WO2012075830A1 - Method for directly preparing double-layer electrode by screen printing at one time, and slurry used therefor - Google Patents

Method for directly preparing double-layer electrode by screen printing at one time, and slurry used therefor Download PDF

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Publication number
WO2012075830A1
WO2012075830A1 PCT/CN2011/078552 CN2011078552W WO2012075830A1 WO 2012075830 A1 WO2012075830 A1 WO 2012075830A1 CN 2011078552 W CN2011078552 W CN 2011078552W WO 2012075830 A1 WO2012075830 A1 WO 2012075830A1
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Prior art keywords
temperature
glass powder
slurry
layer electrode
low
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PCT/CN2011/078552
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French (fr)
Chinese (zh)
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林保平
唐霁楠
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东南大学
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Publication of WO2012075830A1 publication Critical patent/WO2012075830A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/22—Electrodes, e.g. special shape, material or configuration
    • H01J11/24—Sustain electrodes or scan electrodes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/22—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions containing two or more distinct frits having different compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma
    • H01J11/12—AC-PDPs with at least one main electrode being out of contact with the plasma with main electrodes provided on both sides of the discharge space
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems

Definitions

  • the invention relates to a photosensitive silver paste for preparing a two-layer electrode, in particular to a slurry and a preparation method for directly preparing a double-layer electrode by using one screen printing.
  • the front substrate electrodes are two-layer electrodes, that is, a black matrix and a bus electrode.
  • Another layer of electrodes is prepared on one layer of electrodes.
  • the conventional preparation method is sputtering and evaporation, but the preparation cost is high and it is not suitable for industrial production.
  • the commonly used method is screen printing.
  • a layer of electrodes is printed first, and another layer of electrodes is printed on the original electrode after drying. Since the width of the electrode pattern is very thin, accurate alignment is required for secondary printing. Not only the equipment requirements are high, but also the yield is reduced.
  • Patent 200780015075.5 A photocurable conductive paste used in the formation of a two-layer structure bus electrode, and a photocurable black paste and a plasma display panel are proposed, and in the bus electrode of the two-layer structure, the upper layer of the conductive paste is used.
  • the glass powder was 40 ° C higher than the glass powder used in the underlying black paste.
  • this method still requires a secondary screen printing after drying the printing paste, which increases the process difficulty and equipment requirements.
  • the present invention provides a method for directly preparing a two-layer electrode by one screen printing and a slurry thereof.
  • the material has the characteristics of simple process, one screen printing, low equipment requirements and low cost.
  • the technical scheme of the present invention is: a slurry for a two-layer electrode, and the raw material of the slurry is expressed by mass percentage:
  • the organic carrier, the raw materials are in mass percentage:
  • the low-temperature black glass powder is a low-melting lead-free glass powder, and after adding black pigment, the glass liquid is poured into cold water and quenched, and ball-milled to a particle size of ⁇ 3 ⁇ m for drying.
  • the low temperature black glass powder has a melting temperature of 350 to 400 ° C, and the low melting point lead-free glass powder is represented by mass percentage, and the composition is: Bi 2 O 3 45% to 80%, SiO2 2 to 20%, B2O3 5 to 30, ZnO 2 to 15%; the black pigment is selected from any one or more of Co3O4, Fe2O3, Co2O3, Cr2O3 or MnO2, and the addition amount is 4-10% of the total weight of the low temperature black glass powder.
  • the medium temperature glass powder has a melting temperature of 450 to 500 ° C, and the composition is expressed by mass percentage:
  • the resin in the organic vehicle is methyl methacrylate-hydroxyethyl methacrylate-methacrylic acid copolymer resin, and has a weight average molecular weight of 30,000 and an acid value of 120-140.
  • the photosensitive monomer is dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxy Any one or more of the trimethylolpropane triacrylate.
  • the photoinitiator is 1-p-morpholinyl-2-methylamino-2-benzyl-1-butanone, 2-methyl-2-(4-morpholinyl)-1-[4 Any one or more of -(methylthio)phenyl]-1-propanone, ⁇ -hydroxycyclohexyl phenyl ketone or benzoin dimethyl ether.
  • the organic solvent is diethylene glycol monobutyl ether, terpineol, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate Or any one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.
  • the plasticizer is any one of lecithin, dioctyl phthalate or dibutyl phthalate, and the coupling agent is a silane coupling agent.
  • the first step is the preparation of medium-temperature lead-free glass powder: the raw materials are prepared according to the formula ratio of the medium-temperature lead-free glass powder, ground and uniformly mixed in the porcelain mortar, and placed in a high aluminum crucible, 1000 °C melting for 2 hours, melting into a glass state, pouring the glass liquid into cold water, drying the obtained glass slag in an incubator, ball milling to a particle size of ⁇ 1 ⁇ m for drying;
  • the second step is the preparation of low-temperature black glass powder: the low-melting lead-free glass powder is uniformly mixed with the black pigment, and melted at 1000 ° C for 1 hour to form a glass state. Pour the glass liquid into cold water for water quenching, ball milling to a particle size of ⁇ 3 ⁇ m, and then dry in an incubator for use;
  • the third step is to prepare an organic carrier: the resin, the organic solvent, the coupling agent and the plasticizer are weighed in the reaction kettle according to the formula. Heating and stirring until the resin is dissolved, and after cooling, filtering with a 40 mesh screen to control the viscosity of the organic carrier in the range of 100 to 300 Pa•s;
  • the sintering peak temperature is 10 to 30 ° C higher than the melting temperature of the low-temperature black glass powder, and the peak temperature of the second-stage sintering is 10 ° C to 30 ° C higher than that of the medium-temperature lead-free glass powder to obtain a double-layer electrode.
  • the present invention employs two different melting point glass powders, a low melting point black low temperature black glass powder and a transparent higher melting medium temperature unleaded glass powder.
  • Two-stage sintering is used for sintering. At the low-temperature sintering stage, the low-temperature black glass powder melts first, and flows from the gap between the silver powder and the high-melting medium-temperature lead-free glass powder to form a black layer. In the second stage sintering, the silver powder and the glass powder are melted and leveled to form an upper conductive layer.
  • the present invention can prepare a two-layer electrode under the conditions of one printing, one drying, and one sintering.
  • the process is simple and the cost is low.
  • FIG. 1 is a schematic view of a front substrate electrode in the prior art.
  • 1 is a front glass substrate
  • 2 is a black matrix
  • 3 is a bus electrode.
  • Figure 2 is a schematic view of the preparation process of the present invention.
  • a slurry for a two-layer electrode the raw material of the slurry being in mass percentage:
  • the organic carrier, the raw materials are in mass percentage:
  • the low-temperature black glass powder is a medium-temperature lead-free glass powder, and after adding black pigment, the glass liquid is poured into cold water and quenched, and ball-milled to a particle size of ⁇ 3 ⁇ m to obtain a drying result.
  • the low temperature black glass powder has a glass transition temperature of 350 to 400 ° C, and the low melting point lead-free glass powder is represented by mass percentage, and the composition is: Bi 2 O 3 45% to 80%, SiO2 2 to 20%, B2O3 5 to 30, ZnO 2 to 15%; the black pigment is selected from any one or more of Co3O4, Fe2O3, Co2O3, Cr2O3 or MnO2, and the addition amount is 4-10% of the total weight.
  • the medium temperature glass powder has a melting temperature of 450 to 500 ° C, and the composition is expressed by mass percentage:
  • the resin is methyl methacrylate-hydroxyethyl methacrylate-methacrylic acid copolymer resin, and has a weight average molecular weight of 30,000 and an acid value of 120-140.
  • the photosensitive monomer is dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxy Any one or more of the trimethylolpropane triacrylate.
  • the photoinitiator is 1-p-morpholinyl-2-methylamino-2-benzyl-1-butanone, 2-methyl-2-(4-morpholinyl)-1-[4 Any one or more of -(methylthio)phenyl]-1-propanone, ⁇ -hydroxycyclohexyl phenyl ketone or benzoin dimethyl ether.
  • the organic solvent is diethylene glycol monobutyl ether, terpineol, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate Or any one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.
  • the plasticizer is any one of lecithin, dioctyl phthalate or dibutyl phthalate, and the coupling agent is a silane coupling agent.
  • the raw materials are in terms of mass percentage: SiO2 1 to 15%, B2O3 5 to 15%, ZnO 0 to 15%, Al2O3 0 to 5%, BaO 0 ⁇ 5%, and the ratio of Bi2O3 balance is prepared.
  • ZnO, Al2O3 BaO can be added or not, and one or several can be added.
  • the low-melting lead-free glass powder is uniformly mixed with the black pigment, and melted at 1000 ° C for 1 hour to be in a glass state.
  • the glass liquid is poured into cold water and quenched, and after ball milling to a particle size of ⁇ 3 ⁇ m, the glass powder is dried in an incubator.
  • Silver powder, low temperature black glass powder, medium temperature lead-free glass powder, photosensitive monomer, photoinitiator, organic carrier After the dispersion and mixing were uniform, three-roll rolling was performed. Test the fineness and viscosity of the slurry.
  • the prepared slurry is screen-printed onto the substrate, dried, exposed, developed, and sintered.
  • the sintering peak temperature is 10 to 30 ° C higher than the melting temperature of the low-temperature black glass powder, and the peak temperature of the second-stage sintering is lower than that of the medium-temperature lead-free glass powder.
  • the temperature is 10 ° C to 30 ° C to obtain a double layer electrode.
  • Fig. 2 in the case of a calcination, the low-temperature black glass powder is first melted, and then the medium-temperature lead-free glass powder is melted in the second stage.
  • the raw materials are 65% by weight of Bi2O3, 6% by SiO2, 10% by B2O3, 15% by ZnO, BaO 2.5%, 1.5% Al2O3, ground and evenly mixed in a porcelain mortar. Put this batch into a high aluminum crucible, 1000 It was melted at °C for 2 hours and melted into a glass state. The glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 ⁇ m for drying. The melting temperature of the glass is 450 °C
  • the raw materials are 68% by weight of Bi2O3, 14% of SiO2, 12% of B2O3, ZnO 6%, ground and evenly mixed in a porcelain mortar.
  • the batch was placed in a high aluminum crucible, melted at 1000 ° C for 2 hours, and melted into a glass state.
  • the glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 ⁇ m for drying.
  • the lead-free glass powder with a weight ratio of 95% and 2% Fe2O3, 1.5% Cr2O3, 1.5% MnO2 are ground in a porcelain mortar and mixed uniformly into a high aluminum crucible, 1000 Melt at °C for 1 hour.
  • the molten glass was water-quenched, and the planetary ball mill was ball-milled to an average particle diameter of 2 ⁇ m, and then the glass frit was dried in an incubator.
  • the glass powder has a melting temperature of 350 °
  • Methyl methacrylate-hydroxyethyl methacrylate-methacrylic acid copolymer resin (weight average molecular weight 30000, acid value 130) 30%, terpineol 46.5%, diethylene glycol monobutyl ether 22% was weighed according to the ratio. , silane coupling agent 0.5%, lecithin 0.5%, dibutyl phthalate 0.5% heated to 90 in the reactor °C, keep stirring until the resin dissolves. The mixture was kept for 2 hours, cooled and filtered through a wire mesh.
  • the raw materials are 65.4% by weight of Bi2O3, 5.3% of SiO2, 14.3% of B2O3, ZnO. 12.1%, BaO 1.75%, Al2O3 1.15% Grinded and mixed evenly in a porcelain mortar. Put this batch into a high aluminum crucible, 1000 It was melted at °C for 2 hours and melted into a glass state. The glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 ⁇ m for drying. The glass has a melting temperature of 470 °C.
  • the raw materials are 73.6% by weight of Bi2O3, 6.2% by SiO2, 6.2% by B2O3, ZnO. 14%, ground and evenly mixed in a porcelain mortar.
  • the batch was placed in a high aluminum crucible, melted at 1000 ° C for 2 hours, and melted into a glass state.
  • the glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 ⁇ m for drying. Grinding and mixing the lead-free glass powder with a weight ratio of 95% and 5% Co3O4 in a porcelain mortar, and placing it in a high aluminum crucible, 1000 Melt at °C for 1 hour.
  • the molten glass was water-quenched, and the planetary ball mill was ball-milled to an average particle diameter of 2 ⁇ m, and then the glass frit was dried in an incubator.
  • the glass powder has a melting temperature of 400 °C.
  • the raw materials are 65.4% by weight of Bi2O3, 5.3% of SiO2, 14.3% of B2O3, ZnO. 13.85%, Al2O3 1.15% was ground and evenly mixed in a porcelain mortar. Put this batch into a high aluminum crucible, 1000 It was melted at °C for 2 hours and melted into a glass state. The glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 ⁇ m for drying. The glass has a melting temperature of 460 °C.
  • the raw materials are 73.5% by weight of Bi2O3, 2% by SiO2, 10.5% by B2O3, ZnO. 14%, ground and evenly mixed in a porcelain mortar.
  • the batch was placed in a high aluminum crucible, melted at 1000 ° C for 2 hours, and melted into a glass state.
  • the glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 ⁇ m for drying.
  • the lead-free glass powder with a weight ratio of 95% and 3.5% Co3O4, 1.5% MnO2 were ground in a porcelain mortar and mixed uniformly into a high aluminum crucible, 1000 Melt at °C for 1 hour.
  • the molten glass was water-quenched, and the planetary ball mill was ball-milled to an average particle diameter of 2 ⁇ m, and then the glass frit was dried in an incubator.
  • the glass powder has a melting temperature of 380 °C.

Abstract

A method for directly preparing a double-layer electrode by screen printing at one time, and a slurry used therefor. The slurry comprises a low-temperature black glass powder, a medium-temperature lead-free glass powder, a photo-sensitive monomer, a photo initiator, an organic carrier, and the rest of silver powder. The raw material of the organic carrier comprises a plasticizer, a coupling agent, a resin, and the rest of an organic solvent. The low-temperature black glass powder is obtained by adding a black pigment to a low-temperature lead-free glass powder, melting, quenching by pouring the liquid glass into water, ball milling to a particle diameter of equal to or less than 3 μm, and drying. The components are dispersed and mixed uniformly, and subjected to three-roll rolling. The fineness and viscosity of the slurry are measured. The prepared slurry is coated on a substrate by screen printing, drying, exposed, developed, and sintered, to obtain a double-layer electrode, wherein a peak temperature in a first stage of sintering is higher than a melting temperature of the low-temperature black glass powder, and a peak temperature in a second stage of sintering is higher than a melting temperature of the medium-temperature lead-free glass powder. Therefore, a double-layer electrode pattern can be obtained by screen printing at one time, exposure, development, two stages of sintering, and drying.

Description

一次丝网印刷直接制备双层电极的方法及其所用浆料  Method for directly preparing two-layer electrode by screen printing and slurry used therefor 技术领域Technical field
本发明涉及一种制备双层电极的感光性银浆料，特别涉及一种可以采用一次丝网印刷直接制备双层电极的浆料及制备方法。 The invention relates to a photosensitive silver paste for preparing a two-layer electrode, in particular to a slurry and a preparation method for directly preparing a double-layer electrode by using one screen printing.
背景技术Background technique
在等离子显示器制备过程中，前基板电极为双层电极，即黑色矩阵和汇流电极。In the plasma display preparation process, the front substrate electrodes are two-layer electrodes, that is, a black matrix and a bus electrode.
在一层电极上制备另一层电极，通常传统的制备方法为溅射，蒸镀，但制备成本高，不合适工业生产。目前常使用的方法为丝网印刷法，一般是先印刷一层电极，烘干后再在原电极的上面印刷另一层电极，由于电极图形宽度很细，所以二次印刷的时候需要精确对位，不仅对设备要求高，而且成品率降低。Another layer of electrodes is prepared on one layer of electrodes. Usually, the conventional preparation method is sputtering and evaporation, but the preparation cost is high and it is not suitable for industrial production. At present, the commonly used method is screen printing. Generally, a layer of electrodes is printed first, and another layer of electrodes is printed on the original electrode after drying. Since the width of the electrode pattern is very thin, accurate alignment is required for secondary printing. Not only the equipment requirements are high, but also the yield is reduced.
专利200780015075.5在二层结构汇流电极形成中使用的光固化性导电性糊剂、以及光固化性黑色糊剂和等离子体显示器面板，提出在二层结构的汇流电极中，上层的导电性糊剂使用的玻璃粉末比下层的黑色糊剂使用的玻璃粉末高40℃。但是这种方法仍然需要一次印刷浆料烘干后进行二次丝网印刷，增加了工艺难度和设备要求。Patent 200780015075.5 A photocurable conductive paste used in the formation of a two-layer structure bus electrode, and a photocurable black paste and a plasma display panel are proposed, and in the bus electrode of the two-layer structure, the upper layer of the conductive paste is used. The glass powder was 40 ° C higher than the glass powder used in the underlying black paste. However, this method still requires a secondary screen printing after drying the printing paste, which increases the process difficulty and equipment requirements.
技术问题technical problem
为了解决现有技术中存在的工艺复杂，需要一次丝网印刷烘干后再进行二次丝网印刷的问题，本发明提供了一种一次丝网印刷直接制备双层电极的方法及其所用浆料，具有工艺简单，一次丝网印刷即可，设备要求低，降低成本等特点。In order to solve the complexity of the process existing in the prior art, the problem of secondary screen printing after screen printing and drying is required, and the present invention provides a method for directly preparing a two-layer electrode by one screen printing and a slurry thereof. The material has the characteristics of simple process, one screen printing, low equipment requirements and low cost.
技术解决方案Technical solution
本发明的技术方案为：一种双层电极所用的浆料，所述浆料的原料以质量百分比计为：The technical scheme of the present invention is: a slurry for a two-layer electrode, and the raw material of the slurry is expressed by mass percentage:
低温黑玻璃粉 3～15%，Low temperature black glass powder 3~15%,
中温无铅玻璃粉 1～5%，Medium temperature lead-free glass powder 1 to 5%,
光敏单体 4～15%，Photosensitive monomer 4 to 15%,
光引发剂 2～7%， Photoinitiator 2 to 7%,
有机载体 15~40%，Organic carrier 15~40%,
银粉 余量；Silver powder
所述的有机载体，原料以质量百分比计为：The organic carrier, the raw materials are in mass percentage:
增塑剂 0.1～1%，Plasticizer 0.1~1%,
偶联剂 0.1～3%，Coupling agent 0.1 to 3%,
树脂 5～30%，Resin 5 to 30%,
有机溶剂 余量；Organic solvent balance;
所述的低温黑玻璃粉为低熔点无铅玻璃粉加入黑色颜料后熔融后将玻璃液倒入冷水中水淬，球磨至粒径≤3μm烘干得到。The low-temperature black glass powder is a low-melting lead-free glass powder, and after adding black pigment, the glass liquid is poured into cold water and quenched, and ball-milled to a particle size of ≤3 μm for drying.
所述的低温黑玻璃粉熔融温度为350～400 ℃，低熔点无铅玻璃粉以质量百分比计，组成为：Bi2O3 45％～80％，SiO2 2～20％，B2O3 5～30，ZnO 2～15％；所述的黑色颜料选自Co3O4、Fe2O3、Co2O3、Cr2O3或MnO2中的任意一种或几种，添加量占低温黑玻璃粉的总重量的4~10%。The low temperature black glass powder has a melting temperature of 350 to 400 ° C, and the low melting point lead-free glass powder is represented by mass percentage, and the composition is: Bi 2 O 3 45% to 80%, SiO2 2 to 20%, B2O3 5 to 30, ZnO 2 to 15%; the black pigment is selected from any one or more of Co3O4, Fe2O3, Co2O3, Cr2O3 or MnO2, and the addition amount is 4-10% of the total weight of the low temperature black glass powder.
所述的中温玻璃粉的熔融温度为450~500℃，组成以质量百分比计为：The medium temperature glass powder has a melting temperature of 450 to 500 ° C, and the composition is expressed by mass percentage:
SiO2 1～15％，SiO2 1 to 15%,
B2O3 5～15％，B2O3 5~15%,
ZnO 0～15％，ZnO 0 to 15%,
Al2O3 0～5％，Al2O3 0 to 5%,
BaO 0~5%，BaO 0~5%,
Bi2O3 余量。Bi2O3 balance.
所述的有机载体中树脂为甲基丙烯酸甲酯-甲基丙烯酸羟乙酯-甲基丙烯酸共聚树脂，重均分子量30000，酸值120—140。The resin in the organic vehicle is methyl methacrylate-hydroxyethyl methacrylate-methacrylic acid copolymer resin, and has a weight average molecular weight of 30,000 and an acid value of 120-140.
所述的光敏单体为双季戊四醇五丙烯酸酯、双季戊四醇六丙烯酸酯、1,6-己二醇二丙烯酸酯、季戊四醇三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、丙氧基化三羟甲基丙烷三丙烯酸酯中的任意一种或几种。The photosensitive monomer is dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxy Any one or more of the trimethylolpropane triacrylate.
所述的光引发剂为1－对吗啉苯基－2－二甲氨基－2－苄基－1－丁酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、α－羟基环己基苯基酮或安息香二甲醚中的任意一种或几种。The photoinitiator is 1-p-morpholinyl-2-methylamino-2-benzyl-1-butanone, 2-methyl-2-(4-morpholinyl)-1-[4 Any one or more of -(methylthio)phenyl]-1-propanone, α-hydroxycyclohexyl phenyl ketone or benzoin dimethyl ether.
所述的有机溶剂为二乙二醇单丁醚、松油醇、二乙二醇单丁醚醋酸酯、2,2,4-三甲基-1,3-戊二醇单异丁酸酯或2,2,4-三甲基-1,3-戊二醇双异丁酸酯中的任意一种或几种。The organic solvent is diethylene glycol monobutyl ether, terpineol, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate Or any one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.
所述的增塑剂为卵磷脂、邻苯二甲酸二辛酯或邻苯二甲酸二丁酯中的任意一种，所述的偶联剂为硅烷偶联剂。The plasticizer is any one of lecithin, dioctyl phthalate or dibutyl phthalate, and the coupling agent is a silane coupling agent.
使用所述的双层电极所用的浆料一次丝网印刷直接制备双层电极的方法，步骤为：A method for directly preparing a two-layer electrode by using one-time screen printing of the slurry used for the two-layer electrode, the steps are as follows:
第一步，中温无铅玻璃粉制备：将原料按中温无铅玻璃粉的配方比例配制好，在瓷质研钵中研磨、混合均匀，放入高铝坩埚，1000 ℃熔制2小时，熔成玻璃态，将玻璃液倒入冷水中，在恒温箱中将得到的玻璃渣烘干，球磨至粒径≤1μm烘干备用；The first step is the preparation of medium-temperature lead-free glass powder: the raw materials are prepared according to the formula ratio of the medium-temperature lead-free glass powder, ground and uniformly mixed in the porcelain mortar, and placed in a high aluminum crucible, 1000 °C melting for 2 hours, melting into a glass state, pouring the glass liquid into cold water, drying the obtained glass slag in an incubator, ball milling to a particle size of ≤ 1 μm for drying;
第二步，低温黑玻璃粉制备：将低熔点无铅玻璃粉与黑色颜料混合均匀，1000℃熔制1小时熔成玻璃态。将玻璃液倒入冷水中水淬，球磨至粒径≤3μm后，在恒温箱中烘干备用；The second step is the preparation of low-temperature black glass powder: the low-melting lead-free glass powder is uniformly mixed with the black pigment, and melted at 1000 ° C for 1 hour to form a glass state. Pour the glass liquid into cold water for water quenching, ball milling to a particle size of ≤ 3 μm, and then dry in an incubator for use;
第三步，制备有机载体：按配方称取树脂、有机溶剂、偶联剂、增塑剂于反应釜中, 加热并搅拌，直到树脂溶解，冷却后用40目丝网过滤，使有机载体的粘度控制在100～300 Pa•s范围内；The third step is to prepare an organic carrier: the resin, the organic solvent, the coupling agent and the plasticizer are weighed in the reaction kettle according to the formula. Heating and stirring until the resin is dissolved, and after cooling, filtering with a 40 mesh screen to control the viscosity of the organic carrier in the range of 100 to 300 Pa•s;
第四步，浆料调制：将银粉、低温黑玻璃粉、中温无铅玻璃粉、光敏单体、光引发剂和有机载体分散混合均匀后，进行三辊轧制，测试浆料细度≤4μm，粘度200+10 Pa•s后，将制得的浆料用丝网印刷法均匀涂到玻璃基板上，干燥后用紫外光曝光，用0.2~0.4%wt的Na2CO3水溶液显影，清洗、干燥、烧结，烧结时一段烧结峰值温度比低温黑玻璃粉熔融温度高10～30℃，二段烧结峰值温度比中温无铅玻璃粉熔融高10℃～30℃，得到双层电极。The fourth step, slurry preparation: silver powder, low temperature black glass powder, medium temperature lead-free glass powder, photosensitive monomer, photoinitiator and organic carrier are dispersed and uniformly mixed, and then subjected to three-roll rolling, the test slurry fineness ≤ 4 μm , viscosity 200+10 After Pa•s, the prepared slurry is uniformly applied to the glass substrate by screen printing, dried and exposed to ultraviolet light, developed with 0.2~0.4%wt of Na2CO3 aqueous solution, washed, dried, sintered, and sintered. The sintering peak temperature is 10 to 30 ° C higher than the melting temperature of the low-temperature black glass powder, and the peak temperature of the second-stage sintering is 10 ° C to 30 ° C higher than that of the medium-temperature lead-free glass powder to obtain a double-layer electrode.
有益效果Beneficial effect
1、本发明采用两种不同熔点的玻璃粉，低熔点的黑色的低温黑玻璃粉和透明的较高熔点的中温无铅玻璃粉。烧结时采用两段式烧结，在低温烧结阶段低温黑玻璃粉先融化，从银粉和高熔点的中温无铅玻璃粉的缝隙间流到基板上形成黑色层。在二段烧结时，银粉与玻璃粉熔融，流平，形成上层导电层。1. The present invention employs two different melting point glass powders, a low melting point black low temperature black glass powder and a transparent higher melting medium temperature unleaded glass powder. Two-stage sintering is used for sintering. At the low-temperature sintering stage, the low-temperature black glass powder melts first, and flows from the gap between the silver powder and the high-melting medium-temperature lead-free glass powder to form a black layer. In the second stage sintering, the silver powder and the glass powder are melted and leveled to form an upper conductive layer.
2、本发明可以在一次印刷，一次烘干，一次烧结的条件下制备出双层电极。工艺简单，成本低。2. The present invention can prepare a two-layer electrode under the conditions of one printing, one drying, and one sintering. The process is simple and the cost is low.
附图说明DRAWINGS
图1为现有技术中的前基板电极示意图。1 is a schematic view of a front substrate electrode in the prior art.
其中，1为前玻璃基板，2为黑色矩阵，3为汇流电极。Among them, 1 is a front glass substrate, 2 is a black matrix, and 3 is a bus electrode.
图2为本发明的制备方法示意图。Figure 2 is a schematic view of the preparation process of the present invention.
本发明的实施方式Embodiments of the invention
一种双层电极所用的浆料，所述浆料的原料以质量百分比计为：A slurry for a two-layer electrode, the raw material of the slurry being in mass percentage:
低温黑玻璃粉 3～15%，Low temperature black glass powder 3~15%,
中温无铅玻璃粉 1～5%，Medium temperature lead-free glass powder 1 to 5%,
光敏单体 4～15%，Photosensitive monomer 4 to 15%,
光引发剂 2～7%， Photoinitiator 2 to 7%,
有机载体 15~40%，Organic carrier 15~40%,
银粉 余量；Silver powder
所述的有机载体，原料以质量百分比计为：The organic carrier, the raw materials are in mass percentage:
增塑剂 0.1～1%，Plasticizer 0.1~1%,
偶联剂 0.1～3%，Coupling agent 0.1 to 3%,
树脂 5～30%，Resin 5 to 30%,
有机溶剂 余量，Organic solvent balance,
所述的低温黑玻璃粉为中温无铅玻璃粉加入黑色颜料后熔融后将玻璃液倒入冷水中水淬，球磨至粒径≤3μm烘干得到。The low-temperature black glass powder is a medium-temperature lead-free glass powder, and after adding black pigment, the glass liquid is poured into cold water and quenched, and ball-milled to a particle size of ≤3 μm to obtain a drying result.
所述的低温黑玻璃粉玻璃化温度为350～400℃，低熔点无铅玻璃粉以质量百分比计，组成为：Bi2O3 45％～80％，SiO2 2～20％，B2O3 5～30，ZnO 2～15％；所述的黑色颜料选自Co3O4、Fe2O3、Co2O3、Cr2O3或MnO2中的任意一种或几种，添加量占总重量的4~10%。The low temperature black glass powder has a glass transition temperature of 350 to 400 ° C, and the low melting point lead-free glass powder is represented by mass percentage, and the composition is: Bi 2 O 3 45% to 80%, SiO2 2 to 20%, B2O3 5 to 30, ZnO 2 to 15%; the black pigment is selected from any one or more of Co3O4, Fe2O3, Co2O3, Cr2O3 or MnO2, and the addition amount is 4-10% of the total weight.
所述的中温玻璃粉的熔融温度为450~500℃，组成以质量百分比计为：The medium temperature glass powder has a melting temperature of 450 to 500 ° C, and the composition is expressed by mass percentage:
SiO2 1～15％，SiO2 1 to 15%,
B2O3 5～15％，B2O3 5~15%,
ZnO 0～15％，ZnO 0 to 15%,
Al2O3 0～5％，Al2O3 0 to 5%,
BaO 0~5%，BaO 0~5%,
Bi2O3 余量。Bi2O3 balance.
所述的树脂为甲基丙烯酸甲酯-甲基丙烯酸羟乙酯-甲基丙烯酸共聚树脂，重均分子量30000，酸值120—140。The resin is methyl methacrylate-hydroxyethyl methacrylate-methacrylic acid copolymer resin, and has a weight average molecular weight of 30,000 and an acid value of 120-140.
所述的光敏单体为双季戊四醇五丙烯酸酯、双季戊四醇六丙烯酸酯、1,6-己二醇二丙烯酸酯、季戊四醇三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、丙氧基化三羟甲基丙烷三丙烯酸酯中的任意一种或几种。The photosensitive monomer is dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxy Any one or more of the trimethylolpropane triacrylate.
所述的光引发剂为1－对吗啉苯基－2－二甲氨基－2－苄基－1－丁酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、α－羟基环己基苯基酮或安息香二甲醚中的任意一种或几种。The photoinitiator is 1-p-morpholinyl-2-methylamino-2-benzyl-1-butanone, 2-methyl-2-(4-morpholinyl)-1-[4 Any one or more of -(methylthio)phenyl]-1-propanone, α-hydroxycyclohexyl phenyl ketone or benzoin dimethyl ether.
所述的有机溶剂为二乙二醇单丁醚、松油醇、二乙二醇单丁醚醋酸酯、2,2,4-三甲基-1,3-戊二醇单异丁酸酯或2,2,4-三甲基-1,3-戊二醇双异丁酸酯中的任意一种或几种。The organic solvent is diethylene glycol monobutyl ether, terpineol, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate Or any one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.
所述的增塑剂为卵磷脂、邻苯二甲酸二辛酯或邻苯二甲酸二丁酯中的任意一种，所述的偶联剂为硅烷偶联剂。The plasticizer is any one of lecithin, dioctyl phthalate or dibutyl phthalate, and the coupling agent is a silane coupling agent.
中温无铅玻璃粉制备：Medium temperature lead-free glass powder preparation:
将原料按质量百分比计： SiO2 1～15％，B2O3 5～15％，ZnO 0～15％，Al2O3 0～5％，BaO 0~5% ，Bi2O3 余量的比例配制。ZnO、Al2O3 、BaO可以加也可以不加，可以加一种或是几种都可以。在瓷质研钵中研磨、混合均匀。将此配合料放入高铝坩埚，1000 ℃熔制2小时，熔成玻璃态。将玻璃液倒入冷水中，在恒温箱中将玻璃渣烘干，行星式球磨机球磨至粒径≤1μm烘干备用。熔融温度为450~500℃。The raw materials are in terms of mass percentage: SiO2 1 to 15%, B2O3 5 to 15%, ZnO 0 to 15%, Al2O3 0 to 5%, BaO 0~5%, and the ratio of Bi2O3 balance is prepared. ZnO, Al2O3 BaO can be added or not, and one or several can be added. Grind and mix evenly in a porcelain mortar. Put this batch into a high aluminum crucible, 1000 It was melted at °C for 2 hours and melted into a glass state. The glass liquid is poured into cold water, the glass slag is dried in an incubator, and the planetary ball mill is ball-milled to a particle size of ≤ 1 μm for drying. The melting temperature is 450 to 500 °C.
低温黑玻璃粉制备：Low temperature black glass powder preparation:
将低熔点无铅玻璃粉与黑色颜料混合均匀，，1000℃熔制1小时熔成玻璃态。将玻璃液倒入冷水中水淬，球磨至粒径≤3μm要求后，在恒温箱中将玻璃粉烘干。The low-melting lead-free glass powder is uniformly mixed with the black pigment, and melted at 1000 ° C for 1 hour to be in a glass state. The glass liquid is poured into cold water and quenched, and after ball milling to a particle size of ≤ 3 μm, the glass powder is dried in an incubator.
制备有机载体：Preparation of organic carriers:
按配比称取树脂、有机溶剂、偶联剂、增塑剂于反应釜中, 加热至70 ℃，不断搅拌，直到树脂溶解。冷却后用40目的丝网过滤。使有机载体的粘度控制在100～300 Pa•s范围内。Weigh the resin, organic solvent, coupling agent and plasticizer in the reaction kettle according to the ratio and heat to 70 °C, keep stirring until the resin dissolves. After cooling, it was filtered through a 40 mesh screen. The viscosity of the organic vehicle is controlled to be in the range of 100 to 300 Pa•s.
浆料调制：Slurry modulation:
将银粉、低温黑玻璃粉、中温无铅玻璃粉、光敏单体、光引发剂、有机载体, 分散混合均匀后，进行三辊轧制。测试浆料细度，粘度。将制得的浆料丝网印刷到基板上，干燥，曝光，显影，烧结时一段烧结峰值温度比低温黑玻璃粉熔融温度高10～30℃，二段烧结峰值温度比中温无铅玻璃粉熔融高10℃～30℃，得到双层电极。如图2所示，这样在一段煅烧时，低温黑玻璃粉先熔融，然后二段时中温无铅玻璃粉才会熔融。Silver powder, low temperature black glass powder, medium temperature lead-free glass powder, photosensitive monomer, photoinitiator, organic carrier, After the dispersion and mixing were uniform, three-roll rolling was performed. Test the fineness and viscosity of the slurry. The prepared slurry is screen-printed onto the substrate, dried, exposed, developed, and sintered. The sintering peak temperature is 10 to 30 ° C higher than the melting temperature of the low-temperature black glass powder, and the peak temperature of the second-stage sintering is lower than that of the medium-temperature lead-free glass powder. The temperature is 10 ° C to 30 ° C to obtain a double layer electrode. As shown in Fig. 2, in the case of a calcination, the low-temperature black glass powder is first melted, and then the medium-temperature lead-free glass powder is melted in the second stage.
实施例1Example 1
中温玻璃粉制备：Medium temperature glass powder preparation:
将原料按重量比Bi2O3 65%，SiO2 6%，B2O3 10%，ZnO 15%，BaO 2.5%，Al2O3 1.5%，在瓷质研钵中研磨、混合均匀。将此配合料放入高铝坩埚，1000 ℃熔制2小时，熔成玻璃态。将玻璃液倒入冷水中，在恒温箱中将玻璃渣烘干，行星式球磨机球磨至粒径为1μm左右烘干备用。玻璃的熔融温度为450 ℃The raw materials are 65% by weight of Bi2O3, 6% by SiO2, 10% by B2O3, 15% by ZnO, BaO 2.5%, 1.5% Al2O3, ground and evenly mixed in a porcelain mortar. Put this batch into a high aluminum crucible, 1000 It was melted at °C for 2 hours and melted into a glass state. The glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 μm for drying. The melting temperature of the glass is 450 °C
低温黑玻璃粉制备：Low temperature black glass powder preparation:
将原料按重量比Bi2O3 68%，SiO2 14%，B2O3 12%，ZnO 6%，在瓷质研钵中研磨、混合均匀。将此配合料放入高铝坩埚，1000℃熔制2小时，熔成玻璃态。将玻璃液倒入冷水中，在恒温箱中将玻璃渣烘干，行星式球磨机球磨至粒径为1μm左右烘干备用。将重量比为95%的无铅玻璃粉与2%Fe2O3，1.5%Cr2O3，1.5%MnO2在瓷质研钵中研磨、混合均匀放入高铝坩埚，1000 ℃熔制1小时。将玻璃液水淬，行星式球磨机球磨至平均粒径为2 μm后，在恒温箱中将玻璃粉烘干。玻璃粉的熔融温度为350 ℃。The raw materials are 68% by weight of Bi2O3, 14% of SiO2, 12% of B2O3, ZnO 6%, ground and evenly mixed in a porcelain mortar. The batch was placed in a high aluminum crucible, melted at 1000 ° C for 2 hours, and melted into a glass state. The glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 μm for drying. The lead-free glass powder with a weight ratio of 95% and 2% Fe2O3, 1.5% Cr2O3, 1.5% MnO2 are ground in a porcelain mortar and mixed uniformly into a high aluminum crucible, 1000 Melt at °C for 1 hour. The molten glass was water-quenched, and the planetary ball mill was ball-milled to an average particle diameter of 2 μm, and then the glass frit was dried in an incubator. The glass powder has a melting temperature of 350 °C.
有机载体制备：Preparation of organic carrier:
按配比称取甲基丙烯酸甲酯-甲基丙烯酸羟乙酯-甲基丙烯酸共聚树脂（重均分子量30000，酸值130）30%，松油醇46.5%，二乙二醇单丁醚22%，硅烷偶联剂0.5%，卵磷脂0.5%，邻苯二甲酸二丁酯0.5%于反应釜中加热至90 ℃，不断搅拌,直到树脂溶解。保温2小时，冷却后用丝网过滤。Methyl methacrylate-hydroxyethyl methacrylate-methacrylic acid copolymer resin (weight average molecular weight 30000, acid value 130) 30%, terpineol 46.5%, diethylene glycol monobutyl ether 22% was weighed according to the ratio. , silane coupling agent 0.5%, lecithin 0.5%, dibutyl phthalate 0.5% heated to 90 in the reactor °C, keep stirring until the resin dissolves. The mixture was kept for 2 hours, cooled and filtered through a wire mesh.
感光性银浆料的调制：Modulation of photosensitive silver paste:
将中温无铅玻璃粉2.5%，低温黑玻璃粉6.5%，银粉61%，乙氧基化三羟甲基丙烷三丙烯酸酯5%，1-对甲硫基苯基-2-甲基-2-吗啉基-1-丙酮2.0%，有机载体23%置于容器中，分散混合均匀后，进行三辊轧制。测试浆料细度≤4μm，粘度200+10 Pa•s。制得的浆料用丝网印刷法均匀涂在玻璃基板上，干燥后用波长为365nm紫外光曝光，用0.2%～0.4%的Na2CO3水溶液显影、清洗、干燥、烧结。一段烧结温度峰值370℃，保温10分钟；二段烧结温度470℃，保温20分钟，得到双层电极。Medium temperature lead-free glass powder 2.5%, low temperature black glass powder 6.5%, silver powder 61%, ethoxylated trimethylolpropane triacrylate 5%, 1-p-methylthiophenyl-2-methyl-2 - Morpholinyl-1-propanone 2.0%, organic carrier 23% was placed in a container, dispersed and uniformly mixed, and then subjected to three-roll rolling. Test slurry fineness ≤ 4μm, viscosity 200+10 Pa•s. The obtained slurry was uniformly coated on a glass substrate by screen printing, dried, exposed to ultraviolet light having a wavelength of 365 nm, developed with 0.2% to 0.4% aqueous Na2CO3 solution, washed, dried, and sintered. A sintering temperature peaked at 370 ° C for 10 minutes; the second sintering temperature was 470 ° C, and the temperature was kept for 20 minutes to obtain a double-layer electrode.
实施例2Example 2
中温玻璃粉制备：Medium temperature glass powder preparation:
将原料按重量比Bi2O3 65.4%，SiO2 5.3%，B2O3 14.3%，ZnO 12.1%，BaO 1.75%，Al2O3 1.15%在瓷质研钵中研磨、混合均匀。将此配合料放入高铝坩埚，1000 ℃熔制2小时，熔成玻璃态。将玻璃液倒入冷水中，在恒温箱中将玻璃渣烘干，行星式球磨机球磨至粒径为1μm左右烘干备用。玻璃的熔融温度为470 ℃。 The raw materials are 65.4% by weight of Bi2O3, 5.3% of SiO2, 14.3% of B2O3, ZnO. 12.1%, BaO 1.75%, Al2O3 1.15% Grinded and mixed evenly in a porcelain mortar. Put this batch into a high aluminum crucible, 1000 It was melted at °C for 2 hours and melted into a glass state. The glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 μm for drying. The glass has a melting temperature of 470 °C.
低温黑玻璃粉制备：Low temperature black glass powder preparation:
按实施例1制备。Prepared as in Example 1.
制备有机载体：Preparation of organic carriers:
按实施例1制备。 Prepared as in Example 1.
感光性银浆料的调制：Modulation of photosensitive silver paste:
将中温无铅玻璃粉4.0%，低温黑玻璃粉10%，银粉56.0%，乙氧基化三羟甲基丙烷三丙烯酸酯5%，1-对甲硫基苯基-2-甲基-2-吗啉基-1-丙酮2.0%，有机载体23%置于容器中，分散混合均匀后，进行三辊轧制。测试浆料细度≤4μm，粘度200+10 Pa•s。制得的浆料用丝网印刷法均匀涂在玻璃基板上，干燥后用波长为365nm紫外光曝光，用0.2%～0.4%的Na2CO3水溶液显影、清洗、干燥、烧结。一段烧结温度峰值350℃，保温10分钟；二段烧结温度490℃，保温20分钟，得到双层电极。Medium temperature lead-free glass powder 4.0%, low temperature black glass powder 10%, silver powder 56.0%, ethoxylated trimethylolpropane triacrylate 5%, 1-p-methylthiophenyl-2-methyl-2 - Morpholinyl-1-propanone 2.0%, organic carrier 23% was placed in a container, dispersed and uniformly mixed, and then subjected to three-roll rolling. Test slurry fineness ≤ 4μm, viscosity 200+10 Pa•s. The obtained slurry was uniformly coated on a glass substrate by screen printing, dried, exposed to ultraviolet light having a wavelength of 365 nm, developed with 0.2% to 0.4% aqueous Na2CO3 solution, washed, dried, and sintered. A sintering temperature peak of 350 ° C, holding for 10 minutes; two sintering temperature of 490 ° C, holding for 20 minutes, to obtain a two-layer electrode.
实施例3Example 3
中温玻璃粉制备：Medium temperature glass powder preparation:
按实施例1制备。 Prepared as in Example 1.
低温黑玻璃粉制备：Low temperature black glass powder preparation:
将原料按重量比Bi2O3 73.6%，SiO2 6.2%，B2O3 6.2%，ZnO 14%，在瓷质研钵中研磨、混合均匀。将此配合料放入高铝坩埚，1000℃熔制2小时，熔成玻璃态。将玻璃液倒入冷水中，在恒温箱中将玻璃渣烘干，行星式球磨机球磨至粒径为1μm左右烘干备用。将重量比为95%的无铅玻璃粉与5%Co3O4在瓷质研钵中研磨、混合均匀放入高铝坩埚，1000 ℃熔制1小时。将玻璃液水淬，行星式球磨机球磨至平均粒径为2 μm后，在恒温箱中将玻璃粉烘干。玻璃粉的熔融温度为400 ℃。The raw materials are 73.6% by weight of Bi2O3, 6.2% by SiO2, 6.2% by B2O3, ZnO. 14%, ground and evenly mixed in a porcelain mortar. The batch was placed in a high aluminum crucible, melted at 1000 ° C for 2 hours, and melted into a glass state. The glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 μm for drying. Grinding and mixing the lead-free glass powder with a weight ratio of 95% and 5% Co3O4 in a porcelain mortar, and placing it in a high aluminum crucible, 1000 Melt at °C for 1 hour. The molten glass was water-quenched, and the planetary ball mill was ball-milled to an average particle diameter of 2 μm, and then the glass frit was dried in an incubator. The glass powder has a melting temperature of 400 °C.
制备有机载体：Preparation of organic carriers:
按实施例1制备。 Prepared as in Example 1.
感光性银浆料的调制：Modulation of photosensitive silver paste:
将中温无铅玻璃粉3.5%，低温黑色玻璃粉8.5%，银粉58%，乙氧基化三羟甲基丙烷三丙烯酸酯5%，1-对甲硫基苯基-2-甲基-2-吗啉基-1-丙酮2.0%，有机载体23%置于容器中，分散混合均匀后，进行三辊轧制。测试浆料细度≤4μm，粘度200+10 Pa•s。制得的浆料用丝网印刷法均匀涂在玻璃基板上，干燥后用波长为365nm紫外光曝光，用0.2%～0.4%的Na2CO3水溶液显影、清洗、干燥、烧结。一段烧结温度峰值420 ℃，保温10分钟；二段烧结温度470℃，保温20分钟，得到双层电极。Medium temperature lead-free glass powder 3.5%, low temperature black glass powder 8.5%, silver powder 58%, ethoxylated trimethylolpropane triacrylate 5%, 1-p-methylthiophenyl-2-methyl-2 - Morpholinyl-1-propanone 2.0%, organic carrier 23% was placed in a container, dispersed and uniformly mixed, and then subjected to three-roll rolling. Test slurry fineness ≤ 4μm, viscosity 200+10 Pa•s. The obtained slurry was uniformly coated on a glass substrate by screen printing, dried, exposed to ultraviolet light having a wavelength of 365 nm, developed with 0.2% to 0.4% aqueous Na2CO3 solution, washed, dried, and sintered. a section of sintering temperature peak 420 °C, heat preservation for 10 minutes; two-stage sintering temperature of 470 ° C, and keep warm for 20 minutes to obtain a double-layer electrode.
实施例4Example 4
中温玻璃粉制备：Medium temperature glass powder preparation:
将原料按重量比Bi2O3 65.4%，SiO2 5.3%，B2O3 14.3%，ZnO 13.85%，Al2O3 1.15%在瓷质研钵中研磨、混合均匀。将此配合料放入高铝坩埚，1000 ℃熔制2小时，熔成玻璃态。将玻璃液倒入冷水中，在恒温箱中将玻璃渣烘干，行星式球磨机球磨至粒径为1μm左右烘干备用。玻璃的熔融温度为460 ℃。 The raw materials are 65.4% by weight of Bi2O3, 5.3% of SiO2, 14.3% of B2O3, ZnO. 13.85%, Al2O3 1.15% was ground and evenly mixed in a porcelain mortar. Put this batch into a high aluminum crucible, 1000 It was melted at °C for 2 hours and melted into a glass state. The glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 μm for drying. The glass has a melting temperature of 460 °C.
低温黑玻璃粉制备：Low temperature black glass powder preparation:
将原料按重量比Bi2O3 73.5%，SiO2 2%，B2O3 10.5%，ZnO 14%，在瓷质研钵中研磨、混合均匀。将此配合料放入高铝坩埚，1000℃熔制2小时，熔成玻璃态。将玻璃液倒入冷水中，在恒温箱中将玻璃渣烘干，行星式球磨机球磨至粒径为1μm左右烘干备用。将重量比为95%的无铅玻璃粉与3.5%Co3O4，1.5%MnO2在瓷质研钵中研磨、混合均匀放入高铝坩埚，1000 ℃熔制1小时。将玻璃液水淬，行星式球磨机球磨至平均粒径为2 μm后，在恒温箱中将玻璃粉烘干。玻璃粉的熔融温度为380 ℃。The raw materials are 73.5% by weight of Bi2O3, 2% by SiO2, 10.5% by B2O3, ZnO. 14%, ground and evenly mixed in a porcelain mortar. The batch was placed in a high aluminum crucible, melted at 1000 ° C for 2 hours, and melted into a glass state. The glass liquid was poured into cold water, the glass slag was dried in an incubator, and the planetary ball mill was ball milled to a particle size of about 1 μm for drying. The lead-free glass powder with a weight ratio of 95% and 3.5% Co3O4, 1.5% MnO2 were ground in a porcelain mortar and mixed uniformly into a high aluminum crucible, 1000 Melt at °C for 1 hour. The molten glass was water-quenched, and the planetary ball mill was ball-milled to an average particle diameter of 2 μm, and then the glass frit was dried in an incubator. The glass powder has a melting temperature of 380 °C.
制备有机载体：Preparation of organic carriers:
按实施例1制备。 Prepared as in Example 1.
感光性银浆料的调制：Modulation of photosensitive silver paste:
将中温无铅玻璃粉3.5%，低温黑色玻璃粉8.5%，银粉58%，乙氧基化三羟甲基丙烷三丙烯酸酯5%，1-对甲硫基苯基-2-甲基-2-吗啉基-1-丙酮2.0%，有机载体23%置于容器中，分散混合均匀后，进行三辊轧制。测试浆料细度≤4μm，粘度200+10 Pa•s。制得的浆料用丝网印刷法均匀涂在玻璃基板上，干燥后用波长为365nm紫外光曝光，用0.2%～0.4%的Na2CO3水溶液显影、清洗、干燥、烧结。一段烧结温度峰值400 ℃，保温10分钟；二段烧结温度480℃，保温20分钟，得到双层电极。Medium temperature lead-free glass powder 3.5%, low temperature black glass powder 8.5%, silver powder 58%, ethoxylated trimethylolpropane triacrylate 5%, 1-p-methylthiophenyl-2-methyl-2 - Morpholinyl-1-propanone 2.0%, organic carrier 23% was placed in a container, dispersed and uniformly mixed, and then subjected to three-roll rolling. Test slurry fineness ≤ 4μm, viscosity 200+10 Pa•s. The obtained slurry was uniformly coated on a glass substrate by screen printing, dried, exposed to ultraviolet light having a wavelength of 365 nm, developed with 0.2% to 0.4% aqueous Na2CO3 solution, washed, dried, and sintered. a section of sintering temperature peak 400 °C, heat preservation for 10 minutes; two-stage sintering temperature of 480 ° C, and keep warm for 20 minutes to obtain a double-layer electrode.

Claims (9)

  1. 一种双层电极所用的浆料，其特征在于，所述浆料的原料以质量百分比计为：A slurry for a two-layer electrode, characterized in that the raw material of the slurry is expressed by mass percentage:
    低温黑玻璃粉 3～15%，Low temperature black glass powder 3~15%,
    中温无铅玻璃粉 1～5%，Medium temperature lead-free glass powder 1 to 5%,
    光敏单体 4～15%，Photosensitive monomer 4 to 15%,
    光引发剂 2～7%，Photoinitiator 2 to 7%,
    有机载体 15~40%，Organic carrier 15~40%,
    银粉 余量；Silver powder
    所述的有机载体，原料以质量百分比计为：The organic carrier, the raw materials are in mass percentage:
    增塑剂 0.1～1%，Plasticizer 0.1~1%,
    偶联剂 0.1～3%，Coupling agent 0.1 to 3%,
    树脂 5～30%，Resin 5 to 30%,
    有机溶剂 余量；Organic solvent balance;
    所述的低温黑玻璃粉为低熔点无铅玻璃粉加入黑色颜料后熔融后将玻璃液倒入冷水中水淬，球磨至粒径≤3μm烘干得到。The low-temperature black glass powder is a low-melting lead-free glass powder, and after adding black pigment, the glass liquid is poured into cold water and quenched, and ball-milled to a particle size of ≤3 μm for drying.
  2. 根据权利要求1所述的双层电极所用的浆料，其特征在于，所述的低温黑玻璃粉熔融温度为350～400 ℃；低熔点无铅玻璃粉以质量百分比计，组成为：Bi2O3 45％～80％，SiO2 2～20％，B2O3 5～30，ZnO 2～15％；所述的黑色颜料选自Co3O4、Fe2O3、Co2O3、Cr2O3或MnO2中的任意一种或几种，添加量占低温黑玻璃粉的总重量的4~10%。The slurry for a two-layer electrode according to claim 1, wherein said low temperature black glass powder has a melting temperature of 350 to 400 °C; low melting point lead-free glass powder in mass percentage, composition: Bi2O3 45% ~ 80%, SiO2 2 ~ 20%, B2O3 5 ~ 30, ZnO 2 to 15%; the black pigment is selected from any one or more of Co3O4, Fe2O3, Co2O3, Cr2O3 or MnO2, and the addition amount is 4-10% of the total weight of the low temperature black glass powder.
  3. 根据权利要求1所述的双层电极所用的浆料，其特征在于，所述的中温玻璃粉的熔融温度为450~500℃，组成以质量百分比计为：The slurry for a two-layer electrode according to claim 1, wherein the medium temperature glass frit has a melting temperature of 450 to 500 ° C, and the composition is expressed by mass percentage:
    SiO2 1～15％，SiO2 1 to 15%,
    B2O3 5～15％，B2O3 5~15%,
    ZnO 0～15％，ZnO 0 to 15%,
    Al2O3 0～5％，Al2O3 0 to 5%,
    BaO 0~5%，BaO 0~5%,
    Bi2O3 余量。Bi2O3 balance.
  4. 根据权利要求1所述的双层电极所用的浆料，其特征在于，所述的有机载体中树脂为甲基丙烯酸甲酯-甲基丙烯酸羟乙酯-甲基丙烯酸共聚树脂，重均分子量30000，酸值120～140。The slurry for a two-layer electrode according to claim 1, wherein the resin in the organic vehicle is methyl methacrylate-hydroxyethyl methacrylate-methacrylic acid copolymer resin, and the weight average molecular weight is 30,000. The acid value is 120-140.
  5. 根据权利要求1所述的双层电极所用的浆料，其特征在于，所述的光敏单体为双季戊四醇五丙烯酸酯、双季戊四醇六丙烯酸酯、1,6-己二醇二丙烯酸酯、季戊四醇三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、丙氧基化三羟甲基丙烷三丙烯酸酯中的任意一种或几种。The slurry for a two-layer electrode according to claim 1, wherein the photosensitive monomer is dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, pentaerythritol. Any one or more of triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.
  6. 根据权利要求1所述的双层电极所用的浆料，其特征在于，所述的光引发剂为1－对吗啉苯基－2－二甲氨基－2－苄基－1－丁酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、α－羟基环己基苯基酮或安息香二甲醚中的任意一种或几种。The slurry for a two-layer electrode according to claim 1, wherein the photoinitiator is 1-p-morpholinyl-2-dimethylamino-2-benzyl-1-butanone, Any one of 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, α-hydroxycyclohexyl phenyl ketone or benzoin dimethyl ether Kind or several.
  7. 根据权利要求1所述的双层电极所用的浆料，其特征在于，所述的有机溶剂为二乙二醇单丁醚、松油醇、二乙二醇单丁醚醋酸酯、2,2,4-三甲基-1,3-戊二醇单异丁酸酯或2,2,4-三甲基-1,3-戊二醇双异丁酸酯中的任意一种或几种。The slurry for a two-layer electrode according to claim 1, wherein the organic solvent is diethylene glycol monobutyl ether, terpineol, diethylene glycol monobutyl ether acetate, 2, 2 Any one or more of 4-trimethyl-1,3-pentanediol monoisobutyrate or 2,2,4-trimethyl-1,3-pentanediol diisobutyrate .
  8. 根据权利要求1所述的双层电极所用的浆料，其特征在于，所述的增塑剂为卵磷脂、邻苯二甲酸二辛酯或邻苯二甲酸二丁酯中的任意一种，所述的偶联剂为硅烷偶联剂。The slurry for a two-layer electrode according to claim 1, wherein the plasticizer is any one of lecithin, dioctyl phthalate or dibutyl phthalate. The coupling agent is a silane coupling agent.
  9. 使用权利要求1～8任一所述的双层电极所用的浆料一次丝网印刷直接制备双层电极的方法，其特征在于，步骤为：A method for directly preparing a two-layer electrode by using one-time screen printing of a slurry for a two-layer electrode according to any one of claims 1 to 8, wherein the steps are as follows:
    第一步，中温无铅玻璃粉制备：将原料按中温无铅玻璃粉的配方比例配制好，在瓷质研钵中研磨、混合均匀，放入高铝坩埚，1000℃熔制2小时，熔成玻璃态，将玻璃液倒入冷水中，在恒温箱中将得到的玻璃渣烘干，球磨至粒径≤1μm烘干备用；The first step is to prepare medium-temperature lead-free glass powder: prepare the raw materials according to the formula ratio of medium-temperature lead-free glass powder, grind and mix evenly in porcelain mortar, put into high aluminum crucible, melt at 1000 °C for 2 hours, melt In the glass state, the glass liquid is poured into cold water, and the obtained glass slag is dried in an incubator, and ball-milled to a particle size of ≤ 1 μm for drying;
    第二步，低温黑玻璃粉制备：将低熔点无铅玻璃粉与黑色颜料混合均匀，1000℃熔制1小时熔成玻璃态；The second step is the preparation of low-temperature black glass powder: mixing the low-melting lead-free glass powder and the black pigment uniformly, and melting at 1000 ° C for 1 hour to form a glass state;
    将玻璃液倒入冷水中水淬，球磨至粒径≤3μm后，在恒温箱中烘干备用；Pour the glass liquid into cold water for water quenching, ball milling to a particle size of ≤ 3 μm, and then dry in an incubator for use;
    第三步，制备有机载体：按配方称取树脂、有机溶剂、偶联剂、增塑剂于反应釜中, 加热并搅拌，直到树脂溶解，冷却后用40目丝网过滤，使有机载体的粘度控制在100～300 Pa•s范围内；The third step is to prepare an organic carrier: the resin, the organic solvent, the coupling agent and the plasticizer are weighed in the reaction kettle according to the formula. Heating and stirring until the resin is dissolved, and after cooling, filtering with a 40 mesh screen to control the viscosity of the organic carrier in the range of 100 to 300 Pa•s;
    第四步，浆料调制：将银粉、低温黑玻璃粉、中温无铅玻璃粉、光敏单体、光引发剂和有机载体分散混合均匀后，进行三辊轧制，测试浆料细度≤4μm，粘度200+10 Pa•s后，将制得的浆料用丝网印刷法均匀涂到玻璃基板上，干燥后用紫外光曝光，用0.2~0.4%wt的Na2CO3水溶液显影，清洗、干燥、烧结，烧结时一段烧结峰值温度比低温黑玻璃粉熔融温度高10～30℃，二段烧结峰值温度比中温无铅玻璃粉熔融高10℃～30℃，得到双层电极。The fourth step, slurry preparation: silver powder, low temperature black glass powder, medium temperature lead-free glass powder, photosensitive monomer, photoinitiator and organic carrier are dispersed and uniformly mixed, and then subjected to three-roll rolling, the test slurry fineness ≤ 4 μm , viscosity 200+10 After Pa•s, the prepared slurry is uniformly applied to the glass substrate by screen printing, dried and exposed to ultraviolet light, developed with 0.2~0.4%wt of Na2CO3 aqueous solution, washed, dried, sintered, and sintered. The sintering peak temperature is 10 to 30 ° C higher than the melting temperature of the low-temperature black glass powder, and the peak temperature of the second-stage sintering is 10 ° C to 30 ° C higher than that of the medium-temperature lead-free glass powder to obtain a double-layer electrode.
PCT/CN2011/078552 2010-12-09 2011-08-18 Method for directly preparing double-layer electrode by screen printing at one time, and slurry used therefor WO2012075830A1 (en)

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