CN115491059B - Water-fading UV temporary protective coating and application thereof - Google Patents
Water-fading UV temporary protective coating and application thereof Download PDFInfo
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- CN115491059B CN115491059B CN202211301115.5A CN202211301115A CN115491059B CN 115491059 B CN115491059 B CN 115491059B CN 202211301115 A CN202211301115 A CN 202211301115A CN 115491059 B CN115491059 B CN 115491059B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
The invention relates to the technical field of coatings, in particular to a water fading UV temporary protective coating and application thereof. The laser drilling is directly carried out on the surface of the circuit board, copper scraps are very easy to generate, and the drilling precision is further affected. Aiming at the problems, the invention provides the water fading film temporary protective coating, and the water fading UV temporary protective coating is provided, and the photoinitiator is added into a coating system, so that the coating can be cured under a UV lamp to form a temporary protective coating, and the surface of a PCB is protected in the drilling process, so that copper scraps are effectively inhibited, and the drilling precision is improved.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a water fading UV temporary protective coating and application thereof.
Background
The PCB circuit board is used as a core component of electronic products such as mobile phones, and is continuously developed toward a high-precision direction. In order to achieve an increase in the density of fixed-volume circuits, electronics manufacturers have developed high-density interconnect printed circuit boards that are separated from one another by an insulating layer through the superposition of multiple layers of circuit boards. The traditional mode is that holes are drilled among insulating layers, and then the holes are plated with metal, so that circuit conduction among layer-by-layer circuits is realized, and the circuit density is greatly improved.
The laser drilling is directly carried out on the surface of the circuit board, copper scraps are easy to generate, the drilling precision is affected, the method can only be applied to multilayer circuits with fewer layers, and for multilayer boards with more layers, only a drill needle can be used for carrying out the laser drilling, but at present, the multilayer boards with more layers are almost directly drilled, the copper surfaces are free of auxiliary coatings, and the drilling precision is seriously affected. In order to solve the problem, the invention provides the water fading UV temporary protective coating, and the photoinitiator is added into the coating system, so that the coating can be cured and formed into a temporary protective coating under a UV lamp, and the surface of a PCB is protected in the drilling process, thereby effectively inhibiting the generation of copper scraps and further improving the drilling precision.
The self-made modified acrylic resin structure contains DMAA and SBMA fragments, so that the hydrophilic water absorption of the temporary protective coating can be remarkably improved, when the temporary protective coating is soaked in warm water with the temperature of more than 50 ℃, water molecules can quickly enter a resin crosslinked network of the temporary protective coating under the strong adsorption action of the DMAA and SBMA fragments, so that the resin crosslinked network in the temporary protective coating is highly swelled, the temporary protective coating can be automatically fallen from the surface of a substrate finally, and the corrosion action of an alkaline film fading agent on a circuit board is effectively avoided.
Disclosure of Invention
The problems in the prior art are: the laser drilling is directly carried out on the surface of the circuit board, copper scraps are very easy to generate, and the drilling precision is further affected. Aiming at the problems, the invention provides a water fading UV temporary protective coating which comprises the following components in parts by weight:
2. the water-fading UV temporary protective paint as defined in claim 1, wherein the modified acrylic resin is prepared by the steps of:
(1) Weighing HEMA, MA, DMAA, ACMO, SBMA (sulfobetaine methacrylate), AIBN and dioxane in a round bottom flask, wherein the molar ratio of HEMA to MA, DMAA, ACMO, SBMA to the total weight of the five monomers is 1:2:3:3:2, the addition amount of the AIBN is 0.5 percent of the total weight of the monomers, the mass percent of the HEMA in the dioxane is 10 percent, introducing nitrogen into a reaction mixture for 50min to deoxidize, placing the flask under an oil bath pot at 70 ℃ for stirring reaction for 24 hours, collecting a precipitated product after the reaction is finished, washing the precipitated product by adopting normal hexane, and then placing the obtained product in a vacuum oven at 45 ℃ for overnight drying to obtain a product A;
(2) 50g of the product A is added into 350mL of dimethylbenzene, and the mixture is stirred and mixed uniformly to obtain a reaction liquid A;
(3) Adding IPDI and a catalyst DBTDL into dimethylbenzene, stirring and mixing uniformly, wherein the mass percentage of the IPDI in the dimethylbenzene is 20%, and the addition amount of the DBTDL accounts for 0.1% of the weight of the IPDI to obtain a reaction liquid B;
(4) Adding PETA and hydroquinone into dimethylbenzene, wherein the mass percentage of the PETA in the dimethylbenzene is 30%, and the addition amount of the hydroquinone is 0.1% of the weight of the PETA, so as to obtain a reaction solution C;
(5) Continuously dropwise adding the reaction solution B into the reaction solution A, stirring at 70 ℃ for reaction until the hydroxyl absorption peak in the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution B, then starting dropwise adding the reaction solution C, stirring at 70 ℃ until the isocyanate absorption peak dropwise added into the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution C, ending the reaction, and removing the solvent by rotary evaporation to obtain the modified acrylic resin.
Specifically, the average particle size of the mica powder is 5000 meshes, and the mica powder is used in Debo shake chemical industry.
Specifically, the reactive monomer includes at least one of TM9EOPTA, HDDA, TPGDA, DPGDA, PEG600 DMA.
Specifically, the photoinitiator includes at least one of photoinitiators 1173, 184, 819, TPO, BP.
Specifically, the leveling agent comprises at least one of BYK333 and Digao 450.
Specifically, the defoamer is an organosilicon defoamer, digao 815N.
Specifically, the water fading UV temporary protective coating is applied as follows:
under the condition of avoiding light, the raw materials are uniformly stirred and mixed according to the formula amount, then the raw materials are coated on the surface of a PCB, then the PCB is subjected to photocuring under an ultraviolet lamp to obtain a photocuring coating, then a hole is drilled on the surface of the photocuring coating, after the hole is drilled, the PCB is soaked in a 50-80 ℃ aqueous solution, and the photocuring coating rapidly absorbs water and expands, so that the photocuring coating rapidly drops from the surface of the PCB.
Advantageous effects
(1) The water fading UV temporary protective coating provided by the invention is a photocuring coating, can generate photocuring reaction under ultraviolet irradiation, forms a temporary protective coating on the surface of a PCB substrate, protects the surface of a PCB circuit board in the drilling process, effectively inhibits copper scraps, and further improves drilling precision;
(2) The self-made modified acrylic resin structure contains DMAA and SBMA fragments, so that the hydrophilic water absorption of the temporary protective coating can be remarkably improved, when the temporary protective coating is soaked in warm water with the temperature of more than 50 ℃, water molecules can quickly enter a resin crosslinked network of the temporary protective coating under the strong adsorption action of the DMAA and SBMA fragments, so that the resin crosslinked network in the temporary protective coating is highly swelled, the temporary protective coating can be automatically fallen from the surface of a substrate finally, and the corrosion action of an alkaline film fading agent on a circuit board is effectively avoided;
(3) The water-fading UV temporary protective coating is added with the mica powder, and the existence of the mica powder can lubricate the drill point and prolong the service life of the drill point.
Detailed Description
The modified acrylic resins of the following examples of the present invention were prepared as follows:
(1) Weighing HEMA, MA, DMAA, ACMO, SBMA, AIBN and dioxane in a round-bottom flask, wherein the molar ratio of HEMA to MA, DMAA, ACMO, SBMA and the five monomers is 1:2:3:3:2, the addition amount of AIBN is 0.5% of the total weight of the monomers, the mass percentage of HEMA in the dioxane is 10%, introducing nitrogen into a reaction mixed solution for 50min to deoxidize, placing the flask under an oil bath at 70 ℃ for stirring reaction for 24 hours, collecting a precipitate product after the reaction is finished, washing the precipitate product by adopting normal hexane, and then placing the precipitate product in a vacuum oven at 45 ℃ for overnight drying to obtain a product A;
(2) 50g of the product A is added into 350mL of dimethylbenzene, and the mixture is stirred and mixed uniformly to obtain a reaction liquid A;
(3) Adding IPDI and a catalyst DBTDL into dimethylbenzene, stirring and mixing uniformly, wherein the mass percentage of the IPDI in the dimethylbenzene is 20%, and the addition amount of the DBTDL accounts for 0.1% of the weight of the IPDI to obtain a reaction liquid B;
(4) Adding PETA and hydroquinone into dimethylbenzene, wherein the mass percentage of the PETA in the dimethylbenzene is 30%, and the addition amount of the hydroquinone is 0.1% of the weight of the PETA, so as to obtain a reaction solution C;
(5) Continuously dropwise adding the reaction solution B into the reaction solution A, stirring at 70 ℃ for reaction until the hydroxyl absorption peak in the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution B, then starting dropwise adding the reaction solution C, stirring at 70 ℃ until the isocyanate absorption peak dropwise added into the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution C, ending the reaction, and removing the solvent by rotary evaporation to obtain the modified acrylic resin.
The average particle size of the mica powder used in the following examples of the present invention was 5000 mesh and was purchased from the forward Bo chemical industry.
Example 1
The water-fading UV temporary protective coating comprises the following components in parts by weight:
example 2
The water-fading UV temporary protective coating comprises the following components in parts by weight:
example 3
The water-fading UV temporary protective coating comprises the following components in parts by weight:
example 4
The water-fading UV temporary protective coating comprises the following components in parts by weight:
example 5
The water-fading UV temporary protective coating comprises the following components in parts by weight:
comparative example 1 the same as example 1 was carried out, except that comparative example 1 replaced the inventive homemade modified acrylic resin with the conventional commercially available Changxing UV polyurethane oligomer 6145-100.
Comparative example 2 the same as example 1, except that the modified acrylic resin in comparative example 2 was prepared as follows: (1) Weighing HEMA, MA, ACMO, SBMA, AIBN and dioxane in a round-bottom flask, wherein the molar ratio of HEMA to MA, ACMO, SBMA monomers is 1:2:3:5, the addition amount of AIBN is 0.5% of the total weight of the monomers, the mass percentage of HEMA in the dioxane is 10%, introducing nitrogen into a reaction mixture for 50min to deoxidize, placing the flask in an oil bath at 70 ℃ for stirring reaction for 24 hours, collecting a precipitate product after the reaction is finished, washing the precipitate product by adopting normal hexane, and then placing the precipitate product in a vacuum oven at 45 ℃ for overnight drying to obtain a product A;
(2) 50g of the product A is added into 350mL of dimethylbenzene, and the mixture is stirred and mixed uniformly to obtain a reaction liquid A;
(3) Adding IPDI and a catalyst DBTDL into dimethylbenzene, stirring and mixing uniformly, wherein the mass percentage of the IPDI in the dimethylbenzene is 20%, and the addition amount of the DBTDL accounts for 0.1% of the weight of the IPDI to obtain a reaction liquid B;
(4) Adding PETA and hydroquinone into dimethylbenzene, wherein the mass percentage of the PETA in the dimethylbenzene is 30%, and the addition amount of the hydroquinone is 0.1% of the weight of the PETA, so as to obtain a reaction solution C;
(5) Continuously dropwise adding the reaction solution B into the reaction solution A, stirring at 70 ℃ for reaction until the hydroxyl absorption peak in the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution B, then starting dropwise adding the reaction solution C, stirring at 70 ℃ until the isocyanate absorption peak dropwise added into the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution C, ending the reaction, and removing the solvent by rotary evaporation to obtain the modified acrylic resin.
Comparative example 3 the same as example 1, except that the modified acrylic resin in comparative example 3 was prepared as follows: (1) Weighing HEMA, MA, DMAA, ACMO, AIBN and dioxane in a round-bottom flask, wherein the molar ratio of HEMA to MA, DMAA, ACMO monomers is 1:2:5:3, the addition amount of AIBN is 0.5% of the total weight of the monomers, the mass percentage of HEMA in the dioxane is 10%, introducing nitrogen into a reaction mixture for 50min to deoxidize, placing the flask in an oil bath at 70 ℃ for stirring reaction for 24 hours, collecting a precipitate product after the reaction is finished, washing the precipitate product by adopting normal hexane, and then placing the precipitate product in a vacuum oven at 45 ℃ for overnight drying to obtain a product A;
(2) 50g of the product A is added into 350mL of dimethylbenzene, and the mixture is stirred and mixed uniformly to obtain a reaction liquid A;
(3) Adding IPDI and a catalyst DBTDL into dimethylbenzene, stirring and mixing uniformly, wherein the mass percentage of the IPDI in the dimethylbenzene is 20%, and the addition amount of the DBTDL accounts for 0.1% of the weight of the IPDI to obtain a reaction liquid B;
(4) Adding PETA and hydroquinone into dimethylbenzene, wherein the mass percentage of the PETA in the dimethylbenzene is 30%, and the addition amount of the hydroquinone is 0.1% of the weight of the PETA, so as to obtain a reaction solution C;
(5) Continuously dropwise adding the reaction solution B into the reaction solution A, stirring at 70 ℃ for reaction until the hydroxyl absorption peak in the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution B, then starting dropwise adding the reaction solution C, stirring at 70 ℃ until the isocyanate absorption peak dropwise added into the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution C, ending the reaction, and removing the solvent by rotary evaporation to obtain the modified acrylic resin.
Application:
under the condition of avoiding light, the raw materials of the embodiments 1-5 and the comparative examples 1-3 are uniformly stirred and mixed according to the formula amount, then the raw materials are respectively coated on the surface of the same PCB, and then the coating is placed under an ultraviolet lamp for photo-curing, so that the photo-curing coating with the thickness of 150 mu m is respectively obtained. The photo-cured coatings obtained in examples 1 to 5 and comparative examples 1 to 3 were subjected to the related performance test, each group of test was performed three times in parallel, the test results were averaged, then drilling was performed on the surface of the substrate, and after the drilling was completed, the substrate was immersed in an aqueous solution at 50 ℃ for 10 minutes, and whether the coating was peeled off from the surface of the PCB circuit board was observed.
Coating hardness: the test was performed according to standard GB/T6739-2006.
Coating adhesion: the test was carried out in accordance with GB/T9286-1998.
Drilling burrs: and (5) observing and counting by using a 500-fold magnifying glass, and taking a 20-time test burr average value (mu m) of the processed burr value.
TABLE 1
| Test item | Hardness of coating | Coating adhesion (grade) | Mean value of the flash (mum) | Soaking for 10min to determine whether the coating is dropped off |
| Example 1 | H | 0 | 6.29 | Is that |
| Example 2 | F | 0 | 7.21 | Is that |
| Example 3 | F | 0 | 7.51 | Is that |
| Example 4 | F | 0 | 7.38 | Is that |
| Example 5 | H | 0 | 6.54 | Is that |
| Comparative example 1 | H | 1 | 7.89 | Whether or not |
| Comparative example 2 | H | 0 | 6.32 | If not, fall off after 30min |
| Comparative example 3 | H | 0 | 6.28 | If not, fall off after 25min |
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (7)
1. The water-fading UV temporary protective coating is characterized by comprising the following components in parts by weight:
40-60 parts of modified acrylic resin
10-30 parts of mica powder
5-20 parts of active monomer
3-6 parts of photoinitiator
0.1 to 0.5 part of leveling agent
0.1 to 0.5 part of dispersing agent
0.1-0.5 part of defoaming agent;
the modified acrylic resin is prepared according to the following steps:
(1) Weighing HEMA, MA, DMAA, ACMO, SBMA, AIBN and dioxane in a round-bottom flask, wherein the molar ratio of HEMA to MA, DMAA, ACMO, SBMA and the five monomers is 1:2:3:3:2, the addition amount of AIBN is 0.5% of the total weight of the monomers, the mass percentage of HEMA in the dioxane is 10%, introducing nitrogen into a reaction mixed solution for 50min to deoxidize, placing the flask under an oil bath at 70 ℃ for stirring reaction for 24 hours, collecting a precipitate product after the reaction is finished, washing the precipitate product by adopting normal hexane, and then placing the precipitate product in a vacuum oven at 45 ℃ for overnight drying to obtain a product A;
(2) 50g of the product A is added into 350mL of dimethylbenzene, and the mixture is stirred and mixed uniformly to obtain a reaction liquid A;
(3) Adding IPDI and a catalyst DBTDL into dimethylbenzene, stirring and mixing uniformly, wherein the mass percentage of the IPDI in the dimethylbenzene is 20%, and the addition amount of the DBTDL accounts for 0.1% of the weight of the IPDI to obtain a reaction liquid B;
(4) Adding PETA and hydroquinone into dimethylbenzene, wherein the mass percentage of the PETA in the dimethylbenzene is 30%, and the addition amount of the hydroquinone is 0.1% of the weight of the PETA, so as to obtain a reaction solution C;
(5) Continuously dropwise adding the reaction solution B into the reaction solution A, stirring at 70 ℃ for reaction until the hydroxyl absorption peak in the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution B, then starting dropwise adding the reaction solution C, stirring at 70 ℃ until the isocyanate absorption peak dropwise added into the reaction system disappears on the FTIR spectrum, stopping dropwise adding the reaction solution C, ending the reaction, and removing the solvent by rotary evaporation to obtain the modified acrylic resin.
2. A water-fade UV temporary protective coating according to claim 1, characterized in that said mica powder has an average particle size of 5000 mesh.
3. The water fade UV temporary protective paint according to claim 1, wherein said reactive monomer comprises at least one of TM9EOPTA, HDDA, TPGDA, DPGDA, PEG DMA.
4. A water-fade UV temporary protective coating according to claim 1, characterized in that said photoinitiator comprises at least one of photoinitiators 1173, 184, 819, TPO, BP.
5. The water fade UV temporary protective paint of claim 1, wherein said leveling agent comprises at least one of BYK333, dyheight 450.
6. A water-fade UV temporary protective paint according to claim 1, characterized in that said defoamer is a silicone defoamer, di-gao 815N.
7. A water-fade UV temporary protective paint according to any one of claims 1-6, characterized in that it is applied as follows:
under the condition of avoiding light, the raw materials are stirred and mixed uniformly according to the formula amount, then the raw materials are coated on the surface of a PCB, then the PCB is placed under an ultraviolet lamp for light curing, a light-cured coating is obtained, then a drilling hole is positioned on the surface of the light-cured coating, after the drilling hole is finished, the PCB is soaked in a 50-80 ℃ aqueous solution, and the light-cured coating rapidly absorbs water and expands, so that the light-cured coating rapidly drops from the surface of the PCB.
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| US5420171A (en) * | 1991-12-31 | 1995-05-30 | Tech Spray, Inc. | UV curable temporary solder mask |
| WO2007080936A1 (en) * | 2006-01-13 | 2007-07-19 | Denki Kagaku Kogyo Kabushiki Kaisha | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| CN104817881B (en) * | 2015-04-28 | 2017-06-23 | 中科院广州化学有限公司南雄材料生产基地 | A kind of water off-type protection ink and preparation method thereof |
| CN108485507B (en) * | 2018-03-13 | 2020-04-07 | 湖南松井新材料股份有限公司 | Water-based UV coating with temporary protection effect and preparation method and application thereof |
| CN109666119B (en) * | 2018-12-25 | 2020-07-24 | 湖南松井新材料股份有限公司 | Water-based antifogging resin, water-based antifogging coating composition and preparation method thereof |
| CN113773737A (en) * | 2021-09-13 | 2021-12-10 | 广东希贵光固化材料有限公司 | Temporary protective coating demoulded by oxidation-reduction |
| CN114410212B (en) * | 2021-12-09 | 2023-05-16 | 广东希贵光固化材料有限公司 | Waterproof UV (ultraviolet) coating and preparation method thereof |
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