TWI549922B - Glass composition, and glass layer and sealing layer using the same - Google Patents
Glass composition, and glass layer and sealing layer using the same Download PDFInfo
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本發明是關於一種組成物及應用其之層。本發明特別是關於一種玻璃組成物、及應用其之玻璃層和密封層。 The present invention relates to a composition and a layer for use thereof. More particularly, the present invention relates to a glass composition, and a glass layer and a sealing layer using the same.
玻璃材料具有廣泛的應用。除了常見的製成玻璃板的應用方式之外，也有做為形成在基板上之介質層或密封材料的應用方式。在後者的情況下，通常是將玻璃粉體及介質材料混合製成玻璃組成物，隨之將其塗佈在基板上，並進行燒結等進一步的製程。依照用途的不同，玻璃組成物的具體成分及比例都須進行調整。例如，已知的玻璃組成物穩定性明顯不足，無法長期儲存使用，常須反覆進行配置，造成生產和使用效率低落。此外，現行玻璃組成物使用的密著性上明顯不足，易有氣泡產生，影響密著效果。因此，如何提升玻璃組成物的穩定性與密著性成為該領域有待解決的問題。 Glass materials have a wide range of applications. In addition to the usual application methods for making glass sheets, there are also applications for the dielectric layer or sealing material formed on the substrate. In the latter case, a glass powder and a dielectric material are usually mixed to form a glass composition, which is then applied to a substrate, and further processed by sintering or the like. The specific composition and proportion of the glass composition must be adjusted according to the application. For example, known glass compositions are clearly insufficiently stable and cannot be stored for long periods of time, and often need to be repeatedly disposed, resulting in inefficient production and use. In addition, the adhesion of the current glass composition is obviously insufficient, and bubbles are easily generated, which affects the adhesion effect. Therefore, how to improve the stability and adhesion of the glass composition has become a problem to be solved in the field.
本發明提供一種玻璃組成物，其具有一定的穩定性，可長期儲存不須在製成之後便立即使用。此種玻璃組成物特 別是適用於例如接著及密封。本發明並提供應用此種玻璃組成物之玻璃層和密封層。 The present invention provides a glass composition which has a certain stability and can be stored for a long period of time without being used immediately after preparation. Such a glass composition It is not suitable for, for example, sealing and sealing. The present invention also provides a glass layer and a sealing layer to which such a glass composition is applied.
根據一些實施例，玻璃組成物包括含鉍元素(Bi)的玻璃粉體及有機介質。含鉍元素的玻璃粉體占玻璃組成物的70wt%(重量百分比)~90wt%。有機介質占玻璃組成物的10wt%~30wt%。該有機介質包括溶劑，該溶劑為醇醚類溶劑或環氧基醚類溶劑，且溶劑的碳原子總數為11~20。 According to some embodiments, the glass composition comprises a glass powder containing a bismuth element (Bi) and an organic medium. The glass powder containing cerium element accounts for 70% by weight to 90% by weight of the glass composition. The organic medium accounts for 10% by weight to 30% by weight of the glass composition. The organic medium includes a solvent which is an alcohol ether solvent or an epoxy ether solvent, and the total number of carbon atoms of the solvent is 11-20.
根據一些實施例，由所述之玻璃組成物，經塗佈及燒結而形成玻璃層。 According to some embodiments, a glass layer is formed from the glass composition, coated and sintered.
根據一些實施例，由所述之玻璃層，經雷射而形成密封層。 According to some embodiments, a sealing layer is formed by laser from the glass layer.
為了對本發明之上述及其他方面有更佳的瞭解，下文特舉較佳實施例，作詳細說明如下： In order to better understand the above and other aspects of the present invention, the preferred embodiments are described below in detail as follows:
根據本發明的實施例，提供一種玻璃組成物，其具有一定的穩定性。此種玻璃組成物包括含鉍元素的玻璃粉體及有機介質。含鉍元素的玻璃粉體占玻璃組成物的70wt%~90wt%。有機介質占玻璃組成物的10wt%~30wt%。該有機介質包括溶劑，該溶劑為醇醚類溶劑或環氧基醚類溶劑，且溶劑的碳原子總數為11~20。 According to an embodiment of the present invention, there is provided a glass composition having a certain stability. Such a glass composition includes a glass powder containing a cerium element and an organic medium. The glass powder containing cerium element accounts for 70% by weight to 90% by weight of the glass composition. The organic medium accounts for 10% by weight to 30% by weight of the glass composition. The organic medium includes a solvent which is an alcohol ether solvent or an epoxy ether solvent, and the total number of carbon atoms of the solvent is 11-20.
<玻璃粉體><Glass powder>
在一些實施例中，含鉍元素的玻璃粉體占玻璃組成物的70wt%~90wt%，較佳為75wt%~85wt%，更佳為78wt%~83wt%，最佳為78wt%~80wt%。其中含鉍元素的玻璃粉體添加量太高，會使玻璃組成物預燒結後所形成的玻璃層高度(厚度)過高，後續雷射封裝時易失敗；添加量過低，雷射封裝也不易進行。 In some embodiments, the cerium-containing glass powder comprises from 70% by weight to 90% by weight of the glass composition, preferably from 75% by weight to 85% by weight, more preferably from 78% by weight to 83% by weight, most preferably from 78% by weight to 80% by weight. . The addition of the glass powder containing strontium element is too high, so that the height (thickness) of the glass layer formed by pre-sintering the glass composition is too high, and the subsequent laser package is easy to fail; the amount of addition is too low, and the laser package is also too low. Not easy to carry out.
在一些實施例中，含鉍元素的玻璃粉體100wt%中含有70wt%~85wt%的氧化鉍(Bi2O3)。氧化鉍是本發明的玻璃中不可缺少的成分。但是，如果其含量過高，則玻璃組成物容易缺乏穩定性，如果含量過少，則難以得到上述技術效果。因此，氧化鉍成分的含量下限值優選為70%、更優選為72%、最優選為75%；上限值優選為85%、更優選為83%、最優選為80%。 In some embodiments, the cerium-containing glass powder contains 70% by weight to 85% by weight of cerium oxide (Bi 2 O 3 ) in 100% by weight. Cerium oxide is an indispensable component of the glass of the present invention. However, if the content is too high, the glass composition tends to be unstable, and if the content is too small, it is difficult to obtain the above-described technical effects. Therefore, the lower limit of the content of the cerium oxide component is preferably 70%, more preferably 72%, and most preferably 75%; and the upper limit is preferably 85%, more preferably 83%, and most preferably 80%.
在一些實施例中，含鉍元素的玻璃粉體含有70wt%~85wt%的氧化鉍(Bi2O3)、及5wt%~10wt%的氧化硼(B2O3)。其中氧化鉍(Bi2O3)與氧化硼(B2O3)的重量比值為7~17之間為佳。在一些實施例中，含鉍元素的玻璃粉體含有70wt%~85wt%的氧化鉍(Bi2O3)、5wt%~10wt%的氧化硼(B2O3)、及2wt%~5wt%的氧化矽(SiO2)。這些成分可作為構成玻璃網絡的主要成分。根據一些實施例，含鉍元素的玻璃粉體還可包括其他氧化物，例如氧化硼(B2O3)、氧化矽(SiO2)、氧化鋁(Al2O3)、氧化鐵(Fe2O3)、氧化錳(Mn2O3)、及/或氧化鉻(Cr2O3)等等。該其他氧化物的總量佔含鉍元素的玻璃粉體的0wt%~23wt%。其中含鉍元素的玻璃粉體含有70wt%~85wt%的氧化鉍(Bi2O3)時，玻璃組成物穩定性佳， 在後續封裝的應用上不易產生氣泡與裂痕。 In some embodiments, the cerium-containing glass powder contains 70 wt% to 85 wt% of bismuth oxide (Bi 2 O 3 ), and 5 wt% to 10 wt% of boron oxide (B 2 O 3 ). The weight ratio of bismuth oxide (Bi 2 O 3 ) to boron oxide (B 2 O 3 ) is preferably between 7 and 17. In some embodiments, the cerium-containing glass powder contains 70 wt% to 85 wt% of bismuth oxide (Bi 2 O 3 ), 5 wt% to 10 wt% of boron oxide (B 2 O 3 ), and 2 wt% to 5 wt%. Cerium oxide (SiO 2 ). These components can be used as a main component of the glass network. According to some embodiments, the cerium-containing glass frit may further include other oxides such as boron oxide (B 2 O 3 ), cerium oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), iron oxide (Fe 2 ). O 3 ), manganese oxide (Mn 2 O 3 ), and/or chromium oxide (Cr 2 O 3 ), and the like. The total amount of the other oxides is from 0% by weight to 23% by weight based on the cerium-containing glass powder. When the glass powder containing cerium element contains 70 wt% to 85 wt% of bismuth oxide (Bi 2 O 3 ), the stability of the glass composition is good, and bubbles and cracks are less likely to occur in subsequent packaging applications.
以上組成通過混料機混合均勻後，於高溫燒結爐中在800℃~1300℃燒製20分鐘以上得到均勻的金屬氧化物的混合液體，將其倒至玻璃壓片機上壓片後，在球磨罐中進行粗粉碎，再將粗粉碎之後的玻璃料在行星式球磨機中進一步細粉碎就可得到平均粒徑(D90)小於5微米的玻璃粉體。 After the above composition is uniformly mixed by a mixer, it is fired at 800 ° C to 1300 ° C for 20 minutes or more in a high-temperature sintering furnace to obtain a mixed liquid of a uniform metal oxide, which is poured onto a glass tableting machine and then pressed. The glass pulverization can be coarsely pulverized, and the glass cullet after the coarse pulverization is further finely pulverized in a planetary ball mill to obtain a glass powder having an average particle diameter (D 90 ) of less than 5 μm.
<有機介質><organic medium>
適用於本發明中的有機介質要求：對無機玻璃粉體有良好的分散性，並能防止無機玻璃粉體粒子之間的團聚；良好的成膜性及流平性能，以適應塗佈(例如網印)過程的要求，能得到平滑的膜層；不會對無機粉體的燒結過程帶來影響，在達到燒結溫度之前要求有機介質已經基本分解完全，不會因為殘留有機載體而造成氣泡、針孔等缺陷。 The organic medium suitable for use in the present invention requires: good dispersibility to inorganic glass powder and prevention of agglomeration between inorganic glass powder particles; good film forming property and leveling property to suit coating (for example) The requirements of the screen printing process can obtain a smooth film layer; it does not affect the sintering process of the inorganic powder. Before the sintering temperature is reached, the organic medium is required to be substantially completely decomposed, and no bubbles are caused by the residual organic carrier. Defects such as pinholes.
符合上述要求的有機介質一般由高沸點的溶劑和樹脂組成。 Organic media meeting the above requirements generally consist of a solvent having a high boiling point and a resin.
選擇溶劑組成的要求是：樹脂在溶劑中有較高的溶解度，能得到完全溶液；溶劑不與組合物中的其他組成發生反應；應當有適當的揮發性以適用於塗佈如網印過程，並能保證存貯過程中黏度的穩定。 The requirement for selecting the solvent composition is that the resin has a higher solubility in the solvent and a complete solution can be obtained; the solvent does not react with other components in the composition; there should be appropriate volatility for coating, such as a screen printing process, And can ensure the stability of the viscosity during storage.
一些實施例中，有機介質占玻璃組成物的10wt%~30wt%，較佳為15wt%~25wt%，更佳為16wt%~20wt%，最佳為17wt%~20wt%。其中有機介質添加量過高，封裝後易有裂痕，不易封裝完成；添加量過低，雷射封裝易有氣泡和裂痕。 In some embodiments, the organic medium comprises from 10% by weight to 30% by weight of the glass composition, preferably from 15% by weight to 25% by weight, more preferably from 16% by weight to 20% by weight, most preferably from 17% by weight to 20% by weight. Among them, the amount of organic medium added is too high, and it is easy to be cracked after packaging, which is not easy to be packaged; the amount of addition is too low, and the laser package is easy to have bubbles and cracks.
在一些實施例中，使用的溶劑為醇醚類溶劑。根據一些實施例，該醇醚類溶劑的碳原子總數為11~14。更具體地說，根據一些實施例，該醇醚類溶劑的分子結構式可為
C7至C10的烷基的具體例可以是正庚基、正辛基、正壬基和正癸基等碳原子數7至10之直鏈狀、支鏈狀或環狀之烷基。理想之烷基為碳原子數7至9之直鏈狀或支鏈狀烷基，更好為正庚基、正辛基、正壬基。 Specific examples of the alkyl group of C7 to C10 may be a linear, branched or cyclic alkyl group having 7 to 10 carbon atoms such as n-heptyl, n-octyl, n-decyl and n-decyl. The alkyl group is preferably a linear or branched alkyl group having 7 to 9 carbon atoms, more preferably n-heptyl, n-octyl or n-decyl.
芳基的具體例可以是如苯基、萘基等。取代芳基的具體例可以是有取代基之苯基、有取代基之萘基等。芳香雜環基的具體例可以是吡啶基、吡咯基、呋喃基、噻嗯基等。上述取代芳基中的取代基可為鹵素原子、羥基、烷氧基、胺基、硝基、氰基、羰基、磺醯基、三氟甲基等。 Specific examples of the aryl group may be, for example, a phenyl group, a naphthyl group or the like. Specific examples of the substituted aryl group may be a substituted phenyl group, a substituted naphthyl group or the like. Specific examples of the aromatic heterocyclic group may be a pyridyl group, a pyrrolyl group, a furyl group, a thiol group or the like. The substituent in the above substituted aryl group may be a halogen atom, a hydroxyl group, an alkoxy group, an amine group, a nitro group, a cyano group, a carbonyl group, a sulfonyl group, a trifluoromethyl group or the like.
醯基的具體例可以是甲醯基、乙醯基、苄醯基等。 Specific examples of the mercapto group may be a mercapto group, an ethenyl group, a benzinyl group or the like.
氧基羰基較好具體例如羧基、甲氧基羰基、乙氧基羰基、丙氧基羰基、正丁氧基羰基、第二-丁氧基羰基、第三-丁氧基羰基、正戊氧基羰基、苯氧基羰基等。理想之氧基羰基較好為甲氧基羰基、乙氧基羰基。 The oxycarbonyl group is preferably, for example, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a n-butoxycarbonyl group, a second-butoxycarbonyl group, a tert-butoxycarbonyl group or a n-pentyloxy group. A carbonyl group, a phenoxycarbonyl group or the like. The preferred oxycarbonyl group is preferably a methoxycarbonyl group or an ethoxycarbonyl group.
舉例而言，較佳地該醇醚類溶劑的分子可選自由下列選項組成的群組：二乙二醇-2-甲基己基醚、二乙二醇-2-乙基己基醚、二乙二醇-3-乙基己基醚、二乙二醇-4-乙基己基醚、二乙二 醇-2-正丙基己基醚、二乙二醇-3-正丙基己基醚、二乙二醇-4-正丙基己基醚、二乙二醇-2-正丙基己基醚、二乙二醇-2-正丁基己基醚、二乙二醇-3-正丁基己基醚、及二乙二醇-4-正丁基己基醚。 For example, preferably, the molecule of the alcohol ether solvent may be selected from the group consisting of diethylene glycol-2-methylhexyl ether, diethylene glycol-2-ethylhexyl ether, and diethyl Glycol-3-ethylhexyl ether, diethylene glycol-4-ethylhexyl ether, diethylene Alcohol-2-n-propylhexyl ether, diethylene glycol-3-n-propylhexyl ether, diethylene glycol-4-n-propylhexyl ether, diethylene glycol-2-n-propylhexyl ether, two Ethylene glycol-2-n-butylhexyl ether, diethylene glycol-3-n-butylhexyl ether, and diethylene glycol-4-n-butylhexyl ether.
在一些實施例中，使用的溶劑為環氧基醚類溶劑。根據一些實施例，該環氧基醚類溶劑的碳原子總數為14~17。更具體地說，根據一些實施例，該環氧基醚類溶劑的分子結構式可為
根據一些實施例，有機溶劑還可包括樹脂，選自由例如醇酸樹脂、丙烯酸系樹脂、丙烯酸酯樹脂、甲基丙烯酸樹脂、甲基丙烯酸酯樹脂、乙基纖維素、甲基纖維素、甲基纖維素羧甲基纖維素、乙氧基纖維素、苄基纖維素、硝基纖維素及它們的混合物組成的群組。一些實施例中，樹脂含量佔玻璃組成物的0wt%~10wt%；較佳為0wt%~8wt%，更佳為0wt%~5wt%，最佳為1wt%~3wt%。具體來說，玻璃組成物例如包括乙基纖維素(EC-100)。根據一些實施例，有機溶劑還可包括分散劑、防沉劑、消泡劑、流平劑、及/或觸變調節劑等等。 According to some embodiments, the organic solvent may further include a resin selected from, for example, an alkyd resin, an acrylic resin, an acrylate resin, a methacrylic resin, a methacrylate resin, an ethyl cellulose, a methyl cellulose, a methyl group. A group consisting of cellulose carboxymethyl cellulose, ethoxy cellulose, benzyl cellulose, nitro cellulose, and mixtures thereof. In some embodiments, the resin content is from 0% by weight to 10% by weight of the glass composition; preferably from 0% by weight to 8% by weight, more preferably from 0% by weight to 5% by weight, most preferably from 1% by weight to 3% by weight. Specifically, the glass composition includes, for example, ethyl cellulose (EC-100). According to some embodiments, the organic solvent may further include a dispersant, an anti-settling agent, an antifoaming agent, a leveling agent, and/or a thixotropic modifier, and the like.
根據一些實施例，所述玻璃組成物例如可由下述方式製成。首先，依照預定的重量分別稱取含鉍元素的無機玻璃粉體於混合罐中，並加入預定重量的與之相應的有機介質，在高速剪切分散設備上進行分散混合。然後，將混合好的漿料經過三軸輥軋機，進一步促進無機玻璃粉體的分散及其與有機介質的融 合，至漿料中無機玻璃粉體的細度小於5微米。接著，將所得漿料經過過濾機過濾後進行真空脫泡，即可得到所述玻璃組成物。根據一些實施例，玻璃組成物的平均粒徑可為1~5微米。 According to some embodiments, the glass composition can be made, for example, in the following manner. First, the inorganic glass powder containing cerium element is weighed in a mixing tank according to a predetermined weight, and a predetermined weight of the corresponding organic medium is added, and dispersion mixing is performed on the high-speed shearing dispersing apparatus. Then, the mixed slurry is passed through a three-axis rolling mill to further promote the dispersion of the inorganic glass powder and its fusion with the organic medium. The fineness of the inorganic glass powder in the slurry is less than 5 μm. Next, the obtained slurry is filtered through a filter and vacuum defoamed to obtain the glass composition. According to some embodiments, the glass composition may have an average particle size of from 1 to 5 microns.
根據本發明的實施例，還可提供一種玻璃層，其由根據上述任一實施例的具有穩定性的玻璃組成物所形成。具體來說，所述玻璃層可由根據上述任一實施例的具有穩定性的玻璃組成物，經塗佈及燒結而形成。塗佈可例如藉由網印來達成，比如說是使用325目的不鏽鋼絲網進行印刷，並將印刷好的基板置於120℃的乾燥箱中約10分鐘。燒結則例如是先在350℃保溫脫氣20分鐘，然後升溫至510℃並保溫20分鐘後降溫。 According to an embodiment of the present invention, there is also provided a glass layer formed of the glass composition having stability according to any of the above embodiments. Specifically, the glass layer may be formed by coating and sintering a glass composition having stability according to any of the above embodiments. Coating can be achieved, for example, by screen printing, for example using a 325 mesh stainless steel screen, and placing the printed substrate in a 120 ° C oven for about 10 minutes. Sintering is, for example, first degassing at 350 ° C for 20 minutes, then raising the temperature to 510 ° C and holding for 20 minutes to cool down.
根據本發明的實施例，還可提供一種密封層，其由上述玻璃層所形成。具體來說，所述密封層可由上述玻璃層，經雷射而形成。所述玻璃層形成在一基板上，並將另一基板設置於上，使得玻璃層夾設於二基板之間。玻璃層在被雷射照射時熔融，並在脫離雷射之後急冷固化，從而可接著二對置基板，並形成密封層。此種密封層例如可應用於有機電致發光顯示器(OELD)、電漿顯示器(PDP)、液晶顯示器(LCD)、太陽能電池等等。 According to an embodiment of the present invention, a sealing layer which is formed of the above glass layer may also be provided. Specifically, the sealing layer may be formed by laser irradiation from the above glass layer. The glass layer is formed on one substrate, and the other substrate is disposed thereon such that the glass layer is sandwiched between the two substrates. The glass layer is melted when it is irradiated by the laser, and is quenched and solidified after being detached from the laser, so that the two opposing substrates can be bonded and a sealing layer is formed. Such a sealing layer can be applied, for example, to an organic electroluminescent display (OELD), a plasma display (PDP), a liquid crystal display (LCD), a solar cell, or the like.
值得注意的是，含鉍元素的玻璃粉體占玻璃組成物的含量會影響所形成的玻璃層的厚度，甚至進一步地影響後續雷射的效果。因此，其含量不宜過高或過低。 It is worth noting that the content of the glass composition of the cerium-containing element in the glass composition affects the thickness of the formed glass layer and even further affects the effect of subsequent lasers. Therefore, its content should not be too high or too low.
以下，將列舉數個實施例和比較例，以提供對於根據本發明實施例的玻璃組成物更進一步的了解。然而應注意的是，以下列舉的具體實驗內容並非用以限制本發明，本發明所屬 技術領域中具有通常知識者可以採用其他方式來完成本發明。 Hereinafter, several examples and comparative examples will be enumerated to provide a further understanding of the glass composition according to an embodiment of the present invention. However, it should be noted that the specific experimental contents listed below are not intended to limit the present invention, and the present invention belongs to Those skilled in the art can use other means to carry out the invention.
<有機介質的選擇><Selection of organic media>
[玻璃粉體的製備] [Preparation of glass powder]
選取總重2公斤並包含74wt%的氧化鉍(Bi2O3)、9wt%的氧化硼(B2O3)、3wt%的氧化矽(SiO2)、5wt%的氧化鋁(Al2O3)、2wt%的氧化鐵(Fe2O3)、3wt%的氧化錳(Mn2O3)、4wt%的氧化鉻(Cr2O3)的比例的玻璃粉體，且該玻璃粉體的粒子小於1毫米。 A total weight of 2 kg and containing 74 wt% of bismuth oxide (Bi 2 O 3 ), 9 wt% of boron oxide (B 2 O 3 ), 3 wt% of cerium oxide (SiO 2 ), and 5 wt% of alumina (Al 2 O) 3 ) a glass powder having a ratio of 2 wt% of iron oxide (Fe 2 O 3 ), 3 wt% of manganese oxide (Mn 2 O 3 ), and 4 wt% of chromium oxide (Cr 2 O 3 ), and the glass frit The particles are less than 1 mm.
[有機介質的製備] [Preparation of organic media]
依照重量比1：19分別稱量乙基纖維素及溶劑，在攪拌的條件下加熱至60℃並保溫至乙基纖維素完全溶解得到均一透明的溶液。實施例1使用的溶劑為二乙二醇-2-乙基己基醚(diethylene glycol 2-ethylhexyl ether,DEGHE)，其為醇醚類溶劑，分子中具有的碳原子總數為12。比較例1使用的溶劑為二乙二醇己基醚(diethylene glycol hexyl ether,DGHE)，其為醇醚類溶劑，分子中具有的碳原子總數為10。比較例2使用的溶劑為二乙二醇單丁醚(diethylene glycol monobutyl ether,DGME)，其為醇醚類溶劑，分子中具有的碳原子總數為8。比較例3使用的溶劑為1-丁氧基-2-丙醇(1-butoxy-2-propanol,BPOL)，其為醇醚類溶劑，分子中具有的碳原子總數為7。比較例4使用的溶劑為丙二醇甲醚(propylene glycol monomethyl ether,PGME)，其為醇醚類溶劑，分子中具有的碳原子總數為4。比較例5使用的溶劑為二乙二醇單丁基醚乙酸酯(diethylene glycol monobutyl ether acetate, BDGAC)，其為酯醚類溶劑，分子中具有的碳原子總數為10。比較例6使用的溶劑為二乙二醇單***醋酸酯(diethylene glycol monoethyl ether acetate,DCAC)，其為酯醚類溶劑，分子中具有的碳原子總數為7。比較例7使用的溶劑為2,2,4-三甲基-1,3-戊二醇單異丁酸酯(2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,Texanol)，其為酮醚類溶劑，分子中具有的碳原子總數為12。比較例8使用的溶劑為α-萜品醇(α-terpineol,α-TPN)，其為稀醇類溶劑，分子中具有的碳原子總數為10。比較例9使用的溶劑為萜品醇(terpineol,TPN)，其為稀醇類溶劑，分子中具有的碳原子總數為10。實施例2使用的溶劑為十二和十四烷基縮水甘油醚(Dodecyl and tetradecyl glycidyl ethers,AGE)，其為環氧基醚類溶劑，分子中具有的碳原子總數為15~17。 The ethyl cellulose and the solvent were weighed according to a weight ratio of 1:19, heated to 60 ° C under stirring, and kept warm until the ethyl cellulose was completely dissolved to obtain a uniform transparent solution. The solvent used in Example 1 was diethylene glycol 2-ethylhexyl ether (DEGHE) which was an alcohol ether solvent and had a total of 12 carbon atoms in the molecule. The solvent used in Comparative Example 1 was diethylene glycol hexyl ether (DGHE) which was an alcohol ether solvent and had a total of 10 carbon atoms in the molecule. The solvent used in Comparative Example 2 was diethylene glycol monobutyl ether (DGME) which was an alcohol ether solvent and had a total of 8 carbon atoms in the molecule. The solvent used in Comparative Example 3 was 1-butoxy-2-propanol (BPOL) which was an alcohol ether solvent and had a total of 7 carbon atoms in the molecule. The solvent used in Comparative Example 4 was propylene glycol monomethyl ether (PGME) which was an alcohol ether solvent and had a total of 4 carbon atoms in the molecule. The solvent used in Comparative Example 5 was diethylene glycol monobutyl ether acetate (diethylene glycol monobutyl ether acetate, BDGAC), which is an ester ether solvent, has a total of 10 carbon atoms in the molecule. The solvent used in Comparative Example 6 was diethylene glycol monoethyl ether acetate (DCAC) which was an ester ether solvent and had a total of 7 carbon atoms in the molecule. The solvent used in Comparative Example 7 was 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol), which was The ketone ether solvent has a total of 12 carbon atoms in the molecule. The solvent used in Comparative Example 8 was α-terpineol (α-TPN) which was a dilute alcohol solvent and had a total of 10 carbon atoms in the molecule. The solvent used in Comparative Example 9 was terpineol (TPN) which is a dilute alcohol solvent and has a total of 10 carbon atoms in the molecule. The solvent used in Example 2 was Dodecyl and tetradecyl glycidyl ethers (AGE), which is an epoxy ether solvent having a total of 15 to 17 carbon atoms in the molecule.
[漿料的製備] [Preparation of slurry]
依照重量比80：20將玻璃粉體和有機介質混合後，在高速剪切分散設備上進行分散混合。然後，經過三軸輥軋機輥軋至無機粉體粒度小於5微米。將所得漿料過濾後進行真空脫泡。 The glass powder and the organic medium were mixed at a weight ratio of 80:20, and then dispersed and mixed on a high-speed shearing and dispersing device. Then, it was rolled through a three-axis rolling mill until the inorganic powder had a particle size of less than 5 μm. The obtained slurry was filtered and subjected to vacuum defoaming.
[穩定性測試] [stability test]
配置完成的玻璃組成物先量測一次黏度。靜置一個月後再量測一次黏度。評估黏度變化，並觀察是否有其他不穩定的特徵顯示。結果如表1。 The configured glass composition is first measured for viscosity. After standing for one month, measure the viscosity again. Evaluate viscosity changes and see if there are other unstable features. The results are shown in Table 1.
[接著測試] [Next test]
使用325目的不鏽鋼絲網，將配置完成的玻璃組成 物印刷至玻璃基板上。將印刷好的玻璃基板置於120℃的乾燥箱中約10分鐘，測得乾燥的膜層厚度約20微米。接著進行燒結，首先在350℃保溫脫氣20分鐘，然後升溫至510℃並保溫20分鐘後降溫。利用三維輪廓(3D profile)觀察網印是否平坦，並以掃描式電子顯微鏡(SEM)觀察燒結後表面是否平整和緻密。結果如表2。 Using a 325 mesh stainless steel wire mesh, the finished glass is composed The object is printed onto a glass substrate. The printed glass substrate was placed in a drying oven at 120 ° C for about 10 minutes, and the dried film thickness was measured to be about 20 μm. Next, sintering was carried out, first degassing at 350 ° C for 20 minutes, then raising the temperature to 510 ° C and holding for 20 minutes and then cooling. The 3D profile was used to observe whether the screen printing was flat, and the surface after sintering was observed to be flat and dense by a scanning electron microscope (SEM). The results are shown in Table 2.
從表1可看出，使用醇醚類溶劑及環氧基醚類溶劑可得到良好的穩定性。特別是當醇醚類溶劑的碳原子總數大於7時、當環氧基醚類溶劑的碳原子總數為14~17時，可得到良好的穩定性。並且，從表2可進一步可看出，當醇醚類溶劑的碳原子總數為11~14時、當環氧基醚類溶劑的碳原子總數為14~17時，玻璃組成物可應用於接著。 As can be seen from Table 1, good stability can be obtained by using an alcohol ether solvent and an epoxy ether solvent. In particular, when the total number of carbon atoms of the alcohol ether solvent is more than 7, when the total number of carbon atoms of the epoxy ether solvent is 14 to 17, good stability can be obtained. Further, as can be seen from Table 2, when the total number of carbon atoms of the alcohol ether solvent is 11 to 14, when the total number of carbon atoms of the epoxy ether solvent is 14 to 17, the glass composition can be applied to .
<玻璃粉體的選擇><Selection of glass powder>
[玻璃粉體的製備] [Preparation of glass powder]
依照表3、表4的玻璃粉體成分比例，總重為2公斤地稱量各氧化物，混合均勻後在高溫固相燒結爐中1200℃保溫1小時，得到均勻的玻璃液。將該玻璃液倒至對輥壓片機使其迅速冷卻並壓製成約1毫米厚的玻璃碎片，將玻璃碎片放至球磨罐中在球磨機上進行粗粉碎至玻璃粉體的粒子小於1毫米。將玻璃粉體在行星式球磨機中球磨24小時以上，得到用於配製漿料的無機玻璃粉體。 According to the proportions of the glass powder components in Tables 3 and 4, the oxides were weighed to a total weight of 2 kg, and uniformly mixed, and then kept at 1200 ° C for 1 hour in a high-temperature solid phase sintering furnace to obtain a uniform glass liquid. The glass was poured into a pair of roll presses to be rapidly cooled and pressed into pieces of glass of about 1 mm thickness, and the glass pieces were placed in a ball mill pot and coarsely pulverized on a ball mill to a particle size of the glass powder of less than 1 mm. The glass powder was ball milled in a planetary ball mill for 24 hours or more to obtain an inorganic glass powder for preparing a slurry.
[有機介質的製備] [Preparation of organic media]
依照表3、表4的樹脂及溶劑的比例分別稱量乙基纖維素及溶劑，在攪拌的條件下加熱至60℃並保溫至乙基纖維素完全溶解得到均一透明的溶液。表3所列的實施例及比較例使用的溶劑為DEGHE。表4所列的實施例及比較例使用的溶劑為 AGE。 Ethyl cellulose and a solvent were each weighed according to the ratio of the resin and the solvent of Table 3 and Table 4, heated to 60 ° C under stirring, and kept warm until ethyl cellulose was completely dissolved to obtain a uniform transparent solution. The solvent used in the examples and comparative examples listed in Table 3 was DEGHE. The solvents used in the examples and comparative examples listed in Table 4 are AGE.
[漿料的製備] [Preparation of slurry]
依照表3、表4的玻璃粉體和有機介質的比例將玻璃粉體和有機介質混合後，在高速剪切分散設備上進行分散混合。然後，經過三軸輥軋機輥軋至無機粉體粒度小於5微米。將所得漿料過濾後進行真空脫泡。 The glass powder and the organic medium were mixed according to the ratio of the glass powder to the organic medium in Tables 3 and 4, and then dispersed and mixed on a high-speed shearing and dispersing device. Then, it was rolled through a three-axis rolling mill until the inorganic powder had a particle size of less than 5 μm. The obtained slurry was filtered and subjected to vacuum defoaming.
[接著測試] [Next test]
使用325目的不鏽鋼絲網，將配置完成的玻璃組成物印刷至玻璃基板上。將印刷好的玻璃基板置於120℃的乾燥箱中約10分鐘，測得乾燥的膜層厚度約20微米。接著進行燒結，首先在350℃保溫脫氣20分鐘，然後升溫至510℃並保溫20分鐘後降溫。利用三維輪廓(3D profile)觀察網印是否平坦，並以掃描式電子顯微鏡(SEM)觀察燒結後表面是否平整和緻密。結果如表3、表4。 The finished glass composition was printed onto a glass substrate using a 325 mesh stainless steel wire mesh. The printed glass substrate was placed in a drying oven at 120 ° C for about 10 minutes, and the dried film thickness was measured to be about 20 μm. Next, sintering was carried out, first degassing at 350 ° C for 20 minutes, then raising the temperature to 510 ° C and holding for 20 minutes and then cooling. The 3D profile was used to observe whether the screen printing was flat, and the surface after sintering was observed to be flat and dense by a scanning electron microscope (SEM). The results are shown in Tables 3 and 4.
由表3和表4可發現含鉍元素的玻璃粉體占玻璃組成物的70wt%~90wt%，以及有機介質占該玻璃組成物的10wt%~30wt%時，玻璃組成物可形成玻璃層。並且，該玻璃層可應用於密著，而得到良好的接著性，包含緻密性優和黏著並無裂痕等優點。 It can be found from Tables 3 and 4 that the glass powder containing cerium element accounts for 70% by weight to 90% by weight of the glass composition, and when the organic medium accounts for 10% by weight to 30% by weight of the glass composition, the glass composition can form a glass layer. Moreover, the glass layer can be applied to the adhesion to obtain good adhesion, and includes advantages such as excellent compactness and adhesion without cracks.
<雷射封裝><Laser package>
取實施例3~8之玻璃組成物，通過網印在由鈉鈣玻璃(熱膨脹係數：87×10-7/℃)形成的一第二玻璃基板(尺寸：100×100×0.55mmt)的外周區域作為密封材料糊料進行塗佈(線寬W：500微米)後，在120℃×10分鐘的條件下乾燥。對該塗佈層以455℃×10分鐘的條件進行燒結，從而形成膜厚T1為20微米的玻璃層。 The glass compositions of Examples 3 to 8 were obtained by screen printing on the periphery of a second glass substrate (size: 100 × 100 × 0.55 mmt) formed of soda lime glass (thermal expansion coefficient: 87 × 10 -7 / ° C). The area was applied as a sealing material paste (line width W: 500 μm), and then dried at 120 ° C for 10 minutes. The coating layer was sintered at 455 ° C for 10 minutes to form a glass layer having a film thickness T1 of 20 μm.
接著，將具有玻璃層的該第二玻璃基板和具有元件形成區域(形成有OEL元件的區域)的一第一玻璃基板(由與第二 玻璃基板相同組成、相同形狀的鈉鈣玻璃形成的基板)層疊。然後，透過第二玻璃基板以5mm/s的掃瞄速度對密封材料層照射波長940奈米、輸出功率65W的雷射(藉由半導體雷射器)，將玻璃層熔融並急冷固化，從而將第一玻璃基板和第二玻璃基板密封而形成密封層。由此將元件形成區域以玻璃面板密封而得的電子器件供於後述的特性評價。 Next, the second glass substrate having a glass layer and a first glass substrate having an element formation region (a region in which the OEL element is formed) (by the second A substrate formed of soda lime glass having the same composition and the same shape as the glass substrate is laminated. Then, the sealing material layer is irradiated with a laser beam having a wavelength of 940 nm and an output of 65 W through a second glass substrate at a scanning speed of 5 mm/s (by a semiconductor laser), and the glass layer is melted and rapidly solidified, thereby The first glass substrate and the second glass substrate are sealed to form a sealing layer. Thus, the electronic device obtained by sealing the element formation region with a glass panel was subjected to characteristic evaluation described later.
由表5可發現含鉍元素的玻璃粉體占玻璃組成物的70wt%~90wt%，以及有機介質占該玻璃組成物的10wt%~30wt%時，該玻璃組成物可用於形成密封層，且該密封層應用於封裝時接著性佳，包含緻密性優和黏著並無裂痕等優點。 It can be found from Table 5 that the glass powder containing the cerium element accounts for 70% by weight to 90% by weight of the glass composition, and the organic medium accounts for 10% by weight to 30% by weight of the glass composition, the glass composition can be used for forming the sealing layer, and The sealing layer is excellent in adhesion when applied to the package, and has the advantages of excellent compactness and adhesion without cracks.
綜上所述，雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明。本發明所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤 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準。 In conclusion, the present invention has been disclosed in the above preferred embodiments, and is not intended to limit the present invention. Those skilled in the art to which the invention pertains can make various changes and changes without departing from the spirit and scope of the invention. Decoration. Therefore, the scope of the invention is defined by the scope of the appended claims.
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| CN1103057A (en) * | 1993-07-29 | 1995-05-31 | 纳幕尔杜邦公司 | Lead-free thick film paste composition |
| CN1192462A (en) * | 1997-02-13 | 1998-09-09 | 纳幕尔杜邦公司 | Lead and cadimum-free encapsulant composition |
| TW201333975A (en) * | 2011-12-23 | 2013-08-16 | Heraeus Precious Metals Gmbh | Thick-film composition containing antimony oxides and their use in the manufacture of semiconductor devices |
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| CN101950600A (en) * | 2010-09-29 | 2011-01-19 | 彩虹集团公司 | Transparent dielectric paste |
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| CN1103057A (en) * | 1993-07-29 | 1995-05-31 | 纳幕尔杜邦公司 | Lead-free thick film paste composition |
| CN1192462A (en) * | 1997-02-13 | 1998-09-09 | 纳幕尔杜邦公司 | Lead and cadimum-free encapsulant composition |
| TW201333975A (en) * | 2011-12-23 | 2013-08-16 | Heraeus Precious Metals Gmbh | Thick-film composition containing antimony oxides and their use in the manufacture of semiconductor devices |
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|---|---|
| CN106915902A (en) | 2017-07-04 |
| TW201722878A (en) | 2017-07-01 |
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