TWI438215B - Polymers and method for forming the same, optical elements, and photoelectric devices employing the same - Google Patents
Polymers and method for forming the same, optical elements, and photoelectric devices employing the same Download PDFInfo
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本發明關於一種聚合物及包括其之光學元件及光電裝置，特別關於一種高折射率及高透光度聚合物及包括其之光學元件及光電裝置。The present invention relates to a polymer and optical elements and optoelectronic devices therewith, and more particularly to a high refractive index and high transmittance polymer and optical components and optoelectronic devices therewith.
發光二極體(Light Emitting Diode，簡稱LED)因其具有高亮度、體積小、重量輕、不易破損、低耗電量和壽命長等優點，所以被廣泛地應用各式顯示產品中。Light Emitting Diode (LED) is widely used in various display products because of its high brightness, small size, light weight, low damage, low power consumption and long life.
發光二極體(LED)整體之發光效能主要受到晶片、構裝形式與封裝材料所影響。隨著磊晶技術的進步，晶片內部發光效率已達90%以上，不過礙於構裝形式和封裝材料影響，發光二極體(LED)最終外部取光效率僅為30%，足見構裝形式與封裝材料對發光二極體(LED)亮度的重要性。根據史奈爾定律，光線自具有高折射率的區域行進到在某一臨界角度(相對於表面法線方向)內之具有低折射率的區域，將穿越較低折射率的區域。以超過臨界角度到達表面之光線將不會穿出表面，但是會經歷內部全反射(TIR)。在LED的情況中，TIR光線可持續於LED內反射，直到被吸收為止。由於該反射現象，多數由習知LEDs所產生之光線並未發射出去，降低了本身之效率。The overall luminous efficacy of a light-emitting diode (LED) is mainly affected by the wafer, the form of the package, and the packaging material. With the advancement of epitaxial technology, the internal luminous efficiency of the wafer has reached more than 90%. However, due to the influence of the package form and packaging materials, the final external light extraction efficiency of the LED is only 30%, which shows the form of the structure. The importance of the encapsulation material to the brightness of the light-emitting diode (LED). According to Snell's law, light traveling from a region with a high refractive index to a region with a low refractive index at a critical angle (relative to the surface normal direction) will traverse a region of lower refractive index. Light that reaches the surface at a critical angle will not penetrate the surface, but will experience internal total reflection (TIR). In the case of LEDs, TIR light can persist within the LED reflection until it is absorbed. Due to this reflection phenomenon, most of the light generated by the conventional LEDs is not emitted, which reduces the efficiency of itself.
以白光發光二極體(LED)為例，晶片折射率約2~4，如GaN(n=2.5)及GaP(n=3.45)均遠高於環氧樹脂或矽氧烷樹脂封裝材料折射率(n=1.40~1.53)，折射率差異過大導致全反射發生，將光線反射回晶片內部而無法有效導出，因此提高封裝材料的折射率將可減少全反射的發生。以藍光晶片/黃色YAG螢光粉的白光發光二極體(LED)組件為例，藍光發光二極體(LED)晶片折射率為2.5，當封裝材料的折射率從1.5時提升至1.7時，光取出效率提升了近30%。因此，提升封裝材料的折射率降低晶片與封裝材料間折射率差異來達到提升出光效能，是一亟待研究的目標。Taking a white light-emitting diode (LED) as an example, the refractive index of the wafer is about 2 to 4, such as GaN (n=2.5) and GaP (n=3.45), which are much higher than the refractive index of the epoxy resin or siloxane resin package. (n=1.40~1.53), the difference in refractive index is too large, causing total reflection to occur, and the light is reflected back inside the wafer and cannot be effectively exported. Therefore, increasing the refractive index of the package material can reduce the occurrence of total reflection. Taking a white light emitting diode (LED) component of a blue light wafer/yellow YAG phosphor powder as an example, a blue light emitting diode (LED) wafer has a refractive index of 2.5, and when the refractive index of the packaging material is raised from 1.5 to 1.7, Light extraction efficiency has increased by nearly 30%. Therefore, it is an urgent task to improve the refractive index of the packaging material to reduce the refractive index difference between the wafer and the packaging material to improve the light-emitting efficiency.
為解決上述問題，美國專利編號US 5,633,331揭露一具有高折射率的封裝材料，其係由Fluorene Carbonate高分子與Polysulfone進行混掺所得，藉由導入具有高折射率基團的高分子，提升封裝材料的折射率。In order to solve the above problems, U.S. Patent No. 5,633,331 discloses a packaging material having a high refractive index obtained by blending a Fluorene Carbonate polymer with Polysulfone, and introducing a polymer having a high refractive index group to enhance the encapsulating material. Refractive index.
此外，美國專利編號US 7,446,159揭露一具有高折射率的封裝材料，其係以具有壓克力官能基之Fluorene單體(其結構係為，其中X係為、─(CH 2 CH 2 O)─CH 2 CH(OH)CH 2 O─ ，n係為1至5，R係為丙烯酸基或甲基丙烯酸)進行聚合反應所製備而得。然因為其單體黏度過高，成膜性不佳，使其之應用受限(如薄膜塗佈、網印、射出等方式都不易實施)。In addition, U.S. Patent No. 7,446,159 discloses a high refractive index encapsulating material which is a Fluorene monomer having an acrylic functional group (the structure is , where X is - (CH 2 CH 2 O)-CH 2 CH(OH)CH 2 O- , n is 1 to 5, and R is an acrylic group or methacrylic acid. However, because the monomer viscosity is too high, the film formation is not good, so its application is limited (such as film coating, screen printing, injection, etc. are not easy to implement).
大阪瓦斯與新日鐵公司之相關專利揭露由多元硫醇與多元異硫氰酸酯反應而得之聚合物具有不錯之光折射率，適合作為LED之封裝材料。不過，該聚合物之缺點係其會有隨時間而黃變。The related patents of Osaka Gas and Nippon Steel Corporation disclose that the polymer obtained by reacting a polythiol with a polyisothiocyanate has a good refractive index and is suitable as a packaging material for LEDs. However, the disadvantage of this polymer is that it will yellow with time.
本發明之一實施例提出一種高折射率及高透光度的聚合物，其係為以下之起始物聚合所得產物，該起始物包括：One embodiment of the present invention provides a high refractive index and high transmittance polymer which is a product obtained by polymerization of the following starting materials, the starting materials comprising:
(a)雙酚芴衍生物(bisphenol fluorene derivatives)單體，包含具有如公式(I)所示結構之化合物：(a) a bisphenol fluorene derivatives monomer comprising a compound having the structure shown in formula (I):
其中，R係各自獨立且係為氫、C1-8 之烷基、C1-8 之烷氧基、羧基、或鹵素；i及j係各自獨立且係為0或1~~5之整數；以及Wherein R is independently and is hydrogen, C 1-8 alkyl, C 1-8 alkoxy, carboxyl, or halogen; i and j are each independently and are 0 or 1 to 5 integers. ;as well as
(b)二異氰酸酯(diisocyanates)單體。(b) Diisocyanates monomer.
本發明之另一實施例提出一種光學元件，其係包括上述之高折射率及高透光度聚合物，該光學元件係包括封裝材料、透明基板、透鏡、或功能性薄膜。Another embodiment of the present invention provides an optical component comprising the above-described high refractive index and high transmittance polymer, the optical component comprising a packaging material, a transparent substrate, a lens, or a functional film.
本發明之又一實施例亦提供一光電裝置，其係包括上述之光學元件，該光電裝置係包括發光二極體、太陽能電池、半導體裝置、或是顯示裝置。Yet another embodiment of the present invention also provides an optoelectronic device comprising the optical component described above, the optoelectronic device comprising a light emitting diode, a solar cell, a semiconductor device, or a display device.
以下藉由數個實施例並配合所附圖式，以更進一步說明本發明，但並非用來限制本發明之範圍，本發明之範圍應以所附之申請專利範圍為準。The invention is further illustrated by the following examples in conjunction with the accompanying drawings, which are not intended to limit the scope of the invention.
本發明係揭露一種具有高折射率及高透光度的聚合物與其製造方法，以及包括其之光學元件及光電裝置。本發明所述之具有高折射率及高透光度的聚合物，其係為以下之起始物聚合所得產物，該起始物包括：The present invention discloses a polymer having a high refractive index and a high transmittance and a method of manufacturing the same, and an optical element and an optoelectric device including the same. The polymer having high refractive index and high transparency according to the present invention is a product obtained by polymerization of the following starting materials, and the starting materials include:
(a)雙酚芴衍生物(bisphenol fluorene derivatives)單體，包含具有如公式(I)所示結構之化合物：(a) a bisphenol fluorene derivatives monomer comprising a compound having the structure shown in formula (I):
其中，R係各自獨立且係為氫、C1-8 之烷基、C1-8 之烷氧基、羧基、或鹵素；i及j係各自獨立且係為0或1~5之整數。值得注意的，當R為烷基時(例如甲基、丙基、丁基)，由於該雙酚芴衍生物(bisphenol fluorene derivatives)單體具備有烷基取代基於苯環，將可增加化合物對有機溶劑之溶解度，因而可調製出高固含量之高折射率膠狀材料；以及Wherein R is each independently hydrogen, a C 1-8 alkyl group, a C 1-8 alkoxy group, a carboxyl group, or a halogen; and i and j are each independently and are 0 or 1 to 5 integers. It is worth noting that when R is an alkyl group (such as methyl, propyl, butyl), since the bisphenol fluorene derivatives monomer has an alkyl group-based benzene ring, it can increase the compound pair. The solubility of the organic solvent, thus modulating a high solids high refractive index gelatinous material;
(b)二異氰酸酯(diisocyanates)單體。(b) Diisocyanates monomer.
根據本發明所述之實施例，其中該(a)雙酚芴衍生物單體之莫耳數與該(b)二異氰酸酯單體之莫耳數之比係大於或等於0.1，較佳為0.2-1之間。According to an embodiment of the present invention, wherein the ratio of the molar number of the (a) bisphenolphthalein derivative monomer to the molar number of the (b) diisocyanate monomer is greater than or equal to 0.1, preferably 0.2. Between -1.
根據本發明所述之實施例，該(a)雙酚芴衍生物單體可具有以下結構、或，其中R係各自獨立且係為氫、C1-8 之烷基、C1-8 之烷氧基、羧基、或鹵素。According to an embodiment of the present invention, the (a) bisphenolphthalein derivative monomer may have the following structure ,or Wherein R is each independently and is hydrogen, C 1-8 alkyl, C 1-8 alkoxy, carboxyl, or halogen.
根據本發明所述之實施例，該二異氰酸酯單體包含具有如公式(II)所示結構的化合物：According to an embodiment of the invention, the diisocyanate monomer comprises a compound having the structure shown in formula (II):
OCN─A─NCO 公式(II)， OCN-A-NCO formula (II),
其中，A係為脂肪族或芳香族之基團。在本發明中，“脂肪族(aliphatic group)”一詞係代表一非芳香族結構，可以是碳原子與氫原子之任意組合，且可連接鹵素，氧，氮，矽，硫或其他原子以形成各種取代基。脂肪族可以是直鏈、支鏈、或環狀型式，並可能包含一或多個不飽和基，例如雙鍵及/或三鍵；“芳香族(aromatic group)”一詞係代表一單環或多環系統之碳氫芳香環，例如：苯基，甲苯基，萘基，四氫化萘基(tetrahydronaphthyl)，聯苯基(biphenyl)，菲基(phenanthryl)、蒽基(anthracyl)等。此外，芳香環中可具有一或多個雜原子(如氮、氧、硫)而構成一雜芳香環，例如吡啶基(pyridyl)，呋喃基(furyl)，噻吩基(thienyl)，咪唑基(imidazolyl)。Among them, A is an aliphatic or aromatic group. In the present invention, the term "aliphatic group" means a non-aromatic structure, which may be any combination of a carbon atom and a hydrogen atom, and may be bonded to a halogen, oxygen, nitrogen, helium, sulfur or other atom. Various substituents are formed. The aliphatic group may be linear, branched, or cyclic, and may contain one or more unsaturated groups, such as double bonds and/or triple bonds; the term "aromatic group" refers to a single ring. Or a hydrocarbon aromatic ring of a polycyclic system, for example, phenyl, tolyl, naphthyl, tetrahydronaphthyl, biphenyl, phenanthryl, anthracyl, and the like. In addition, the aromatic ring may have one or more heteroatoms (such as nitrogen, oxygen, sulfur) to form a heteroaromatic ring, such as pyridyl, furyl, thienyl, imidazolyl ( Imidazolyl).
此外，根據本發明所述之某些實施例，該(b)二異氰酸酯單體可包：脂肪族(aliphatic)二異氰酸酯單體、脂環族(alicyclic)二異氰酸酯單體、芳代脂肪族(araliphatic)二異氰酸酯單體、芳香族(aromatic)二異氰酸酯單體、或其混合。該芳香族(aromatic)二異氰酸酯單體可包含2,4-和2,6-甲苯二異氰酸酯(TDI)、全氫-2,4’-和-4,4’-二苯基甲烷二異氰酸酯(HMDI)、4,4’-2,4’-和2,2’-二苯基甲烷二異氰酸酯(MDI)、萘-1,5-二異氰酸酯(NDI)、亞苯基二異氰酸酯(PPDI)、2,3,5,6-四甲基-1,4-二異氰酸根合苯、3,3’-二甲基-4,4’-二異氰酸根合聯苯(TODI)、或其混合。該脂環族(alicyclic)二異氰酸酯單體可包含二環己基甲烷二異氰酸酯(H1 2MDI)、1-異氰酸根合-3,3,5-三甲基-5-異氰酸根合甲基-環己烷(IPDI)、環己烷-1,3-和-1,4-二異氰酸酯(CHDI)、1,3-和1,4-二-(異氰酸根合甲基)-環己烷(H6 XDI)、1,3-和1,4-二(異氰酸根合甲基)環己烷(BIC)、或其混合。該脂肪族(araliphatic)二異氰酸酯單體包含1,6-六亞甲基二異氰酸酯(HDI)、1,12-十二亞甲基二異氰酸酯、2,2,4-和2,4,4-三甲基-1,6-六亞甲基二異氰酸酯(TMDI)、2-甲基五亞甲基-1,5-二異氰酸酯、1,4-二異氰酸根合-2,2,6-三甲基環己烷(TMCDI)、賴氨酸-和賴氨酸酯二異氰酸酯、或其混合。該芳代脂肪族(araliphatic)二異氰酸酯單體包含1,3-和1,4-四甲基苯二亞甲基二異氰酸酯(TMXDI)、間和對苯二亞甲基二異氰酸酯(XDI)、或其混合。Further, according to some embodiments of the present invention, the (b) diisocyanate monomer may comprise: an aliphatic diisocyanate monomer, an alicyclic diisocyanate monomer, an aromatic aliphatic group ( Arapiphic) a diisocyanate monomer, an aromatic diisocyanate monomer, or a mixture thereof. The aromatic diisocyanate monomer may comprise 2,4- and 2,6-toluene diisocyanate (TDI), perhydro-2,4'- and-4,4'-diphenylmethane diisocyanate ( HMDI), 4,4'-2,4'- and 2,2'-diphenylmethane diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), phenylene diisocyanate (PPDI), 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl (TODI), or mixing. The alicyclic diisocyanate monomer may comprise dicyclohexylmethane diisocyanate (H 1 2MDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl -cyclohexane (IPDI), cyclohexane-1,3- and -1,4-diisocyanate (CHDI), 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane Alkane (H 6 XDI), 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane (BIC), or a mixture thereof. The araliphatic diisocyanate monomer comprises 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecyl diisocyanate, 2,2,4- and 2,4,4- Trimethyl-1,6-hexamethylene diisocyanate (TMDI), 2-methylpentamethylene-1,5-diisocyanate, 1,4-diisocyanato-2,2,6- Trimethylcyclohexane (TMCDI), lysine- and lysine ester diisocyanate, or mixtures thereof. The araliphatic diisocyanate monomer comprises 1,3- and 1,4-tetramethylbenzenedimethylene diisocyanate (TMXDI), meta- and p-xylylene diisocyanate (XDI), Or a mixture thereof.
根據本發明所述之其他實施例，該具有高折射率及高透光度的聚合物，可包含由(a)雙酚芴衍生物(bisphenol fluorene derivatives)單體、(b)二異氰酸酯(diisocyanates)單體、以及(c)二元醇單體等起始物進行聚合反應所得產物。其中該(a)雙酚芴衍生物單體與該(c)二元醇單體之總莫耳數與該(b)二異氰酸酯單體之莫耳數比係大於或等於1，或係介於1-5間。According to other embodiments of the present invention, the polymer having high refractive index and high transparency may comprise (a) bisphenol fluorene derivatives monomer, (b) diisocyanates (diisocyanates) a product obtained by carrying out a polymerization reaction of a monomer, and a starting material such as (c) a glycol monomer. Wherein the molar ratio of the (a) bisphenolphthalein derivative monomer to the (c) glycol monomer to the (b) diisocyanate monomer molar ratio is greater than or equal to 1, or In 1-5 rooms.
根據本發明所述之實施例，該二元醇單體可包含具有如公式(III)所示結構的化合物：According to an embodiment of the present invention, the diol monomer may comprise a compound having a structure as shown in formula (III):
其中，B係為、或，X係各自獨立且係為鹵素，R係各自獨立且係為氫、C1-8 之烷基、C1-8 之烷氧基、羧基、或鹵素，n等於1或2。此外，該二元醇單體亦可同時包含具有如公式(IV)所示結構之化合物：Among them, the B system is ,or X is independently and halogen, and R is each independently hydrogen, a C 1-8 alkyl group, a C 1-8 alkoxy group, a carboxyl group, or a halogen, and n is equal to 1 or 2. Further, the diol monomer may also contain a compound having a structure as shown in the formula (IV):
(HO) 2 Q(COOH) m 公式(IV)，其中，Q係為C2-12 直鏈或分枝之烴類基團，m係為0、或1~4之整數。 (HO) 2 Q(COOH) m Formula (IV) wherein Q is a C 2-12 linear or branched hydrocarbon group, and m is an integer of 0 or 1-4.
符合上述之二元醇單體可例如為：雙酚A(Bisphenol A)、四溴雙酚A(TBBPA)、雙酚B(Bisphenol B)、雙酚E(Bisphenol E)、雙酚F(Bisphenol F)、雙酚S(Bisphenol S)、3,3’-二羥基二苯二硫醚、乙二醇、丙二醇、丁二醇、戊二醇、己二醇、二羥甲基丙酸(DMPA)、或酒石酸此外，為增加聚合物之柔軟性，亦可以在反應後段合成配方時將聚乙二醇(PEG，分子量較佳係小於1000，例如PEG-200、PEG-600)導入，以避免所得之聚合物薄膜產生龜裂之現象。The diol monomer meeting the above may be, for example, bisphenol A (Bisphenol A), tetrabromobisphenol A (TBBPA), bisphenol B (Bisphenol B), bisphenol E (Bisphenol E), bisphenol F (Bisphenol). F), Bisphenol S, 3,3'-dihydroxydiphenyl disulfide, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, dimethylolpropionic acid (DMPA In addition, in order to increase the flexibility of the polymer, it is also possible to introduce polyethylene glycol (PEG, preferably having a molecular weight of less than 1000, such as PEG-200, PEG-600) in the synthesis of the latter stage of the reaction to avoid The resulting polymer film produced a crack phenomenon.
根據本發明所述之其他實施例，該起始物可更包含一硬化劑，其中該硬化劑係包含具有如公式(V)所示結構之化合物
本發明主要技術特徵之一係將體積較小且為高折射率、高耐熱之具有醇基的雙酚芴衍生物(bisphenol fluorene derivatives)與二異氰酸酯之單體(例如：TDI、MDI、IPDI、HDI等等)進行聚合，並可進一步加入具備有氯、溴、或硫原子之二元醇單體進行聚合，以增加折射率以及熱聚合效率。此外，將具有羧酸官能基之二元醇化成物(例如：酒石酸、DMPA)導入聚合反應，主要功能係可提供所得之聚合物在後段製程時，可與一硬化劑進行熱固化(thermal curing)。One of the main technical features of the present invention is a monomer having a small volume and having a high refractive index and a high heat resistance, an bisphenol fluorene derivative having an alcohol group, and a monomer of a diisocyanate (for example, TDI, MDI, IPDI, HDI or the like) is polymerized, and further polymerization may be carried out by adding a glycol monomer having a chlorine, bromine or sulfur atom to increase the refractive index and thermal polymerization efficiency. In addition, a diol-forming product having a carboxylic acid functional group (for example, tartaric acid, DMPA) is introduced into the polymerization reaction, and the main function is to provide the obtained polymer to be thermally cured with a curing agent in the latter stage process. ).
此外，本發明亦提供一上述高折射率及高透光度聚合物的製造方法，包括以下步驟：In addition, the present invention also provides a method for producing the above high refractive index and high transmittance polymer, comprising the following steps:
配製一組合物，該組合物包含上述之(a)雙酚芴衍生物(bisphenol fluorene derivatives)單體、及(b)二異氰酸酯(diisocyanates)單體，或可進一步包含(C)二元醇單體、及一熱起始劑。接著，加熱該組合物以進行一聚合反應，得到該高折射率及高透光度聚合物。此外，在加熱該組合物前，可將一硬化劑加入該組合物。值得注意的是，由於上述反應用來作為反應單體之雙酚芴衍生物(bisphenol fluorene derivatives)單體及二元醇單體本身具有極佳之溶劑能力，因此在製備反應組合物時，可提高固含量，甚至可以不需要外加溶劑。換言之，上述組合物可不包含其他不參與該聚合反應之有機溶劑。因此，上述組合物進以聚合反應(或固合)時，可以降低製膜時因為溶劑揮發時造成所得之聚 合物膜厚劇烈變化。A composition comprising the above-mentioned (a) bisphenol fluorene derivatives monomer, and (b) a diisocyanates monomer, or may further comprise (C) a glycol Body, and a hot starter. Next, the composition is heated to carry out a polymerization reaction to obtain the high refractive index and high transmittance polymer. Additionally, a hardener may be added to the composition prior to heating the composition. It is worth noting that since the above reaction is used as a reactive monomer, the bisphenol fluorene derivatives monomer and the diol monomer themselves have excellent solvent ability, and therefore, when preparing the reaction composition, Increase the solids content and even eliminate the need for additional solvents. In other words, the above composition may not contain other organic solvents that do not participate in the polymerization. Therefore, when the above composition is subjected to polymerization (or fixation), the resulting aggregation can be reduced when the film is volatilized during film formation. The film thickness changes drastically.
以下藉由下列實施例來說明本發明所述之高折射率及高透光度聚合物，用以進一步闡明本發明之技術特徵。The high refractive index and high transmittance polymers of the present invention are illustrated by the following examples to further clarify the technical features of the present invention.
高折射率及高透光度聚合物的合成Synthesis of high refractive index and high transmittance polymers
表1係列舉出本發明各實施例用來合成高折射率及高透光度聚合物所使用之雙酚芴衍生物(bisphenol fluorene derivatives)單體、二異氰酸酯(diisocyanates)單體及二元醇單體，其各自之化學結構均詳列於表中。Table 1 is a series of bisphenol fluorene derivatives, diisocyanates, and diols used in the synthesis of high refractive index and high transmittance polymers according to various embodiments of the present invention. The individual monomers, their respective chemical structures are detailed in the table.
為進一步說明本發明有機化合物的製備方法，以下特別詳述實施例1、2、4、5、7、9、及11-13所述之聚合物製備方式。In order to further illustrate the preparation method of the organic compound of the present invention, the preparation methods of the polymers described in Examples 1, 2, 4, 5, 7, 9, and 11-13 are specifically described below.
取0.1mole之F9PEO粉體置入於500ml之反應瓶，加入r-丁內脂(r-butyro-lactone、GBL)之溶劑(固含量約為30%)，並通入氮氣30分鐘，攪拌均勻使其溶解，其溶解溫度約為90℃。接著，利用滴加漏斗將0.1mole的IPDI加入反應瓶中，直到異氰酸基(-NCO)的含量消失(每30分鐘用IR檢測)，即可將反應停止(反應時間約16小時)。在此，該F9PEO與該IPDI之莫耳數比為1：1。接著，利用GPC量測所得之聚合物，測得其分子量Mw=7240、Mn=3485、以及Mw/Mn=2.07。0.1 mole of F9PEO powder was placed in a 500 ml reaction flask, and r-butyro-lactone (GBL) solvent (solid content: about 30%) was added, and nitrogen gas was introduced for 30 minutes, and the mixture was uniformly stirred. It was dissolved and its dissolution temperature was about 90 °C. Next, 0.1 mole of IPDI was added to the reaction flask using a dropping funnel until the content of isocyanate (-NCO) disappeared (detected by IR every 30 minutes), and the reaction was stopped (reaction time was about 16 hours). Here, the molar ratio of the F9PEO to the IPDI is 1:1. Next, the polymer obtained by GPC measurement was found to have a molecular weight of Mw = 7240, Mn = 3485, and Mw / Mn = 2.07.
上述聚合反應之反應式如下所示：
接著，在固化前將該聚合物組合物(5g)加入硬化劑(0.25g)並在100℃烘箱中烘烤1小時，並成1mm薄膜。測量後，可知該薄膜的折射率為1.56。在此，該硬化劑包含溶解於40克γ-丁內酯溶劑中的0.01mole F9PG(4.62克)和酸酐(順式-1,2,3,6-四氫鄰苯二甲酸酐)(1.52克)。Next, the polymer composition (5 g) was added to a hardener (0.25 g) before curing and baked in an oven at 100 ° C for 1 hour to form a 1 mm film. After the measurement, the refractive index of the film was found to be 1.56. Here, the hardener comprises 0.01 mole F9PG (4.62 g) and anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) dissolved in 40 g of γ-butyrolactone solvent (1.52). Gram).
取0.05mole之F9PEO、及0.05mole之DMPA置入於 500ml之反應瓶，加入r-丁內脂(r-butyro-lactone、GBL)之溶劑(固含量約為30%)，並通入氮氣30分鐘，攪拌均勻使其溶解，其溶解溫度約為110℃。並加入數滴熱安定劑CHINOX TP-10H(臺灣雙鍵化工)以防止合成時之黃變現象。接著，利用滴加漏斗將0.1molc的IPDI加入反應瓶中，直到異氰酸基(-NCO)的含量消失(每30分鐘用IR檢測)，即可將反應停止(反應時間約5小時)，即可將反應停止。在此，該F9PEO、該DMPA與該IPDI之莫耳數比為1：1：2。接著，利用GPC量測所得之聚合物，測得其分子量Mw=8008、Mn=3782、以及Mw/Mn=2.11。Take 0.05mole of F9PEO and 0.05mole of DMPA into 500ml reaction bottle, adding r-butyro-lactone (GBL) solvent (solid content is about 30%), and introducing nitrogen gas for 30 minutes, stirring and evenly dissolving, the dissolution temperature is about 110 °C. And add a few drops of heat stabilizer CHINOOX TP-10H (Taiwan double bond chemical) to prevent yellowing during synthesis. Next, 0.1 molc of IPDI was added to the reaction flask using a dropping funnel until the content of isocyanate (-NCO) disappeared (detected by IR every 30 minutes), and the reaction was stopped (reaction time was about 5 hours). The reaction can be stopped. Here, the F9PEO, the molar ratio of the DMPA to the IPDI is 1:1:2. Next, the polymer obtained by GPC measurement was found to have a molecular weight of Mw = 8008, Mn = 3782, and Mw / Mn = 2.11.
上述聚合反應之反應式如下所示：
接著，在固化前將該聚合物組合物(5g)加入硬化劑(0.25g)並在100℃烘箱中烘烤1小時，並成1mm薄膜。測量後，可知該薄膜的折射率為1.57。在此，該硬化劑包含 溶解於40克γ-丁內酯溶劑中的0.01mole F9PG(4.62克)和酸酐(順式-1,2,3,6-四氫鄰苯二甲酸酐)(1.52克)。Next, the polymer composition (5 g) was added to a hardener (0.25 g) before curing and baked in an oven at 100 ° C for 1 hour to form a 1 mm film. After the measurement, the film had a refractive index of 1.57. Here, the hardener contains 0.01 mole of F9PG (4.62 g) and anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) (1.52 g) dissolved in 40 g of γ-butyrolactone solvent.
取0.05mole之F9PEO、及0.05mole之Bisphenol S置入於500ml之反應瓶，加入r-丁內脂(r-butyro-lactone、GBL)之溶劑(固含量約為30%)，並通入氮氣30分鐘，攪拌均勻使其溶解，其溶解溫度約為90℃。並加入數滴熱安定劑CHINOX TP-10H以防止合成時之黃變現象。接著，利用滴加漏斗將0.1mole的IPDI加入反應瓶中，直到異氰酸基(-NCO)的含量消失(每30分鐘用IR檢測)，即可將反應停止，即可將反應停止在此，該F9PEO、該Bisphenol S與該IPDI之莫耳數比為1：1：2。接著，利用GPC量測所得之聚合物，測得其分子量Mw=11774、Mn=6419、以及Mw/Mn=1.82。Take 0.05 mole of F9PEO and 0.05 mole of Bisphenol S in a 500 ml reaction flask, add r-butyro-lactone (GBL) solvent (solid content is about 30%), and pass nitrogen. After 30 minutes, the mixture was uniformly stirred to dissolve, and the dissolution temperature was about 90 °C. A few drops of thermal stabilizer CHINOX TP-10H was added to prevent yellowing during synthesis. Next, 0.1 mole of IPDI was added to the reaction flask using a dropping funnel until the content of isocyanate (-NCO) disappeared (detected by IR every 30 minutes), the reaction was stopped, and the reaction was stopped here. The ratio of the molar ratio of the F9PEO, the Bisphenol S to the IPDI is 1:1:2. Next, the polymer obtained by GPC measurement was found to have a molecular weight of Mw = 11774, Mn = 6419, and Mw / Mn = 1.82.
上述聚合反應之反應式如下所示：
接著，在固化前將該聚合物組合物(5g)加入硬化劑(0.25g)並在100℃烘箱中烘烤1小時，並成1mm薄膜。測量後，可知該薄膜的折射率為1.57。在此，該硬化劑包含溶解於40克γ-丁內酯溶劑中的0.01mole F9PG(4.62克)和酸酐(順式-1,2,3,6-四氫鄰苯二甲酸酐)(1.52克)。Next, the polymer composition (5 g) was added to a hardener (0.25 g) before curing and baked in an oven at 100 ° C for 1 hour to form a 1 mm film. After the measurement, the film had a refractive index of 1.57. Here, the hardener comprises 0.01 mole F9PG (4.62 g) and anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) dissolved in 40 g of γ-butyrolactone solvent (1.52). Gram).
取0.03mole之F9PEO、0.03mole之Bisphenol S及0.04mole之DMPA置入於500ml之反應瓶，加入r-丁內脂(r-butyro-lactone、GBL)之溶劑(固含量約為30%)，並通入氮氣30分鐘，攪拌均勻使其溶解，其溶解溫度約為100℃。並加入數滴熱安定劑CHINOX TP-10H以防止合成時之黃變現象。接著，利用滴加漏斗將0.11mole的IPDI加入反應瓶中，直到異氰酸基(-NCO)的含量消失(每30分鐘用IR檢測)，即可將反應停止，即可將反應停止。在此，該F9PEO、該Bisphenol S、該DMPA與該IPDI之莫耳數比為3:3:4:11。接著，利用GPC量測所得之聚合物，測得其分子量Mw=69334、Mn=2980、以及Mw/Mn=2.32。0.03 mole of F9PEO, 0.03 mole of Bisphenol S and 0.04 mole of DMPA were placed in a 500 ml reaction flask, and a solvent of r-butyro-lactone (GBL) (solid content of about 30%) was added. Nitrogen gas was introduced for 30 minutes, and uniformly stirred to dissolve. The dissolution temperature was about 100 °C. A few drops of thermal stabilizer CHINOX TP-10H was added to prevent yellowing during synthesis. Next, 0.11 mole of IPDI was added to the reaction flask using a dropping funnel until the content of isocyanate (-NCO) disappeared (detected by IR every 30 minutes), and the reaction was stopped to stop the reaction. Here, the ratio of the molar ratio of the F9PEO, the Bisphenol S, the DMPA and the IPDI is 3:3:4:11. Next, the polymer obtained by GPC measurement was found to have a molecular weight of Mw = 69334, Mn = 2980, and Mw / Mn = 2.32.
上述聚合反應之反應式如下所示：The reaction formula of the above polymerization reaction is as follows:
接著，在固化前將該聚合物組合物(5g)加入硬化劑(0.25g)並在100℃烘箱中烘烤1小時，並成1mm薄膜。測量後，可知該薄膜的折射率為1.57。在此，該硬化劑包含溶解於40克γ-丁內酯溶劑中的0.01mole F9PG(4.62克)和酸酐(順式-1,2,3,6-四氫鄰苯二甲酸酐)(1.52克)。Next, the polymer composition (5 g) was added to a hardener (0.25 g) before curing and baked in an oven at 100 ° C for 1 hour to form a 1 mm film. After the measurement, the film had a refractive index of 1.57. Here, the hardener comprises 0.01 mole F9PG (4.62 g) and anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) dissolved in 40 g of γ-butyrolactone solvent (1.52). Gram).
實施例7Example 7
取0.03mole之F9PEO、0.01mole之TBBPA及0.04mole之DMPA置入於500ml之反應瓶，加入r-丁內脂(r-butyro-lactone、GBL)之溶劑(固含量約為30%)，並通入氮氣30分鐘，攪拌均勻使其溶解，其溶解溫度約為100℃。並加入數滴熱安定劑CHINOX TP-10H以防止合成時之黃變現象。接著，利用滴加漏斗將0.1mole的IPDI加入反應瓶中，直到異氰酸基(-NCO)的含量消失(每30分鐘用IR檢測)，即可將反應停止，即可將反應停止。在此，該F9PEO、該TBBPA、該DMPA與該IPDI之莫耳數比為3:1:4:10。0.03 mole of F9PEO, 0.01 mole of TBBPA and 0.04 mole of DMPA were placed in a 500 ml reaction flask, and a solvent of r-butyro-lactone (GBL) was added (solid content was about 30%), and Nitrogen gas was bubbled through for 30 minutes, and the mixture was uniformly stirred to dissolve, and the dissolution temperature was about 100 °C. A few drops of thermal stabilizer CHINOX TP-10H was added to prevent yellowing during synthesis. Next, 0.1 mole of IPDI was added to the reaction flask using a dropping funnel until the content of isocyanate (-NCO) disappeared (detected by IR every 30 minutes), and the reaction was stopped to stop the reaction. Here, the ratio of the molar ratio of the F9PEO, the TBBPA, the DMPA, and the IPDI is 3:1:4:10.
上述聚合反應之反應式如下所示：The reaction formula of the above polymerization reaction is as follows:
接著，在固化前將該聚合物組合物(5g)加入硬化劑(0.25g)並在100℃烘箱中烘烤1小時，並成1mm薄膜。測量後，可知該薄膜的折射率為1.59。在此，該硬化劑包含溶解於40克γ-丁內酯溶劑中的0.01mole F9PG(4.62克)和酸酐(順式-1,2,3,6-四氫鄰苯二甲酸酐)(1.52克)。Next, the polymer composition (5 g) was added to a hardener (0.25 g) before curing and baked in an oven at 100 ° C for 1 hour to form a 1 mm film. After the measurement, the film had a refractive index of 1.59. Here, the hardener comprises 0.01 mole F9PG (4.62 g) and anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) dissolved in 40 g of γ-butyrolactone solvent (1.52). Gram).
實施例9Example 9
取0.1mole之F9Ph置入於500ml之反應瓶，加入r-丁內脂(r-butyro-lactone、GBL)之溶劑(固含量約為35%)，並通入氮氣30分鐘，攪拌均勻使其溶解，其溶解溫度約為45℃。並加入數滴熱安定劑CHINOX TP-10H以防止合成時之黃變現象。接著，利用滴加漏斗將0.1mole的MDI加入反應瓶中，直到異氰酸基(-NCO)的含量消失(每30分鐘用IR檢測)，即可將反應停止，即可將反應停止。在此，該F9Ph、與該MDI之莫耳數比為1:1。0.1 mol of F9Ph was placed in a 500 ml reaction flask, and a solvent of r-butyro-lactone (GBL) (solid content of about 35%) was added, and nitrogen gas was introduced for 30 minutes, and the mixture was uniformly stirred. Dissolved, its dissolution temperature was about 45 °C. A few drops of thermal stabilizer CHINOX TP-10H was added to prevent yellowing during synthesis. Next, 0.1 mole of MDI was added to the reaction flask using a dropping funnel until the content of isocyanate (-NCO) disappeared (detected by IR every 30 minutes), and the reaction was stopped to stop the reaction. Here, the F9Ph and the MDI molar ratio are 1:1.
上述聚合反應之反應式如下所示：The reaction formula of the above polymerization reaction is as follows:
接著，在固化前將該聚合物組合物(5g)加入硬化劑(0.25g)並在100℃烘箱中烘烤1小時，並成1mm薄膜。測量後，可知該薄膜的折射率為1.59。在此，該硬化劑包含溶解於40克γ-丁內酯溶劑中的0.01mole F9PG(4.62克)和酸酐(順式-1,2,3,6-四氫鄰苯二甲酸酐)(1.52克)。Next, the polymer composition (5 g) was added to a hardener (0.25 g) before curing and baked in an oven at 100 ° C for 1 hour to form a 1 mm film. After the measurement, the film had a refractive index of 1.59. Here, the hardener comprises 0.01 mole F9PG (4.62 g) and anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) dissolved in 40 g of γ-butyrolactone solvent (1.52). Gram).
實施例11Example 11
取0.05mole之F9Ph、及0.04mol的TBBA置入於500ml之反應瓶，加入r-丁內脂(r-butyro-lactone、GBL)之溶劑(固含量約為35%)，並通入氮氣30分鐘，攪拌均勻使其溶解，其溶解溫度約為45℃。並加入數滴熱安定劑CHINOX TP-10H以防止合成時之黃變現象。充分攪拌後，加入0.01mole的PEG600加入反應瓶中通入氮氣30分鐘。接著，利用滴加漏斗將0.1mole的MDI加入反應瓶中，直到異氰酸基(-NCO)的含量消失(每30分鐘用IR檢測)，即可將反應停止，即可將反應停止。加入部分軟鏈的PEG600主要在調控高分子材料之柔軟度，以防止材料在製膜的過程中產生龜裂之現象。0.05 mol of F9Ph and 0.04 mol of TBBA were placed in a 500 ml reaction flask, and a solvent of r-butyro-lactone (GBL) (solid content of about 35%) was added, and nitrogen gas was introduced. After a minute, the mixture was uniformly stirred to dissolve, and the dissolution temperature was about 45 °C. A few drops of thermal stabilizer CHINOX TP-10H was added to prevent yellowing during synthesis. After thorough stirring, 0.01 mole of PEG 600 was added to the reaction flask and nitrogen gas was introduced for 30 minutes. Next, 0.1 mole of MDI was added to the reaction flask using a dropping funnel until the content of isocyanate (-NCO) disappeared (detected by IR every 30 minutes), and the reaction was stopped to stop the reaction. PEG600 added to a part of the soft chain mainly regulates the softness of the polymer material to prevent the material from cracking during the film formation process.
上述聚合反應之反應式如下所示The reaction formula of the above polymerization reaction is as follows
接著，在固化前將該聚合物組合物(5g)加入硬化劑(0.25g)並在100℃烘箱中烘烤1小時，並成1mm薄膜。測量後，可知該薄膜的折射率為1.59。在此，該硬化劑包含溶解於40克γ-丁內酯溶劑中的0.01mole F9PG(4.62克)和酸酐(順式-1,2,3,6-四氫鄰苯二甲酸酐)(1.52克)。Next, the polymer composition (5 g) was added to a hardener (0.25 g) before curing and baked in an oven at 100 ° C for 1 hour to form a 1 mm film. After the measurement, the film had a refractive index of 1.59. Here, the hardener comprises 0.01 mole F9PG (4.62 g) and anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) dissolved in 40 g of γ-butyrolactone solvent (1.52). Gram).
實施例12Example 12
取0.05mole之F9Ph、及0.05mole之Bisphenol S置入於500ml之反應瓶，加入r-丁內脂(r-butyro-lactone、GBL)之溶劑(固含量約為35%)，並通入氮氣30分鐘，攪拌均勻使其溶解，其溶解溫度約為45℃。並加入數滴熱安定劑CHINOX TP-10H以防止合成時之黃變現象。充分攪拌後，加入0.01mole的PEG600加入反應瓶中通入氮氣30分鐘。接著，利用滴加漏斗將0.05mole的MDI及0.05mole的IPDI加入反應瓶中，直到異氰酸基(-NCO)的含量消失(每30分鐘用IR檢測)，即可將反應停止。該F9Ph、該Bisphenol S、該MDI、該IPDI之莫耳數比為=1:1:1:1。Take 0.05 mole of F9Ph and 0.05 mole of Bisphenol S in a 500 ml reaction flask, add r-butyro-lactone (GBL) solvent (solid content is about 35%), and pass nitrogen. After 30 minutes, the mixture was uniformly stirred to dissolve, and the dissolution temperature was about 45 °C. A few drops of thermal stabilizer CHINOX TP-10H was added to prevent yellowing during synthesis. After thorough stirring, 0.01 mole of PEG 600 was added to the reaction flask and nitrogen gas was introduced for 30 minutes. Next, 0.05 mole of MDI and 0.05 mole of IPDI were added to the reaction flask using a dropping funnel until the content of isocyanate (-NCO) disappeared (detected by IR every 30 minutes), and the reaction was stopped. The molar ratio of the F9Ph, the Bisphenol S, the MDI, and the IPDI is 1:1:1:1.
接著，在固化前將該聚合物組合物(5g)加入硬化劑(0.25g)並在100℃烘箱中烘烤1小時，並成0.88mm薄膜。測量後，可知該薄膜的UV透過率與折射率分別為86%與1.573。在此，該硬化劑包含溶解於40克γ-丁內酯溶劑中的0.01mole F9PG(4.62克)和酸酐(順式-1,2,3,6-四氫鄰苯二甲酸酐)(1.52克)。Next, the polymer composition (5 g) was added to a hardener (0.25 g) before curing and baked in an oven at 100 ° C for 1 hour to form a 0.88 mm film. After the measurement, it was found that the film had a UV transmittance and a refractive index of 86% and 1.573, respectively. Here, the hardener comprises 0.01 mole F9PG (4.62 g) and anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) dissolved in 40 g of γ-butyrolactone solvent (1.52). Gram).
實施例13Example 13
取0.06mole之F9Ph、及0.04mole之PEG200置入於500ml之反應瓶，加入r-丁內脂(r-butyro-lactone、GBL)之溶劑(固含量約為35%)，並通入氮氣30分鐘，攪拌均勻使其溶解，其溶解溫度約為45℃。並加入數滴熱安定劑CHINOX TP-10H以防止合成時之黃變現象。充分攪拌後，利用滴加漏斗將0.09mole的MDI及0.01mole的IPDI加入反應瓶中，直到異氰酸基(-NCO)的含量消失(每30分鐘用IR檢測)，即可將反應停止，即可將反應停止。該F9Ph、該PEG200、該MDI、該IPDI之莫耳數比為=6:4:9:1。Take 0.06 mole of F9Ph and 0.04 mole of PEG200 into a 500 ml reaction flask, add r-butyro-lactone (GBL) solvent (solid content is about 35%), and pass nitrogen gas 30 After a minute, the mixture was uniformly stirred to dissolve, and the dissolution temperature was about 45 °C. A few drops of thermal stabilizer CHINOX TP-10H was added to prevent yellowing during synthesis. After thorough stirring, 0.09 mole of MDI and 0.01 mole of IPDI were added to the reaction flask using a dropping funnel until the content of isocyanate (-NCO) disappeared (detected by IR every 30 minutes), and the reaction was stopped. The reaction can be stopped. The molar ratio of the F9Ph, the PEG 200, the MDI, and the IPDI is =6:4:9:1.
上述聚合反應之反應式如下所示：The reaction formula of the above polymerization reaction is as follows:
接著，在固化前將該聚合物組成物(5g)加入一硬化劑(0.25g)於100℃烘箱中烘烤1小時，並製成薄膜。量測後，可知該薄膜的UV穿透度與折射率分別為95%與1.615。其波長與穿穿透度的關係如第1圖所示。在此，該硬化劑係包含0.01mole之F9PG(4.62克)與酸酐(順式-1,2,3,6-四氫鄰苯二甲酸酐)(1.52克)溶解於40克r-丁內脂溶劑中。Next, the polymer composition (5 g) was added to a hardener (0.25 g) in an oven at 100 ° C for 1 hour before curing, and a film was formed. After the measurement, the UV transmittance and refractive index of the film were 95% and 1.615, respectively. The relationship between the wavelength and the penetration is as shown in Fig. 1. Here, the hardener comprises 0.01 mole of F9PG (4.62 g) and an acid anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) (1.52 g) dissolved in 40 g of r-butyl. In a lipid solvent.
此外，將上述聚合物形成一附著於銀基材上之薄膜，並利用100℃之烘烤溫度(烘烤1小時)。接著，將試片放置於配製於一紅墨水水溶液。浸泡30分鐘後，並無觀察到紅墨水滲透入於薄膜內。此表示該聚合物具有極佳之附著能力。Further, the above polymer was formed into a film attached to a silver substrate, and baked at a baking temperature of 100 ° C (bake for 1 hour). Next, the test piece was placed in an aqueous solution of red ink. After soaking for 30 minutes, no red ink was observed to penetrate into the film. This means that the polymer has excellent adhesion.
綜合上述，本發明利用分子結構設計的方式，導入含高折射率之雙酚芴衍生物單體(例如F9Ph、F9PEO)與具有二異氰酸(isocyanate)官能基之衍生物透過加成聚合之方式，來合成出具有高折射率之高分子材料。此外，亦進一步透過加入含有硫或溴之異原子基團之雙酚或二元醇來調控其材料之折射率。再者，在本發明某些實施例中，亦使用具有軟鏈的PEG寡聚物作為二元醇，以平衡整體聚合物的撓曲性；或是加入具有雙酚芴結構之硬化劑，加強耐熱性及硬度。In summary, the present invention utilizes a molecular structure design method to introduce a bisphenolphthalein derivative monomer having a high refractive index (for example, F9Ph, F9PEO) and a derivative having an isocyanate functional group by addition polymerization. In a manner, a polymer material having a high refractive index is synthesized. Further, the refractive index of the material is further regulated by the addition of a bisphenol or a glycol containing a hetero atom group of sulfur or bromine. Furthermore, in certain embodiments of the invention, a PEG oligomer having a soft chain is also used as a glycol to balance the flexibility of the overall polymer; or a hardener having a bisphenolphthalein structure is added to strengthen Heat resistance and hardness.
本發明所述之聚合物，除了具有高折射率、高透光性外，亦具有高耐熱性、高附著力、低黃變性及高成膜性等性質，可作為封裝材料、透明基板、透鏡(例如：菲涅爾透鏡(fresnel lenes))、或功能性薄膜等光學元件，更符合發光二極體、太陽能電池(例如：聚光型太陽能電池(concentrator photovoltaic)、半導體裝置、或是顯示裝置等光學元件之應用要求。The polymer of the present invention has high heat resistance, high adhesion, low yellowing property and high film forming property in addition to high refractive index and high light transmittance, and can be used as a packaging material, a transparent substrate, and a lens. (for example, Fresnel lens), or an optical element such as a functional film, more in line with a light-emitting diode, a solar cell (for example, a concentrator photovoltaic device, a semiconductor device, or a display device) Application requirements for optical components.
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為基準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope is based on the definition of the scope of the patent application attached.
第1圖係為實施例13所得之聚合物薄膜其穿透率及波長的關係圖。Fig. 1 is a graph showing the relationship between the transmittance and the wavelength of the polymer film obtained in Example 13.
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