CN112002458A - Inorganic filler surface coated silver, waterborne photocuring conductive silver paste thereof and preparation method thereof - Google Patents
Inorganic filler surface coated silver, waterborne photocuring conductive silver paste thereof and preparation method thereof Download PDFInfo
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
The invention discloses an aqueous photocuring conductive silver paste with a silver-coated inorganic filler surface, which is characterized by comprising the following components in parts by weight: the conductive silver paste comprises the following components in percentage by mass: 10-70% of inorganic filler with silver coated on the surface, 15-60% of polyacrylate water-based resin, 5-40% of water and 0.1-5% of photoinitiator. The aqueous photocuring silver paste can be used for printing a film silver layer with high density and good uniformity, has excellent conductivity, and is suitable for film printing of various electronic devices.
Description
Technical Field
The invention belongs to the technical field of inorganic fillers, and particularly relates to an inorganic filler surface silver coating and aqueous photocuring conductive silver paste and a preparation method thereof.
Technical Field
The conductive silver paste has various types, and according to a curing system, the conductive silver paste can be further classified into room-temperature curing conductive silver paste, medium-temperature curing conductive silver paste, high-temperature sintering conductive silver paste, ultraviolet curing conductive silver paste and the like. The room-temperature curing conductive silver paste system is unstable, and the surface resistivity is easy to change during room-temperature storage; the high-temperature conductive silver paste needs high-temperature sintering, has high use temperature, is not suitable for semiconductors, sensitive elements and base materials which cannot tolerate high temperature, such as flexible substrates, ITO films and the like, and has narrow application range, long process period and high energy consumption; at present, the intermediate-temperature curing conductive silver paste is mostly applied at home and abroad, the curing temperature is moderate, the intermediate-temperature curing conductive silver paste is matched with the temperature resistance and the use temperature of electronic components, the mechanical property is excellent, but the intermediate-temperature curing conductive silver paste is still limited for heat sensitive elements, flexible base materials and ITO films.
The principle of the aqueous photocuring conductive silver paste is that under the irradiation of ultraviolet light, a photoinitiator absorbs photons with specific wavelengths, is excited to an excited state to form free radicals or cations, then through the transmission of intermolecular energy, a polymerizable prepolymer, a photosensitive monomer and the like are converted into an excited state to generate charge transfer polymers, and the polymers are continuously crosslinked and polymerized to generate a high molecular weight polymer which is solidified into a three-dimensional network structure and has a high molecular weight in a very short time. The photocuring conductive silver paste combines an ultraviolet curing technology with the conductive paste, gives the conductive paste new performance and enlarges the application range, but the traditional solid silver powder usually uses an oily solvent, so that the environment is polluted, the cost is high, and the photocuring conductive silver paste is only suitable for thick film printing and is difficult to reduce the thickness of a printed film.
Disclosure of Invention
The invention aims to solve the technical problems and provides the inorganic filler surface silver coating, the waterborne photocuring conductive silver paste and the preparation method thereof.
In order to achieve the purpose, the invention designs the waterborne photocuring conductive silver paste with the surface coated with the silver on the inorganic filler, which is characterized in that: the conductive silver paste comprises the following components in percentage by mass: 10-70% of inorganic filler with silver coated on the surface, 15-60% of polyacrylate water-based resin, 5-40% of water and 0.1-5% of photoinitiator.
The inorganic filler is one or more of alumina, silicon oxide, titanium oxide, zirconium oxide, ferric oxide, calcium oxide, copper oxide, zinc oxide and the like and hollow glass beads, and is ground into particles of 0.1-100 um for use through a ball milling process.
The photoinitiator is one or more of Benzoyl Peroxide (BPO), Azobisisobutyronitrile (AIBN), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl phenylpropyl ketone.
The preparation method of the waterborne photocuring conductive silver paste comprises the steps of adding polyacrylate waterborne resin into water, stirring and dissolving, adding a photoinitiator and inorganic filler with silver coated on the surface, mixing by a stirrer, grinding and dispersing uniformly by a three-roll grinder, and filtering by a 200-mesh gauze when the particle size is smaller than 2 mu m to obtain the waterborne photocuring conductive silver paste.
A preparation method of silver-coated inorganic filler surface comprises the following steps:
step 1: firstly, adding absolute ethyl alcohol into an inorganic filler, putting the inorganic filler into an ultrasonic cleaner for cleaning, filtering after cleaning, and then drying;
step 2: preparing a citric acid solution with the pH value of 6-8, adding the inorganic filler subjected to drying treatment in the step 1 into the citric acid solution, stirring for reaction, filtering the inorganic filler grafted with citric acid after the reaction is finished, and drying;
and step 3: pouring ammonia water into the silver nitrate solution to obtain a silver-ammonia solution;
and 4, step 4: and (3) adding the citric acid grafted inorganic filler obtained in the step (2) into the silver-ammonia solution, dropwise adding a glucose solution into the solution, filtering and drying the inorganic filler with silver coated on the surface to obtain the inorganic filler silver-coated particles.
In the step 1 of the technical scheme, the glass fiber is placed into an ultrasonic cleaner to be cleaned for 1-10 min, then is cleaned for 1-10 min by using deionized water in an ultrasonic mode, is filtered after being cleaned, and is placed into a vacuum dryer at the temperature of 30-100 ℃ to be dried for 6-24 h.
In the step 2 of the technical scheme, 450-550 ml of citric acid solution with the mass percentage concentration of 1-10% is prepared, the pH value of the citric acid solution is adjusted to 6-8 by using NaOH solution, 1-10 g of cleaned and dried inorganic filler is weighed and added into the citric acid solution, the mixture is stirred at normal temperature for 5-24 hours at the stirring speed of 50-150 RPM, the inorganic filler grafted with the citric acid is filtered after the reaction is finished, and the mixture is placed in a vacuum drier with the temperature of 30-100 ℃ for drying for 6-24 hours.
In the step 3 of the technical scheme, 9-11 ml of silver nitrate solution with the mass percentage concentration of 5-40% and 9-11 ml of ammonia water solution with the mass percentage concentration of 5-40% are prepared, the ammonia water solution is poured into the silver nitrate solution to obtain silver ammonia solution, and 9-11 ml of glucose solution with the mass percentage concentration of 5-30% is prepared.
In the step 4 of the technical scheme, the inorganic filler grafted by citric acid is weighed and added into the silver ammonia solution, glucose solution is dropwise added into the solution at the dropping speed of 1-2 drops/second, the reaction is continued for 10-60 min after the dropwise addition is finished, the inorganic filler with silver coated on the surface is filtered, and the inorganic filler is dried in a vacuum drier at the temperature of 30-100 ℃ for 6-24 h to obtain the inorganic filler silver coated particles.
A preparation method of polyacrylate waterborne resin in waterborne photocuring conductive silver paste with silver coated on the surface of inorganic filler is disclosed, and the method is characterized in that pentaerythritol, benzenesulfonic acid, toluene and thioglycollic acid are added into a flask, wherein the mass percentages of the components are as follows: 5-30% of pentaerythritol, 0.1-20% of benzenesulfonic acid, 10-50% of toluene and 10-50% of thioglycolic acid, heating (at 110 ℃) to reflux the toluene for 1-5 hours, pouring the mixture in a flask into a saturated sodium bicarbonate solution, extracting by using ethyl acetate, washing an extract by using hydrochloric acid with the mass percentage concentration of 9-11% and a saturated sodium chloride solution, drying by using anhydrous magnesium sulfate to obtain a solid product, namely a 4-branched-chain prepolymer, adding acrylic acid (the molar ratio of acrylic acid to itaconic acid is 8:2), itaconic acid, the 4-branched-chain prepolymer, deionized water and azodiisobutyronitrile into the other flask, wherein the mass percentages of the components are as follows: 10-50% of acrylic acid, 10-40% of itaconic acid, 10-50% of 4-branched chain prepolymer, 1-10% of deionized water and 0.01-1% of azodiisobutyronitrile, wherein the solution is vacuumized and filled with nitrogen, the temperature of the solution is raised to 50-80 ℃ and kept for 10-24 hours, and acrylic water-based resins with different molecular weights are obtained by changing the dosage of the 4-branched chain prepolymer, so that the acrylic water-based resin is finally formed. And freeze-drying and storing. The yield was greater than 96%.
The invention adopts the matching of the inorganic filler with silver coated on the surface and the water-based polyacrylate, has low cost and environmental protection, can realize the rapid curing of ultraviolet light and effectively improve the conductivity of the slurry, and the water-based light-cured conductive slurry can be printed on the surfaces of materials such as electronic circuit boards, film switches, Radio Frequency Identification (RFID), flexible coils, wearable products, thin-film solar cells, metals, plastics, ITO films and the like in a printing way. The adhesive can be widely applied to the rapid bonding and conduction in the fields of touch screens, CSPs, FPCs, FPC/ITO, PET/ITO glass, PET/PET, Flip chips (Flip chips), Liquid Crystal Displays (LCDs), Radio Frequency Identification (RFID), membrane switches, EL backlight terminals and the like.
The aqueous photocuring conductive silver paste has photochemical sensitivity, so that the production efficiency can be greatly improved; and (4) construction safety: the product is an environment-friendly product without organic solvent, has low curing temperature, is particularly excellent for thermosensitive materials, and can solve deep curing; the curing energy consumption is low, and the cost is saved; after curing, the adhesive has good adhesiveness and solvent resistance; the adhesive strength is high, and the resistivity is low; and is suitable for large-scale production of an automatic assembly line.
The waterborne photocuring conductive silver paste prepared by selecting the inorganic filler surface to be coated with silver and simultaneously matching the waterborne polyacrylate resin and the photoinitiator has the following advantages: (1) no volatilization, and the solvent is environment-friendly water; (2) the cost is low, the inorganic filler is used for coating silver on the surface, and the using amount of the silver is small; (3) the preparation process of the conductive paste is simple, and less equipment is used; (4) the cured adhesive film has excellent conductivity; (5) can be rapidly cured at room temperature, meets the requirement of industrial high-efficiency production, and is energy-saving and environment-friendly.
Detailed Description
The present invention is further illustrated in detail by the following examples:
example 1
1. Preparation of silver-coated aluminum oxide particles: adding absolute ethyl alcohol into a beaker filled with alumina (the particle size is 0.1-1.0 um), putting the beaker into an ultrasonic cleaner, cleaning for 5min, and then ultrasonically cleaning for 5min by using deionized water. After cleaning, filtering, and drying in a vacuum drier at 50 ℃ for 12 h. Preparing 500ml of citric acid solution with the mass fraction of 5%, adjusting the pH value of the citric acid solution to 8 by using NaOH solution, weighing 5g of cleaned and dried alumina, adding the alumina into the citric acid solution, and stirring at the normal temperature for 12 hours at the stirring speed of 50-150 RPM. After the reaction is finished, filtering the alumina grafted with the citric acid, and drying in a vacuum drier at 50 ℃ for 12 hours.
Preparing a silver plating solution: 10ml of silver nitrate solution with the mass ratio of 20% and 10ml of 20% ammonia water solution are prepared, and the ammonia water is poured into the silver nitrate solution to obtain the silver ammonia solution. 10ml of 10% glucose solution was prepared. Weighing the citric acid grafted alumina, adding the citric acid grafted alumina into the silver ammonia solution, and dropwise adding a glucose solution into the solution at a dropwise adding speed of 1-2 d/s. And (3) continuing the reaction for 30min after the dropwise addition, filtering the silver-coated aluminum oxide, and drying the silver-coated aluminum oxide in a vacuum drier at 50 ℃ for 12h to obtain silver-coated aluminum oxide particles.
2. Preparation of polyacrylate water-based resin: 11.10g of pentaerythritol, 1.25g of benzenesulfonic acid and 50g of toluene, and 37.1g of mercaptoacetic acid were weighed in. Reflux (110 ℃ C.) in toluene for 3.5h, pour the mixture into saturated sodium bicarbonate solution and extract with ethyl acetate. The extract is washed by hydrochloric acid with the mass fraction of 10% and saturated sodium chloride solution, and dried by anhydrous magnesium sulfate to obtain a solid product, namely the 4-branched chain prepolymer. 5.19g of acrylic acid, 2.34g of itaconic acid, 5g of 4-branched prepolymer, 5g of deionized water and 0.09g of azobisisobutyronitrile were added to the flask, and the solution was heated to 70 ℃ and held for 17 hours by evacuation and nitrogen injection. (acrylic acid: itaconic acid molar ratio 8: 2). The different molecular weights are obtained by varying the amount of prepolymer used. And finally, freeze-drying and storing the acrylic waterborne resin. The yield was greater than 96%.
The preparation method of the waterborne photocuring conductive silver paste comprises the following steps of:
1. the components comprise 50 mass percent of silver-coated aluminum oxide, namely 50 mass percent of inorganic filler (the particle size is 0.1-1.0 um) coated with silver on the surface, 40 mass percent of polyacrylate water-based resin, 9.5 mass percent of water and 0.5 mass percent of photoinitiator. Continuously stirring and premixing to prepare viscous slurry for later use; 2. adopting a planetary mixer, and continuously mixing and dispersing the slurry according to rotation at 3000RPM and revolution at 1000RPM to prepare a paste mixture; 3. and grinding the paste mixture by using a three-roll grinder to obtain the waterborne photocuring conductive silver paste with the fineness less than 2 um.
Example 2
1. Preparation of silver-coated silicon oxide particles: adding absolute ethyl alcohol into a beaker filled with silicon oxide (the particle size is 0.5-1.5 um), putting the beaker into an ultrasonic cleaner, cleaning for 5min, and then ultrasonically cleaning for 5min by using deionized water. After cleaning, filtering, and drying in a vacuum drier at 50 ℃ for 12 h. Preparing 500ml of citric acid solution with the mass fraction of 5%, adjusting the pH value of the citric acid solution to 8 by using NaOH solution, weighing 5g of cleaned and dried silicon oxide, adding the silicon oxide into the citric acid solution, and stirring at the normal temperature for 12 hours at the stirring speed of 50-150 RPM. After the reaction is finished, filtering the silica grafted with the citric acid, and drying in a vacuum drier at 50 ℃ for 12 hours.
Preparing a silver plating solution: 10ml of silver nitrate solution with the mass fraction of 20% and 10ml of 20% ammonia water solution are prepared, and the ammonia water is poured into the silver nitrate solution to obtain the silver ammonia solution. 10ml of glucose solution with the mass percentage concentration of 10 percent is prepared. Weighing the citric acid grafted silicon oxide, adding the silicon oxide into the silver ammonia solution, and dropwise adding a glucose solution into the solution at a dropwise adding speed of 1-2 d/s. And after the dropwise addition, continuing the reaction for 30min, filtering the silver-coated silicon oxide, and drying the silver-coated silicon oxide in a vacuum dryer at the temperature of 50 ℃ for 12h to obtain silver-coated silicon oxide particles.
2. Preparation of polyacrylate water-based resin: 11.10g of pentaerythritol, 1.25g of benzenesulfonic acid and 50g of toluene, and 37.1g of mercaptoacetic acid were weighed in. Reflux (110 ℃ C.) in toluene for 3.5h, pour the mixture into saturated sodium bicarbonate solution and extract with ethyl acetate. The extract is washed by hydrochloric acid with the mass fraction of 10% and saturated sodium chloride solution, and dried by anhydrous magnesium sulfate to obtain a solid product, namely the 4-branched chain prepolymer. 5.19g of acrylic acid, 2.34g of itaconic acid, 5g of 4-branched prepolymer, 5g of deionized water and 0.09g of azobisisobutyronitrile were added to the flask, and the solution was heated to 70 ℃ and held for 17 hours by evacuation and nitrogen injection. (acrylic acid: itaconic acid molar ratio 8: 2). The acrylic waterborne resins with different molecular weights are obtained by changing the dosage of the 4-branched prepolymer. And finally, freeze-drying and storing the acrylic waterborne resin. The yield was greater than 96%.
The preparation method of the waterborne photocuring conductive silver paste comprises the following steps of:
1. the components comprise 47 mass percent of silver-coated silicon oxide (the particle size is 0.5-1.0 um), 45 mass percent of polyacrylate water-based resin, 7.5 mass percent of water and 0.5 mass percent of photoinitiator. Continuously stirring and premixing to prepare viscous slurry for later use; 2. continuously mixing and dispersing the viscous slurry by adopting a planetary mixer according to the rotation speed of 3000RPM and the revolution speed of 1000RPM to prepare a pasty mixture; (3) and grinding the paste mixture by using a three-roll grinder to obtain the waterborne photocuring conductive silver paste with the fineness less than 2 um.
Example 3
1. Preparation of silver-coated zirconia particles: adding absolute ethyl alcohol into a beaker filled with zirconium oxide (the particle size is 1.0-2.0 um), putting the beaker into an ultrasonic cleaner, cleaning for 5min, and then ultrasonically cleaning for 5min by using deionized water. After cleaning, filtering, and drying in a vacuum drier at 50 ℃ for 12 h. Preparing 500ml of citric acid solution with the mass fraction of 5%, adjusting the pH value of the citric acid solution to 8 by using NaOH solution, weighing 5g of cleaned and dried zirconium oxide, adding the zirconium oxide into the citric acid solution, and stirring at the normal temperature for 12 hours at the stirring speed of 50-150 RPM. After the reaction is finished, filtering the zirconium oxide grafted with the citric acid, and drying in a vacuum drier at 50 ℃ for 12 hours.
Preparing a silver plating solution: 10ml of silver nitrate solution with the mass fraction of 20% and 10ml of 20% ammonia water solution are prepared, and the ammonia water is poured into the silver nitrate solution to form silver ammonia solution. 10ml of 10% glucose solution was prepared.
Weighing the citric acid grafted zirconia, adding the citric acid grafted zirconia into the silver ammonia solution, and dropwise adding a glucose solution into the solution at a speed of 1-2 d/s. And (3) continuing the reaction for 30min after the dropwise addition, filtering the silver-coated zirconium oxide, and drying the silver-coated zirconium oxide in a vacuum drier at the temperature of 50 ℃ for 12h to obtain silver-coated zirconium oxide particles.
2. Preparation of polyacrylate water-based resin: 11.10g of pentaerythritol, 1.25g of benzenesulfonic acid, 50g of toluene and 37.1g of mercaptoacetic acid were weighed in. Reflux (110 ℃ C.) in toluene for 3.5h, pour the mixture into saturated sodium bicarbonate solution and extract with ethyl acetate. The extract is washed by hydrochloric acid with the mass fraction of 10% and saturated sodium chloride solution, and dried by anhydrous magnesium sulfate to obtain a solid product, namely the 4-branched chain prepolymer. 5.19g of acrylic acid, 2.34g of itaconic acid, 5g of 4-branched prepolymer, 5g of deionized water and 0.09g of azobisisobutyronitrile were added to the flask, and the solution was heated to 70 ℃ and held for 17 hours by evacuation and nitrogen injection. (acrylic acid: itaconic acid molar ratio 8: 2). The different molecular weights are obtained by varying the amount of prepolymer used. And finally, freeze-drying and storing the acrylic waterborne resin. The yield was greater than 96%.
The preparation method of the waterborne photocuring conductive silver paste comprises the following steps of:
1. the components comprise 45 mass percent of silver-coated zirconium oxide (the particle size is 1.0-2.0 um), 45 mass percent of polyacrylate water-based resin, 9.5 mass percent of water and 0.5 mass percent of photoinitiator. Continuously stirring and premixing to prepare viscous slurry for later use; 2. continuously mixing and dispersing the viscous slurry by adopting a planetary mixer according to the rotation speed of 3000RPM and the revolution speed of 1000RPM to prepare a pasty mixture; and 3, grinding the paste mixture by using a three-roll grinder to obtain the waterborne photocuring conductive silver paste with the fineness less than 2 um.
Testing the performance of the waterborne photocuring conductive silver paste:
1. ultraviolet light curing conductive silver paste printing test: on manual silk screen printing platform, 300 mesh polyester half tone, thickness 20um, print 10um, 15um, 20um, 100um, 150um, 200um lines on the ITO film of shrink. Then passing through a UV curing machine with dominant wavelength of 365nm, and observing the line resolution by using a high power microscope with Hai Yi (UM 038);
2. and (3) testing the viscosity of the ultraviolet light cured conductive silver paste: measuring the viscosity of the aqueous photocuring conductive silver paste at 10RPM after keeping the temperature at 25 ℃ for 1h by using a Rongjida (NDJ-5S) rotational viscometer;
3. testing the adhesive force of the ultraviolet curing silver paste: drawing test lattices on the square pattern by using a lattice knife, and then testing the test lattices by using an adhesive tape (3M810 type), wherein the falling area is not more than 5 percent, and the falling area is qualified, otherwise, the falling area is unqualified;
4. testing the resistance of the ultraviolet light curing conductive silver paste: testing the square resistance by using an RTS-8 type four-probe instrument of Guangzhou four-probe company;
5. and (3) thickness testing: the thickness of the film was measured by Hitachi S-4800 scanning electron microscope.
And (3) testing results:
resistivity is sheet resistance and film thickness.
Thixotropy is viscosity at 100 RPM/viscosity at 10 RPM.
The above results show that: comparative example 1 demonstrates that an aqueous photocurable silver paste prepared using silver-coated aluminum oxide particles and a polyacrylate water-based resin has excellent resolution and adhesion of printed fine lines; meanwhile, the silver-coated inorganic filler is used in comparative examples 2 and 3, so that the thickness of a printing film layer can be conveniently regulated and controlled, the film printing is realized, the filling is compact and uniform, the conductivity of the slurry is good, and the silver-coated inorganic filler can be applied to the fields of circuit boards, touch screens, photovoltaic cells, electromagnetic shielding and the like, and can meet the requirement of high-performance conductivity of modern electronic equipment.
Details not described in this specification are within the skill of the art that are well known to those skilled in the art.
Claims (10)
1. The water-based photocuring conductive silver paste with the surface coated with silver on the inorganic filler is characterized in that: the conductive silver paste comprises the following components in percentage by mass: 10-70% of inorganic filler with silver coated on the surface, 15-60% of polyacrylate water-based resin, 5-40% of water and 0.1-5% of photoinitiator.
2. The aqueous light-cured conductive silver paste with silver coated surface of inorganic filler according to claim 1, characterized in that: the inorganic filler is one or more of alumina, silicon oxide, titanium oxide, zirconium oxide, ferric oxide, calcium oxide, copper oxide, zinc oxide and the like and hollow glass beads, and is ground into particles of 0.1-100 um for use through a ball milling process.
3. The aqueous light-cured conductive silver paste with silver coated surface of inorganic filler according to claim 1, characterized in that: the photoinitiator is one or more of benzoyl peroxide, azobisisobutyronitrile, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
4. The preparation method of the waterborne photocuring conductive silver paste of claim 1, which is characterized by comprising the following steps: adding polyacrylate water-based resin into water, stirring and dissolving, adding a photoinitiator and inorganic filler with silver coated on the surface, mixing by a stirrer, grinding and dispersing uniformly by a three-roll grinder, and filtering by a 200-mesh gauze when the particle size is less than 2 mu m to obtain the waterborne photocuring conductive silver paste.
5. A preparation method of silver-coated inorganic filler is characterized by comprising the following steps:
step 1: firstly, adding absolute ethyl alcohol into an inorganic filler, putting the inorganic filler into an ultrasonic cleaner for cleaning, filtering after cleaning, and then drying;
step 2: preparing a citric acid solution with the pH value of 6-8, adding the inorganic filler subjected to drying treatment in the step 1 into the citric acid solution, stirring for reaction, filtering the inorganic filler grafted with citric acid after the reaction is finished, and drying;
and step 3: pouring ammonia water into the silver nitrate solution to obtain a silver-ammonia solution;
and 4, step 4: and (3) adding the citric acid grafted inorganic filler obtained in the step (2) into the silver-ammonia solution, dropwise adding a glucose solution into the solution, filtering and drying the inorganic filler with silver coated on the surface to obtain the inorganic filler silver-coated particles.
6. The method for preparing the inorganic filler coated with silver on the surface according to claim 5, wherein:
and in the step 1, putting the mixture into an ultrasonic cleaner, cleaning for 1-10 min, then ultrasonically cleaning for 1-10 min by using deionized water, filtering after cleaning, and putting the mixture into a vacuum dryer at the temperature of 30-100 ℃ for drying for 6-24 h.
7. The method for preparing the inorganic filler coated with silver on the surface according to claim 6, wherein: in the step 2, 450-550 ml of citric acid solution with the mass percentage concentration of 1-10% is prepared, the pH value of the citric acid solution is adjusted to 6-8 by NaOH solution, 1-10 g of cleaned and dried inorganic filler is weighed and added into the citric acid solution, the mixture is stirred at normal temperature for 5-24 hours, the stirring speed is 50-150 RPM, the inorganic filler grafted with the citric acid is filtered after the reaction is finished, and the mixture is placed in a vacuum drier with the temperature of 30-100 ℃ for drying for 6-24 hours.
8. The method for preparing the inorganic filler coated with silver on the surface according to claim 7, wherein: in the step 3, 9-11 ml of silver nitrate solution with the mass percentage concentration of 5-40% and 9-11 ml of ammonia water solution with the mass percentage concentration of 5-40% are prepared, the ammonia water solution is poured into the silver nitrate solution to obtain silver ammonia solution, and 9-11 ml of glucose solution with the mass percentage concentration of 5-30% is prepared.
9. The method for preparing the inorganic filler coated with silver on the surface according to claim 8, wherein: and 4, weighing the inorganic filler grafted by the citric acid, adding the inorganic filler into the silver-ammonia solution, dropwise adding a glucose solution into the solution at the dropping speed of 1-2 drops/second, continuing to react for 10-60 min after the dropwise adding is finished, filtering the inorganic filler with the silver coated on the surface, and drying the inorganic filler in a vacuum drier at the temperature of 30-100 ℃ for 6-24 h to obtain the silver-coated inorganic filler particles.
10. A preparation method of polyacrylate waterborne resin in waterborne photocuring conductive silver paste with silver coated on the surface of inorganic filler is characterized by comprising the following steps: pentaerythritol, benzenesulfonic acid, toluene and thioglycollic acid are added into a flask, wherein the mass percentage of each component is as follows: 5-30% of pentaerythritol, 0.1-20% of benzenesulfonic acid, 10-50% of toluene and 10-50% of thioglycollic acid, heating to reflux toluene for 1-5 hours, pouring a mixture in a flask into a saturated sodium bicarbonate solution, extracting by ethyl acetate, washing an extract by using hydrochloric acid with the mass percentage concentration of 9-11% and a saturated sodium chloride solution, drying by using anhydrous magnesium sulfate to obtain a solid product, namely a 4-branched chain prepolymer, and adding acrylic acid, itaconic acid, the 4-branched chain prepolymer, deionized water and azobisisobutyronitrile into another flask, wherein the mass percentages of the components are as follows: 10-50% of acrylic acid, 10-40% of itaconic acid, 10-50% of 4-branched chain prepolymer, 1-10% of deionized water and 0.01-1% of azodiisobutyronitrile, wherein the solution is vacuumized and filled with nitrogen, the temperature of the solution is raised to 50-80 ℃ and kept for 10-24 hours, and acrylic water-based resins with different molecular weights are obtained by changing the dosage of the 4-branched chain prepolymer, so that the acrylic water-based resin is finally formed.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728001A (en) * | 2009-11-12 | 2010-06-09 | 东南大学 | Lead-free and low-silver photosensitive silver paste and preparation method thereof |
| CN102329257A (en) * | 2011-09-24 | 2012-01-25 | 潍坊加华化工有限公司 | Production method of thioglycolic acid pentaerythritol ester |
| CN102369240A (en) * | 2009-03-24 | 2012-03-07 | 赢创罗姆有限公司 | Composition comprising as the aqueous dispersion preferably (meth)acrylate polymers containing benzophenone in a mixture with (meth)acrylate polymers different therefrom and the use of said composition |
| CN102903418A (en) * | 2011-07-29 | 2013-01-30 | 硕禾电子材料股份有限公司 | Conductive composition |
| CN103341643A (en) * | 2013-07-26 | 2013-10-09 | 武汉理工大学 | Preparation method of composite reducing agent liquid phase for conductive composite particles coated with silver shell layers |
| CN105907357A (en) * | 2016-05-06 | 2016-08-31 | 金宝丽科技（苏州）有限公司 | Photo-curing and thermal curing heat-resistant conductive adhesive material and preparation method thereof |
| US20170081532A1 (en) * | 2015-09-17 | 2017-03-23 | Eastman Kodak Company | Ink jettable, uv-curable compositions |
| CN107858039A (en) * | 2017-11-13 | 2018-03-30 | 天津宝兴威科技股份有限公司 | A kind of preparation method of water-based UV conductive oils ink film |
-
2020
- 2020-08-03 CN CN202010770065.XA patent/CN112002458A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102369240A (en) * | 2009-03-24 | 2012-03-07 | 赢创罗姆有限公司 | Composition comprising as the aqueous dispersion preferably (meth)acrylate polymers containing benzophenone in a mixture with (meth)acrylate polymers different therefrom and the use of said composition |
| CN101728001A (en) * | 2009-11-12 | 2010-06-09 | 东南大学 | Lead-free and low-silver photosensitive silver paste and preparation method thereof |
| CN102903418A (en) * | 2011-07-29 | 2013-01-30 | 硕禾电子材料股份有限公司 | Conductive composition |
| CN102329257A (en) * | 2011-09-24 | 2012-01-25 | 潍坊加华化工有限公司 | Production method of thioglycolic acid pentaerythritol ester |
| CN103341643A (en) * | 2013-07-26 | 2013-10-09 | 武汉理工大学 | Preparation method of composite reducing agent liquid phase for conductive composite particles coated with silver shell layers |
| US20170081532A1 (en) * | 2015-09-17 | 2017-03-23 | Eastman Kodak Company | Ink jettable, uv-curable compositions |
| CN105907357A (en) * | 2016-05-06 | 2016-08-31 | 金宝丽科技（苏州）有限公司 | Photo-curing and thermal curing heat-resistant conductive adhesive material and preparation method thereof |
| CN107858039A (en) * | 2017-11-13 | 2018-03-30 | 天津宝兴威科技股份有限公司 | A kind of preparation method of water-based UV conductive oils ink film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113192665A (en) * | 2021-04-28 | 2021-07-30 | 北京梦之墨科技有限公司 | Electronic device and manufacturing method thereof |
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