200904851 九、發明說明 【發明所屬之技術領域】 本發明係關於有效地作爲被覆材料、成型或注型成形 所彳 之；7t學材料及電氣絕緣材料、封裝半導體發光裝置（ LED )等之氧雜環丁烷樹脂組成物。此氧雜環丁烷樹脂組 成物係賦予透明性、耐熱性、低吸水率性、低介電常數性 優異之硬化物。 【先前技術】 傳統上’已知環氧化合物及氧雜環丁烷化合物之熱硬 化或藉由活性能量線硬化之陽離子硬化技術，市售各種環 氧化合物、各種氧雜環丁烷化合物、各種陽離子聚合開始 劑。作爲環氧化合物，有雙酚A之二縮水甘油醚、雙酚ρ 之二縮水甘油醚、酚醛型環氧樹脂等之芳香族環氧樹脂、 環鏈烯烴之過醋酸氧化所得之3,4 -環氧基環己基甲基一 3’，4’ -環氧基環己烷羧酸鹽等之環狀脂肪族環氧樹脂或氫 化雙酚A二縮水甘油醚所得之氫化環氧樹脂等。作爲氧雜 環丁烷化合物，有3-乙基_3-羥甲基氧雜環丁烷、二甲 苯氧雜環丁烷 '雙（3 -乙基一 3—氧雜環丁烷基甲基）醚 、4,4’ 一雙[(3 -乙基一3_氧雜環丁 A兀基）甲氧基甲基] 聯苯等。 電氣用途中，近年來因電器的小型化而發展電路之多 層化、高密度化。因此，對於其所使用之環氧樹脂，要求 低介電常數化、耐電弧性、耐漏電性。爲提升此等電氣特 -5- 200904851 性’已知不具有芳香環之環狀脂肪族環氧樹脂或氫化型環 氧樹脂比芳香族環氧樹脂有效。另一方面，近年來各種顯 示板、影像讀取用光源、交通訊號、大型顯示用單位、行 動電話之背光等所實用化之發光二極體（led)等之發光 裝置’一般係使用脂環式酸酐作爲硬化劑於芳香族環氧樹 脂者’進行樹脂封裝所製造。但是，已知此樹脂系中酸酐 容易變色、或需要長時間硬化。另外，放置硬化封裝樹脂 於室外時、或曝曬於發生紫外線之光源時，有封裝樹脂發 生黃變色等之問題。 作爲解決此等問題點之手段，揭示如專利文獻1記載 之將氫化雙酚A二縮水甘油醚與脂環式環氧單體，藉由熱 陽離子聚合而使硬化之環氧樹脂。 但是，已知環氧化合物以陽離子聚合，因爲產生聚合 物鏈中氧原子之鹼性高於單體的鹼性，所以活性末端之氧 鐵陽離子與聚合物鏈中氧原子反應，因爲發生聚合停止， 所以聚合度無法上升。聚合度低係指分子鏈中之羥基濃度 高，成爲吸水率上升、介電常數上升之原因。另外，因爲 羥基之反應性高，成爲因熱或光而變色之重要原因。 另外，於專利文獻2揭示由脂肪族及環式脂肪族氧雜 環丁烷與陽離子聚合開始劑所形成之氧雜環丁烷樹脂組成 物。但是，僅脂肪族氧雜環丁烷之硬化物，因結構柔軟， 所以Tg低’不適合於上述用途。 〔專利文獻1〕特開2003 — 73452號公報 〔專利文獻2〕特開200 5 - 290 1 4 1號公報 200904851 【發明內容】 發明之揭示 發明所欲解決之課題 本發明係提供賦予透明性、耐熱性、低吸水率性、低 介電常數性優異之硬化物之硬化性氧雜環丁烷樹脂組成物 課題之解決手段 本發明者等爲解決上述課題，重複努力硏究的結果， 發現可達成此等目的之氧雜環丁烷樹脂組成物，而完成本 發明。 亦即，本發明係配合1 〇〜8 8重量％之環式脂肪族氧雜 環丁烷樹脂（A ) 、1 0〜8 8重量％之環狀脂肪族環氧樹脂 (B )、及相對於合計1 〇 〇重量份之環式脂肪族氧雜環丁 烷樹脂（A)及環狀脂肪族環氧樹脂（B)爲0.0 1〜20重 量份之熱陽離子聚合開始劑（C)而成爲特徵之氧雜環丁 烷樹脂組成物。 在此’環式脂肪族氧雜環丁烷樹脂（A )及環狀脂肪 族環氧樹脂（B)中任一種之分子量皆於1〇〇〜20〇〇之範 圍。 作爲環式脂肪族氧雜環丁烷樹脂（A )係可舉例如 4，4’ 一雙[(3~乙基一 3_氧雜環丁烷基）甲氧基甲基]雙 環己基、1，4 一雙[(3_乙基一 3 —氧雜環丁烷基）甲氧基 -7- 200904851 甲基]環己烷或此等之混合物。另外，作爲環狀脂肪族環 氧樹脂（B )係可舉例如3,4 -環氧基環己基甲基- 3’，4’ -環氧基環己垸殘酸酯。 另外，本發明係加熱硬化上述氧雜環丁烷樹脂組成物 所得之硬化物。 以下係詳細地說明關於本發明之氧雜環丁烷樹脂組成 物。 本發明之氧雜環丁烷樹脂組成物係含有環式脂肪族氧 雜環丁烷樹脂（A)、環狀脂肪族環氧樹脂（B )、及熱陽 離子聚合開始劑（C )作爲必要成份。在此，環式脂肪族 氧雜環丁烷樹脂（A)及環狀脂肪族環氧樹脂（B)係可爲 單一化合物，亦可爲由重複單位數量相異之化合物所成之 混合物。因此，關於環式脂肪族氧雜環丁烷樹脂（A )及 環狀脂肪族環氧樹脂（B )，亦可說爲脂肪族氧雜環丁烷 樹脂及環狀脂肪族環氧化合物。接著，以環式脂肪族氧雜 環丁烷樹脂（A )爲（A )成份，環狀脂肪族環氧樹脂（B )爲（B)成份，及熱陽離子聚合開始劑（C)爲（C)成 份。 本發明所使用之環式脂肪族氧雜環丁烷樹脂（A )係 藉由含脂環結構之醇所衍生者或氫化芳香環所得之氧雜環 丁烷樹脂。由氫化芳香環所得之氫化氧雜環丁烷樹脂時， 雖指芳香環之氫化率爲8 0%以上之氧雜環丁烷樹脂，但以 氫化率爲90 %以上者爲宜。氧雜環丁烷樹脂中之芳香環之 氫化率係芳香環變化成脂環之比率’可由核磁共振而求出 -8- 200904851 。此芳香環之氫化率若未滿80%時，因氧雜環丁痕 化物之電氣特性或耐候性大幅降低，所以不適宜。 因氧雜環丁烷化合物之分子中氧之鹼性高，所 離子聚合’具有可得到高分子量者之特徵。因此， 子鏈中之羥基濃度變低，低吸水率、低介電常數之 另外，亦提升耐熱性、耐光性。 (A )成份之環式脂肪族氧雜環丁烷樹脂係具 結構及鍵結於其之氧雜環丁烷基之化合物。其分 100以上，以 100〜2000爲宜，以120〜2000尤 150〜1 000之範圍更好。分子量過小時，環式脂肪 環丁烷化合物之揮發性高，使作業環境或塗佈時之 性明顯惡化。分子量過大時，因爲樹脂組成物之黏 ，變得難以注型、成型成所定形狀或均勻塗佈。 環式脂肪族氧雜環丁烷樹脂係有效地藉由將芳 雜環丁烷樹脂於觸媒之存在下，加壓下選擇地進行 應而可容易得到。在此所使用之芳香族氧雜環丁院 可舉例如雙酚A型氧雜環丁烷樹脂、雙酚F型氧雜 樹脂及雙酚S型氧雜環丁烷樹脂等之雙酚型氧雜環 脂、二苯酚之氧雜環丁烷基醚、四甲基二苯酚之氧 烷基醚等之二苯酚型氧雜環丁烷樹脂、萘酚之氧雜 基醚等之萘型氧雜環丁烷樹脂、雙羥甲基苯之氧雜 基醚等之二甲苯型氧雜環丁烷樹脂、雙羥甲基聯苯 環丁烷基醚等之二甲基聯苯型氧雜環丁烷樹脂、雙 萘之氧雜環丁烷基醚等之二甲基萘型氧雜環丁烷樹 樹脂硬 以於陽 表現分 特徵。 有脂環 子量係 佳，以 族氧雜 加工特 度變高 香族氧 氫化反 樹脂， 環丁烷 丁烷樹 雜環丁 環丁烷 環丁烷 之氧雜 羥甲基 脂、環 -9- 200904851 己烷二羧酸二氧雜環丁烷酯樹脂、苯酚漆用酚醛氧雜環丁 烷樹脂、甲酚漆用酚醛氧雜環丁烷樹脂、羥苯甲醛苯酚漆 用酚醛氧雜環丁烷樹脂等之酚醛型氧雜環丁烷樹脂、四氫 苯基甲烷之氧雜環丁烷基醚、四氫二苯甲酮之氧雜環丁烷 基醚及氧雜環丁烷化聚乙烯基苯酚等之多官能型氧雜環丁 烷樹脂等。 作爲環式脂肪族氧雜環丁院樹脂之具體例，可舉例如 下述（1 )〜（8 )所示之化合物。 【化1】200904851 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to an effective use as a coating material, molding or injection molding; 7t materials and electrical insulating materials, packaged semiconductor light-emitting devices (LED), etc. Cyclobutane resin composition. This oxetane resin composition imparts a cured product excellent in transparency, heat resistance, low water absorption, and low dielectric constant. [Prior Art] Conventionally, it is known that the epoxy compound and the oxetane compound are thermally hardened or the cation hardening technique by active energy ray hardening, various commercially available epoxy compounds, various oxetane compounds, various Cationic polymerization initiator. Examples of the epoxy compound include an aromatic epoxy resin such as bisphenol A diglycidyl ether, bisphenol ρ diglycidyl ether, and a novolac epoxy resin, and 3,4 - obtained by oxidation of a cyclic olefin by peracetic acid. A hydrogenated epoxy resin obtained by a cyclic aliphatic epoxy resin such as epoxycyclohexylmethyl- 3',4'-epoxycyclohexanecarboxylate or hydrogenated bisphenol A diglycidyl ether. As the oxetane compound, there are 3-ethyl-3-hydroxymethyl oxetane, xylene oxetane 'bis(3-ethyl-3-oxetanylmethyl) Ether, 4,4'-double [(3-ethyl-3-oxobutaninyl)methoxymethyl]biphenyl, and the like. In electrical applications, in recent years, the number of circuits has increased and the density has increased due to the miniaturization of electrical appliances. Therefore, for the epoxy resin used, low dielectric constant, arc resistance, and electric leakage resistance are required. In order to enhance these electrical properties, it is known that a cyclic aliphatic epoxy resin or a hydrogenated epoxy resin which does not have an aromatic ring is more effective than an aromatic epoxy resin. On the other hand, in recent years, various types of display panels, light sources for image reading, communication numbers, large display units, backlights for mobile phones, and the like have been used in light-emitting devices such as light-emitting diodes (LEDs). An acid anhydride is produced as a curing agent in a resin package of an aromatic epoxy resin. However, it is known that the acid anhydride in the resin is easily discolored or needs to be hardened for a long period of time. Further, when the hardened encapsulating resin is placed outdoors, or when exposed to a light source that generates ultraviolet rays, there is a problem that the encapsulating resin is yellow discolored or the like. As a means for solving such problems, an epoxy resin which is cured by thermal cationic polymerization of hydrogenated bisphenol A diglycidyl ether and an alicyclic epoxy monomer as disclosed in Patent Document 1 is disclosed. However, it is known that an epoxy compound is cationically polymerized because the basicity of the oxygen atom in the polymer chain is higher than the basicity of the monomer, so the active terminal oxy iron cation reacts with the oxygen atom in the polymer chain because polymerization stops. , so the degree of polymerization cannot rise. The low degree of polymerization means that the concentration of the hydroxyl group in the molecular chain is high, which causes the water absorption rate to rise and the dielectric constant to rise. Further, since the reactivity of the hydroxyl group is high, it is an important cause of discoloration due to heat or light. Further, Patent Document 2 discloses an oxetane resin composition formed of an aliphatic and cyclic aliphatic oxacyclobutane and a cationic polymerization initiator. However, since only the cured product of the aliphatic oxetane has a soft structure, the Tg is low is not suitable for the above use. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-73452 (Patent Document 2) JP-A-200- 290-119 discloses a problem to be solved by the present invention. In order to solve the above problems, the inventors of the present invention have found that the above-mentioned problems can be solved by resolving the above-mentioned problems, and it is found that the above-mentioned problems are solved by the inventors of the present invention. The oxetane resin composition for achieving such purposes is completed to complete the present invention. That is, the present invention is formulated with 1 to 88% by weight of a cyclic aliphatic oxetane resin (A), 10 to 88% by weight of a cyclic aliphatic epoxy resin (B), and relative The total amount of the cyclic aliphatic oxetane resin (A) and the cyclic aliphatic epoxy resin (B) is from 0.01 to 20 parts by weight of the thermal cationic polymerization initiator (C). A characteristic oxetane resin composition. The molecular weight of any of the 'cycloaliphatic oxetane resin (A) and the cyclic aliphatic epoxy resin (B) is in the range of from 1 Torr to 20 Torr. The cyclic aliphatic oxetane resin (A) may, for example, be 4,4'-bis[(3-ethyl-3-oxobutanealkyl)methoxymethyl]bicyclohexyl, 1 , 4 a pair of [(3_ethyl-3-oxobutanealkyl)methoxy-7- 200904851 methyl]cyclohexane or a mixture of these. Further, examples of the cyclic aliphatic epoxy resin (B) include a 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanolate residue. Further, the present invention is a cured product obtained by heating and curing the above oxetane resin composition. Hereinafter, the oxetane resin composition of the present invention will be described in detail. The oxetane resin composition of the present invention contains a cyclic aliphatic oxetane resin (A), a cyclic aliphatic epoxy resin (B), and a thermal cationic polymerization initiator (C) as essential components. . Here, the cyclic aliphatic oxetane resin (A) and the cyclic aliphatic epoxy resin (B) may be a single compound or a mixture of compounds having a different number of repeating units. Therefore, the cyclic aliphatic oxetane resin (A) and the cyclic aliphatic epoxy resin (B) may be referred to as an aliphatic oxetane resin and a cyclic aliphatic epoxy compound. Next, the cyclic aliphatic oxetane resin (A) is the component (A), the cyclic aliphatic epoxy resin (B) is the component (B), and the thermal cationic polymerization initiator (C) is (C). ) ingredients. The cyclic aliphatic oxetane resin (A) used in the present invention is an oxetane resin obtained by deriving an alcohol having an alicyclic structure or hydrogenating an aromatic ring. When the hydrogenated oxetane resin obtained by hydrogenating the aromatic ring is an oxetane resin having a hydrogenation ratio of the aromatic ring of 80% or more, the hydrogenation ratio is preferably 90% or more. The hydrogenation rate of the aromatic ring in the oxetane resin is a ratio of the aromatic ring to the alicyclic ring, which can be determined by nuclear magnetic resonance -8-200904851. When the hydrogenation rate of the aromatic ring is less than 80%, the electrical properties or weather resistance of the oxetane derivative are largely lowered, which is not preferable. Since the oxygen is highly basic in the molecule of the oxetane compound, the ion polymerization 'is characterized by a high molecular weight. Therefore, the concentration of the hydroxyl group in the sub-chain is lowered, and the low water absorption rate and the low dielectric constant are also improved in heat resistance and light resistance. The cyclic aliphatic oxetane resin of the component (A) has a structure and a compound bonded to the oxetane group. It is more than 100, preferably 100~2000, and more preferably in the range of 120~2000 especially 150~1 000. When the molecular weight is too small, the cyclic aliphatic cyclobutane compound has a high volatility, and the work environment or the coating property is remarkably deteriorated. When the molecular weight is too large, it becomes difficult to form, form into a predetermined shape or uniformly coat because of the viscosity of the resin composition. The cyclic aliphatic oxetane resin can be easily obtained by selectively carrying out the azetidine resin in the presence of a catalyst under pressure. The aromatic oxetane used herein may, for example, be a bisphenol type oxygen such as a bisphenol A type oxetane resin, a bisphenol F type oxygen resin or a bisphenol S type oxetane resin. a naphtho-type oxalate such as a diphenol type oxetane resin such as a heterocyclic ester, an oxetanyl ether of diphenol or an oxyalkyl ether of tetramethyl phenol, or an oxalyl ether of naphthol a dimethyl benzene type oxetane resin such as a cyclobutane resin or a xyloyl ether of bishydroxymethyl benzene or a dimethyl biphenyl butyl succinyl ether or the like The dimethylnaphthalene type oxetane resin such as an alkane resin or a biscyclo naphthyloxycyclobutane ether is hardly characterized by aging. It has a good amount of alicyclic ring, and has a high degree of aromatic oxygenation anti-resin, cyclobutane butane butane butane cyclobutane cyclobutane oxahydroxymethyl ester, ring-9 - 200904851 Hexanedicarboxylate dioxetane resin, phenolic oxetane resin for phenol paint, phenolic oxetane resin for cresol paint, phenolic oxetane for hydroxybenzaldehyde phenol paint Phenolic oxetane resin such as alkane resin, oxetanyl ether of tetrahydrophenylmethane, oxetanyl ether of tetrahydrobenzophenone, and oxetane polyethylene A polyfunctional oxetane resin such as phenol. Specific examples of the cyclic aliphatic oxetane resin include compounds represented by the following (1) to (8). 【化1】
-10- 200904851 【化2】-10- 200904851 【化2】
此等中，就原料取得之容易度等，以式（1)所表示 之〗，4 一雙[(3 —乙基一 3 —氧雜環丁烷基）甲氧基甲基] 環己院、或以式（2)所表示之4，4,一雙[(3 -乙基一 3 -氧雜環丁烷基）甲氧基甲基]雙環己基爲宜。 (B )成份之環狀脂肪族環氧樹脂係可有效地將環鏈 烯烴環氧化所得。 (B )成份之環狀脂肪族環氧樹脂係鍵結環氧基於脂 肪族環之化合物。分子量係100以上，以1〇〇〜2000爲宜 ，以120〜2000尤佳，以12〇〜100〇更好。分子量過小時 ’環狀脂肪族環氧樹脂之揮發性高，使作業環境或塗佈時 之加工特性明顯惡化。分子量過大時，因爲所得組成物之 黏度變高’變得難以注型 '成型成所定形狀或均勻塗佈。 -11 - 200904851 作爲環狀脂肪族環氧樹脂之具體例 )所示之化合物（例如Daicel化學製， 式（10)所示之化合物（例如旭Ciba公= AralditeCY178 等）、式（11)所示之化 Chisso 公司製，Chissonox206 等）、式 物（例如 Chisso 公司製，Chissonox205 )〜式（1 8 )所表示之化合物等。此等Γ{ 組成物之低黏度化及耐熱性之提升功效 所示之3，4 —環氧基環己基甲基一 3，，4’ -酸酯爲宜。 ，可舉例如式（9 CEL2021Ρ 等）、 司製’ 合物（例如 (1 2 )所示之化合 等）、或式（13 3 ’就提升本發明 上，係以式（9 ) 環氧基環己烷竣 -12- 200904851 【化3】 ΟIn the above, the ease of obtaining the raw materials, etc., represented by the formula (1), 4 bis[(3-ethyl-3-oxobutanealkyl)methoxymethyl]cyclohexanin Or, 4,4, a bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexyl group represented by the formula (2) is preferred. The cyclic aliphatic epoxy resin of the component (B) is effective for epoxidizing a cyclic olefin. The cyclic aliphatic epoxy resin-bonded epoxy of (B) component is a compound based on an aliphatic ring. The molecular weight is 100 or more, preferably from 1 to 2000, more preferably from 120 to 2,000, and even more preferably from 12 to 100. When the molecular weight is too small, the volatility of the cyclic aliphatic epoxy resin is high, and the processing characteristics in the working environment or coating are remarkably deteriorated. When the molecular weight is too large, the viscosity of the obtained composition becomes high, and it becomes difficult to form a shape. It is molded into a predetermined shape or uniformly coated. -11 - 200904851 A compound represented by a specific example of a cyclic aliphatic epoxy resin (for example, a compound represented by Daicel Chemical, a compound represented by the formula (10) (for example, Asahi Ciba = Araldite CY178, etc.), and a formula (11) A compound represented by Chisso Co., Ltd., Chissonox 206, etc., a compound (for example, Chissonox 205 manufactured by Chisso Co., Ltd.), and a compound represented by the formula (18). These 3,4-epoxycyclohexylmethyl-3,4'-esters are preferred for the low viscosity and heat resistance of the composition. For example, the formula (9 CEL2021Ρ, etc.), the compound (for example, the compound represented by (1 2 ), etc.), or the formula (13 3 ' enhances the present invention, and the epoxy group of the formula (9) Cyclohexane 竣-12- 200904851 【化3】 Ο
-13- 200904851 【化4】 Ο-13- 200904851 【化4】 Ο
ΟΟ
(15)(15)
作爲（C )成份之熱陽離子聚合開始劑係 熱而發生布朗斯台德酸、路易斯酸等之陽離子 種皆可使用。例如有機矽烷及有機鋁化合物觸 銹鹽等之鎗鹽、雜多酸。發生陽離子種之溫度 異’多爲50°C以上，就常溫之保存性，以使用 者爲宜。 具體上，作爲有機矽烷，可舉例如甲氧基 、乙氧基三乙基矽烷、丙氧基三丙基矽烷、丁 ，要藉由加 i者，任一 ;、鎏鹽、 〖依觸媒而 100°C以上 L甲基矽烷 ^基三丁基 -14- 200904851 矽烷、甲氧基三辛基矽烷、甲氧基三苯基矽烷、 苯甲基矽烷、三苯基羥基矽烷等之1官能矽烷化 甲氧基二甲基矽烷' 二甲氧基二乙基矽烷、二乙 基矽烷、二丙氧基二丙基矽烷、二甲氧基二月桂 二甲氧基二苯基矽烷、二甲氧基二苯甲基矽烷、 甲基氧二丙基矽烷、甲氧基2-乙基己基氧二丙 二苯基矽烷二醇等之2官能矽烷化合物；三甲氧 烷、三乙氧基乙基矽烷、三丙氧基丙基矽烷、三 脂醯基矽烷、三甲氧基苯基矽烷、三甲氧基苯甲 甲氧基二苯甲基氧丙基矽烷、甲氧基三羥基矽烷 羥基矽烷等之3官能矽烷化合物；四甲氧基矽烷 基矽烷、四丙氧基矽烷、四丁氧基矽烷、三甲氧 氧矽烷、二甲氧基二2 —乙基己基矽烷、四羥基 4官能矽烷化合物；上述3官能矽烷化合物及/或 烷化合物之低縮合物（約2〜5 0量體）；乙烯基 矽烷、乙烯基三乙氧基矽烷、乙烯基三（2 —甲 基）砂院、T 一（甲基）丙烯酶基氧丙基三甲氧 r_ (甲基）丙烯醯基氧丙基三乙氧基矽烷、r )丙烯醯基氧丙基甲基二甲氧基矽烷、々-（甲 醯基氧乙基丙基三甲氧基矽烷等之含反應性矽基 不飽和單體及因應需要之與上述其他之自由基聚 和單體之（共）聚合物等。可使用上述化合物之 合2種以上。作爲上述3官能矽烷化合物及/或 烷化合物之低縮合物（約2〜5 0量體），亦可使 甲氧基三 合物；二 氧基二丁 基矽烷、 甲氧基苯 基矽烷、 基甲基矽 甲氧基硬 基矽烷、 ' 苯基二 、四乙氧 基苯甲基 矽烷等之 4官能矽 三甲氧基 氧基乙氧 基矽烷、 —(甲基 基）丙烯 之乙烯性 合性不飽 1種或組 4官能矽 用取得商 -15- 200904851 品名SH6018(Toray Silicone (股）製：徑基單量4〇〇，分 子量1 6 00之甲基苯基聚砂氧烷）等之聚矽氧烷樹脂。就 反應性、取得容易度’以取得二苯基砂院醇、SH6018等 商品名之聚矽氧烷樹脂爲宜。 作爲有機鋁化合物’可使用烷氧基金屬、螯合物等。 具體上’可舉例如三乙氧基鋁、三異丙氧基鋁、仲丁酸銘 等之院氧基金屬類、乙基乙醯乙酸鋁二異丙酸酯、三（乙 基乙酿乙酸）銘、二（丙基乙酸）銘、三（丁基乙酸乙酸 )鋁、丙氧基雙（乙基乙醯乙酸）鋁、三（乙醯丙酮）銘 、三（丙醯丙酮）鋁、三（乙醯替丙酮）鋁等之酮.烯醇 互變異構物之螯化物等。可使用此等之1種或組合2種以 上。此等中，若考慮硬化性、經濟性時，以三異丙氧基鋁 、乙基乙醯替乙酸鋁二異丙酸酯、三（乙醯替丙酮）鋁爲 宜。 作爲錢鹽，可舉例如苯甲基-4 -羥基苯基甲基鎏六 氟銻酸鹽、苯甲基- 4一羥基苯基甲基鎏六氟磷酸鹽、4-乙酸基苯基苯甲基甲基鎏六氟銻酸鹽、4 -乙酸基苯基二 甲基鎏六氟銻酸鹽、苯甲基一4 一甲氧基苯基甲基鎏六氟 銻酸鹽、苯甲基一 2—甲基一4一羥基苯基甲基鎏六氟銻酸 鹽、苯甲基一 3—氯一 4 —羥基苯基甲基鎏六氟砷酸鹽、苯 甲基一3 —甲基一 4一羥基一5 —叔丁基苯基甲基鎏六氟銻 酸鹽、4一甲氧基苯甲基- 4一羥基苯基甲基鎏六氟磷酸鹽 、二苯甲基一 4一羥基苯基鎏六氟銻酸鹽、二苯甲基一4 一 羥基苯基鎏六氟磷酸鹽、4 -甲氧基苯基二苯甲基鎏六氟 -16- 200904851 銻酸鹽、二苯甲基一 4 一甲氧基苯基鎏六氟銻酸鹽、硝基 苯甲基—4 —羥基苯基甲基鎏六氟銻酸鹽、3,5 一二硝基苯 甲基一 4 -羥基苯基甲基鎏六氟銻酸鹽、点一萘基甲基—4 一羥基苯基甲基鎏六氟銻酸鹽等。作爲鎏鹽之市售品，可 舉例如8311-八1(181-[85、8&11-八1(131-[110、3&11-八1(181-L145 ' San-Aid SI-L160 ' San-Aid SI-H15 ' San-Aid SI-H20、San-Aid SI-H25、San-Aid SI-H40、San-Aid SI-H50 、San-Aid SI-60L' San-Aid SI-80L > San-Aid SI-100L、 San-Aid SI-80' San-Aid SI-100 (三新化學工業股份有限 公司製，商品名）、CP_ 77 ( ADEKA股份有限公司製） 等。就取得之容易度，以San-Aid SI類、CP — 77爲宜。 關於雜多酸，例如單鉬（IV )或鎢（VI )離子於水中 成爲羰酸。此等羰酸聚合而成高分子多羰酸。此時，不僅 同種類之羰酸聚合，亦有某羰酸周圍聚合其他種類之羰酸 。如此之化合物稱爲雜多酸。形成中心羰酸之元素稱爲雜 元素，其周圍聚合羰酸之元素稱爲多元素。作爲雜元素， 有Si、P、As、S、Fe、Co等，作爲多元素，有Mo、W、 V等。因爲聚合時，對雜元素之多元素數量亦有多種，所 以此等之組合係可製造許多雜多酸。本說明中只要爲如此 之雜多酸，皆可使用，並無限制。 就硬化性能、取得容易度上’以磷鎢酸、磷鉬酸、矽 鎢酸、矽鉬酸爲宜，以矽鎢酸、矽鉬酸尤佳。另外，亦可 使用此等之鹽、鈉鹽、鉋鹽、銨鹽、吡啶鎗鹽等。 本發明之硬化性氧雜環丁烷樹脂組成物係含有1 0〜8 8 -17- 200904851 重量％之（A )成份，以2 5〜7 5重量％爲宜’ 1 〇〜8 8重量 %之（Β)成份，以25〜75重量％爲宜’含有（C)成份’ 相對於合計1 00重量份之（A )成份及（Β )成份爲〇.〇1 〜20重量份，以0.02〜10重量份爲宜，以〇.1〜2重量份 尤佳。 就其他觀點，相對於5 0重量份之（A )成份’ （B ) 成份爲10〜200重量份，以使用25〜75重量份爲宜。此 (B)成份係有效地用以提升硬化物之耐熱性。（B )成份 之環狀脂肪族環氧樹脂若未滿1 〇重量％時’硬化物之耐熱 改良效果減少，另外，若超過9 0重量％時’硬化物變脆’ 所以不適宜。組合物中之（C )成份爲0.02〜10重量％ ’ 以0.1〜2重量％爲宜。此時，含有（A)成份爲20〜70重 量％，以25〜75重量％爲宜，（B)成份爲20〜70重量％ ，以2 3〜7 3重量％爲宜。 (C )成份之熱陽離子聚合開始劑係配合相對於合計 1 〇〇重量份之（A )成份之環式脂肪族氧雜環丁烷樹脂及 (B )成份之環狀脂肪族環氧樹脂爲0.01〜20重量份。熱 陽離子硬化觸媒之含量若過剩時，保存安定性可能降低。 另外，熱陽離子硬化觸媒之含量若少時，硬化速度降低， 組成物之硬化不足。 本發明之氧雜環丁烷樹脂組成物中，以改善樹脂性質 爲目的，因應需要，作爲上述（A)〜（C)成份以外之成 份，可配合各種硬化性單體、寡聚物及合成樹脂。例如單 環氧基等之環氧樹脂用稀釋劑、二元醇或三元醇類、乙烯 -18- 200904851 醚類、（A )成份以外之氧雜環丁烷化合物、氟樹脂、丙 稀酸樹脂、聚砍氧院樹脂 '聚酯樹脂等。但是’此等成份 配合比率之使用範圍，因爲有損害本發明樹脂組成物原本 性質之虞，所以以樹脂組成物之3 0重量％以下爲宜，以 2 0重量％以下之尤佳。 另外，本發明之氧雜環丁烷樹脂組成物中，雖亦可配 合無機塡充材料’但因爲使用此等可能阻礙本發明特徵之 透明性，所以適合不損害其者，例如粒徑非常小之經表面 處理之二氧化矽粒子。即使使用其時，相對於1 〇〇重量份 之樹脂組成物，使用範圍以40重量份以下爲宜，尤其以 2 0重量份以下尤佳。另外’如大量配合之無機塡充材料之 增量材料、如溶劑之稀釋劑係可作爲氧雜環丁烷樹脂組成 物之外數計算。 另外，本發明之組成物中，因應其目的，可配合顏料 等之著色劑、難燃劑、交聯劑、上述以外之安定劑等之其 他添加劑。 本發明之氧雜環丁烷樹脂組成物係可於上述（A )〜 (C )成份’因應需要，配合其他成份，可加熱溶融混合 、由滾輪、捏和機之溶融混練、使用適當有機溶劑之濕式 混合及乾式混合等而製造。 如此所製造之氧雜環丁烷樹脂組成物係由熱所硬化， 成爲本發明之硬化物。熱陽離子聚合時，通常係於該熱陽 離子聚合開始劑開始發生陽離子種或路易斯酸之溫度以上 進行，通常於50〜200 t實施。 -19- 200904851 用以實施發明之最佳形態 以下係舉實施例及比較例，更詳細地說明本發明。 簡稱如下所示。 BMBH:4,4,一雙[(3-乙基一 3—氧雜環丁烷基）甲氧 基甲基]雙環己基As the thermal cationic polymerization initiator of the component (C), a cationic species such as a Bronsted acid or a Lewis acid can be used. For example, organic decane and organoaluminum compounds can be used as a salt and a heteropoly acid. The temperature at which the cationic species is generated is more than 50 ° C, and the storage property at normal temperature is preferably used by the user. Specifically, examples of the organic decane include a methoxy group, an ethoxy triethyl decane, a propoxy tripropyl decane, and a butyl group, which are to be added by any of them, a cerium salt, and a catalyst. And 100 ° C or more L-methyl decane-tributyl-14-200904851 decane, methoxy trioctyl decane, methoxy triphenyl decane, benzyl decane, triphenyl hydroxy decane, etc. Dealkylated methoxy dimethyl decane 'dimethoxy diethyl decane, diethyl decane, dipropoxy dipropyl decane, dimethoxy dilaurodimethoxy diphenyl decane, dimethyl a 2-functional decane compound such as oxydiphenylmethyl decane, methyl oxydipropyl decane, methoxy 2-ethylhexyloxy dipropylene diphenyl decane diol; trimethoxy hydride, triethoxyethyl Decane, tripropoxypropyl decane, tris-decyl decane, trimethoxyphenyl decane, trimethoxy benzyl methoxy dibenzomethyl propyl decane, methoxy trihydroxy decane hydroxy decane, etc. 3-functional decane compound; tetramethoxy decyl decane, tetrapropoxy decane, tetrabutoxy decane, trimethoxy oxane Dimethoxydi-2-ethylhexyldecane, tetrahydroxy 4-functional decane compound; low condensate of the above 3-functional decane compound and/or alkyl compound (about 2 to 50 vol); vinyl decane, vinyl three Ethoxy decane, vinyl tris(2-methyl) sand, T-(meth)propenyloxypropyltrimethoxy r_(methyl)propenyloxypropyltriethoxydecane, r) a reactive thiol-unsaturated monomer such as acrylonitrile methoxypropylmethyldimethoxy decane or hydrazine-(methyl decyloxyethyl propyl trimethoxy decane and the like and other free radicals as described above The poly(mono) polymer or the like may be used. Two or more kinds of the above compounds may be used. The low condensate (about 2 to 50 parts) of the above trifunctional decane compound and/or the alkyl compound may be used. a methoxytriene; a dioxydibutyl decane, a methoxyphenyl decane, a methyl methoxy methoxy decane, a 4-functional group such as 'phenyl di-tetraethoxy benzyl decane Ethylene triacetoxyethoxy decane, (meth) propylene ethylene heterosis 1 Or a group of 4 functional 取得 取得 -15-200904851 Product name SH6018 (Toray Silicone (stock): diameter basis amount 4 〇〇, molecular weight 1 600 00 methyl phenyl polyoxaxane) and other polyoxyalkylene oxide In the case of the resin, it is preferable to obtain a polyoxyalkylene resin of a trade name such as diphenyl sand alcohol or SH6018. As the organoaluminum compound, an alkoxide metal, a chelate compound or the like can be used. The above can be mentioned, for example, triethoxy aluminum, triisopropoxy aluminum, sec-butyric acid, etc., an epoxy metal, ethyl acetoacetate aluminum diisopropylate, tris(ethyl ethyl acetate) Ming, di(propyl acetate), tris(butylacetate)aluminum, propoxy bis(ethylacetamidineacetic acid)aluminum, tris(acetonitrile)aluminum, tris(propionylacetone)aluminum, three ( Acetone is a ketone of aluminum or the like, a chelate of an enol tautomer, and the like. One type or a combination of two or more types can be used. Among these, in view of hardenability and economy, it is preferred to use aluminum triisopropoxide, ethyl acetoacetate, aluminum diisopropylate or tris(acetonitrile) aluminum. As the money salt, for example, benzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzene Methyl hydrazine hexafluoroantimonate, 4-acetoxyphenyl dimethyl hexafluoroantimonate, benzyl 4-tetramethoxyphenylmethyl hexafluoroantimonate, benzyl one 2-methyl-1,4-hydroxyphenylmethyl hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethyl hexafluoroarsenate, benzyl-3-methyl- 4-hydroxy-5-t-butylphenylmethylphosphonium hexafluoroantimonate, 4-methoxybenzyl- 4-hydroxyphenylmethylphosphonium hexafluorophosphate, diphenylmethyl-4-hydroxyl Phenyl hydrazine hexafluoroantimonate, diphenylmethyl-4-hydroxyphenyl sulfonium hexafluorophosphate, 4-methoxyphenyl diphenylmethyl hexafluoro-16- 200904851 phthalate, diphenyl 4-Methoxyphenylphosphonium hexafluoroantimonate, nitrobenzyl- 4-hydroxyphenylmethylphosphonium hexafluoroantimonate, 3,5-dinitrobenzyl- 4-hydroxyl Phenylmethyl hydrazine hexafluoroantimonate, p-naphthylmethyl-4 tetrahydroxyphenyl Gilt hexafluoroantimonate and the like. As a commercial product of strontium salt, for example, 8311-eight 1 (181-[85, 8&11-eight 1 (131-[110, 3&11-eight 1 (181-L145 ' San-Aid SI-L160) ' San-Aid SI-H15 ' San-Aid SI-H20, San-Aid SI-H25, San-Aid SI-H40, San-Aid SI-H50, San-Aid SI-60L' San-Aid SI-80L > ; San-Aid SI-100L, San-Aid SI-80' San-Aid SI-100 (made by Sanshin Chemical Industry Co., Ltd., trade name), CP_ 77 (made by ADEKA Co., Ltd.), etc. Degrees, such as San-Aid SI, CP-77. About heteropolyacids, such as mono-molybdenum (IV) or tungsten (VI) ions, become carboxylic acid in water. These carboxylic acids are polymerized to form polymer polycarboxylic acid. At this time, not only the same type of carboxylic acid is polymerized, but also some other carboxylic acid is polymerized around the carboxylic acid. Such a compound is called a heteropoly acid. The element forming the central carboxylic acid is called a hetero element, and the surrounding carboxylic acid is polymerized. The element is called a multi-element. As a hetero element, there are Si, P, As, S, Fe, Co, etc. As a multi-element, there are Mo, W, V, etc. Because of polymerization, the number of elements of the hetero element is also a variety, so the combination of these can be Many heteropoly acids are produced. In this description, as long as it is such a heteropoly acid, it can be used without limitation. In terms of hardening properties and ease of use, it is made of phosphotungstic acid, phosphomolybdic acid, tungstic acid, and lanthanum molybdate. Preferably, lanthanum tungstic acid or lanthanum molybdate is used. Further, such salts, sodium salts, planing salts, ammonium salts, pyridine gun salts, etc. may be used. The curable oxetane resin of the present invention is composed of The system contains 10 to 8 8 -17- 200904851% by weight of (A) component, and 2 5 to 7 5 wt% is preferably '1 〇~8 8 wt% (Β) component, 25 to 75 wt% Preferably, the component (C) is contained in an amount of (A) component and (Β) component is 〇. 〇1 to 20 parts by weight, preferably 0.02 to 10 parts by weight, preferably 〇.1~ 2 parts by weight is particularly preferred. From other points of view, the component (B) of the component (B) is 10 to 200 parts by weight, preferably 25 to 75 parts by weight, based on 50 parts by weight. The component (B) is effective. The ground is used to improve the heat resistance of the cured product. If the cyclic aliphatic epoxy resin of the component (B) is less than 1% by weight, the heat-resistant improvement effect of the cured product is reduced, and When it exceeds 90% by weight, the 'hardened material becomes brittle', so it is not suitable. The component (C) in the composition is 0.02 to 10% by weight, preferably 0.1 to 2% by weight. In this case, the component (A) is 20 It is preferably from 70 to 75% by weight, and the component (B) is from 20 to 70% by weight, preferably from 2 3 to 73% by weight. The thermal cationic polymerization initiator of the component (C) is blended with a cyclic aliphatic oxetane resin having a total of 1 part by weight of the component (A) and a cyclic aliphatic epoxy resin of the component (B). 0.01 to 20 parts by weight. If the content of the thermal cation hardening catalyst is excessive, the storage stability may be lowered. Further, when the content of the thermal cation hardening catalyst is small, the curing rate is lowered and the hardening of the composition is insufficient. In the oxetane resin composition of the present invention, for the purpose of improving the properties of the resin, if necessary, various components other than the components (A) to (C) may be blended with various curable monomers, oligomers and synthetics. Resin. For example, a diluent for an epoxy resin such as a monoepoxy group, a glycol or a triol, an ethylene-18-200904851 ether, an oxetane compound other than the component (A), a fluororesin, or an acrylic acid Resin, polyoxane resin 'polyester resin, etc. However, the use range of the component blending ratio is preferably 30% by weight or less of the resin composition, and more preferably 20% by weight or less, because it has a defect in the original properties of the resin composition of the present invention. Further, in the oxetane resin composition of the present invention, an inorganic chelating material may be blended. However, since the use of these may hinder the transparency of the features of the present invention, it is suitable for not impairing, for example, the particle size is very small. The surface treated cerium oxide particles. When it is used, the use range is preferably 40 parts by weight or less, particularly preferably 20 parts by weight or less, based on 1 part by weight of the resin composition. Further, an incremental material such as a solvent which is a large amount of an inorganic chelating material, such as a solvent, can be calculated as a octetane resin composition. Further, in the composition of the present invention, other additives such as a coloring agent such as a pigment, a flame retardant, a crosslinking agent, and a stabilizer other than the above may be blended in accordance with the purpose. The oxetane resin composition of the present invention can be combined with other components in the above (A) to (C) components, and can be heated and melted and mixed, melted by a roller and a kneader, and used with an appropriate organic solvent. Manufactured by wet mixing, dry mixing, and the like. The oxetane resin composition thus produced is cured by heat and becomes a cured product of the present invention. In the case of thermal cationic polymerization, it is usually carried out at a temperature above the temperature at which the cationic cation polymerization initiator starts to generate a cationic species or a Lewis acid, and is usually carried out at 50 to 200 t. -19- 200904851 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. The abbreviation is as follows. BMBH: 4,4, a pair of [(3-ethyl-3-oxetanyl)methoxymethyl]dicyclohexyl
CEL202 1 P: 3,4-環氧基環己基甲基一 3’，4’ 一環氧基 環己烷羧酸酯（Daicel化學製 CEL202 1 P) 【實施方式】 實施例 實施例1 將 50重量份之 BMBH、50重量份之 CEL202 1 P、 0.3 3 5重量份之CP— 77 ( ADEKA股份有限公司製鎏鹽系 陽離子聚合開始劑），於室溫下攪拌混合，使均勻後，減 壓去泡，得到氧雜環丁烷樹脂組成物。 實施例2 將50重量份之BMBH、50重量份之CEL202 1 P、0.5 重量份之乙醯乙酸鋁（東京化成工業股份有限公司製）、 0.5重量份之三苯基矽烷醇（東京化成工業股份有限公司 製），於室溫下攪拌混合，使均勻後，減壓去泡，得到氧 雜環丁烷樹脂組成物。 -20- 200904851 實施例3 將50重量份之1,4_雙[(3—乙基_3-氧雜環丁烷 基）甲氧基甲基]環己烷、50重量份之CEL2021P、0.67重 量份之CP _ 77，於室溫下攪拌混合，使均勻後，減壓去 泡，得到氧雜環丁烷樹脂組成物。 實施例4 (比較） 將50重量份之氫化雙酧A二縮水甘油醚（宇部興產 化學股份有限公司製）、50重量份之 CEL2021P、0.335 重量份之CP — 7 7，於室溫下攪拌混合，使均勻後，減壓 去泡’得到氧雜環丁烷樹脂組成物。 將實施例及比較例所得之各樹脂組物，倒入模型，以 6 0 °C，4小時，進而1 5 0 °C，2小時，藉由於烤箱中加熱而得 硬化物。關於此等硬化物，進行玻璃轉移點、初期穿透率 、耐熱性、彎曲強度、吸濕性、介電常數之試驗。其結果 係如表1所示。 玻璃轉移點（Tg )係依DMA法。初期穿透率係測定 厚度4mm硬化物之4〇〇nm之穿透度。耐熱性係保持硬化 物於空氣中1 5〇。(：，24小時後，與初期穿透率同樣地測定 4〇Onm之穿透度。彎曲強度係由JIS 691丨所記載之方法測 定。吸濕性係於85〇C，85%RH，100小時之條件測定。介 電常數係於空洞共振器攝動法（perturbation )中之2GHz 之測定値。 -21 - 200904851 〔表1〕 Tg rc ) 初期穿透率 (%) 耐熱性 (%) 彎曲強度 (Mpa) 吸濕率 (%) 介電常數 實施例1 136 86 69 98 2.03 2.33 實施例2 138 85 54 88 1.71 2.34 實施例3 155 83 68 78 2.81 2.36 實施例4 171 65 35 83 3.96 2.58 產業上利用性 依據本發明，可得到賦予透明性、耐熱性、低吸水率 性、低介電常數性優異之硬化物之氧雜環丁烷樹脂組成物 。此氧雜環丁烷樹脂組成物係可使用於作爲被覆材料、成 型或注型成形所得之光學材料及電氣絕緣材料之廣泛用途 。另外，運用其透明性及低熱變色性之特性，可適合使用 爲發光二極體（LED )等之發光裝置之封裝樹脂。 -22-CEL202 1 P: 3,4-epoxycyclohexylmethyl- 3',4'-epoxycyclohexanecarboxylate (CEL202 1 P, manufactured by Daicel Chemical Co., Ltd.) [Embodiment] Example 1 B parts by weight of BMBH, 50 parts by weight of CEL202 1 P, 0.33 parts by weight of CP-77 (a salt-based cationic polymerization initiator prepared by ADEKA Co., Ltd.), stirred and mixed at room temperature to make it uniform, and then decompressed. Defoaming gives an oxetane resin composition. Example 2 50 parts by weight of BMBH, 50 parts by weight of CEL202 1 P, 0.5 parts by weight of aluminum acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.5 parts by weight of triphenylstanol (Tokyo Chemical Industry Co., Ltd.) The product was prepared by stirring at room temperature, homogenizing, and defoaming under reduced pressure to obtain an oxetane resin composition. -20- 200904851 Example 3 50 parts by weight of 1,4 bis[(3-ethyl-3-octophenanthryl)methoxymethyl]cyclohexane, 50 parts by weight of CEL2021P, 0.67 The parts by weight of CP _ 77 were stirred and mixed at room temperature to homogenize, and then defoamed under reduced pressure to obtain an oxetane resin composition. Example 4 (Comparative) 50 parts by weight of hydrogenated biguanide A diglycidyl ether (manufactured by Ube Industries, Ltd.), 50 parts by weight of CEL2021P, and 0.335 parts by weight of CP-77 were stirred at room temperature. After mixing, the mixture was degassed under reduced pressure to obtain an oxetane resin composition. Each of the resin compositions obtained in the examples and the comparative examples was poured into a mold to obtain a cured product by heating in an oven at 60 ° C for 4 hours and further at 150 ° C for 2 hours. For these cured products, tests for glass transition point, initial transmittance, heat resistance, bending strength, hygroscopicity, and dielectric constant were carried out. The results are shown in Table 1. The glass transfer point (Tg) is based on the DMA method. The initial penetration rate was measured at a penetration of 4 〇〇 nm of a 4 mm thick cured product. The heat resistance keeps the hardened material in the air at 15 Torr. (: After 24 hours, the penetration of 4 〇 Onm was measured in the same manner as the initial penetration rate. The bending strength was measured by the method described in JIS 691. The hygroscopicity was 85 〇C, 85% RH, 100. The measurement of the hour is based on the measurement of 2 GHz in the cavity resonator perturbation method. -21 - 200904851 [Table 1] Tg rc ) Initial transmittance (%) Heat resistance (%) Bending Strength (Mpa) Moisture absorption (%) Dielectric constant Example 1 136 86 69 98 2.03 2.33 Example 2 138 85 54 88 1.71 2.34 Example 3 155 83 68 78 2.81 2.36 Example 4 171 65 35 83 3.96 2.58 Industry According to the present invention, an oxetane resin composition which imparts a cured product excellent in transparency, heat resistance, low water absorption, and low dielectric constant can be obtained. The oxetane resin composition can be used for a wide range of applications as optical materials and electrical insulating materials obtained as a coating material, molding or injection molding. Further, by using the characteristics of transparency and low thermal discoloration, it is suitable to use a sealing resin which is a light-emitting device such as a light-emitting diode (LED). -twenty two-