Self-repairing microcapsule solution and preparation method thereof

Abstract

The invention discloses a self-repairing micro-capsule solution and a preparation method thereof, and relates to the technical field of material science, the self-repairing micro-capsule solution is composed of a carrier, a repairing agent, a catalyst and an organic solvent, and the self-repairing micro-capsule solution is prepared by stirring raw materials in a specific proportion in a polymerization reactor and then filtering. The ink-jet printing insulating ink contains a self-repairing microcapsule solution, mono-or multi-functional acrylate, a photoinitiator, an auxiliary agent and a pigment, and is prepared by mixing, stirring, grinding and filtering. The ink can be cured into an insulating protective film on the surfaces of a printed circuit board, a ceramic substrate and the like under the conditions of UV illumination and heating. The protective film has a self-repairing function, and if micron-sized scratches or cracks appear on the protective film, the protective film can be repaired through directional UV illumination and heating. Meanwhile, the ink has excellent adhesion to a base material, and a formed insulating coating film has good thermal shock resistance and good insulation reliability, can effectively meet the electronic packaging process requirements, and has a good application prospect.

Description

Technical Field

[0001] The present invention relates to the field of material science, and in particular to a self-repairing microcapsule solution and a preparation method thereof. Background Art

[0002] In the manufacturing process of modern electronic devices, printed circuit boards (PCBs) and ceramic substrates are key components, and the quality of the insulating protective film on their surfaces directly impacts the performance, reliability, and lifespan of these devices. Traditional insulating ink-based protective films, when subjected to external forces and micron-level scratches or cracks during or after the manufacturing process, are often difficult to repair. This can lead to reduced insulation performance and short circuits in electronic devices, seriously impacting product quality and stability.

[0003] At the same time, as electronic products develop towards miniaturization and high performance, higher requirements are placed on the adhesion, thermal shock resistance, and insulation reliability of insulating inks. Existing inkjet-printed insulating inks have shortcomings in these aspects and cannot fully meet the growing market demand. For example, some inks have poor adhesion to the substrate and are prone to falling off during subsequent processing or use. When undergoing processes such as high-temperature welding, they will discolor and fall off, and cannot withstand thermal shock. Moreover, during long-term use, the insulation performance will gradually decline, making it difficult to ensure the stable operation of electronic devices. Therefore, it is urgent to develop an inkjet-printed insulating ink with self-healing functions, as well as excellent adhesion, thermal shock resistance, and insulation reliability.

[0004] In view of this, this application is hereby filed. Summary of the Invention

[0005] The object of the present invention is to provide a self-repairing microcapsule solution and a preparation method thereof to solve the problems mentioned in the above background technology.

[0006] In order to solve the above technical problems, the present invention provides a self-repairing microcapsule solution, comprising: a) a carrier; b) a repairing agent distributed on the carrier; c) a catalyst distributed on the carrier; d) an organic solvent;

[0007] wherein the a) carrier is selected from one or more of the following: polyurethane or urea-formaldehyde microcapsules, core-shell structures, dendrimers, carbon nanotubes, boron nitride nanotubes and other materials with a cavity structure;

[0008] wherein the b) repair agent is selected from one or more of the following: acrylate resin, epoxy-modified acrylate resin, phenolic-modified acrylate resin, polyurethane-modified acrylate, polyester-modified acrylate, silicone-modified acrylate, etc.;

[0009] wherein c) the catalyst is selected from one or more of the following: cationic photoinitiators, free radical photoinitiators, thiols, nano-titanium nitride, nano-titanium carbide, etc.; wherein the cationic photoinitiator is selected from one or more of the following: diaryliodonium salts, triaryliodonium salts, alkyliodonium salts, isopropylphenylferrocenium hexafluorophosphate, etc.; wherein the free radical photoinitiator is selected from one or more of the following: benzoins and their derivatives, alkylphenones and their derivatives, acylphosphine oxides and their derivatives, anthrone and their derivatives, etc.;

[0010] The organic solvent d) is selected from one or more of the following: benzene, toluene, pentane, isoprene, tetrachloromethane, methanol, ethanol, acetonitrile, acetone, etc.

[0011] A method for preparing a self-repairing microcapsule solution comprises the following steps: stirring and dispersing a) a carrier, b) a repairing agent, c) a catalyst, and d) an organic solvent as a solvent at a certain temperature to fully load the repairing agent and the catalyst on the carrier, and filtering to form the self-repairing microcapsule solution.

[0012] Furthermore, 20% to 50% by mass of a) a carrier, 30% to 70% by mass of b) a repair agent, 0.1% to 7% by mass of c) a catalyst, and 5% to 40% by mass of d) an organic solvent are stirred in a polymerization reactor at a stirring speed of 50 rpm to 1000 rpm, at a temperature of 25° C. to 45° C., preferably at 40° C., for 1-2 hours, and then filtered through a 1 μm filter.

[0013] A method for preparing a self-repairing microcapsule solution is provided to prepare a self-repairing microcapsule solution for use in preparing insulating ink for inkjet printing. The self-repairing microcapsule solution can be used in combination with multiple types.

[0014] Preparation of inkjet printing insulating ink, including: a self-healing microcapsule solution with a mass percentage of 0.1%-30%, the self-healing microcapsule solution can be used in combination of multiple types, a monofunctional or multifunctional acrylate with a mass percentage of 30%-90%, a photoinitiator with a mass percentage of 1%-10%, an auxiliary agent with a mass percentage of 1%-10%, and a pigment with a mass percentage of 1%-10%; the above raw materials are mixed evenly according to the formula ratio, stirred for 1-2 hours with a disperser at a stirring speed of 50rpm to 1000rpm, and then the evenly stirred raw material slurry is ground at a speed of 100-1500rpm for 1-2 hours using a ball mill or a sand mill, and then filtered with a 1μm filter to obtain the inkjet printing insulating ink described in this scheme.

[0015] Furthermore, the monofunctional or multifunctional acrylate is selected from one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, 2-trimethylolpropane tetraacrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, trihydroxypropane diacrylate, hydroxystyrene acrylate, hydroxypropyl methacrylate, and the like.

[0016] Furthermore, the photoinitiator is a free radical photoinitiator, selected from one or more of the following: benzoins and their derivatives, alkyl phenones and their derivatives, acylphosphine oxides and their derivatives, anthrone and their derivatives, etc.

[0017] Furthermore, the auxiliary agent is one or more of a leveling agent, a defoaming agent, a film-forming auxiliary agent, and the like.

[0018] Furthermore, the pigment is selected from one or more pigments or dyes such as red, yellow, blue, white, black, and purple.

[0019] An application of inkjet printing insulating ink, which can be cured into an insulating protective film on the surface of substrates such as printed circuit boards and ceramic substrates under UV light and heating conditions.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. Self-repair function: After the self-repairing microcapsule solution of the present invention is applied to inkjet printing insulating ink, if micron-level scratches or cracks appear on the insulating protective film under UV light and heating conditions, the material can be self-repaired through the mutual cross-linking reaction of the self-repairing microcapsules, effectively extending the service life of the insulating protective film and reducing the risk of electronic device failure due to damage to the protective film.

[0022] 2. High adhesion: The inkjet-printed insulating ink has excellent adhesion to various substrates such as printed circuit boards and ceramic substrates. When tested using the 100-grid method, the ink coatings of Examples 1-5 showed no signs of falling off, which is significantly superior to Comparative Example 1. It can ensure that the insulating protective film is firmly adhered to the surface of the substrate, avoid falling off during use, and ensure the stability of electronic devices.

[0023] 3. Good thermal shock resistance: After immersion testing in a 288°C tin furnace, the insulating coatings prepared in Examples 1-5 showed no color change, peeling, or bulging, indicating that they have good thermal shock resistance and can withstand the high-temperature soldering process in the manufacturing process of electronic devices, reducing coating damage caused by thermal shock and improving the product qualification rate.

[0024] 4. Excellent insulation reliability: After insulation reliability testing under specific temperature cycles and humidity conditions, the resistance values ​​of the samples of Examples 1-5 did not decrease, and no surface changes were observed at all, demonstrating excellent insulation reliability. This can effectively protect the insulation performance of electronic devices in complex environments and ensure the stable operation of electronic equipment.

[0025] 5. Wide applicability: The inkjet-printable insulating ink of the present invention can be cured into an insulating protective film on the surface of various substrates such as printed circuit boards and ceramic substrates. It has a wide range of applications and can meet the needs of manufacturing different electronic devices, providing a material option with excellent performance in the field of electronic packaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The figure shows a principle block diagram of a self-repairing microcapsule solution and its preparation method. DETAILED DESCRIPTION

[0027] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0028] See also Figure 1 The present invention provides a technical solution: a self-repairing microcapsule solution and a preparation method thereof, comprising:

[0029] (1) A self-repairing microcapsule solution and its preparation method

[0030] A) carrier, b) repair agent, c) catalyst, and d) organic solvent were placed in a polymerization reactor in the following proportions, stirred at a stirring speed of 1000 rpm and a temperature of 40° C. for 1 hour, and then filtered with a 1 μm filter to obtain self-healing microcapsule solutions S1-S4.

[0031]

[0032] in:

[0033] Dendrimer: Weihai Chenyuan Molecular New Materials Co., Ltd., polyhydroxy dendrimer toughening modifier CYD-T60;

[0034] Acrylate resin: Shandong Derui Chemical Raw Materials Co., Ltd., HEA (2-hydroxyethyl acrylate);

[0035] Mercaptan: Lisennoko (China) Investment Co., Ltd., Ke Ruizhi PE1 (pentaerythritol tetrakis (3-mercaptobutyrate));

[0036] Carbon nanotubes: Jiangsu Super Carbon Xianfeng Technology Co., Ltd., carbon nanotube powder CT-M-003;

[0037] Epoxy modified acrylate resin: Kunshan Custer Polymer Materials Co., Ltd., modified epoxy acrylate U-Cure9252;

[0038] Diaryliodonium salt: Nanjing Jiazhong Chemical Technology Co., Ltd., diaryliodonium salt;

[0039] Boron nitride nanotubes: Beijing Zhongke Leiming Technology Co., Ltd., boron nitride nanotubes;

[0040] Polyester modified acrylate resin: Kunshan Custer Polymer Materials Co., Ltd., polyester acrylic resin U-Cure9216;

[0041] Nano-titanium nitride: Anhui AVIC Nano-Technology Development Co., Ltd., nano-titanium nitride powder;

[0042] Core-shell structure: Xi'an Qiyue Biotechnology Co., Ltd., TiO2 / ZnO core-shell structure material;

[0043] Polyurethane modified acrylate: Kunshan Custer Polymer Materials Co., Ltd., polyurethane acrylate U-Cure9100;

[0044] TPO (trimethylbenzoyl-diphenylphosphine oxide) was from Nanjing Milan New Materials Co., Ltd.;

[0045] Toluene, ethanol, acetone, and methanol were all from Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0046] (2) Preparation of an Inkjet Printable Insulating Ink

[0047] The raw materials were mixed evenly according to the following formula ratio and stirred at 900 rpm for 1 hour using a disperser. The evenly stirred raw material slurry was ground at 1200 rpm using a ball mill or a sand mill for 1 hour, and then filtered using a 1 μm filter to obtain the inkjet printing insulating inks of Examples 1-5 and Comparative Example 1 described in this scheme.

[0048]

[0049] in:

[0050] HEA (2-hydroxyethyl acrylate) was from Shandong Derui Chemical Raw Materials Co., Ltd.;

[0051] THFA (tetrahydrofuran acrylate) was from Shandong Derui Chemical Raw Materials Co., Ltd.;

[0052] PDDA (diethylene glycol phthalate diacrylate) was from Shandong Derui Chemical Raw Materials Co., Ltd.;

[0053] TPO (trimethylbenzoyl-diphenylphosphine oxide) was from Nanjing Milan New Materials Co., Ltd.;

[0054] BYK1797 is from BYK Additives (Shanghai) Co., Ltd.;

[0055] Phthalocyanine green G (PG7) was obtained from Hongrun Chemical Raw Materials Distribution Department in Shahe, Laizhou City.

[0056] (3) Performance testing

[0057] The inkjet printing inks prepared in Examples 1-5 and Comparative Example 1 were injected into the ink cartridge of an inkjet printer. A 395 nm LED lamp was used, and the exposure lamp energy was set to 300-500 mJ / cm 2 , the nozzle temperature is set to 45-55℃, the substrate can be ceramic / glass / FCCL / FR-4 substrate, etc., enable a specific printing mode program for inkjet printing, and then place the sample in a 150℃ oven and bake for 1h to obtain a test sample.

[0058] (1) Adhesion test

[0059] Adhesion test of the sample was carried out using the 100-grid method. The inkjet ink coating was cut to the substrate surface to form a grid-like scratch. The surface was then pasted with 3M tape and torn off. The coating peeling was observed and then evaluated.

[0060] Adhesion test standards are as follows:

[0061] ○: No signs of falling off;

[0062] △: There is slight corner loss but no flakes falling off;

[0063] ×: There is large-scale flake peeling.

[0064] (2) Insulation reliability test

[0065] A DC100V bias voltage was applied to the IPC-B comb-type electrode on the sample. The sample was placed in a constant temperature and humidity chamber at 90% RH for one week under the condition of 25-65°C temperature cycling. Then, the sample was treated at room temperature and DC500V for 1 minute. The resistance value was measured with a multimeter and observed under an optical metallographic microscope.

[0066] The insulation reliability test standards are as follows:

[0067] ○: No decrease in resistance, no surface change observed;

[0068] △: The resistance value decreases slightly, or / and a small amount of copper ion migration is observed on the sample surface;

[0069] ×: The resistance value decreased significantly, or / and a large amount of copper ion migration was observed on the sample surface.

[0070] (3) Solder thermal shock resistance test

[0071] Place the sample in a tin furnace at a temperature of 288°C, immerse the sample in the tin furnace for 10 seconds, and then take it out and cool it to room temperature, a total of three times.

[0072] The test standards for resistance to solder thermal shock are as follows:

[0073] ○: No discoloration, peeling or swelling;

[0074] △: There is color change, but no shedding or bulging;

[0075] ×: The appearance shows obvious color change, peeling and swelling.

[0076] (4) Acid resistance test

[0077] Immerse the sample in a 10% volume fraction H2SO4 aqueous solution for 30 minutes, take it out, rinse it with deionized water, air-dry it, and observe it.

[0078] The acid resistance test evaluation criteria are as follows:

[0079] ○: No discoloration, peeling or swelling;

[0080] △: There is color change, but no shedding or bulging;

[0081] ×: The appearance shows obvious color change, peeling and swelling.

[0082] (5) Alkali resistance test

[0083] The sample was immersed in a 10% volume fraction NaOH aqueous solution for 30 min, taken out, washed with deionized water, air-dried, and observed.

[0084] The acid resistance test evaluation criteria are as follows:

[0085] ○: No discoloration, peeling or swelling;

[0086] △: There is color change, but no shedding or bulging;

[0087] ×: The appearance shows obvious color change, peeling and swelling.

[0088] (6) Solvent resistance test

[0089] Soak the sample in PMA (propylene glycol methyl ether acetate) solution for 30 minutes, take it out, rinse it with deionized water, air-dry it, and observe it.

[0090] The acid resistance test evaluation criteria are as follows:

[0091] ○: No discoloration, peeling or swelling;

[0092] △: There is color change, but no shedding or bulging;

[0093] ×: The appearance shows obvious color change, peeling and swelling.

[0094] (7) Self-repair performance test

[0095] The PB1000-meter mechanical comprehensive testing system of NANOVEA Instruments of the United States was used, and the micron scratch / friction tester mode was selected. The parameters were set to a minimum scratch positive force load of 10 mN and a scratch speed of 100 mm / min. Micron scratches were formed on the surface of the sample and observed with an optical metallographic microscope.

[0096] Then, a 395nm LED light was used to expose the sample surface, and the exposure light energy was set to 300-500mJ / cm 2 , and placed it in an oven at 150℃ to heat it, and then the self-repairing situation was observed using an optical metallographic microscope.

[0097] The self-repair test evaluation criteria are as follows:

[0098] ○: The surface is restored to its original state and the scratches disappear;

[0099] △: The surface scratch is partially recovered, the length is shortened, and / or the depth is shallower, but residual scratches still exist;

[0100] ×: The surface scratch condition has not improved at all and has even worsened.

[0101] The results of the above tests on Examples 1-5 and Comparative Example 1 are shown in the following table:

[0102] Evaluation Project Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Adhesion test ○ ○ ○ ○ ○ △ Insulation reliability test ○ ○ ○ ○ ○ △ Solder thermal shock resistance test ○ ○ ○ ○ ○ △ Acid resistance test ○ ○ ○ ○ ○ ○ Alkali resistance test ○ ○ ○ ○ ○ ○ Solvent resistance test ○ ○ ○ ○ ○ ○ Self-repair performance test ○ ○ ○ ○ ○ ×

[0103] In summary: From the test results, it can be seen that the inkjet printing insulating inks prepared in Examples 1-5 have the best performance in all aspects, especially in adhesion, heat shock resistance, insulation reliability and self-repairing performance.

Claims

1. A self-repairing microcapsule solution, characterized by: include: a) carrier; b) a repair agent distributed on the carrier; c) a catalyst distributed on the support; d) organic solvents; wherein the a) carrier is selected from one or more of the following: polyurethane or urea-formaldehyde microcapsules, core-shell structures, dendrimers, carbon nanotubes, boron nitride nanotubes and materials having a cavity structure; wherein the b) repair agent is selected from one or more of the following: acrylate resin, epoxy-modified acrylate resin, phenolic-modified acrylate resin, polyurethane-modified acrylate, polyester-modified acrylate, and silicone-modified acrylate resin; wherein c) the catalyst is selected from one or more of the following: a cationic photoinitiator, a free radical photoinitiator, a thiol, nano-titanium nitride, and nano-titanium carbide; wherein the cationic photoinitiator is selected from one or more of the following: diaryl iodonium salts, triaryl iodonium salts, alkyl iodonium salts, and cumene ferrocenium hexafluorophosphate; wherein the free radical photoinitiator is selected from one or more of the following: benzoins and their derivatives, alkyl phenones and their derivatives, acylphosphine oxides and their derivatives, and anthrone and their derivatives; The organic solvent d) is selected from one or more of the following: benzene, toluene, pentane, isoprene, tetrachloromethane, methanol, ethanol, acetonitrile, and acetone.

2. A method for preparing a self-repairing microcapsule solution, characterized in that: The a) carrier, b) repair agent, c) catalyst and d) organic solvent are stirred and dispersed at a certain temperature to fully load the repair agent and catalyst on the carrier, and filtered to form the self-repairing microcapsule solution.

3. The method for preparing a self-repairing microcapsule solution according to claim 2, wherein: 20% to 50% by mass of a) a carrier, 30% to 70% by mass of b) a repair agent, 0.1% to 7% by mass of c) a catalyst, and 5% to 40% by mass of d) an organic solvent are stirred in a polymerization reactor at a stirring speed of 50 rpm to 1000 rpm and a temperature of 25° C. to 45° C. for 1 to 2 hours, and then filtered through a 1 μm filter.

4. The method for preparing a self-repairing microcapsule solution according to any one of claims 2 to 3, wherein: Used for the preparation of insulating ink for inkjet printing, the self-repairing microcapsule solution can be used in combination with multiple types.

5. The preparation of the inkjet printing insulating ink according to claim 4, characterized in that: include: A self-healing microcapsule solution with a mass percentage of 0.1%-30%, a monofunctional or multifunctional acrylate with a mass percentage of 30%-90%, a photoinitiator with a mass percentage of 1%-10%, an additive with a mass percentage of 1%-10%, and a pigment with a mass percentage of 1%-10%; the above raw materials are mixed evenly according to the formula ratio, stirred for 1-2 hours with a disperser at a stirring speed of 50rpm to 1000rpm, and then the evenly stirred raw material slurry is ground at a speed of 100-1500rpm with a ball mill or a sand mill for 1-2 hours, and then filtered with a 1μm filter to obtain the inkjet printing insulating ink described in this scheme.

6. The preparation of an inkjet printing insulating ink according to claim 5, characterized in that: The monofunctional or multifunctional acrylate is selected from one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, 2-trimethylolpropane tetraacrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, trihydroxypropane diacrylate, hydroxystyrene acrylate, and hydroxypropyl methacrylate.

7. The preparation of an inkjet printing insulating ink according to claim 5, characterized in that: The photoinitiator is a free radical photoinitiator, selected from one or more of the following: benzoins and their derivatives, alkylphenones and their derivatives, acylphosphine oxides and their derivatives, anthrone and their derivatives.

8. The preparation of an inkjet printing insulating ink according to claim 5, characterized in that: The auxiliary agent is one or more of a leveling agent, a defoaming agent, and a film-forming auxiliary agent.

9. The preparation of an inkjet printing insulating ink according to claim 5, characterized in that: The pigment is selected from one or more pigments or dyes such as red, yellow, blue, white, black, and purple.

10. Use of the inkjet printing insulating ink according to any one of claims 5 to 9 to prepare a finished product, characterized in that: Under UV light and heating conditions, it can be cured into an insulating protective film on the surface of printed circuit boards and ceramic substrates.

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