CN117866468A - Dual-curable high-wettability UV three-proofing paint and preparation method thereof - Google Patents
Dual-curable high-wettability UV three-proofing paint and preparation method thereof Download PDFInfo
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- CN117866468A CN117866468A CN202410216160.3A CN202410216160A CN117866468A CN 117866468 A CN117866468 A CN 117866468A CN 202410216160 A CN202410216160 A CN 202410216160A CN 117866468 A CN117866468 A CN 117866468A
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- acrylate
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- stirring
- agent
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- 239000003973 paint Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 61
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 59
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010703 silicon Substances 0.000 claims abstract description 56
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 56
- 238000000016 photochemical curing Methods 0.000 claims abstract description 45
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 26
- -1 heterocyclic organic compounds Chemical class 0.000 claims abstract description 21
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 239000012949 free radical photoinitiator Substances 0.000 claims abstract description 18
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 229920002545 silicone oil Polymers 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 7
- ROBVLQBZPQQRTQ-UHFFFAOYSA-N [N].C1=CN=NN=C1 Chemical compound [N].C1=CN=NN=C1 ROBVLQBZPQQRTQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 115
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 27
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 27
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 26
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 26
- 239000000080 wetting agent Substances 0.000 claims description 26
- 239000012024 dehydrating agents Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 230000009977 dual effect Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000004922 lacquer Substances 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 150000005215 alkyl ethers Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 3
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 claims description 3
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 claims description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 3
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 claims description 3
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 3
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 3
- ZYMCJDAUBJFVSM-UHFFFAOYSA-N 6-methylheptyl 4-(dimethylamino)benzoate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 ZYMCJDAUBJFVSM-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- RDHSUTIDSFVNJL-UHFFFAOYSA-N OC(=O)C=C.CCCCCCCCCCCC(O)=O Chemical compound OC(=O)C=C.CCCCCCCCCCCC(O)=O RDHSUTIDSFVNJL-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 claims description 3
- KGGBUGLHJUGXEF-UHFFFAOYSA-N [6-hydroxy-4-(2-hydroxyethoxy)-6-methylcyclohexa-2,4-dien-1-yl]-phenylmethanone Chemical compound OC1(C(C(=O)C2=CC=CC=C2)C=CC(=C1)OCCO)C KGGBUGLHJUGXEF-UHFFFAOYSA-N 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 2
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 claims description 2
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 claims description 2
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002519 antifouling agent Substances 0.000 claims 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 claims 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 44
- 239000000463 material Substances 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000000498 cooling water Substances 0.000 description 21
- 238000001914 filtration Methods 0.000 description 21
- 238000004806 packaging method and process Methods 0.000 description 21
- 238000001723 curing Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 10
- 238000009736 wetting Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 description 3
- 238000003847 radiation curing Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- WVXMNBDPVYOPLX-UHFFFAOYSA-N 2-isocyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCC[N+]#[C-] WVXMNBDPVYOPLX-UHFFFAOYSA-N 0.000 description 2
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 2
- GZRMYMORHJHLPE-UHFFFAOYSA-N Mikrolin Natural products CC=C(/Cl)C1=CC(=O)C23CC2C(C)(CO)OC3(O)C1=O GZRMYMORHJHLPE-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000013100 final test Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- FEUIEHHLVZUGPB-UHFFFAOYSA-N oxolan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCO1 FEUIEHHLVZUGPB-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
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- DYRUVFJAAMUHRF-UHFFFAOYSA-N (2,3-diphenylphenyl)-phenylmethanone Chemical compound C=1C=CC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 DYRUVFJAAMUHRF-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
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Abstract
In order to overcome the problem that the electrical performance between an electronic element and a connecting point is reduced due to the fact that the electronic device is in a high humidity environment for a long time, the invention provides the double-curable high-wettability UV three-proofing paint and a preparation method thereof. The double-curable high-wettability UV three-proofing paint comprises photo-curing isocyanic acid acrylic resin, silicon-based resin, reactive diluent and free radical photoinitiator; the preparation of the photo-curing isocyanic acid acrylic resin comprises the following reaction raw materials: triazine nitrogen-containing heterocyclic organic compounds containing three isocyanate groups, hydroxyl-containing acrylic acid derivatives and double-end hydroxyl polyisobutene; the number average molecular weight of the double-end hydroxyl polyisobutene is 1000-3000; the silicon-based resin comprises the following reaction raw materials: monoisocyanate monomer and double-end hydroxyl polyether modified silicone oil; the number average molecular weight of the double-end hydroxyl polyether modified silicone oil is 1000-2000. Meanwhile, the invention also discloses a preparation method of the double-curable high-wettability UV three-proofing paint.
Description
Technical Field
The invention belongs to the field of photo-curing, and particularly relates to a double-curable high-wettability UV three-proofing paint and a preparation method thereof.
Background
With the rapid development of new generation information technologies such as cloud computing, internet of things and artificial intelligence, demands for printed circuit boards (Printed Circuit Board, PCBs) are greatly increasing in various application fields such as 5G communication, consumer electronics, automotive electronics and aerospace. Therefore, the PCB industry in China becomes one of the largest industries in the electronic industry. The PCB is one of the fundamental electronic components of critical importance in the electronics industry, and it implements the functions of a circuit through the installation and connection of electronic components. With the rapid development of electronic technology, PCBs are gradually evolving from original single-sided boards to double-sided boards, multi-layer boards, and flexible boards, while continuously evolving toward high precision, high density, and high reliability. In the PCB manufacturing process, the three-proofing lacquer of the circuit board is a vital material, which provides permanent protection for the printed circuit board. The three-proofing paint for the circuit board meets higher requirements while coping with the development of new generation information technology.
One of the most widely used three-proofing paint in the market is solvent-based three-proofing paint, and has the characteristics of low price, quick curing time, excellent leveling and wetting properties, good compatibility, easy repair and the like. For example, in patent CN 115011230B, a polyurethane three-proofing paint is disclosed, which consists of isocyanate-terminated silane, film-forming resin solution, solvent, catalyst. The invention realizes better interaction, has the characteristics of good high temperature resistance, no yellowing and good adhesiveness, and simultaneously has low viscosity and quick surface drying, thereby being beneficial to the coating of the circuit board. But the solvents are butanone, ethyl acetate, propyl acetate and butyl acetate. However, the polyurethane three-proofing paint can cause environmental pollution and bring physical injury to operators in the using process. With the improvement of environmental protection and safety production requirements, the environmental protection solvent-free three-proofing paint gradually reaches the brand-new corner. The UV curing technology has been attracting attention because of its advantages of fast curing speed, high production efficiency, etc. For example, in patent CN 110698974A, a low odor UV curable three-proofing paint composition is disclosed. The hydroxyl of the photoinitiator reacts with the isocyanate group, and the small molecular photoinitiator is grafted on the side chain of the prepolymer macromolecule, so that the odor of a coating film is reduced, the initiation effect of the photoinitiator is increased, and the finished product after the curing construction process is low in odor, green and environment-friendly. However, curing is poor, for example, in places where light is insufficient. In order to fully exploit the advantages of UV curing while overcoming its drawbacks, one solution is to employ dual cure systems, in combination with moisture curing. The dual curing technology can effectively overcome the defect of a single curing mode, and simultaneously comprehensively utilizes the advantages of the two curing modes, thereby becoming one of the most advanced coating curing technologies at present.
However, in the development of the electronic assembly industry, more and more no-clean soldering flux is used in the welding process of the circuit board, so that the surface energy of the circuit board is reduced, and the wettability of the ultraviolet light-curable solvent-free three-proofing paint in the spraying process is affected, which may cause problems such as shrinkage cavity and the like in a part of the circuit board, and the convenience of process operation, such as repair and repair paint, is affected. In extreme environments, the circuit board can work in a long-term humid environment, so the requirement on the water vapor transmittance of the three-proofing paint can be high. Three-proofing paint with the performance of the two is very rare in the market. Therefore, the three-proofing paint has good water vapor barrier property and excellent wetting property on a low-surface-energy circuit board, which are the preconditions of higher protective performance of the paint. The market is urgent to develop novel high-wettability three-proofing paint and has good water vapor protection capability to meet the electronic industry of high-speed development.
Disclosure of Invention
The invention aims at providing a three-proofing paint with good crosslinking and curing effects, good water vapor barrier function and high wetting performance aiming at the requirements of the circuit board surface energy reduction and the electronic device on wettability and water vapor transmittance in a long-term wet environment caused by more and more no-clean soldering flux used in the welding process of the circuit board. The material can fully utilize the advantages of ultraviolet light and moisture in two curing modes at the same time, and provides higher comprehensive performance for PCB manufacture.
The second aim of the invention is to provide a preparation method of the double-curable high-wettability UV three-proofing paint.
In order to achieve the above object, the present invention provides the following:
the double-curable high-wettability UV three-proofing paint comprises photo-curing isocyanic acid acrylic resin, silicon-based resin, reactive diluent and free radical photoinitiator;
the reaction raw materials for preparing the photo-curing isocyanic acid acrylic resin comprise triazine nitrogen-containing heterocyclic organic compounds containing three isocyanate groups, hydroxyl-containing acrylic acid derivatives and double-end hydroxyl polyisobutene;
the reaction raw materials of the silicon-based resin comprise a monoisocyanate monomer and double-end hydroxyl polyether modified silicone oil.
Alternatively, the triazine nitrogen-containing heterocyclic organic compound containing three isocyanate groups includes an HDI trimer.
Optionally, the dual-curable high-wettability UV three-proofing paint comprises the following components in parts by weight: 24-48 parts of light-cured isocyanic acrylic resin, 8-17 parts of silicon-based resin, 35-70 parts of reactive diluent and 2-6 parts of free radical photoinitiator.
Optionally, the hydroxyl-containing acrylic acid derivative comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxyethyl acrylamide, hydroxypropyl methacrylate, and hydroxypropyl acrylate.
Optionally, the molecular structure of the monoisocyanate monomer comprises an isocyanate group and a double bond functional group; the number average molecular weight of the double-end hydroxyl polyisobutene is 1000-3000; the number average molecular weight of the double-end hydroxyl polyether modified silicone oil is 1000-2000.
Optionally, the photocurable isocyanuric acid acrylic resin has a structure as shown in the general formula (I):
in the general formula (I), R is 1 、R 3 、R 4 And R is 6 Independently selected from H or CH 3 One of R 2 And R is 5 Represents an oxygen atom or-NH-, l and n each independently represent a positive integer of 1 to 4, m represents a positive integer of 4 to 7, and z is a positive integer of 15 to 60.
Optionally, the silicon-based resin has a structure according to formula (ii):
in the general formula (II), R is 11 And R is 16 Independently selected from H or CH 3 One of R 12 And R is 15 Independently selected from alkyl or alkyl ether having 2 to 4 carbon atoms, wherein R 13 And R is 14 Is an alkyl chain.
Optionally, the reactive diluent is selected from at least one of isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, isooctyl methacrylate, tetrahydrofuranyl acrylate, tetrahydrofuranyl methacrylate, trimethylolpropane triacrylate, 2-phenoxyethyl acrylate, ethoxylated trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, n-butyl acrylate, isodecyl acrylate, lauric acid acrylate, cyclohexyl acrylate, 3, 5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, dicyclopentenyl acrylate, pentaerythritol tetraacrylate.
Alternatively, the process may be carried out in a single-stage, the free radical photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone 4-benzoyl-4 '-methyl-diphenyl sulfide, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-1-hexanone, bis 2, 6-difluoro-3-pyrrolidocenetitanium, methyl benzoate, benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, at least one of methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4' -bis (diethylamino) benzophenone, isopropyl thioxanthone, 2, 4-diethyl thioxanthone and 2-ethyl anthraquinone.
Optionally, the dual-curable high-wettability UV three-proofing paint further comprises the following components in parts by weight: 0.05-2 parts of polymerization inhibitor and 0.1-5 parts of auxiliary agent.
Optionally, the auxiliary agent comprises one or more of fluorescent agent, color-changing powder, leveling agent, wetting agent, defoaming agent, silane coupling agent, antioxidant, antibacterial agent, flame retardant, dehydrating agent and filler.
On the other hand, the invention also provides a preparation method of the double-curable high-wettability UV three-proofing paint, which comprises the following steps:
(1) Preparing raw materials comprising photo-curing isocyanic acid acrylic resin, silicon-based resin, reactive diluent, free radical photoinitiator, polymerization inhibitor and auxiliary agent according to the proportion; the method comprises the steps of (1) stirring photo-curing acrylic resin isocyanate, silicon-based resin, reactive diluent and polymerization inhibitor until the components are uniformly mixed to obtain primary mixed solution;
(2) Under the condition of avoiding light, adding a free radical photoinitiator into the primary mixed solution, and continuously stirring to obtain a reaction solution;
(3) Under the condition of avoiding light, adding an auxiliary agent into the reaction liquid, and uniformly stirring to obtain the double-curable high-wettability UV three-proofing paint.
The beneficial effects of the invention are as follows:
1. the UV three-proofing paint is formed by combining the photo-curing isocyanic acid acrylic resin, the silicon-based resin, the reactive diluent, the free radical photoinitiator and the like, so that the problems that the solvent three-proofing paint causes environmental pollution due to solvent volatilization and the shadow area cannot be completely cured by the single UV photo-curing three-proofing paint are solved, and the UV three-proofing paint has the characteristics of environment friendliness, good paint film flexibility, excellent adhesive force, high protection performance, excellent leveling wettability and the like.
2. According to the invention, the photo-curing isocyanic acid acrylic resin with a specific structure and the silicon-based resin are reasonably matched, and because the polysiloxane chain segment is introduced into the oligomer, the three-proofing paint has good flexibility, meanwhile, the photo-curing isocyanic acid acrylic resin has rigid carbon nitrogen heterocycle and rich nitrogen, oxygen and other heteroatoms, and the adhesive force and flexibility of the three-proofing paint are effectively improved through the synergistic effect of the rigid chain segment and the flexible chain segment with good cohesive force, so that the high-low temperature impact resistance of the three-proofing paint is improved, and the more complex and harsh application environment is dealt with.
3. According to the invention, the polyisobutene chain segment with high stability and excellent sealing performance is introduced into the photo-curing isocyanic acid acrylic resin, and is matched with polysiloxane with high wettability in the silicon-based resin, so that the problem that the three-proofing paint is difficult to infiltrate a low-surface-energy circuit board is effectively solved by improving the water vapor barrier capability of a paint film, and the three-proofing paint has excellent leveling wetting capability and protective performance.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The dual-curable high-wettability UV three-proofing paint comprises photo-curable isocyanic acid acrylic resin, silicon-based resin, reactive diluent and free radical photoinitiator;
the reaction raw materials for preparing the photo-curing isocyanic acid acrylic resin comprise triazine nitrogen-containing heterocyclic organic compounds containing three isocyanate groups, hydroxyl-containing acrylic acid derivatives and double-end hydroxyl polyisobutene;
the reaction raw materials of the silicon-based resin comprise a monoisocyanate monomer and double-end hydroxyl polyether modified silicone oil;
in the embodiment, the UV three-proofing paint is formed by combining photo-curing isocyanic acid acrylic resin, silicon-based resin, reactive diluent, free radical photoinitiator and the like, so that the problems that the solvent three-proofing paint causes environmental pollution due to solvent volatilization and the shadow area cannot be completely cured by single UV photo-curing three-proofing paint are avoided, and the UV three-proofing paint has the characteristics of environmental protection, good paint film flexibility, excellent adhesive force, high protection performance, excellent leveling wettability and the like.
The light-cured isocyanic acid acrylic resin with a specific structure and the silicon-based resin are reasonably matched, and because the polysiloxane chain segment is introduced into the oligomer, the three-proofing paint has good flexibility, meanwhile, the light-cured isocyanic acid acrylic resin has rigid carbon nitrogen heterocycle and rich nitrogen, oxygen and other heteroatoms, and the adhesive force and flexibility of the three-proofing paint are effectively improved through the synergistic effect of the rigid chain segment with good cohesive force and the polyisobutene chain segment with smaller molecular distance, so that the high-low temperature impact resistance of the three-proofing paint is improved, and the more complex and harsh application environment is responded.
The polyisobutene chain segment with high stability and excellent sealing performance is introduced into the photo-curing isocyanic acid acrylic resin, and simultaneously the polyisobutene chain segment is matched with polysiloxane with high wettability in the silicon-based resin, so that the waterproof coating has excellent leveling wettability and protective performance by improving the water vapor barrier capability of a paint film, improving the flexibility of the paint film and simultaneously effectively solving the problem that the three-proofing paint is difficult to infiltrate a low-surface-energy circuit board.
In a preferred embodiment, the triazine nitrogen-containing heterocyclic organic compound containing three isocyanate groups comprises an HDI trimer.
In some embodiments of the invention, the monoisocyanate monomer includes one isocyanate group and one double bond functional group in its molecular structure.
The number average molecular weight of the double-ended hydroxyl polyisobutene is 1000 to 3000, such as 1000, 1200, 1400, 1500, 1800, 2000, 2200, 2500, 2800, 3000, etc., but is not limited to the values recited, and combinations not recited in the range are equally applicable.
When the number average molecular weight of the polyisobutylene chain segment of the photo-curing isocyanic acid acrylic resin is smaller than 1000, the curing shrinkage rate is increased due to the excessively high crosslinking degree, so that the adhesive capacity of the three-proofing paint is reduced, and the flexibility of the three-proofing paint is influenced; when the number average molecular weight of the polyisobutene chain segment is more than 3000, the reactivity of the three-proofing paint system is reduced due to the fact that the density of the active functional groups is too low, so that the cross-linked network structure of the three-proofing paint is not compact enough, the barrier property of water vapor and small molecules is reduced, and meanwhile, the number of polar groups is reduced, so that the three-proofing paint is difficult to surface dry and the adhesive capacity is reduced;
The number average molecular weight of the double-end hydroxyl polyether modified silicone oil is 1000 to 2000, such as 1000, 1200, 1400, 1500, 1800, 2000, etc., but is not limited to the values recited, and combinations not recited in the range are equally applicable.
Because the polysiloxane chain segment is introduced into the silicon-based resin, the prepared three-proofing paint has lower surface tension, so that the three-proofing paint has excellent leveling and wetting properties on a low-surface circuit board, and meanwhile, the silicon-oxygen bond in the polysiloxane chain segment can promote the flexibility of the three-proofing paint, so that the high-low temperature impact resistance of the three-proofing paint is improved, and the more complex and harsh application environment can be dealt with; when the number average molecular weight of the polysiloxane chain segment of the silicon-based resin is smaller than 1000, the toughness of the three-proofing paint is reduced due to the fact that the content of the polysiloxane chain segment is too low and the crosslinking degree is too high, the volume shrinkage rate after curing is too high, the internal stress is increased, and the adhesive force of a cured film is reduced; when the number average molecular weight of the polysiloxane chain segment is more than 2000, the hydrophilicity of the three-proofing lacquer can be increased due to the excessively high content of the polysiloxane chain segment, so that the water vapor barrier property of the three-proofing lacquer is reduced, and the protective effect of the three-proofing lacquer is reduced due to the excessively low crosslinking density.
In some embodiments of the present invention, the reaction raw materials of the photocurable acrylic resin and the silicon-based resin further include catalysts, each of which is independently selected from one or more of stannous octoate, dibutyltin dilaurate, and an acetylacetonate chelate of dibutyltin dilaurate.
In a preferred embodiment, the catalysts are each dibutyltin dilaurate.
In some embodiments of the invention, the hydroxyl-containing acrylic acid derivative comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxyethyl acrylamide, hydroxypropyl methacrylate, and hydroxypropyl acrylate.
In some embodiments of the invention, the photocurable isocyanuric acid acrylic resin comprises 24-48 parts by weight, such as 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 48 parts by weight or any value therebetween; the silicon-based resin comprises 8 to 17 parts by weight, such as 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 parts by weight or any value therebetween; the reactive diluent comprises 35 to 70 parts by weight, such as 35, 37, 40, 43, 45, 47, 50, 53, 55, 57, 60, 63, 65, 67, 70 parts by weight or any value therebetween; the free radical photoinitiator comprises 2 to 6 parts by weight, such as 2, 3, 4, 5, 6 parts by weight or any value therebetween; the polymerization inhibitor comprises 0.05 to 2 parts, such as 0.05, 0.10, 0.15, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1.50, 2.00 parts by weight or any value therebetween; the auxiliary comprises 0.1 to 5 parts by weight, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.00 parts by weight or any value therebetween.
In some embodiments of the invention, the photocurable isocyanuric acid acrylic resin has a structure according to formula (i):
in the general formula (I), R is 1 、R 3 、R 4 And R is 6 Independently selected from H or CH 3 One of R 2 And R is 5 Represents an oxygen atom or-NH-, l and n each independently represent a positive integer from 1 to 4, m represents a positive integer from 4 to 7, and z is a positive integer from 15 to 60; the l and n can be at least one of methylene, ethylene, propylene and butylene.
In some embodiments of the invention, the silicon-based resin has a structure according to formula (ii):
wherein in the general formula (II), R is 11 And R is 16 Independently selected from H or CH 3 One of R 12 And R is 15 Independently selected from alkyl or alkyl ether having 2 to 4 carbon atoms, wherein R 13 And R is 14 Is an alkyl chain. Specific examples of the alkyl group or alkyl ether having 2 to 4 carbon atoms include, but are not limited to: at least one of ethylene, propylene, butylene and ethoxyethyl. EO is ethylene oxide.
In some embodiments of the present invention, the reactive diluent is selected from at least one of isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, isooctyl methacrylate, tetrahydrofuranyl acrylate, tetrahydrofuranyl methacrylate, trimethylolpropane triacrylate, 2-phenoxyethyl acrylate, ethoxylated trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, n-butyl acrylate, isodecyl acrylate, lauric acid acrylate, cyclohexyl acrylate, 3, 5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, dicyclopentenyl acrylate, pentaerythritol tetraacrylate;
In a preferred embodiment, the reactive diluent is a combination of isobornyl acrylate and tetrahydrofuranyl methacrylate.
In some embodiments of the present invention, the free radical photoinitiator is selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl-phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone, 4-benzoyl-4 '-methyl-diphenyl sulfide, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-clamp, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], 2-dimethoxy-phenyl, 2-diethoxy-2-diphenyl ketone, 2-diphenyl-2-benzyl-2-dimethyl-2-phenylketone, diphenyl-benzophenone, 4-dimethyl-phenylketone, 4-diphenyl-benzophenone, 3-dimethyl-benzophenone, and 3-phenylketone At least one of methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4' -bis (diethylamino) benzophenone, isopropyl thioxanthone, 2, 4-diethyl thioxanthone and 2-ethyl anthraquinone.
In a preferred embodiment, the free radical photoinitiator is a combination of 1-hydroxycyclohexylphenyl ketone and (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide.
In some embodiments of the invention, the auxiliary agent includes one or more of a fluorescent agent, a color changing powder, a leveling agent, a wetting agent, a defoaming agent, a silane coupling agent, an antioxidant, an antimicrobial agent, a flame retardant, a dehydrating agent, and a filler.
In a preferred embodiment, the auxiliary agents are silane coupling agents, wetting agents, dehydrating agents and fluorescent agents.
The invention also provides a preparation method of the double-curable high-wettability UV three-proofing paint, which comprises the following steps:
(1) Preparing raw materials comprising photo-curing isocyanic acid acrylic resin, silicon-based resin, reactive diluent, free radical photoinitiator, polymerization inhibitor and auxiliary agent according to the proportion; the method comprises the steps of (1) stirring photo-curing acrylic resin isocyanate, silicon-based resin, reactive diluent and polymerization inhibitor until the components are uniformly mixed to obtain primary mixed solution;
(2) Under the condition of avoiding light, adding a free radical photoinitiator into the primary mixed solution, and continuously stirring to obtain a reaction solution;
(3) Under the condition of avoiding light, adding an auxiliary agent into the reaction liquid, and uniformly stirring to obtain the double-curable high-wettability UV three-proofing paint.
In step (1), the order of addition of the components is not particularly limited. The temperature and pressure, and stirring conditions described in the preparation method of the high adhesion type UV three-proofing paint are not limited to the ranges in the specific examples, and all conditions that can achieve the effects of the present invention are within the scope of the present invention.
The raw materials and sources used in the following examples and comparative examples:
isobornyl acrylate, brand EM 214, derived from taiwan changxing in china; tetrahydrofuran methacrylate, brand SR203 NS, derived from sartomer; 1-hydroxycyclohexyl phenyl ketone, trade name Omnirad 184, derived from Ai Jianmeng; (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, trade name Omnirad TPO, derived from Ai Jianmeng; p-benzoquinone, derived from guangdong Weng Jiang; silane coupling agent, trade name Silquest A-174, from Michaelis diagram; a wetting agent, with the brand BYK-333, from Pick Germany; dehydrating agent, brand number Additive TI, from Borchers, germany; fluorescent agent, brand Tinopal OB, derived from Basoff, germany; 1,3, 5-tris (6-isocyanatohexyl) -1,3, 5-triazine-2, 4, 6-trione, brand TPA-90SB, derived from the Japanese Asahi chemical; hydroxyethyl acrylate, brand HEA, derived from microphone; 4-hydroxybutyl acrylate, grade 4-HBA, from Osaka organic Japan; hydroxylated polyisobutene, with the brand PIB-2OH, derived from the organism Raschia; dibutyl tin dilaurate, brand DBTDL, from mikrolin; di-tert-butyl-4-methylphenol, derived from Shanghai solvent and chemical industry; hydroquinone, HQ, from isman in the united states; isocyanoethyl acrylate, karenz AOI, from Japanese Showa electrician; the double-end hydroxyl polyether modified silicone oil has the brand number of ZRM5667 and is derived from synthetic materials Co-Ltd; dibutyl tin dilaurate, brand DBTDL, from mikrolin; a commercially available photo-curable acrylic resin, ebecry-4150, is available from Zhan Xin.
Preparation example 1
The preparation example is used for explaining the preparation of the photo-curing isocyanic acid acrylic resin A1, and the specific reaction process and steps are as follows:
100g of 1,3, 5-tris (6-isocyanatohexyl) -1,3, 5-triazine-2, 4, 6-trione, 12.8mg of hydroquinone and 256mg of di-tert-butyl-4-methylphenol are put into a reactor, vacuumized, filled with nitrogen and stirred, heated to 80-90 ℃, 21g of hydroxyethyl acrylate is dropwise added into the reactor, stirred for 1-4 hours under heat preservation, 135g of hydroxylated polyisobutene (number average molecular weight 1500) and 5.12mg of catalyst dibutyltin dilaurate are continuously added, the temperature is adjusted to 70-80 ℃, and the mixture is discharged after being cooled to room temperature, thus obtaining the photo-cured isocyanic acid acrylic resin A1.
Preparation example 2
The preparation example is used for explaining the preparation of the photo-curing isocyanic acid acrylic resin A2, and the specific reaction process and steps are as follows:
100g of 1,3, 5-tris (6-isocyanatohexyl) -1,3, 5-triazine-2, 4, 6-trione, 12.8mg of hydroquinone and 256mg of di-tert-butyl-4-methylphenol are put into a reactor, vacuum pumping, nitrogen charging and stirring are carried out, the temperature is heated to 80-90 ℃, 25.9g of 4-hydroxybutyl acrylate is dropwise added into the reactor, the temperature is kept and stirred for 1-4h, 135g of hydroxylated polyisobutene (with the number average molecular weight of 1500) is continuously added, 5.12mg of catalyst dibutyltin dilaurate is continuously added, the temperature is adjusted to 70-80 ℃, and the mixture is discharged after the temperature is reduced to room temperature, thus obtaining the photocuring isocyanic acid acrylic resin A2.
Preparation example 3
The preparation example is used for describing the preparation of the silicon-based resin B, and the specific reaction process and steps are as follows:
100g of isocyanoethyl acrylate is put into a reactor, when the temperature reaches 40-80 ℃ while stirring and heating, 531g of alpha, omega-dihydroxyl end-capped polydimethylsiloxane (double-end hydroxyl polyether modified silicone oil) (data molecular weight 1000-2000) and 12.6mg of catalyst dibutyltin dilaurate are sequentially added, the temperature is raised to 80-85 ℃ and the reaction is carried out for 180 minutes, the content of-OH groups is analyzed by an infrared spectrometer, the peak of-OH completely disappears, and the reaction is stopped, thus obtaining the silicon-based resin B.
Example 1
The preparation method comprises the following steps:
37 parts of photo-curing isocyanic acid acrylic resin A1, 13 parts of silicon-based resin B, 28 parts of isobornyl acrylate, 26 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 2
The preparation method comprises the following steps:
26 parts of photo-curing acrylic resin A1, 9 parts of silicon-based resin B, 19 parts of isobornyl acrylate, 20 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 3
The preparation method comprises the following steps:
45 parts of photo-curing isocyanic acid acrylic resin A1, 15 parts of silicon-based resin B, 34 parts of isobornyl acrylate, 34 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 4
The preparation method comprises the following steps:
30 parts of photo-curing isocyanic acid acrylic resin A1, 11 parts of silicon-based resin B, 22 parts of isobornyl acrylate, 24 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 5
The preparation method comprises the following steps:
40 parts of photo-curing isocyanic acid acrylic resin A1, 14 parts of silicon-based resin B, 31 parts of isobornyl acrylate, 30 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 6
The preparation method comprises the following steps:
37 parts of photo-curing isocyanic acid acrylic resin A1, 9 parts of silicon-based resin B, 24 parts of isobornyl acrylate, 26 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 7
The preparation method comprises the following steps:
37 parts of photo-curing isocyanic acid acrylic resin A1, 17 parts of silicon-based resin B, 29 parts of isobornyl acrylate, 30 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 8
The preparation method comprises the following steps:
37 parts of photo-curing isocyanic acid acrylic resin A1, 20 parts of silicon-based resin B, 31 parts of isobornyl acrylate, 31 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 9
The preparation method comprises the following steps:
37 parts of photo-curing isocyanic acid acrylic resin A1, 5 parts of silicon-based resin B, 21 parts of isobornyl acrylate, 24 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 10
The preparation method comprises the following steps:
28 parts of photo-curing acrylic resin A1, 13 parts of silicon-based resin B, 21 parts of isobornyl acrylate, 22 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 11
The preparation method comprises the following steps:
46 parts of photo-curing acrylic resin A1, 13 parts of silicon-based resin B, 31 parts of isobornyl acrylate, 31 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 12
The preparation method comprises the following steps:
55 parts of photo-curing acrylic resin A1, 13 parts of silicon-based resin B, 37 parts of isobornyl acrylate, 35 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 13
The preparation method comprises the following steps:
18 parts of photo-curing acrylic resin A1, 13 parts of silicon-based resin B, 16 parts of isobornyl acrylate, 17 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 14
The preparation method comprises the following steps:
37 parts of photo-curing isocyanic acid acrylic resin A2, 13 parts of silicon-based resin B, 28 parts of isobornyl acrylate, 26 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 15
The preparation method comprises the following steps:
26 parts of photo-curing acrylic resin A2, 9 parts of silicon-based resin B, 19 parts of isobornyl acrylate, 20 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 16
The preparation method comprises the following steps:
45 parts of photo-curing acrylic resin A2, 15 parts of silicon-based resin B, 34 parts of isobornyl acrylate, 34 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 17
The preparation method comprises the following steps:
30 parts of photo-curing acrylic resin A2, 11 parts of silicon-based resin B, 22 parts of isobornyl acrylate, 24 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Example 18
The preparation method comprises the following steps:
40 parts of photo-curing isocyanic acid acrylic resin A2, 14 parts of silicon-based resin B, 31 parts of isobornyl acrylate, 30 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Comparative example 1
Comparative example 1 was prepared as in example 1, except that the photocurable acrylic resin and the silicon-based resin were replaced with the same parts by weight of the new Ebecry-4150, and the other conditions were the same as in example 1, and the preparation method was as follows:
50 parts of Zhan Xin Ebecry-4150, 28 parts of isobornyl acrylate, 26 parts of isobornyl acrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to the room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Comparative example 2
Comparative example 2 was prepared as in example 1, except that the photocurable isocyanuric acid acrylic resin was replaced with the same parts by weight of virgin Ebecry-4150, and the other conditions were the same as in example 1, and the preparation method was as follows:
37 parts of Zhan Xin Ebecry-4150, 13 parts of silicon-based resin B, 28 parts of isobornyl acrylate, 26 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 revolutions per minute, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Comparative example 3
Comparative example 3 was prepared as in example 1, except that a photocurable acrylic resin having a novel and skillful Ebecry-4150 was used in combination, and the other conditions were the same as in example 1, and the preparation method was as follows:
25 parts of Zhan Xin Ebecry-4150, 25 parts of photo-curing acrylic resin A1, 28 parts of isobornyl acrylate, 26 parts of tetrahydrofuran methacrylate and 0.15 part of p-benzoquinone are added into a stirring kettle, stirring is started, the rotating speed reaches 500-1000 rpm, the temperature is kept at 40-60 ℃, and cooling water is started after stirring for 1-4 hours to cool the temperature in the kettle to room temperature. Under the condition of avoiding light, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are continuously added, and stirring is continued at room temperature until the materials are uniform; and finally adding 1 part of silane coupling agent, 1.5 parts of wetting agent, 0.5 part of dehydrating agent and 0.5 part of fluorescent agent, continuously maintaining the rotating speed at 50-1000 rpm for stirring for 1-2 hours, uniformly mixing all materials in the kettle, and finally filtering and packaging through a 150-mesh screen to obtain a finished product.
Performance testing
The samples obtained in examples 1 to 18 and comparative examples 1 to 3 were subjected to the following performance tests, respectively:
(1) Water drop angle degree: the finished products obtained in the examples and the comparative examples are added into a syringe, a full-automatic water drop angle tester is used for testing the water drop angle, a sitting drop method is adopted, the paint amount is 3 mu L, a PCB board with a dyne value of 30-32 is adopted as a substrate, after the substrate is dropped by a sample, the sample is placed for 5 seconds, the data of the water drop angle is read, 5 samples are tested in each group, and the final test result is averaged to obtain the water drop angle number of the resin composition.
(2) Water vapor transmission rate (g/m) 2 Day): the finished products obtained in the above examples and comparative examples were coated on a polytetrafluoroethylene film using a 200 μm bar coater, and after standing for 2 minutes, they were irradiated with an ultraviolet light source (a mercury lamp having a wavelength of 200 to 400nm, 300 mW/cm) 2 ) And (3) carrying out radiation curing for 5 seconds, placing the samples in a constant temperature and humidity box with the speed of 25 ℃/75% RH for 3 days, preparing the completely cured resin composition into a sheet with the thickness of 100mm multiplied by 100mm, carrying out a water vapor transmittance test by using a water vapor transmittance tester, carrying out a test on each group of 5 samples, and finally taking the average value of the test results to obtain the water vapor transmittance of the UV three-proofing paint after curing.
(3) Hardness: the finished products obtained in the above examples and comparative examples were respectively poured into tetrafluoroethylene molds at room temperature, scraped, and irradiated with ultraviolet light (wavelength of 200 to 400nm mercury lamp, 300 mW/cm) 2 ) Curing for 5 seconds by radiation, placing the sample in a constant temperature and humidity box with the speed of 25 ℃/75% RH for 3 days, and using the Shore hardness of the cured resin compositionAnd (5) performing hardness test on each group of samples, and taking an average value of final test results to obtain the hardness of the cured three-proofing paint.
(4) Adhesion force: the finished products obtained in the above examples and comparative examples were applied to a PCB using a 100 μm bar coater, and left standing for 2 minutes, and then irradiated with ultraviolet light (a mercury lamp having a wavelength of 200 to 400nm, 300 mW/cm) 2 ) And (3) carrying out radiation curing for 5 seconds, placing the sample in a constant temperature and humidity box with the speed of 25 ℃/75% RH for 3 days, and then carrying out adhesion test on the sample by using a hundred-blade according to GB/T9286-2021 colored paint/varnish cross-cut test standard, wherein the cutting interval is 2mm, so as to determine the adhesion grade of the three-proofing paint after curing.
(5) Drawing strength (MPa): the finished products obtained in the above examples and comparative examples were applied to a PCB using a 100 μm bar coater, and left standing for 2 minutes, and then irradiated with ultraviolet light (a mercury lamp having a wavelength of 200 to 400nm, 300 mW/cm) 2 ) And (3) carrying out radiation curing for 5 seconds, placing the sample in a constant temperature and humidity box with the speed of 25 ℃/75%RH, standing for 3 days, then using HB 8280-FD335BL epoxy adhesive to adhere a metal spindle with the diameter of 2mm above a paint film, standing and curing for 24 hours, using a BEVS2201 type automatic pull-off method adhesive force tester of Guangzhou Shenghua instrument to carry out a pull-out strength test, testing 5 samples in each group, and finally taking the average value of test results to obtain the pull-out strength of the cured three-proofing paint.
Table 1 the results of the performance tests for the examples and comparative examples are as follows:
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from the data in the table it is possible to derive:
comparative example 1 and comparative example 1 show that the three-proofing lacquer prepared by using the purchased and new Ebecry-4150 has higher water vapor transmittance after curing, larger hardness, lower adhesive force, small drawing strength, and can be used for wetting a PCB with a 30-32 dyne value through larger water drop angle The three-proofing paint prepared by the embodiment of the invention maintains the hardness of 74A after curing, has the highest adhesive force of 0 level, has the drawing strength of 0.95MPa and the water vapor permeability of 0.98g/m 2 And (2) the water drop angle of the PCB board with the dyne value of 30-32 is 37 degrees, and the PCB board shows excellent water vapor protection performance and leveling wetting capability.
Through comparative analysis of comparative examples 1 and 2-3, it can be seen that the addition of the photo-curing isocyanic acid acrylic resin A1 and the silicon-based resin B in comparative examples 2 and 3, by the collocation with Zhan Xin Ebecry-4150 (commercial dual-curing resin), the hardness of the tri-proof paint is reduced, the drawing strength is increased to some extent, the water drop angle is obviously reduced along with the addition of the silicon-based resin B, and the reasonable collocation of the visible silicon-based resin B and the dual-curing resin provided by the invention can improve the flexibility, the adhesive force and the wetting effect of the system of the tri-proof paint.
It can be seen from examples 1 to 7 and examples 10 to 11 that the three-proofing paint prepared by matching the photo-curing isocyanic acid acrylic resin A1 or A2 with the silicon-based resin B has better performance than the Zhan Xin Ebecry-4150 matched with the silicon-based resin B. After a large number of experiments prove that the formula composition with high wettability is reasonable, the hardness of the formula is not higher than 78A within the protection range, the adhesion level is 0 level, the drawing strength is higher than 0.9MPa, and the water vapor transmittance is less than 1.05g/m 2 And (2) the day, the water drop angle of the PCB with the dyne value of 30-32 is smaller than 40 degrees, and each performance is excellent.
As can be seen from comparative examples 1, 8-9 and 12-13, when the photo-curable isocyanic acrylic resin A1 and the silicon-based resin B are blended out of the ratio, the synergistic effect is lost, resulting in a water vapor transmission rate of more than 0.9g/m 2 And the day or the water drop angle is larger than 40 degrees, so that the water vapor barrier property and the wettability of the three-proofing paint resin can not meet the use requirements at the same time.
In conclusion, the three-proofing paint provided by the invention has high adhesive force and good water vapor protection property, and has excellent wetting effect on a PCB circuit board with low surface energy, so that the three-proofing paint prepared by the invention has excellent comprehensive performance and high application value.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (10)
1. The double-curable high-wettability UV three-proofing paint is characterized by comprising photo-curable isocyanic acid acrylic resin, silicon-based resin, reactive diluent and free radical photoinitiator;
the reaction raw materials for preparing the photo-curing isocyanic acid acrylic resin comprise triazine nitrogen-containing heterocyclic organic compounds containing three isocyanate groups, hydroxyl-containing acrylic acid derivatives and double-end hydroxyl polyisobutene;
the reaction raw materials of the silicon-based resin comprise a monoisocyanate monomer and double-end hydroxyl polyether modified silicone oil.
2. The dual curable high wettability UV three protective paint of claim 1, comprising the following components by weight: 24-48 parts of light-cured isocyanic acrylic resin, 8-17 parts of silicon-based resin, 35-70 parts of reactive diluent and 2-6 parts of free radical photoinitiator.
3. The dual curable high wettability UV three protective paint according to claim 1, wherein,
the molecular structure of the monoisocyanate monomer comprises an isocyanate group and a double bond functional group;
the number average molecular weight of the double-end hydroxyl polyisobutene is 1000-3000; the number average molecular weight of the double-end hydroxyl polyether modified silicone oil is 1000-2000.
4. The dual curable high wettability UV three protective lacquer according to claim 1, wherein the hydroxyl-containing acrylic derivatives comprise at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxyethyl acrylamide, hydroxypropyl methacrylate and hydroxypropyl acrylate.
5. The dual curable high wettability UV three protective lacquer according to claim 1, wherein the photo curable isocyanic acrylic resin has the structure according to general formula (i):
in the general formula (I), R is 1 、R 3 、R 4 And R is 6 Independently selected from H or CH 3 One of R 2 And R is 5 Represents an oxygen atom or-NH-, l and n each independently represent a positive integer of 1 to 4, m represents a positive integer of 4 to 7, and z is a positive integer of 15 to 60.
6. The dual curable high wettability UV three protective lacquer according to claim 1, wherein the silicon based resin has a structure according to general formula (ii):
in the general formula (II), R is 11 And R is 16 Independently selected from H or CH 3 One of R 12 And R is 15 Independently selected from alkyl or alkyl ether having 2 to 4 carbon atoms, wherein R 13 And R is 14 Is an alkyl chain.
7. The dual curable high wettability UV three protective paint according to claim 1, wherein,
The reactive diluent comprises at least one of isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, isooctyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, trimethylolpropane triacrylate, 2-phenoxyethyl acrylate, ethoxylated trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, n-butyl acrylate, isodecyl acrylate, lauric acid acrylate, cyclohexyl acrylate, 3, 5-trimethylcyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, dicyclopentenyl acrylate and pentaerythritol tetraacrylate;
the free radical photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone 4-benzoyl-4 '-methyl-diphenyl sulfide, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-1-hexanone, bis 2, 6-difluoro-3-pyrrolidocenetitanium, methyl benzoate, benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl phthalate, at least one of ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4' -bis (diethylamino) benzophenone, isopropyl thioxanthone, 2, 4-diethyl thioxanthone and 2-ethyl anthraquinone.
8. The dual curable high wettability UV three protective paint of claim 1, further comprising the following components by weight: 0.05-2 parts of polymerization inhibitor and 0.1-5 parts of auxiliary agent.
9. The dual curable high wettability UV three protective paint of claim 8, wherein the auxiliary agent comprises one or more of a fluorescent agent, a color changing powder, a leveling agent, a wetting agent, a defoaming agent, a silane coupling agent, an antioxidant, an antibacterial agent, a flame retardant, a dehydrating agent, and a filler.
10. A method of preparing a dual curable high wettability UV three protective lacquer according to any one of claims 1-9, comprising the steps of:
uniformly mixing photo-curing isocyanic acid acrylic resin, silicon-based resin, reactive diluent and polymerization inhibitor to obtain primary mixed solution;
under the condition of avoiding light, adding a free radical photoinitiator into the primary mixed solution, and uniformly mixing to obtain a reaction solution;
and under the condition of avoiding light, adding an auxiliary agent into the reaction liquid, and uniformly stirring to obtain the double-curable high-wettability UV three-proofing paint.
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| CN202410216160.3A CN117866468A (en) | 2024-02-27 | 2024-02-27 | Dual-curable high-wettability UV three-proofing paint and preparation method thereof |
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