circuit board ink-jet printing conductive LED photocuring ink and preparation method thereof
阅读说明：本技术 一种线路板喷墨打印导电led光固化墨水及其制备方法 (circuit board ink-jet printing conductive LED photocuring ink and preparation method thereof ) 是由 冉淑燕 宋雪霞 李文彬 于 2019-09-29 设计创作，主要内容包括：本发明涉及一种线路板喷墨打印导电LED光固化墨水及其制备方法。该墨水组分按照质量百分比包括：8.0～20.0％预聚体树脂,2.0～4.0％颜料,3.0～10.0％银纳米粒子,1.0～3.0％分散剂,40.0～70.0％活性稀释剂,5.0～10.0％光引发剂,0.5～1.0％流平剂,0.1～1.0％阻聚剂。该方法包括：含银纳米粒子的颜料色浆制备,混合液制备,光固化墨水制备。该墨水精准度高、固化快、稳定性好、导电性能好、适合不同颜色线路打印。(The invention relates to a circuit board ink-jet printing conductive LED photocuring ink and a preparation method thereof. The ink comprises the following components in percentage by mass: 8.0-20.0% of prepolymer resin, 2.0-4.0% of pigment, 3.0-10.0% of silver nanoparticles, 1.0-3.0% of dispersing agent, 40.0-70.0% of reactive diluent, 5.0-10.0% of photoinitiator, 0.5-1.0% of flatting agent and 0.1-1.0% of polymerization inhibitor. The method comprises the following steps: preparing pigment color paste containing silver nanoparticles, preparing mixed liquid and preparing photocureable ink. The ink has high precision, fast curing, high stability, high conductivity and suitability for printing different color lines.)
1. The LED photocuring ink is characterized by comprising the following components in percentage by mass: 8.0-20.0% of prepolymer resin, 2.0-4.0% of pigment, 3.0-10.0% of silver nanoparticles, 1.0-3.0% of dispersing agent, 40.0-70.0% of reactive diluent, 5.0-10.0% of photoinitiator, 0.5-1.0% of flatting agent and 0.1-1.0% of polymerization inhibitor.
2. The ink of claim 1, wherein the prepolymer resin is one or more of epoxy acrylate, polyester acrylate, and urethane acrylate.
3. The ink of claim 1, wherein the pigment is a Cyan, Magenta Yellow or Black four primary color.
4. The ink according to claim 1, wherein the silver nanoparticles have a particle size of 20 to 40 nm; the dispersant is one or more of Efka6225, Efka6230, Efka7731, Efka7732, Efka6230, Efka4340 and Efka 7701.
5. The ink according to claim 1, wherein the reactive diluent is one or more selected from the group consisting of cyclic trimethylolpropane formal methacrylate, tetrahydrofuran methacrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, lauric acid acrylic acid, tripropylene glycol methyl ether acrylate, trimethylol cyclohexyl acrylate, 4-tert-butyl cyclohexyl acrylate, 2 (propoxylated) neopentyl glycol diacrylate, (ethoxylated) 1, 6-hexanediol diacrylate, propoxylated (2) dipropylene glycol acrylate, pentaerythritol triacrylate, and (3) glycerol propylene oxide triacrylate.
6. The ink according to claim 1, wherein the photoinitiator is prepared by compounding an acyl phosphorus oxide initiator and a thioxanthone initiator according to a mass ratio of 5: 1-8: 1.
7. The ink of claim 1, wherein the leveling agent is a crosslinkable leveling agent containing acrylic functional groups, and the crosslinkable leveling agent containing acrylic functional groups comprisesRad2010、Rad2011、Rad2200N、Rad2100、Rad2250、One or more of Rad 2300.
8. The ink according to claim 1, wherein the polymerization inhibitor is at least one of a methylphenol-based polymerization inhibitor and an amine-based polymerization inhibitor.
9. A method of making the ink of claim 1, comprising:
(1) dissolving a dispersing agent into 20-50% of an active diluent, stirring, adding the pigment and the silver nanoparticles, and grinding and dispersing to obtain pigment color paste containing the silver nanoparticles;
(2) Adding prepolymer resin, a photoinitiator, a flatting agent and a polymerization inhibitor into the rest of the reactive diluent, and stirring to obtain a mixed solution;
(3) And (3) adding the pigment color paste containing the silver nanoparticles in the step (1) into the mixed liquid in the step (2), stirring, centrifuging and filtering to obtain the circuit board ink-jet printing conductive LED photocuring ink.
10. Use of the ink of claim 1 in conductive lines.
Technical Field
The invention belongs to the field of photocuring ink and preparation thereof, and particularly relates to conductive LED photocuring ink for ink-jet printing of a circuit board and a preparation method thereof.
background
The traditional circuit board line mainly takes printing as a main part, the printing process is complex in process, plate making is needed, the printing precision is not high, and the requirement on a tiny electric line cannot be met, so that the application on the tiny electric line is limited.
The ink-jet printing technology has the advantages of digitalization, refinement, material waste reduction, non-contact printing and extremely simple process, and the required patterns can be printed out only by inputting the patterns stored in the computer into the computer under the control of the computer, so that the ink-jet printing technology is rapidly developed and has penetrated into various fields of our lives, including the technical field of circuit boards. The conductive ink jet printing technology is an advanced technology of circuit board printing, and is a development trend of the circuit board technology, at present, the conductive ink for ink jet printing mainly takes water-based ink and solvent-based ink, the water-based ink needs to be added with a large amount of humectant in the preparation process to prevent a spray head from being blocked, so that the drying speed after printing is too slow, if moisture can not be completely dried, the conductivity is greatly influenced, the solvent-based conductive ink also needs to prevent the spray head from being moisturized, a large amount of high boiling point solvent is added in a formula, so that the drying speed is influenced, and the solvent is volatilized to cause environmental pollution.
At present, the UV ink-jet printing conductive ink is fast in curing and small in environmental pollution, so that the UV ink-jet printing conductive ink becomes a hot point for research, and is represented by patent CN201910500243.4, a large amount of nano metal is directly added into a monomer, the nano metal dispersion stability is obviously insufficient, and nano metal sedimentation is more and more serious along with the prolonging of time, so that the printing fluency is poor, and even a jet orifice is seriously blocked.
Therefore, in order to solve the above technical problems, there is an urgent need to develop a stable photo-curable conductive ink.
Disclosure of Invention
The invention aims to solve the technical problem of providing the circuit board ink-jet printing conductive LED photocuring ink and the preparation method thereof, so as to overcome the defects of slow drying, poor conductivity, poor stability, low printing precision and unsuitability for printing tiny circuits in the prior art.
The invention provides a circuit board ink-jet printing conductive LED photocuring ink which comprises the following components in percentage by mass: 8.0-20.0% of prepolymer resin, 2.0-4.0% of pigment, 3.0-10.0% of silver nanoparticles, 1.0-3.0% of dispersing agent, 40.0-70.0% of reactive diluent, 5.0-10.0% of photoinitiator, 0.5-1.0% of flatting agent and 0.1-1.0% of polymerization inhibitor.
the prepolymer resin is one or more of epoxy acrylate, polyester acrylate and polyurethane acrylate.
The epoxy acrylate is one or more of CN110NS, CN117, CN131NS and CN159 NS.
The polyester acrylate is one or more of CN7001NS, CN8010NS, CN790 and CN 750.
The polyurethane acrylate is one or more of CN9013NS, CN9021NS, CN9178NS and CN9110 NS.
The pigment is four primary colors of Cyan Cyan, Magenta, Yellow or Black Black.
The pigment is one of C.I. pigment blue 15:3, C.I. pigment blue 15:4, C.I. pigment red 122, C.I. pigment red 202, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 155 and C.I. pigment black 7.
The particle size of the silver nanoparticles is 20-40 nm.
The dispersant is one or more of Efka6225, Efka6230, Efka7731, Efka7732, Efka6230, Efka4340 and Efka 7701.
The active diluent is one or more of cyclic trimethylolpropane formal methacrylate, tetrahydrofuran methacrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, lauric acid acrylic acid, tripropylene glycol methyl ether acrylate, trimethylol cyclohexyl acrylate, 4-tert-butyl cyclohexyl acrylate, 2 (propoxylated) neopentyl glycol diacrylate, (ethoxylated) 1, 6-hexanediol diacrylate, propoxylated (2) dipropylene glycol acrylate, pentaerythritol triacrylate and (3) glycerol propylene oxide triacrylate.
The photoinitiator is prepared by compounding an acyl phosphorus oxide initiator and a thioxanthone initiator according to the mass ratio of 5: 1-8: 1.
The acyl phosphorous oxide initiator includes one of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (photoinitiator 819).
The thioxanthone initiator comprises one of 2-isopropyl thioxanthone ITX and 2, 4-diethyl thioxanthone DETX.
The leveling agent is a crosslinkable leveling agent containing acrylic functional groups.
The crosslinkable leveling agent containing acrylic functional group comprisesRad2010、Rad2011、Rad2200N、Rad2100、Rad2250、One or more of Rad 2300.
The polymerization inhibitor is at least one of methyl phenol polymerization inhibitor and amine polymerization inhibitor.
The methylphenol polymerization inhibitor comprises at least one of methoxyphenol and 2, 6-di-tert-butyl-p-methylphenol.
The amine polymerization inhibitor comprises vulcanized diphenylamine.
The ink has the viscosity of 9.0-11.0 cP (at 40 ℃), the particle size of 80-250 nm and the surface tension of 20-30 mN/m, and can be applied to industrial nozzles such as Ricoh (RICOH), Konika (KONICA), Kyocera (KYOCERA), SeIKO (SEIKO) and the like.
The invention also provides a preparation method of the circuit board ink-jet printing conductive LED photocuring ink, which comprises the following steps:
(1) Dissolving a dispersing agent into 20-50% of an active diluent, stirring, adding the pigment and the silver nanoparticles, and grinding and dispersing to obtain pigment color paste containing the silver nanoparticles;
(2) Adding prepolymer resin, a photoinitiator, a flatting agent and a polymerization inhibitor into the rest of the reactive diluent, and stirring to obtain a mixed solution;
(3) And (3) adding the pigment color paste containing the silver nanoparticles in the step (1) into the mixed liquid in the step (2), stirring, centrifuging and filtering to obtain the circuit board ink-jet printing conductive LED photocuring ink.
In the step (1), the stirring speed is 1000-3000 rad/min, and the stirring time is 30-60 min.
The preparation method of the silver nanoparticles in the step (1) comprises the following steps: (1) mixing AgNO3Dispersing in n-butylamine, adding toluene, lauric acid and a reducing agent, uniformly mixing, and heating to 110 ℃; (2) after complete cooling, adding a mixed liquid of methanol, ethanol and acetone to completely precipitate Ag nanoparticles, filtering with filter paper, and washing the precipitate for 3-8 times with the mixed liquid of methanol, ethanol and acetone; (3) drying to obtain the silver nano particles.
In the step (1), the grinding dispersion speed is 3000-5000 rad/min, and the grinding dispersion time is 2-5 h.
In the step (2), the prepolymer resin, the photoinitiator, the flatting agent and the polymerization inhibitor are added into the rest of the reactive diluent under the condition of keeping out of the sun.
in the step (2), the stirring speed is 1000-3000 rad/min, and the stirring time is 30-80 min.
In the step (3), the stirring speed is 1000-2000 rad/min, and the stirring time is 30-50 min.
In the step (3), the centrifugation speed is 3000-5000 rad/min, and the centrifugation time is 30-50 min.
In the step (3), a filter membrane with the diameter of 0.5-1.0 mu m is used for filtration.
The invention also provides application of the circuit board ink-jet printing conductive LED photocuring ink in a conductive circuit.
Advantageous effects
(1) The invention has high ink precision. The ink-jet printing mode is adopted, the printing precision is particularly high, and the ink-jet printing method is particularly suitable for printing of tiny circuit wires.
(2) The ink of the invention is fast in curing. The LED light curing is adopted, and the drying and curing can be carried out instantly.
(3) The ink has good stability. The silver nano particles and the pigment are dispersed and ground together, so that the stability of the ink is particularly good.
(4) The ink is suitable for printing lines with different colors. The four primary colors are added in the formula, so that lines of various colors can be printed, all conductive lines can be distinguished clearly, and the printing ink is very practical.
(5) The ink has good conductivity. The silver nanoparticles are adopted for conducting, so that the silver particles are small in resistance and strong in conductivity.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Epoxy acrylates CN110NS, CN117, CN131NS, CN159NS in the present invention; polyester acrylates CN7001NS, CN8010NS, CN790 and CN 750; urethane acrylates CN9013NS, CN9021NS, CN9178NS, CN9110NS are available from sandomoma, guangzhou chemical ltd.
The pigment c.i. pigment blue 15:3, c.i. pigment blue 15:4, c.i. pigment red 122, c.i. pigment red 202, c.i. pigment yellow 150, c.i. pigment yellow 151, c.i. pigment yellow 155 of the present invention are available from clariant chemical (china) ltd; c.i. pigment black 7 is available from mitsubishi chemical company, japan.
The dispersant of the invention is: efka6225, Efka6230, Efka7731, Efka7732, Efka6230, Efka4340, Efka7701 are available from basf chemical ltd.
Reactive dilutions in the present invention are cyclic trimethylolpropane formal methacrylate, tetrahydrofuran methacrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, lauric acid acrylic acid, tripropylene glycol methyl ether acrylate, trimethylol cyclohexyl acrylate, 4-tert-butyl cyclohexyl acrylate, 2 (propoxylated) neopentyl glycol diacrylate, (ethoxylated) 1, 6-hexanediol diacrylate, propoxylated (2) dipropylene glycol acrylate, pentaerythritol triacrylate, and (3) glycerol propylene oxide triacrylate available from sandoma guanzhou chemical co.
The photoinitiator agent of the invention, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (photoinitiator 819), and 2-isopropyl thioxanthone ITX and 2, 4-diethyl thioxanthone DETX can be purchased from Hubei Gurun science and technology Ltd.
Leveling agent in the inventionRad2010、Rad2011、Rad2200N、Rad2100、Rad2250、rad2300 is available from Yongchu specialty Chemicals (Shanghai) Co., Ltd.
The polymerization inhibitor p-methoxyphenol, diphenylamine sulfide and 2, 6-di-tert-butyl-p-methylphenol in the invention can be purchased from IGM company in the Netherlands.
The preparation method of the silver nano particles comprises the following steps: (1) 5g of AgNO3Dispersed in 30g of n-butylamine and then 50ml of toluene, 5.6g of lauric acid and 0.7g of NaBH as reducing agent are added4Uniformly mixing, heating to 110 ℃, and keeping the temperature at 110 ℃ for 2 h; (2) after complete cooling, adding mixed liquid of methanol, ethanol and acetone in a ratio of 1:1:1 to completely precipitate Ag nano particles, filtering by using filter paper, and washing the precipitate for 5 times by using mixed liquid of methanol, ethanol and acetone in a ratio of 1:1: 1; (3) drying at 50 ℃ to obtain the silver nano particles, wherein the average particle size of the silver nano particles is 30.5nm through testing.
The raw material AgNO used for preparing the silver nano particles3N-butylamine, toluene, lauric acid, NaBH4Methanol, ethanol, and acetone are available from chemical reagents of national drug group, Inc.