- propylene oxide) methyl)] ether, and the like. In the photocationic polymerizable resin composition of the present invention, the amounts of (a) the fluorine-containing highly branched polymer and (b) the photocationic polymerizable resin prepolymer are as follows. That is, the (a) fluorine-containing highly branched polymer is preferably from 0. 01% by mass to 20% by mass, particularly from 0.05% by mass to 15% by mass, based on the mass of the (b) prepolymer. More preferably, it is 1% by mass to 1% by mass. [(c) Photoacid generator] The photocationic polymer resin composition of the present invention is obtained by further containing (c) a photoacid generator. -26- 201235369 The above (C) photoacid generator may be one which can directly or indirectly generate an acid by irradiation with light, such as a sulfonic acid compound and other sulfonic acid derivatives, a diazomethane compound, and a key. a salt compound, a sulfonimide compound, a bismuth compound, a nitrocarbyl compound, a benzoin p-toluenesulfonate compound, an iron arene compound, a halogen-containing compound, an acetophenone derivative compound, and a cyanide-containing compound Base sulfonate compounds and the like. The present invention is applicable to any photoacid generator previously known or previously used, and is not particularly limited. The photoacid generator of the component (C) may be used singly or in combination of two or more. Specific examples of the photoacid generator are as follows. These compounds are one of the most suitable photoacid generators, and are of course not limited thereto. -27- 201235369

式⑴ 0 0Formula (1) 0 0

N-O-f-O- 式(2) y cf3 式⑶ l!N-O-f-O- (2) y cf3 (3) l!

式（4>Formula (4>

二苯基碘鐺氯化物、二苯基碘鑰三氟甲烷磺酸鹽、二苯基碘鑰甲磺酸鹽、二苯基碘鑰甲苯磺酸鹽、二苯基碘鑰溴化物、二苯基碘鐵四氟硼酸鹽、二苯基碘鑰六氟銻酸鹽、二苯基碘鑰六氟砷酸鹽、雙（p-tert-丁基苯基）碘鑰六氟磷酸鹽、雙（p-tert-丁基苯基）碘鐺甲磺酸鹽、雙（p-tert-丁基苯基）碘鑰甲苯磺醯鹽、雙（P-tert-丁基苯基）碘鑰三氟甲烷磺酸鹽、雙（p-tert-丁基苯基）碘鑰四氟硼酸鹽、雙（p-tert-丁 -28- 201235369 基苯基）碘鑰氯化物、雙（Ρ·氯苯基）碘鑰氯化物苯基）碘鑰四氟硼酸鹽、三苯基硫鐺氯化物、三溴化物、三苯基硫鑰三氟甲烷磺酸鹽、雙（P-甲；硫鑰四氟硼酸鹽、三（P-甲氧基苯基）硫鑰六氟膦 (P-乙氧基苯基）硫鑰四氟硼酸鹽、三苯基鐵氯化基錢溴化物、三（P-甲氧基苯基）鍈四氟硼酸鹽、基苯基）鱗六氟膦酸鹽、三（P-乙氧基苯基）鱗四氟、雙（P-氯苯基硫鑰氧基苯基）酸鹽、三物、三苯三（P-甲氧硼酸鹽、Diphenyl iodonium chloride, diphenyl iodine trifluoromethane sulfonate, diphenyl iodine mesylate, diphenyl iodine toluene sulfonate, diphenyl iodine bromide, diphenyl Iodine iron tetrafluoroborate, diphenyl iodine hexafluoroantimonate, diphenyl iodine hexafluoroarsenate, bis(p-tert-butylphenyl) iodine hexafluorophosphate, double P-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodotoluenesulfonate, bis(P-tert-butylphenyl)iodotrifluoromethane Sulfonic acid salt, bis(p-tert-butylphenyl) iodine tetrafluoroborate, bis(p-tert-butyl-28- 201235369 phenyl) iodine chloride, bis(indenyl chlorophenyl) Iodine chloride phenyl) iodine tetrafluoroborate, triphenylsulfonium chloride, tribromide, triphenylsulfonyl trifluoromethanesulfonate, bis (P-methyl; sulphur tetrafluoroborate) , tris(P-methoxyphenyl)sulfide hexafluorophosphine (P-ethoxyphenyl) sulfonate tetrafluoroborate, triphenyl iron chlorohydrin bromide, tris(P-methoxyl) Phenyl) guanidine tetrafluoroborate, phenyl) hexafluorophosphonate, tris(P-ethoxyl) Phenyl) quaternary tetrafluoro, bis(P-chlorophenylthioloxyphenyl) acid salt, tris, triphenyl tris(P-methoxyborate,

OH OHOH OH

201235369 【化8】201235369 【化8】

Q|jLf〇式(i"〇jxf〇^(16)Q|jLf〇 (i"〇jxf〇^(16)

-30- 201235369 【化9】-30- 201235369 【化9】

e_ •r-J -31 - 201235369 【化1 〇 i r\E_ •r-J -31 - 201235369 【化1 〇 i r\

32 201235369 【化1 1】32 201235369 【化1 1】

/式(42)/式(42)

0 -〇4 -0^9 式（43)0 -〇4 -0^9 (43)

式(44> 式州(44> state

33- 201235369 【化1 2】33- 201235369 【化1 2】

-34- 201235369-34- 201235369

【化1 3 I[1 1 I

-35- 201235369 【化1 41-35- 201235369 【化1 41

其中較佳爲鑰鹽，具體例如，苯基二氮鑰六氟磷酸鹽、4-甲氧基苯基二氮鑰六氟銻酸鹽、4-甲氧苯基二氮鑰六氟磷酸鹽等之芳基二氮鎰鹽；二苯基碘鑰六氟銻酸鹽、二 (4-甲基苯基）碘鑰六氟磷酸鹽、二（4-tert-丁基苯基）碘鐵六氟磷酸鹽等之二芳基碘鑰鹽；三苯基硫鑰六氟銻酸鹽、三 (4-甲氧基苯基）硫鐵六氟磷酸鹽、二苯基-4-硫苯氧基苯基硫鍚六氟銻酸鹽、二苯基-4-硫苯氧基苯基硫鐺六氟磷酸鹽、4,4’ -雙（二苯基suruhonio)苯基硫化物雙六氟鍊酸鹽、 4,4’-雙（二苯基suruhonio)苯基硫化物雙六氟磷酸鹽、4,4’- -36- 201235369 雙[二（/3-羥基乙氧基）苯基suruhonio]苯基硫化物雙六氟銻酸鹽、4,4’-雙[二（冷-羥基乙氧基）苯基suruhonio]苯基硫化物雙六氟磷酸鹽、4-[4’-(苯醯）苯硫基]苯基二（4-氟苯基）硫鑰六氟銻酸鹽、4-[4’-(苯醯）苯硫基]苯基二（4_氟苯基）硫鎗六氟磷酸鹽等之三芳基硫鑰鹽等。上述之鎗鹽衍生物可由市售品取得，例如，C PI -1 0 0 P 、CPI-100A、CPI-200K、CPI-200S(以上爲山普洛（股）製）、亞當卡3?-150、8?-151、3?-170、3?-171(以上爲八〇£反八( 股）製、Irgacure261(BASF公司（舊吉巴斯公司）製）等。前述（c)光酸發生劑相對於前述（b)光陽離子聚合性樹脂預聚物係使用〇·〇5至30質量％之量，較佳爲〇.1至20 質量％之量，更佳爲0.1至10質量％之量。 [其他添加物] 又’本發明之光陽離子聚合性樹脂組成物於無損本發明之效果下，必要時可適當添加一般所添加之添加劑，例如，光增感劑、聚合禁止劑 '聚合起始劑、塗平劑、表面活性劑、密合性賦予劑、可塑劑、紫外線吸收劑、防氧化劑、貯藏安定劑、防靜電劑、無機塡充劑、顏料、染料等。又必要時可混合溶劑。 <硬化物> 將本發明之光陽離子聚合性樹脂組成物塡入一定之模具後’藉由光聚合（硬化）可得硬化物。較佳於光聚合後藉 -37- 201235369 由後烘烤，具體上可使用熱板、烤箱等加熱而完成聚合。由此而得之主體（成型品）之厚度，於乾燥、硬化後一般爲0.02至10mm，較佳爲0.5至5mm。本發明之光陽離子聚合性樹脂組成物又可藉由包覆於基材上後進行光聚合（硬化），形成硬化膜及層合體等之硬化物（成型品）。此時之前述基材如，塑料（聚碳酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚酯、聚烯烴、環氧、三聚氰胺、三乙醯纖維素、AB S、A S、降冰片烯系樹脂等）、金屬、木材、紙、玻璃、石板等。該等基材之形狀可爲板狀、薄膜狀或 3次元成型體。包覆於前述基材上之方法可適當選擇鑄覆法、旋覆法、刮覆法、浸覆法、輥覆法、棒覆法、模頭覆法、噴墨法、印刷法（凸版 '凹版、平版、網版印刷等）等，其中較佳爲使用’具有可短時間塗佈而可利用揮發性較高之溶液，且可進行塗佈均勻性較高之優點之旋覆法。又以事前使用孔徑爲〇.2μιη之濾器等過濾光陽離子聚合性樹脂組成物後，再供給包覆用爲佳。又包覆時’必要時可將溶劑加入該樹脂組成物中形成漆形態’例如使用丙酮、四氫呋喃（THF)、甲苯、Ν，Ν-二甲基甲醯胺（DMF)、環己酮、丙二醇單甲基醚（PGME)、丙二醇單甲基醚乙酸酯（PGM EA)、丙二醇單乙基醚、乳酸乙酯、二乙二醇單乙基醚、丁基溶纖劑、丁內酯等之溶劑形成漆形態。 -38- 201235369 包覆後較佳爲，其次以熱板或烤箱等預先乾燥後，照射紫外線等之活性光線而光硬化。活性光線如，紫外線、電子線、X線等。紫外線照射用之光源可使用太陽光、化學燈、低壓水銀燈、高壓水銀燈、金屬鹵素燈、氙燈等。其後藉由後烘烤，具體上可使用熱板、烤箱等加熱以結束聚合。包覆所得之膜之厚度於乾燥、硬化後一般爲0.01至 5〇μηι，較佳爲 0.05 至 2.0μιη。本發明之硬化物如前述爲，比較硬化物內部（深部），前述含氟高分支聚合物多半係存在於硬化物表面（界面）之狀態。因此可形成，相對於硬化物製作時所使用之混合、成型機械等之各種機械及模具具有優良離模性，及相對於薄膜等之其他樹脂成型品具有優良剝離性等，具有優良之撥水撥油性、防污性之硬化物。【實施方式】 [實施例] 下面將舉實施例更具體說明本發明，但本發明非限定於下述實施例。又，實施例中調製試料及分析物性用之裝置及條件如下所述。 (1)凝膠滲透色譜法（GPC)Preferably, it is a key salt, and specific examples thereof include phenyldiazepine hexafluorophosphate, 4-methoxyphenyldiazepine hexafluoroantimonate, 4-methoxyphenyldiazepine hexafluorophosphate, and the like. Aryl diazonium salt; diphenyl iodine hexafluoroantimonate, bis(4-methylphenyl) iodine hexafluorophosphate, bis(4-tert-butylphenyl) iodine hexafluorophosphate Diaryl iodine salt of phosphate, etc.; triphenyl sulfonium hexafluoroantimonate, tris(4-methoxyphenyl) sulphur iron hexafluorophosphate, diphenyl-4-thiophenoxybenzene Thiosulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4,4'-bis(diphenylsuruhonio)phenyl sulfide dihexafluorocarbonate , 4,4'-bis(diphenyl suruhonio) phenyl sulfide bis hexafluorophosphate, 4,4'- -36- 201235369 bis [bis(/3-hydroxyethoxy)phenyl suruhonio] phenyl Sulfide bishexafluoroantimonate, 4,4'-bis[di(col-hydroxyethoxy)phenyl suruhonio]phenyl sulfide bishexafluorophosphate, 4-[4'-(benzoquinone)benzene Thio]phenylbis(4-fluorophenyl)sulfide hexafluoroantimonate, 4-[4'-(benzoquinone)phenylthio]phenyldi(4-fluorophenyl) Sulfur gun hexafluorophosphate of triarylsulfonium salts keys. The above-mentioned gun salt derivatives can be obtained from commercially available products, for example, C PI -1 0 0 P, CPI-100A, CPI-200K, CPI-200S (above is Samprao), Adamka 3?- 150, 8?-151, 3?-170, 3?-171 (above is the eight-inch anti-eight (share) system, Irgacure261 (manufactured by BASF Corporation (old Gibbs)), etc. The aforementioned (c) photoacid The amount of the generator is from 5 to 30% by mass, preferably from 0.1 to 20% by mass, more preferably from 0.1 to 10% by mass, based on the above (b) photocationic polymerizable resin prepolymer. [Other Additives] Further, the photocationic polymerizable resin composition of the present invention can be appropriately added with a conventionally added additive, for example, a photosensitizer or a polymerization inhibitor, without impairing the effects of the present invention. a polymerization initiator, a coating agent, a surfactant, an adhesion imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic chelating agent, a pigment, a dye, etc., if necessary The solvent can be mixed. <Cured product> After the photocationic polymer resin composition of the present invention is poured into a certain mold The cured product can be obtained by photopolymerization (hardening). It is preferably post-baked by -37-201235369 after photopolymerization, and specifically by heating using a hot plate, an oven or the like to complete the polymerization. The thickness of the product is generally 0.02 to 10 mm, preferably 0.5 to 5 mm after drying and hardening. The photocationically polymerizable resin composition of the present invention can be photopolymerized (hardened) by coating on a substrate. Forming a cured product (molded article) such as a cured film and a laminate. The aforementioned substrate such as plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine) , triacetyl cellulose, AB S, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, etc. The shape of the substrates may be a plate shape, a film shape or a ternary molded body. The method of coating on the substrate may be selected by a casting method, a spin coating method, a doctoring method, a dipping method, a roll coating method, a bar coating method, a die coating method, an inkjet method, and a printing method (embossing ' Gravure, lithography, screen printing, etc.), among which it is preferred to use 'There is a spin coating method which can coat a solution with a high volatility in a short time and which can take advantage of the high uniformity of coating. The photocationic polymerization property is filtered by a filter having a pore size of 〇.2μιη beforehand. After the resin composition, it is preferably supplied for coating. When coating, if necessary, a solvent may be added to the resin composition to form a lacquer form, for example, using acetone, tetrahydrofuran (THF), toluene, hydrazine, hydrazine-dimethyl Methylguanamine (DMF), cyclohexanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGM EA), propylene glycol monoethyl ether, ethyl lactate, diethylene glycol monoethyl The solvent of the base ether, butyl cellosolve, butyrolactone or the like forms a lacquer form. -38- 201235369 Preferably, after coating, it is pre-dried by a hot plate or an oven, and then photo-cured by irradiating active rays such as ultraviolet rays. Active light such as ultraviolet light, electronic wire, X-ray, etc. For the light source for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like can be used. Thereafter, by post-baking, specifically, heating using a hot plate, an oven or the like can be used to terminate the polymerization. The thickness of the film obtained by coating is usually from 0.01 to 5 μηηι, preferably from 0.05 to 2.0 μηη, after drying and hardening. As described above, the cured product of the present invention is such that the inside of the cured product (deep portion) is relatively large, and the fluorine-containing highly branched polymer is mostly present on the surface (interface) of the cured product. Therefore, it is possible to form an excellent water repellent property with respect to various machines and molds used for mixing and molding machines used in the production of a cured product, and excellent releasability with respect to other resin molded articles such as a film, and excellent water repellency. Hardened oily and antifouling. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the following Examples. Further, the apparatus and conditions for modulating the sample and analyzing the physical properties in the examples are as follows. (1) Gel Permeation Chromatography (GPC)

裝置：東索（股）製HLC-8220GPC -39- 201235369Device: Honda-8(GPC) -39-201235369

管柱：Shodex KF-804L > KF-805 L 管柱溫度：40°C 溶劑：四氫呋氫檢驗器：RI PVHNMR光譜及l3CNMR光譜裝置：日本電子（股）製JNM-ECA700 溶劑：CDC13 內部標準：四甲基矽烷 (3)離子色譜法（氟定量分析）裝置：日本戴歐那（股）製ICS-1500 溶劑：（2.7mmolNa2CO8 + 0.3mmolNaHCO3)/L 水溶液檢驗器：電器傳導度 (4)旋覆機裝置：密卡薩（股）製MS-A100 (5)橢圓對稱法（折射率及膜厚測定）裝置：J.A.Woollam 公司製 EC-400 (6)接觸角測定裝置：AST Products 公司製 VCA OptimaColumn: Shodex KF-804L > KF-805 L Column temperature: 40 ° C Solvent: Tetrahydrofuran tester: RI PVH NMR spectrum and l3C NMR Spectrometer: JNM-ECA700 manufactured by JEOL Ltd. Solvent: CDC13 internal Standard: Tetramethyl decane (3) ion chromatography (fluorine quantitative analysis) Device: ICS-1500, manufactured by Dionne, Japan Solvent: (2.7 mmol Na2CO8 + 0.3 mmol NaHCO3) / L Aqueous solution tester: Electrical conductivity (4 )Covering machine: MS-A100 manufactured by Mikhasas (5) Elliptical symmetry method (measurement of refractive index and film thickness) Device: EC-400 manufactured by JAWoollam Co., Ltd. (6) Contact angle measuring device: AST Products VCA Optima

測定溫度：2 0 °C -40- 201235369 測定法：測定5次將測定媒體滴在被測定表面上1 0秒後之接觸角，再以最大値及最小値除外之3値之平均値爲接觸角値。 (7) 玻璃化溫度（Tg)測定裝置：NETZSC Η公司製DSC204 FI Phoenix(登記商標）測定條件：氮環境下升溫速度1 : 30°C /分（25至20CTC )(實施例1、3、4、5、比較例1 ) 升溫速度2 : 5°C /分（25至160°C )(實施例2 '比較例2) 升溫速度3 : lOt /分（0至150°C )(實施例18至24) (8) 5 %重量減少時溫度（Td5%)測定裝置：里凱庫（股）製TG8120 測定條件：空氣環境下升溫速度：l〇°C /分（25至5 00 °C ) (9) UV照射裝置裝置：艾古拉（股）製H02-L4 1 強度：16mW/cm2( 3 65nm) (10) 濁度計器（濁度測定）裝置：日本電色工業（股）製NDH5000 又，代號之含義如下所述。 -41 - 201235369 DCP:三環[5.2.1.02’6]癸烷二甲醇二甲基丙烯酸酯[新中村化學工業（股）製DCP] EGDMA :乙二醇二甲基丙烯酸酯[新中村化學工業（股 )製 1G] C6FA : 2-(全氟己基）乙基丙烯酸酯[戴金工業（股）製 R-1620] 3FEA ： 2,2,2-三氟乙基丙烯酸酯[大阪有機化學工業（股）製V-3F] OXMA: (3-乙基環氧丙烷-3-基）甲基甲基丙烯酸酯[宇部興產（股）製耶塔那] CYM: 3，4-環氧環己基甲基甲基丙烯酸酯[戴歇爾（股）製賽庫洛-M100] GMA :縮水甘油基甲基丙烯酸酯[純正化學（股）製] STA :硬脂醯丙烯酸酯[大阪有機化學工業（股）製STA] ISTA :異硬脂醯丙烯酸酯[大阪有機化學工業（股）製 ISTA] LA :月桂基丙烯酸酯[大阪有機化學工業（股）製LA] BA :二十二烷基丙烯酸酯[新中村化學工業（股）製A-BH] DCHC :二甲基1，1’·偶氮雙（1-環己烷羧酸酯）[和光純藥工業（股）製VE-073] MAIB : 2,2’-偶氮雙異丁酸二甲酯[大塚化學（股）製 MAIB] AMBN : 2,2’-偶氮雙（2-甲基丁腈）[和光純藥工業（股）製 V-59] -42- 201235369 CEL202 1P: 3,4-環氧環己基3’，4’-環氧環己烷羧酸酯[. 戴歇爾（股）製歇洛吉202 1P] CEL3000: 1,2:8,9-二環氧檸檬烯[戴歇爾（股）製歇洛吉 3000] GT40 1 :環氧化丁烷四羧酸四（3_環己烯基甲酯）修飾 ε-己內酯[戴歇爾（股）製耶波里GT401] CPI-100P:二苯基（4-(苯硫基）苯基）硫鑰六氟磷酸鹽 (V)(山普洛（股）製CPI-100P) MIBK :甲基異丁基酮 PGME :丙二醇單甲基醚 DO : 1，4-二噁烷 [實施例1]合成高分支聚合物1 將MIBK 67g放入3 00mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度1 1 6°C )。Measurement temperature: 20 °C -40-201235369 Determination method: The contact angle of the measurement medium on the surface to be measured after 10 seconds was measured 5 times, and then the average 値 of 3 値 except the maximum 値 and the minimum 値 was contacted. Horns. (7) Glass transition temperature (Tg) measuring device: DSC204 FI Phoenix (registered trademark) manufactured by NETZSC Co., Ltd. Measurement conditions: Temperature increase rate in nitrogen environment: 30 °C / min (25 to 20 CTC) (Examples 1, 3, 4, 5, Comparative Example 1) Heating rate 2: 5 ° C / min (25 to 160 ° C) (Example 2 'Comparative Example 2) Temperature rising rate 3: lOt / min (0 to 150 ° C) (Example 18 to 24) (8) 5% reduction in temperature (Td5%) measuring device: TG8120 manufactured by Rikaiku (stock) Measurement conditions: heating rate in air environment: l〇°C / min (25 to 500 °C (9) UV irradiation device: H02-L4 manufactured by Egola (strand) 1 Intensity: 16mW/cm2 (3 65nm) (10) Turbidity meter (turbidity measurement) Device: Nippon Denshoku Industrial Co., Ltd. NDH5000 Again, the meaning of the code is as follows. -41 - 201235369 DCP: Tricyclo[5.2.1.02'6]decane dimethanol dimethacrylate [DCP manufactured by Shin-Nakamura Chemical Co., Ltd.] EGDMA: ethylene glycol dimethacrylate [Xinzhongcun Chemical Industry] (share) 1G] C6FA: 2-(perfluorohexyl)ethyl acrylate [R-1620 manufactured by Daikin Industries Co., Ltd.] 3FEA: 2,2,2-trifluoroethyl acrylate [Osaka Organic Chemical Industry (Stock) V-3F] OXMA: (3-Ethyloxypropan-3-yl)methyl methacrylate [Yutagen of Ube Industries Co., Ltd.] CYM: 3,4-epoxy ring Hexylmethyl methacrylate [Daischer (Secure) 赛库洛-M100] GMA: glycidyl methacrylate [made by pure chemical (stock)] STA: stearic acid acrylate [Osaka organic chemical industry (Stock) STA] ISTA: Isostearyl acrylate [ISTA, Osaka Organic Chemical Industry Co., Ltd.] LA: Lauryl acrylate [LA] made by Osaka Organic Chemical Industry Co., Ltd. BA: Twenty-second acrylic acid Ester [A-BH, manufactured by Shin-Nakamura Chemical Co., Ltd.] DCHC: dimethyl 1,1'-azobis(1-cyclohexanecarboxylate) [Wako Pure Chemical Industries Co., Ltd. VE-073] MAIB : 2,2'-even Dimethyl bis-butyrate [MAIB] manufactured by Otsuka Chemical Co., Ltd. AMBN : 2,2'-azobis(2-methylbutyronitrile) [Wako Pure Chemical Industries Co., Ltd. V-59] -42- 201235369 CEL202 1P: 3,4-epoxycyclohexyl 3',4'-epoxycyclohexanecarboxylate [.Daischer (single) shangluoji 202 1P] CEL3000: 1,2:8,9 - Diepoxy limonene [Daischer (stock) system Shuluji 3000] GT40 1 : epoxidized butane tetracarboxylic acid tetrakis(3-cyclohexenylmethyl ester) modified ε-caprolactone [Daischer ( ) 制耶 GT GT GT GT GT C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C Isobutyl ketone PGME : propylene glycol monomethyl ether DO : 1,4-dioxane [Example 1] Synthesis of high-branched polymer 1 MIBK 67 g was placed in a 300 mL reaction flask, and nitrogen was introduced for 5 minutes with stirring. , and then heated to the internal liquid reflux (about 1 1 6 ° C).

將 DCP 6.7g(20mmol)、C6FA 4.2g(10mmol)、OXMA 1 . 8g( 1 Ommol) ' DCHC 3.7g(12mmol)及 MIBK 67g 放入'另一 2 OOmL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，再將液溫加熱至約3 5 t。使用滴液唧筒以25分鐘由放入DCP、C6FA、OXMA 及DCHC之前述200mL之反應燒瓶中，將內容物滴入前述之300mL之反應燒瓶中回流下之MIBK中。滴液結朿後熟成1小時。其次使用旋轉蒸發器由該反應液餾去MIBK 45g後’ -43- 201235369 加入〇°C之甲醇465 g中使聚合物以淤漿狀態沈澱。減壓過濾該淤漿後真空乾燥，得白色粉末之目的物（高分支聚合物 l)7.5g(產率 47%)。所得之目的物之1H NMR及l3C NMR光譜如圖1及圖 2所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw爲3,700，分散度：Mw(重量平均分子量 )/Mn(數平均分子量）爲2.1。 [實施例2]合成高分支聚合物2. 將MIBK 67g放入3 00mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度1 1 6 °C )。將 DCP 6.7g(20mmol)、C6FA 4.2g(10mmol)、CYM 2.0g(10mmol)、DCHC 3.7g(12mmol)及 MIBK 74g 放入另一 2 OOmL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，再加熱使液溫至約3 5 °C。使用滴液唧筒以35分鐘由放入DCP、C6FA、CYM及 DCHC之前述200mL之反應燒瓶中，將內容物滴入前述 3 OOmL之反應燒瓶中回流下之MIBK中。滴液結束後熟成 1小時。其次使用旋轉蒸發器由該反應液餾去MIBK 61g後，加入〇°C之甲醇470g中使聚合物以淤漿狀態沈澱。減壓過濾該淤漿後真空乾燥，得白色粉末之目的物（高分支聚合物 2)9.9g(產率 73%)。所得之目的物之1HNMR及13CNMR光譜如圖3及圖 -44 - 201235369 4所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw爲5,300，分散度：Mw/Mn爲1.9。 [實施例3]合成高分支聚合物3 將MIBK 6 7g放入300mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度1 16°C )。將 DCP 6.7g(20mmol)、C6FA 4.2g(10mmol)、CYM 2.0g(10mmol)、MAIB 2.8g(12mmol)及 MIBK 67g 放入另一 2 OOmL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，再以冰浴冷卻至5°C。使用滴液唧筒以30分鐘由放入DCP、C6FA、CYM及 MAIB之前述200mL之反應燒瓶中，將內容物滴入前述 3 OOmL之反應燒瓶中回流下之MIBK中。滴液結束後熟成 1小時。其次使用旋轉蒸發器由該反應液餾去MIBK 5 8g後，加入己烷277g與乙醇44g之混合溶液中使聚合物沈澱，再傾析上層澄清液。使用MIBK 7g再溶解殘存之沈澱物’ 將該聚合物之MIBK溶液加入甲醇202g中使聚合物以淤漿狀態再沈澱。減壓過濾該派漿後真空乾燥’得白色粉末之目的物（高分支聚合物3)5.2g(產率41%)。所得之目的物之1H NMR及13c NMR光譜如圖5及圖 6所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw爲4,700，分散度：Mw/Mn爲1.6。 -45- 201235369 [實施例4]合成高分支聚合物4 將MIBK 67g放入30 0mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度1 1 6°C )。將 DCP 6.7g(20mmol)、C6FA 4.2g(10mmol)、CYM 2.0g(10mmol)、AMBN 2.5g(12mmol)及 MIBK 67g 放入另一 2 OOmL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，再以冰浴冷卻至。使用滴液啷筒以30分鐘由放入DCP ' C6FA、CYM及 AMBN之前述200mL之反應燒瓶中，將內容物滴入前述 300mL之反應燒瓶中回流下之MIBK中。滴液結束後熟成 1小時。其次使用旋轉蒸發器由反應液餾去MIBK 4 7g後，加入甲醇3 79g中使聚合物以淤漿狀態沈澱。減壓過濾該淤漿後真空乾燥，得白色粉末之目的物（高分支聚合物4)4.8g( 產率3 8 %)。所得之目的物之1H NMR及13C NMR光譜如圖7及圖 8所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw爲5,700，分散度：Mw/Mn爲2.0。 [實施例5]合成高分支聚合物5 將MIBK 40g放入200mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度1 1 6 °C )。將 EGDMA 4.0g(20mmol)、C6FA 4.2g(10mmol)、CYM 2.0g(10mmol)、M AIB 2.8 g (1 2 m mo 1)及 ΜIB K 4 0 g 放入另一 -46 - 201235369 1 0 OmL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，再以冰浴冷卻至5 °C。使用滴液唧筒以 40分鐘由放入 EGDMA、C6FA、 CYM及MAIB之前述200mL之反應燒瓶中，將內容物滴入前述200mL之反應燒瓶中回流下之MIBK中。滴液結束後熟成1小時。其次使用旋轉蒸發器由反應液餾去MIBK 3 3g後，加入甲醇2 84g中使聚合物以淤漿狀態沈澱。減壓過濾該淤漿後真空乾燥，得白色粉末之目的物（高分支聚合物5)6.Og( 產率5 9 %)。所得之目的物之1H NMR及13C NMR光譜如圖9及圖 10所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw爲6,700，分散度：Mw/Mn爲2.0。 [實施例18]合成高分支聚合物8 將MIBK 67g放入200mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度1 1 6 °C )。將 DCP 6.8g(20mmol)、C6FA 4.2g(10mmol)、C:YM 2.0g(10mmol)、S T A 3.3g(10mmol)、MAIB 2.8g(12mmol) 及MIBK 67g放入另一l〇〇mL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，室溫（17°C )下攪拌溶解各單體。使用滴液啣筒以45分鐘由放入DCP、C6FA、CYM、 STA及MAIB之前述i〇〇mL之反應燒瓶中，將內容物滴入前述200mL之反應燒瓶中回流下之MIBK中。滴液結束後 -47 - 201235369 熟成70分鐘》其次使用旋轉蒸發器由該反應液餾去MIBK 118g後，滴入〇°C之甲醇227g中使聚合物以淤漿狀態沈澱。減壓過濾該淤漿後真空乾燥，得透明玻璃狀固體之目的物（高分支聚合物8)11.6g(產率90%)。所得之目的物之13C NMR光譜如圖15所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw 爲 5,000，分散度：Mw/Mn 爲 1.7» [實施例19]合成高分支聚合物9 將MIBK 67g放入200mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度！丨6它）^ 將 DCP 6.8g(20mmol)、C6FA 4.2g(10mmol)、CYM 2.1 g(l 1 mmol) ' ISTA 3.3 g (1 〇 m m o 1) ' MAIB 2.8g(12mmol) 及MIBK 67g放入另一i〇〇mL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代’冰冷下（5 «c)攪拌溶解各單體。使用滴液啷筒以25分鐘由放入DCP、C6FA、CYM、 I S T A及M AIB之前述1 〇〇 m L之反應燒瓶中，將內容物滴入前述200mL之反應燒瓶中回流下之MIBK中。滴液結束後熟成90分鐘。其次使用旋轉蒸發器由該反應液餾去MIBK 116g後，滴入〇°C之甲醇203g中使聚合物以淤漿狀態沈澱。減壓過濾該浙獎後真空乾燥，得白色固體之目的物（高分支聚合物 9)7.6g(產率 59°/。）。 -48- 201235369 所得之目的物之13C NMR光譜如圖16所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw 爲 6,700，分散度：Mw/Mn 爲 2.2。 [實施例20]合成高分支聚合物10 將MIBK 67g放入200mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度1 1 6°C )。將 DCP 6.7g(20mmol) ' C6FA 4.2g(10mmol)、CYM 2.0 g (1 0 m m ο 1)、L A 2.4 g (1 0 m m ο 1).、M AIB 2.8 g (1 2 m m ο 1)及 MIBK 67g放入另一 l〇〇mL之反應燒瓶中，攪拌下流入氮 5分鐘進行氮取代，冰冷下（7 °C )下攪拌溶解各單體。使用滴液啷筒以20分鐘由放入DCP、C6FA、CYM、 LA及MAIB之前述lOOmL之反應燒瓶中，將內容物滴入前述200mL之反應燒瓶中回流下之MIBK中。滴液結束後熟成60 '分鐘。其次使用旋轉蒸發器由該反應液餾去MIBK 1 12g後’ 滴入〇°C之甲醇203 g中使聚合物以淤漿狀態沈澱。減壓過濾該淤漿後真空乾燥，得白色粉體之目的物（高分支聚合物 10)9.4g(產率 73°/〇)。所得之目的物之13C NMR光譜如圖17所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw 爲 6,700，分散度：Mw/Mn 爲 2.2。 [實施例21]合成高分支聚合物Π -49- 201235369 將MIBK 67g放入200mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度1 16°C )。將 DCP 6.7g(20mmol)、C6FA 4.4g( 1 1 mmol) ' CYM 2.0g (lOmmol)、BA 3.7 g (1 0 m m o 1)、M AIB 2.8 g (1 2 m m o 1)、 MIBK 67g及甲苯12g放入另一 lOOmL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，再以內溫3 0°C加熱攪拌溶解各單體。使用滴液啷筒以3.0分鐘由放入DCP、C6FA ' CYM、 BA及MAIB之前述lOOmL之反應燒瓶中，將內容物滴入前述200mL之反應燒瓶中回流下之MIBK中。滴液結束後熟成70分鐘。其次使用旋轉蒸發器由該反應液餾去MIBK與甲苯之混合溶液127g後，滴入0°C之甲醇243g中使聚合物沈澱，再藉由傾析去除上層澄清液。將甲苯1 1 g均勻加入所得之黏性固體20g中，再度滴入0°C之甲醇1 1 lg中使聚合物沈澱，其後藉由傾析精製。將所得之黏稠物乾燥後，定量得乳白色黏稠物之目的物（高分支聚合物ll)13g。所得之目的物之13C NMR光譜如圖18所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw 爲 6,800，分散度：Mw/Mn 爲 1.8。 [實施例22]合成高分支聚合物12 將MIBK 33g放入lOOmL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度1 1 6°C )。 -50- 201235369 將 DCP 3.4g(10mmol)、C6FA 2.1g(5mmol)、ΟΧΜΑ 0.9g(5mmol)、STA 1,6 g (5 m m o 1)、M AIB 1 . 4 g (6 m m o 1)及 MIBK 3 4g放入另一50mL之反應燒瓶中，攪拌下流入氮5 分鐘進行氮取代，冰冷下（內溫5 °C )攪拌溶解各單體。使用滴液啷筒以30分鐘由放入DCP、C6FA、OXMA 、STA及MAIB之前述50mL之反應燒瓶中，將內容物滴入前述100mL之反應燒瓶中回流下之MIBK中。滴液結束後熟成60分鐘。其次使用旋轉蒸發器由該反應液餾.去MIBK 63g後，再度加入MIBK 6g，其後滴入0°C之甲醇157g中使聚合物以淤漿狀態沈澱。減壓過濾該淤漿後真空乾燥，得白色粉末之目的物（高分支聚合物12)3.0g(產率47%)。所得之目的物之13C NMR光譜如圖19所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw 爲 6,900，分散度：Mw/Mn 爲 2.0。 [實施例23]合成高分支聚合物13 將MIBK-甲苯混合溶劑（質量比1: l)34g放入20 0mL 之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流 (約溫度l〇5°C )。將 DCP 3.3g(10mmol)、C6FA 2.2g(6mmol)、CYM l.lg (6mmo 1)、ST A 1.6g(5mmo 1)、DCHC 1 · 5 g(5 mmo 1)及 MIBK-甲苯混合溶劑（質量比1: l)36g放入另一 l〇〇mL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，室溫（內溫22°C ) -51 - 201235369 下攪拌溶解各單體。使用滴液啷筒以25分鐘由放入DCP、C6FA、CYM、 STA及DCHC之前述l〇〇mL之反應燒瓶中，將內容物滴入前述200mL之反應燒瓶中回流下之MIBK-甲苯混合劑中。滴液結束後熟成60分鐘。其次使用旋轉蒸發器由該反應液餾去MIBK-甲苯混合溶劑61g後，滴入〇°C之甲醇l〇lg中使聚合物沈澱。減壓過濾該淤漿後真空乾燥，得白色粉末之目的物（高分支聚合物 13)2.5g(產率 36%)。所得之目的物之13C NMR光譜如圖20所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw 爲 7,700，分熬度：Mw/Mn 爲 2.6。 [實施例24]合成商分支聚合物14 將MIBK 6 8g放入200mL之反應燒瓶中，攪拌下流入氮5分鐘，再加熱至內液回流（約溫度！丨6°C )。DCP 6.7g (20mmol), C6FA 4.2g (10mmol), OXMA 1.8g (1Ommol) 'DCHC 3.7g (12mmol) and MIBK 67g were placed in 'other 200 mL reaction flask, and nitrogen was added under stirring. Nitrogen substitution was carried out in minutes and the liquid temperature was heated to about 35 Torr. The contents were dropped into the above-mentioned 200 mL reaction flask in a 300 mL reaction flask and refluxed in MIBK using a dropping cartridge for 25 minutes from the above 200 mL reaction flask in which DCP, C6FA, OXMA and DCHC were placed. After the drip was crusted, it was cooked for 1 hour. Next, 45 g of MIBK was distilled off from the reaction liquid using a rotary evaporator, and -43-201235369 was added to 465 g of methanol at 〇 °C to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to give white powder (yield: </ br) 7.5 g (yield 47%). The 1H NMR and l3C NMR spectra of the obtained target are shown in Fig. 1 and Fig. 2. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 3,700, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 2.1. [Example 2] Synthesis of high-branched polymer 2. MIBK 67g was placed in a 300 mL reaction flask, and nitrogen was bubbled under stirring for 5 minutes, and then heated to reflux (about 1 1 6 ° C). DCP 6.7g (20mmol), C6FA 4.2g (10mmol), CYM 2.0g (10mmol), DCHC 3.7g (12mmol) and MIBK 74g were placed in another 200 mL reaction flask, and nitrogen was added for 5 minutes with stirring. Instead, reheat to bring the liquid to a temperature of about 35 °C. The contents were dropped into the above-mentioned 300 mL reaction flask under reflux of MIBK using a dropping cartridge for 35 minutes from the above 200 mL reaction flask in which DCP, C6FA, CYM and DCHC were placed. The mixture was aged for 1 hour after the completion of the dropping. Next, 61 g of MIBK was distilled off from the reaction liquid using a rotary evaporator, and then 470 g of methanol was added to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to give white powder (yield: s. The 1H NMR and 13 C NMR spectra of the obtained target are shown in Fig. 3 and Fig. -44 - 201235369 4. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 5,300, and the degree of dispersion: Mw/Mn was 1.9. [Example 3] Synthesis of highly branched polymer 3 MIBK 6 7g was placed in a 300 mL reaction flask, and nitrogen was introduced for 5 minutes while stirring, and then heated to reflux (about 1 16 ° C). DCP 6.7g (20mmol), C6FA 4.2g (10mmol), CYM 2.0g (10mmol), MAIB 2.8g (12mmol) and MIBK 67g were placed in another 200 mL reaction flask, and nitrogen was added for 5 minutes with stirring. Instead, it was cooled to 5 ° C in an ice bath. The contents were dropped into the above-mentioned 300 mL reaction flask and refluxed in MIBK using a dropping cartridge for 30 minutes from the aforementioned 200 mL reaction flask in which DCP, C6FA, CYM and MAIB were placed. The mixture was aged for 1 hour after the completion of the dropping. Next, 8 g of MIBK was distilled off from the reaction liquid using a rotary evaporator, and then a mixture of 277 g of hexane and 44 g of ethanol was added to precipitate a polymer, and the supernatant liquid was decanted. The remaining precipitate was redissolved using MIBK 7g. The MIBK solution of the polymer was added to 202 g of methanol to reprecipitate the polymer in a slurry state. The pellet was filtered under reduced pressure, and then 5.2 g (yield: 41%) of the object (high-branched polymer 3) of white powder was obtained. The 1H NMR and 13c NMR spectra of the obtained target are shown in Fig. 5 and Fig. 6. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 4,700, and the degree of dispersion: Mw/Mn was 1.6. -45-201235369 [Example 4] Synthesis of high-branched polymer 4 MIBK 67 g was placed in a 30 mL reaction flask, and nitrogen was bubbled under stirring for 5 minutes, and then heated to reflux (about 1 1 6 ° C). DCP 6.7g (20mmol), C6FA 4.2g (10mmol), CYM 2.0g (10mmol), AMBN 2.5g (12mmol) and MIBK 67g were placed in another 200 mL reaction flask, and nitrogen was added for 5 minutes under stirring to carry out nitrogen. Instead, cool it to an ice bath. The contents were dropped into the above-mentioned 300 mL reaction flask under reflux of MIBK using a dropping cartridge for 30 minutes from the aforementioned 200 mL reaction flask in which DCP 'C6FA, CYM and AMBN were placed. The mixture was aged for 1 hour after the completion of the dropping. Next, 7 g of MIBK 4 was distilled off from the reaction liquid using a rotary evaporator, and then added to methanol (79 g) to precipitate a polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to give white powder (yield: y. The 1H NMR and 13C NMR spectra of the obtained target are shown in Fig. 7 and Fig. 8. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 5,700, and the degree of dispersion: Mw/Mn was 2.0. [Example 5] Synthesis of highly branched polymer 5 40 g of MIBK was placed in a 200 mL reaction flask, and nitrogen was introduced for 5 minutes while stirring, and then heated to reflux (about 1 1 6 ° C). EGDMA 4.0g (20mmol), C6FA 4.2g (10mmol), CYM 2.0g (10mmol), M AIB 2.8 g (1 2 m mo 1) and ΜIB K 4 0 g were placed in another -46 - 201235369 1 0 OmL In the reaction flask, nitrogen was introduced for 5 minutes while stirring, and nitrogen substitution was carried out, followed by cooling to 5 ° C in an ice bath. The contents were dropped into the 200 mL reaction flask under reflux of MIBK using a dropping cartridge for 40 minutes from the aforementioned 200 mL reaction flask containing EGDMA, C6FA, CYM and MAIB. The mixture was aged for 1 hour after the completion of the dropping. Next, 3 g of MIBK 3 was distilled off from the reaction liquid using a rotary evaporator, and then added to methanol (84 g) to precipitate a polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to give a white powder (yield: 5). The 1H NMR and 13C NMR spectra of the obtained target are shown in Fig. 9 and Fig. 10. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 6,700, and the degree of dispersion: Mw/Mn was 2.0. [Example 18] Synthesis of high-branched polymer 8 MIBK 67 g was placed in a 200 mL reaction flask, and nitrogen was bubbled under stirring for 5 minutes, and then heated to reflux (about 1 1 6 ° C). The reaction of DCP 6.8g (20mmol), C6FA 4.2g (10mmol), C:YM 2.0g (10mmol), STA 3.3g (10mmol), MAIB 2.8g (12mmol) and MIBK 67g into another l〇〇mL In the flask, nitrogen was introduced for 5 minutes while stirring, and nitrogen substitution was carried out, and each monomer was stirred and stirred at room temperature (17 ° C). The contents were dropped into the above-mentioned 200 mL reaction flask under reflux of MIBK using a dropping cartridge for 45 minutes from the above-mentioned i〇〇mL reaction flask containing DCP, C6FA, CYM, STA and MAIB. After the completion of the dropping -47 - 201235369 aging for 70 minutes. Next, 118 g of MIBK was distilled off from the reaction liquid using a rotary evaporator, and then poured into 227 g of methanol at 〇 ° C to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to give 11.6 g (yield: 90%) of the objective material (high-branched polymer 8) as a transparent glassy solid. The 13 C NMR spectrum of the obtained target product is shown in FIG. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 5,000, and the degree of dispersion: Mw/Mn was 1.7» [Example 19] Synthesis of highly branched polymer 9 Reaction of MIBK 67g into 200 mL In the flask, nitrogen was added to the mixture for 5 minutes while stirring, and then heated to reflux (about temperature! 丨6). DCP 6.8 g (20 mmol), C6FA 4.2 g (10 mmol), CYM 2.1 g (l 1 mmol) ' ISTA 3.3 g (1 〇mmo 1) ' MAIB 2.8g (12mmol) and MIBK 67g were placed in another i〇〇mL reaction flask, and nitrogen was added for 5 minutes under stirring to carry out nitrogen substitution '5 «c) stirring and dissolving Each monomer. The contents were dropped into the above-mentioned 200 mL reaction flask under reflux of MIBK using a dropping cartridge in a reaction flask of the above 1 〇〇 m L in which DCP, C6FA, CYM, I S T A and M AIB were placed for 25 minutes. After the dripping, the mixture was aged for 90 minutes. Next, 116 g of MIBK was distilled off from the reaction liquid using a rotary evaporator, and then dropped into 203 g of methanol at 〇 ° C to precipitate the polymer in a slurry state. The product was vacuum-dried under reduced pressure and dried under vacuum to give 7.6 g (yield: 59°/) of the object of the white solid (high-branched polymer 9). -48- 201235369 The 13C NMR spectrum of the obtained target is shown in FIG. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 6,700, and the degree of dispersion: Mw/Mn was 2.2. [Example 20] Synthesis of highly branched polymer 10 MIBK 67 g was placed in a 200 mL reaction flask, and nitrogen was introduced for 5 minutes while stirring, and then heated to reflux (about 1 1 6 ° C). DCP 6.7g (20mmol) 'C6FA 4.2g (10mmol), CYM 2.0 g (1 0 mm ο 1), LA 2.4 g (10 mm ο 1), M AIB 2.8 g (1 2 mm ο 1) and MIBK 67g was placed in another l〇〇mL reaction flask, nitrogen was added thereto for 5 minutes with stirring, and nitrogen substitution was carried out, and each monomer was dissolved by stirring under ice cooling (7 ° C). The contents were poured into the above-mentioned 100 mL reaction flask of DCP, C6FA, CYM, LA and MAIB using a dropping cartridge for 20 minutes, and the contents were dropped into MIBK under reflux in the above 200 mL reaction flask. After the drip is finished, it is cooked for 60' minutes. Next, 12 g of MIBK 1 was distilled off from the reaction liquid using a rotary evaporator, and the polymer was precipitated by dropping into 203 g of methanol at 〇 °C. The slurry was filtered under reduced pressure and dried in vacuo to give white powder (yield: </ RTI> </ RTI> <RTIgt; The 13 C NMR spectrum of the obtained target product is shown in FIG. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 6,700, and the degree of dispersion: Mw/Mn was 2.2. [Example 21] Synthesis of high-branched polymer Π -49- 201235369 MIBK 67g was placed in a 200 mL reaction flask, and nitrogen was bubbled under stirring for 5 minutes, and then heated to reflux (about 1 16 ° C). DCP 6.7g (20mmol), C6FA 4.4g (1 1 mmol) ' CYM 2.0g (10mmol), BA 3.7 g (1 0 mmo 1), M AIB 2.8 g (1 2 mmo 1), MIBK 67g and toluene 12g The mixture was placed in another 100 mL reaction flask, and nitrogen was introduced for 5 minutes under stirring to carry out nitrogen substitution, and the monomers were dissolved by heating at an internal temperature of 30 ° C. The contents were poured into the above-mentioned 100 mL reaction flask of DCL, C6FA 'CYM, BA and MAIB using a dropping cartridge for 3.0 minutes, and the contents were dropped into MIBK under reflux in the above 200 mL reaction flask. After the dripping, the mixture was aged for 70 minutes. Next, 127 g of a mixed solution of MIBK and toluene was distilled off from the reaction liquid using a rotary evaporator, and then 243 g of methanol at 0 ° C was added to precipitate a polymer, and the supernatant liquid was removed by decantation. Toluene (1 g) was uniformly added to 20 g of the obtained viscous solid, and the polymer was again precipitated by dropwise addition of 1 liter of methanol at 0 ° C, followed by purification by decantation. After drying the obtained viscous material, 13 g of the object of the milky white viscous material (high-branched polymer ll) was quantified. The 13 C NMR spectrum of the obtained target product is shown in FIG. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 6,800, and the degree of dispersion: Mw/Mn was 1.8. [Example 22] Synthesis of high-branched polymer 12 MIBK 33 g was placed in a 100 mL reaction flask, and nitrogen was bubbled under stirring for 5 minutes, and then heated to reflux (about 1 1 6 ° C). -50- 201235369 DCP 3.4g (10mmol), C6FA 2.1g (5mmol), ΟΧΜΑ 0.9g (5mmol), STA 1,6 g (5 mmo 1), M AIB 1.4 g (6 mmo 1) and MIBK 3 4 g was placed in another 50 mL reaction flask, and nitrogen was introduced for 5 minutes under stirring to carry out nitrogen substitution, and each monomer was stirred and stirred under ice cooling (internal temperature 5 ° C). The contents were dropped into the above-mentioned 100 mL reaction flask under reflux of MIBK using a dropping cartridge for 30 minutes from the above 50 mL reaction flask in which DCP, C6FA, OXMA, STA and MAIB were placed. After the dripping, the mixture was aged for 60 minutes. Next, the reaction liquid was distilled off using a rotary evaporator. After removing 63 g of MIBK, 6 g of MIBK was further added, followed by dropping 157 g of methanol at 0 ° C to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to give white crystals (yield: 47%). The 13 C NMR spectrum of the obtained target product is shown in FIG. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 6,900, and the degree of dispersion: Mw/Mn was 2.0. [Example 23] Synthesis of high-branched polymer 13 34 g of MIBK-toluene mixed solvent (mass ratio: 1:1) was placed in a 20 mL reaction flask, and nitrogen was introduced for 5 minutes while stirring, and then heated to reflux (about temperature). L〇5°C). DCP 3.3g (10mmol), C6FA 2.2g (6mmol), CYM l.lg (6mmo 1), ST A 1.6g (5mmo 1), DCHC 1 · 5 g (5 mmo 1) and MIBK-toluene mixed solvent ( Mass ratio 1: l) 36 g was placed in another l〇〇mL reaction flask, nitrogen was added for 5 minutes under stirring to carry out nitrogen substitution, and each monomer was stirred and stirred at room temperature (internal temperature 22 ° C) -51 - 201235369. The contents were dropped into the reaction flask of DCL, C6FA, CYM, STA and DCHC for 25 minutes using a dropping cartridge for 25 minutes, and the contents were dropped into the 200 mL reaction flask to reflux the MIBK-toluene mixture. in. The mixture was aged for 60 minutes after the completion of the dropping. Next, 61 g of a MIBK-toluene mixed solvent was distilled off from the reaction liquid using a rotary evaporator, and then the mixture was poured into methanol 〇 lg to precipitate a polymer. The slurry was filtered under reduced pressure and dried in vacuo to give white crystals (yield of product 36) (yield 36%). The 13 C NMR spectrum of the obtained target product is shown in FIG. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 7,700, and the degree of branching: Mw/Mn was 2.6. [Example 24] Synthetic branched polymer 14 MIBK 6 8g was placed in a 200 mL reaction flask, and nitrogen was introduced for 5 minutes while stirring, and then heated to reflux (about temperature: 丨 6 ° C).

將 DCP 6.7g(20mmol)、3FEA 0.3g(2mmol)、CYM 2. 1 g(l lmmol) > STA 3 . 3 g (1 0 m m o 1) ' MAIB 2.8g(12mmol) 及MIBK 68g放入另一i〇〇mL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，冰冷下（內溫5 °C )攪拌溶解各單體〇使用滴液啷筒以40分鐘由放入DCP、3FEA、CYM、 STA及MAIB之前述l〇〇mL之反應燒瓶中，將內容物滴入前述200mL之反應燒瓶中回流下之MIBK中。滴液結束後 -52- 201235369 熟成60分鐘。其次使用旋轉蒸發器由該反應液餾去MIBK 121g後’ 滴入〇°C之甲醇214g中使聚合物沈澱。減壓過濾該淤漿後真空乾燥’得透明玻璃狀固體之目的物（高分支聚合物 14)2.9g(產率 32%)。所得之目的物之13C NMR光譜如圖21所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw 爲 5,500，分散度：Mw/Mn 爲 2.1。 [比較例1]合成高分支聚合物6 將甲苯66g放入200mL之反應燒瓶中，攪拌下流入氮 5分鐘，再加熱至內液回流（約溫度11〇 °c)。將 DCP 6.7g(20mmol)、C6FA 4.2g(10mmol)、DCHC 3.7g(12mmol)及甲苯66g放入另一 200mL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，再以冰浴冷卻至〇 t。使用滴液唧筒以30分鐘由放入DCP、C6FA及DCHC 之前述200mL之反應燒瓶中，將內容物滴入前述200mL 之反應燒瓶中。滴液結束後熟成1小時。其次使用旋轉蒸發器由該反應液餾去甲苯55g後，加入己烷510g中使聚合物以淤漿狀態沈澱。減壓過濾該淤漿後真空乾燥，得白色粉末之目的物（高分支聚合物 6)3.8g(產率 27%)。所得之目的物之1H NMR及13C NMR光譜如圖1 1及圖1 2所示。又，目的物藉由GPC以聚苯乙烯換算測得之 -53- 201235369 重量平均分子量Mw爲7,200，分散度：Mw/Mn爲2.9。 [比較例2]合成高分支聚合物7 將甲苯66g放入200mL之反應燒瓶中，攪拌下流入氮 5分鐘，再加熱至內液回流（約溫度1 10°C )。將 DCP 6.7 g(20mmο 1)、C 6F A 5 · 4g(1 2 · 5 mmo 1)、GM A 1.4g( 1 Ommol)、DCHC 3.7g( 1 2mmol)及甲苯 66g 放入另一 10 OmL之反應燒瓶中，攪拌下流入氮5分鐘進行氮取代，再以冰浴冷卻至〇°C。使用滴液唧筒以30分鐘由放入DCP、C6FA、GMA及 DCHC之前述10 0mL之反應燒瓶中，將內容物滴入前述 2 0 OmL之反應燒瓶中回流下之甲苯中。滴液結束後熟成1 小時。其次將該反應液加入己烷51 Og中使聚合物以淤漿狀態沈澱。減壓過濾該淤漿後真空乾燥，得白色粉末之目的物（高分支聚合物7)6.4g(產率40%)。所得之目的物之1H NMR及l3C NMR光譜如圖1 3及圖14所示。又，目的物藉由GPC以聚苯乙烯換算測得之重量平均分子量Mw爲8,000，分散度：Mw/Mn爲1.9。實施例1至5、實施例1 8至24及比較例1、2所得之高分支聚合物1至14之，各單體及起始劑之種類與相對於單體A之添加量[mol%](單體B、單體C、聚合起始劑D 、單體E)、由13C NMR光譜所算出之氟單體（單體B)導入量[mol%]，以及由氟定量分析所算出之氟原子含量[質量 -54- 201235369 %]如表1所示。 [表1] 表1 高分支聚合 S} 單體A 單體B 單體c 聚合起始劑D 單體E 單體B 導入量 DnoIX] F原子含量 MX] mm. 添加量 [mo(X] 種類添加量 [mol%] 麵添加量 [mol%] 種類添加量 [mol%] 1 DCP C6FA 50 OXMA $0 OCHC 60 無 — 24 15 2 DCP C6PA 5D CYM 50 DCHC 60 fnr 一 28 15 3 DCP C6FA 50 CYM 50 MAIB 60 4rrr 挑一 22 16 4 DCP C6FA 50 CYM 50 AMBN 60 4rrr m - 20 17 5 EGDMA C6FA $0 CYM SO MAIB 60 無 — 20 20 8 DCP C6FA 50 CYM 50 MAIB 60 STA 50 19 13 9 DCP C6FA 50 CYM 55 MAIB 60 ISTA 50 21 14 10 DCP C6FA 50 CYM 50 MAIB 60 LA SO 17 14 11 DCP C6FA $5 CYM 50 MAIB «0 BA 50 22 14 12 DCP C6FA 50 OXMA 50 MAIB 60 STA 50 19 14 13 DCP C6FA 60 CYM 60 DCHC 50 STA 50 23 14 14 DCP 3FEA 10 CYM 55 MAIB 60 STA 50 10 0,6 6 DCP C6FA 5D M — DCHC 60 無一 29 14 7 DCP C6FA 63 GMA 50 DCHC 60 無一 19 17 [各高分支聚合物之物性評估] 將實施例1至5、實施例18至24及比較例1、2所得之高分支聚合物1至14各50mg，溶解於表2所記載之溶劑95 Omg後進行濾器過濾，調製各高分支聚合物溶液。將該高分支聚合物溶液旋覆（slope 5秒，其次l,500rpm 30 秒，再s 1 〇 p e 5秒）於玻璃基板上，以1 〇〇 °C熱處理3 0分鐘使溶劑蒸發而成膜。評估所得之薄膜之波長6 3 3 n m下的折射率，與水及二 -55- 201235369 碘甲烷之接觸角。又由接觸角之結果算出表面能量。又，測定各高分支聚合物粉末之玻璃化溫度（Tg)及5%重量減少溫度（Td5%)。所得之結果如表2所示。 [表2] 表2 聚合物溶劑 Tg TdeH 膜厚折射率接觸角[度] 表面能量 [mJ/m*] [ec] [eC] irwnj (833nm) h2o CHal, 高分支聚合物1 MIBK 79.1 279.1 175-β 1472 100.5 49.1 35.2 高分支聚合物2 MIBK 53.6 2$4.4 174-9 1476 104.3 38.9 42.2 高分支聚合物3 MIBK 74J 271.0 161,0 1.472 99.1 60.6 28.2 髙分支聚合物4 Μ旧K 77.1 254.1 140,0 1,479 102.6 β1·1 28.0 髙分支聚合物5 PGME 60.8 260*2 180.4 1.448 99.1 69.6 23.3 高分支聚合物8 MIBK 51.1 274.1 470.7 1.494 99.8 35.7 42A 髙分支聚合物9 MIBK 40.0 290.2 319.1 1.509 101.3 42.» 39.1 高分支聚合物10 MIBK 56.0 275.4 314.0 1.494 101.0 36.9 42.5 高分支聚合物11 MIBK 43,0 277,3 429.2 1.474 100.2 44^ 38.1 高分支聚合物12 MIBK 71.3 272.8 284.4 1.523 102.9 44.6 3β·4 高分支聚合物13 MIBK 76,9 270.2 S41.0 1.490 103.2 45.7 37.8 髙分支聚合物14 M旧K 59.0 260.2 392,4 1.500 84.6 19.2 48.0 高分支聚合物6 MIBK 83,9 262.7 164.7 1472 102.3 64.1 26.2 高分支聚合物7 DO 6Θ.1 271.5 275.3 1.463 102.5 57.5 30,2 [實施例6]藉由具有環氧丙烷構造之高分支聚合物的環氧樹脂之表面改質將實施例1所得之高分支聚合物1 50mg加入CEL202 1 P 5. 〇g中，加熱至約70 °C使其溶解。將該混合物冷卻至室溫（約25°C )後，製作添加CPI-100P 3 00mg之環氧樹脂組成物。將所得之環氧樹脂組成物流入，置於經剝離包覆處理 -56- 201235369 之玻璃基板上，中央部切除30mm四方之50mm四方xlmm 厚之聚矽氧製模框中。將曝光量12.5 J/cm2之UV光照射於該模框中之樹脂組成物進行曝光，製作環氧樹脂硬化物。測定所得之硬化物之濁度（haze値）後，藉由下述基準評估透明性。又，測定所得之硬化物之水及二碘甲烷的接觸角評估撥液性。另外將該硬化物浸漬於丙酮中1分鐘，以空氣槍乾燥後，再度測定水之接觸角，評估撥液性之有機溶劑耐性。所得之結果如表3所示。 [透明性之評估基準] ◎ : h a z e 値 < 1 〇：IS haze 値 <10 Δ ： 1 0 ^ haze fg <50 x: 50^ haze ίϋ [實施例7至10、25至30]藉由具有脂環式環氧基之高分支聚合物的環氧樹脂之表面改質除了各自使用實施例2至5及實施例1 8至23所得之高分支聚合物2至5及高分支聚合物8至13取代高分支聚合物1以外，與實施例6相同操作 '評估。結果倂示於表3。 [實施例11、12]藉由具有脂環式環氧基之高分支聚合物的環氧樹脂之表面改質DCP 6.7g (20mmol), 3FEA 0.3g (2mmol), CYM 2. 1 g (l lmmol) > STA 3 . 3 g (1 0 mmo 1) ' MAIB 2.8g (12mmol) and MIBK 68g In a reaction flask of i〇〇mL, nitrogen was added to the mixture for 5 minutes under stirring, and nitrogen substitution was carried out. The monomer was stirred and dissolved under ice cooling (internal temperature 5 ° C), and DCP, 3FEA was placed in 40 minutes using a dropping cartridge. In the above reaction flask of CYM, STA and MAIB, the contents were dropped into MIBK under reflux in the above 200 mL reaction flask. After the end of the drip -52- 201235369 cooked for 60 minutes. Next, 121 g of MIBK was distilled off from the reaction liquid using a rotary evaporator, and the polymer was precipitated by dropping 214 g of methanol into 〇 °C. After the slurry was filtered under reduced pressure, 2.9 g (yield: 32%) of the objective material (high-branched polymer 14) obtained as a transparent glassy solid. The 13 C NMR spectrum of the obtained target product is shown in FIG. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 5,500, and the degree of dispersion: Mw/Mn was 2.1. [Comparative Example 1] Synthesis of high-branched polymer 6 66 g of toluene was placed in a 200 mL reaction flask, and nitrogen was introduced for 5 minutes while stirring, and then heated to reflux (about 11 ° C). DCP 6.7g (20mmol), C6FA 4.2g (10mmol), DCHC 3.7g (12mmol) and toluene 66g were placed in another 200mL reaction flask, nitrogen was added for 5 minutes with stirring, nitrogen substitution, and then cooled to an ice bath. 〇t. The contents were dropped into the 200 mL reaction flask by using a dropping cartridge for 30 minutes from the 200 mL reaction flask in which DCP, C6FA and DCHC were placed. The mixture was aged for 1 hour after the completion of the dropping. Next, 55 g of toluene was distilled off from the reaction liquid using a rotary evaporator, and then 510 g of hexane was added to precipitate a polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to give 3.8 g (yield: 27%) of the object as a white powder. The 1H NMR and 13C NMR spectra of the obtained target are shown in Fig. 11 and Fig. 12. Further, the object was measured by GPC in terms of polystyrene -53 - 201235369 The weight average molecular weight Mw was 7,200, and the degree of dispersion: Mw/Mn was 2.9. [Comparative Example 2] Synthesis of high-branched polymer 7 66 g of toluene was placed in a 200 mL reaction flask, and nitrogen was introduced thereto for 5 minutes while stirring, and then heated to reflux (about 1 10 ° C). DCP 6.7 g (20 mmο 1), C 6F A 5 · 4 g (1 2 · 5 mmo 1), GM A 1.4 g (1 Ommol), DCHC 3.7 g (12 mmol) and toluene 66 g were placed in another 10 OmL In the reaction flask, nitrogen was introduced for 5 minutes while stirring, and nitrogen substitution was carried out, followed by cooling to 〇 ° C in an ice bath. The contents were dropped into the toluene under reflux of the above-mentioned 20 mL flask in a reaction flask of DCO, C6FA, GMA and DCHC in a 30 mL reaction flask for 30 minutes using a dropping cartridge. The mixture was aged for 1 hour after the completion of the dropping. Next, the reaction liquid was added to 51 Og of hexane to precipitate a polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to give white crystals (yield: y. The 1H NMR and l3C NMR spectra of the obtained target are shown in Fig. 13 and Fig. 14. Further, the weight average molecular weight Mw of the object measured by GPC in terms of polystyrene was 8,000, and the degree of dispersion: Mw/Mn was 1.9. The amount of each monomer and initiator and the amount of addition to monomer A in the high-branched polymers 1 to 14 obtained in Examples 1 to 5, Examples 1 to 8 and Comparative Examples 1 and 2 [mol% (monomer B, monomer C, polymerization initiator D, monomer E), the amount of fluorine monomer (monomer B) introduced by 13C NMR spectrum [mol%], and calculated by quantitative analysis of fluorine The fluorine atom content [mass - 54 - 201235369 %] is shown in Table 1. [Table 1] Table 1 High-branched polymerization S} Monomer A Monomer B Monomer c Polymerization initiator D Monomer E Monomer B Introduction amount DnoIX] F atom content MX] mm. Addition amount [mo(X] type Addition amount [mol%] Surface addition amount [mol%] Type addition amount [mol%] 1 DCP C6FA 50 OXMA $0 OCHC 60 None - 24 15 2 DCP C6PA 5D CYM 50 DCHC 60 fnr One 28 15 3 DCP C6FA 50 CYM 50 MAIB 60 4rrr Pick a 22 16 4 DCP C6FA 50 CYM 50 AMBN 60 4rrr m - 20 17 5 EGDMA C6FA $0 CYM SO MAIB 60 None — 20 20 8 DCP C6FA 50 CYM 50 MAIB 60 STA 50 19 13 9 DCP C6FA 50 CYM 55 MAIB 60 ISTA 50 21 14 10 DCP C6FA 50 CYM 50 MAIB 60 LA SO 17 14 11 DCP C6FA $5 CYM 50 MAIB «0 BA 50 22 14 12 DCP C6FA 50 OXMA 50 MAIB 60 STA 50 19 14 13 DCP C6FA 60 CYM 60 DCHC 50 STA 50 23 14 14 DCP 3FEA 10 CYM 55 MAIB 60 STA 50 10 0,6 6 DCP C6FA 5D M — DCHC 60 None 29 14 7 DCP C6FA 63 GMA 50 DCHC 60 None 19 17 [Highly branched polymer Physical property evaluation] 50 mg of each of the high-branched polymers 1 to 14 obtained in Examples 1 to 5, Examples 18 to 24, and Comparative Examples 1 and 2 was dissolved in Table 2 The solvent was filtered at 95 Omg, and the high-branched polymer solution was prepared. The high-branched polymer solution was spun (slope for 5 seconds, followed by 1,500 rpm for 30 seconds, and then s 1 〇pe for 5 seconds) on the glass substrate. The film was evaporated by heat treatment at 1 ° C for 30 minutes to form a film. The refractive index of the obtained film at a wavelength of 6 3 3 nm was evaluated, and the contact angle with water and bis-55-201235369 iodomethane was again contacted. The surface energy was calculated as a result of the angle. Further, the glass transition temperature (Tg) and the 5% weight loss temperature (Td 5%) of each of the high-branched polymer powders were measured. The results obtained are shown in Table 2. [Table 2] Table 2 Polymer solvent Tg TdeH Film thickness refractive index contact angle [degrees] Surface energy [mJ/m*] [ec] [eC] irwnj (833 nm) h2o CHal, high branched polymer 1 MIBK 79.1 279.1 175 -β 1472 100.5 49.1 35.2 Highly branched polymer 2 MIBK 53.6 2$4.4 174-9 1476 104.3 38.9 42.2 High branched polymer 3 MIBK 74J 271.0 161,0 1.472 99.1 60.6 28.2 髙 branched polymer 4 Μ old K 77.1 254.1 140,0 1,479 102.6 β1·1 28.0 髙 branched polymer 5 PGME 60.8 260*2 180.4 1.448 99.1 69.6 23.3 high branched polymer 8 MIBK 51.1 274.1 470.7 1.494 99.8 35.7 42A 髙 branched polymer 9 MIBK 40.0 290.2 319.1 1.509 101.3 42.» 39.1 high Branch Polymer 10 MIBK 56.0 275.4 314.0 1.494 101.0 36.9 42.5 High Branch Polymer 11 MIBK 43,0 277,3 429.2 1.474 100.2 44^ 38.1 High Branch Polymer 12 MIBK 71.3 272.8 284.4 1.523 102.9 44.6 3β·4 High Branch Polymer 13 MIBK 76,9 270.2 S41.0 1.490 103.2 45.7 37.8 Bismuth branched polymer 14 M old K 59.0 260.2 392,4 1.500 84.6 19.2 48.0 High branched polymer 6 MIBK 83,9 262.7 164.7 1472 102.3 64.1 26.2 Highly branched polymer 7 DO 6 27.1 271.5 275.3 1.463 102.5 57.5 30,2 [Example 6] Surface modification of epoxy resin having a highly branched polymer having a propylene oxide structure The 50 mg of the highly branched polymer obtained in Example 1 was added to CEL202. 1 P 5. In 〇g, heat to about 70 °C to dissolve. After the mixture was cooled to room temperature (about 25 ° C), an epoxy resin composition containing CPI-100P 3 00 mg was prepared. The obtained epoxy resin composition was flowed into a glass substrate which was subjected to peel-coating treatment -56-201235369, and a central portion was cut out of a 30 mm square 50 mm square x lmm thick polyxylene mold frame. UV light having an exposure amount of 12.5 J/cm 2 was irradiated onto the resin composition in the mold frame to expose it, thereby producing an epoxy resin cured product. After the turbidity (haze値) of the obtained cured product was measured, the transparency was evaluated by the following criteria. Further, the liquidity of the obtained cured product and the contact angle of diiodomethane were measured to evaluate the liquid repellency. Further, the cured product was immersed in acetone for 1 minute, dried with an air gun, and the contact angle of water was measured again to evaluate the organic solvent resistance of the liquid repellency. The results obtained are shown in Table 3. [Evaluation Criteria for Transparency] ◎ : haze 値 < 1 〇: IS haze 値 <10 Δ : 1 0 ^ haze fg <50 x: 50^ haze ϋ [Examples 7 to 10, 25 to 30] The surface modification of the epoxy resin from the highly branched polymer having an alicyclic epoxy group except for the highly branched polymers 2 to 5 and the highly branched polymer obtained by using Examples 2 to 5 and Examples 18 to 23, respectively. The evaluation was carried out in the same manner as in Example 6 except that 8 to 13 was substituted for the highly branched polymer 1. The results are shown in Table 3. [Examples 11 and 12] Surface modification of epoxy resin by a highly branched polymer having an alicyclic epoxy group

S -57- 201235369 除了各自使用實施例3、5所得之高分支聚合物3、5 取代高分支聚合物1，及曝光後以1501進行10分鐘後烘烤以外，與實施例6相同操作、評估。結果倂示於表3。 [比較例3 ]未添加表面改質劑之環氧樹脂之表面特性除了未添加高分支聚合物1以外，與實施例6相同操作、評估。結果併示於表3。 [比較例4]藉由不具有光陽離子聚合性基之高分支聚合物的環氧樹脂之表面改質除了使用比較例1所得之高分支聚合物6取代高分支聚合物1以外，與實施例6相同操作、評估。結果倂示於表3。 [比較例5]藉由具有環氧基之高分支聚合物的環氧樹脂之表面改質除了使用比較例2所得之高分支聚合物7取代高分支聚合物1以外’與實施例6相同操作、評估。結果倂示於表3。 [比較例6]未添加表面改質劑之環氧樹脂之表面特性除了未添加高分支聚合物1，及曝光後以l5(rc進行 1 0分鐘後烘烤以外’與實施例6相同操作、評估。結果倂示於表3。 •58- 201235369 [比較例7]藉由不具有光陽離子聚合性基之高分支聚合物的環氧樹脂之表面改質除了使用比較例1所得之高分支聚合物6取代高分支聚合物1，及曝光後以1 5 0 °C進行1 0分鐘後烘烤以外，與實施例6相同操作、評估。結果倂示於表3。 [表3] 表3 添加聚合物有to IJ y» v\ 讎烤诱明件接觸角[度] Η,Ο 浸漬前丙酮浸漬前減少率 ί« 實施例6 高分支聚合物1 4nf- 無 © 102<4 83.4 18.6 77.9 實施例7 高分支聚合物2 Μ JiW 101.2 85.$ 15,4 79.0 實施例8 高分支聚合物3 Μ ◎ 101,8 97.7 4.0 75.5 實施例9 高分支聚合物4 Μ 102,7 84.1 18.1 73.5 實施例10 高分支聚合物5 Μ /1 \\ Δ 103.1 93.8 9,0 69.1 實施例25 高分支聚合物8 te yi\> ο 101.1 90.8 10.1 62.9 實施例26 高分支聚合物9 無 Δ 103,4 91.8 11.2 67.6 實施例27 高分支聚合物10 /frrr 無 Δ 103J 99.5 4,1 69,9 實施例28 高分支聚合物11 無 Δ 103.9 94,5 9.0 67,3 實施例29 高分支聚合物12 Μ Jtw △ 104.0 96.8 β.9 6$.9 實施例30 高分支聚合物13 無 Δ 104.9 95.5 9.0 65.8 實施例11 高分支聚合物3 有 ◎ 101.1 1010 0.1 71,S 實施例12 高分支聚合物5 有厶 101.6 100.8 0,8 75.6 比較例3 並 J\\\ "5~ 73.1 68.2 6.7 35,1 比較例4 高分支聚合物6 Μ JiW Δ 102.8 38,3 14.1 67.8 比較例5 高分支聚合物7 te jw\ Δ 98.3 92.2 6.2 77.4 比較例6 Μ j\w 有 ◎ 78,2 72.9 6.8 39.e 比較例7 高分支聚合物6 有 Δ 101.4 94,3 7,0 69.6 -59- 201235369 [實施例13]藉由具有環氧丙烷構造之高分支聚合物的環氧樹脂之表面改質將實施例1所得之高分支聚合物1 40mg加入CEL3 000 2.0g及GT401 2.0g之混合物中，加熱至約7〇°C使其溶解。將該混合物冷卻至室溫（約 25°C )後，加入 CPI-100P 2 4 0m g製作環氧樹脂組成物。將所得之環氧樹脂組成物旋覆（2〇〇rpm 15秒後，slope 15秒，再2, OOOrpm 60秒，其後slope 5秒）於玻璃基板上，得塗佈膜。將曝光量6.2J/cm2之UV光照射於該塗膜全面進行曝光後，以1 20°C之熱板進行1 〇分鐘後烘烤，製作環氧樹脂硬化膜。測定所得之硬化膜之濁度（haze値），再藉由下述基準評估透明性。又，測定所得之硬化膜之水的接觸角評估撥液性。又將該硬化膜浸漬於丙酮中1分鐘後，以空氣槍乾燥，再度測定水之接觸角，評估撥液性之有機溶劑耐性。所得之結果如表4所示。 [透明性之評估基準] ◎ : h a z e 値 < 1 〇：IShaze 値 <10 △ : lOShaze 値 <50 X: 50$haze 値 [實施例14至17]藉由具有脂環式環氧基之高分支聚合物 -60- 201235369 的環氧樹脂之表面改質除了各自使用實施例2至5所得之高分支聚合物2至 5取代高分支聚合物1以外，與實施例1 3相同操作、評估。結果倂示於表4。 [比較例8]未添加表面改質劑之環氧樹脂之表面特性除了未添加高分支聚合物1以外，與實施例1 3相同操作、評估。結果倂示於表4。 [比較例9]藉由不具有光陽離子聚合性基之高分支聚合物的環氧樹脂之表面改質除了使用比較例1所得之闻分支聚合物6取代高分支聚合物1以外，與實施例1 3相同操作、評估。結果倂示於表4。 [比較例1〇]藉由具有環氧基之高分支聚合物的環氧樹脂之表面改質除了使用比較例2所之商分支聚合物7取代高分支聚合物1以外，與實施例13相同操作、評估。結果倂示於表4。 -61 - 201235369 [表4] 表4 添加聚合物透明性接觸角[度] 浸漬前丙酮浸漬前減少率【*】實施例13 高分支聚合物1 ◎ 93.7 80·$ 14-3 實施例14 高分支聚合物2 ◎ 100.5 92.3 8·2 實施例15 高分支聚合物3 ◎ 93.9 80.0 14力實施例16 高分支聚合物4 ◎ 78.6 12 實施例Π 高分支聚合物5 ◎ 94.6 83.4 11.8 比較例8 無 ◎ 63.8 68.4 .7.2 比較例9 高分支聚合物6 ◎ 98.3 61.1 17.8 比較例10 高分支聚合物7 ◎ 100.2 63.7 36.4 [實施例31]製作添加具有環氧丙烷構造之高分支環氧樹脂硬化物將實施例1所得之高分支聚合物1 40mg加入 2.0g及GT401 2.0g之混合物中，加熱至約70°C 。將該混合物冷卻至室溫（約25 °C )後，添加 2 4 0 m g製作環氧樹脂組成物》將所得之環氧樹脂組成物流入置於經剝離包玻璃基板上，中央部切除30mm四方之50mm I 厚之聚矽氧製模框中。將曝光量6.2 J/cm2之UV 該模框中之樹脂組成物進行曝光後，以120 °C之 1 〇分鐘後烘烤，製作環氧樹脂硬化物。測定所得之硬化物之濁度（haze値），藉由下估透明性。所得之結果如表5所示。 [透明性之評估基準] 聚合物之 CEL3000 使其溶解 CPI-1 OOP 覆處理之 g 方 X 1 m m 光照射於熱板進行述基準評 -62- 201235369 ◎ : h a z e 値 < 1 〇：IShaze 値 <5 △ : 5$haze 値 <10 X: l〇S haze 値 [實施例32至34]製作添加具有脂環式環氧基之高分支聚合物的環氧樹脂硬化物除了各自使用實施例2至4所得之高分支聚合物2至 4取代高分支聚合物1以外，與實施例31相同操作、評估。結果倂示於表5。 [比較例1 1 ]製作未添加表面改質劑之環氧樹脂硬化物除了未添加高分支聚合物1以外，與實施例31相同操作、評估。結果倂示於表5。 [比較例12]製作添加不具有光陽離子聚合性基之高分支聚合物之環氧樹脂硬化物除了使用比較例1所得之高分支聚合物6取代高分支聚合物1以外，與實施例31相同操作、評估。結果倂示於表5。 [比較例13]製作添加具有環氧基之筒分支聚合物之環氧樹脂硬化物除了使用比較例2所得之高分支聚合物7取代高分支 -63- 201235369 聚合物1以外，與實施例31相同操作、評估。結果倂示於表5。 [表5] 表5S-57-201235369 The same operation and evaluation as in Example 6 except that the high-branched polymer 3, 5 obtained by using Examples 3 and 5 was used instead of the high-branched polymer 1, and the post-exposure was carried out at 1501 for 10 minutes after exposure. . The results are shown in Table 3. [Comparative Example 3] Surface properties of epoxy resin to which no surface modifier was added The operation and evaluation were carried out in the same manner as in Example 6 except that the high-branched polymer 1 was not added. The results are also shown in Table 3. [Comparative Example 4] Surface modification of epoxy resin by high-branched polymer having no photocationic polymerizable group, except that the high-branched polymer 6 obtained in Comparative Example 1 was used in place of the high-branched polymer 1, and Examples 6 same operation, evaluation. The results are shown in Table 3. [Comparative Example 5] Surface modification of epoxy resin by high-branched polymer having an epoxy group except that the high-branched polymer 7 obtained in Comparative Example 2 was used in place of the high-branched polymer 1 'the same operation as in Example 6 Evaluation. The results are shown in Table 3. [Comparative Example 6] The surface characteristics of the epoxy resin to which the surface modifier was not added were the same as in Example 6, except that the high-branched polymer 1 was not added, and after the exposure, the film was baked at 10 minutes after the rc was performed for 10 minutes. The results are shown in Table 3. • 58-201235369 [Comparative Example 7] Surface modification of epoxy resin by high-branched polymer having no photocationic polymerizable group except for the use of the high-branched polymerization obtained in Comparative Example 1. The same operation and evaluation as in Example 6 were carried out except that the high-branched polymer 1 was replaced with the material 6 and after the exposure was carried out at 150 ° C for 10 minutes, and the results are shown in Table 3. [Table 3] Table 3 The polymer has a contact angle of [I] y» v\ 雠诱 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ Example 7 Highly branched polymer 2 Μ JiW 101.2 85.$ 15,4 79.0 Example 8 Highly branched polymer 3 Μ ◎ 101,8 97.7 4.0 75.5 Example 9 Highly branched polymer 4 Μ 102,7 84.1 18.1 73.5 Example 10 high branched polymer 5 Μ /1 \\ Δ 103.1 93.8 9,0 69.1 Example 25 High branching Compound 8 te yi\> ο 101.1 90.8 10.1 62.9 Example 26 High branched polymer 9 No Δ 103,4 91.8 11.2 67.6 Example 27 High branched polymer 10 /frrr No Δ 103J 99.5 4,1 69,9 Implementation Example 28 Highly branched polymer 11 No Δ 103.9 94,5 9.0 67,3 Example 29 Highly branched polymer 12 Μ Jtw Δ 104.0 96.8 β.9 6$.9 Example 30 Highly branched polymer 13 No Δ 104.9 95.5 9.0 65.8 Example 11 High branched polymer 3 ◎ 101.1 1010 0.1 71, S Example 12 High branched polymer 5 厶 101.6 100.8 0, 8 75.6 Comparative Example 3 and J\\\ "5~ 73.1 68.2 6.7 35, 1 Comparative Example 4 High-branched polymer 6 Μ JiW Δ 102.8 38, 3 14.1 67.8 Comparative Example 5 High-branched polymer 7 te jw\ Δ 98.3 92.2 6.2 77.4 Comparative Example 6 Μ j\w Yes ◎ 78, 2 72.9 6.8 39. e Comparative Example 7 High-branched polymer 6 having Δ 101.4 94, 3 7,0 69.6 -59- 201235369 [Example 13] Surface modification by epoxy resin having a highly branched polymer having a propylene oxide structure will be carried out 40 mg of the highly branched polymer obtained in Example 1 was added to a mixture of CEL3 000 2.0 g and GT401 2.0 g, and heated to about 7 ° C to dissolve it.After the mixture was cooled to room temperature (about 25 ° C), an epoxy resin composition was prepared by adding CPI-100P 2 4 m g. The obtained epoxy resin composition was spun (15 rpm for 15 seconds, slope for 15 seconds, then 2, OOO rpm for 60 seconds, and then slope for 5 seconds) on a glass substrate to obtain a coating film. UV light having an exposure amount of 6.2 J/cm 2 was irradiated onto the entire surface of the coating film, and then exposed to a hot plate at 1200 ° C for 1 minute and then baked to prepare an epoxy resin cured film. The turbidity (haze値) of the obtained cured film was measured, and the transparency was evaluated by the following criteria. Further, the contact angle of the water of the obtained cured film was measured to evaluate the liquid repellency. Further, the cured film was immersed in acetone for 1 minute, dried with an air gun, and the contact angle of water was measured again to evaluate the organic solvent resistance of liquid repellency. The results obtained are shown in Table 4. [Evaluation criteria for transparency] ◎ : haze 値 < 1 〇: IShaze 値 <10 Δ : lOShaze 値 <50 X: 50$haze 値 [Examples 14 to 17] by having an alicyclic epoxy group The surface modification of the epoxy resin of the high-branched polymer-60-201235369 is the same as that of the embodiment 13 except that the high-branched polymer 2 to 5 obtained by using Examples 2 to 5 is used instead of the high-branched polymer 1. Evaluation. The results are shown in Table 4. [Comparative Example 8] Surface properties of epoxy resin to which no surface modifier was added The operation and evaluation were carried out in the same manner as in Example 13 except that the high-branched polymer 1 was not added. The results are shown in Table 4. [Comparative Example 9] Surface modification of epoxy resin by high-branched polymer having no photocationic polymerizable group, except that the branched polymer 6 obtained in Comparative Example 1 was used in place of the high-branched polymer 1, and Examples 1 3 same operation, evaluation. The results are shown in Table 4. [Comparative Example 1] Surface modification of an epoxy resin having a highly branched polymer having an epoxy group was the same as in Example 13 except that the high branched polymer 1 was replaced with the quotient branched polymer 7 of Comparative Example 2. Operation, evaluation. The results are shown in Table 4. -61 - 201235369 [Table 4] Table 4 Addition of polymer transparency contact angle [degrees] Reduction rate before acetone impregnation before impregnation [*] Example 13 High-branched polymer 1 ◎ 93.7 80·$ 14-3 Example 14 High Branched polymer 2 ◎ 100.5 92.3 8·2 Example 15 Highly branched polymer 3 ◎ 93.9 80.0 14 Force Example 16 Highly branched polymer 4 ◎ 78.6 12 Example Π Highly branched polymer 5 ◎ 94.6 83.4 11.8 Comparative Example 8 ◎ 63.8 68.4 .7.2 Comparative Example 9 High-branched polymer 6 ◎ 98.3 61.1 17.8 Comparative Example 10 High-branched polymer 7 ◎ 100.2 63.7 36.4 [Example 31] Preparation of a cured high-branched epoxy resin having a propylene oxide structure 40 mg of the highly branched polymer obtained in Example 1 was added to a mixture of 2.0 g and GT401 2.0 g, and heated to about 70 °C. After cooling the mixture to room temperature (about 25 ° C), adding 240 mg of epoxy resin composition, the resulting epoxy resin composition was placed on a peeled glass substrate, and the central portion was cut 30 mm square. 50mm I thick polyoxyl molding frame. UV exposure of 6.2 J/cm2 The resin composition in the mold frame was exposed to light, and then baked at 120 ° C for 1 minute to prepare an epoxy resin cured product. The turbidity (haze 値) of the obtained cured product was measured by estimating the transparency. The results obtained are shown in Table 5. [Evaluation criteria for transparency] CEL3000 of polymer is dissolved in CPI-1 OOP treatment g side X 1 mm Light is irradiated on hot plate for reference evaluation -62- 201235369 ◎ : haze 値< 1 〇:IShaze 値<5 Δ : 5$haze 値<10 X: l〇S haze 値 [Examples 32 to 34] An epoxy resin cured product obtained by adding a highly branched polymer having an alicyclic epoxy group was used in addition to the respective use. The high-branched polymers 2 to 4 obtained in Examples 2 to 4 were substituted for the high-branched polymer 1, and evaluated and evaluated in the same manner as in Example 31. The results are shown in Table 5. [Comparative Example 1 1] An epoxy resin cured product to which no surface modifying agent was added was produced, and the same operation and evaluation as in Example 31 were carried out except that the high branched polymer 1 was not added. The results are shown in Table 5. [Comparative Example 12] An epoxy resin cured product obtained by adding a highly branched polymer having no photocationic polymerizable group was prepared in the same manner as in Example 31 except that the high branched polymer 6 obtained in Comparative Example 1 was used instead of the high branched polymer 1. Operation, evaluation. The results are shown in Table 5. [Comparative Example 13] An epoxy resin cured product obtained by adding a tubular branched polymer having an epoxy group was prepared in the same manner as in Example 31 except that the high branched polymer 7 obtained in Comparative Example 2 was used instead of the high branched-63-201235369 polymer 1. The same operation, evaluation. The results are shown in Table 5. [Table 5] Table 5

添加聚合物透明性實施例31 高分支聚合物1 〇實施例32 高分支聚合物2 一 ◎ 實施例33 高分支聚合物3 〇實施例34 高分支聚合物4 〇比較例11 4τττ. 無〇比較例12 高分支聚合物6 X 比較例13 局分支聚合物7 XAddition of Polymer Transparency Example 31 High Branch Polymer 1 〇 Example 32 High Branch Polymer 2 ◎ Example 33 High Branch Polymer 3 〇 Example 34 High Branch Polymer 4 〇 Comparative Example 11 4τττ. Example 12 High Branch Polymer 6 X Comparative Example 13 Branch Branch Polymer 7 X

[實施例35]藉由具有脂環式環氧基之高分支聚合物的環氧樹脂之表面改質將實施例2所得之高分支聚合物2 3 0mg加入CEL2 02 1 P 3.〇g中，加熱至約70 °C使其溶解。將該混合物冷卻至室溫（約25°C)後，添加CPI-100P 180mg製作環氧樹脂組成物A。將所得之環氧樹脂組成物流入置於經離模劑（歐普滋（商標）DSX[戴金工業（股）製])處理之玻璃基板上，中央部切除3 0mm四方之50 mm四方xl mm厚之聚矽氧製模框中，再於上方覆蓋未經離模處理之另一玻璃基板。將曝光量 12J/cm2之UV光照射於該二枚玻璃基板挾持之模框中之樹脂組成物進行曝光，製作環氧樹脂硬化物。硬化後移除經 -64 - 201235369 離模處理之玻璃基板及模框，得表面改質之環氧樹脂硬化物。將一滴另行調整之環氧樹脂組成物B(CEL202 1 P 100 質量份+CPI-100P 6質量份）滴在該硬化物表面上，上方再覆蓋未經離模處理之另一玻璃基板。將曝光量12 J/cm2之 UV光照射於該二枚玻璃基板挾持之硬化物進行曝光，得介有表面改質之環氧樹脂硬化物與環氧樹脂組成物B之硬化物而接合的二枚玻璃基板。以手剝離所得之接合之玻璃基板，藉由下述基準評估表面改質之環氧樹脂硬化物之離模性。又，接著同樣操作、評估環氧樹脂相互間（表面改質之環氧樹脂硬化物與環氧樹脂組成物B之硬化物）剝離後之物，確認其耐久性。所得之結果如表6所示。 [離模性之評估基準] ◎:環氧樹脂相互間可於幾乎未施力下剝離〇：環氧樹脂相互間於施力下可剝離 X :環氧樹脂相互間無法剝離 [實施例36至39]藉由具有脂環式環氧基之高分支聚合物的環氧樹脂之表面改質除了各自使用實施例3、18、19及21所得之高分支聚合物3、8、9及1 1取代高分支聚合物2以外，與實施例3 5相同操作、評估。結果倂示於表6。 -65- 201235369 [比較例1 4]未添加表面改質劑之環氧樹脂之表面特性未添加高分支聚合物2以外，與實施例35相同操作、評估。結果倂示於表6。 [比較例15]藉由具有環氧基之高分支聚合物的環氧樹脂之表面改質除了使用比較例2所得之高分支聚合物7取代高分支聚合物2以外’與實施例3 5相同操作、評估。結果倂示於表6。 [表6] 表6[Example 35] Surface modification of epoxy resin having a highly branched polymer having an alicyclic epoxy group The high branched polymer obtained in Example 2 was added to CEL2 02 1 P 3.〇g Heat to about 70 ° C to dissolve. After the mixture was cooled to room temperature (about 25 ° C), 180 mg of CPI-100P was added to prepare an epoxy resin composition A. The obtained epoxy resin composition was transferred into a glass substrate which was treated by a release agent (Opson (trademark) DSX [Daijin Industrial Co., Ltd.]), and a central portion was cut out of 50 mm square 50 mm square xl mm. The thick polycrystalline oxygen mold frame is covered with another glass substrate which has not been subjected to the mold release treatment. UV light having an exposure amount of 12 J/cm 2 was irradiated onto the resin composition in the mold frame held by the two glass substrates to expose an epoxy resin cured product. After hardening, the glass substrate and the mold frame which were subjected to the mold treatment were removed, and the surface-modified epoxy resin hardened material was obtained. A drop of the separately adjusted epoxy resin composition B (CEL202 1 P 100 parts by mass + CPI-100P 6 parts by mass) was dropped on the surface of the cured product, and the other glass substrate which was not subjected to the mold release treatment was overlaid thereon. UV light having an exposure amount of 12 J/cm 2 is irradiated onto the cured material held by the two glass substrates, and exposed to obtain a cured product of the surface-modified epoxy resin cured product and the epoxy resin composition B. A glass substrate. The obtained bonded glass substrate was peeled off by hand, and the mold release property of the surface-modified epoxy cured product was evaluated by the following criteria. Then, the peeling of the epoxy resin from each other (the cured epoxy resin of the surface modification and the cured product of the epoxy resin composition B) was evaluated in the same manner, and the durability was confirmed. The results obtained are shown in Table 6. [Evaluation criteria for mold release] ◎: Epoxy resins can be peeled off from each other with almost no force. 环氧树脂: Epoxy resins can be peeled off from each other under application of force X: Epoxy resins cannot be peeled off from each other [Example 36 to 39] Surface modification of an epoxy resin by a highly branched polymer having an alicyclic epoxy group, except for the highly branched polymers 3, 8, 9 and 1 1 obtained by using Examples 3, 18, 19 and 21, respectively. The operation and evaluation were carried out in the same manner as in Example 35 except that the high-branched polymer 2 was replaced. The results are shown in Table 6. -65-201235369 [Comparative Example 1 4] Surface properties of epoxy resin to which no surface modifier was added The operation and evaluation were carried out in the same manner as in Example 35 except that the high-branched polymer 2 was not added. The results are shown in Table 6. [Comparative Example 15] Surface modification of epoxy resin by high-branched polymer having an epoxy group except that the high-branched polymer 7 obtained in Comparative Example 2 was used instead of the high-branched polymer 2' was the same as Example 35 Operation, evaluation. The results are shown in Table 6. [Table 6] Table 6

添加聚合物離模性初次第2次實施例35 高分支聚合物2 〇〇實施例36 高分支聚合物3 〇〇實施例37 高分支聚合物8 ◎ X 實施例38 高分支聚合物9 ◎ X 實施例39 高分支聚合物11 ◎ X 比較例14 X 比較例15 高分支聚合物7 X 如上述本發明之含氟高分支聚合物爲，接觸角較高，且具有優良水及二碘甲烷之撥液性之物。因此環氧樹脂等之光陽離子聚合性樹脂混合少量該聚合物形成硬化物時， -66 - 201235369 結果該硬化物可具有優良透明性，又其表面具有優良撥液性，且浸漬於丙酮後可保有較高之該撥液性。特別是硬化後藉由後烘烤’可使浸漬於丙酮後保有更高之撥液性，由此可確認’本發明之含氣局分支聚合物非常適合作爲可簡便將環氧樹脂等之光陽離子聚合性樹脂之表面改質的表面改質劑用。【圖式簡單說明】Addition of polymer release property First time Example 35 High-branched polymer 2 〇〇 Example 36 High-branched polymer 3 〇〇 Example 37 High-branched polymer 8 ◎ X Example 38 High-branched polymer 9 ◎ X Example 39 High-branched polymer 11 ◎ X Comparative Example 14 X Comparative Example 15 High-branched polymer 7 X The fluorine-containing highly branched polymer of the present invention has a high contact angle and excellent water and diiodomethane. Liquid-repellent. Therefore, when a photocationic polymerizable resin such as an epoxy resin is mixed with a small amount of the polymer to form a cured product, the cured product can have excellent transparency, and the surface thereof has excellent liquid repellency, and can be immersed in acetone. Maintain a higher liquidity. In particular, after the hardening, the post-baking can maintain a higher liquid repellency after immersion in acetone, thereby confirming that the gas-containing branched polymer of the present invention is very suitable as a light for epoxy resin. A surface modifying agent for surface modification of a cationically polymerizable resin. [Simple description of the map]

圖1爲，實施例1所製造之高分支聚合物1之1 H NMR 光譜圖。Fig. 1 is a 1 H NMR spectrum chart of the highly branched polymer 1 produced in Example 1.

圖2爲，實施例1所製造之高分支聚合物1之13C NMR 光譜圖。圖3爲，實施例2所製造之高分支聚合物2之1H NMR 光譜圖。圖4爲，實施例2所製造之高分支聚合物2之l3C NMR 光譜圖。2 is a 13C NMR spectrum chart of the highly branched polymer 1 produced in Example 1. Figure 3 is a 1H NMR spectrum of the highly branched polymer 2 produced in Example 2. 4 is a 13C NMR spectrum of the highly branched polymer 2 produced in Example 2.

圖5爲，實施例3所製造之高分支聚合物3之1H NMR 光譜圖。圖6爲，實施例3所製造之高分支聚合物3之13C NMR 光譜圖。圖7爲，實施例4所製造之高分支聚合物4之1H NMR 光譜圖。圖8爲，實施例4所製造之高分支聚合物4之13C NMR 光譜圖。 -67- 201235369 圖9爲，實施例5所製造之高分支聚合物5之1H NMR 光譜圖。Fig. 5 is a 1H NMR spectrum chart of the highly branched polymer 3 produced in Example 3. Fig. 6 is a 13C NMR spectrum chart of the highly branched polymer 3 produced in Example 3. Fig. 7 is a 1H NMR spectrum chart of the highly branched polymer 4 produced in Example 4. Figure 8 is a 13C NMR spectrum of the highly branched polymer 4 produced in Example 4. -67- 201235369 Figure 9 is a 1H NMR spectrum of the highly branched polymer 5 produced in Example 5.

圖10爲，實施例5所製造之高分支聚合物5之l3C NMR 光譜圖。圖Π爲，比較例1所製造之高分支聚合物6之1H NMR 光譜圖。圖12爲，比較例1所製造之高分支聚合物6之13C NMR 光譜圖。圖13爲，比較例2所製造之高分支聚合物7之1H NMR 光譜圖。圖14爲，比較例2所製造之高分支聚合物7之13C NMR 光譜圖。圖15爲，實施例18所製造之高分支聚合物8之13C NMR 光譜圖。圖16爲，實施例19所製造之高分支聚合物9之13C NMR 光譜圖。Figure 10 is a 13C NMR spectrum of the highly branched polymer 5 produced in Example 5. The graph is the 1H NMR spectrum of the highly branched polymer 6 produced in Comparative Example 1. Fig. 12 is a 13C NMR spectrum chart of the highly branched polymer 6 produced in Comparative Example 1. Fig. 13 is a 1H NMR spectrum chart of the highly branched polymer 7 produced in Comparative Example 2. Fig. 14 is a 13C NMR spectrum chart of the highly branched polymer 7 produced in Comparative Example 2. Figure 15 is a 13C NMR spectrum of the highly branched polymer 8 produced in Example 18. Figure 16 is a 13C NMR spectrum of the highly branched polymer 9 produced in Example 19.

圖17爲，實施例20所製造之高分支聚合物10之13C NMR 光譜圖。圖】8爲，實施例21所製造之高分支聚合物11之13C NMR 光譜圖。圖19爲，實施例22所製造之高分支聚合物12之13C NMR 光譜圖。圖20爲，實施例23所製造之高分支聚合物13之13C NMR 光譜圖。 • 68 - 201235369 圖2 1爲光譜圖。，實施例24所製造之高分支聚合物14之Figure 17 is a 13C NMR spectrum of the highly branched polymer 10 produced in Example 20. 8 is a 13C NMR spectrum of the highly branched polymer 11 produced in Example 21. Figure 19 is a 13C NMR spectrum of the highly branched polymer 12 produced in Example 22. Figure 20 is a 13C NMR spectrum of the highly branched polymer 13 produced in Example 23. • 68 - 201235369 Figure 2 1 is a spectrum. , the high-branched polymer 14 produced in Example 24

13C NMR -69-13C NMR -69-

Claims

201235369 VII. Patent application scope: 1. A fluorine-containing high-branched polymer, which is a monomer A having two or more radical polymerizable double bonds in a molecule, and a fluoroalkyl group in the molecule and at least a monomer B having a radically polymerizable double bond, and at least one photocationic polymerizable group selected from the group consisting of an alicyclic epoxy group and an oxypropylene group, and at least one radical The monomer C of the polymerizable double bond is polymerized in the presence of the polymerization initiator D in an amount of from 5 to 20 mol% relative to the monomer A. 2. The fluorine-containing highly branched polymer according to claim 1, wherein the monomer A is a compound having one or both of a vinyl group or a (meth)acryl group. 3. The fluorine-containing highly branched polymer of claim 2, wherein the monomer A is a divinyl compound or a (meth) acrylate compound. 4. The fluorine-containing highly branched polymer of claim 3, wherein the monomer A is an alicyclic di(meth)acrylate. 5. The fluorine-containing highly branched polymer of claim 4, wherein the monomer A is tricyclodecane dimethanol di(meth)acrylate. 6. The fluorine-containing high-branched polymer of claim 1, wherein the monomer B is used in an amount of from 5 to 300 mol% relative to the monomer A. 7. The fluorine-containing tubular branched polymer of claim 6, wherein the monomer B is a compound having one or both of a vinyl group or a (meth)acryl group. 8. The fluorine-containing highly branched polymer according to item 7 of the patent application, wherein -70 to 201235369, the monomer B is a compound represented by the following formula [1], wherein R1 represents a hydrogen atom or a methyl group. R2 represents a fluoroalkyl group having 2 to 12 carbon atoms which may be substituted by a hydroxyl group. 9. The fluorine-containing highly branched polymer according to item 8 of the patent application, wherein the monomer oxime is a compound represented by the following formula [2],

(wherein R1 represents the same definition as the above formula [1], X represents a hydrogen atom or a fluorine atom, m represents 1 or 2, and η represents an integer of 0 to 5). The fluorine-containing highly branched polymer of the first aspect of the patent application, wherein the monomer C is used in an amount of 10 to 300 mol% relative to the monomer. 11. The fluorine-containing highly branched polymer of claim 1, wherein the monomer C is a compound having one or both of a vinyl group or a (meth)acryl group. 12. The fluorine-containing highly branched polymer of claim 11, wherein the monomer C is a compound represented by the following formula [3], -71 - 201235369

(wherein R3 represents a hydrogen atom or a methyl group, L represents a single bond, or an alkylene group having 1 to 6 carbon atoms which may have an ether bond or an ester bond). 13. Fluorine-containing according to item 11 of the patent application scope a highly branched polymer wherein the aforementioned monomer C is a compound represented by the following formula [4],

(wherein R4 represents a hydrogen atom or a methyl group, R5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L represents a single bond, or an alkylene group having 1 to 6 carbon atoms which may have an ether bond or an ester bond base). The fluorine-containing high-branched polymer according to any one of claims 1 to 3, wherein the polymerization initiator D is an azo polymerization initiator 〇15. A fluorine-containing highly branched polymer of the fourth aspect, wherein the polymerization initiator D is dimethyl i,i'-azobis(1-cyclohexanecarboxylate). 1 6 · The fluorine-containing high-branched polymer according to claim 14 of the patent application, wherein the molar amount of the molar amount of 5 to 300 mol to 201235369 Å relative to the monomer A is the following formula [ 5] The monomer e is represented by copolymerization, [5] 乂 [51 (wherein R6 represents a hydrogen atom or a methyl group, and R7 represents an alkyl group having 6 to 30 carbon atoms or a carbon number of 3 to 30). Alicyclic group). A surface modifying agent for a photocationic polymerizable resin which is formed by a fluorine-containing high-branched polymer according to any one of claims 1 to 16 of the patent application. 18. Photocatalytic polymerization A resin composition comprising (a) a fluorine-containing highly branched polymer as described in any one of claims 1 to 6 and (b) a photocationic polymerizable resin prepolymer. The resin composition of claim 18, wherein the (a) fluorine-containing branched polymer is contained in an amount of from 0.2 to 2% by mass based on the mass of the (b) prepolymer. 20. The resin composition of claim 19, wherein the (b) prepolymer is a compound having at least one alicyclic epoxy group. 2 1 · A resin composition as claimed in claim 18, which additionally contains (c) a photoacid generator. 22. The resin composition according to claim 21, wherein the (c) photoacid generator is contained in an amount of from 5 to 30% by mass based on the mass of the prepolymer (b). 2 3. A hardened material obtained by a resin composition as claimed in any one of claims 18 to 22-73 to 201235369. A method for producing a fluorine-containing highly branched polymer, which comprises a monomer a having two or more radical polymerizable double bonds in a molecule, a fluoroalkyl group in the molecule, and at least one free a monomer B having a radical double bond, and at least one photocationic polymerizable group selected from the group consisting of an alicyclic epoxy group and an oxypropylene group, and at least one radical polymerizable group The monomer C of the double bond is polymerized in the presence of the polymerization initiator D in an amount of from 5 to 200 mol% relative to the monomer A. -74 -