CN114927257A - Special conductive paste for glass substrate and preparation method thereof - Google Patents
Special conductive paste for glass substrate and preparation method thereof Download PDFInfo
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- CN114927257A CN114927257A CN202210478573.XA CN202210478573A CN114927257A CN 114927257 A CN114927257 A CN 114927257A CN 202210478573 A CN202210478573 A CN 202210478573A CN 114927257 A CN114927257 A CN 114927257A
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- 239000011521 glass Substances 0.000 title claims abstract description 147
- 239000000758 substrate Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000004020 conductor Substances 0.000 claims abstract description 47
- 239000000853 adhesive Substances 0.000 claims abstract description 37
- 230000001070 adhesive effect Effects 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- 239000002042 Silver nanowire Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000001739 pinus spp. Substances 0.000 claims description 3
- 229940036248 turpentine Drugs 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 25
- 239000002002 slurry Substances 0.000 abstract description 7
- 239000012776 electronic material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 32
- 238000005245 sintering Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- 229910001947 lithium oxide Inorganic materials 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
- 229910001950 potassium oxide Inorganic materials 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 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
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000000203 mixture Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 oleum Terebinthinae Chemical compound 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a special conductive paste for a glass substrate and a preparation method thereof, belonging to the technical field of electronic materials. The conductive paste comprises the following preparation raw materials in parts by weight: 100 parts of conductive material, 8-10 parts of adhesive and 10-15 parts of glass powder; the conductive material is prepared from the following preparation raw materials in parts by weight: 10 parts of silver powder, 5-7 parts of silver nanowires and 15-25 parts of graphene. The special conductive paste for the glass-based circuit enhances the conductive performance of the circuit by improving the mass proportion of the special conductive material; and by selecting the adhesive and the glass powder with excellent performance and selecting a proper proportion, the slurry has moderate viscosity, good fluidity and strong adhesive force, and the special conductive material particles are more tightly contacted, so that a continuous and compact conductive film layer is easy to form and the resistivity is small.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a special conductive paste for a glass substrate and a preparation method thereof.
Background
The traditional glass-based circuit board is manufactured by using a coating etching process or a low-temperature silver paste process. The film coating etching process is to plate one layer of conducting slurry on the surface of glass plate and to make circuit with etching method, and the electronic circuit of the glass base circuit board is combined with the glass plate via adhesive. The low-temperature silver paste process is realized by silk-screening a low-temperature silver paste circuit on the surface of a glass plate and baking and curing at the temperature of 200 ℃, and the method cannot achieve high conductivity because the silver paste also contains a large amount of organic bonding materials, so that electronic elements are still difficult to weld and have poor adhesion. Due to the process limitation of the traditional glass-based circuit board, in the manufactured glass-based circuit board, the connection between the glass plate and the conducting circuit is not tight, the conducting circuit floats on the surface of the glass plate, the surface of the whole glass-based circuit board is not smooth, the conducting circuit is easy to damage and fall off, and finally the conducting capacity is poor.
The conductive paste is generally composed of conductive metal powder, a binder, a solvent and other auxiliary agents, is printed on a paste carrier by a certain printing method, and is solidified under the action of a certain temperature and time to form a conductive circuit. The content of the metal conductive material in the slurry directly influences the conductive performance of the circuit, the conductive performance has a space for improving in the related technology, and the brittleness of the conductive circuit is greatly increased due to the large amount of the additive, so that the conductive circuit is easy to break when a glass substrate deforms, and the glass substrate circuit board is damaged.
Therefore, it is necessary to develop a conductive paste for a glass substrate, which has good conductivity.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the special conductive paste for the glass substrate, and the conductive paste has good conductivity.
The invention also provides a preparation method of the special conductive paste for the glass substrate.
The method comprises the following specific steps: the invention provides a special conductive paste for a glass substrate, which comprises the following preparation raw materials in parts by weight: 100 parts of conductive material, 8-10 parts of adhesive and 10-15 parts of glass powder;
the conductive material comprises the following preparation raw materials in parts by weight: 10 parts of silver powder, 5-7 parts of silver nanowires and 15-25 parts of graphene.
According to one technical scheme of the conductive paste, the conductive paste has the following beneficial effects:
the special conductive paste for the glass-based circuit enhances the conductive performance of the circuit by improving the mass ratio of the conductive material; and the adhesive and the glass powder are selected and the proper proportion is selected, so that the slurry has moderate viscosity, good fluidity and strong adhesive force, the conductive material particles are in closer contact, a continuous and compact conductive film layer is easy to form, and the resistivity is small.
The graphene is a sheet material, the silver nanowires are linear materials, and the silver powder is a spherical material; the graphene mainly plays a role in providing surface contact in the conductive material; the silver nanowires mainly play a role in line contact in the conductive material; the silver powder mainly plays a role of point contact (conductive bridge); by effectively matching the three materials, a point-line-surface three-dimensional conductive network is formed, so that the conductivity of the conductive material is improved.
According to some embodiments of the invention, the adhesive is prepared from the following preparation raw materials in parts by mass: 10 to 30 parts of ethyl cellulose, 1 to 5 parts of turpentine, 20 to 35 parts of dibutyl phthalate and 5 to 20 parts of polyamide wax micro powder.
The adhesive used in the invention has good chemical stability and bonding property, is not easy to volatilize, has good rheological property and higher boiling point, and the toxicity of each preparation raw material in the adhesive is very low, the curing speed is fast, the proportion of the adhesive, the glass powder and the conductive material is reasonable, so that the viscosity of the conductive slurry special for the glass-based circuit is moderate, the fluidity is good, the adhesive force is strong, the contact among the conductive material particles is tighter, a continuous and compact conductive film layer is easy to form during the printing of a circuit board, the resistivity is small, the conductive circuit can be effectively formed, the electric conductivity of the circuit is high, the bonding force is strong, the soldering resistance is good, the glass substrate is not easy to break when being deformed, and the service life of the glass-based circuit board is prolonged.
According to some embodiments of the invention, the glass frit is prepared from the following preparation raw materials: 10 to 30 parts of silicon dioxide, 2 to 10 parts of aluminum oxide, 0.05 to 3 parts of alkali metal oxide, 1 to 4 parts of zinc oxide and 10 to 20 parts of calcium oxide.
Silica has a strong glass forming ability, mainly represented by [ SiO ] 4 ]Tetrahedral states exist. SiO 2 2 The higher the content, the tighter the glass network structure and the higher the corresponding melting temperature. Therefore, the amount thereof needs to be controlled within a certain range.
Calcium oxide is a divalent network exo-oxide that increases the chemical stability and mechanical strength of the glass frit, but at higher levels, the glass has an increased tendency to crystallize.
The alkali metal oxide is the external oxide of the glass network, is positioned in the cavity of the glass structure network, can provide free oxygen to increase the O/Si ratio in the glass structure and generate bond breaking, thereby reducing the viscosity of the glass, leading the glass to be easy to melt, and being good fluxing agent.
Alumina is an essential component for improving the chemical stability of glass, reducing the tendency of glass to devitrify, and simultaneously improving the hardness and mechanical strength of glass and the tensile elastic modulus. In the glass network structure, alumina is a network intermediate oxide, between the network former and the network outer body.
Zinc oxide is used as a fluxing agent; increase transparency, brightness, and resistance to tensile deformation, and reduce thermal expansion coefficient.
The glass powder is prepared by melting and mixing silicon dioxide and metal oxide according to a certain proportion and then quenching and crushing the mixture, and the glass powder forms the key component of the conductive slurry. The addition of the glass powder helps to reduce the sintering temperature and enhance the adhesion between the conductive paste and the glass substrate.
And the performance of the conductive paste is directly influenced by the performance of the glass powder. The glass powder plays an important role in the conductive paste, the glass powder is melted during sintering to generate a liquid phase, and after cooling, the conductive particles in the conductive material form a conductive film layer which is firmly attached to the glass substrate.
According to some embodiments of the invention, the alkali metal oxide comprises at least one of lithium oxide, sodium oxide and potassium oxide.
According to some embodiments of the invention, the alkali metal oxide consists of lithium oxide, sodium oxide and potassium oxide.
According to some embodiments of the invention, the alkali metal oxide has a mass ratio of lithium oxide, sodium oxide and potassium oxide of 1:0.5 to 1.5.
According to some embodiments of the invention, the method of making the glass frit comprises the steps of: mixing the silicon dioxide, the aluminum oxide, the alkali metal oxide, the zinc oxide and the calcium oxide, calcining at 1000-1200 ℃, and ball-milling.
According to some embodiments of the invention, the calcination is for a time period of 30mim to 60 min.
According to some embodiments of the invention, the glass frit has a D50 of 1 μm to 5 μm.
According to some embodiments of the invention, the silver powder has a D50 of 1 to 2 μm.
Before high-temperature sintering, the conductive particles and the glass powder particles in the conductive film layer are relatively uniformly mixed and arranged together, if the particles of the glass powder are larger, the relative distance between the conductive particles is also larger, the glass powder is gradually softened and converted into a liquid phase in the sintering process, and the silver powder is infiltrated by the glass liquid.
When the diameter of the glass powder is within the range, the glass powder and the conductive particles are uniformly distributed, the glass powder and the conductive particles are melted into liquid and then uniformly soaked, the conductive particles are fully spread on a glass substrate, the wettability of the conductive particles is good, the distribution of conductive ions is also uniform gradually, holes in the conductive film layer are gradually reduced, the compactness is gradually increased, the conductivity is better and better, and the sheet resistance is reduced. In other words, in the sintering process, the conductive particles, the glass powder and the glass substrate are well matched, so that the conductive film layer obtained by sintering has excellent conductivity.
After being sintered, the conductive paste is firmly attached to the glass substrate, and firstly, the conductive paste before being sintered and the glass substrate are well wetted, and secondly, the molten glass powder is well infiltrated to the glass substrate during sintering, so that the contact and bonding action between the glass liquid (formed by melting the glass powder) and the molecules on the surface of the glass substrate can be ensured due to the good wetting property, and the strong adhesive force is generated.
According to some embodiments of the invention, the silver nanowires have a diameter of 20nm to 110 nm.
According to some embodiments of the invention, the silver nanowires have a diameter of 60nm to 80 nm.
According to some embodiments of the invention, the silver nanowires have a length of 100 μm to 200 μm.
The diameter of the silver nanowire is controlled within the range, so that the graphene, the silver powder and the silver nanowire are fully contacted, and the conductivity of the conductive paste is improved.
According to some embodiments of the invention, the graphene has a sheet diameter of 1 μm to 10 μm.
According to some embodiments of the invention, the graphene has a sheet diameter of 5 μm to 10 μm.
The sheet diameter of the graphene is controlled within the range, so that the graphene, the silver powder and the silver nanowires are fully contacted, and the conductivity of the conductive paste is improved.
According to some embodiments of the present invention, the raw material for preparing the conductive paste further includes an organic solvent.
According to some embodiments of the invention, the organic solvent is an alcoholic solvent.
According to some embodiments of the invention, the mass-to-volume ratio of the silver nanowires to the alcoholic solvent is 15mg to 25 mg: 1 mL.
According to some embodiments of the invention, the alcoholic solvent comprises at least one of ethanol, propanol, isopropanol.
The second aspect of the invention discloses a preparation method of the special conductive paste for the glass substrate, which comprises the following steps:
adding the conductive material and the glass powder into the adhesive, and dispersing.
According to some embodiments of the invention, the adhesive dissolves at a temperature of 60 ℃ to 100 ℃.
According to some embodiments of the present invention, the conductive material is dispersed in an organic solvent to prepare a conductive material dispersion liquid.
According to some embodiments of the invention, the method of preparing the conductive material dispersion comprises the steps of:
and adding the graphene and the silver powder into the silver nanowire dispersion liquid, and dispersing for 5-10 min at a dispersion speed of 300-500 rpm to obtain the graphene/silver nanowire composite material.
According to some embodiments of the present invention, the dispersion medium in the silver nanowire dispersion is an organic solvent.
According to some embodiments of the invention, the organic solvent is selected from alcoholic solvents.
According to some embodiments of the invention, the alcoholic solvent is ethanol.
According to some embodiments of the present invention, the silver nanowire dispersion has a mass concentration of 15mg/mL to 25 mg/mL.
According to some embodiments of the present invention, the method for preparing the conductive paste dedicated for glass substrates comprises the following steps:
and adding the conductive material dispersion liquid and the glass powder into the adhesive, and dispersing for 5-10 min at a dispersion speed of 300-500 rpm to obtain the conductive material.
The conductive material is dispersed in the organic solvent, so that the conductive material is fully dispersed, and the graphene, the silver powder and the silver nanowires in the conductive material are fully contacted to form a conductive network.
According to the invention, after the adhesive is dissolved, the conductive material dispersion liquid and the glass powder are added into the adhesive, and in the process, the fully dispersed conductive material is fixed in the adhesive, so that a stable three-dimensional conductive network is formed.
According to some embodiments of the present invention, the glass substrate-dedicated conductive paste is sintered after the glass substrate by screen printing; and preparing the conductive film layer.
The conductive paste is subjected to screen printing, a pattern with a certain shape is printed on the glass substrate, the conductive paste is conductive to a certain extent, but because the conductive paste is not subjected to a sintering process, a conductive network is incomplete, a large amount of adhesive exists among conductive channels, and the silver paste is not subjected to solid-liquid interaction and rearrangement of a conductive material and glass powder in the sintering process, so that the conductive effect is poor.
After the conductive film layer on the glass substrate is sintered, only glass powder and conductive materials are left in the film layer, and the adhesive is effectively volatilized. And after the conductive paste is sintered and then cooled, the glass powder is connected with the glass substrate and the conductive material to enable the glass substrate and the conductive material to form a conductive network, and conductive particles in the conductive material are mutually contacted and connected, so that the conductive film layer is prepared, and the sintered conductive film layer has better conductivity.
The mobile electrons between the conductive particles in the conductive film layer form an electron channel, which is formed by current excitation generated by a high-intensity electric field between the conductive particles.
The glass powder in the conductive paste mainly has the function of providing enough glass phase for sintering, so that enough glass liquid phase content is provided, the glass phase liquid phase content is insufficient when the glass powder content is at a lower level, conductive particles in the conductive material cannot be fully soaked, sintering densification of the conductive film layer is influenced, similarly, although the glass substrate is in contact with the liquid phase, wettability is not good enough, bonding effect is not obvious, and adhesive force of the conductive film layer is influenced. When the content of the glass powder is increased and is in a proper amount, the conductive particles are wetted by the liquid-phase glass powder and rearranged, gaps are densely filled, the conductive particles are close to each other, the gaps in the sintered conductive film layer are reduced, in addition, the sufficient liquid phase soaks the surface of the glass substrate, the bonding effect is enhanced, so that the glass powder can tightly bond the conductive particles together and enhance the bonding strength with the glass substrate, the glass phase is positioned between the conductive particles and the glass substrate to effectively connect the conductive particles and the glass substrate, meanwhile, the adhesive force between the conductive film layer and the substrate is further enhanced, and the adhesive strength is improved.
However, when the content of the glass powder continues to increase, the trend of increasing the adhesion of the conductive film layer is obviously weakened, which is mainly likely to cause the increase of the glass powder and the increase of the liquid phase amount, and the excessive glass liquid phase immerses the conductive particles in the glass liquid, so that the effective exposed area of the conductive particles on the surface of the conductive film layer is reduced, the welding performance of the conductive film layer is deteriorated, and the adhesion is reduced.
According to some embodiments of the invention, the sintering temperature is 550 ℃ to 730 ℃.
According to some embodiments of the invention, the atmosphere of the sintering is a protective gas atmosphere.
According to some embodiments of the invention, the protective gas is selected from at least one of nitrogen, helium, neon, argon, krypton.
According to some embodiments of the invention, the temperature control procedure for sintering is:
keeping the temperature at 550-600 ℃ for 5-10 min; heating to 680-730 deg.C, and keeping for 2-4 min.
Firstly, the glass substrate begins to soften at 500 ℃, molecules on the surface of the glass substrate begin to be in an active state at 550 ℃, the adhesive in the conductive paste volatilizes, and the glass powder melts and carries the conductive material to fuse with the glass molecules on the surface of the glass substrate in the active state; in this process, the glass molecules are not active when the temperature is lower than 550 ℃, and the glass plate is easy to crack when the temperature is higher than 600 ℃.
Subsequently, the temperature is increased to increase the activity of the conductive material and to achieve deep fusion with the more active glass substrate molecules, and the excessive temperature in the process may cause excessive deformation of the glass substrate.
At the moment, the surface of the glass substrate is fully fused with the conductive material into a whole, the fusion is molecular, and has stronger bonding force compared with the bonding agent used in the related technology, and the surface of the glass substrate and the surface of the circuit layer can be integrated into a whole, so that the whole glass substrate circuit board is smooth and is suitable for various application occasions.
According to some embodiments of the invention, the conductive film layer has a thickness of 20 μm to 30 μm.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Specific examples of the present invention are described in detail below.
Example 1
The embodiment is a preparation method of a conductive paste special for a glass substrate, which is prepared from the following preparation raw materials:
s1, preparing a conductive material dispersion liquid:
adding 10g of silver powder and 15g of graphene into 300mL of silver nanowire dispersion (Xianfeng nanometer, XFJ81, the product number is 101502; the diameter is 30nm +/-5 nm; the length is 100-200 mu m; the mass concentration is 20 mg/mL; and the solvent is ethanol); dispersing for 10min at a dispersion speed of 400rpm to prepare a conductive material dispersion liquid;
s2, preparing conductive paste:
adding the conductive material dispersion liquid and the glass powder into the adhesive (the temperature of the adhesive is 100 ℃); dispersing for 10min at a dispersion speed of 400rpm to prepare the conductive paste.
The mass ratio of the conductive material, the binder and the glass powder in the conductive paste prepared in this embodiment is 100:8: 10.
The conductive material was composed of 10g of silver powder, 15g of graphene, and 6g of silver nanowires.
The glass powder in the embodiment is prepared from the following preparation raw materials: 30 parts of silicon dioxide, 2 parts of aluminum oxide, 3 parts of alkali metal oxide (the mass ratio of lithium oxide to sodium oxide to potassium oxide is 1:1:1), 4 parts of zinc oxide and 10 parts of calcium oxide.
The preparation method of the glass powder in the embodiment comprises the following steps: mixing silicon dioxide, aluminum oxide, alkali metal oxide, zinc oxide and calcium oxide, calcining at 1200 ℃, and performing ball milling to obtain glass powder with the D50 of 1-2 mu m.
The adhesive in the embodiment is prepared from the following preparation raw materials:
20 parts of ethyl cellulose (CAS number: 9004-57-3), 4 parts of turpentine (Shandong gold beautifying chemical Co., Ltd., CAS number: 8006-64-2), 20 parts of dibutyl phthalate (CAS number: 84-74-2), and 10 parts of polyamide wax micropowder (Jiangsu Changxing collaborating high polymer material Co., Ltd., RC-800).
The preparation method of the adhesive in the embodiment comprises the following steps: mixing ethyl cellulose, oleum Terebinthinae, dibutyl phthalate, and polyamide wax micropowder, heating to 100 deg.C, and maintaining for 10 min.
Example 2
The embodiment is a method for preparing a conductive paste special for a glass substrate, and the difference from the embodiment 1 is that: the graphene is replaced by the following model: xifeng nano, XF021, the cargo number is: 102064, respectively; the sheet diameter is 1-3 μm.
Example 3
The embodiment is a method for preparing a conductive paste special for a glass substrate, and the difference from the embodiment 1 is that: the silver nanowire dispersion is replaced by the following types (in parts by weight based on solute): xianfeng nanometer, XFJ80, the product number is: 101508, diameter: 70nm +/-5 nm, ethanol as solvent, mass concentration of 20mg/mL, length: 100-200 μm.
Example 4
The embodiment is a method for preparing a conductive paste special for a glass substrate, and the difference from the embodiment 1 is that: the silver nanowires are replaced by the following models (in parts by weight based on solute): xianfeng nanometer, XFJ59, the product number is: 101110, diameter: 100nm +/-5 nm, ethanol as a solvent, 20mg/mL of mass concentration, length: 100-200 μm.
Comparative example 1
The comparative example is a preparation method of the conductive paste special for the glass substrate, and is different from the example 1 in that: no graphene was added to the conductive paste of this comparative example.
Comparative example 2
The comparative example is a preparation method of the conductive paste special for the glass substrate, and is different from the example 1 in that: the silver nanowire dispersion was replaced with an equal volume of ethanol.
Comparative example 3
The comparative example is a conductive paste special for a glass substrate, and is different from the conductive paste of the example 1 in that: silver powder was not added to the conductive paste of this comparative example.
Comparative example 4
The comparative example is a conductive paste special for a glass substrate, and is different from the conductive paste of the example 1 in that: the amount of the silver nanowire dispersion used in this comparative example was 500mL (10 g converted to silver nanowires).
Comparative example 5
The comparative example is a conductive paste special for a glass substrate, and is different from the conductive paste of the example 1 in that: the amount of graphene used in this comparative example was 10 g.
Comparative example 6
The comparative example is a conductive paste special for a glass substrate, and is different from the conductive paste of the example 1 in that: in the comparative example, the mass ratio of the conductive material, the adhesive and the glass powder is 100:8: 20.
the preparation method of the conductive paste in the embodiments 1 to 4 and the comparative examples 1 to 6 of the invention comprises the following steps:
test example:
the conductive paste in examples 1 to 4 and comparative examples 1 to 6 was printed on the surface of a glass substrate by screen printing and then sintered to form a conductive film layer (the thickness of the conductive film layer was 25 μm).
The temperature program of sintering is: maintaining at 580 deg.C for 5 min; the temperature is raised to 680 ℃ and kept for 4 min.
The atmosphere for sintering was argon.
Testing the sheet resistance and the adhesive force of the conductive paste by adopting the following method, wherein the sheet resistance testing method refers to GB/T17473.3-2008; the adhesion test method refers to GB/T17473.4-2008; the test results are shown in Table 1.
TABLE 1 test results of performance data of conductive pastes prepared in examples 1 to 4 of the present invention and comparative examples 1 to 6
| - | Square resistance (m omega/□) | Adhesion (N) |
| Example 1 | 1.53 | 20 |
| Example 2 | 2.73 | 21 |
| Example 3 | 0.38 | 23 |
| Example 4 | 1.59 | 25 |
| Comparative example 1 | 8.32 | 19 |
| Comparative example 2 | 7.65 | 20 |
| Comparative example 3 | 10.62 | 18 |
| Comparative example 4 | 5.96 | 12 |
| Comparative example 5 | 5.65 | 22 |
| Comparative example 6 | 18.25 | 25 |
The difference between the embodiment 1 and the embodiment 2 of the invention is that: sheet diameter of graphene; in example 2, the sheet diameter of the graphene is smaller than that in example 1, and the test result shows that the sheet diameter of the graphene is smaller; the sheet resistance can be influenced to a certain extent; the reason for this is that: the sheet diameter of the graphene is smaller; the contact area between the silver powder and the silver powder is reduced to a certain degree, so that the formation of a conductive network is influenced, and the conductivity is finally influenced.
The difference between the embodiment 1 of the present invention and the embodiments 2 to 4 is that: the diameter of the silver nanowires; from the test results it follows that: the grain size of the silver nanowires can influence the sheet resistance to a certain extent; the reason for this is that: in a certain range, the diameter of the silver nanowire is increased, and the contact area between the silver nanowire and graphene and silver powder is increased to a certain extent, so that the conductivity of the silver nanowire is improved; meanwhile, the diameter of the silver nanowire is increased, so that the difficulty in dispersing the silver nanowire in the conductive paste is increased, and the silver nanowire cannot be in full contact with graphene and silver powder; resulting in a certain reduction in the conductivity.
The difference between inventive example 1 and comparative example 1 is that: without adding graphene, a three-dimensional conductive network cannot be formed, thereby reducing the conductivity.
The difference between inventive example 1 and comparative example 2 is that: without adding silver nanowires, a three-dimensional conductive network cannot be formed, resulting in a decrease in conductivity.
The difference between inventive example 1 and comparative example 3 is that: without adding silver powder, a three-dimensional conductive network cannot be formed, resulting in a decrease in conductivity.
The difference between the inventive example 1 and the comparative example 4 is that: the addition amount of the silver nanowires is too large, so that part of graphene and silver powder are difficult to form surface contact, the contact between the graphene and the silver powder is poor, and the conductivity is reduced.
The difference between inventive example 1 and comparative example 5 is that: the addition amount of the graphene is reduced, so that the surface contact effect between the graphene and the silver nanowire and the silver powder is reduced, and the conductivity is reduced.
The difference between inventive example 1 and comparative example 6 is that: the addition amount of the glass powder is too much, so that the proportion of the conductive material is reduced, and the conductivity is greatly deteriorated.
In conclusion, the special conductive paste for the glass-based circuit enhances the conductive performance of the circuit by improving the mass ratio of the conductive material; and by selecting the adhesive and the glass powder with excellent performance and selecting a proper proportion, the slurry has moderate viscosity, good fluidity and strong adhesive force, and the conductive material particles are more tightly contacted, so that a continuous and compact conductive film layer is easy to form and the resistivity is small.
While the embodiments of the present invention have been described in detail with reference to the specific embodiments, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The special conductive paste for the glass substrate is characterized by comprising the following components in parts by weight: the preparation method comprises the following raw materials in parts by weight: 100 parts of conductive material, 8-10 parts of adhesive and 10-15 parts of glass powder;
the conductive material comprises the following preparation raw materials in parts by weight: 10 parts of silver powder, 5-7 parts of silver nanowires and 15-25 parts of graphene.
2. The conductive paste for glass substrates according to claim 1, wherein: the adhesive is prepared from the following preparation raw materials in parts by mass: 10 to 30 parts of ethyl cellulose, 1 to 5 parts of turpentine, 20 to 35 parts of dibutyl phthalate and 5 to 20 parts of polyamide wax micro powder.
3. The conductive paste for glass substrates according to claim 1, wherein: the glass powder is prepared from the following preparation raw materials: 10 to 30 parts of silicon dioxide, 2 to 10 parts of aluminum oxide, 0.05 to 3 parts of alkali metal oxide, 1 to 4 parts of zinc oxide and 10 to 20 parts of calcium oxide.
4. The conductive paste for glass substrates according to claim 3, wherein: the preparation method of the glass powder comprises the following steps: mixing the silicon dioxide, the aluminum oxide, the alkali metal oxide, the zinc oxide and the calcium oxide, calcining at 1000-1200 ℃, and ball-milling.
5. The conductive paste for glass substrates according to claim 4, wherein: the D50 of the glass powder is 1-5 mu m.
6. The conductive paste for glass substrates according to claim 1, wherein: the D50 of the silver powder is 1-2 mu m.
7. The conductive paste for glass substrates according to claim 1, wherein: the diameter of the silver nanowire is 20 nm-110 nm.
8. The conductive paste for glass substrates according to claim 1, wherein: the sheet diameter of the graphene is 1-10 mu m.
9. A method for preparing the conductive paste for glass substrates according to any one of claims 1 to 8, wherein: the method comprises the following steps:
adding the conductive material and the glass powder to the adhesive, and dispersing.
10. The method of claim 9, wherein: the adhesive is dissolved at a temperature of 60 ℃ to 100 ℃.
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