TW202423865A - Glass for addition to electrical conductors - Google Patents
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- 239000011521 glass Substances 0.000 title claims abstract description 131
- 239000004020 conductor Substances 0.000 title description 27
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 13
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 238000004455 differential thermal analysis Methods 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 4
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 abstract description 22
- 239000013078 crystal Substances 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 30
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000006060 molten glass Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000005355 lead glass Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000005385 borate glass Substances 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000005287 barium borate glass Substances 0.000 description 1
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
發明領域 本發明是有關於一種添加於導體糊料之玻璃，該導體糊料是在電子零件當中，用於形成包含有例如銀、銅等金屬之電極等的導體糊料。 Field of the invention The present invention relates to a glass added to a conductor paste, wherein the conductor paste is used in electronic components to form an electrode containing metals such as silver and copper.
發明背景 例如，在形成電子零件之電極時，會調製導體糊料，該導體糊料包含有如銀、銅等金屬粉末(導體粉末)、以及使該金屬粉末緊密附著之玻璃粉末、賦形劑等。之後，將導體糊料以網版印刷等方法進行塗布、乾燥後，再透過燒成就能形成電極。此時，玻璃粉末需要在形成電極之溫度(燒成溫度)下降低黏度、並在金屬粉末之間浸潤擴散。 Background of the invention For example, when forming an electrode of an electronic component, a conductor paste is prepared, which contains metal powders such as silver and copper (conductor powder), glass powders to make the metal powders adhere tightly, and a shaping agent. After that, the conductor paste is applied by screen printing and other methods, dried, and then fired to form an electrode. At this time, the glass powder needs to reduce its viscosity at the temperature of forming the electrode (firing temperature) and infiltrate and diffuse between the metal powders.
近年來，上述金屬粉末從銀漸漸地替換成鎳、銅等，伴隨而來的是燒成溫度亦改成採用700~850℃這般低於習知之溫度。然而迄今為止，添加至導體糊料之玻璃是以鉛玻璃為主流，但使用銅等作為金屬粉末時，必須在惰性氣體環境或還原性氣體環境下進行燒成，此時鉛玻璃會有造成鉛成分被還原之問題。又，因為針對有害環境之物質的規範管制而使得取代鉛玻璃之材料的需求提高。In recent years, the above metal powder has gradually replaced silver with nickel, copper, etc., and the sintering temperature has also been changed to 700~850℃, which is lower than the conventional temperature. However, up to now, the glass added to the conductor paste is mainly lead glass. However, when copper is used as the metal powder, it must be sintered in an inert gas environment or a reducing gas environment. At this time, the lead glass will cause the lead component to be reduced. In addition, due to the regulation of environmentally harmful substances, the demand for materials to replace lead glass has increased.
作為取代鉛玻璃之玻璃，已提出有硼酸鋇系玻璃、硼酸鋅系玻璃等。As a glass to replace lead glass, barium borate-based glass, zinc borate-based glass, and the like have been proposed.
然而，硼酸鋇系玻璃有耐酸性低之問題。而硼酸鋅系玻璃則有軟化點高，故燒成溫度無法降低之問題。此外，硼酸鋅系玻璃容易分相、容易析出結晶，故接合強度弱，耐酸性差。However, barium borate glass has a problem of low acid resistance. Zinc borate glass has a high softening point, so the sintering temperature cannot be lowered. In addition, zinc borate glass is easy to phase separate and precipitate crystals, so the bonding strength is weak and the acid resistance is poor.
例如，專利文獻1揭示有一種硼酸鋅系之結晶化玻璃，不過因為屬於結晶化玻璃，故燒成時的玻璃流動性差，而無法在金屬粉末間浸潤擴散，密著性不足夠。又，因含有多量鹼金屬氧化物，亦有耐酸性低之問題。For example, Patent Document 1 discloses a zinc borate-based crystallized glass. However, because it is a crystallized glass, the glass has poor fluidity during sintering and cannot penetrate and diffuse between metal powders, resulting in insufficient adhesion. In addition, because it contains a large amount of alkaline metal oxides, it also has the problem of low acid resistance.
又例如，專利文獻2揭示有一種在硼酸鋅系玻璃中含有MnO 2作為必須成分之玻璃，然而因為屬於結晶化玻璃，故與專利文獻1相同，會有無法在金屬粉末間浸潤擴散之問題。又，因為會在玻璃熔融時與爐材產生反應，故還會有爐材消耗加劇之問題。 先前技術文獻 For example, Patent Document 2 discloses a glass containing MnO2 as an essential component in zinc borate glass. However, because it is a crystallized glass, it has the same problem as Patent Document 1 that it cannot penetrate and diffuse between metal powders. In addition, because it reacts with furnace materials when the glass is melted, there is also the problem of increased furnace material consumption.
專利文獻 [專利文獻1]日本特開2012-25637 [專利文獻2]日本特許第4300786號 Patent Documents [Patent Document 1] Japanese Patent Application No. 2012-25637 [Patent Document 2] Japanese Patent No. 4300786
發明概要 發明欲解決之課題 因此，本發明之主要目的在於提供一種可在700~850℃溫度區域進行燒成，且耐酸性優異，有效地抑制結晶析出之玻璃。 用以解決課題之手段 Summary of the invention Problem to be solved by the invention Therefore, the main purpose of the present invention is to provide a glass that can be sintered in the temperature range of 700~850℃, has excellent acid resistance, and effectively inhibits crystallization. Means for solving the problem
本發明人根據習知技術之問題點進行反覆深入研究，結果發現具有特定組成之玻璃能達成上述目的，進而完成本發明。The inventors of the present invention have repeatedly conducted in-depth research based on the problems of the prior art and have found that glass with a specific composition can achieve the above-mentioned purpose, thereby completing the present invention.
亦即，本發明是有關於下述導體添加用玻璃組成物。 1.一種導體添加用玻璃，是用於添加在導電性組成物之玻璃，其特徵在於： 含有(1)SiO 2：5~18重量%、 (2)B 2O 3：28~45重量%、 (3)ZnO：38~58重量%、 (4)Al 2O 3及ZrO 2之至少1種：合計1~15重量%、及 (5)Li 2O、Na 2O及K 2O當中至少1種：合計0~7重量%； 且實質上不含氧化鉛。 2.如前述項1之導體添加用玻璃，其中(1)SiO 2：7~14重量%、(2)B 2O 3：33~40重量%、(3)ZnO：40~50重量%、(4)Al 2O 3及ZrO 2之至少1種：合計2~12重量%、及(5)Li 2O、Na 2O及K 2O當中至少1種：合計1~7重量%。 3.如前述項1之導體添加用玻璃，其中SiO 2及B 2O 3之合計量為40重量%以上。 4.如前述項1之導體添加用玻璃，其含有0~5重量%之CuO。 5.如前述項1之導體添加用玻璃，其含有MgO、CaO、SrO及BaO當中至少1種，且合計0~10重量%。 6.如前述項1之導體添加用玻璃，其在差熱分析(DTA)之DTA曲線當中，在900℃以下沒有確認到結晶化峰值溫度(Tp)。 7.一種導電性組成物，其含有如前述項1~6中任一項之導體添加用玻璃及導電性粒子。 發明效果 That is, the present invention relates to the following conductor-additive glass composition. 1. A conductor-additive glass is a glass used for adding to a conductive composition, characterized in that: it contains (1) SiO 2 : 5-18 wt %, (2) B 2 O 3 : 28-45 wt %, (3) ZnO : 38-58 wt %, (4) at least one of Al 2 O 3 and ZrO 2 : 1-15 wt % in total, and (5) at least one of Li 2 O, Na 2 O and K 2 O : 0-7 wt % in total; and does not substantially contain lead oxide. 2. The glass for conductor addition as described in item 1 above, wherein (1) SiO 2 : 7-14 wt %, (2) B 2 O 3 : 33-40 wt %, (3) ZnO: 40-50 wt %, (4) at least one of Al 2 O 3 and ZrO 2 : 2-12 wt % in total, and (5) at least one of Li 2 O, Na 2 O and K 2 O: 1-7 wt % in total. 3. The glass for conductor addition as described in item 1 above, wherein the total amount of SiO 2 and B 2 O 3 is 40 wt % or more. 4. The glass for conductor addition as described in item 1 above, which contains 0-5 wt % of CuO. 5. The glass for conductor addition as described in item 1 above, which contains at least one of MgO, CaO, SrO and BaO, which contains 0-10 wt % in total. 6. The glass for adding a conductor as described in item 1 above, wherein in the DTA curve of differential thermal analysis (DTA), no crystallization peak temperature (Tp) is confirmed below 900°C. 7. A conductive composition comprising the glass for adding a conductor as described in any one of items 1 to 6 above and conductive particles. Effect of the invention
依據本發明，可提供一種可在700~850℃溫度區域燒成，且耐酸性優異，有效地抑制結晶析出之玻璃。According to the present invention, a glass can be provided which can be sintered in the temperature range of 700-850°C, has excellent acid resistance, and effectively inhibits crystallization.
特別是，本發明之導體添加用玻璃因為具備含有特定成分之玻璃組成，故能在700~850℃這般相對低的溫度區域進行燒成。在燒成之際，從玻璃亦不會析出結晶，或是即使析出亦屬極微量，故能獲得優異流動性。此外，可用來作為耐酸性優異之材料。又，因為不含氧化鉛等有害物質，故具有環境適應性，且不受針對有害環境之物質的規範所約束。又，熱膨脹係數亦可在例如約40×10 -7~70×10 -7/℃範圍內可任選地進行設定。 In particular, the conductor-adding glass of the present invention can be fired at a relatively low temperature range of 700-850°C because it has a glass composition containing specific components. During firing, no crystals will precipitate from the glass, or even if they precipitate, they are extremely small, so excellent fluidity can be obtained. In addition, it can be used as a material with excellent acid resistance. In addition, because it does not contain harmful substances such as lead oxide, it has environmental adaptability and is not restricted by the regulations for substances harmful to the environment. In addition, the thermal expansion coefficient can also be arbitrarily set within the range of, for example, about 40×10 -7 ~70×10 -7 /°C.
如此，本發明之玻璃可使用作為導體形成用糊料之添加玻璃。特別是適合作為含鎳、銅等之導體形成用糊料所使用的玻璃成分。Thus, the glass of the present invention can be used as an additive glass for conductor forming paste, and is particularly suitable as a glass component used in conductor forming paste containing nickel, copper, etc.
用以實施發明之形態 本發明之導體添加用玻璃(本發明玻璃) 是用於添加在導電性組成物之玻璃，其特徵在於： 含有(1)SiO 2：5~18重量%、 (2)B 2O 3：28~45重量%、 (3)ZnO：38~58重量%、 (4)Al 2O 3及ZrO 2之至少1種：合計1~15重量%、及 (5)Li 2O、Na 2O及K 2O當中至少1種：合計0~7重量%； 且實質上不含氧化鉛。 Form for Implementing the Invention The conductor-adding glass of the present invention (the glass of the present invention) is a glass for adding to a conductive composition, and is characterized in that: it contains (1) SiO 2 : 5-18 wt %, (2) B 2 O 3 : 28-45 wt %, (3) ZnO: 38-58 wt %, (4) at least one of Al 2 O 3 and ZrO 2 : 1-15 wt % in total, and (5) at least one of Li 2 O, Na 2 O and K 2 O: 0-7 wt % in total; and does not substantially contain lead oxide.
A.關於本發明玻璃之組成 SiO 2本發明玻璃當中，SiO 2主要是形成玻璃之氧化物。其含量通常在5~18重量%之範圍。若SiO 2小於5重量%時，會有無法獲得玻璃之虞，或是即便獲得亦有耐酸性變低之虞。若SiO 2比18重量%多時，玻璃會變得不易熔融，或是會有SiO 2作為未熔融物殘留之虞。考慮到玻璃之成形性、耐酸性等，SiO 2之含量特別是7~14重量%較佳，其中更佳為10~13重量%。 A. About the composition of SiO2 in the glass of the present invention: In the glass of the present invention, SiO2 is mainly an oxide that forms glass. Its content is usually in the range of 5 to 18% by weight. If SiO2 is less than 5% by weight, there is a risk that glass cannot be obtained, or even if it is obtained, the acid resistance may be reduced. If SiO2 is more than 18% by weight, the glass will become difficult to melt, or there is a risk that SiO2 will remain as unmelted residue. Taking into account the formability and acid resistance of the glass, the SiO2 content is preferably 7 to 14% by weight, and more preferably 10 to 13% by weight.
B 2O 3本發明玻璃當中，B 2O 3主要是形成玻璃之成分。其含量通常在28~45重量%之範圍。若B 2O 3小於28重量%時，會有無法獲得玻璃之虞，或是即便獲得但軟化溫度變高。若B 2O 3大於45重量%時，會有耐酸性變低之虞。考慮到玻璃之軟化溫度、耐酸性等，B 2O 3之含量特別是33~40重量%較佳，其中更佳為大於35重量%且在39重量%以下。 B2O3 In the glass of the present invention , B2O3 is mainly a glass-forming component. Its content is usually in the range of 28 to 45 wt%. If B2O3 is less than 28 wt%, there is a risk that glass cannot be obtained, or even if it is obtained , the softening temperature becomes higher. If B2O3 is greater than 45 wt%, there is a risk that the acid resistance becomes lower. Considering the softening temperature and acid resistance of the glass , the B2O3 content is particularly preferably 33 to 40 wt%, and more preferably greater than 35 wt% and less than 39 wt%.
又，本發明當中，較佳為SiO 2及B 2O 3之合計量為40重量%以上，特別是45重量%以上更佳。藉此，能使燒成時不易從玻璃析出結晶。 In the present invention, the total amount of SiO2 and B2O3 is preferably 40% by weight or more, and more preferably 45% by weight or more. This can prevent crystals from being easily precipitated from the glass during sintering.
ZnO 本發明玻璃當中，ZnO主要是發揮了提高玻璃成形性、且降低軟化溫度的效果之成分。其含量通常為38~58重量%。若ZnO含量比38重量%更少時，會有軟化溫度降得不夠低之虞。若ZnO含量比58重量%更多時，會有無法獲得玻璃之虞。考慮到玻璃之成形性等，特別是40~50重量%為佳，其中更佳為40~47重量%。 ZnO In the glass of the present invention, ZnO is a component that mainly plays the role of improving the formability of the glass and lowering the softening temperature. Its content is usually 38~58% by weight. If the ZnO content is less than 38% by weight, there is a risk that the softening temperature will not be lowered enough. If the ZnO content is more than 58% by weight, there is a risk that the glass cannot be obtained. Considering the formability of the glass, 40~50% by weight is particularly preferred, and 40~47% by weight is more preferred.
Al 2O 3、ZrO 2本發明玻璃當中，Al 2O 3、ZrO 2主要是抑制分相、且提高玻璃之成形性、耐酸性等之成分。其含量是合計為1~15重量%。若前述合計量比1重量%更少時，無法充分獲得提高玻璃之成形性、耐酸性的效果。另一方面，若前述合計量比15重量%更多時，會有作為未熔融物殘留之虞。考慮到玻璃之成形性等，前述合計量特別是2~12重量%較佳，其中更佳為2~7重量%。 Al 2 O 3 , ZrO 2 In the glass of the present invention, Al 2 O 3 and ZrO 2 are mainly components that inhibit phase separation and improve the formability and acid resistance of the glass. The total content is 1 to 15% by weight. If the total amount is less than 1% by weight, the effect of improving the formability and acid resistance of the glass cannot be fully obtained. On the other hand, if the total amount is more than 15% by weight, there is a risk of unmelted residues remaining. Considering the formability of the glass, the total amount is preferably 2 to 12% by weight, and more preferably 2 to 7% by weight.
Li 2O、Na 2O、K 2O(鹼金屬氧化物) 本發明玻璃當中，鹼金屬氧化物主要是使熱物理性質降低之成分，且是可任選的成分。若含有鹼金屬氧化物時，較佳為含有任1種以上且合計量不超過7重量%。若其合計量超過7重量%，則玻璃之成形性變差，除了容易析出結晶，還有耐酸性降低之虞。考慮到玻璃之成形性等，前述合計量特別是1~7重量%較佳，其中更佳為2~5重量%。 Li 2 O, Na 2 O, K 2 O (alkali metal oxides) In the glass of the present invention, alkali metal oxides are mainly components that reduce thermophysical properties and are optional components. If alkali metal oxides are contained, it is preferred that at least one of them is contained and the total amount does not exceed 7% by weight. If the total amount exceeds 7% by weight, the formability of the glass deteriorates, crystals are easily precipitated, and there is a risk of reduced acid resistance. Taking into account the formability of the glass, etc., the total amount is preferably 1 to 7% by weight, and more preferably 2 to 5% by weight.
CuO 本發明玻璃當中，CuO主要是使熱物理性質降低之成分，且是可任選的成分。若含有CuO時，較佳為含有不超過5重量%。若CuO比5重量%更多時，會有玻璃之成形性變差之虞。 CuO In the glass of the present invention, CuO is a component that mainly reduces the thermophysical properties and is an optional component. If CuO is contained, it is preferably contained in an amount not exceeding 5% by weight. If CuO is more than 5% by weight, there is a risk that the formability of the glass will deteriorate.
MgO、CaO、SrO、BaO(鹼土金屬氧化物) 本發明玻璃當中，鹼土金屬氧化物主要是提高玻璃之成形性之成分，且是可任選的成分。若含有鹼土金屬氧化物時，較佳為含有任1種以上且合計量不超過10重量%。若其合計量比10重量%多時，會有無法獲得玻璃之虞。 MgO, CaO, SrO, BaO (alkali metal oxides) In the glass of the present invention, alkali metal oxides are mainly components that improve the formability of the glass and are optional components. If alkali metal oxides are contained, it is preferred that at least one of them is contained and the total amount does not exceed 10% by weight. If the total amount is more than 10% by weight, there is a risk that glass cannot be obtained.
其他成分 本發明玻璃當中，在不妨礙本發明效果之範圍內，可含有前述各成分以外之成分。例如，為了提高玻璃製造時的安定性、抑制結晶化、及調整熱膨脹係數等任一目的，可含有La 2O 3、Y 2O 3、TiO 2等至少1種且合計量為5重量%以下。又，以本發明玻璃來說，可在本發明玻璃中含有V 2O 5，然而從維持優異耐酸性之觀點來看，較佳為5重量%以下。 Other components The glass of the present invention may contain components other than the above components within the range that does not hinder the effect of the present invention. For example, in order to improve the stability of glass manufacturing, inhibit crystallization, and adjust the thermal expansion coefficient, at least one of La2O3, Y2O3 , TiO2 , etc. may be contained, and the total amount may be 5 % by weight or less. In addition, the glass of the present invention may contain V2O5 , but from the viewpoint of maintaining excellent acid resistance, it is preferably 5% by weight or less.
氧化鉛 本發明玻璃實質上不含氧化鉛。因為該成分被還原會有對於玻璃造成不良影響之虞，故設定為實質上不含。此外，本發明當中所謂「實質上不含」並非連含有雜質程度之情況都禁止，例如只是在用於製作玻璃之原材料等當中含有作為雜質的程度，這般含有的情況是可容許的。更具體來說，若該等之合計重量以氧化物換算計為1000ppm以下，即使是在本發明玻璃當中含有，但實質上會造成問題的可能性低，即屬於「實質上不含」。 Lead oxide The glass of the present invention does not substantially contain lead oxide. Since this component may have an adverse effect on the glass if reduced, it is set to be substantially free of lead oxide. In addition, the so-called "substantially free of lead oxide" in the present invention does not prohibit even the presence of impurities. For example, if it is contained as an impurity in the raw materials used to make glass, such a situation is allowed. More specifically, if the total weight of such is less than 1000ppm in terms of oxide, even if it is contained in the glass of the present invention, the possibility of causing substantial problems is low, which means it is "substantially free of lead oxide".
＜本發明玻璃之組成例＞ 作為本發明玻璃之具體組成例，可舉出： 含有(1)SiO 2：6~12重量%、 (2)B 2O 3：30~42重量%、 (3)ZnO：40~48重量%、 (4)Al 2O 3及ZrO 2之至少1種：合計1~11重量%、及 (5)Li 2O、Na 2O及K 2O當中至少1種：合計2~6重量%； 且實質上不含氧化鉛之組成。 <Composition Examples of Glass of the Present Invention> Specific examples of the composition of the glass of the present invention include: a composition containing (1) SiO2 : 6 to 12 wt%, (2) B2O3 : 30 to 42 wt%, (3) ZnO: 40 to 48 wt%, (4) at least one of Al2O3 and ZrO2 : 1 to 11 wt% in total, and (5) at least one of Li2O , Na2O and K2O : 2 to 6 wt% in total; and substantially no lead oxide.
又，作為另一實施型態之組成例，可舉出： 含有(1)SiO 2：6~10重量%、 (2)B 2O 3：32~40重量%、 (3)ZnO：41~47重量%、 (4)Al 2O 3及ZrO 2之至少1種：合計1~5重量%、及 (5)Li 2O、Na 2O及K 2O當中至少1種：合計3~6重量%； 且實質上不含氧化鉛之組成。 As another example of a composition of an embodiment, there can be cited: a composition containing (1) SiO2 : 6-10 wt%, (2) B2O3 : 32-40 wt%, (3) ZnO: 41-47 wt%, (4) at least one of Al2O3 and ZrO2 : 1-5 wt% in total, and (5) at least one of Li2O , Na2O and K2O : 3-6 wt% in total; and substantially no lead oxide.
此外，作為另一組成例，可舉出： 含有(1)SiO 2：6~10重量%、 (2)B 2O 3：32~40重量%、 (3)ZnO：41~47重量%、 (4)Al 2O 3及ZrO 2之至少1種：合計1~5重量%、 (5)Li 2O、Na 2O及K 2O當中至少1種：合計3~6重量%、及 (6)CuO：0.5~3重量%； 且實質上不含氧化鉛及之組成。 In addition, as another composition example, there can be cited: a composition containing (1) SiO2 : 6 to 10 wt%, (2) B2O3 : 32 to 40 wt%, (3) ZnO: 41 to 47 wt%, (4) at least one of Al2O3 and ZrO2 : 1 to 5 wt% in total, (5) at least one of Li2O , Na2O and K2O : 3 to 6 wt% in total, and (6) CuO: 0.5 to 3 wt%; and substantially no lead oxide.
B.關於本發明玻璃之性狀、特性 本發明玻璃之性狀(形態)並無特別限定，通常來說粉末形態較適合使用。本發明玻璃以粉末狀態使用時，考慮到燒成時的流動性、與基材之密著性，其粒度較佳為平均粒徑(D 50)設為0.5~3.0μm左右，特別是1.0~2.0μm更佳。 B. Properties and characteristics of the glass of the present invention The properties (morphology) of the glass of the present invention are not particularly limited, and generally, the powder form is more suitable for use. When the glass of the present invention is used in a powder state, considering the fluidity during sintering and the adhesion to the substrate, the particle size is preferably set to an average particle size (D 50 ) of about 0.5 to 3.0 μm, and more preferably 1.0 to 2.0 μm.
本發明玻璃粉末之玻璃轉移點(Tg)並無限定，通常來說在450~600℃左右之範圍即可。因此，可設為例如480~560℃。The glass transition point (Tg) of the glass powder of the present invention is not limited, but is generally in the range of about 450-600°C. Therefore, it can be set to 480-560°C, for example.
本發明玻璃粉末之軟化點(Ts)並無限定，通常來說在580~680℃左右之範圍即可。因此，可設為例如600~660℃。The softening point (Ts) of the glass powder of the present invention is not limited, but is generally in the range of about 580 to 680°C. Therefore, it can be set to, for example, 600 to 660°C.
又，本發明玻璃粉末在差熱分析(DTA)之DTA曲線當中，較佳為沒有確認到結晶化峰值溫度(Tp)，或是具有結晶化峰值溫度之情況下，Tp=750~950℃左右，特別是沒有確認到結晶化峰值溫度(Tp)更佳。其中，最佳是在差熱分析(DTA)之DTA曲線當中，在900℃以下沒有確認到結晶化峰值溫度(Tp)。In addition, the glass powder of the present invention preferably has no crystallization peak temperature (Tp) in the DTA curve of differential thermal analysis (DTA), or when having a crystallization peak temperature, Tp=750~950°C, and more preferably has no crystallization peak temperature (Tp). Among them, it is most preferable that the crystallization peak temperature (Tp) is not confirmed below 900°C in the DTA curve of differential thermal analysis (DTA).
關於本發明玻璃之熱膨脹係數α(50-300℃)，通常是在40×10 -7~70×10 -7/℃左右之範圍內當中，可依據例如與本發明玻璃一起使用的導電性粒子之種類、或使用本發明玻璃之基板的材質等來作適當設定，然而並不限定於此。 The thermal expansion coefficient α (50-300°C) of the glass of the present invention is generally in the range of about 40×10 -7 to 70×10 -7 /°C and can be appropriately set according to, for example, the type of conductive particles used with the glass of the present invention or the material of the substrate using the glass of the present invention, but is not limited thereto.
C.本發明玻璃之製造 本發明玻璃之製造方法本身並無特別限定，可依據例如下述製造方法來製造，該方法包含：1)將調合成本發明玻璃粉末之組成的原料進行混合之步驟(混合步驟)、2)將獲得之混合物在1250~1350℃溫度下熔融並調製熔融玻璃之步驟(熔融步驟)、及3)以不使熔融玻璃結晶化之方式進行冷卻之步驟(冷卻)。 C. Manufacturing of the glass of the present invention The manufacturing method of the glass of the present invention itself is not particularly limited, and can be manufactured according to, for example, the following manufacturing method, which includes: 1) a step of mixing raw materials for blending the composition of the glass powder of the present invention (mixing step), 2) a step of melting the obtained mixture at a temperature of 1250-1350°C and preparing molten glass (melting step), and 3) a step of cooling the molten glass in a manner that does not crystallize (cooling).
原料就使用能成為玻璃成分供給源之化合物作為起始原料即可。通常來說，使用本發明玻璃粉末所含元素(Si、Al、Zn、B、Cu等)之氧化物作為起始原料即可，亦可使用前述元素之氫氧化物、碳酸鹽、硝酸鹽等。例如可適當地使用B 2O 3等作為B來源；CuO等作為Cu來源；Al 2O 3、Al(OH) 3等作為Al來源。該等原料通常是使用粉末狀物即可，且可將該等粉末均勻地混合並調製混合粉末。 As the raw materials, compounds that can be the supply source of glass components can be used as the starting raw materials. Generally speaking, oxides of the elements (Si, Al, Zn, B, Cu, etc.) contained in the glass powder of the present invention can be used as the starting raw materials, and hydroxides, carbonates, nitrates, etc. of the aforementioned elements can also be used. For example, B 2 O 3 , etc. can be appropriately used as the B source; CuO, etc. can be used as the Cu source; Al 2 O 3 , Al(OH) 3 , etc. can be used as the Al source. These raw materials can usually be used in powder form, and these powders can be uniformly mixed to prepare a mixed powder.
如此獲得之混合物(混合粉末)通常會在1250~1350℃左右之溫度下熔融以調製熔融玻璃。熔融氣體環境並無限定，通常是在大氣中(或是氧化性氣體環境中)並在大氣壓下實施熔融步驟即可。The mixture (mixed powder) thus obtained is usually melted at a temperature of about 1250-1350°C to prepare molten glass. The melting gas environment is not limited, and the melting step is usually carried out in the atmosphere (or in an oxidizing gas environment) and under atmospheric pressure.
其次，在冷卻步驟中，是以不使熔融玻璃結晶化之方式進行冷卻。如此冷卻條件並無特別限定，可採用與周知玻璃製造時相同之方式即可。因此，可採用例如使熔融玻璃與不銹鋼製冷卻輥接觸，而使其急速冷卻之方法。Secondly, in the cooling step, the molten glass is cooled in a manner that does not allow crystallization. The cooling conditions are not particularly limited, and the same method as in the known glass manufacturing can be adopted. Therefore, for example, a method can be adopted in which the molten glass is brought into contact with a stainless steel cooling roller to rapidly cool it.
如此獲得之本發明玻璃仍可因應需要而施行粉碎、分級等之處理。在此，若是藉由粉碎、分級等進行粒度調整時，可將平均粒徑D 50控制在如前述之0.5~3.0μm，並將最大粒徑調整成較佳為20μm以下即可。 The glass of the present invention thus obtained can still be processed by crushing, grading, etc. as needed. Here, if the particle size is adjusted by crushing, grading, etc., the average particle size D50 can be controlled within the aforementioned 0.5-3.0 μm, and the maximum particle size can be adjusted to preferably less than 20 μm.
D.本發明玻璃之使用 本發明玻璃可適宜地使用作為用於添加在導電性組成物之玻璃。亦即，本發明玻璃適合作為用於形成電極等之導體的組成物所含之玻璃。 D. Use of the glass of the present invention The glass of the present invention can be suitably used as glass to be added to a conductive composition. That is, the glass of the present invention is suitable as glass contained in a composition for forming a conductor such as an electrode.
導電性組成物(以下稱「本發明組成物」。)可適宜地採用含有(a)導電性粒子及(b)玻璃成分之組成且是以本發明玻璃(特別是玻璃粉末)作為(b)玻璃成分。The conductive composition (hereinafter referred to as "the composition of the present invention") can be preferably a composition containing (a) conductive particles and (b) a glass component, wherein the glass of the present invention (particularly glass powder) is used as the (b) glass component.
導電性粒子並無特別限定，可使用例如金屬等。金屬可使用例如銀、銅、金、鎳、鈀、鐵等，此外還有含有該等之合金或金屬間化合物。該等可因應用途等作適宜選擇。例如，欲形成積層陶瓷電容、晶片電阻、積層電感、LTCC(低溫燒成多層基板)等之外部電極等的導體時，可適宜地使用例如銅、銀或鈀等之至少1種。特別是，本發明玻璃因為是用來添加於含有導電性粒子之導電性組成物的玻璃，且該導電性粒子是比銀更容易氧化之金屬(鎳、銅等)，故更加適合。There is no particular limitation on the conductive particles, and metals, for example, can be used. Examples of metals that can be used include silver, copper, gold, nickel, palladium, iron, and alloys or intermetallic compounds containing these. These can be appropriately selected according to the intended use. For example, when forming a conductor such as an external electrode of a multilayer ceramic capacitor, a chip resistor, a multilayer inductor, or a LTCC (low temperature fired multilayer substrate), at least one of copper, silver, or palladium can be appropriately used. In particular, the glass of the present invention is more suitable because it is a glass to be added to a conductive composition containing conductive particles, and the conductive particles are metals (nickel, copper, etc.) that are more easily oxidized than silver.
導電性粒子(導電性粉末)之平均粒徑可因應所形成之導體的形狀作變更，然而通常為0.1~10μm左右即可。又，導電性粒子之形狀亦無限定，可以是例如球狀、薄片(flake)狀等任一形狀。The average particle size of the conductive particles (conductive powder) may vary depending on the shape of the conductor to be formed, but is generally about 0.1 to 10 μm. The shape of the conductive particles is not limited, and may be any shape such as spherical or flake.
本發明組成物之固體成分當中，導電性粒子(粉末)之含量可依據所欲之導電性、用途等作適當設定，通常為70~99重量%左右即可。The content of the conductive particles (powder) in the solid components of the composition of the present invention can be appropriately set according to the desired conductivity, application, etc., and is usually about 70 to 99% by weight.
又，導電性粒子與本發明玻璃之比率可因應所欲之導電性等作適當設定，通常來說相對於導電性粒子100重量份，本發明玻璃為1~30重量份，特別是1~10重量份較佳。The ratio of the conductive particles to the glass of the present invention can be appropriately set according to the desired conductivity, etc. Generally, the ratio of the glass of the present invention is 1 to 30 parts by weight, and preferably 1 to 10 parts by weight, relative to 100 parts by weight of the conductive particles.
本發明組成物可以是粉末狀，但特別適合以糊料狀(導體糊料)之形態作使用。亦即，適合以含有1)溶劑及黏結劑之至少1種、2)本發明玻璃、及3)導電性粒子(粉末)之糊料的形態使用。例如，前述糊料適合以使用了乙基纖維素之導體糊料(導電性糊料)進行調製。此種情況下，將本發明玻璃及導電性粒子(粉末)均勻分散至下述載體中即可，前述載體是使乙基纖維素溶解於松油醇等溶劑而成之溶液所構成者、或是在前述溶液中因應需要而含有其他添加物所構成者。當本發明組成物以糊料狀形態使用時，其固體成分含量通常設為60~90重量%左右即可。The composition of the present invention can be in powder form, but is particularly suitable for use in the form of a paste (conductor paste). That is, it is suitable for use in the form of a paste containing 1) at least one of a solvent and a binder, 2) the glass of the present invention, and 3) conductive particles (powder). For example, the aforementioned paste is suitable for preparation with a conductive paste (conductive paste) using ethyl cellulose. In this case, the glass of the present invention and the conductive particles (powder) are uniformly dispersed in the following carrier, which is composed of a solution in which ethyl cellulose is dissolved in a solvent such as pine alcohol, or other additives are contained in the aforementioned solution as needed. When the composition of the present invention is used in the form of a paste, its solid content is usually set to about 60~90% by weight.
如此，本發明組成物亦可作為導電性糊料來使用，因此適合用於各種導體(特別是電極及導線之至少1種)之形成。例如，適合用於積層陶瓷電容之導體的形成。Thus, the composition of the present invention can also be used as a conductive paste, and is therefore suitable for forming various conductors (especially at least one of electrodes and conductors). For example, it is suitable for forming conductors of multilayer ceramic capacitors.
作為使用導體糊料形成導體(電導體)之方法，可採用例如下述方法來實施，該方法包含有以導體糊料形成塗膜之步驟及燒成前述塗膜之步驟。形成塗膜之方法本身可依照周知之方法即可，可依照例如網版印刷等各種印刷方法、還有塗布、噴塗等方法實施。形成塗膜後，在燒成之前可因應需要進行乾燥。例如使用本發明組成物來形成積層陶瓷電容、晶片電阻、積層電感、LTCC(低溫燒成多層基板)等之外部電極時，燒成時的燒成溫度一般是設為700~900℃左右即可。又，燒成氣體環境可因應導電性粒子之種類等，從例如大氣中、惰性氣體環境、還原性氣體環境等之中作適當選擇即可。 [實施例] As a method of forming a conductor (electric conductor) using a conductive paste, the following method can be used, for example, and the method includes the steps of forming a coating using a conductive paste and firing the coating. The method of forming the coating itself can be carried out according to a well-known method, and can be carried out according to various printing methods such as screen printing, as well as coating, spraying and the like. After the coating is formed, it can be dried as needed before firing. For example, when the composition of the present invention is used to form external electrodes of multilayer ceramic capacitors, chip resistors, multilayer inductors, LTCC (low temperature fired multilayer substrates), etc., the firing temperature during firing is generally set to about 700~900°C. Furthermore, the combustion gas environment can be appropriately selected from, for example, the atmosphere, an inert gas environment, a reducing gas environment, etc., depending on the type of conductive particles. [Example]
以下揭示實施例及比較例，並進一步具體地說明本發明特徵。然而本發明之範圍不受實施例限定。The following discloses embodiments and comparative examples and further specifically describes the features of the present invention. However, the scope of the present invention is not limited to the embodiments.
實施例1~29及比較例1~2 將原料調合成如表1~2所示之玻璃組成並混合，將該混合物放入白金坩堝，在1250~1350℃溫度下熔融1小時之後，以雙輥法急速冷卻而獲得玻璃薄片。又，將玻璃薄片放入罐式磨機，粉碎後成為玻璃粉末。又，另外將前述熔融物流出至預先加熱之碳板，製作出塊狀物。其後，將所得之塊狀物放入溫度已設定成比預想之玻璃轉移點高約50℃的電爐中，徐徐冷卻。 Examples 1-29 and Comparative Examples 1-2 The raw materials were blended into the glass composition shown in Tables 1-2 and mixed. The mixture was placed in a platinum crucible and melted at 1250-1350°C for 1 hour. The mixture was rapidly cooled by a double roll method to obtain glass flakes. The glass flakes were placed in a pot mill and crushed into glass powder. The melt was then flowed onto a preheated carbon plate to produce a block. The obtained block was then placed in an electric furnace set at a temperature about 50°C higher than the expected glass transition point and slowly cooled.
試驗例1 關於各實施例及比較例所得之玻璃粉末與塊狀物，以下述方法測定玻璃粉末之玻璃轉移溫度、軟化溫度、結晶化溫度及熱膨脹係數。又，關於實施例之玻璃的一部分以及比較例1之玻璃，以下述方法測定玻璃之耐酸性。將該等結果揭示於表1~2。 Test Example 1 Regarding the glass powder and block obtained in each embodiment and comparative example, the glass transition temperature, softening temperature, crystallization temperature and thermal expansion coefficient of the glass powder were measured by the following method. In addition, regarding a part of the glass of the embodiment and the glass of comparative example 1, the acid resistance of the glass was measured by the following method. The results are disclosed in Tables 1~2.
(1)玻璃轉移溫度、軟化溫度、結晶化溫度 將玻璃粉末約60~80mg填充至白金器皿，使用DTA測定裝置(Rigaku公司製Thermo Plus TG8120)，從室溫開始以20℃/分鐘升溫並分別測定玻璃轉移溫度(Tg)、軟化溫度(Ts)及結晶化溫度(Tp)。 (1) Glass transition temperature, softening temperature, and crystallization temperature Approximately 60 to 80 mg of glass powder was filled into a platinum container, and the temperature was raised at 20°C/min from room temperature using a DTA measuring device (Thermo Plus TG8120 manufactured by Rigaku Corporation) to measure the glass transition temperature (Tg), softening temperature (Ts), and crystallization temperature (Tp).
(2)玻璃之熱膨脹係數 從獲得之玻璃塊切取出約5mm×5mm×15mm，經研磨後作為測定用之樣品。使用TMA測定裝置，從室溫開始以10℃/分鐘升溫之際獲得熱膨脹曲線，並由此求出以50℃與300℃這2點為基準之熱膨脹係數(α)(單位：×10 -7/℃)。 (2) Thermal expansion coefficient of glass A sample of about 5 mm × 5 mm × 15 mm was cut from the obtained glass block and ground to prepare it. The thermal expansion curve was obtained by heating the sample at 10°C/min from room temperature using a TMA measuring device. The thermal expansion coefficient (α) (unit: ×10 -7 /°C) was calculated based on the two points of 50°C and 300°C.
(3)玻璃之耐酸性 以一部分實施例及比較例所得之樣品作為代表例，從該玻璃塊切取出約5mm×5mm×15mm，浸漬於60%硝酸並在室溫下靜置2小時。求出浸漬後的玻璃塊相對於浸漬前之重量變化的比例(%)。 (3) Acid resistance of glass Taking samples obtained from some of the examples and comparative examples as representative examples, a piece of about 5 mm × 5 mm × 15 mm was cut out from the glass block, immersed in 60% nitric acid and left at room temperature for 2 hours. The ratio (%) of the weight change of the glass block after immersion relative to that before immersion was calculated.
[表1] [Table 1]
[表2] [Table 2]
由表1~2結果可明確得知，實施例1~29的玻璃之軟化溫度在600~700℃範圍內，在燒成時表現出充分的流動性。又，耐酸性試驗中的重量減少較少，可知具有高耐酸性。As can be clearly seen from the results in Tables 1-2, the softening temperatures of the glasses of Examples 1-29 are in the range of 600-700°C, and they exhibit sufficient fluidity when fired. In addition, the weight loss in the acid resistance test is small, indicating that they have high acid resistance.
相對於此，比較例1之玻璃雖然軟化溫度是適合用於導體添加用，然而耐酸性試驗中的重量變化顯著(亦即，耐酸性不足夠。)。又，比較例2之玻璃因產生分相，已變得不適合本發明之目的。 產業上之可利用性 In contrast, although the softening temperature of the glass of Comparative Example 1 is suitable for conductor addition, the weight change in the acid resistance test is significant (that is, the acid resistance is insufficient). In addition, the glass of Comparative Example 2 has become unsuitable for the purpose of the present invention due to phase separation. Industrial Applicability
本發明玻璃可在例如700~850℃溫度進行燒成，而且不會從玻璃析出結晶，或是即使析出亦屬極微量，故流動性優異，能有效地黏合金屬導體粉末。又，因耐酸性高，可使用作為適用在形成電極等之導體糊料的材料。The glass of the present invention can be fired at a temperature of 700-850°C, for example, and crystals will not precipitate from the glass, or even if they do, they will be extremely small, so it has excellent fluidity and can effectively bond metal conductor powders. In addition, due to its high acid resistance, it can be used as a material for conductor pastes suitable for forming electrodes, etc.
(無)(without)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2022-144612 | 2022-09-12 |
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