TW201331253A - Epoxy resin system, use of the epoxy resin system, age-resistant epoxy resin molding material, and component with the epoxy resin molding material - Google Patents
Epoxy resin system, use of the epoxy resin system, age-resistant epoxy resin molding material, and component with the epoxy resin molding material Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
Abstract
Description
環氧樹脂，環氧樹脂之用途，耐老化環氧樹脂模塑材料及含有該環氧樹脂模塑材料之元件。 Epoxy resin, use of epoxy resin, anti-aging epoxy resin molding material and components containing the epoxy resin molding material.
本發明主張德國專利登記10 2011 056 295.8之優先權以及入其公開說明書之內容。 The present invention claims the priority of German Patent Registration No. 10 2011 056 295.8 and the contents of its disclosure.
本發明涉及一種環氧樹脂系統及該環氧樹脂系統之用途。此外，本發明還涉及該環氧樹脂系統製成的耐老化環氧樹脂模塑材料，以及含有該環氧樹脂模塑材料之元件。 The present invention relates to an epoxy resin system and the use of the epoxy resin system. Further, the present invention relates to an anti-aging epoxy resin molding material made of the epoxy resin system, and an element containing the epoxy resin molding material.
為了確保電子元件(尤其是光電電子元件或其產品)的功能性及可靠性，必須保護電子元件免於受到有害的環境影響，例如受到濕氣或空氣的影響。為此經常使用環氧樹脂氫化物胚料製成的流延胚料。但是實務經驗顯示，已知的流延材料除了反應性稀釋劑外，其所含有環氧化物成分(例如芳香環氧樹脂)的耐老化性並不足夠。該等流延胚料在電子元件或其產品的使用壽命內就會出現發黃的現象，因此可能變得易脆，也就是說其力學不穩定性會升高，因而可能導致出現裂痕或斷裂，以及降低結合強度，例如導致層壓層分開。發黃現象主要是源自所使用之芳香族環氧化物。所謂的SMD元件(表面安裝元件)，例如被焊接固定在載體上的元件，尤其容易出現這些損害。焊接時產生的跳躍式溫度升高，會使鑄件承受很高的熱應力或熱機械應力。 In order to ensure the functionality and reliability of electronic components, especially optoelectronic components or their products, electronic components must be protected from harmful environmental influences, such as moisture or air. Cast billets made of epoxy hydride billets are often used for this purpose. However, practical experience has shown that the known casting materials, in addition to the reactive diluent, do not have sufficient aging resistance of the epoxide component (for example, an aromatic epoxy resin). These cast billets may yellow during the life of the electronic component or its products, and thus may become brittle, that is, its mechanical instability may increase, which may cause cracks or breaks. And reducing the bond strength, for example, causing the laminate layers to separate. The yellowing phenomenon is mainly due to the aromatic epoxide used. So-called SMD components (surface mount components), such as components that are soldered to the carrier, are particularly susceptible to such damage. The jumper temperature rise during welding causes the casting to withstand high thermal or thermomechanical stresses.
因此業界需要能夠製造出具有很好的耐老化性、很好的抗發黃性、以及良好的低應力特性的環氧樹脂模塑材料的環氧樹脂系統。例如，低應力特性包括在低儲存模數時具有高玻璃轉換溫度TG、受熱時的熱膨脹量小、熱穩定性高、以及很好的耐溫度交變性能。因此具有良好的低應力特性的環氧化物模塑材料及/或材料複合物可承受很大的負荷及具有很好抗斷裂性。 Therefore, there is a need in the industry for an epoxy resin system capable of producing an epoxy resin molding material having excellent aging resistance, good yellowing resistance, and good low stress characteristics. For example, low stress characteristics include having a high glass transition temperature T G at the low storage modulus, thermal expansion during heating amount is small, high thermal stability, and good resistance to temperature changes properties. Therefore, the epoxy molding materials and/or material composites having good low stress characteristics can withstand a large load and have excellent fracture resistance.
本發明的目的是提出一種能夠製造出具有較佳之特性的環氧樹脂模塑材料的環氧樹脂系統。所謂較佳的特性包括較佳的耐老化性、較佳的抗發黃性、以及較佳的低應力特性。本發明的其他目的包括環氧樹脂之用途、一種以環氧樹脂系統製造出的環氧樹脂模塑材料、以及一種含有該環氧樹脂模塑材料的電子元件、光電電子元件或光學元件。 SUMMARY OF THE INVENTION An object of the present invention is to provide an epoxy resin system capable of producing an epoxy resin molding material having preferable characteristics. Preferred properties include better aging resistance, better resistance to yellowing, and better low stress characteristics. Other objects of the present invention include the use of an epoxy resin, an epoxy resin molding material produced by an epoxy resin system, and an electronic component, an optoelectronic electronic component or an optical component containing the epoxy resin molding material.
透過本發明之環氧樹脂系統的至少一種實施方式可以達到以上目的中的至少一個目的。其他目的則可以透過本發明之環氧樹脂系統、環氧樹脂模塑材料、以及電子元件、光電電子元件或光學元件的至少一種實施方式獲得實現。 At least one of the above objects can be attained by at least one embodiment of the epoxy resin system of the present invention. Other objects are achieved by at least one embodiment of the epoxy resin system, epoxy molding material, and electronic, optoelectronic, or optical components of the present invention.
本發明提出一種環氧樹脂系統。根據至少一種實施方式，環氧樹脂系統含有：-- 含有第一環氧化物及第二環氧化物的成分A，其中第一環氧化物是一種帶有至少兩個環氧化官能基的芳香族化合物，同時第二環氧化物是從一組化合物中選出 的一種化合物或化合物的組合：氫化雙酚A二縮水甘油醚，氫化雙酚A二縮水甘油醚寡聚物，氫化雙酚F二縮水甘油醚，氫化雙酚F二縮水甘油醚寡聚物，氫化經取代之雙酚A二縮水甘油醚，氫化經取代之雙酚A二縮水甘油醚寡聚物，氫化經取代之雙酚F二縮水甘油醚，氫化經取代之雙酚F二縮水甘油醚寡聚物；及-- 含有碳酸酐的B成分。 The present invention provides an epoxy resin system. According to at least one embodiment, the epoxy resin system comprises: -- a component A comprising a first epoxide and a second epoxide, wherein the first epoxide is an aromatic having at least two epoxidized functional groups a compound while the second epoxide is selected from a group of compounds a compound or combination of compounds: hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether oligomer, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol F diglycidyl ether oligomer, Hydrogenated substituted bisphenol A diglycidyl ether, hydrogenated substituted bisphenol A diglycidyl ether oligomer, hydrogenated substituted bisphenol F diglycidyl ether, hydrogenated substituted bisphenol F diglycidyl ether Oligomer; and -- B component containing carbonic anhydride.
根據本發明，第一環氧化物及第二環氧化物是不同的。也可以將環氧樹脂系統稱為環氧樹脂酸酐胚料或熱塑合成樹脂胚料。 According to the invention, the first epoxide and the second epoxide are different. The epoxy resin system can also be referred to as an epoxy resin anhydride blank or a thermoplastic synthetic resin blank.
所謂“芳香族化合物”是指含有至少一個芳香環的化合物。這種化合物也可以含有非芳香族結構。 By "aromatic compound" is meant a compound containing at least one aromatic ring. Such compounds may also contain non-aromatic structures.
根據本發明，所謂“組合”可以是(但不是必須)包括整個組的成分(這些成分通常是化合物)。這個組中的一或數個成分也可以具有多種不同的改質體。 According to the invention, the term "combination" may be, but is not required to include, the entire group of ingredients (these ingredients are typically compounds). One or more of the components in this group can also have a variety of different modifications.
如前面所述，第二環氧化物是一種氫化雙酚A衍生物及/或氫化雙酚F衍生物，其中氫化雙酚A衍生物是從一組化合物中選出的一種化合物或化合物的組合：氫化雙酚A二縮水甘油醚，氫化雙酚A二縮水甘油醚寡聚物，氫化經取代之雙酚A二縮水甘油醚，氫化經取代之雙酚A二縮水甘油醚寡聚物，其中雙酚F衍生物是從一組化合物中選出的一種化合物或化合物的組合：氫化雙酚F二縮水甘油醚，氫化雙酚F二縮水甘油醚寡聚物，氫化經取代之雙酚F二縮水甘油醚，氫化經取代之雙酚F二縮水甘油醚寡聚物。根據本發明，「氫化雙酚A衍生 物」及/或「氫化雙酚F衍生物」中的「氫化」一詞是指該芳香族雙酚A衍生物及/或雙酚F衍生物的形式氫化產物。也就是說，在這些化合物內，雙酚A衍生物及/或雙酚F衍生物的苯單元在形式上被環己烷單元取代。可以(但不是必須)使用氫化應產生雙酚A衍生物及/或雙酚F衍生物，如果是使用氫化反應，則最好是執行完全的氫化反應。 As described above, the second epoxide is a hydrogenated bisphenol A derivative and/or a hydrogenated bisphenol F derivative, wherein the hydrogenated bisphenol A derivative is a compound or a combination of compounds selected from the group consisting of: Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether oligomer, hydrogenated substituted bisphenol A diglycidyl ether, hydrogenated substituted bisphenol A diglycidyl ether oligomer, wherein A phenol F derivative is a compound or a combination of compounds selected from the group consisting of hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol F diglycidyl ether oligomer, hydrogenated substituted bisphenol F diglycidyl Ether, hydrogenated substituted bisphenol F diglycidyl ether oligomer. According to the invention, "hydrogenated bisphenol A derived The term "hydrogenation" in the "product" and/or "hydrogenated bisphenol F derivative" means a hydrogenated product in the form of the aromatic bisphenol A derivative and/or the bisphenol F derivative. That is, within these compounds, the benzene units of the bisphenol A derivative and/or the bisphenol F derivative are formally substituted with a cyclohexane unit. It is possible, but not necessary, to use hydrogenation to produce a bisphenol A derivative and/or a bisphenol F derivative, and if a hydrogenation reaction is used, it is preferred to carry out a complete hydrogenation reaction.
根據本發明，氫化雙酚A二縮水甘油醚是指一種具有以下之構造式I(其中n=0)的化合物，氫化雙酚A二縮水甘油醚寡聚物的n=1至30，尤其是n=1至20。所選擇的n值應使化合物為液態，或是熔點最高不超過60℃。也可以使用n值較低的化合物，例如n=1至10，尤其是n=0至1。 According to the present invention, hydrogenated bisphenol A diglycidyl ether means a compound having the following structural formula I (wherein n = 0), n = 1 to 30 of a hydrogenated bisphenol A diglycidyl ether oligomer, especially n=1 to 20. The value of n chosen should be such that the compound is in a liquid state or has a melting point of no more than 60 °C. Compounds having a lower value of n can also be used, for example n = 1 to 10, especially n = 0 to 1.
根據本發明，氫化雙酚F二縮水甘油醚是指一種具有以下之構造式II(其中n=0)的化合物，氫化雙酚F二縮水甘油醚寡聚物的n=1至30，尤其是n=1至20。所選擇的n值應使化合物為液態，或是熔點最高不超過60℃。也可以使用n值較低的化合物，例如n=1至10，尤其是n=0至1。 According to the present invention, hydrogenated bisphenol F diglycidyl ether refers to a compound having the following structural formula II (where n = 0), hydrogenated bisphenol F diglycidyl ether oligomer n = 1 to 30, especially n=1 to 20. The value of n chosen should be such that the compound is in a liquid state or has a melting point of no more than 60 °C. Compounds having a lower value of n can also be used, for example n = 1 to 10, especially n = 0 to 1.
例如，上述化合物之相應的經取代之化合物可以在氫化雙酚A單元及/或氫化雙酚F單元的環己烷環上帶有取代基。這些取代基可以是鹵素(尤其是氟)及/或帶有1至6個碳原子的烷基。環己烷基主要或全部是在對氧原子的2及2’位置(鄰位及對鄰位)被經取代之，其中雙酚A單元及/或雙酚F單元的一、二、三、或全部四個位置可以被經取代之。這些位置較佳是帶有一個氫原子及由氟及/或帶有1至6個碳原子的烷基構成的取代基。較佳是全部四個位置都被相同的取代基取代。其他的取代方法包括將氫化雙酚A單元的甲基氟化，尤其是過氟化。 For example, the corresponding substituted compound of the above compound may have a substituent on the cyclohexane ring of the hydrogenated bisphenol A unit and/or the hydrogenated bisphenol F unit. These substituents may be halogen (especially fluorine) and/or alkyl groups having 1 to 6 carbon atoms. The cyclohexane group is mainly or wholly substituted at the 2 and 2' positions (ortho and ortho) to the oxygen atom, wherein the bisphenol A unit and/or the bisphenol F unit is one, two, three. Or all four positions can be replaced. These positions are preferably a substituent having one hydrogen atom and an alkyl group having fluorine and/or having 1 to 6 carbon atoms. Preferably all four positions are replaced by the same substituent. Other substitution methods include methylation of the hydrogenated bisphenol A unit, especially perfluorination.
通常是將成分A及成分B分開存放，直到使環氧樹脂系統硬化之前才將二者混合。透過環氧樹脂系統的硬化可以產生一種模塑材料，這種模塑材料也稱為「環氧樹脂模塑材料」。因此環氧樹脂模塑材料的特性主要或全部是由環氧樹脂系統的成分決定。 Component A and component B are typically stored separately until the epoxy system is allowed to harden before mixing. Hardening through an epoxy resin system produces a molding material, which is also referred to as an "epoxy molding material." Therefore, the characteristics of the epoxy resin molding material are mainly or entirely determined by the composition of the epoxy resin system.
以本發明之環氧樹脂系統製成的環氧樹脂模塑材料一方面具有很好的耐老化性及抗發黃性，另一方面還具有很好的低應力特性。這種環氧樹脂模塑材料的最大特徵是具有很高的強度、很高的耐溫度衝擊性、很高的形狀穩定性、以及不易出現脆裂、孔隙或裂痕等現象。這 些特性也會出現在含有不易發生分層的環氧樹脂模塑材料的材料複合物上。較佳的低應力特性伴隨高玻璃轉換溫度TG及環氧樹脂模塑材料的低儲存模數。由於環氧樹脂模塑材料可以耐受焊接，因此環氧樹脂系統亦可應用於SMD元件，例如發光二極體(LED)。相較於一般的環氧樹脂模塑材料，本發明之環氧樹脂模塑材料之所以具有較佳的特性主要是來自於本發明之環氧樹脂系統之成分A中的第一環氧化物及第二氧化物的組合。 The epoxy resin molding material prepared by the epoxy resin system of the present invention has excellent aging resistance and yellowing resistance on the one hand, and has excellent low stress characteristics on the other hand. The most important characteristics of this epoxy resin molding material are high strength, high temperature shock resistance, high shape stability, and the occurrence of brittle cracks, cracks or cracks. These characteristics also occur in material composites containing epoxy molding materials that are less susceptible to delamination. The preferred low stress characteristics are accompanied by a high glass transition temperature TG and a low storage modulus of the epoxy molding material. Since epoxy molding materials can withstand soldering, epoxy systems can also be applied to SMD components such as light emitting diodes (LEDs). Compared with a general epoxy resin molding material, the epoxy resin molding material of the present invention has preferable properties mainly derived from the first epoxide in the component A of the epoxy resin system of the present invention and A combination of second oxides.
根據另一種實施方式，第一環氧化物是從一組化合物中選出的一種化合物或化合物的組合：雙酚A二縮水甘油醚，雙酚A二縮水甘油醚寡聚物，雙酚F二縮水甘油醚，雙酚F二縮水甘油醚寡聚物，環氧化物-酚醛清漆，經取代之雙酚A二縮水甘油醚，經取代之雙酚A二縮水甘油醚寡聚物，經取代之雙酚F二縮水甘油醚，經取代之雙酚F二縮水甘油醚寡聚物。雙酚A二縮水甘油醚具有構造式III(其中n=0)。雙酚A二縮水甘油醚寡聚物的n=1至30，尤其是n=1至20。雙酚F二縮水甘油醚具有構造式IV(其中n=0)。雙酚F二縮水甘油醚寡聚物的n=1至30，尤其是n=1至20。也可以使用n值較低的化合物(構造式III及/或構造式IV)，例如n=1至10，尤其是n=0至1。例如可以使用Huntsman公司生產之MY790-1作為第一環氧化物。其他可在市面上購得的第一環氧化物還包括Dow Chemical公司生產的D.E.R.332及Leuna Harze公司生產的Epilox-A 17-01。 According to another embodiment, the first epoxide is a compound or a combination of compounds selected from the group consisting of bisphenol A diglycidyl ether, bisphenol A diglycidyl ether oligomer, bisphenol F condensed water Glycerol ether, bisphenol F diglycidyl ether oligomer, epoxide-novolac, substituted bisphenol A diglycidyl ether, substituted bisphenol A diglycidyl ether oligomer, substituted double Phenol F diglycidyl ether, substituted bisphenol F diglycidyl ether oligomer. Bisphenol A diglycidyl ether has the structural formula III (where n = 0). The bisphenol A diglycidyl ether oligomer has n = 1 to 30, especially n = 1 to 20. Bisphenol F diglycidyl ether has the structural formula IV (where n = 0). The bisphenol F diglycidyl ether oligomer has n = 1 to 30, especially n = 1 to 20. Compounds of lower n value (formula III and/or formula IV) may also be used, for example n=1 to 10, especially n=0 to 1. For example, MY790-1 manufactured by Huntsman Corporation can be used as the first epoxide. Other commercially available first epoxides include D.E.R. 332 manufactured by Dow Chemical Company and Epilox-A 17-01 manufactured by Leuna Harze Corporation.
例如，上述化合物之相應的經取代之化合物可以在雙酚A單元及/或雙酚F單元的苯環上帶有取代基。這些取代基可以是鹵素(尤其是氟)及/或帶有1至6個碳原子的烷基。苯基主要或全部是在對氧原子的鄰位及對鄰位被取代，其中一、二、三、或全部四個位置可以被取代。較佳是全部四個位置都被相同的取代基取代。其他的取代方法包括將雙酚A單元的甲基氟化，尤其是過氟化。 For example, the corresponding substituted compound of the above compound may have a substituent on the benzene ring of the bisphenol A unit and/or the bisphenol F unit. These substituents may be halogen (especially fluorine) and/or alkyl groups having 1 to 6 carbon atoms. The phenyl group is mainly or wholly substituted in the ortho and the ortho position to the oxygen atom, and one, two, three, or all four positions may be substituted. Preferably all four positions are replaced by the same substituent. Other substitution methods include methylation of the bisphenol A unit, especially perfluorination.
根另外一種實施方式，第一環氧化物是從一組化合物中選出的一種化合物或化合物的組合：雙酚A二縮水甘油醚，雙酚A二縮水甘油醚寡聚物，經甲基及/或氟取代之雙酚A二縮水甘油醚，經甲基及/或氟取代之雙酚A二縮水甘油醚寡聚物。 In another embodiment, the first epoxide is a compound or combination of compounds selected from the group consisting of bisphenol A diglycidyl ether, bisphenol A diglycidyl ether oligomer, methyl and/or Or a fluorine-substituted bisphenol A diglycidyl ether, a bisphenol A diglycidyl ether oligomer substituted with methyl and/or fluorine.
令人訝異的是，本發明證實第一環氧化物雖然含有這些芳香族基，但仍非常適於用來製造具有很好的低應力特性的抗發黃性環氧樹脂模塑材料。抗發黃性之所以會提高，主要是因為成分A中除了第一環氧化物外，還含有第二環氧化物的關係。與此相反的是，一般的流延 胚料的基本環氧化物(除了可能含有的反應性稀釋劑外)全部來自芳香族多官能基化合物，而這種化合物出現發黃現象的傾向明顯較高。 Surprisingly, the present invention demonstrates that the first epoxide, although containing these aromatic groups, is well suited for use in the manufacture of anti-yellowing epoxy resin molding materials having very good low stress characteristics. The reason why the anti-yellowing property is increased is mainly because the component A contains a second epoxide in addition to the first epoxide. Contrary to this, the general casting The basic epoxide of the billet (except for the reactive diluents that may be present) is all derived from aromatic polyfunctional compounds, and the tendency of such compounds to appear yellow is significantly higher.
此外，也可以不添加環脂肪族環氧化物，這樣做是很有利的，因為環脂肪族環氧化物的價格比較高，而且與芳香族二縮水甘油醚混合後可能會有致癌的風險。此外，高含量的環脂肪族環氧化物會導致模塑材料易脆及週期穩定性變低。根據本發明，所謂環脂肪族環氧化物是指環氧化官能基是環脂肪族基的一部分的化合物。環脂肪族環氧化物的一個例子是3,4-環氧環己基甲基-3,4-環氧環己基甲酸酯，此種化合物具有以下的構造式V。 Further, it is also possible to add no cycloaliphatic epoxide, which is advantageous because the price of the cycloaliphatic epoxide is relatively high, and there is a risk of carcinogenicity when mixed with the aromatic diglycidyl ether. In addition, a high content of the cyclic aliphatic epoxide causes the molding material to be brittle and the cycle stability to be low. According to the invention, a cycloaliphatic epoxide refers to a compound in which the epoxidation functional group is part of a cycloaliphatic group. An example of a cycloaliphatic epoxide is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylformate, which has the following structural formula V.
與環脂肪族環氧化物相反，芳香族第一環氧化物能夠使環氧樹脂模塑材料具有很高的力學穩定性。因此本發明的環氧樹脂模塑材料的吸水性較低，並具有較高的結合強度及對化學藥劑具有較高的穩定性。但是在某些情況下，成分A也可能含有一部分的環脂肪族環氧化物。這個部分可以是小於20%(重量百分比)，尤其是小於10%(重量百分比)。一種有利的方式是完全不含環脂肪族環氧化物。 In contrast to the cycloaliphatic epoxide, the aromatic first epoxide enables the epoxy resin molding material to have high mechanical stability. Therefore, the epoxy resin molding material of the present invention has low water absorbability, high bonding strength, and high stability to chemicals. However, in some cases, component A may also contain a portion of the cycloaliphatic epoxide. This portion may be less than 20% by weight, especially less than 10% by weight. An advantageous way is to be completely free of cycloaliphatic epoxides.
根據另外一種實施方式，第一環氧化物是雙酚A二縮水甘油醚、雙酚A二縮水甘油醚寡聚物、或是此二者 的組合。這些化合物在室溫中可以具有最高不超過20000mPa*s的黏滯性，這會使構造式III中的n值相當低。例如n=1至10，尤其是n=0至1。利用成分A中的這種第一環氧化物加上第二環氧化物，可以獲得具有非常好的特性的環氧樹脂模塑材料，而且由於雙酚A二縮水甘油醚的價格低廉，因此可以用很低的成本製造出環氧樹脂模塑材料。 According to another embodiment, the first epoxide is bisphenol A diglycidyl ether, bisphenol A diglycidyl ether oligomer, or both The combination. These compounds may have a viscosity of up to 20,000 mPa*s at room temperature, which results in a relatively low value of n in the formula III. For example, n=1 to 10, especially n=0 to 1. By using such a first epoxide in the component A plus a second epoxide, an epoxy resin molding material having very good characteristics can be obtained, and since bisphenol A diglycidyl ether is inexpensive, it can be Epoxy resin molding materials are produced at a very low cost.
根據另外一種實施方式，第二環氧化物是從一組化合物中選出的一種化合物或化合物的組合：氫化雙酚A二縮水甘油醚，氫化雙酚A二縮水甘油醚寡聚物，氫化雙酚F二縮水甘油醚，氫化雙酚F二縮水甘油醚寡聚物，氫化經甲基及/或氟取代之雙酚A二縮水甘油醚，氫化經甲基及/或氟取代之雙酚A二縮水甘油醚寡聚物，氫化經甲基及/或氟取代之雙酚F二縮水甘油醚，氫化經甲基及/或氟取代之雙酚F二縮水甘油醚寡聚。例如可以用Mitsubishi Chemical股份有限公司生產的化合物YX8000或YX8034作為第二環氧化物。 According to another embodiment, the second epoxide is a compound or combination of compounds selected from the group consisting of hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether oligomer, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol F diglycidyl ether oligomer, hydrogenated bisphenol A diglycidyl ether substituted by methyl and/or fluorine, hydrogenated bisphenol A substituted by methyl and/or fluorine A glycidyl ether oligomer, hydrogenated with a methyl and/or fluorine substituted bisphenol F diglycidyl ether, hydrogenated with a methyl and/or fluorine substituted bisphenol F diglycidyl ether oligomer. For example, a compound YX8000 or YX8034 produced by Mitsubishi Chemical Co., Ltd. can be used as the second epoxide.
例如，經甲基及/或氟取代可以提高環氧樹脂模塑材料的穩定性，因為這些取代基可以抑制分解反應。此外，氟取代基可以進一步提高抗發黃性。這對於第一環氧化物及第二環氧化物都是如此。 For example, substitution with methyl and/or fluorine can improve the stability of the epoxy resin molding material because these substituents can inhibit the decomposition reaction. In addition, the fluorine substituent can further enhance the anti-yellowing property. This is true for both the first epoxide and the second epoxide.
根據另外一種實施方式，第二環氧化物是氫化雙酚A二縮水甘油醚、氫化雙酚A二縮水甘油醚寡聚物、或是此二者的組合。這些化合物在室溫中可以具有最高不超過20000mPa*s的黏滯性，這會使構造式I中的n值相 當低。例如n=1至10，尤其是n=0至1。由於這些化合物的性價比很高，因此非常有利。尤其是這種第二環氧化物與作為第一環氧化物的雙酚A二縮水甘油醚的組合產生的環氧樹脂模塑材料不但具有很好的耐老化性及抗發黃性，而且還具有很好的熱力學特性。 According to another embodiment, the second epoxide is hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether oligomer, or a combination of the two. These compounds may have a viscosity of up to 20,000 mPa*s at room temperature, which results in an n-value phase in the formula I. When low. For example, n=1 to 10, especially n=0 to 1. These compounds are very advantageous due to their high cost performance. In particular, the epoxy resin molding material produced by the combination of the second epoxide and the bisphenol A diglycidyl ether as the first epoxide not only has good aging resistance and yellowing resistance, but also Has very good thermodynamic properties.
根據另外一種實施方式，成分A含有5%至90%(重量百分比)的第二環氧化物。成分A可以含有10%至80%(重量百分比)、10%至60%(重量百分比)、或最好是10%至45%(重量百分比)的第二環氧化物。含有這種含量之第二環氧化物的成分A與帶有芳香族基的第一環氧化物的組合可以產生低應力特性非常好且具有較佳之抗發黃性的環氧樹脂模塑材料。本發明發現，成分A甚至只要含有15%至30%(重量百分比)的第二環氧化物，就可以製造出非常有利的環氧樹脂模塑材料。這是一個很大的優點，因為第二環氧化物的價格通常高於第一環氧化物，原因是製造第二環氧化物通常比製造第一環氧化物多一個步驟，例如多一個氫化反應步驟。 According to another embodiment, ingredient A contains from 5% to 90% by weight of the second epoxide. Ingredient A may contain from 10% to 80% by weight, from 10% to 60% by weight, or preferably from 10% to 45% by weight, of the second epoxide. The combination of the component A containing the second epoxide of such a content and the first epoxide having an aromatic group can produce an epoxy resin molding material having excellent low stress characteristics and preferably excellent yellowing resistance. The present inventors have found that component A can produce a very advantageous epoxy molding material even if it contains 15% to 30% by weight of the second epoxide. This is a great advantage because the price of the second epoxide is generally higher than that of the first epoxide because the second epoxide is usually produced in one more step than the first epoxide, for example one more hydrogenation reaction. step.
根據另外一種實施方式，成分A含有至少20%、或最好是至少40%(重量百分比)的第一環氧化物。例如成分A可以含有20%至90%的第一環氧化物。尤其是成分A可以含有50%至90%、或最好是55%至85%(重量百分比)的第一環氧化物。利用含有這種含量之第一環氧化物的成分A可以用低廉的成本製造出玻璃轉換溫度TG很高的環氧樹脂模塑材料。 According to another embodiment, component A contains at least 20%, or preferably at least 40% by weight, of the first epoxide. For example, component A may contain from 20% to 90% of the first epoxide. In particular, component A may contain from 50% to 90%, or preferably from 55% to 85% by weight, of the first epoxide. By using the component A containing the first epoxide of such a content, an epoxy resin molding material having a high glass transition temperature T G can be produced at a low cost.
根據另外一種實施方式，碳酸酐是從一組酐中選出 的一種酐或酐的組合：環脂肪族或芳香族雙碳酸酐，環脂肪族或芳香族四碳酸的雙酐。碳酸酐是六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、或是二者的組合。較佳是使用液態、本身顏色不明顯、而且對改善抗發黃性的效果較芳香族碳酸酐佳的環脂肪族碳酸酐。 According to another embodiment, the carbonic anhydride is selected from the group consisting of anhydrides A combination of anhydrides or anhydrides: cycloaliphatic or aromatic dicarbonic anhydrides, cycloaliphatic or aromatic tetracarbonic dianhydrides. The carbonic anhydride is hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, or a combination of the two. It is preferred to use a cycloaliphatic carbonic anhydride which is liquid, has an insignificant color, and which is more effective in improving the anti-yellowing property than aromatic carbonic anhydride.
根據另外一種實施方式，成分B含有55%至95%(重量百分比)、或最好是60%至90%(重量百分比)的碳酸酐。例如，成分B可以含有75%(重量百分比)的碳酸酐。這種含量的碳酸酐能夠給予環氧樹脂模塑材料必要的強度，以及足夠高的玻璃轉換溫度TG。 According to another embodiment, component B contains from 55% to 95% by weight, or preferably from 60% to 90% by weight, of carbonic anhydride. For example, ingredient B may contain 75% by weight of carbonic anhydride. This amount of carbonic anhydride can impart the necessary strength to the epoxy molding material, as well as a sufficiently high glass transition temperature T G .
根據另外一種實施方式，成分B另外含有至少一種酸性碳酸酯。這種酸性碳酸酯含有至少一個自由碳酸基及至少一個酯基。較佳是使用能夠透過本發明使用之碳酸酐與醇進行醇解而產生的酸性碳酸酯。但也可以用其他方式產生酸性碳酸酯。酸性碳酸酯可以加速環氧樹脂系統硬化成環氧樹脂模塑材料的過程。 According to another embodiment, component B additionally contains at least one acidic carbonate. This acidic carbonate contains at least one free carbonic acid group and at least one ester group. It is preferred to use an acidic carbonate which can be produced by alcoholysis of a carbonic anhydride used in the present invention with an alcohol. However, acidic carbonates can also be produced in other ways. Acidic carbonates accelerate the process of hardening epoxy resin systems into epoxy molding materials.
較適合的醇包括脂肪族醇及/或環脂肪族醇。醇與一個羧基共同構成酸性碳酸酯的至少一個酯基。例如，這些脂肪族醇及/或環脂肪族醇可以是帶有1至12個碳原子的單醇、二醇、多醇、聚醚醇、或這些醇的組合。對於二醇、多醇及聚醚醇的選擇並無特別的限制。例如可以使用1,2-丙二醇、乙二醇、或是由一個、數個或甚至是許多個官能基(例如醚基)結合成的脂肪族二醇。以下均為適當的醇：乙醇，1,2-丙二醇，1,4-丁二醇，1,6-己二醇，Isorbide(CAS 652-67-5)，甘油，二乙二醇，聚乙 二醇，環己烷二甲醇，三甲醇基三環癸烷(CAS 26896-48-0)，三甲醇基丙烷。 More suitable alcohols include aliphatic alcohols and/or cycloaliphatic alcohols. The alcohol and a carboxyl group together form at least one ester group of the acidic carbonate. For example, these aliphatic alcohols and/or cycloaliphatic alcohols may be monoalcohols, diols, polyols, polyether alcohols having from 1 to 12 carbon atoms, or a combination of these alcohols. There is no particular limitation on the choice of the diol, the polyol, and the polyether alcohol. For example, 1,2-propanediol, ethylene glycol, or an aliphatic diol in which one, several or even many functional groups such as an ether group are combined can be used. The following are all suitable alcohols: ethanol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, Isorbide (CAS 652-67-5), glycerin, diethylene glycol, polyethyl Glycol, cyclohexanedimethanol, trimethylol tricyclodecane (CAS 26896-48-0), trimethylolpropane.
根據另外一種實施方式，成分B含有5%至40%(重量百分比)、或最好是10%至25%(重量百分比)的酸性碳酸酯。例如，成分B可以含最多不超過20%(重量百分比)的酸性碳酸酯。 According to another embodiment, ingredient B contains from 5% to 40% by weight, or preferably from 10% to 25% by weight, of an acidic carbonate. For example, ingredient B may contain up to no more than 20% by weight of acidic carbonate.
根據另外一種實施方式，成分B另外含有一種有機磷化合物及/或一種金屬鹽。利用一或數種這種化合物可以加速硬化過程，尤其是加速在高溫(例如150℃以上)中進行的無氣泡硬化過程。 According to another embodiment, component B additionally contains an organophosphorus compound and/or a metal salt. The use of one or several of such compounds accelerates the hardening process, especially the bubble-free hardening process carried out at elevated temperatures (e.g., above 150 °C).
根據另外一種實施方式，所使用的有機磷化合物是一種亞磷酸烷酯及/或芳香族亞磷酸酯。例如可以使用亞磷酸三苯酯。有機磷化合物除了可以加速硬化過程外，還可以提高環氧樹脂系統及/或相應之模塑材料的氧化穩定性。例如，成分B可以含有1%至12%(重量百分比)、或最好是3%至10%(重量百分比)的一或數種有機磷化合物。例如成分B可以含有最多不超過5%(重量百分比)的有機磷化合物。 According to another embodiment, the organophosphorus compound used is an alkyl phosphite and/or an aromatic phosphite. For example, triphenyl phosphite can be used. In addition to accelerating the hardening process, the organophosphorus compound can also increase the oxidative stability of the epoxy resin system and/or the corresponding molding material. For example, component B may contain from 1% to 12% by weight, or preferably from 3% to 10% by weight, of one or more organophosphorus compounds. For example, component B may contain up to 5% by weight of an organophosphorus compound.
根據另外一種實施方式，金屬鹽是鋅、釔、鋯等金屬的醇鹽及/或羧酸鹽，或是這些鹽的組合。較佳是使用鋅辛酸鹽作為金屬鹽。根據本發明，B成分可以含有1-12%(重量百分比)、尤其是3-10%(重量百分比)的金屬鹽。例如B成分可含有5%(重量百分比)的金屬鹽。和有機磷酸化合物一樣，金屬鹽具有反應加速劑的作用，能夠使環氧樹脂係統以更快的速度硬化，而且不會產生氣 泡。這可以在很短的硬化循環中完成。 According to another embodiment, the metal salt is an alkoxide and/or a carboxylate of a metal such as zinc, cerium, zirconium or the like, or a combination of these salts. It is preferred to use zinc octoate as the metal salt. According to the invention, the component B may contain from 1 to 12% by weight, in particular from 3 to 10% by weight, of the metal salt. For example, the component B may contain 5% by weight of a metal salt. Like organic phosphate compounds, metal salts act as reaction accelerators, allowing epoxy systems to harden at a faster rate without generating gas. bubble. This can be done in a short hardening cycle.
根據另外一種實施方式，成分A含有第三環氧化物。第三環氧化物是脂肪族醇及/或聚醚多元醇的縮水甘油醚。第三環氧化物可產生反應性稀釋劑的作用。較佳是選擇帶有1至12個碳原子的單醇的縮水甘油醚、帶有1至12個碳原子的脂肪族二醇的二縮水甘油醚、聚醚型多元醇的縮水甘油醚、帶有1至12個碳原子的脂肪族二醇的二縮水甘油醚、或是此二者的組合作為第三環氧化物。例如第三環氧化物是丁二醇二縮水甘油醚或己二醇二縮水甘油醚。第三環氧化物可以調整環氧樹脂系統的黏滯性。第三環氧化物也可以作為所謂的反應性稀釋劑。反應性稀釋劑是一種在硬化過程中作為塑膠的一種成分的稀釋劑。例如，成分A可以含有1%至20%(重量百分比)的在第三環氧化物。 According to another embodiment, ingredient A contains a third epoxide. The third epoxide is a glycidyl ether of an aliphatic alcohol and/or a polyether polyol. The third epoxide can function as a reactive diluent. It is preferred to select a glycidyl ether of a monool having 1 to 12 carbon atoms, a diglycidyl ether of an aliphatic diol having 1 to 12 carbon atoms, a glycidyl ether of a polyether polyol, and a band. A diglycidyl ether of an aliphatic diol having 1 to 12 carbon atoms, or a combination of the two as a third epoxide. For example, the third epoxide is butanediol diglycidyl ether or hexanediol diglycidyl ether. The third epoxide can adjust the viscosity of the epoxy system. The third epoxide can also serve as a so-called reactive diluent. The reactive diluent is a diluent that acts as a component of the plastic during the hardening process. For example, ingredient A may contain from 1% to 20% by weight of the third epoxide.
根據另外一種實施方式，成分A含有以下至少一種添加劑：醇、增黏劑、排氣劑、內部分離劑、發黃穩定劑、觸變劑、擴散顏料、轉換材料、添加材料、色素、及/或增亮劑。可以用一般的化合物作為添加劑。例如可以用矽烷作為增黏劑，例如構造式為(RO)3Si-丙基-X的三烷氧基丙基矽烷，其中R=烷基，X代表丙基上的一個原子或一個基，尤其是(2,3-環氧丙氧)丙基三甲基矽烷(也就是說X=環氧丙氧基)，ABCR GmbH公司生產的矽烷A-187就是這種矽烷。所謂的排氣劑可以含在氟有機化合物及/或含矽氧烷的化合物中，由於排氣劑是一種高效物質，因此在該等化合物中的含量很低。例如可以用BYK Chemie公司生產的BYK A-506作為排氣劑。例如 可以用CIBASCININ公司生產的Masterbatch 09作為增亮劑。可以用白色顏料作為擴散顏料，例如以CaF2、TiO2、Al2O3、ZrO2為基的白色顏料。 According to another embodiment, the component A contains at least one of the following additives: an alcohol, a tackifier, a venting agent, an internal separating agent, a yellowing stabilizer, a thixotropic agent, a diffusion pigment, a conversion material, an additive material, a pigment, and/or Or brightener. A general compound can be used as an additive. For example, decane can be used as a tackifier, for example, a trialkoxypropyl decane of the formula (RO) 3 Si-propyl-X, wherein R = an alkyl group, and X represents an atom or a group on the propyl group. In particular, (2,3-epoxypropoxy)propyltrimethylnonane (that is, X = glycidoxy), decane A-187 produced by ABCR GmbH is such a decane. The so-called venting agent may be contained in a fluoroorganic compound and/or a siloxane-containing compound, and since the venting agent is a highly efficient substance, the content in the compounds is low. For example, BYK A-506 manufactured by BYK Chemie can be used as a venting agent. For example, Masterbatch 09 manufactured by CIBASCININ can be used as a brightener. A white pigment can be used as the diffusion pigment, for example, a white pigment based on CaF 2 , TiO 2 , Al 2 O 3 , ZrO 2 .
根據環氧樹脂系統的另外一種實施方式，成分A含有以下的成分：
成分A並非一定必須具備以上所有的成分，而是可以不含其中的數種成分。例如”≦3%(重量百分比)”代表含量從0%到3%都可以。其他成分亦同。 Ingredient A does not necessarily have to have all of the above ingredients, but may not contain several of them. For example, "≦3% (% by weight)" means that the content is from 0% to 3%. The other ingredients are the same.
根據環氧樹脂系統的另外一種實施方式，成分A含有20%至90%(重量百分比)的第一環氧化物及10%至80%(重量百分比)的第二環氧化物，成分B含有60%至90%(重量百分比)的碳酸酐及5%至40%的酸性碳酸酯。較佳是成分A含有55%至90%(重量百分比)的第一環氧化物及10%至45%(重量百分比)的第二環氧化物，成分B含有60%至90%(重量百分比)的碳酸酐及5%至40%的酸性碳酸酯。根據這種實施方式，也可以選擇使成分A含有1%至20%(重量百分比)的第三環氧化物。尤其是在這個含量範圍內的環氧樹脂系統可以經由硬化形成一種具有很好的耐老化性及抗發黃性及非常好的低應力特性的模塑材料，因此使用這個成分範圍是很有利的。 According to another embodiment of the epoxy resin system, component A contains 20% to 90% by weight of the first epoxide and 10% to 80% by weight of the second epoxide, and component B contains 60. % to 90% by weight of carbonic anhydride and 5% to 40% of acidic carbonate. Preferably, component A contains from 55% to 90% by weight of the first epoxide and from 10% to 45% by weight of the second epoxide, and component B contains from 60% to 90% by weight. Carbonic anhydride and 5% to 40% acidic carbonate. According to this embodiment, it is also possible to select the component A to contain 1% to 20% by weight of the third epoxide. In particular, epoxy resin systems in this content range can be hardened to form a molding material having excellent aging resistance and yellowing resistance and very good low stress characteristics, so it is advantageous to use this composition range. .
根據另外一種實施方式，環氧樹脂系統之成分A比成分B的例在100：60至100：120之間。這個成分A比成分B的比例是質量比。 According to another embodiment, the composition of component A of the epoxy resin system is between 100:60 and 100:120. The ratio of this component A to component B is the mass ratio.
本發明的成分A及成分B可以在室溫(25℃)中分開存放至少6個月，而且不會產生需注意的副產物或分解產物。本發明的環氧樹脂系統(包含成分A及成分B)至少可以在室溫中存放3小時、較佳是至少可以存放4小時，而且環氧樹脂系統的黏滯性提高的程度不會超過50%。這種特性可以使環氧樹脂系統的應用變得更容易。 Ingredient A and Component B of the present invention can be stored separately at room temperature (25 ° C) for at least 6 months without causing undesirable by-products or decomposition products. The epoxy resin system of the present invention (including component A and component B) can be stored for at least 3 hours at room temperature, preferably for at least 4 hours, and the viscosity of the epoxy resin system is not increased to more than 50. %. This feature makes the application of epoxy systems easier.
根據另外一種實施方式，環氧樹脂系統在25℃時的黏滯性≦5000mPa*s。尤其是黏滯性≦3000mPa*s。黏滯性在這個範圍內的環氧樹脂系統適於應用在捲軸到捲軸法加工，因為可以快速的對環氧樹脂系統進行配料。 According to another embodiment, the epoxy resin system has a viscosity of ≦ 5000 mPa*s at 25 °C. Especially the viscous ≦ 3000mPa*s. Epoxy systems with viscosities in this range are suitable for use in reel-to-reel processing because the epoxy system can be quickly compounded.
根據另外一種實施方式，在溫度>125℃時，環氧樹脂系統可以在30分鐘內預硬化(所謂的預塑化)。環氧樹脂系統可以在溫度>145℃、尤其是溫度>150℃時硬化。例如，這個現象可以在最多15分鐘內、尤其是在最多8分鐘內發生。例如，可以在所謂的硬化周期中進行環氧樹脂系統的預硬化。透過酸性碳酸酯、有機磷化合物及/或金屬鹽的組合可以使環氧樹脂系統快速硬化。較佳是以無氣泡產生的方式進行硬化。由於硬化時間很短，使環氧樹脂系統適於應用在大批量生產電子元件、尤其是光電電子元件，或是用於生產或固定光學元件。例如，可以利用捲軸到捲軸加工法實現這種大批量生產。 According to another embodiment, the epoxy resin system can be pre-hardened in 30 minutes (so-called pre-plasticization) at temperatures > 125 °C. The epoxy resin system can be hardened at temperatures > 145 ° C, especially at temperatures > 150 ° C. For example, this phenomenon can occur in up to 15 minutes, especially in up to 8 minutes. For example, pre-hardening of the epoxy resin system can be carried out in a so-called hardening cycle. The epoxy resin system can be rapidly hardened by a combination of acidic carbonates, organophosphorus compounds and/or metal salts. It is preferred to carry out hardening in such a manner that no bubbles are generated. Due to the short hardening time, the epoxy resin system is suitable for use in the mass production of electronic components, especially optoelectronic components, or for the production or fixation of optical components. For example, such a mass production can be achieved by a reel-to-reel processing method.
以前面提及的條件使環氧樹脂硬化，可以透過交聯產生不能流動的模塑材料。通常是在下一個硬化步驟(所謂的後硬化)使環氧樹脂系統完全硬化及/或交聯成環氧樹脂模塑材料。例如加熱到溫度>140℃，時間4個小時。 The epoxy resin is hardened under the conditions mentioned above, and can be crosslinked to produce a molding material which cannot flow. The epoxy resin system is typically fully cured and/or crosslinked into an epoxy molding material in the next hardening step (so-called post-hardening). For example, heating to a temperature > 140 ° C for 4 hours.
根據另外一種實施方式，環氧樹脂系統的氯含量<900ppm。氯含量甚至可以低到<600ppm。較低的氯含量有利於減少熱分解(例如加熱期間)產生的有害健康的化合物。 According to another embodiment, the epoxy resin system has a chlorine content of <900 ppm. The chlorine content can even be as low as <600ppm. A lower chlorine content is beneficial to reduce harmful health-producing compounds produced during thermal decomposition, such as during heating.
本發明還提出一種環氧樹脂模塑材料。本發明的環氧樹脂模塑材料可以含有如本發明之至少一種實施方式之硬化的環氧樹脂系統，或是由該至少一種硬化的環氧樹脂系統構成或產生。為此可以按照前面描述的方式使環氧樹脂系統硬化。因此環氧樹脂模塑材料的成分及特性主要或完全由環氧樹脂系統及其硬化過程決定。 The present invention also proposes an epoxy resin molding material. The epoxy resin molding material of the present invention may contain or be formed or produced from a hardened epoxy resin system according to at least one embodiment of the present invention. To this end, the epoxy resin system can be hardened in the manner previously described. Therefore, the composition and characteristics of the epoxy resin molding material are mainly or completely determined by the epoxy resin system and its hardening process.
根據另外一種實施方式，環氧樹脂模塑材料的玻璃 轉換溫度TG>130℃。玻璃轉換溫度TG可以是≧135℃。以最高260℃，加熱速率10K/min進行6次DSC測量(DSC：示差掃描熱卡計)的結果顯示，玻璃轉換溫度TG幾乎保持不變。所謂幾乎保持不變是指玻璃轉換溫度TG的變化小於5℃，尤其是小於2℃。 According to another embodiment, the epoxy resin molding material has a glass transition temperature T G >130 ° C. The glass transition temperature T G can be ≧ 135 ° C. The results of 6 DSC measurements (DSC: differential scanning calorimeter) at a maximum of 260 ° C and a heating rate of 10 K/min showed that the glass transition temperature T G remained almost unchanged. By almost constant, it is meant that the change in glass transition temperature T G is less than 5 ° C, especially less than 2 ° C.
此外，本發明之環氧樹脂模塑材料在高溫時僅有很小的重量損耗，顯示其具有很高的受熱形狀穩定性。在260℃及加熱速率10K/min的條件下在空氣中進行的熱解重量分析(TGA)顯示，試體的重量損耗<1.0%，尤其是<0.5%。試體的重量損耗甚至可以達到<0.3%的程度。 Further, the epoxy resin molding material of the present invention has only a small weight loss at a high temperature, showing that it has a high heat-resistant shape stability. Thermogravimetric analysis (TGA) performed in air at 260 ° C and a heating rate of 10 K/min showed that the weight loss of the test piece was <1.0%, especially <0.5%. The weight loss of the test piece can even reach <0.3%.
根據另外一種實施方式，環氧樹脂模塑材料的熱膨脹係數<80ppm/K。熱膨脹係數可以是≦70ppm/K，尤其是≦65ppm/K。以上數值是以熱解重量分析(TGA)在-50℃至+50℃之溫度範圍測得的結果。 According to another embodiment, the epoxy resin molding material has a coefficient of thermal expansion of <80 ppm/K. The coefficient of thermal expansion may be ≦70 ppm/K, especially ≦65 ppm/K. The above values are measured by thermogravimetric analysis (TGA) at a temperature range of -50 ° C to +50 ° C.
根據另外一種實施方式，環氧樹脂模塑材料在20℃時的儲存模數<2600MPa，尤其是<2500 MPa。根據本發明，儲存模數是以動態熱機械分析(DMTA)在拉力模式下以1Hz的測量頻率測得。 According to another embodiment, the epoxy resin molding material has a storage modulus of <2600 MPa at 20 ° C, especially < 2500 MPa. According to the present invention, the storage modulus is measured by dynamic thermomechanical analysis (DMTA) in a tensile mode at a measurement frequency of 1 Hz.
環氧樹脂模塑材料在低儲存模數下表現出非常好的低應力特性。尤其是在玻璃轉換溫度TG>130℃時，可以達到低儲存模數。反之，僅使用芳香族環氧化物(不考慮反應性稀釋劑)製造的一般環氧樹脂模塑材料在20℃時的儲存模數則明顯較高，例如可能高達2800MPa左右。因此本發明的環氧樹脂模塑材料在元件中具有較好的耐老化性，例如在對機械力敏感的LED晶片中，而且對熱 機械應力(例如焊接時出現的熱機械應力)非常不敏感，因此亦可應用於適用SMD的元件。本發明的環氧樹脂模塑材料不易脆裂、出現裂痕或斷裂，因此能夠為電子元件提供長期的保護，使其免於受到空氣及濕氣的影響。 Epoxy resin molding materials exhibit very good low stress characteristics at low storage modulus. Especially at a glass transition temperature T G >130 ° C, a low storage modulus can be achieved. Conversely, a typical epoxy resin molding material made using only an aromatic epoxide (regardless of reactive diluent) has a significantly higher storage modulus at 20 ° C, for example, up to about 2800 MPa. Therefore, the epoxy resin molding material of the present invention has better aging resistance in the component, for example, in a mechanically sensitive LED wafer, and is very insensitive to thermo-mechanical stress such as thermo-mechanical stress occurring during soldering. Therefore, it can also be applied to components suitable for SMD. The epoxy resin molding material of the present invention is less susceptible to embrittlement, cracking or breakage, and thus provides long-term protection for electronic components from being affected by air and moisture.
本發明的環氧樹脂模塑材料的吸水性較低。在溫度23℃的冷水中存放14天後的冷水吸收量可達到≦0.55%的程度，例如≦0.48%。因此可以對電子元件提供有效的保護作用。因此環氧樹脂模塑材料亦可用於保護位於封閉空間之外的元件或組件。 The epoxy resin molding material of the present invention has low water absorbability. The cold water absorption after storage for 14 days in cold water at a temperature of 23 ° C can reach ≦ 0.55%, for example, ≦ 0.48%. Therefore, it is possible to provide effective protection for electronic components. Thus epoxy molding materials can also be used to protect components or components that are located outside of the enclosed space.
根據另外一種實施方式，環氧樹脂模塑材料對可見光是透明的。環氧樹脂模塑材料也可以是無色的，尤其是在環氧樹脂系統不含具有本身之體色的轉換材料、色素或顏料的情況下。例如，波長在400nm至800nm之間的光線對環氧樹脂模塑材料的透過率>85%，尤其是88%。因此環氧樹脂系統及/或環氧樹脂模塑材料亦適於設置在光電電子元件的光程上。 According to another embodiment, the epoxy resin molding material is transparent to visible light. The epoxy resin molding material may also be colorless, especially in the case where the epoxy resin system does not contain a conversion material, pigment or pigment having its own body color. For example, light having a wavelength between 400 nm and 800 nm has a transmittance of >85%, especially 88%, to the epoxy resin molding material. Therefore, the epoxy resin system and/or the epoxy resin molding material are also suitable for being disposed on the optical path of the optoelectronic electronic component.
此外，本發明的環氧樹脂模塑材料可以具有很高的抗發黃性。本發明的環氧樹脂模塑材料接受強度60mW/cm2的紫外線寬帶幅射照射3天後，只出現很輕微的變色。這個發黃程度低於以芳香族環氧化物為基的環氧樹脂製成的一般模塑材料。 Further, the epoxy resin molding material of the present invention can have high resistance to yellowing. The epoxy resin molding material of the present invention exhibited only a slight discoloration after being irradiated by ultraviolet broadband radiation of a strength of 60 mW/cm 2 for 3 days. This yellowing degree is lower than that of a general molding material made of an epoxy resin based on an aromatic epoxide.
本發明還包括應用一種環氧樹脂系統。根據至少一種本發明之實施方式的環氧樹脂系統在電子學領城可應用於製造及/或固定光學元件。例如，環氧樹脂系統可用於電子元件、光電電子元件及光學元件的流延、覆蓋、 鍍膜、包覆、封裝、黏合、固定或其他類似加工。例如，透鏡、棱鏡、濾鏡、光學視窗、反射元件、反射罩等都是能夠以環氧樹脂系統固定及/或製造的光學元件及/或組件。根據本發明，也可以將元件稱為組件。製造反射元件及/或反射罩用的環氧樹脂模塑材料及/或環氧樹脂系統可以含有白色顏料。該白色顏料尤其是以CaF2、TiO2、Al2O3、ZrO2之類為基底。 The invention also includes the use of an epoxy resin system. An epoxy resin system in accordance with at least one embodiment of the present invention is applicable to the manufacture and/or immobilization of optical components in electronics. For example, epoxy systems can be used for casting, covering, coating, cladding, encapsulating, bonding, fixing, or the like of electronic components, optoelectronic components, and optical components. For example, lenses, prisms, filters, optical windows, reflective elements, reflectors, and the like are all optical components and/or components that can be secured and/or fabricated in an epoxy system. Elements may also be referred to as components in accordance with the present invention. The epoxy resin molding material and/or epoxy resin system for producing the reflective member and/or the reflector may contain a white pigment. The white pigment is particularly based on CaF 2 , TiO 2 , Al 2 O 3 , ZrO 2 or the like.
本發明環氧樹脂系統及/或以其製造出的環氧樹脂模塑材料在電子學領域上的應用是沒有限制的。因為以環氧樹脂系統可以製造出耐老化性及抗發黃性及低應力特性都非常好的環氧樹脂模塑材料，因此本發明的環氧樹脂系統可應用於適用SMD的電子元件，尤其是光電電子元件，例如LED。例如可用於元件(例如LED)的流延、外殼及/或反射器。此外，環氧樹脂系統也可以應用於汽車業及戶外應用領域的元件及元件組。 The epoxy resin system of the present invention and/or the epoxy resin molding material produced therefrom is not limited in the field of electronics. Since the epoxy resin system can produce an epoxy resin molding material which is excellent in aging resistance, yellowing resistance and low stress characteristics, the epoxy resin system of the present invention can be applied to electronic components suitable for SMD, especially It is a photoelectric electronic component such as an LED. For example, it can be used for casting, housing and/or reflectors of components such as LEDs. In addition, epoxy systems can also be used in components and component groups for the automotive and outdoor applications.
另一個例子是將環氧樹脂系統應用於光電電子元件(例如LED，尤其是白光LED)作為轉換元件。為此環氧樹脂系統可以含有轉換材料。 Another example is the application of an epoxy resin system to optoelectronic components (such as LEDs, especially white LEDs) as conversion elements. To this end, the epoxy resin system can contain conversion materials.
此外，本發明還包括一種含有本發明之至少一種環氧樹脂模塑材料的電子元件、光電電子元件或光學元件。該元件也可以是由環氧樹脂模塑材料構成。 Further, the present invention also includes an electronic component, an optoelectronic component or an optical component comprising at least one epoxy resin molding material of the present invention. The element may also be constructed of an epoxy molding material.
根據另外一種實施方式，該元件是一種螢光二極體、光電二極體、光電電晶體、光電陣列、光耦合器、SMD元件、或適用SMD的元件。該元件較佳是一種光電電子元件。例如，該元件可以應用於汽車業及/或戶外 應用。該元件也可以是前面提及之應用環氧樹脂系統的元件中的另一種元件。 According to another embodiment, the element is a fluorescent diode, a photodiode, an optoelectronic transistor, a photovoltaic array, an optocoupler, an SMD component, or an element suitable for SMD. The component is preferably an optoelectronic component. For example, the component can be used in the automotive industry and/or outdoors. application. The element may also be another of the elements of the aforementioned epoxy resin system.
根據另外一種實施方式，光學元件及/或組件是一種透鏡、棱鏡、濾鏡、光學視窗、反射元件、反射罩或轉換元件。 According to another embodiment, the optical element and/or component is a lens, prism, filter, optical window, reflective element, reflector or conversion element.
與根據本發明的成分B混合，並按照前面描述的方式使其硬化。其中Araldit MY790-1是第一環氧化物，YX8000是第二環氧化物，BYK A-506是一種排氣劑，Masterbatch 09是一種增亮劑。成分B含有>75%(重量百分比)的甲基六氫鄰苯二甲酸酐、<20%(重量百分比)的酸性碳酸酯、<8%(重量百分比)的Zinkoktoat、以及<5%(重量百分比)的三苯基亞磷酸鹽。 It is mixed with the component B according to the invention and hardened in the manner previously described. Among them, Araldit MY790-1 is the first epoxide, YX8000 is the second epoxide, BYK A-506 is a venting agent, and Masterbatch 09 is a brightening agent. Ingredient B contains >75% by weight of methylhexahydrophthalic anhydride, <20% by weight of acidic carbonate, <8% by weight of Zinkoktoat, and <5% (% by weight) Triphenyl phosphite.
以這種方式產生的環氧樹脂模塑材料的玻璃轉換溫度TG為137℃，經過6次DSC測量這個數值幾乎都保持不變。測量條件為40℃至260℃，加熱速率為10K/min。在20℃時的儲存模數為2424Mpa。在260℃時的重量損 耗小於0.3%，從室溫開始以10K/min的速率加熱(TGA測量)。在-50℃至+50℃之間的熱膨脹係數為63ppm/K(TMA測量)。氯含量為515ppm。在溫度23℃的冷水中存放14天後的冷水吸收量為0.48%。 The epoxy resin molding material produced in this manner had a glass transition temperature T G of 137 ° C, and this value remained almost unchanged after 6 times of DSC measurement. The measurement conditions were 40 ° C to 260 ° C and the heating rate was 10 K/min. The storage modulus at 20 ° C was 2424 MPa. The weight loss at 260 ° C was less than 0.3%, and it was heated at a rate of 10 K/min from the room temperature (TGA measurement). The coefficient of thermal expansion between -50 ° C and +50 ° C was 63 ppm / K (measured by TMA). The chlorine content was 515 ppm. The cold water absorption after storage for 14 days in cold water having a temperature of 23 ° C was 0.48%.
與根據本發明的成分B混合，並按照前面描述的方式使其硬化。成分B含有>75%(重量百分比)的甲基六氫鄰苯二甲酸酐、<20%(重量百分比)的酸性碳酸酯、<8%(重量百分比)的Zinkoktoat、以及<5%(重量百分比)的亞磷酸三苯酯。 It is mixed with the component B according to the invention and hardened in the manner previously described. Ingredient B contains >75% by weight of methylhexahydrophthalic anhydride, <20% by weight of acidic carbonate, <8% by weight of Zinkoktoat, and <5% (% by weight) Triphenyl phosphite.
以這種方式產生的環氧樹脂模塑材料的玻璃轉換溫度TG為139℃，經過6次DSC測量這個數值幾乎都保持不變。測量條件為40℃至260℃，加熱速率為10K/min。在20℃時的儲存模數為2213Mpa。在260℃時的重量損耗小於0.3%，從室溫開始以10K/min的速率加熱(TGA測量)。在-50℃至+50℃之間的熱膨脹係數為65ppm/K(TMA測量)。 The epoxy resin molding material produced in this manner had a glass transition temperature T G of 139 ° C, and this value remained almost unchanged after 6 times of DSC measurement. The measurement conditions were 40 ° C to 260 ° C and the heating rate was 10 K/min. The storage modulus at 20 ° C was 2213 MPa. The weight loss at 260 ° C was less than 0.3%, and it was heated at a rate of 10 K/min from the room temperature (TGA measurement). The coefficient of thermal expansion between -50 ° C and +50 ° C is 65 ppm / K (measured by TMA).
以下將配合圖式及實施例說明本發明的其他優點、有利的實施方式及改良方式。 Further advantages, advantageous embodiments and improvements of the invention will be described in the following with reference to the drawings and embodiments.
第1圖顯示按照第一個實施例之方式產生之環氧樹脂模塑材料的DMTA測量。曲線1描述在溫度以3 K/min的加熱速率上升時，儲存模式的變化。0℃時測得的儲存模數為2535Mpa，20℃時測得的儲存模數為2424Mpa，100℃時測得的儲存模數為1633Mpa。曲線2描述可用來測定玻璃轉換溫度TG(此處為139℃)的Tan Delta(Tan △)。 Figure 1 shows the DMTA measurement of the epoxy resin molding material produced in the manner of the first embodiment. Curve 1 describes the change in storage mode as the temperature rises at a heating rate of 3 K/min. The storage modulus measured at 0 ° C was 2535 MPa, the storage modulus measured at 20 ° C was 2424 MPa, and the storage modulus measured at 100 ° C was 1633 MPa. Curve 2 describes the Tan Delta (Tan Δ) that can be used to determine the glass transition temperature T G (here 139 ° C).
第一個實施例的環氧樹脂模塑材料具有很高的玻璃轉換溫度，以及相當低的儲存模數，這表現在很好的耐老化性及優異的低應力特性。 The epoxy resin molding material of the first embodiment has a high glass transition temperature and a relatively low storage modulus, which exhibits excellent aging resistance and excellent low stress characteristics.
第2圖顯示按照第一個實施例之方式產生之環氧樹脂模塑材料的TMA測量。從第2圖可以看出，在-50℃至+50℃之溫度範圍測得的熱膨脹係數為63ppm/K。在這個溫度範圍內產生的熱膨脹基本上是直線式的。這個測量是在厚度2.20mm的樣品上進行。 Figure 2 shows the TMA measurement of the epoxy resin molding material produced in the manner of the first embodiment. As can be seen from Fig. 2, the coefficient of thermal expansion measured at a temperature range of -50 ° C to +50 ° C was 63 ppm / K. The thermal expansion produced in this temperature range is substantially linear. This measurement was made on a sample having a thickness of 2.20 mm.
第3圖顯示按照第一個實施例之方式產生之環氧樹脂模塑材料的TGA測量。曲線3描述試體的剩餘質量(%)與時間的關係。曲線4描述在空氣中以10K/min的加熱速率從室溫加熱到320℃時，溫度與時間的關係。在溫度為260℃時測得質量耗<0.3%。 Figure 3 shows the TGA measurement of the epoxy resin molding material produced in the manner of the first embodiment. Curve 3 describes the residual mass (%) of the sample versus time. Curve 4 describes the temperature versus time when heated from room temperature to 320 ° C at a heating rate of 10 K/min in air. The mass loss was <0.3% at a temperature of 260 °C.
第4圖至第6圖顯示按照第二個實施例之方式產生之環氧樹脂模塑材料的相應測量的頻譜。 Figures 4 to 6 show the corresponding measured spectra of the epoxy resin molding material produced in the manner of the second embodiment.
從第4圖的DMTA測量結果可以看出，0℃時測得的儲存模數為2322Mpa，20℃時測得的儲存模數為 2213Mpa，100℃時測得的儲存模數為1729Mpa(曲線5)。加熱速率仍為3K/min。曲線5描述可用來測定玻璃轉換溫度TG(此處為139℃)的Tan Delta(Tan △)。 It can be seen from the DMTA measurement results in Fig. 4 that the storage modulus measured at 0 °C is 2322 MPa, the storage modulus measured at 20 ° C is 2213 MPa, and the storage modulus measured at 100 ° C is 1729 MPa (curve 5). ). The heating rate is still 3 K/min. Curve 5 describes the Tan Delta (Tan Δ) which can be used to determine the glass transition temperature T G (here 139 ° C).
第二個實施例的環氧樹脂模塑材料具有很高的玻璃轉換溫度，以及相當低的儲存模數，這表現在很好的耐老化性及優異的低應力特性。 The epoxy resin molding material of the second embodiment has a high glass transition temperature and a relatively low storage modulus, which exhibits excellent aging resistance and excellent low stress characteristics.
從第5圖的TMA測量結果可以看出，在-50℃至+50℃之溫度範圍測得的熱膨脹係數為65ppm/K。在這個溫度範圍內產生的熱膨脹基本上是直線式的。這個測量是在厚度4.27mm的樣品上進行。 As can be seen from the TMA measurement results in Fig. 5, the coefficient of thermal expansion measured at a temperature range of -50 ° C to +50 ° C was 65 ppm / K. The thermal expansion produced in this temperature range is substantially linear. This measurement was performed on a sample having a thickness of 4.27 mm.
從第6圖的TMA測量結果可以看出，在溫度為260℃時測得質量耗<0.3%。曲線7描述在空氣中以10K/min的加熱速率從室溫加熱到320℃時，溫度與時間的關係，曲線8描溫度變化的情況。 From the TMA measurement results in Fig. 6, it can be seen that the mass loss is <0.3% at a temperature of 260 °C. Curve 7 describes the relationship between temperature and time when heated from room temperature to 320 ° C at a heating rate of 10 K/min in air, and curve 8 shows the change in temperature.
本發明的範圍並非僅限於以上所舉的實施例。每一種新的特徵及特徵的所有組合方式(尤其是申請專利範圍中提及的特徵的所有組合方式)均屬於本發明的範圍，即使這些特徵或特徵的組合方式未在本說明書之說明部分或實施例中被明確指出。 The scope of the invention is not limited to the embodiments set forth above. All combinations of new features and features, especially all combinations of features mentioned in the claims, are intended to be within the scope of the invention, even if the features or combinations of features are not It is clearly indicated in the examples.
第1圖至第3圖：第一個實施例之環氧樹脂模塑材料的DMTA頻譜、TMA頻譜及/或TGA頻譜。 Figs. 1 to 3: DMTA spectrum, TMA spectrum and/or TGA spectrum of the epoxy resin molding material of the first embodiment.
第4圖至第6圖：第一個實施例之環氧樹脂模塑材料的DMTA頻譜、TMA頻譜及/或TGA頻譜。 4 to 6: DMTA spectrum, TMA spectrum and/or TGA spectrum of the epoxy resin molding material of the first embodiment.
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| DE2642465C3 (en) | 1976-09-21 | 1981-01-22 | Siemens Ag, 1000 Berlin Und 8000 Muenchen | Process for the production of a casting compound |
| DE3016097A1 (en) | 1980-04-25 | 1981-10-29 | Siemens AG, 1000 Berlin und 8000 München | QUICK-HARDING EPOXY RESINS |
| DD240553B1 (en) | 1985-08-29 | 1989-11-15 | Leuna Werke Veb | METHOD FOR PRODUCING OPTICALLY TRANSPARENT POLLUTANTS |
| EP0235077B1 (en) | 1986-01-17 | 1990-09-19 | Ciba-Geigy Ag | Curable mixtures based on diglycidyl compounds and metal complexes |
| JPS62273226A (en) | 1986-05-20 | 1987-11-27 | Nippon Soda Co Ltd | Photo-setting resist resin composition for electroless plating |
| JP3442006B2 (en) * | 1999-08-24 | 2003-09-02 | 日東電工株式会社 | Epoxy resin composition for casting |
| DE10027206A1 (en) | 2000-05-31 | 2001-12-13 | Osram Opto Semiconductors Gmbh | Age-stable epoxy resin systems, molded materials and components made from them and their use |
| JP3654353B2 (en) | 2001-09-03 | 2005-06-02 | スタンレー電気株式会社 | Epoxy resin and epoxy resin material for ultraviolet light emitting device |
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| KR101186452B1 (en) | 2004-06-17 | 2012-09-27 | 가부시끼가이샤 쓰리본드 | Cationically photopolymerizable composition and optoelectronic component using same |
| DE102005060348A1 (en) | 2005-09-28 | 2007-03-29 | Osram Opto Semiconductors Gmbh | Epoxy resin system, useful in encapsulation or assembly of optoelectronic element, comprises epoxy containing first component comprising epoxy resin and a second component comprising an acid anhydride and acid ester of carboxylic acid |
| EP2308909A4 (en) * | 2008-07-31 | 2016-08-03 | Daicel Chem | Optical semiconductor sealing resin composition and optical semiconductor device using same |
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