CN114686084A - EB (Electron Beam) curing wear-resistant and high-temperature-resistant coating for aluminum-based copper-clad plate - Google Patents
EB (Electron Beam) curing wear-resistant and high-temperature-resistant coating for aluminum-based copper-clad plate Download PDFInfo
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- CN114686084A CN114686084A CN202111489436.8A CN202111489436A CN114686084A CN 114686084 A CN114686084 A CN 114686084A CN 202111489436 A CN202111489436 A CN 202111489436A CN 114686084 A CN114686084 A CN 114686084A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000010894 electron beam technology Methods 0.000 title claims abstract description 24
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 60
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 76
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 32
- 239000008096 xylene Substances 0.000 claims description 32
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 23
- 229920002635 polyurethane Polymers 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 19
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 17
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 15
- 238000001157 Fourier transform infrared spectrum Methods 0.000 claims description 11
- 239000002518 antifoaming agent Substances 0.000 claims description 11
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 10
- 238000012544 monitoring process Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 8
- 102100026735 Coagulation factor VIII Human genes 0.000 claims description 8
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- -1 TCDMA Chemical compound 0.000 claims description 2
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 9
- 239000011253 protective coating Substances 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001227 electron beam curing Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 239000011889 copper foil Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000005062 Polybutadiene Chemical group 0.000 description 1
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical compound [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002857 polybutadiene Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of coatings, in particular to an EB (electron beam) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate. The aluminum substrate and the copper foil need to be hot-pressed for nearly 3 hours at 200 ℃ in the compounding process, the high-temperature resistance of the coating is extremely high, and the high-temperature resistance of the conventional EB curing coating is poor. Based on the problems, the invention provides an EB (ethylene-boron) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate, which is characterized in that isocyanuric acid structure modified polyurethane resin and ester ring structure modified polyurethane resin are added into the formula of the coating, and the two resins are matched for use, so that the wear resistance of a protective coating is improved, and the high-temperature resistance stability of the protective coating is also obviously improved.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to an EB (electron beam) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate.
Background
The aluminum-based copper clad laminate is a metal-based copper clad laminate with a good heat dissipation function, is one of aluminum-based printed circuit board raw materials, and is widely applied to LED lighting products. Generally, an aluminum-based single panel is composed of three layers, namely a circuit layer (copper foil), an insulating layer and an aluminum base layer.
The circuit layer is manufactured by etching the aluminum base layer to form a printed circuit for realizing the assembly and connection of devices, and the main process is grinding the plate, pasting the film, exposing, developing, etching and stripping the film. Aluminum is a metal with strong activity and can easily react with acidic/alkaline solution used in the etching and stripping processes, so that in order to prevent the surface of the aluminum base layer from being corroded, effective measures must be taken to protect the aluminum plate of the aluminum base layer. At present, most of aluminum plates of aluminum substrates are protected by paving and pasting PVC or PE plastic films, but in the film pasting process, due to reasons of electrostatic adsorption, space pollution, plate edge shearing particles and the like, impurities are easily adsorbed on the aluminum surfaces, and the impurities are easily scratched on the aluminum surfaces or scratch the protective films after being extruded, so that the aluminum surfaces are exposed to acid-base corrosion, and finally aluminum-base defects are caused.
Based on the problems, the problem caused by a PVC or PE plastic film can be basically solved by adopting the high-wear-resistance UV or EB curing coating to protect the aluminum substrate, but the high-temperature resistance of the coating is extremely high because the aluminum substrate and the copper foil are required to be hot-pressed for nearly 3 hours at 200 ℃ in the compounding process, and the conventional UV or EB curing coating has poor high-temperature resistance and is easy to crack in the hot-pressing process, so that the protection function is lost.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: the aluminum substrate and the copper foil need to be hot-pressed for nearly 3 hours at 200 ℃ in the compounding process, the high-temperature resistance of the coating is extremely high, and the high-temperature resistance of the conventional EB curing coating is poor.
The technical scheme adopted by the invention for solving the technical problems is as follows: the invention provides an EB (Electron beam) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate, which comprises the following components in parts by weight:
the modified polyurethane consists of a modified polyurethane resin A and a modified polyurethane resin B according to the weight ratio of 1-3: 3-1.
Specifically, the modified polyurethane consists of a modified polyurethane resin A and a modified polyurethane resin B according to the weight ratio of 1.5-2: 1.
Specifically, the modified polyurethane resin a is an isocyanuric acid-modified polyurethane resin.
Specifically, the isocyanuric acid modified polyurethane resin is prepared according to the following steps:
(1) adding 28.2g of THEICA, 0.05g of photoinitiator 1173 and 70mL of toluene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 50 ℃, dropwise adding 10.4g of mercaptoethanol into the flask under the protection of nitrogen, irradiating the mercaptoethanol with an LED lamp with the wavelength of 365nm while stirring, monitoring the reaction by FTIR, and removing the solvent by rotary evaporation when the double bond absorption peak in the reaction system disappears to obtain a product a;
(2) adding 30.2g of IPDI, 0.04g of catalyst DBTDL and 70mL of THF into a three-hole round-bottom flask, then raising the temperature of a reaction system to 70 ℃, dropwise adding 30.4g of product a into the flask under the protection of nitrogen, stirring for reaction after the dropwise addition is finished, monitoring the reaction by FTIR, adding 0.005g of hydroquinone into the reaction system until a hydroxyl absorption peak in the reaction system disappears, continuously dropwise adding PETA, continuously stirring for reaction at 70 ℃ until an isocyanate absorption peak in the reaction system disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent by rotary evaporation to obtain the isocyanuric acid modified polyurethane resin.
Specifically, the modified polyurethane resin B is prepared according to the following steps:
(1) weighing HEMA, TCDMA, MMA, AIBN and dioxane in a round bottom flask, wherein the weight ratio of the three monomers of HEMA, TCDMA and MMA is 3:5:3, the addition amount of AIBN is 0.5 percent of the total weight of the monomers, and the weight ratio of the dioxane to the total weight of the monomers is 7:3, introducing nitrogen for 45min to remove oxygen into a reaction mixed solution, placing the flask under a 70 ℃ oil bath pan, stirring and reacting for 24h, washing a precipitated product with n-hexane after the reaction is finished, and carrying out vacuum drying at 45 ℃ overnight to obtain a product e;
(2) adding 30.2g of product e, 0.04g of catalyst p-toluenesulfonic acid, 0.005g of hydroquinone and 70mL of xylene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 70 ℃, dropwise adding hydroxyl-terminated polybutadiene (with the number average molecular weight of 3000) into the flask, stirring for reaction after the dropwise addition is completed, monitoring the reaction by FTIR, stopping dropwise adding the hydroxyl-terminated polybutadiene when the absorption peak of carboxyl in the reaction system disappears, then adding a xylene solution dissolved with IPDI and a catalyst DBTDL into the reaction system in a dropwise manner, continuing stirring for reaction at 70 ℃, wherein the mass percentage content of IPDI in the xylene solution is 20%, the addition amount of the catalyst DBTDL in the xylene solution is 0.1% of the mass of IPDI until the absorption peak of hydroxyl in the reaction system disappears on an FTIR spectrum, dropwise adding a xylene solution dissolved with IPDI and the catalyst DBTDL, then dropwise adding the xylene solution dissolved with PETA and the catalyst hydroquinone into the reaction system, and (2) continuously stirring and reacting at 70 ℃, wherein the mass percentage of the PETA in the xylene solution is 30%, and the addition amount of the hydroquinone in the xylene solution is 0.1% of the mass of the PETA, until an isocyanato absorption peak in a reaction system disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent through rotary evaporation to obtain the modified polyurethane resin B.
Specifically, the active monomer is one or more of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-hexanediol diacrylate and tripropylene glycol diacrylate.
Specifically, the leveling agent is an organic silicon leveling agent.
Specifically, the dispersant is a polymeric dispersant.
Specifically, the defoaming agent is an organic silicon defoaming agent or a polyether modified organic silicon defoaming agent.
Specifically, the EB curing wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate is prepared according to the following steps:
according to the formula amount, the modified polyurethane, the active monomer, the flatting agent, the dispersing agent, the defoaming agent and the absolute ethyl alcohol are stirred and mixed uniformly to obtain the polyurethane adhesive.
The invention has the beneficial effects that:
(1) the self-made modified polyurethane resin A contains an isocyanuric acid structure, so that the high-temperature resistance of the protective coating can be effectively improved;
(2) the modified polyurethane resin A is brittle and high in rigidity and poor in wear resistance, and can effectively improve the wear resistance of the protective coating when used in combination with the self-made modified polyurethane resin B, because the modified polyurethane resin B is introduced with the ester ring structure, the brittleness and the rigidity of the modified polyurethane resin A can be effectively improved, the modified polyurethane resin A and the modified polyurethane resin B are crosslinked with each other in the curing process, the modified polyurethane resin A adopts multifunctional THEICA in the preparation process, so that the obtained modified polyurethane resin A is in a porous structure, when the modified polyurethane resin A is used in combination with the modified polyurethane resin B, the molecular chains of the modified polyurethane resin A and the modified polyurethane resin B are mutually interpenetrated, the high temperature resistance, the wear resistance and other properties of the protective coating are improved, and the modified polyurethane A has a better effect compared with the situation that an isocyanuric acid structure and the ester ring structure are introduced into the polyurethane structure at the same time;
(3) abundant N atoms in the structure of the modified polyurethane resin A and hydrogen atoms in the structure of the modified polyurethane resin B form a large number of hydrogen bonds in the curing and crosslinking process, so that the high-temperature resistance stability of the protective coating can be obviously improved.
Detailed Description
The present invention will now be described in further detail.
The modified polyurethane resin A in the following examples of the invention is prepared by the following steps:
(1) adding 28.2g of THEICA (CAS No.:40220-08-40), 0.05g of photoinitiator 1173 and 70mL of toluene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 50 ℃, dropwise adding 10.4g of mercaptoethanol into the flask under the protection of nitrogen, irradiating the mercaptoethanol with an LED lamp with the wavelength of 365nm while stirring, monitoring the reaction by FTIR, and when the double bond absorption peak in the reaction system disappears, finishing the reaction, and removing the solvent by rotary evaporation to obtain a product a;
(2) adding 30.2g of IPDI, 0.04g of catalyst DBTDL and 70mL of THF into a three-hole round-bottom flask, then raising the temperature of a reaction system to 70 ℃, dropwise adding 30.4g of product a into the flask under the protection of nitrogen, stirring for reaction after the dropwise addition is finished, monitoring the reaction by FTIR, adding 0.005g of hydroquinone into the reaction system until a hydroxyl absorption peak in the reaction system disappears, continuously dropwise adding PETA, continuously stirring for reaction at 70 ℃ until an isocyanate absorption peak in the reaction system disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent by rotary evaporation to obtain the isocyanuric acid modified polyurethane resin.
The modified polyurethane resin B in the following examples of the invention is prepared by the following steps:
(1) weighing HEMA, TCDMA (CAS:43048-08-4), MMA, AIBN and dioxane in a round bottom flask, wherein the weight ratio of the three monomers of HEMA, TCDMA and MMA is 3:5:3, the addition amount of AIBN is 0.5 percent of the total weight of the monomers, and the ratio of the total weight of the dioxane and the monomers is 7:3, introducing 45min of nitrogen into a reaction mixed solution for deoxygenation, placing the flask in an oil bath kettle at 70 ℃, stirring for reaction for 24h, washing a precipitated product by using normal hexane after the reaction is finished, and drying the product in vacuum at 45 ℃ overnight to obtain a product e;
(2) adding 30.2g of product e, 0.04g of catalyst p-toluenesulfonic acid, 0.005g of hydroquinone and 70mL of xylene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 70 ℃, dropwise adding hydroxyl-terminated polybutadiene (with the number average molecular weight of 3000) into the flask, stirring for reaction after the dropwise addition is completed, monitoring the reaction by FTIR, stopping dropwise adding the hydroxyl-terminated polybutadiene when the absorption peak of carboxyl in the reaction system disappears, then adding a xylene solution dissolved with IPDI and a catalyst DBTDL into the reaction system in a dropwise manner, continuing stirring for reaction at 70 ℃, wherein the mass percentage content of IPDI in the xylene solution is 20%, the addition amount of the catalyst DBTDL in the xylene solution is 0.1% of the mass of IPDI until the absorption peak of hydroxyl in the reaction system disappears on an FTIR spectrum, dropwise adding a xylene solution dissolved with IPDI and the catalyst DBTDL, then dropwise adding the xylene solution dissolved with PETA and the catalyst hydroquinone into the reaction system, and (2) continuously stirring and reacting at 70 ℃, wherein the mass percentage of the PETA in the xylene solution is 30%, and the addition amount of the hydroquinone in the xylene solution is 0.1% of the mass of the PETA, until an isocyanato absorption peak in a reaction system disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent through rotary evaporation to obtain the modified polyurethane resin B.
The polymeric dispersant used in the following examples of the present invention was BYK-AT204 or BYK-163.
The leveling agent used in the following examples of the present invention was JS-3038 or BYK-300.
The defoaming agent adopted in the following examples of the invention is Z-3646 organosilicon defoaming agent or
Polyether modified silicon defoamer.
Example 1
An EB (Electron beam) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate comprises the following components in parts by weight:
the modified polyurethane consists of a modified polyurethane resin A and a modified polyurethane resin B according to the weight ratio of 1:1.
Example 2
An EB (Electron Beam) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate comprises the following components in parts by weight:
the modified polyurethane consists of a modified polyurethane resin A and a modified polyurethane resin B according to the weight ratio of 1: 3.
Example 3
An EB (Electron Beam) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate comprises the following components in parts by weight:
the modified polyurethane consists of a modified polyurethane resin A and a modified polyurethane resin B according to the weight ratio of 1: 2.
Example 4
An EB (Electron beam) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate comprises the following components in parts by weight:
the modified polyurethane consists of a modified polyurethane resin A and a modified polyurethane resin B according to the weight ratio of 2: 1.
Example 5
An EB (Electron beam) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate comprises the following components in parts by weight:
the modified polyurethane consists of a modified polyurethane resin A and a modified polyurethane resin B according to the weight ratio of 3: 1.
Example 6 is the same as example 1 except that the modified polyurethane in example 6 is composed of the modified polyurethane resin A and the modified polyurethane resin B at a weight ratio of 1.5: 1.
Example 7 is the same as example 1 except that the modified polyurethane in example 7 is composed of the modified polyurethane resin a and the modified polyurethane resin B at a weight ratio of 2: 1.
Example 8 is the same as example 1 except that the modified polyurethane in example 8 is composed of the modified polyurethane resin A and the modified polyurethane resin B at a weight ratio of 3: 1.
Example 9 is the same as example 1 except that the modified polyurethane in example 9 is composed of the modified polyurethane resin A and the modified polyurethane resin B at a weight ratio of 1: 1.5.
The difference between the comparative example 1 and the example 7 is that the modified polyurethane in the comparative example 1 is prepared by simultaneously introducing isocyanuric acid, alicyclic group and polybutadiene structures into a polyurethane structure, and the specific preparation method is as follows:
(1) weighing HEMA, TCDMA, THEICA, MMA, AIBN and dioxane in a round bottom flask, wherein the weight ratio of four monomers of HEMA, TCDMA, THEICA and MMA is 3:5:3:3, the addition amount of AIBN is 0.5 percent of the total weight of the monomers, the ratio of dioxane to the total weight of the monomers is 7:3, introducing 4min of nitrogen into a reaction mixed solution to remove oxygen, placing the flask in an oil bath kettle at 70 ℃, stirring and reacting for 24h, washing a precipitated product by using normal hexane after the reaction is finished, and drying the product overnight in vacuum at 45 ℃ to obtain a product f;
(2) adding 30.2g of product f, 0.04g of catalyst p-toluenesulfonic acid, 0.005g of hydroquinone and 70mL of xylene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 70 ℃, dropwise adding hydroxyl-terminated polybutadiene (with the number average molecular weight of 3000) into the flask, stirring for reaction after the dropwise addition is completed, monitoring the reaction by FTIR, stopping dropwise adding the hydroxyl-terminated polybutadiene when the absorption peak of carboxyl in the reaction system disappears, then adding a xylene solution dissolved with IPDI and a catalyst DBTDL into the reaction system in a dropwise manner, continuing stirring for reaction at 70 ℃, wherein the mass percentage content of IPDI in the xylene solution is 20%, the addition amount of the catalyst DBTDL in the xylene solution is 0.1% of the mass of IPDI until the absorption peak of hydroxyl in the reaction system disappears on an FTIR spectrum, dropwise adding a xylene solution dissolved with IPDI and the catalyst DBTDL, then dropwise adding the xylene solution dissolved with PETA and the catalyst hydroquinone into the reaction system, and (2) continuously stirring and reacting at 70 ℃, wherein the mass percentage of the PETA in the xylene solution is 30%, and the addition amount of the hydroquinone in the xylene solution is 0.1% of the mass of the PETA, until an isocyanato absorption peak in a reaction system disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent through rotary evaporation to obtain the modified polyurethane resin.
Application and performance evaluation:
the EB curing wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate, which is obtained according to the formulas of the embodiments 1 to 9 and the comparative example 1 of the invention, is prepared according to the following steps:
according to the formula amount, the modified polyurethane, the active monomer, the flatting agent, the dispersing agent, the defoaming agent and the absolute ethyl alcohol are stirred and mixed uniformly to obtain the polyurethane adhesive.
Coating the coatings obtained in the embodiments 1-9 and the comparative example 1 on the surface of an aluminum-based copper-clad plate, curing by EB, forming a protective coating with the thickness of 3 mu m on the surface of the aluminum-based copper-clad plate, and then carrying out related performance tests on the obtained protective coating:
wear resistance: the test was performed according to GB/T1768-2006, 100 r.
Scratch resistance: test according to BSEN16094-2012
High temperature resistance: baking in an oven at 250 ℃ for 4 hours, and observing cracking
Flexibility: bending the aluminum substrate by 180 degrees to see whether the paint film cracks
Hardness: testing was carried out according to GB/T6739-2006
Adhesion force: testing according to GB/T9286-1998
Specific test results are shown in table 1:
TABLE 1
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. An EB (Electron beam) curing wear-resistant and high-temperature-resistant coating for an aluminum-based copper-clad plate is characterized by comprising the following components in parts by weight:
the modified polyurethane consists of a modified polyurethane resin A and a modified polyurethane resin B according to the weight ratio of 1-3: 3-1.
2. The EB-cured wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate according to claim 1, wherein the modified polyurethane consists of a modified polyurethane resin A and a modified polyurethane resin B according to a weight ratio of 1.5-2: 1.
3. The EB-cured wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate according to claim 1, wherein the modified polyurethane resin A is isocyanuric acid modified polyurethane resin.
4. The EB-cured wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate according to claim 3, wherein the isocyanuric acid modified polyurethane resin is prepared by the following steps:
(1) adding 28.2g of THEICA, 0.05g of photoinitiator 1173 and 70mL of toluene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 50 ℃, dropwise adding 10.4g of mercaptoethanol into the flask under the protection of nitrogen, irradiating the mercaptoethanol with an LED lamp with the wavelength of 365nm while stirring, monitoring the reaction by FTIR, and removing the solvent by rotary evaporation when the double bond absorption peak in the reaction system disappears to obtain a product a;
(2) adding 30.2g of IPDI, 0.04g of catalyst DBTDL and 70mL of THF into a three-hole round-bottom flask, then raising the temperature of a reaction system to 70 ℃, dropwise adding 30.4g of product a into the flask under the protection of nitrogen, stirring for reaction after the dropwise adding is completed, monitoring the reaction by FTIR, adding 0.005g of hydroquinone into the reaction system when a hydroxyl absorption peak in the reaction system disappears, continuously dropwise adding PETA, continuously stirring for reaction at 70 ℃ until an isocyanate absorption peak in the reaction system disappears on an FTIR spectrum, ending the reaction, and finally removing the solvent by rotary evaporation to obtain the isocyanuric acid modified polyurethane resin.
5. The EB-cured wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate according to claim 1, wherein the modified polyurethane resin B is prepared according to the following steps:
(1) weighing HEMA, TCDMA, MMA, AIBN and dioxane in a round bottom flask, wherein the weight ratio of the three monomers of HEMA, TCDMA and MMA is 3:5:3, the addition amount of AIBN is 0.5 percent of the total weight of the monomers, and the weight ratio of the dioxane to the total weight of the monomers is 7:3, introducing nitrogen for 45min to remove oxygen into a reaction mixed solution, placing the flask under a 70 ℃ oil bath pan, stirring and reacting for 24h, washing a precipitated product with n-hexane after the reaction is finished, and carrying out vacuum drying at 45 ℃ overnight to obtain a product e;
(2) adding 30.2g of product e, 0.04g of catalyst p-toluenesulfonic acid, 0.005g of hydroquinone and 70mL of xylene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 70 ℃, dropwise adding hydroxyl-terminated polybutadiene into the flask, stirring for reaction after the dropwise addition is finished, monitoring the reaction by FTIR, stopping dropwise adding the hydroxyl-terminated polybutadiene when the absorption peak of carboxyl in the reaction system disappears, then adding a xylene solution dissolved with IPDI and a catalyst DBTDL into the reaction system in a dropwise manner, continuing stirring for reaction at 70 ℃, wherein the mass percentage content of IPDI in the xylene solution is 20%, the addition amount of the catalyst DBTDL in the xylene solution is 0.1% of the mass of IPDI until the absorption peak of hydroxyl in the reaction system disappears on an FTIR spectrum, stopping dropwise adding the xylene solution dissolved with IPDI and the catalyst DBTDL, then adding the xylene solution dissolved with PETA and the catalyst hydroquinone into the reaction system in a dropwise addition manner, and (2) continuously stirring and reacting at 70 ℃, wherein the mass percentage of the PETA in the xylene solution is 30%, and the addition amount of the hydroquinone in the xylene solution is 0.1% of the mass of the PETA, until an isocyanato absorption peak in a reaction system disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent through rotary evaporation to obtain the modified polyurethane resin B.
6. The EB-cured wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate according to claim 1, wherein the active monomer is one or more of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-hexanediol diacrylate and tripropylene glycol diacrylate.
7. The EB-cured wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate according to claim 1, wherein the leveling agent is an organic silicon leveling agent.
8. The EB-cured wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate according to claim 1, wherein the dispersant is a polymer dispersant.
9. The EB-cured wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate according to claim 1, wherein the defoaming agent is an organic silicon defoaming agent or a polyether modified organic silicon defoaming agent.
10. The EB-cured wear-resistant and high-temperature-resistant coating for the aluminum-based copper-clad plate according to claims 1 to 9, which is characterized by being prepared according to the following steps:
according to the formula amount, the modified polyurethane, the active monomer, the flatting agent, the dispersing agent, the defoaming agent and the absolute ethyl alcohol are stirred and mixed uniformly to obtain the polyurethane adhesive.
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| CN116426157A (en) * | 2023-03-02 | 2023-07-14 | 广东希贵光固化材料有限公司 | Scratch-resistant and wear-resistant UV glass ink |
| CN116694160A (en) * | 2023-06-16 | 2023-09-05 | 广东希贵光固化材料有限公司 | Water-based UV finishing paint for vacuum plating |
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