CN101209903A - Lead-free glass powder for high temperature resistant glass screen printing ink, its preparation and application - Google Patents
Lead-free glass powder for high temperature resistant glass screen printing ink, its preparation and application Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 91
- 239000000843 powder Substances 0.000 title claims abstract description 37
- 238000007650 screen-printing Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 18
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 16
- 238000007639 printing Methods 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 239000010453 quartz Substances 0.000 claims abstract description 7
- 239000005329 float glass Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- -1 B 2 O 3 Inorganic materials 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 43
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 229910002114 biscuit porcelain Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910020203 CeO Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种耐高温玻璃丝网印刷油墨用无铅玻璃粉、其制备及其应用，该玻璃粉的重量百分比组分：30～50％ Bi2O3、10～50％ B2O3、0～30％ ZnO、0～10％ Al2O3、0～10％ SiO2、0～10％ MgO、0～6％ K2O、0～6％ Na2O、0～6％ Li2O；制备：按照各组分的重量百分比称取各原料，并充分混合放入石英坩埚中，放入炉温电炉中，保温，熔化后的玻璃液倒入压片机压成薄片或者倒入冷水中并干燥，球磨、过300目网筛，干燥保存。该玻璃粉应用于基板为浮法玻璃的印刷，也可和一切在此温度和膨胀系数相符的玻璃、陶瓷、金属封接。The invention relates to a lead-free glass powder for high-temperature-resistant glass screen printing ink, its preparation and application. The weight percentage components of the glass powder are: 30-50% Bi 2 O 3 , 10-50% B 2 O 3 , 0~30% ZnO, 0~10% Al 2 O 3 , 0~10% SiO 2 , 0~10% MgO, 0~6% K 2 O, 0~6% Na 2 O, 0~6% Li 2 O; Preparation: Weigh each raw material according to the weight percentage of each component, and fully mix them into a quartz crucible, put them into a furnace temperature electric furnace, keep warm, pour the melted glass liquid into a tablet machine and press it into thin slices or pour it into a Dried in cold water, ball milled, passed through a 300-mesh sieve, and stored in a dry place. The glass frit is applied to the printing of float glass as the substrate, and it can also be sealed with all glass, ceramics, and metals that match the temperature and expansion coefficient.
Description
技术领域technical field
本发明属无铅玻璃粉领域，特别是涉及耐高温玻璃丝网印刷油墨用无铅玻璃粉。The invention belongs to the field of lead-free glass powder, in particular to lead-free glass powder for high-temperature-resistant glass screen printing ink.
背景技术Background technique
网版印刷的蓬勃发展，使得相应的各种新型网印油墨的发展也很迅速，比如有香味油墨、荧光油墨、发泡油墨、快固油墨等，这些油墨一般都是在常温下干燥，只有玻璃印刷和陶瓷印刷是在高温下干燥。所以耐高温油墨常指玻璃和陶瓷印刷用的油墨。耐高温油墨根据不同的承印材料和不同的印刷工艺，所要求的耐热的温度也是不同的。The vigorous development of screen printing has led to the rapid development of various new screen printing inks, such as scented inks, fluorescent inks, foaming inks, and fast-curing inks. These inks are generally dried at room temperature. Glass printing and ceramic printing are dried at high temperature. Therefore, high temperature resistant inks often refer to inks for glass and ceramic printing. According to different printing materials and different printing processes, the heat-resistant temperature required by high-temperature-resistant inks is also different.
无机玻璃网印用两种油墨，一种是无机色素经过研磨后，达到一定细度，再加入丙烯酸酯，网印在玻璃表面，需经高温(600℃以上)焙烧1～2min，墨层和玻璃表层熔化在一起，牢度极佳。这种油墨的耐热温度就在600℃以上。但是因为这种网印工艺耗资大，工艺较复杂。There are two kinds of inks for screen printing on inorganic glass. One is that after the inorganic pigment is ground to a certain fineness, then adding acrylic ester, the screen printing is on the surface of the glass. The glass surfaces are fused together for excellent fastness. The heat-resistant temperature of this ink is above 600°C. But because this screen printing process is costly and complicated.
另一种是以高分子化合物为黏结剂的无机玻璃油墨，氨基型和环氧型均需要烘烤，国内市场广泛应用的油墨是网印之后在1300～1400℃烘烤30min，这种油墨的耐热温度就相对要低，但是烘烤的时间较长，油墨的牢度和硬度均佳，亮度也非常好，能耐低浓度的电解质及乙醇、丙酮、苯类、环己酮等溶剂的腐蚀。The other is inorganic glass ink with polymer compound as binder. Both amino type and epoxy type need to be baked. The ink widely used in the domestic market is baked at 1300-1400°C for 30 minutes after screen printing. The heat-resistant temperature is relatively low, but the baking time is longer, the fastness and hardness of the ink are good, the brightness is also very good, and it can withstand the corrosion of low-concentration electrolytes and solvents such as ethanol, acetone, benzene, and cyclohexanone. .
陶瓷的印刷温度根据烧制方法可以分为两种：一种是最初在700～800℃的温度下进行素烧，素烧后上釉，然后再在1100～1300℃的温度下进行烧制。这种烧制方式下用的油墨耐热温度要求达到1100～1300℃；另一种是先在高温1100～1250℃下进行烧制，然后上釉再以900～1000℃的温度进行烧制。这种油墨要求的耐热温度是比前一种要低，达到900～1000℃。The printing temperature of ceramics can be divided into two types according to the firing method: one is bisque firing at a temperature of 700-800°C initially, glaze after bisque firing, and then firing at a temperature of 1100-1300°C. The heat-resistant temperature of the ink used in this firing method is required to reach 1100-1300°C; the other is to fire at a high temperature of 1100-1250°C first, then glaze and then fire at a temperature of 900-1000°C. The heat-resistant temperature required by this ink is lower than that of the previous one, reaching 900-1000°C.
现有的用在陶瓷和玻璃上的耐高温油墨，耐高温温度都比较高，在600℃以上，甚至1000℃以上。而在一些玻璃容器上印刷，有时油墨的耐热温度较陶瓷上用的低，比如180～200℃，这种油墨也叫低温玻璃油墨，是用有机涂料和有机颜料或仿金色料代替无机盐料和纯金制成的，用来装饰玻璃，在200℃下烘烤10min。Existing high-temperature-resistant inks used on ceramics and glass have relatively high high-temperature resistance, above 600°C, or even above 1000°C. When printing on some glass containers, sometimes the heat-resistant temperature of the ink is lower than that used on ceramics, such as 180-200°C. This ink is also called low-temperature glass ink, which uses organic coatings and organic pigments or imitation gold materials instead of inorganic salts. It is made of raw material and pure gold, used to decorate glass, and baked at 200°C for 10 minutes.
在现有的耐高温油墨中，耐热温度达到1800～2000℃的油墨比较少，如果要求在这个温度下长时间烘烤，能满足这一要求的油墨就更少了。目前，能耐200℃左右温度烘烤不变色的油墨国内几乎没有，主要靠进口，但国外生产的厂家也比较少，而且生产的油墨的耐热性不是很稳定，比如印刷砂轮标签，印刷后要在200℃温度下烘烤3h，经常出现变色现象，应用中能达到要求的油墨其成本比较高。目前，一些网印业发达的国家能研制这类油墨，同时成品价格比较高，因此这种油墨具有很高的使用价值，可取代同类进口油墨，降低了产品生产的印刷成本。Among the existing high-temperature-resistant inks, there are relatively few inks with a heat-resistant temperature of 1800-2000°C. If it is required to bake at this temperature for a long time, there will be even fewer inks that can meet this requirement. At present, there are almost no domestic inks that can withstand baking at a temperature of about 200°C and do not change color. They mainly rely on imports, but there are relatively few foreign manufacturers, and the heat resistance of the inks produced is not very stable. Baking at 200°C for 3 hours often causes discoloration, and the cost of the ink that can meet the requirements in the application is relatively high. At present, some countries with developed screen printing industry can develop this kind of ink, and the finished product price is relatively high. Therefore, this kind of ink has high use value and can replace similar imported inks, reducing the printing cost of product production.
随着2006年提出的环保认证，对高温环保油墨在环保性方面又提出了新的要求，特别是对于发达国家的出口，都需要经过环保认证，能通过认证的环保油墨由于无铅无镉，产品的光泽感、鲜艳度就会有所改变，因而，开发出能满足上述优点，但又符合环保要求、价格合适的耐高温玻璃丝网印刷油墨用无铅玻璃粉具有广阔的市场应用前景。With the environmental protection certification proposed in 2006, new requirements have been put forward for high-temperature environmental protection inks in terms of environmental protection, especially for the export of developed countries, they all need to pass environmental protection certification. The environmentally friendly inks that can pass the certification are lead-free and cadmium-free. The luster and vividness of the product will change. Therefore, the development of lead-free glass powder for high temperature resistant glass screen printing inks that can meet the above advantages, meet environmental protection requirements, and have a broad market application prospect.
旭硝子特公平7-25568提出能用于离子显示器(PDP)和荧光显示器(VFD)电介体层的PbO-SiO2系玻璃料浆料，其玻璃组成含有：PbO、SiO2、Al2O3、SnO2、TiO2、CaO、BaO、CeO2、La2O3、B2O3、ZnO、SrO、MgO，膨胀系数在80～90×10-7/℃附近，是通过添加填料的方法降低膨胀系数的，通过铅玻璃组成的优化及填料的适当配比，实现了介质层的致密化，但是，最大的缺点是含有大量的氧化铅(＞50wt％)，不能满足现在无铅化的需求。Asahi Glass Special Publication No. 7-25568 proposes a PbO-SiO 2- based glass frit paste that can be used for the dielectric layer of ion display (PDP) and fluorescent display (VFD). The glass composition contains: PbO, SiO 2 , Al 2 O 3 , SnO 2 , TiO 2 , CaO, BaO, CeO 2 , La 2 O 3 , B 2 O 3 , ZnO, SrO, MgO, the expansion coefficient is around 80～90×10 -7 /℃, it is by adding fillers To reduce the expansion coefficient, the densification of the dielectric layer is realized through the optimization of the composition of the lead glass and the appropriate proportion of the filler. However, the biggest disadvantage is that it contains a large amount of lead oxide (> 50wt%), which cannot meet the current lead-free requirements. need.
日本专利第H7-69672号公开的玻璃组成的摩尔百分数为：P2O5 25～50％、SnO 30～70％、ZnO 0～25％，在此基础上添加B2O3、WO3、Li2O等，该玻璃的转变温度为350～450℃，热膨胀系数大于120×10-7/℃，专利中采用填充剂的方法降低玻璃的膨胀系数，但影响到玻璃封接时的流动性和气密性，同时其化学稳定性不高。The molar percentages of the glass composition disclosed in Japanese Patent No. H7-69672 are: P 2 O 5 25-50%, SnO 30-70%, ZnO 0-25%, and on this basis, B 2 O 3 , WO 3 , Li 2 O, etc., the transition temperature of the glass is 350-450°C, and the coefficient of thermal expansion is greater than 120×10 -7 /°C. In the patent, fillers are used to reduce the expansion coefficient of the glass, but it affects the fluidity of the glass during sealing. And air tightness, while its chemical stability is not high.
杜邦公司USP：5378408提出了无铅的Bi2O3-B2O3-SiO2系统低熔点玻璃，其重量百分比组成为：65～95％Bi2O3、0.1～9％B2O3、2～15％SiO2、0～5％Al2O3、0～5％CaO、0～20％ZnO，Tf＝400～650℃，膨胀系数也可以到80×10-7/℃以下，但由于Bi2O3的含量较高，因而成本较高，在价格方面不具有优势。DuPont USP: 5378408 proposes lead-free Bi 2 O 3 -B 2 O 3 -SiO 2 system low-melting point glass, whose weight percent composition is: 65-95% Bi 2 O 3 , 0.1-9% B 2 O 3 , 2 to 15% SiO 2 , 0 to 5% Al 2 O 3 , 0 to 5% CaO, 0 to 20% ZnO, T f = 400 to 650°C, and the expansion coefficient can also be below 80×10 -7 /°C , but due to the high content of Bi 2 O 3 , the cost is high, and it does not have an advantage in terms of price.
发明内容Contents of the invention
本发明的目的是提供一种耐高温玻璃丝网印刷油墨用无铅玻璃粉、其制备及其应用，该玻璃粉所制的油墨特别适用于基板为浮法玻璃的高温丝网印刷。The object of the present invention is to provide a lead-free glass powder for high temperature resistant glass screen printing ink, its preparation and application. The ink made from the glass powder is especially suitable for high temperature screen printing with float glass substrate.
本发明的一种耐高温玻璃丝网印刷油墨用无铅玻璃粉，其重量百分比组分：30～50％Bi2O3、10～50％B2O3、0～30％ZnO、0～10％Al2O3、0～10％SiO2、0～10％MgO、0～6％K2O、0～6％Na2O、0～6％Li2O，其中Bi2O3、B2O3、ZnO的总的重量百分比为70～95％，Al2O3、SiO2的总的重量百分比为0～18％，K2O、Na2O、Li2O的总的重量百分比为0～10％。A lead-free glass powder for high-temperature-resistant glass screen printing ink of the present invention, its components in weight percent: 30-50% Bi 2 O 3 , 10-50% B 2 O 3 , 0-30% ZnO, 0-10 %Al 2 O 3 , 0-10% SiO 2 , 0-10% MgO, 0-6% K 2 O, 0-6% Na 2 O, 0-6% Li 2 O, among which Bi 2 O 3 , B The total weight percentage of 2 O 3 and ZnO is 70-95%, the total weight percentage of Al 2 O 3 and SiO 2 is 0-18%, and the total weight percentage of K 2 O, Na 2 O and Li 2 O 0 to 10%.
所述的耐高温玻璃丝网印刷油墨用无铅玻璃粉，其优选重量百分比组分：30～45％Bi2O3、15～45％B2O3、0～25％ZnO、0～7％Al2O3、0～10％SiO2、0～10％MgO、0～6％K2O、0～6％Na2O、0～6％Li2O，其中Bi2O3、B2O3、ZnO的总的重量百分比为75～95％，Al2O3、SiO2的总的重量百分比为0～15％，K2O、Na2O、Li2O的总的重量百分比为0～8％；优选重量百分比组分：35～45％Bi2O3、20～40％B2O3、5～20％ZnO、0～5％Al2O3、0～8％SiO2、0～6％MgO、0～6％K2O、0～6％Na2O、0～6％Li2O，其中Bi2O3、B2O3、ZnO的总的重量百分比为80～95％，Al2O3、SiO2的总的重量百分比为0～10％，K2O、Na2O、Li2O的总的重量百分比为0～6％；最优选重量百分比组分：35～40％Bi2O3、20～40％B2O3、5～20％ZnO、0～5％Al2O3、0～8％SiO2、0～6％MgO、0～6％K2O、0～6％Na2O、0～6％Li2O，其中Bi2O3、B2O3、ZnO的总的重量百分比为80～95％，Al2O3、SiO2的总的重量百分比为0～10％，K2O、Na2O、Li2O的总的重量百分比为0～6％。The lead-free glass powder for high-temperature-resistant glass screen printing inks preferably has components in weight percent: 30-45% Bi 2 O 3 , 15-45% B 2 O 3 , 0-25% ZnO, 0-7% Al 2 O 3 , 0-10% SiO 2 , 0-10% MgO, 0-6% K 2 O, 0-6% Na 2 O, 0-6% Li 2 O, among which Bi 2 O 3 , B 2 The total weight percentage of O 3 and ZnO is 75-95%, the total weight percentage of Al 2 O 3 and SiO 2 is 0-15%, and the total weight percentage of K 2 O, Na 2 O and Li 2 O is 0-8%; preferred weight percentage components: 35-45% Bi 2 O 3 , 20-40% B 2 O 3 , 5-20% ZnO, 0-5% Al 2 O 3 , 0-8% SiO 2 , 0-6% MgO, 0-6% K 2 O, 0-6% Na 2 O, 0-6% Li 2 O, wherein the total weight percentage of Bi 2 O 3 , B 2 O 3 , and ZnO is 80 ～95%, the total weight percentage of Al2O3 , SiO2 is 0～10%, the total weight percentage of K2O , Na2O , Li2O is 0～6%; the most preferred weight percent component : 35-40% Bi 2 O 3 , 20-40% B 2 O 3 , 5-20% ZnO, 0-5% Al 2 O 3 , 0-8% SiO 2 , 0-6% MgO, 0-6 %K 2 O, 0-6% Na 2 O, 0-6% Li 2 O, wherein the total weight percentage of Bi 2 O 3 , B 2 O 3 , ZnO is 80-95%, Al 2 O 3 , SiO The total weight percentage of 2 is 0-10%, and the total weight percentage of K 2 O, Na 2 O and Li 2 O is 0-6%.
所述的耐高温玻璃丝网印刷油墨用无铅玻璃粉的膨胀系数为78～82×10-7/℃，封接温度为535～550℃。The expansion coefficient of the lead-free glass powder for high temperature resistant glass screen printing ink is 78-82×10 -7 /°C, and the sealing temperature is 535-550°C.
本发明的耐高温玻璃丝网印刷油墨用无铅玻璃粉，适用于基板为浮法玻璃的印刷，烧结温度为590～610℃，还可以和一切在此温度和膨胀系数相符的玻璃、陶瓷、金属封接。The lead-free glass powder for high-temperature-resistant glass screen printing ink of the present invention is suitable for the printing of float glass as the substrate, and the sintering temperature is 590-610°C, and it can also be used with all glass, ceramics, and metals that are consistent with the temperature and expansion coefficient. seal.
本发明的耐高温玻璃丝网印刷油墨用无铅玻璃粉的制备方法，包括以下步骤：The preparation method of lead-free glass powder for high temperature resistant glass screen printing ink of the present invention comprises the following steps:
(1)按照各组分的重量百分比称取各原料，并充分混合；(1) Take each raw material according to the weight percentage of each component, and fully mix;
(2)将混合后的混合料放入石英坩埚中，然后放入炉温为1150℃～1250℃的电炉中，保温10～30min；(2) Put the mixed material into a quartz crucible, then put it into an electric furnace with a furnace temperature of 1150°C-1250°C, and keep it warm for 10-30min;
(3)将熔化后的玻璃液倒入压片机压成薄片或者倒入冷水中并干燥，球磨、过300目网筛，干燥保存。(3) Pour the melted glass liquid into a tablet machine to form thin slices or pour it into cold water and dry it, ball mill it, pass it through a 300-mesh sieve, and store it dry.
本发明的有益效果：Beneficial effects of the present invention:
本专利的无铅玻璃粉所制的油墨特别适用于基板为浮法玻璃的丝网印刷，该浮法玻璃基板的膨胀系数为80×10-7/℃，烧结温度为590～610℃，印刷厚度为50μm，因而要求玻璃粉的膨胀系数也在80×10-7/℃附近，按重量百分比色素添加3％，则玻璃粉自身的封接温度不能高于550℃，同时，Bi2O3的最优重量百分比为35～40％，具有显著的成本优势。The ink made of the lead-free glass powder of this patent is especially suitable for screen printing with float glass as the substrate. The thickness is 50μm, so the expansion coefficient of the glass frit is also required to be around 80×10 -7 /°C. If the pigment is added by 3% by weight, the sealing temperature of the glass frit itself cannot be higher than 550°C. At the same time, Bi 2 O 3 The optimal weight percentage of the compound is 35-40%, which has a significant cost advantage.
本发明的耐高温玻璃丝网印刷油墨用无铅玻璃粉制得的油墨烧结后光泽好、色彩鲜艳、不含铅、牢固度好，具有良好的耐水、耐溶剂，耐磨性能以及流动性好等优点。The high-temperature-resistant glass screen printing ink of the present invention is made of lead-free glass powder. After sintering, the ink has good gloss, bright colors, no lead, good firmness, good water resistance, solvent resistance, wear resistance and good fluidity. advantage.
具体实施方式Detailed ways
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
按表1的组成重量百分比配料并混合均匀，将玻璃料放入石英坩埚内，在硅碳棒电炉内加热熔制，加料分三次添加，第一次添加温度为1150℃，第二次添加温度为1200℃，第三次添加温度为1170℃，在不同次数的添加混合料后的保温时间不同，保温时间一共为1.5-2.0小时。According to the composition weight percentage in Table 1 and mix evenly, put the glass frit into the quartz crucible, heat and melt it in the silicon carbon rod electric furnace, add the material in three times, the temperature of the first addition is 1150 ℃, and the temperature of the second addition is It is 1200°C, and the temperature for the third addition is 1170°C. The holding time is different after adding the mixture for different times, and the holding time is 1.5-2.0 hours in total.
热膨胀系数采用WRP-1微机热膨胀仪测量，由室温升至300℃，升温速率为5℃/min，将退火后的样品研磨成φ5×25mm规格的圆柱体试样测定；封接温度是通过半球实验得到地，测试结果见表2。The coefficient of thermal expansion is measured by a WRP-1 microcomputer thermal dilatometer, from room temperature to 300°C, the heating rate is 5°C/min, and the annealed sample is ground into a cylindrical sample of φ5×25mm for measurement; the sealing temperature is determined by The hemispheric experiment was obtained, and the test results are shown in Table 2.
熔制好的玻璃倒入压片机中压片，经过球磨机球磨成粉末状的玻璃粉，过筛后的玻璃粉经包装后供用户使用。The melted glass is poured into a tablet press to be pressed into tablets, and then it is ball-milled into powdered glass powder, and the sieved glass powder is packaged for use by users.
表1 实施例1-4中的玻璃成分Glass composition in table 1 embodiment 1-4
实施例2Example 2
按表1的组成重量百分比配料并混合均匀，将玻璃料放入石英坩埚内，在硅碳棒电炉内加热熔制，加料分三次添加，第一次添加温度为1160℃，第二次添加温度为1200℃，第三次添加温度为1180℃，在不同次数的添加混合料后的保温时间不同，保温时间一共为1.5-2.0小时。According to the composition weight percentage in Table 1 and mix evenly, put the glass frit into the quartz crucible, heat and melt it in the silicon carbide rod electric furnace, add the material in three times, the temperature of the first addition is 1160°C, and the temperature of the second addition is It is 1200°C, and the temperature for the third addition is 1180°C. The holding time is different after adding the mixture for different times, and the holding time is 1.5-2.0 hours in total.
热膨胀系数采用WRP-1微机热膨胀仪测量，由室温升至300℃，升温速率为5℃/min，将退火后的样品研磨成φ5×25mm规格的圆柱体试样测定；封接温度是通过半球实验得到地，测试结果见表2。The coefficient of thermal expansion is measured by a WRP-1 microcomputer thermal dilatometer, from room temperature to 300°C, the heating rate is 5°C/min, and the annealed sample is ground into a cylindrical sample of φ5×25mm for measurement; the sealing temperature is determined by The hemispheric experiment was obtained, and the test results are shown in Table 2.
熔制好的玻璃倒入压片机中压片，经过球磨机球磨成粉末状的玻璃粉，过筛后的玻璃粉经包装后供用户使用。The melted glass is poured into a tablet press to be pressed into tablets, and then it is ball-milled into powdered glass powder, and the sieved glass powder is packaged for use by users.
实施例3Example 3
按表1的组成重量百分比配料并混合均匀，将玻璃料放入石英坩埚内，在硅碳棒电炉内加热熔制，加料分三次添加，第一次添加温度为1150℃，第二次添加温度为1200℃，第三次添加温度为1180℃，在不同次数的添加混合料后的保温时间不同，保温时间一共为1.5-2.0小时。According to the composition weight percentage in Table 1 and mix evenly, put the glass frit into the quartz crucible, heat and melt it in the silicon carbon rod electric furnace, add the material in three times, the temperature of the first addition is 1150 ℃, and the temperature of the second addition is It is 1200°C, and the temperature for the third addition is 1180°C. The holding time is different after adding the mixture for different times, and the holding time is 1.5-2.0 hours in total.
热膨胀系数采用WRP-1微机热膨胀仪测量，由室温升至300℃，升温速率为5℃/min，将退火后的样品研磨成φ5×25mm规格的圆柱体试样测定；封接温度是通过半球实验得到地，测试结果见表2。The coefficient of thermal expansion is measured by a WRP-1 microcomputer thermal dilatometer, from room temperature to 300°C, the heating rate is 5°C/min, and the annealed sample is ground into a cylindrical sample of φ5×25mm for measurement; the sealing temperature is determined by The hemispheric experiment was obtained, and the test results are shown in Table 2.
熔制好的玻璃倒入压片机中压片，经过球磨机球磨成粉末状的玻璃粉，过筛后的玻璃粉经包装后供用户使用。The melted glass is poured into a tablet press to be pressed into tablets, and then it is ball-milled into powdered glass powder, and the sieved glass powder is packaged for use by users.
实施例4Example 4
按表1的组成重量百分比配料并混合均匀，将玻璃料放入石英坩埚内，在硅碳棒电炉内加热熔制，加料分三次添加，第一次添加温度为1160℃，第二次添加温度为1200℃，第三次添加温度为1170℃，在不同次数的添加混合料后的保温时间不同，保温时间一共为1.5-2.0小时。According to the composition weight percentage in Table 1 and mix evenly, put the glass frit into the quartz crucible, heat and melt it in the silicon carbide rod electric furnace, add the material in three times, the temperature of the first addition is 1160°C, and the temperature of the second addition is It is 1200°C, and the temperature for the third addition is 1170°C. The holding time is different after adding the mixture for different times, and the holding time is 1.5-2.0 hours in total.
热膨胀系数采用WRP-1微机热膨胀仪测量，由室温升至300℃，升温速率为5℃/min，将退火后的样品研磨成φ5×25mm规格的圆柱体试样测定；封接温度是通过半球实验得到地，测试结果见表2。The coefficient of thermal expansion is measured by a WRP-1 microcomputer thermal dilatometer, from room temperature to 300°C, the heating rate is 5°C/min, and the annealed sample is ground into a cylindrical sample of φ5×25mm for measurement; the sealing temperature is determined by The hemispheric experiment was obtained, and the test results are shown in Table 2.
熔制好的玻璃倒入压片机中压片，经过球磨机球磨成粉末状的玻璃粉，过筛后的玻璃粉经包装后供用户使用。The melted glass is poured into a tablet press to be pressed into tablets, and then it is ball-milled into powdered glass powder, and the sieved glass powder is packaged for use by users.
表2实施例中所制得的玻璃的性能The performance of the glass obtained in the embodiment of table 2
所述的玻璃粉在熔制的过程中对不同添加阶段的温度应严格的控制，熔制温度和保温时间对于玻璃粉烧结后的颜色及光泽度有重要的影响。The temperature of the glass powder in different addition stages should be strictly controlled during the melting process, and the melting temperature and holding time have an important influence on the color and gloss of the glass powder after sintering.
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| CN115895332B (en) * | 2022-12-29 | 2024-02-02 | 湖南松井新材料股份有限公司 | Smooth low-blackness glass high-temperature ink and preparation method and application thereof |
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