TWI261727B - Epoxy copolymer and resin composition thereof - Google Patents
Epoxy copolymer and resin composition thereof Download PDFInfo
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1261727 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種多環氧基之高分子及其樹脂組成 物，尤指一種適於微機電系統用感光材料，即厚膜光阻， 以及塗料、油墨、或光阻等光硬化和熱硬化領域之多環氧 基之局分子及其樹脂組成物。 【先前技術】 4 機電系統（Micro Electro-Mechanical System)是結合 1〇半導體技術與超精密加工的前瞻技術。系統微小化帶來許 多優點，如節省材料、空間、環保、節約能源，更重要的 是如果技術成熟，還可以經濟量產。由於產品的大小，符 合黾子產u口輕、溥、短、小的未來發展趨勢，因此，微機 電系統技術被認為將是21世紀產業技術的主流。 15 微機電系統包含微感測器、微致動器、電子系統三部 刀。自然界的類比訊號如聲、光、震動、溫度等，經由微 感測杰（sensor)接收上述訊號之後，經過類比數位轉換 (ADC)成為數位訊號之後，交由控制器處理， 處理過後的數位訊號在經類比轉換（DAC)後交由微致動器 2〇 (aCtUat〇r)反應做出控制器所欲傳達的動作至外界。 臧感測器技術層次高，含有半導體技術、微電子技術， 因技術進步快，造成製程難度高、發展尚未成熟等障礙。 /、中光阻材料疋影響製程的關鍵材料。目前，微感測器 產°口製程中使用的光阻最常用的SU-8光阻如下式（2)， 1261727BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyepoxy group polymer and a resin composition thereof, and more particularly to a photosensitive material suitable for a microelectromechanical system, that is, a thick film photoresist, and A polyepoxy group in the field of photohardening and thermal hardening such as coatings, inks, or photoresists, and a resin composition thereof. [Prior Art] 4 The Micro Electro-Mechanical System is a forward-looking technology that combines semiconductor technology with ultra-precision machining. System miniaturization brings many advantages, such as saving materials, space, environmental protection, energy conservation, and more importantly, if the technology is mature, it can also be mass-produced. Due to the size of the product, it is in line with the future development trend of light, sputum, short and small. Therefore, the microcomputer system technology is considered to be the mainstream of the 21st century industrial technology. 15 The MEMS system consists of a micro-sensor, a microactuator, and an electronic system. The analog signal of nature, such as sound, light, vibration, temperature, etc., receives the signal through the sensor, and after the analog-to-digital conversion (ADC) becomes a digital signal, it is processed by the controller, and the processed digital signal is processed. After the analog conversion (DAC), the microactuator 2A (aCtUat〇r) reacts to make the controller want to convey the action to the outside world. The sensor technology has a high level of technology, including semiconductor technology and microelectronic technology. Due to rapid technological advancement, the process is difficult and the development is not yet mature. /, medium photoresist material 疋 affects the key materials of the process. At present, the most commonly used SU-8 photoresist for the photoresist used in the micro-sensor production process is as follows (2), 1261727
(式2) 〜 cn2 ch2 > \> {> \>(Formula 2) ~ cn2 ch2 >\>{>\>
雖然具有低分子量可提高光阻之固含量，降低溶劑使 用量，高光穿透性可製作厚膜，具化學增幅性而有高感度、 易:坦化等優點，但是也具有如下的缺點：（1)高交聯 使得收縮量過大，易造成矽晶片碎裂及變形，（2)黏結 (binder)树月曰無法因應需求而變化，（3)雖能耐受電鑄液， 但完成電鑄後，脫膜困難。 一般光阻組成物可應用於印刷電路板和封裝等領域， 組成物含有多環氧基樹脂，如SU-8等、反應型稀釋劑和 10陽離子型光起始劑。其中，多環氧基樹脂（su-8等）具有低 分子量和多個環氧基，所以交聯度很高，使得收縮量過大-，Although having a low molecular weight can increase the solid content of the photoresist, reduce the amount of solvent used, high light transmittance can be made into a thick film, has chemical amplification, and has high sensitivity, easy to bened, etc., but has the following disadvantages: 1) High cross-linking makes the shrinkage too large, which is easy to cause chipping and deformation of the crucible wafer. (2) The binder cannot be changed according to the demand. (3) Although it can withstand electroforming, but after electroforming, It is difficult to remove the film. The general photoresist composition can be applied to fields such as printed circuit boards and packages, and the composition contains a polyepoxy resin such as SU-8 or the like, a reactive diluent, and a 10 cationic photoinitiator. Among them, a polyepoxy resin (su-8 or the like) has a low molecular weight and a plurality of epoxy groups, so that the degree of crosslinking is high, so that the amount of shrinkage is too large -
易造成基材碎裂及變形，而且樹脂分子固定無法因應需 而變化調整。 本發明之樹脂組成物中，多環氧基之高分子是經 Ί 工田鱗_ 鎖聚合反應形成。並由共聚物組成設計，可輕易調整枣氧 基數量（即交聯數），不會使基材碎裂或變形。另外也可二。 整共聚物單體，應付其他不同物性需求。 周 【發明内容】 7 1261727 本發明之主要目的係在提供一種樹脂組成物，俾能增 加感光性、提升而ί熱性、並輕易地調整各官能基含量，因 應各種製程需求。 本發明之另一目的係在提供一種多環氧基之高分 5 子，俾能同時具有良好之顯影性及解析度，並可提升耐熱 性。 為達成上述目的，本發明之樹脂組成物，主要包括一 種具有環氧基之高分子，該高分子由異三聚氰酸鹽 (isocyanurate)所聚合或共聚合而成，該高分子重量百分比 10 為該樹脂組成物之1%〜99% ;以及一反應性稀釋劑，其重 量百分比為總重量之1%〜99%。 為達成上述目的，本發明之多環氧基之高分子係經由 鏈鎖聚合反應形成，其中環氧基由異三聚氰酸鹽 (isocyanurate)系化合物所提供。 15 【實施方式】 本發明之樹脂組成物，包含由鏈鎖聚合反應得到具多 環氧基之高分子，此聚合反應所使用之異三聚氰酸鹽 (isocyanurate)，R!較佳為 Ci_C6 之連接基或為-COO-，R2 20 較佳為-CH3或-H。此外，多環氧基之高分子亦可為異三聚 氰酸鹽（isocyanurate)與至少一具不飽合雙鍵之單體共聚合 而成，此不飽合雙鍵之單體，可調整各官能基含量，其較 佳選自由丙浠酸曱醋（methyl acrylate)、曱基丙烯酸曱酉旨 (methyl methacrylate)、丙烯酸乙醋（ethyl acrylate)、曱基 1261727 丙稀酸乙酉旨（ethyl methacrylate)、丙稀酸丙醋（propyl acrylate)、曱基丙稀酸丙酯（propyl methacrylate)、丙稀酸 異丙酉旨（isopropyl acrylate)、曱基丙稀酸異丙醋（isopropyl methacrylate)、丙烯酸丁酯（butyl acrylate)、曱基丙稀酸丁 5 S旨（butyl methacrylate)、丙稀酸異丁酯（isobutyl acrylate)、 曱基丙稀酸異丁醋（isobutyl methacrylate)、丙稀酸三級丁 酯（t-butyl acrylate)、曱基丙烯酸三級丁酯（t-butyl methacrylate)、丙稀酸乙基己基酯（ethylhexyl acrylate)、曱 基丙稀酸乙基己基@旨（ethylhexyl methacrylate)、丙稀酸苯 10 曱S旨（benzyl acrylate)、曱基丙稀酸苯曱酉旨（benzyl methacrylate)、丙浠酸苯酯（phenyl acrylate)、甲基丙烯酸 苯酯（phenyl methacrylate)、丙稀酸環己酉旨（cyclohexyl acrylate)、曱基丙烯酸環己醋（cyclohexyl methacrylate)、丙 稀酸苯氧基乙醋（phenoxyethyl acrylate)、曱基丙稀酸苯氧 15 基乙酯（phenoxyethyl methacrylate)、丙烯酸異冰片酯 (isobornyl acrylate)、曱基丙稀酸異冰片酯（isobornyl methacrylate)、丙稀酸四氫糠酉旨（tetrahydrofurfuryl acrylate)、甲基丙稀酸四氫糠酉旨（tetrahydrofurfuryl methacrylate)、苯乙稀（styrene)及其衍生物、α -曱基苯乙 20 稀（a -methylstyrene)、馬來酸酐（maleic anhydride)、醋酸 乙稀酯（vinyl acetat) 、N-乙稀基-2-氮五圜酮 (N-vinyl-2-pyrrolidone)、乙稀基石比咬（vinylpyridine)、丙酸 乙烯酯（vinyl propionate)、丙稀（acrylonitrile)、α -曱基 丙稀腈（methacrylonitrile)、丙烯酸（acrylic acid)、甲基丙 1261727 烤酸（methacrylic acid)、巴豆酸（crotonic acid)、肉桂酸 (cinnamic acid)、2-曱基丙稀酿基氧乙基破珀酸酯 (2 - methacryloyloxyethyl succinate)、2_ 丙稀酸基氧乙基破 珀酸醋（2-acryloyloxyethyl succinate)、2-甲基丙稀酸基氧 5 乙基六氫鄰苯二甲酸酉旨（2-methacryloyloxyethyl hexahydrophthalate)、2-丙稀醯基氧乙基六氫鄰苯二甲酸酯 (2-acryloyloxyethyl hexahydrophthalate)、2-甲基丙稀醯基 氧乙基鄰苯二甲酸酷（2-methacryloyloxyethyl phthalate)、 以及2-丙稀醯基氧乙基鄰苯二曱酸酉旨（2-acryloyloxyethyl 10 phthalate)所組成之群組。一般多環氧基之高分子之重量平 均分子量為500〜1，000,000 g/mol。 在樹脂組成物中，反應性稀釋劑無特定限制，一般為 具有兩個或兩個以上環氧基之化合物。而此具有兩個或兩 個以上環氧基之反應性稀釋劑較佳為3,4-環氧基環己基曱 15 基-3,4 環氧基環己基 ^^^_(3,4-epoxycyclohexylmetliyl-3,4epoxycyclohexyl carboxylate)、7_ 氧雙環（4.1.0)庚烧3-魏酸（7-oxabicyclo (4.1_0)heptane 3-carboxylic acid)、7-氧 雙環（4·1·0)庚基-3-甲基酯（7-oxabicyclo (4.1.0) heptyl-3-methyl ester)、1，4環己烧二曱醇二縮水甘油醚 20 (1，4-cyclohexanedimethanol diglycidyl ether)、甘油丙氧基 酉旨三縮水甘油鱗（glycerol propoxylate triglycidyl ether)、 1，1，1-三（對羥基苯）乙烷三縮水#&_(l，l，l-tris-(p-hydroxyphenyl)ethane triglycidyl ether)、4,4’-亞甲雙（N，N-二 縮 水 甘 油 苯 胺）(4,4’-methylenebis(N，N- 1261727 diglycidylaniline))、四個（4-經基苯基）乙烧之四縮水甘油 (tetraglycidyl ether of tetrakis(4-hydroxyphenyl) ethane)、 三縮水甘油·對-氨基齡（triglycidyl -p-aminophenol)、三縮水甘油異三聚氰酸鹽（triglycidyl 5 isocyanurate)、二縮水甘油六氫鄰苯二曱酸酯（diglycidyl hexahydrophthalate)、3,4-二縮水甘油環氧基環己基環氧乙 烧（3,4-epoxycyclohexyloxirane)、2-(3’4’-環氧基環己 基螺-3’’，4”-環氧基環己基-1，3-二氧陸圜 (2-(3 ’，4’-epoxycyclohexyl)-5,1 ’’-spiro-3 ”，4”-epoxy cyclohe 10 xane-l，3- dioxane、二（3,4_環氧基-環己基曱基）己二酸 (bis(3,4-epoxy-cyclohexylmethyl) adipate)、1，4-二縮水甘油 氧基-丁烧（l，4-diglycidyloxy- butane)、1，2-二縮水甘油連氧 基乙烧（l，2-diglycidyloxyethane)、二縮水甘油氧基新戊烧 (diglycidyloxyneopentane)、盼曱烧之二縮水甘油醚 15 (diglycidyl ether of bisphenol A)、雙紛 F 之二縮水甘油醚 (diglycidyl ether of bisphenol F)、鄰苯二驗之二縮水甘油 醚（diglycidyl ether of catechol)、間苯二盼之二縮水甘油醚 (diglycidyl ether of resorcinol)、丙三醇之二縮水甘油醚 (diglycidyl ether of glycerol)、1，3-丙醇之二縮水甘油醚 20 (diglycidyl ether of 1，3-propanol)、偏苯三酸酯之三縮水甘 油醚（triglycidyl ether of trimellitate)、苯三曱酯之三縮水 甘油醚（triglycidyl ether of trimesate)、1，2-3,4_丁烧二環氧 化物（l，2-3,4-butane diepoxide)、1，2,7,8_ 環氧基辛烧 (l，2,7,8-diepoxy octane)、對-苯雙環氧化合物（p-benzene 25 diepoxide)、雙酉分 A 環氧樹脂（bisphenol A epoxy resins)、 1261727It is easy to cause cracking and deformation of the substrate, and the resin molecules cannot be adjusted and adjusted according to the needs. In the resin composition of the present invention, the polyepoxy group polymer is formed by a kiln scale-lock polymerization reaction. It is designed by copolymer and can easily adjust the amount of jujube oxygen (ie, the number of cross-linking) without cracking or deforming the substrate. In addition, it can also be two. Copolymer monomer to meet other different physical requirements. [Description of the Invention] 7 1261727 The main object of the present invention is to provide a resin composition which can increase the photosensitivity, enhance the heat, and easily adjust the content of each functional group in accordance with various process requirements. Another object of the present invention is to provide a high-concentration of a polyepoxy group which has good developability and resolution at the same time and which can improve heat resistance. In order to achieve the above object, the resin composition of the present invention mainly comprises a polymer having an epoxy group which is polymerized or copolymerized by isocyanurate, and the polymer has a weight percentage of 10 It is 1% to 99% of the resin composition; and a reactive diluent is 1% to 99% by weight based on the total weight. In order to achieve the above object, the polyepoxy group-containing polymer of the present invention is formed by a chain-locking polymerization reaction in which an epoxy group is provided by an isocyanurate-based compound. [Embodiment] The resin composition of the present invention comprises a polymer having a polyepoxy group obtained by chain-locking polymerization, an isocyanurate used for the polymerization reaction, and R! is preferably a Ci_C6. The linker is either -COO-, and R2 20 is preferably -CH3 or -H. In addition, the polyepoxy group polymer may be obtained by copolymerizing an isocyanurate with at least one monomer having an unsaturated double bond, and the monomer which is not saturated with a double bond may be adjusted. The content of each functional group is preferably selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, thiol 1261727, ethyl methacrylate. ), propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid Butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, acrylic acid T-butyl acrylate, t-butyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate Acetone benzoic acid 10 曱S purpose (benz Yl acrylate), benzyl methacrylate, phenyl acrylate, phenyl methacrylate, cyclohexyl acrylate, Cyclohexyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, isobornyl acrylate, hydrazine Isobornyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, styrene and its derivatives , a-methylstyrene, maleic anhydride, vinyl acetat, N-vinyl-2-azinone (N-vinyl-2) -pyrrolidone), vinylpyridine, vinyl propionate, acrylonitrile, methacrylonitrile, acrylic acid, methyl propyl 1261727 Methacrylic acid, crotonic acid, cinnamic acid, 2-methacryloyloxyethyl succinate, 2_ acryloxy succinate 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl hexahydrophthalate, 2-propanyloxyethylhexahydrophthalate 2-acryloyloxyethyl hexahydrophthalate, 2-methacryloyloxyethyl phthalate, and 2-acrylamidooxyethyl phthalate A group consisting of 2-acryloyloxyethyl 10 phthalate. Generally, the polyepoxy group polymer has a weight average molecular weight of 500 to 1,000,000 g/mol. In the resin composition, the reactive diluent is not particularly limited, and is generally a compound having two or more epoxy groups. Further, the reactive diluent having two or more epoxy groups is preferably 3,4-epoxycyclohexylfluorenyl 15 -3,4 epoxycyclohexyl^^^(3,4- Epoxycyclohexylmetliyl-3,4epoxycyclohexyl carboxylate), 7_oxybicyclo(4.1.0) heptazone 3-carboxylic acid (7-oxabicyclo (4.1_0) heptane 3-carboxylic acid), 7-oxobicyclo(4·1·0) heptyl -3--methylbicyclo (4.1.0) heptyl-3-methyl ester, 1, 4-cyclohexanedimethanol diglycidyl ether, glycerol Glycerol propoxylate triglycidyl ether, 1,1,1-tris(p-hydroxyphenyl)ethane tricondensate#&_(l,l,l-tris-(p-hydroxyphenyl)ethane triglycidyl Ether), 4,4'-methylenebis(N,N-diglycidylaniline), four (4-phenylphenyl) ethene Tetralys (tetrahydroxylyl ether of tetrakis (4-hydroxyphenyl) ethane), triglycidyl, triglycidyl-p-aminophenol, triglycidyl isocyanate (triglycidy) l 5 isocyanurate), diglycidyl hexahydrophthalate, 3,4-diglycidoxycyclohexyloxirane, 2-(3' 4'-Epoxycyclohexylspiro-3'',4"-epoxycyclohexyl-1,3-dioxanthene (2-(3',4'-epoxycyclohexyl)-5,1 ''- Spiro-3",4"-epoxy cyclohe 10 xane-l,3-dioxane, bis(3,4-epoxy-cyclohexylmethyl) adipate , 1,4-diglycidyloxy-butane, 1,2-diglycidyloxyethane, diglycidyloxypentane (diglycidyloxyneopentane), diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether Of catechol), diglycidyl ether of resorcinol, diglycidyl ether of glycerol, 1 Diglycidyl ether of 1,3-propanol, triglycidyl ether of trimellitate, triglycidyl ether Of trimesate), 1,2-3,4-butadiene diepoxide, 1,2,7,8-epoxyoctyl (1,2,7, 8-diepoxy octane), p-benzene 25 diepoxide, bisphenol A epoxy resins, 1261727
雙齡F環氧樹脂（bisphenol F epoxy resins)或上述之混合 物。樹脂組成物更可包含一陽離子型光起始劑，係經光照 射引起陽離子型聚合反應者，其較佳為芳香烴基二重氮銨 鹽（aryl diazonium salts)、二芳香烴基峨敍言（diary liodonium 5 salts)、三芳香烴基硫化石粦錄鹽（triaryl sulphonium salts)、 三芳香烴基礙酸敍鹽（triarylphosphonium salts)、三芳香烴 基亞石西銨鹽（triarylselenonium salts)、二烧基苯酉元（先）甲基 硫化石粦銨鹽（dialkylphenacylsulphonium salts)、二：)：完基-4-經基苯硫化石粦銨鹽（dialkyl-4-hydroxyphenylsulphonium 10 salts)、硫化石粦酸酯（sulphonic acid ester)、石夕醇基-銘錯合 物（silanol-aluminium complexes)、或二茂鐵銨鹽 (Ferrocenium salts)。此陽離子型光起始劑較佳還再包含一 增感劑，其為癸（perylene)、蒽（anthracene)、或上述之衍生 物。本發明之樹脂組成物還可再包含一添加劑，其可為熱 15 安定劑、抗氧化劑、光安定劑、潤滑劑、著色劑、消泡‘劑、 平坦劑、填充劑以及補強材所組成之族群。Bisphenol F epoxy resins or a mixture of the above. The resin composition may further comprise a cationic photoinitiator which is a cationic polymerization reaction by light irradiation, and is preferably an aromatic hydrocarbon diazonium salt or a diaryl hydrocarbon group. Liodonium 5 salts), triaryl sulphonium salts, triarylphosphonium salts, triarylselenonium salts, dialkyl benzophenones Dialkylphenacylsulphonium salts, two:): dialkyl-4-hydroxyphenylsulphonium 10 salts, sulphonic acid ester , silanol-aluminium complexes, or ferrocenium salts. Preferably, the cationic photoinitiator further comprises a sensitizer which is perylene, anthracene, or a derivative thereof. The resin composition of the present invention may further comprise an additive which may be composed of a thermal 15 stabilizer, an antioxidant, a light stabilizer, a lubricant, a colorant, a defoaming agent, a flat agent, a filler, and a reinforcing material. Ethnic group.
本發明之多環氧基之高分子與樹脂組成物可應用於油 墨、塗料、光阻、或微機電系統用感光材料。且由於經由 鏈鎖聚合反應形成之含環氧基之高分子中，環氧基可由異 20 三聚氰酸鹽系化合物所提供，故樹脂組成物同時具有環氧 基、異三聚氰酸鹽等官能基。使其具有以下之優點：一、 導入異三聚氰酸鹽系化合物，因含有2個環氧基，使感光 基倍增，增加感光性。二、導入異三聚氰酸鹽系化合物， 因含有異三聚氰酸鹽，為含氮雜環，可提升耐熱性。三、 12 1261727 多環氧基之高分子可藉由變化單體組成，輕易調整各官能 基含量，因應各種製程需求。 為能讓貴審查委員能更瞭解本發明之技術内容，特 舉五較佳具體實施例說明如下。 5 實施例1 :感光榭脂合成The polyepoxy group-containing polymer and resin composition of the present invention can be applied to a photosensitive material for an ink, a coating, a photoresist, or a microelectromechanical system. And in the epoxy group-containing polymer formed by the chain-locking polymerization reaction, the epoxy group may be provided by an iso 20-cyanocyanate compound, so the resin composition has both an epoxy group and an iso-cyanate. Isofunctional group. It has the following advantages: First, the introduction of an isomeric cyanide-based compound, which contains two epoxy groups, doubles the photosensitive group and increases the photosensitivity. 2. The isocyanurate-based compound is introduced, and since it contains a hetero-cyanyanate, it is a nitrogen-containing hetero ring, and heat resistance can be improved. 3, 12 1261727 Polyepoxy polymers can easily adjust the content of each functional group by changing the monomer composition, in response to various process requirements. In order to enable the reviewing committee to better understand the technical contents of the present invention, the following five preferred embodiments are described below. 5 Example 1: Photosensitive resin synthesis
將 500g 溶劑 diethylene glycol monomethyl ether acetate 置於四口反應瓶中，通氮氣，保持80°C。單體丙烯基二縮 水甘油異三聚氰酸鹽（allyl diglycidyl isocyanurate)200g 與 起始劑 2,2’-azobis(isobutyronitrile)20g 充分混合後，滴入 10 反應器中，再持續反應4hr。得如下式3之感光樹脂a，分 子量為4700，其中以為-CH2-，R2為Η。500 g of solvent diethylene glycol monomethyl ether acetate was placed in a four-neck reaction flask, and nitrogen gas was passed through to maintain 80 °C. 200 g of allyl diglycidyl isocyanurate was thoroughly mixed with 20 g of the initiator 2,2'-azobis (isobutyronitrile), and then dropped into a 10 reactor, and the reaction was continued for 4 hr. The photosensitive resin a of the following formula 3 was obtained, and the molecular weight was 4,700, wherein -CH2-, and R2 was Η.
實施例2 :感光樹脂合成 同實施例1的合成步驟，單體丙烯基二縮水甘油異三聚 15 氰酸鹽（allyl diglycidyl isocyanurate)200g 改為單體 allyl diglycidyl isocyanurate 100g 和曱基丙烯酸甲酯（methyl methacrylate) 72g，可得感光樹脂b，分子量37000。故本 發明之感光樹脂可任意加入其他單體共聚合，以調整所需 13 1261727 物性。 實施例3 :熱硬化樹脂組成物Example 2: Synthesis of Photosensitive Resin Synthesize the same procedure as in Example 1, monomeric propylene diglycidyl isocyanurate 200g was changed to monomer allyl diglycidyl isocyanurate 100g and methyl methacrylate ( Methyl methacrylate) 72g, photoreceptor b, molecular weight 37000. Therefore, the photosensitive resin of the present invention can be arbitrarily added to other monomers to copolymerize to adjust the physical properties of 13 1261727. Example 3: Thermosetting resin composition
將4 · 5 g感光樹脂a，0.1 8 g硬化劑雙氰胺 (dicyandiamide)，lg溶劑二曱基甲酰胺縮二曱醇（diniethyl 5 f〇rmamide) ’〇·〇〇 1 g 觸媒 2-曱基口米 口坐（2-methyl imidazole) 混合並擾拌均勻成熱硬化樹脂組成物。將熱硬化樹脂組成 物旋轉塗佈在銅箔基板上，置於80°C烘箱中預烘30min。 170°C下熱硬化2小時。使用熱重分析儀（Tga)分析此硬化 後的樹脂組成物，以20°C /min速率自25°C升溫至850°C， 10在300°C時熱重量損失只有5%，耐熱性佳。故本發明之感 光樹脂可應用於熱硬化樹脂組成物。 實施例4 _·光硬化樹脂組成物a 將2g感光樹脂a，0.3g曱酚酚醛清漆環氧樹脂（cres〇1 novolac type epoxy resin)，lg 溶劑 diethylene glycol 15 monomethyl ether acetate，O.lg 染料，〇.i5g 陽離子型光起 始劑 bis{4-(diphenylsulfonio)-phenyl}-sulfide-bis-hexa4 · 5 g of photosensitive resin a, 0.1 8 g of hardener dicyandiamide, lg of solvent diniethyl 5 f〇rmamide '〇·〇〇1 g catalyst 2 The 2-methyl imidazole is mixed and disturbed to form a thermosetting resin composition. The thermosetting resin composition was spin-coated on a copper foil substrate and prebaked in an oven at 80 ° C for 30 min. Heat hardened at 170 ° C for 2 hours. The hardened resin composition was analyzed by a thermogravimetric analyzer (Tga), and the temperature was raised from 25 ° C to 850 ° C at a rate of 20 ° C / min, and the thermal weight loss was only 5% at 300 ° C, and the heat resistance was good. . Therefore, the photosensitive resin of the present invention can be applied to a thermosetting resin composition. Example 4 _· Photohardenable resin composition a 2 g of photosensitive resin a, 0.3 g of cres 〇 novolac type epoxy resin, lg solvent diethylene glycol 15 monomethyl ether acetate, O. lg dye, 〇.i5g cationic photoinitiator bis{4-(diphenylsulfonio)-phenyl}-sulfide-bis-hexa
fluorophosphate混合並攪拌均勻成光硬化樹脂組成物。將 光硬化樹脂組成物旋轉塗佈在銅箔基板上，置於7〇°c烘箱 中預烘30min。待冷卻後，蓋上圖樣光罩，使用紫外線平 20 行曝光機曝光800 mJ/cm2，以i%Na2C03(aq)顯影，接著 用清水洗淨試片乾燥，可得到清晰圖形。 膏施例5 :光硬化榭脂組成物b 將2g感光樹脂b，0.3g曱酚醛清漆環氧樹脂（cres〇1 novolac type epoxy resin)，lg 溶劑 diethylene glyc〇1 14 1261727 monomethyl ether acetate，O.lg 染料，〇.15g 陽離子型光起 始劑 bis{4-(diphenylsulf〇ni〇)-phenyl}-sulfide-bis-hexa fluorophosphate混合並攪拌均勻成光硬化樹脂組成物。將 光硬化樹脂組成物旋轉塗佈在銅箔基板上，置於7〇t洪箱 5中預烘30min。待冷卻後，蓋上圖樣光罩，使用紫外線平 行曝光機曝光800 mJ/cm2 ’以i%Na2C〇3(aq)顯影，接著 用清水洗淨試片乾燥，可得到清晰圖形。The fluorophosphate is mixed and stirred to form a photohardenable resin composition. The photohardenable resin composition was spin-coated on a copper foil substrate and prebaked in a 7 ° C oven for 30 min. After cooling, cover the pattern mask, expose it to 800 mJ/cm2 using an ultraviolet 20-line exposure machine, develop it with i% Na2C03 (aq), and then dry it with water to obtain a clear pattern. Paste Example 5: Photohardening rouge composition b 2 g of photosensitive resin b, 0.3 g of cres 〇 novolac type epoxy resin, lg solvent diethylene glyc 〇 1 14 1261727 monomethyl ether acetate, O. Lg dye, 〇. 15g cationic photoinitiator bis{4-(diphenylsulf〇ni〇)-phenyl}-sulfide-bis-hexa fluorophosphate is mixed and stirred to form a photohardenable resin composition. The photohardenable resin composition was spin-coated on a copper foil substrate and pre-baked in a 7 〇t tank 5 for 30 minutes. After cooling, cover the pattern mask and develop it with an ultraviolet exposure scanner at 800 mJ/cm2' with i% Na2C〇3 (aq), then rinse the test piece with water to obtain a clear pattern.
本發明之多環氧基之高分子與樹脂組成物可增加减 光性、提升耐熱性、並輕易地調整各官能基含量，因應各 10種製程需求。唯上述實施例僅係為了方便說明而舉例而 已’本發明所主張之權利範圍自應以申請專利範圍所述為 準，而非僅限於上述實施例。 【圖式簡單說明】 15 無。The polyepoxy group-containing polymer and resin composition of the present invention can increase the light-reducing property, improve the heat resistance, and easily adjust the content of each functional group in accordance with each of the 10 process requirements. The above-mentioned embodiments are merely examples for the convenience of the description, and the claims are intended to be based on the scope of the claims, and are not limited to the above embodiments. [Simple description of the diagram] 15 None.
【圖號說明】 fe 〇 15[Description of the figure] fe 〇 15
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