Silk-screen printing circuit electrode and preparation method thereofTechnical field
The present invention relates to a kind of electrocondution slurry technical field, more particularly, to a kind of silk-screen printing circuit electrode and its preparationMethod.
Background technology
Electric slurry is a kind of new material, compared to other traditional circuit equipment have efficiently, environmental protection, energy-conservation, it is low intoThis features such as, solar cell, space flight and aviation, sensing element, resistor network, display, lithium-ion electric have been widely used in itThe technical fields such as the electrode material in pond.
Electric slurry is mixed into uniform paste by conductive phase, Binder Phase, organic phase by three-roll rolling, on substrateIt is several microns of film layers to some tens of pm to form thickness by printing-sintering technology, can be used as manufacturing the base of various electronic componentsPlinth material；Wherein, conductive phase is various metal dusts, and Binder Phase is various glass and oxide powder, and organic phase is have airborneBody or organic bond, it includes thickener, solvent, dispersant and thixotropic agent.
In recent decades, Precious Metal, such as production technology such as Ag conductor pastes are quite ripe and obtain extensively shouldWith；Cheap metal slurry, such as Ni, Al, Cu, Zn slurry are not sent out well due to its electric conductivity, inoxidizability limitationExhibition.Copper with the only choosing that its high conductivity and cheap performance are the electric slurry conductive phases for being only second to Ag, but but because itsEasily oxidizable is restricted.
The content of the invention
Based on this, it is necessary in view of the shortcomings of the prior art, there is provided there is one kind high conduction performance to be not easy to oxidation simultaneouslySilk-screen printing circuit electrode and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted in the present invention is：A kind of silk-screen printing circuit electrode, includingBase material and copper alloy electric slurry, the copper alloy electric slurry are coated on base material, and the copper alloy electric slurry includes weightAmount percentage is 50~80% conductive phase, 10~40% organic phase and 5~10% Binder Phase, and the conductive phase is copperThe mixture of powder, silver powder and titanium valve, wherein, the percentage by weight of copper powder, silver powder and titanium valve is 10~90%：5~10%：5~10%.
A kind of preparation method of silk-screen printing circuit electrode, it is characterised in that comprise the following steps：
(1) conductive phase, is prepared：According to percentage by weight by 10~90% copper powder, 5~10% silver powder and 5~10%Titanium valve carry out proportioning mixing, obtain final product conductive phase；
(2) Binder Phase, is prepared：According to weight than 0~20：0~20：60~80 respectively by zinc-aluminium-silica glass powder, titanium-Aluminium-silica glass powder and conductive crystallite glass dust are mixed at a temperature of being less than 300 DEG C, obtain final product Binder Phase；
(3) organic phase, is prepared：By weight percentage by 10~20% thickener, 75~80% organic solvent, 5~15% dispersant and 0~10% thixotropic agent are mixed, and obtain final product organic phase；
(4) blister copper alloy electric slurry, is prepared：By the conductive phase in step (1), (2), (3), Binder Phase and organic phase warpAgitator is obtained blister copper alloy electric slurry after being sufficiently mixed；
(5) thin copper alloy electric slurry, is prepared：Blister copper alloy electric slurry is placed in three-roll grinder and is groundTreatment, after grinding preset times, is obtained thin copper alloy electric slurry；
(6) semi-finished product silk-screen printing circuit electrode, is prepared：Obtained copper alloy electric slurry is printed by screen process pressBrush is obtained screen printing electrode or circuit on base material, obtains semi-finished product silk-screen printing circuit electrode；
(7), dumping：Semi-finished product silk-screen printing circuit electrode is carried out into dumping operation in continuous tunnel furnace；
(8), sinter：Semi-finished product silk-screen printing circuit electrode is sintered operation in continuous tunnel furnace；
(9), cool down：Open tunnel furnace door to take out semi-finished product silk-screen printing circuit electrode, cooled down rapidly with ventilating fanTo room temperature, silk-screen printing circuit electrode finished product is obtained final product.
In sum, silk-screen printing circuit electrode of the present invention and preparation method thereof sinters to be formed by copper alloy electric slurryAlloy can well prevent copper of the copper alloy electric slurry in sintering process from aoxidizing, copper alloy electric slurry can be attached wellOn base material, adhesive property is good, good with cheap, easy preparation, adhesive property, solderability, tensile strength, electric conductivityThe advantages of.
Specific embodiment
It is specific purposes, the function that can further appreciate that feature of the invention, technological means and reached, with reference toSpecific embodiment is described in further detail to the present invention.
Silk-screen printing circuit electrode of the present invention includes base material and copper alloy electric slurry, and the copper alloy electric slurry is coatedOn base material, the copper alloy electric slurry includes conductive phase, 10~40% organic phase that percentage by weight is 50~80%And 5~10% Binder Phase, the conductive phase for copper powder, silver powder and titanium valve mixture, wherein, copper powder, silver powder and titanium valvePercentage by weight is 10~90%：5~10%：5~10%, the particle diameter of the copper powder is nanoscale or micron order；The bondingMutually for zinc-aluminium-silica glass powder, titanium-aluminium-silica glass powder and conductive crystallite glass dust mixture, the zinc-aluminium-silica glass powder,The particle size range of titanium-aluminium-silica glass powder and conductive crystallite glass dust is 1~10 μm.
The organic phase include thickener, organic solvent, thixotropic agent and dispersant, wherein, thickener, organic solvent, pointThe percentage by weight of powder and thixotropic agent is 10~20%：75~80%：5~15%：0~10%, the thickener is ethylAt least one in cellulose, NC Nitroncellulose, butyral resin, the organic solvent is terpinol, butyl click pyrrole alcohol, citric acidAt least one in tributyl, the thixotropic agent is castor oil, and the dispersant is oleic acid.
According to the invention described above silk-screen printing circuit electrode, the present invention provides a kind of preparation side of silk-screen printing circuit electrodeMethod, the technical characteristic that the copper alloy electric slurry being related in the method can be illustrated with above-mentioned silk-screen printing circuit electrode embodimentIt is identical, and identical technique effect can be produced.The preparation method of silk-screen printing circuit electrode of the present invention is starched by copper alloy electronicsThe copper that the alloy that material sintering is formed can well prevent copper alloy electric slurry in sintering process is aoxidized；Copper alloy of the inventionElectric slurry can be perfectly adhered on base material, and adhesive property is good；Copper alloy electric slurry of the invention can apply to very wellThe printing of circuit and the printing of electrode；Copper alloy electric slurry of the invention have it is cheap, easily preparation, adhesive property, solderability,The advantages of tensile strength, good electric conductivity.
The preparation method of silk-screen printing circuit electrode of the present invention, comprises the following steps：
(1) conductive phase, is prepared：According to percentage by weight by 10~90% copper powder, 5~10% silver powder and 5~10%Titanium valve carry out proportioning mixing, obtain final product conductive phase, wherein, copper powder size value range be nanoscale or micron order；
(2) Binder Phase, is prepared：According to weight than 0~20：0~20：60~80 respectively by zinc-aluminium-silica glass powder, titanium-Aluminium-silica glass powder and conductive crystallite glass dust are mixed at a temperature of being less than 300 DEG C, obtain final product Binder Phase, wherein, zinc-aluminium-silicon glassThe particle size range of glass powder, titanium-aluminium-silica glass powder and conductive crystallite glass dust is 1~10 μm；
(3) organic phase, is prepared：By weight percentage by 10~20% thickener, 75~80% organic solvent, 5~15% dispersant and 0~10% thixotropic agent are mixed, and obtain final product organic phase, wherein, the thickener be ethyl cellulose,At least one in NC Nitroncellulose, butyral resin, the organic solvent is terpinol, butyl click pyrrole alcohol, ATBCIn at least one, the thixotropic agent be castor oil, the dispersant be oleic acid；
(4) blister copper alloy electric slurry, is prepared：By the conductive phase in step (1), (2), (3), Binder Phase and organic phase warpAgitator is obtained blister copper alloy electric slurry after being sufficiently mixed；
(5) thin copper alloy electric slurry, is prepared：Blister copper alloy electric slurry is placed in three-roll grinder and is groundTreatment, after grinding preset times, is obtained thin copper alloy electric slurry, wherein, the milling gap of three-roll grinder is respectively set as10~15 μm and 5~10 μm, preset times are 3 times；
(6) semi-finished product silk-screen printing circuit electrode, is prepared：Obtained copper alloy electric slurry is printed by screen process pressBrush is obtained screen printing electrode or circuit on base material, obtains semi-finished product silk-screen printing circuit electrode；
(7), dumping：Semi-finished product silk-screen printing circuit electrode is carried out into dumping operation in continuous tunnel furnace, is led in continuous tunnel furnaceNitrogen excludes air, and the oxygen content in continuous tunnel furnace is reduced into 1~10%, and it is 200~300 to set the temperature value in continuous tunnel furnaceDEG C, dumping activity time is 10~15min；
(8), sinter：Semi-finished product silk-screen printing circuit electrode is sintered operation in continuous tunnel furnace, to being taken out in continuous tunnel furnaceVacuum and logical nitrogen, control oxygen content for 10~50ppm, and it is 400~600 DEG C to set the sintered heat insulating temperature in continuous tunnel furnace,Wherein, the programming rate in continuous tunnel furnace is set as 10~15 DEG C/min, and the heating-up time is set as 40~60min, during sintered heat insulatingBetween be set as 10~15min；
(9), cool down：Open tunnel furnace door to take out semi-finished product silk-screen printing circuit electrode, cooled down rapidly with ventilating fanTo room temperature, cool time is not higher than 10min, obtains final product silk-screen printing circuit electrode finished product.
Silk-screen printing circuit electrode after being sintered through continuous tunnel furnace is in glassy yellow, has carried out electric conductivity, tension to its performance strongDegree, solderability, metallographic pattern, air inoxidizability dependence test, as a result show：Copper alloy electric slurry is in substrate surface shapeInto two electrodes, the film layer of three electrodes, each performance indications are all good, reach industrial application requirement, and specific embodiment is as follows：
Embodiment one
It is spherical silver powder, the spherical titanium that 10g granularities are 1um of the spherical copper powder of 1um, 10g granularities for 1um to take 80g granularitiesPowder obtains 100g conduction phase mixtures；300 DEG C of Low Temperature Zn-aluminium-silica glass powder, titanium-aluminium-silica glass powder and conductive crystallite glass dust1000 mesh sieves are crossed respectively, the lower glass dust of sieve is taken, and 1g zinc-aluminium-silica glass powder, 1g titanium-aluminium-silica glass powder, 8g conductions are taken respectively micro-Crystal glass powder is mutually mixed and obtains 10g bonding phase mixtures；Take 1g butyral resins, 8g terpinols, 0.5g castor oil, 0.5g oleic acidIt is mutually mixed and heating water bath is to whole dissolvings, 100g organic phase solutions is obtained；Take 80gA, 10gB, 10gC mixing, agitated deviceStirring 2h, grinds through three-roll grinder, and grinding space is 10um and 5um, repeatedly 3 times.Copper alloy slurry is obtained, using metatitanic acidStrontium piezoresistor will print electrode in continuous tunnel furnace dumping for base material in silk screen brush electrode, then through continuous tunnel furnace；Dumping process：Logical nitrogenGas excludes air to oxygen content 1%；Gas moves in circles mixing in continuous tunnel furnace；250 DEG C of dump temperature；The dumping time from enter stove toCome out of the stove 15min；Above-mentioned printing electrode is sintered again in continuous tunnel furnace；Sintering process：Vacuumize same nitrogen control oxygen content10ppm；Gas moves in circles in continuous tunnel furnace and is used in mixed way；600 DEG C of sintering temperature；15 DEG C/min of programming rate；Heating-up time40min；Sintered heat insulating time 15min；Blow-on door and ventilating fan are rapidly cooled to room temperature；Cool time 5min, is obtained product warpCross and detect qualified, as shown in table 1, prepared copper electrode and circuit material are qualified by detection, and specific data are shown in Table one for specific data.
Embodiment two
The spherical copper powder of 80g granularities 1um, the spherical silver powder of 5g granularities 1um, the spherical titanium valve of 15g granularities 1um is taken to obtain100g conduction phase mixtures；300 DEG C of Low Temperature Zn-aluminium-silica glass powder, titanium-aluminium-silica glass powder and conductive crystallite glass dust cross 1000Mesh sieve, takes the lower glass dust of sieve, and 1g zinc-aluminium-silica glass powder, 1g titanium-aluminium-silica glass powder, 8g conductive crystallite glass dust phases are taken respectivelyMutually it is mixed to get 10g and bonds phase mixture；1g butyral resins, 8g terpinols, 0.5g castor oil, 0.5g oleic acid are taken, is mutually mixedAnd heating water bath is to whole dissolvings, 10g organic phase solutions are obtained；80gA, 10gB, 10gC mixing are taken, after agitated device stirring 2h,Ground through three-roll grinder again, grind space 10um and 5um, repeatedly 3 times.Copper alloy slurry is obtained, it is pressure-sensitive using strontium titanatesResistor will print electrode in continuous tunnel furnace dumping for base material in silk screen brush electrode, then through continuous tunnel furnace；Dumping process：Logical nitrogen is excludedTo oxygen content 1%, gas moves in circles mixing air in continuous tunnel furnace；250 DEG C of dump temperature；The dumping time is from entering stove to coming out of the stove15min；Above-mentioned printing electrode is sintered again in continuous tunnel furnace；Sintering process：Vacuumize same nitrogen control oxygen content 10ppm；GasBody moves in circles in continuous tunnel furnace and is used in mixed way；600 DEG C of sintering temperature；15 DEG C/min of programming rate；Heating-up time 40min；SinteringSoaking time 15min；Blow-on door and ventilating fan are rapidly cooled to room temperature；Cool time 5min, prepared product is qualified by detection,As shown in table 1, prepared copper electrode and circuit material are qualified by detection, and specific data are shown in Table one for specific data.
Embodiment three
The spherical copper powder of 80g granularities 3um is taken, the spherical silver powder of 15g granularities 1um, the spherical titanium valve of 5g granularities 1um are obtained100g conduction phase mixtures；300 DEG C of Low Temperature Zn-aluminium-silica glass powder, titanium-aluminium-silica glass powder and conductive crystallite glass dust cross 1000Mesh sieve, takes the lower glass dust of sieve, and 1g zinc-aluminium-silica glass powder, 1g titanium-aluminium-silica glass powder, 8g conductive crystallite glass dust phases are taken respectivelyMutually it is mixed to get 10g and bonds phase mixture；1g butyral resins, 8g terpinols, 0.5g castor oil, 0.5g oleic acid are taken, is mutually mixedAnd heating water bath is to whole dissolvings, 100g organic phase solutions are obtained；80gA, 10gB, 10gC mixing are taken, agitated device stirs 2hAfterwards, then through three-roll grinder grind, grinding space is 10um and 5um, repeatedly 3 times.Copper alloy slurry is obtained, using strontium titanatesPiezoresistor will print electrode in continuous tunnel furnace dumping for base material in silk screen brush electrode, then through continuous tunnel furnace；Dumping process：Logical nitrogenExclude air to oxygen content 1%；Gas moves in circles mixing in continuous tunnel furnace；250 DEG C of dump temperature；The dumping time is from entering stove to going outStove 15min；Above-mentioned printing electrode is sintered again in continuous tunnel furnace；Sintering process：Same nitrogen control oxygen content 10ppm is vacuumized,Gas moves in circles in continuous tunnel furnace and is used in mixed way；Sintered heat insulating temperature is 600 DEG C, 15 DEG C/min of programming rate, heating-up time40min, sintered heat insulating time 15min；Product is rapidly cooled to room temperature cool time 5min by blow-on door and ventilating fan, is obtained and is producedProduct are qualified by detection, and specific data are as shown in Table 1.
Example IV
The spherical copper powder of 80g granularities 1um, the spherical silver powder of 10g granularities 1um, the spherical titanium valve of 10g granularities 1um is taken to obtain100g conduction phase mixtures；300 DEG C of Low Temperature Zn-aluminium-silica glass powder, titanium-aluminium-silica glass powder and conductive crystallite glass dust cross 1000Mesh sieve, takes the lower glass dust of sieve, and 1g zinc-aluminium-silica glass powder, 1g titanium-aluminium-silica glass powder, 8g conductive crystallite glass dust phases are taken respectivelyMutually it is mixed to get 10g and bonds phase mixture；2g ethyl celluloses, 7g terpinols, 0.5g castor oil, 0.5g oleic acid are taken, it is mutually mixedMerge heating water bath to whole dissolvings, 100g organic phase solutions are obtained；80gA, 10gB, 10gC mixing are taken, agitated device stirs 2hAfterwards, then through three-roll grinder grind, grinding space is 10um and 5um, repeatedly 3 times.Copper alloy slurry is obtained, using strontium titanatesPiezoresistor will print electrode in continuous tunnel furnace dumping for base material in silk screen brush electrode, then through continuous tunnel furnace；Dumping process：Logical nitrogenAir is excluded to oxygen content 1%, gas moves in circles mixing in continuous tunnel furnace；250 DEG C of dump temperature；The dumping time is from entering stove to going outStove 15min；Above-mentioned printing electrode is sintered again in continuous tunnel furnace；Sintering process：Same nitrogen control oxygen content 10ppm is vacuumized,Gas moves in circles in continuous tunnel furnace and is used in mixed way；Sintered heat insulating temperature is 600 DEG C, 15 DEG C/min of programming rate, heating-up time40min；Sintered heat insulating time 15min；Product is rapidly cooled to room temperature cool time 5min by blow-on door and ventilating fan, is obtained and is producedProduct are qualified by detection, and specific data are as shown in Table 1.
The copper alloy electric slurry of table one forms electric conductivity, thickness and the tensile strength properties of three electrode film layers in substrate surface
Wherein, E10 is the magnitude of voltage that logical 10V voltages reflect on three electrodes, the good critical field of electric conductivityFor：Higher limit 6.60V, lower limit 4.00V.
In sum, silk-screen printing circuit electrode of the present invention and preparation method thereof sinters to be formed by copper alloy electric slurryAlloy can well prevent copper of the copper alloy electric slurry in sintering process from aoxidizing, copper alloy electric slurry can be attached wellOn base material, adhesive property is good, good with cheap, easy preparation, adhesive property, solderability, tensile strength, electric conductivityThe advantages of.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneouslyTherefore limitation of the scope of the invention can not be interpreted as.It should be pointed out that for the person of ordinary skill of the art,Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection model of the inventionEnclose.Therefore, protection scope of the present invention should be determined by the appended claims.