CN111672719B - Protective coating and preparation method thereof - Google Patents
Protective coating and preparation method thereof Download PDFInfo
- Publication number
- CN111672719B CN111672719B CN202010526684.4A CN202010526684A CN111672719B CN 111672719 B CN111672719 B CN 111672719B CN 202010526684 A CN202010526684 A CN 202010526684A CN 111672719 B CN111672719 B CN 111672719B
- Authority
- CN
- China
- Prior art keywords
- coating
- monomer
- protective coating
- plasma
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011253 protective coating Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 118
- 238000000576 coating method Methods 0.000 claims abstract description 98
- 239000011248 coating agent Substances 0.000 claims abstract description 96
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 12
- 150000002430 hydrocarbons Chemical group 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 description 53
- 150000002367 halogens Chemical group 0.000 description 34
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 15
- 239000011777 magnesium Chemical group 0.000 description 14
- 230000007613 environmental effect Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000009834 vaporization Methods 0.000 description 10
- 230000008016 vaporization Effects 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000002309 gasification Methods 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 5
- -1 bis (3, 4-epoxycyclohexyl) methyl Chemical group 0.000 description 5
- 229910052801 chlorine Chemical group 0.000 description 5
- 239000000460 chlorine Chemical group 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 3
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 3
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 3
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 3
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- GDUZPNKSJOOIDA-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-methylprop-2-enoate Chemical compound C1C(OC(=O)C(=C)C)CCC2OC21 GDUZPNKSJOOIDA-UHFFFAOYSA-N 0.000 description 2
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 2
- ZXUJYIQZKNWLQN-UHFFFAOYSA-N [3-(7-oxabicyclo[4.1.0]heptan-3-ylmethyl)-7-oxabicyclo[4.1.0]heptan-3-yl] formate Chemical compound C(=O)OC1(CC2C(CC1)O2)CC1CC2C(CC1)O2 ZXUJYIQZKNWLQN-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CKMOZOIJQBUCGR-UHFFFAOYSA-N 2-cyclopentyloxy-6-oxabicyclo[3.1.0]hexane Chemical compound C1CCCC1OC1C2OC2CC1 CKMOZOIJQBUCGR-UHFFFAOYSA-N 0.000 description 1
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical compound CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ISDGWTZFJKFKMO-UHFFFAOYSA-N 2-phenyl-1,3-dioxane-4,6-dione Chemical compound O1C(=O)CC(=O)OC1C1=CC=CC=C1 ISDGWTZFJKFKMO-UHFFFAOYSA-N 0.000 description 1
- CDXFIRXEAJABAZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDXFIRXEAJABAZ-UHFFFAOYSA-N 0.000 description 1
- SWTZSHBOMGAQKX-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-pentacosafluorotetradecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C SWTZSHBOMGAQKX-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- DPTGFYXXFXSRIR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl prop-2-enoate Chemical compound C1C(COC(=O)C=C)CCC2OC21 DPTGFYXXFXSRIR-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LYUUVYQGUMRKOV-UHFFFAOYSA-N Diethyl diallylmalonate Chemical compound CCOC(=O)C(CC=C)(CC=C)C(=O)OCC LYUUVYQGUMRKOV-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- MJYSISMEPNOHEG-UHFFFAOYSA-N anthracen-9-ylmethyl 2-methylprop-2-enoate Chemical compound C1=CC=C2C(COC(=O)C(=C)C)=C(C=CC=C3)C3=CC2=C1 MJYSISMEPNOHEG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- UZUFPBIDKMEQEQ-UHFFFAOYSA-N perfluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UZUFPBIDKMEQEQ-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D135/02—Homopolymers or copolymers of esters
-
- 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
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a protective coating, which is a coating with excellent protective performance to a base material, and is formed by plasma polymerizing a monomer with an alicyclic epoxy structural unit to form a compact anticorrosive coating with a rigid molecular structure and simultaneously forming a hydrophobic coating on the plasma polymerizing coating of the monomer with the alicyclic epoxy structural unit.
Description
Technical Field
The invention belongs to the field of plasma chemistry, and particularly relates to a plasma polymerization protective coating and a preparation method thereof.
Background
Providing selective protection against corrosion for various types of products, such as electronic devices and components, metals, etc., against the effects of weather, is critical to the reliability of these products. The organic polymer coating can effectively protect the surfaces of different materials, and the method for preparing the polymer protective coating on the surface of the base material by a vapor deposition method is a mainstream method in the method for preparing the organic polymer coating, is economic and applicable and easy to operate, and particularly has the characteristics of plasma chemical vapor deposition, and reaction monomer gas is activated by plasma and deposited on the surface of the base material.
In the case of plasma-resistant coatings, it is common to plasma-coat a substrate with a perfluorinated monomer, which has poor adhesion to the substrate due to the perfluorinated group of the monomer, and the fluoropolymer tends to release toxic substances such as perfluorooctyl carboxylate or perfluorooctyl sulfonate to the environment, which is likely to cause environmental pollution, and thus stricter regulations have been issued by the U.S. Environmental Protection Agency (EPA) to prohibit the use of fluoropolymers having long carbon chains. For this reason, it is necessary to develop plasma coatings that replace perfluoromonomers.
Disclosure of Invention
The specific embodiment of the invention is to provide a novel anticorrosion protective coating formed by depositing a hydrophobic coating on a monomer plasma polymerization coating with an alicyclic epoxy structure and a preparation method thereof, and the specific scheme is as follows:
a protective coating comprising a coating I and a coating II deposited on a substrate,
the coating II is a plasma polymerization coating formed by plasma containing a monomer alpha;
the coating I is contacted with plasma containing monomer beta by the coating II, so that a plasma polymerization coating is formed on the coating II;
the monomer alpha comprises an alicyclic epoxy structural unit represented by the formula (1),
wherein A is a 3-20 membered alicyclic structure;
the monomer beta is selected from one or more of alkane, halogenated alkane, alkene, halogenated alkene, alkyne, halogenated alkyne, acrylate or halogenated acrylate.
Optionally, a is a five-membered alicyclic structure or a six-membered alicyclic structure.
Optionally, the monomer α further comprises at least one of a carbon-carbon unsaturated structural unit or an epoxy structural unit.
Optionally, the monomer alpha has a structure shown in a formula (2),
wherein R is1、R2And R3Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10A halogen atom-substituted alkyl group of (1);
R4is a connecting bond, C1-C10Alkylene or C1-C10The halogen atom of (1) is substituted with an alkylene group.
Optionally, the R is1、R2And R3Each independently is selected from hydrogen atom or methyl; the R is4Is a bond, methylene or ethylene.
Optionally, the monomer α has a structure represented by formula (3) or formula (4)
Optionally, the monomer alpha has a structure shown in formula (5),
wherein R is5Is a connecting bond, C1-C10Alkylene or C1-C10A halogen atom-substituted alkylene group of (1); r6Is composed of
Or
Optionally, the monomer alpha has a structure shown in a formula (6) or a formula (7),
optionally, the monomer alpha has a structure shown in a formula (8),
wherein R is7And R9Each independently selected from the group consisting of a connecting bond, C1-C10Alkylene or C1-C10A halogen atom-substituted alkylene group of (1);
R8is C1-C10Alkylene or C1-C10A halogen atom-substituted alkylene group of (1);
x and Y are respectively and independently selected from a connecting bond, an oxygen atom, a carbonyl group or an ester group.
Optionally, the monomer alpha has a structure shown in a formula (9) or a formula (10),
optionally, the coating II is a plasma polymerization coating formed by plasma containing a monomer alpha and a monomer gamma; the monomer gamma comprises a structural unit a having a structure represented by formula (11);
wherein R is10、R11And R12Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10The halogen atom of (1) is substituted with an alkyl group.
Optionally, the monomer γ further comprises a structural unit b, and the structural unit b is at least one of a carbon-carbon unsaturated structural unit or an epoxy structural unit.
Optionally, the structural unit b has a structure shown in formula (12);
wherein R is13、R14And R15Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10The halogen atom of (1) is substituted with an alkyl group.
Optionally, the monomer γ has a structure represented by formula (13);
wherein R is16Is C2-C10Alkylene or C2-C10The halogen atom of (a) is substituted with an alkylene group,n is an integer of 1 to 10.
Optionally, R10、R11、R12、R13、R14And R15Each independently selected from a hydrogen atom or a methyl group.
Optionally, the monomer beta has a structure represented by formula (14),
wherein R is17、R18And R19Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10A halogen atom-substituted alkyl group of (1); r20Is C1-C20Or C is a hydrocarbon group1-C20A halogen atom-substituted hydrocarbon group of (1).
Optionally, the R is17、R18And R19Each independently is selected from hydrogen atom or methyl; the R is20Is C4-C20Or C is a hydrocarbon group4-C20A halogen atom-substituted hydrocarbon group of (1).
Optionally, the monomer beta has a structure represented by formula (15),
wherein R is21Is a connecting bond, C1-C10Alkylene or C1-C10A halogen atom-substituted alkylene group of (1); b is an aromatic ring structure or a 3-to 20-membered alicyclic structure.
Optionally, the R is21Is a bond, methylene or ethylene, and B is cyclohexyl or cyclopentyl.
Optionally, the coating further comprises a coating III, wherein the coating III is a plasma polymerization coating formed by contacting the substrate with plasma containing the monomer delta;
coating II is a plasma polymerized coating formed on coating III by contacting coating III with a plasma comprising monomer alpha;
the monomer delta comprises a structural unit c and a structural unit d, wherein the structural unit c and the structural unit d respectively have a carbon-carbon double bond structure and an ester group structure.
Optionally, the structural unit c has a structure represented by formula (16);
wherein R is22、R23And R24Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10A halogen atom-substituted alkyl group of (1);
optionally, the structural unit d has a structure shown in formula (17);
wherein R is25、R26And R27Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10The halogen atom of (1) is substituted with an alkyl group.
Optionally, the monomer delta has a structure shown in formula (18),
wherein R is28Is C2-C10Alkylene or C2-C10N is an integer of 0 to 10, wherein R is22、R23、R24、R25、R26And R27Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10The halogen atom of (1) is substituted with an alkyl group.
Optionally, R22、R23、R24、R25、R26And R27Each independently selected from a hydrogen atom or a methyl group.
Optionally, the substrate is a metal, plastic, fabric, glass, electrical component, optical instrument, or electrical component.
A method for preparing the above protective coating, comprising: providing a substrate; the protective coating is formed on the substrate by plasma depositing the coating.
Optionally, the plasma is a pulsed plasma.
Optionally, the pulsed plasma is generated by applying pulsed voltage for discharging, wherein the pulse power is 20-500W, the pulse frequency is 20Hz-80KHz, the pulse duty ratio is 1% o-80%, and the plasma discharge time is 100s-20000 s.
A device having at least a portion of a surface thereof a protective coating comprising the above.
The protective coating of the specific embodiment of the invention is a compact rigid molecular structure anticorrosive coating formed by a monomer plasma polymerization coating with an alicyclic epoxy structural unit, and a hydrophobic coating is formed by plasma polymerization on the monomer plasma polymerization coating with the alicyclic epoxy structural unit to form a coating with excellent protective performance on a base material; furthermore, when the plasma monomer of the hydrophobic coating adopts a monomer with an alicyclic epoxy structural unit, the hydrophobic layer is tightly attached to the anticorrosive layer, and the hydrophobic coating has more excellent protective performance.
Detailed Description
A protective coating according to embodiments of the present invention comprises a coating I and a coating II deposited on a substrate,
the coating II is a plasma polymerization coating formed by plasma containing a monomer alpha;
the coating I is contacted with plasma containing monomer beta by the coating II, so that a plasma polymerization coating is formed on the coating II;
the monomer alpha comprises an alicyclic epoxy structural unit represented by the formula (1),
wherein A is a 3-20 membered alicyclic structure;
the monomer beta is selected from one or more of alkane, halogenated alkane, alkene, halogenated alkene, alkyne, halogenated alkyne, acrylate or halogenated acrylate.
In particular embodiments of the protective coatings of the present invention, the alicyclic structure is unsubstituted. In other embodiments, the alicyclic structure may have one or more substituents, such as alkyl substituents including methyl, ethyl, propyl, and butyl, halogen substituents including fluorine and chlorine, and halogen substituted alkyl substituents including fluorine substituted methyl, chlorine substituted methyl, fluorine substituted ethyl, chlorine substituted ethyl, fluorine substituted propyl, chlorine substituted propyl, fluorine substituted butyl, and chlorine substituted butyl. In view of the influence of halogen elements on the environment, it is preferable that the alicyclic structure has no substituent or that the substituent is an alkyl substituent.
In some embodiments, A is a five-membered alicyclic structure or a six-membered alicyclic structure, which is more stable in rigid structure.
The protective coating according to the embodiment of the present invention, wherein the monomer α further comprises at least one of a carbon-carbon double bond structural unit, a carbon-carbon triple bond structural unit or an epoxy structural unit, which facilitates the formation of a dense network structure by crosslinking a plurality of active sites, may be, for example, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate, 3, 4-epoxycyclohexylmethyl methacrylate, 3, 4-epoxycyclohexylmethyl acrylate, 1, 2-epoxy-4-vinylcyclohexane, bis (2, 3-epoxycyclopentyl) ether, 2, 3-epoxycyclopentylcyclopentyl ether, vinylcyclohexene diepoxide, diisoprenyl diepoxide, bis ((3, 4-epoxycyclohexyl) methyl) adipate, bis (3, 4-epoxycyclohexyl) methyl) adipate, or the like, 3,4 epoxy-6-methylcyclohexanecarboxylic acid-3 ',4' -epoxy-6 ' -methylcyclohexanemethyl ester, dicyclopentadiene diepoxide or the like, and in some embodiments, the monomer a has a structure represented by formula (2),
wherein R is1、R2And R3Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10A halogen atom-substituted alkyl group of R4Is a connecting bond, C1-C10Alkylene or C1-C10A halogen atom-substituted alkylene group of (1); in particular, said R1、R2And R3Each independently selected from hydrogen atom, C1-C4Alkylene or C1-C4A halogen atom-substituted alkyl group of (A), said R4Is a connecting bond, C1-C4Alkylene or C1-C4A halogen atom-substituted alkylene group of (1); in some embodiments, R takes into account the environmental impact of the halogen element1、R2And R3Each independently selected from hydrogen atom or C1-C10Alkyl of (2), especially a hydrogen atom or C1-C4Alkyl of R4Is a connecting bond, C1-C10Alkylene of (2), especially a connecting bond or C1-C4Alkylene of (b), especially, the R1、R2And R3Each independently selected from hydrogen atom or methyl, R4Is a bond, methylene or ethylene. Specifically, the monomer α may be 3, 4-epoxycyclohexyl methacrylate having a structure represented by formula (3) or 3, 4-epoxycyclohexyl methacrylate having a structure represented by formula (4), for example.
In some embodiments, the monomer α has a structure represented by formula (5),
wherein R is5Is a connecting bond, C1-C10Alkylene or C1-C10A halogen atom-substituted alkylene group of (1); r6Is composed of
Or
In particular, R5Is a connecting bond, C1-C4Alkylene or C1-C4A halogen atom-substituted alkylene group of (1); in some embodiments, R takes into account the environmental impact of the halogen element5Is a connecting bond or C1-C10Alkylene of (2), especially a connecting bond or C1-C4An alkylene group of (a). As a specific example, the monomer α may be 1, 2-epoxy-4-vinylcyclohexane having a structure represented by formula (6) or vinylcyclohexene diepoxide having a structure represented by formula (7).
In some embodiments, the monomer α has a structure represented by formula (8),
wherein R is7And R9Each independently selected from the group consisting of a connecting bond, C1-C10Alkylene or C1-C10A halogen atom-substituted alkylene group of (2), especially R7And R9Each independently selected from the group consisting of a connecting bond, C1-C4Alkylene or C1-C4A halogen atom-substituted alkylene group of (1); r8Is C1-C10Alkylene orC1-C10A halogen atom-substituted alkylene group of (2), especially R8Is C1-C4Alkylene or C1-C4A halogen atom-substituted alkylene group of (1); x and Y are respectively and independently selected from a connecting bond, an oxygen atom, a carbonyl group or an ester group; in some embodiments, R takes into account the environmental impact of the halogen element7And R9Each independently selected from the group consisting of a connecting bond, C1-C10Alkylene of (2), especially R7And R9Each independently selected from the group consisting of a connecting bond, C1-C4Alkylene of (A), R8Is C1-C10Alkylene of (2), especially R8Is C1-C4An alkylene group of (a). Specifically, the monomer α may be 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate having a structure represented by formula (9) or bis ((3, 4-epoxycyclohexyl) methyl) adipate having a structure represented by formula (10).
The protective coating of embodiments of the present invention, in some embodiments, comprises a plasma of only monomer alpha. In some other embodiments, to facilitate the formation of a dense protective layer with high bonding force of the plasma coating to the substrate, the plasma is composed of a plasma of a monomer α and a plasma of a monomer γ, the monomer γ comprising a structural unit a; the structural unit a has a structure shown in formula (11);
wherein R is10、R11And R12Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10A halogen atom-substituted alkyl group of (1), in particular, the R10、R11And R12Each independently selected from hydrogen atom, C1-C4Alkyl or C1-C4A halogen atom-substituted alkyl group of (1); in some embodiments, R takes into account the environmental impact of the halogen element10、R11And R12Each independently selected from hydrogen atom, C1-C10In particular, the R radical10、R11And R12Each independently selected from hydrogen atom, C1-C4In particular, said R10、R11And R12Each independently is selected from hydrogen atom or methyl; as specific examples, the monomer γ may be one or more of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, butyl acrylate, 1, 4-butylene glycol methacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and the like. In some embodiments, the monomer γ further comprises a structural unit b, which is at least one of a carbon-carbon double bond structural unit, a carbon-carbon triple bond structural unit, or an epoxy structural unit, particularly a double bond structural unit having a structure represented by formula (12);
wherein R is13、R14And R15Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10A halogen atom-substituted alkyl group of (1), in particular, the R13、R14And R15Each independently selected from hydrogen atom, C1-C4Alkyl or C1-C4A halogen atom-substituted alkyl group of (1); in some embodiments, the R is selected from the group consisting of sodium, potassium, magnesium, aluminum, magnesium, and magnesium13、R14And R15Each independently selected from hydrogen atom or C1-C10In particular, said R13、R14And R15Each independently selected from hydrogen atom or C1-C4In particular, said R13、R14And R15Each independently selected from hydrogen atom or methyl. In some embodiments, the monomer γ has a structure represented by formula (13);
wherein R is16Is C2-C10Alkylene or C2-C10N is an integer of 1 to 10; specifically, for example, n is 1 and R11Is ethylene, propylene, butylene, pentylene, or the like C2-C10An alkylene group of (a); or n is 1, R11Is C such as halogen atom-substituted ethylene, halogen atom-substituted propylene, halogen atom-substituted butylene, halogen atom-substituted pentylene, or the like2-C10A halogen atom-substituted alkylene group of (1); or n is an integer from 2 to 10, R11Ethylene or propylene, and the like. In some embodiments, R takes into account the environmental impact of the halogen element16Is C2-C10An alkylene group of (a). In the specific embodiment of the invention, the monomer alpha with the epoxy alicyclic structure is combined with the monomer gamma with the acrylate structure, and particularly when the monomer gamma adopts a double acrylate structure shown as a formula (13), the monomer alpha is more beneficial to forming a dense protective layer with high binding force after plasma coating, and the corrosion resistance of the base material is further improved.
In the protective coating according to the embodiment of the present invention, the specific addition amount of the monomer γ and the monomer α may be adjusted according to actual conditions, and the mass ratio of the monomer γ to the monomer α is usually 1:10 to 10:1, specifically, for example, 1:1, 1:2, 1:3, 2:3, 1:4, 1:5, 2:1, 3:2, 4:1 or 5: 1.
The protective coating of embodiments of the present invention, in some embodiments, coating I is formed on coating ii by contacting coating ii with a plasma comprising a monomer β represented by formula (14) below, thereby forming a plasma polymerized coating on coating ii.
Wherein R is17、R18And R19Each independently selected from hydrogen atom, C1-C10Alkyl or C1-C10A halogen atom-substituted alkyl group of R20Is C1-C20Or C is a hydrocarbon group1-C20The halogen atom-substituted hydrocarbon group of (1), particularly further improving the hydrophobicity, R20Is C4-C20Or C is a hydrocarbon group4-C20A halogen atom-substituted hydrocarbon group of (1); in some embodiments, R takes into account the environmental impact of the halogen element17、R18And R19Each independently selected from hydrogen atom or C1-C10In particular, said R17、R18And R19Each independently selected from hydrogen atom or methyl, R20Is C1-C20Of (a) a hydrocarbon group, in particular of said R20Is C4-C20A hydrocarbon group of (1). In some embodiments of the invention, the hydrocarbyl group is a saturated alkanyl group, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, or octadecyl, and the like, and in other embodiments of the invention, the hydrocarbyl group is an unsaturated alkylene, alkynyl, or aryl group. As a specific example, the monomer beta can be one or more of cyclohexyl methacrylate, octadecyl acrylate, isodecyl methacrylate, allyl methacrylate, isobornyl methacrylate, tert-butyl methacrylate, benzyl methacrylate, phenyl methacrylate, isopropyl methacrylate and 9-anthracenemethyl methacrylate. In some embodiments, the monomer β has a structure represented by formula (15),
wherein R is21Is a connecting bond, C1-C10Alkylene or C1-C10B is an aromatic ring structure or a 3-to 20-membered alicyclic structure, particularly, B is a 5-or 6-membered alicyclic structure, particularly, B is cyclohexyl or cyclopentyl; in some embodiments, R takes into account the environmental impact of the halogen element21Is a connecting bond or C1-C10Alkylene of (A), especially R21Is a bond, methylene or ethylene. Monomer beta has the structure that formula (15) is shown, and when B was the alicyclic structure, there was the alicyclic structure simultaneously in coating I and coating II, had better laminating effect to, the cooperation of coating I and coating II can have better barrier propterty.
Protective coatings according to embodiments of the invention, in some embodiments, further comprise a coating iii formed by plasma polymerization of the substrate in contact with a plasma of monomer δ; coating II is a plasma polymerized coating formed on coating III by contacting coating III with a plasma comprising monomer alpha; the monomer delta comprises a structural unit c and a structural unit d, the structural unit c and the structural unit d respectively have a carbon-carbon double bond structure and an ester group structure, and a coating III formed by adopting the plasma chemical vapor deposition of the monomer delta with the double unsaturated ester structure is beneficial to improving the tight combination of a base material and a coating II, so that the compactness and the combination force of a protective coating are improved. As specific examples, the monomer δ may be one or more of 1, 4-butanediol methacrylate, 1, 6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, neopentyl glycol dimethacrylate, methacrylic anhydride, dipropylene-2-enyl 2-benzylidene malonate, diethyl diallyl malonate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate or 1, 6-hexanediol diacrylate. In some embodiments, the structural unit c has a structure represented by formula (16);
wherein, in some embodiments, R22、R23And R24Are each independently selected from the group consisting of1-C10Halogen atom-substituted alkyl of, especially C1-C4A halogen atom-substituted alkyl group of (1); in some embodiments, R takes into account the environmental impact of the halogen element22、R23And R24Each independently selected from hydrogen atom or C1-C10Alkyl of (2), especially a hydrogen atom or C1-C4Alkyl of (2), in particular a hydrogen atom or a methyl group; in some embodiments, the structural unit d has a carbon-carbon double bond structural unit having a structure represented by formula (17);
wherein, in some embodiments, R25、R26And R27Are each independently selected from the group consisting of1-C10Halogen atom-substituted alkyl of, especially C1-C4A halogen atom-substituted alkyl group of (1); in some embodiments, R takes into account the environmental impact of the halogen element25、R26And R27Each independently selected from hydrogen atom or C1-C10Alkyl of (2), especially a hydrogen atom or C1-C4Alkyl groups of (a); in particular, said R25、R26And R27Each independently selected from hydrogen atom or methyl, especially hydrogen atom or methyl. In some embodiments, the monomer δ has a structure represented by formula (18);
wherein, in some embodiments, R28Is C2-C10N is an integer of 0 to 10, specifically for example n is 1, R28Is C such as halogen atom-substituted ethylene, halogen atom-substituted propylene, halogen atom-substituted butylene, halogen atom-substituted pentylene, or the like2-C10A halogen atom-substituted alkylene group of (1); in view of the environmental impact of the halogen element, in some embodiments, R28Is C2-C10N is an integer of 1 to 10, specifically for example, n is 1, R28Is ethylene, propylene, butylene, pentylene, or the like C2-C10Or n is an integer of 2 to 10, R22Ethylene or propylene, and the like. Through the coating III, particularly the monomer delta of the coating III is a diacrylate ester structure shown in a formula (18), the coating II and the base material are more tightly combined, and the compactness and the bonding force of the protective coating are further improved.
The protective coating of embodiments of the present invention, in some embodiments, is a metal, such as, for example, iron, magnesium, aluminum, copper, or alloys thereof, and in other embodiments, is a variety of plastics, fabrics, glass, electrical components, optical instruments, or the like. Specifically, the electrical component may be a Printed Circuit Board (PCB), an electronic product, or an electronic assembly semi-finished product, or the like. When the substrate is an electronic product, for example but not limited to a cell phone, a tablet, a keyboard, an e-reader, a wearable device, a display, and the like. The substrate may also be any suitable electrical component of an electrical assembly, in particular a resistor, a capacitor, a transistor, a diode, an amplifier, a relay, a transformer, a battery, a fuse, an integrated circuit, a switch, an LED display, a piezoelectric element, an optoelectronic component or an antenna or oscillator, etc.
In order to further enhance the bonding force between the plasma coating and the substrate, in some embodiments, the substrate is pretreated by using continuous plasma, for example, under an inert gas atmosphere, the plasma discharge power is 100-500W, the discharge duration is 60-600 s, and in other embodiments, the substrate is pretreated by using heat, oxygen, or high-energy radiation.
The protective coating of embodiments of the present invention, in some embodiments, is a continuous wave plasma, and in other embodiments, is a pulsed plasma. The specific conditions of the plasma coating can adopt corresponding conditions in the prior art, for example, the substrate is placed in a reaction cavity of a plasma chamber, the vacuum is pumped to 1-250 mTorr, inert gas such as He, Ar, O2 or mixed gas of several gases is introduced, monomers participating in the reaction enter the cavity in a gaseous state, the monomer flow is 40-2000ul/min, a power supply is turned on to generate plasma, so that chemical vapor deposition is generated on the surface of the substrate to respectively form the coating III, the coating II and the coating I, wherein the temperature in the cavity is controlled to be 20-80 ℃, the monomer gasification temperature is 70-150 ℃, the gasification is carried out under the vacuum condition, the plasma is excited in a continuous wave mode, the plasma discharge power is 10-180W, the continuous discharge time is 100-7200 s, or the plasma is excited in a pulse mode, in the pulse mode, the pulse power is 20-500W, the pulse frequency is 20Hz-80KHz, the pulse duty ratio is 1 per thousand-80%, and the plasma discharge time is 100s-20000 s.
The protective coating according to the embodiment of the present invention may be formed by any of various conventional discharge methods, such as electrodeless discharge (e.g., rf inductively coupled discharge, microwave discharge), single electrode discharge (e.g., corona discharge, plasma jet formed by unipolar discharge), double electrode discharge (e.g., dielectric barrier discharge, bare electrode rf glow discharge), and multiple electrode discharge (e.g., discharge using a floating electrode as the third electrode).
Embodiments of the present invention also provide a method for preparing a protective coating formed on a substrate by plasma deposition of the coating.
The present invention is further illustrated by the following specific examples.
Examples
Description of the test methods
5V saline test: the test procedure was as follows: 1. the power supply provides 5V voltage for the circuit board; 2. soaking the circuit board in 3.6% saline water; 3. detecting the current by using a computer; 4. the time to failure (current > 0.6mA) was recorded. Salt spray resistance test: the detection is carried out according to the GB/T2423.18-2000 environmental test method of electrical and electronic products.
Example 1
Placing the circuit board, the Mg and the Fe sheet in a plasma chamber, vacuumizing the chamber to 20 mTorr, introducing helium gas with the flow of 80sccm, starting radio frequency plasma discharge to carry out pretreatment on a substrate, wherein the discharge power in the pretreatment stage is 100W, and the continuous discharge lasts for 600 s;
then, introducing 1, 4-butanediol dimethacrylate, gasifying at the gasification temperature of 100 ℃, introducing the gasified monomer into the cavity, and performing plasma chemical vapor deposition, wherein the monomer flow is 150 mu L/min, the plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 25%, the pulse frequency is 1000Hz, the discharge power is 50W, and the discharge time is 3600 s;
then introducing a mixed monomer of 1, 6-hexanediol diacrylate and 1, 2-epoxy-4-vinylcyclohexane (mass ratio of 2:1), wherein the flow rate of the mixed monomer is 40ul/min, the vaporization temperature of the monomer is 120 ℃, a radio frequency discharge mode is adopted for generating plasma in the cavity, the output mode is a pulse, the pulse duty ratio is 25%, the pulse frequency is 1000Hz, the discharge power is 10w, and the discharge time is 7200 s;
then, octadecyl acrylate steam is introduced, the flow rate is 100ul/min, the monomer vaporization temperature is 120 ℃, a radio frequency discharge mode is adopted for generating plasma in the cavity, the output mode is a pulse, the pulse duty ratio is 25%, the pulse frequency is 1000Hz, the discharge power is 180w, and the discharge time is 7200 s; and finishing coating.
After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. Samples of the circuit board, the Mg and the Fe sheets were taken out and subjected to a salt water test and a salt spray test, and the test results are shown in Table 1.
Example 2
Placing the circuit board, the Mg and the Fe sheet in a plasma chamber, vacuumizing the chamber to 8 mTorr, introducing helium gas with the flow of 80sccm, starting radio frequency plasma discharge to carry out pretreatment on a substrate, wherein the discharge power in the pretreatment stage is 100W, and the continuous discharge lasts for 600 s;
then, introducing 1, 6-hexanediol dimethacrylate, gasifying at the gasification temperature of 100 ℃, and introducing into the cavity for plasma chemical vapor deposition, wherein the monomer flow is 150 mu L/min; the plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 45%, the pulse frequency is 500Hz, the discharge power is 50W, and the discharge time is 3600 s;
then introducing a mixed monomer of 1, 6-hexanediol dimethacrylate and vinylcyclohexene diepoxide (mass ratio is 1:2), wherein the flow rate of the mixed monomer is 40ul/min, the vaporization temperature of the monomer is 120 ℃, a radio frequency discharge mode is adopted for generating plasma in the cavity, the output mode is pulse, the pulse duty ratio is 45%, the pulse frequency is 500Hz, the discharge power is 10W, and the discharge time is 7200 s;
then, introducing tert-butyl methacrylate steam, wherein the flow rate is 100ul/min, the monomer vaporization temperature is 120 ℃, the plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 45%, the pulse frequency is 500Hz, the discharge power is 25W, and the discharge time is 7200 s; and finishing coating.
After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. Samples of the circuit board, the Mg and the Fe sheets were taken out and subjected to a salt water test and a salt spray test, and the test results are shown in Table 1.
Example 3
Placing the circuit board, the Mg and the Fe sheet in a plasma chamber, vacuumizing the chamber to 100 mTorr, introducing helium gas with the flow rate of 120sccm, starting radio frequency plasma discharge to carry out pretreatment on a substrate, wherein the discharge power in the pretreatment stage is 180W, and the continuous discharge lasts for 300 s;
then, introducing 1, 6-hexanediol dimethacrylate, gasifying at the gasification temperature of 110 ℃, and introducing into the cavity for plasma chemical vapor deposition, wherein the monomer flow is 220 muL/min; the plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 45%, the pulse frequency is 5000Hz, the discharge power is 25W, and the discharge time is 2200 s;
then introducing a mixed monomer of triethylene glycol dimethacrylate and 3, 4-epoxy cyclohexyl methyl methacrylate (the mass ratio is 3:2), wherein the flow rate of the mixed monomer is 40ul/min, the vaporization temperature of the monomer is 120 ℃, a radio frequency discharge mode is adopted for generating plasma in the cavity, the output mode is pulse, the pulse duty ratio is 45%, the pulse frequency is 5000Hz, the discharge power is 10w, and the discharge time is 7200 s;
then, isobornyl methacrylate steam is introduced, the flow rate is 100ul/min, the monomer vaporization temperature is 120 ℃, the plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 45%, the pulse frequency is 5000Hz, the discharge power is 25w, and the discharge time is 7200 s; and finishing coating.
After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. Samples of the circuit board, the Mg and the Fe sheets were taken out and subjected to a salt water test and a salt spray test, and the test results are shown in Table 1.
Example 4
Placing a circuit board and an Mg sheet in a plasma chamber, vacuumizing the chamber to 80 mTorr, introducing helium gas with the flow rate of 120sccm, starting radio frequency plasma discharge to carry out pretreatment on a substrate, wherein the discharge power in the pretreatment stage is 180W, and the continuous discharge lasts for 300 s;
then, introducing 1, 4-butanediol dimethacrylate, gasifying at the gasification temperature of 110 ℃, and introducing into the cavity for plasma chemical vapor deposition, wherein the monomer flow is 120 mu L/min; the plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 25%, the pulse frequency is 20kHz, the discharge power is 20W, and the discharge time is 3600 s;
then introducing a mixed monomer of 1, 6-hexanediol diacrylate and bis ((3, 4-epoxycyclohexyl) methyl) adipate (mass ratio is 2:1), wherein the flow rate of the mixed monomer is 150ul/min, the vaporization temperature of the monomer is 120 ℃, a radio frequency discharge mode is adopted for generating plasma in the cavity, the output mode is a pulse, the pulse duty ratio is 25%, the pulse frequency is 20kHz, the discharge power is 10w, and the discharge time is 3600 s;
then, benzyl methacrylate steam is introduced, the flow rate is 150ul/min, the monomer vaporization temperature is 150 ℃, the plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 25%, the pulse frequency is 20kHz, the discharge power is 150w, and the discharge time is 7200 s; and finishing coating.
After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. Samples of the circuit board, the Mg and the Fe sheets were taken out and subjected to a salt water test and a salt spray test, and the test results are shown in Table 1.
Comparative example 1
Placing the circuit board, the Mg and the Fe sheet in a plasma chamber, vacuumizing the chamber to 80 mTorr, introducing helium gas with the flow rate of 120sccm, starting radio frequency plasma discharge to carry out pretreatment on a substrate, wherein the discharge power in the pretreatment stage is 180W, and the continuous discharge lasts for 300 s;
then, 1, 4-butanediol diacrylate is introduced, gasified at the gasification temperature of 110 ℃, and then introduced into the cavity for plasma chemical vapor deposition, wherein the monomer flow is 120 mu L/min; the plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 25%, the pulse frequency is 20kHz, the discharge power is 20W, and the discharge time is 3600 s;
then, 2- (perfluorohexyl) ethyl methacrylate is introduced, the monomer flow is 120ul/min, the monomer vaporization temperature is 110 ℃, plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 25%, the pulse frequency is 20kHz, the discharge time is 3600s, and the discharge power is 180 w;
then, 2- (perfluorododecyl) ethyl acrylate steam is introduced, the flow is 160ul/min, the monomer vaporization temperature is 110 ℃, the plasma in the cavity is generated in a radio frequency discharge mode, the output mode is pulse, the pulse duty ratio is 25%, the pulse frequency is 20kHz, the discharge time is 7200s, and the discharge power is 180 w; and finishing coating.
After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. Samples of the circuit board, the Mg and the Fe sheets were taken out and subjected to a salt water test and a salt spray test, and the test results are shown in Table 1.
TABLE 1 results of Performance test of examples 1-4 and comparative example 1
From the results in table 1 above, it can be shown that the protective coating of the present invention has better protective properties than plasma protective coatings formed from perfluoromonomers even in the absence of halogen F.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (28)
1. A protective coating, comprising a coating I and a coating II deposited on a substrate,
the coating II is a plasma polymerization coating formed by plasma containing a monomer alpha;
the coating I is contacted with plasma containing monomer beta by the coating II, so that a plasma polymerization coating is formed on the coating II;
the monomer alpha comprises an alicyclic epoxy structural unit represented by the formula (1),
wherein A is a 3-20 membered alicyclic structure;
the monomer beta is selected from one or more of alkane, alkene, alkyne or acrylate; the acrylate has a structure represented by formula (14),
wherein R is17、R18And R19Each independently selected from hydrogen atom or C1-C10Alkyl groups of (a); r20Is C1-C20A hydrocarbon group of (1).
2. The protective coating of claim 1 wherein a is a five-membered alicyclic structure or a six-membered alicyclic structure.
3. The protective coating of claim 1 wherein the monomer a further comprises at least one of a carbon-carbon unsaturated structural unit or an epoxy structural unit.
4. The protective coating of claim 3, wherein the monomer a has a structure represented by formula (2),
wherein R is1、R2And R3Each independently selected from hydrogen atom or C1-C10Alkyl groups of (a);
R4is a connecting bond or C1-C10An alkylene group of (a).
5. The protective coating of claim 4, wherein R is1、R2And R3Each independently is selected from hydrogen atom or methyl; the R is4Is a bond, methylene or ethylene.
6. The protective coating of claim 5, wherein the monomer a has a structure of formula (3) or formula (4)
7. The protective coating of claim 3, wherein the monomer a has a structure represented by formula (5),
wherein R is5Is a connecting bond, C1-C10An alkylene group of (a);
R6is composed of
8. The protective coating of claim 7, wherein the monomer a has a structure represented by formula (6) or formula (7),
9. the protective coating of claim 3, wherein the monomer a has a structure represented by formula (8),
wherein R is7And R9Each independently selected from the group consisting of a bond or C1-C10An alkylene group of (a);
R8is C1-C10An alkylene group of (a);
x and Y are respectively and independently selected from a connecting bond, an oxygen atom, a carbonyl group or an ester group.
10. The protective coating of claim 9, wherein the monomer a has a structure of formula (9) or formula (10).
11. The protective coating of claim 1 wherein said coating ii is a plasma polymerized coating formed from a plasma comprising monomer α and monomer γ; the monomer gamma comprises a structural unit a having a structure represented by formula (11);
wherein R is10、R11And R12Each independently selected from hydrogen atom or C1-C10Alkyl group of (1).
12. The protective coating of claim 11, wherein the monomer γ further comprises a structural unit b, the structural unit b being at least one of a carbon-carbon unsaturated structural unit or an epoxy structural unit.
13. The protective coating according to claim 12, wherein the structural unit b has a structure represented by formula (12);
wherein R is13、R14And R15Each independently selected from hydrogen atom or C1-C10Alkyl group of (1).
14. The protective coating of claim 13, wherein the monomer γ has a structure represented by formula (13);
wherein R is16Is C2-C10N is an integer of 1 to 10.
15. The protective coating of claim 14, wherein R10、R11、R12、R13、R14And R15Each independently selected from a hydrogen atom or a methyl group.
16. The protective coating of claim 1, wherein R is17、R18And R19Each independently is selected from hydrogen atom or methyl; the R is20Is C4-C20A hydrocarbon group of (1).
17. The protective coating of claim 1, wherein the monomer β has a structure represented by formula (15),
wherein R is21Is a connecting bond or C1-C10An alkylene group of (a);
b is an aromatic ring structure or a 3-to 20-membered alicyclic structure.
18. The protective coating of claim 17, wherein R is21Is a bond, methylene or ethylene, and B is cyclohexyl or cyclopentyl.
19. The protective coating of claim 1, wherein the coating further comprises a coating iii formed by plasma polymerization of the substrate by contact with a plasma comprising monomer δ;
coating II is a plasma polymerized coating formed on coating III by contacting coating III with a plasma comprising monomer alpha;
the monomer delta comprises a structural unit c and a structural unit d, wherein the structural unit c and the structural unit d respectively have a carbon-carbon double bond structure and an ester group structure.
20. The protective coating of claim 19, wherein the structural unit c has a structure represented by formula (16);
wherein R is22、R23And R24Each independently selected from hydrogen atom or C1-C10Alkyl group of (1).
21. The protective coating of claim 20, wherein the structural unit d has a structure represented by formula (17);
wherein R is25、R26And R27Each independently selected from hydrogen atom or C1-C10Alkyl group of (1).
22. The protective coating of claim 20, wherein said monomer δ has a structure represented by formula (18),
wherein R is28Is C2-C10N is an integer of 0 to 10, wherein R22、R23、R24、R25、R26And R27Each independently selected from hydrogen atom or C1-C10Alkyl group of (1).
23. The protective coating of claim 22, wherein R22、R23、R24、R25、R26And R27Each independently selected from a hydrogen atom or a methyl group.
24. The protective coating of claim 1 wherein the substrate is a metal, plastic, fabric, glass, electrical component, optical instrument, or electrical component.
25. A method of producing the protective coating of any one of claims 1 to 24, comprising:
providing a substrate;
the protective coating is formed on the substrate by plasma depositing the coating.
26. The method of producing a protective coating according to claim 25, said plasma being a pulsed plasma.
27. The method for preparing a protective coating according to claim 26, wherein the pulsed plasma is generated by applying a pulsed voltage discharge, wherein the pulse power is 20-500W, the pulse frequency is 20Hz-80KHz, the pulse duty ratio is 1% o-80%, and the plasma discharge time is 100s-20000 s.
28. A device, wherein at least a portion of a surface of the device comprises a protective coating according to any one of claims 1-24.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010526684.4A CN111672719B (en) | 2020-06-09 | 2020-06-09 | Protective coating and preparation method thereof |
| JP2022575847A JP2023528674A (en) | 2020-06-09 | 2021-05-20 | Protective coating and method of making same |
| KR1020237000772A KR20230021131A (en) | 2020-06-09 | 2021-05-20 | Protective coatings and methods for their preparation |
| US18/009,302 US20230227666A1 (en) | 2020-06-09 | 2021-05-20 | Protective coating and preparation method therefor |
| PCT/CN2021/094737 WO2021249145A1 (en) | 2020-06-09 | 2021-05-20 | Protective coating and preparation method thereof |
| EP21821377.5A EP4183840A1 (en) | 2020-06-09 | 2021-05-20 | Protective coating and preparation method thereof |
| TW110120899A TW202212382A (en) | 2020-06-09 | 2021-06-07 | Protective coating and method for preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010526684.4A CN111672719B (en) | 2020-06-09 | 2020-06-09 | Protective coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111672719A CN111672719A (en) | 2020-09-18 |
| CN111672719B true CN111672719B (en) | 2022-02-08 |
Family
ID=72435324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010526684.4A Active CN111672719B (en) | 2020-06-09 | 2020-06-09 | Protective coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111672719B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230227666A1 (en) * | 2020-06-09 | 2023-07-20 | Jiangsu Favored Nanotechnology Co., Ltd. | Protective coating and preparation method therefor |
| CN113025096A (en) * | 2021-03-04 | 2021-06-25 | 江苏菲沃泰纳米科技股份有限公司 | Composite coating, preparation method and device |
| CN112980223B (en) * | 2021-03-04 | 2021-12-21 | 江苏菲沃泰纳米科技股份有限公司 | Composite coating, preparation method and device |
| CN115411420A (en) * | 2021-05-26 | 2022-11-29 | 江苏菲沃泰纳米科技股份有限公司 | Battery with coating and preparation method thereof |
| CN115991951B (en) * | 2021-10-20 | 2024-02-20 | 江苏菲沃泰纳米科技股份有限公司 | Composite coating, preparation method and device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1063247A1 (en) * | 1998-12-28 | 2000-12-27 | DAICEL CHEMICAL INDUSTRIES, Ltd. | Curable resin composition, modified copolymer and resin composition, and alkali development type photocurable glass paste |
| CN110158060A (en) * | 2019-06-24 | 2019-08-23 | 清华大学深圳研究生院 | A kind of multilayered structure and preparation method thereof |
-
2020
- 2020-06-09 CN CN202010526684.4A patent/CN111672719B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1063247A1 (en) * | 1998-12-28 | 2000-12-27 | DAICEL CHEMICAL INDUSTRIES, Ltd. | Curable resin composition, modified copolymer and resin composition, and alkali development type photocurable glass paste |
| CN110158060A (en) * | 2019-06-24 | 2019-08-23 | 清华大学深圳研究生院 | A kind of multilayered structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111672719A (en) | 2020-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111672719B (en) | Protective coating and preparation method thereof | |
| CN112980223B (en) | Composite coating, preparation method and device | |
| CN111635655B (en) | Protective coating and preparation method thereof | |
| CN111303673B (en) | Hydrophobic surface coating and preparation method thereof | |
| CN107058979B (en) | A kind of preparation method of waterproof electrical breakdown withstand coating | |
| CN109277269B (en) | Epoxy nano coating and preparation method thereof | |
| WO2014155099A1 (en) | Coated electrical assembly | |
| CN109354903B (en) | High-transparency low-chromatic-aberration nano coating and preparation method thereof | |
| CN113025096A (en) | Composite coating, preparation method and device | |
| KR20230021131A (en) | Protective coatings and methods for their preparation | |
| TWI837894B (en) | Composite coating, preparation method and device | |
| CN115991951B (en) | Composite coating, preparation method and device | |
| TWI827055B (en) | Plasma polymerization coating, preparation method and device | |
| TWI784560B (en) | Protective coating and method for preparation thereof | |
| CN118240436A (en) | Coating, preparation method and device | |
| CN118085669A (en) | Hydrophobic and oleophobic film layer and preparation method thereof | |
| CN118240474A (en) | Composite coating, preparation method and device | |
| CN118240257A (en) | Waterproof film layer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No. 182, East Ring Road, Yuqi supporting area, Huishan Economic Development Zone, Wuxi City, Jiangsu Province, 214000 Applicant after: Jiangsu feiwotai nanotechnology Co.,Ltd. Address before: No. 108, Xixian Road, Meicun street, Xinwu District, Wuxi City, Jiangsu Province, 214112 Applicant before: Jiangsu Favored Nanotechnology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20200918 Assignee: Feiwotai Nanotechnology (Shenzhen) Co.,Ltd. Assignor: Jiangsu feiwotai nanotechnology Co.,Ltd. Contract record no.: X2024980005116 Denomination of invention: A protective coating and its preparation method Granted publication date: 20220208 License type: Common License Record date: 20240430 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A protective coating and its preparation method Granted publication date: 20220208 Pledgee: Wuxi Branch of China CITIC Bank Co.,Ltd. Pledgor: Jiangsu feiwotai nanotechnology Co.,Ltd. Registration number: Y2024980016337 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |