CN118359953B - A photocurable coating, optical film and application thereof - Google Patents
A photocurable coating, optical film and application thereof Download PDFInfo
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- CN118359953B CN118359953B CN202410794066.6A CN202410794066A CN118359953B CN 118359953 B CN118359953 B CN 118359953B CN 202410794066 A CN202410794066 A CN 202410794066A CN 118359953 B CN118359953 B CN 118359953B
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- Prior art keywords
- coating
- photo
- compound
- acrylate
- curing
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- 238000000576 coating method Methods 0.000 title claims abstract description 323
- 239000011248 coating agent Substances 0.000 title claims abstract description 313
- 239000012788 optical film Substances 0.000 title claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 claims abstract description 163
- 239000002270 dispersing agent Substances 0.000 claims abstract description 146
- 150000001875 compounds Chemical class 0.000 claims abstract description 94
- 239000000178 monomer Substances 0.000 claims abstract description 76
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 29
- 150000002634 lipophilic molecules Chemical class 0.000 claims abstract description 7
- 238000000016 photochemical curing Methods 0.000 claims description 154
- 239000002245 particle Substances 0.000 claims description 47
- -1 (2 ethoxy) o-phenylphenoxyethyl Chemical group 0.000 claims description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- BXSPZNVFEYWSLZ-UHFFFAOYSA-N (3-phenoxyphenyl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 BXSPZNVFEYWSLZ-UHFFFAOYSA-N 0.000 claims description 24
- 229920002545 silicone oil Polymers 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 15
- 238000010146 3D printing Methods 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- XTLZRWNIJGNTCE-UHFFFAOYSA-N (2-ethoxyphenyl) prop-2-enoate Chemical compound CCOC1=CC=CC=C1OC(=O)C=C XTLZRWNIJGNTCE-UHFFFAOYSA-N 0.000 claims description 12
- KSXJRXNHRYSLLC-UHFFFAOYSA-N 9H-fluorene prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.C1=CC=C2CC3=CC=CC=C3C2=C1 KSXJRXNHRYSLLC-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 125000004386 diacrylate group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 229930185605 Bisphenol Natural products 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 7
- 239000012952 cationic photoinitiator Substances 0.000 claims description 7
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 6
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 6
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 6
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 6
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 5
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 claims description 4
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 claims description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012949 free radical photoinitiator Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 4
- PCLLJCFJFOBGDE-UHFFFAOYSA-N (5-bromo-2-chlorophenyl)methanamine Chemical compound NCC1=CC(Br)=CC=C1Cl PCLLJCFJFOBGDE-UHFFFAOYSA-N 0.000 claims description 3
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 3
- 229930194542 Keto Natural products 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
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-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
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 3
- LGEJUGBHYJDUJO-UHFFFAOYSA-N 1,1'-biphenyl;methyl prop-2-enoate Chemical compound COC(=O)C=C.C1=CC=CC=C1C1=CC=CC=C1 LGEJUGBHYJDUJO-UHFFFAOYSA-N 0.000 claims description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 claims description 2
- XYRRJTMWSSGQGR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO.OCC(CO)(CO)CO XYRRJTMWSSGQGR-UHFFFAOYSA-N 0.000 claims description 2
- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 claims description 2
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 11
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000001723 curing Methods 0.000 description 49
- 239000000463 material Substances 0.000 description 49
- 239000002904 solvent Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 230000009286 beneficial effect Effects 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 238000002834 transmittance Methods 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 238000006757 chemical reactions by type Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PKMSXGVLJHFQHJ-UHFFFAOYSA-N (2-phenylphenyl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1C1=CC=CC=C1 PKMSXGVLJHFQHJ-UHFFFAOYSA-N 0.000 description 2
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 2
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical class C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 150000002433 hydrophilic molecules Chemical class 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000010982 man-made stone Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 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
- 238000012545 processing Methods 0.000 description 2
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
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- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- UBPXWZDJZFZKGH-UHFFFAOYSA-N 1-ethenyl-3-methylpyrrolidin-2-one Chemical compound CC1CCN(C=C)C1=O UBPXWZDJZFZKGH-UHFFFAOYSA-N 0.000 description 1
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
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- XFQDAAPROSJLSX-UHFFFAOYSA-N 2-[4-(9h-fluoren-1-yl)phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C21 XFQDAAPROSJLSX-UHFFFAOYSA-N 0.000 description 1
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- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
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- 239000006087 Silane Coupling Agent Substances 0.000 description 1
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- 239000012752 auxiliary agent Substances 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical class C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 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 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- WELLGRANCAVMDP-UHFFFAOYSA-N isocyanatoethane;prop-2-enoic acid Chemical compound CCN=C=O.OC(=O)C=C WELLGRANCAVMDP-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
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- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- HJLIDWGXYNDLNY-UHFFFAOYSA-M sodium;ethanesulfonic acid;2-methylprop-2-enoate Chemical compound [Na+].CCS(O)(=O)=O.CC(=C)C([O-])=O HJLIDWGXYNDLNY-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
本发明公开了一种光固化涂料、光学膜及其应用。该光固化涂料包括光固化化合物、纳米粒子、光引发剂和反应型分散剂，反应型分散剂包括亲水基团、亲油基团和丙烯酸酯基团，其中，亲油基团衍生自包括折射率大于1.5的单官能高折单体的亲油化合物。该光固化涂料中的反应型分散剂分别与纳米粒子和光固化化合物相容性好，降粘效果显著，可将纳米粒子稳定的分散在光固化化合物中，有利于制备高透明性、高纳米粒子含量的光固化涂料，同时该反应型分散剂可与光固化化合物之间发生反应以提升光固化涂料制备的涂层的表面性能和耐磨性。The present invention discloses a photocurable coating, an optical film and applications thereof. The photocurable coating comprises a photocurable compound, nanoparticles, a photoinitiator and a reactive dispersant, wherein the reactive dispersant comprises a hydrophilic group, a lipophilic group and an acrylate group, wherein the lipophilic group is derived from a lipophilic compound comprising a monofunctional high-refractive monomer having a refractive index greater than 1.5. The reactive dispersant in the photocurable coating has good compatibility with the nanoparticles and the photocurable compound, respectively, and has a significant viscosity reduction effect, and can stably disperse the nanoparticles in the photocurable compound, which is conducive to the preparation of a photocurable coating with high transparency and high nanoparticle content. At the same time, the reactive dispersant can react with the photocurable compound to improve the surface performance and wear resistance of the coating prepared by the photocurable coating.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a photo-curing coating, an optical film and application thereof.
Background
In many application fields, such as optical communication technology, photonic computers, display panels, photonic integration with high refractive index materials is required to increase system efficiency or protect devices. The refractive index of most of the photo-curing resins is relatively low, generally in the range of 1.45-1.55, a certain amount of inorganic nano particles are generally required to be added into the photo-curing resins to improve the refractive index of the photo-curing resins, and the more the inorganic nano particles are added, the more obvious the improvement of the refractive index of the photo-curing resins is. However, the inorganic nanoparticles are inorganic materials, the photo-curing resin is organic materials, the inorganic nanoparticles are incompatible, and the inorganic nanoparticles are difficult to uniformly disperse in the photo-curing resin.
In the prior art, the compatibility between inorganic nanoparticles and photo-curing resin is usually improved by modifying the inorganic nanoparticles, for example, the surface of zirconium dioxide nanoparticles is modified by a silane coupling agent, although the compatibility between the modified particles and acrylate resin is improved, the particle performance is improved to a limited extent, the compatibility between the modified particles and high-refraction acrylate is still not ideal, a photo-curing resin system with high particle content cannot be prepared, the improvement of refractive index is limited (see patent publication No. CN 114958068A), the surface of zirconium dioxide nanoparticles is modified by organic acid, and although the particles can be dissolved in most organic solvents after the simple modification, the compatibility in the acrylic resin system is poor, and the method cannot be well applied to the photo-curing system (see patent publication No. CN 109971413A).
Therefore, to meet market demands, there is a need to design a new high particle content photocurable coating system.
Disclosure of Invention
Therefore, the present application has been made to overcome the above-mentioned drawbacks of the prior art, and it is an object of the present application to provide a photocurable coating material having a high particle content, which can not only effectively reduce the influence of the introduction of a reactive dispersant on the refractive index of the photocurable coating material, but also, more importantly, can achieve a remarkable viscosity reduction effect by stably dispersing nanoparticles in a photocurable compound for a long period of time, thereby facilitating the preparation of a photocurable coating material having a high nanoparticle content, and at the same time, can react with the photocurable compound to improve the abrasion resistance, adhesion and strength of a coating layer prepared from the photocurable coating material.
In a first aspect of the present application, there is provided a photocurable coating comprising a photocurable compound, nanoparticles, a photoinitiator, and a reactive dispersant comprising a hydrophilic group, a lipophilic group, and an acrylate group;
Wherein the lipophilic group is derived from a lipophilic compound comprising a monofunctional high-refractive monomer having a refractive index greater than 1.5.
The addition of the reactive dispersing agent in the application can obviously reduce the viscosity of the photo-curing coating, reduce the precipitation and precipitation phenomenon of nano particles in the photo-curing coating, not only improve the light transmittance and luster of the coating after the photo-curing coating is cured, but also prevent the coating from being colored and whitened after the photo-curing coating is cured due to precipitation or instability of the nano particles in the photo-curing coating, and obviously improve the stability of the photo-curing coating. In addition, the reactive dispersing agent can react with acrylate monomer compounds in the photo-curing coating to generate excellent binding force, hydrophilic groups in the reactive dispersing agent can react with nano particles to generate excellent binding force, for example, carboxyl or amido in the hydrophilic groups can react with hydroxyl in the nano particles, so that the stability of the photo-curing coating and the weather resistance and structural stability of a coating formed by curing the photo-curing coating are effectively improved, and the reactive dispersing agent participates in the reaction process of the photo-curing coating, and the monofunctional high-folding monomer is introduced into the reactive dispersing agent, so that the influence of the introduction of the reactive dispersing agent on the mechanical property and the optical property of the photo-curing coating and the coating thereof is reduced.
In any embodiment, the reactive dispersant further comprises structural units derived from a vinyl silicone oil monomer.
The introduction of the vinyl silicone oil monomer can obviously improve the dispersion effect of the reactive dispersing agent, further reduce the viscosity of the photo-curing coating, greatly improve the dispersion stability of the nano particles in the photo-curing compound, further improve the refractive index of the photo-curing coating and the wear resistance of the coating prepared by curing the photo-curing coating, and meanwhile, the reactive dispersing agent can also play roles of leveling assistance and defoaming.
In any embodiment, the nanoparticle comprises at least one of an unmodified nanoparticle, a modified nanoparticle comprising a multifunctional high-refractive monomer modified nanoparticle having a refractive index greater than 1.5.
The modified nano particles obtained by modifying the nano particles through the multifunctional high-refractive monomer can obviously increase the compatibility between the modified nano particles and the photo-curing compound due to the introduction of the multifunctional high-refractive monomer, is beneficial to the dispersion of the modified nano particles in the photo-curing compound, improves the dispersion stability of the photo-curing coating, is beneficial to the preparation of the photo-curing coating with the high-quality modified nano particles, obviously improves the refractive index and the transparency of a coating formed after the photo-curing coating is cured, can reduce the generation of defects on the surface of the coating, such as uneven coating surface or obvious defect of particles on the surface of the coating, is further beneficial to the improvement of the refractive index of the coating, and simultaneously, the photo-curing coating with the high-quality modified nano particles has lower photo-curing shrinkage rate, improves the wear resistance and the adhesive force of the coating.
In any embodiment, the mass ratio of the modified nanoparticle to the reactive dispersant is 1 (0.001 to 0.1), and optionally 1 (0.01 to 0.08).
In any embodiment, the ratio of the number average molecular weight Mn of the reactive dispersant to the average particle size D of the modified nanoparticles satisfies 10000.ltoreq.Mn.times.D.ltoreq.100000, optionally 20000.ltoreq.Mn.times.D.ltoreq.50000,
Wherein the unit of the number average molecular weight Mn of the reactive dispersant is Da, and the unit of the average particle diameter D of the modified nano particles is nm.
In any embodiment, the hydrophilic group is derived from the formulaCompounds of the structure shownCompounds of the structure shownAt least one of the compounds of the structure shown,
And,
And,
And,
Wherein R 1、R6、R7、R8、R9 each independently comprises at least one of hydrogen, alkyl of substituted or unsubstituted C 1-4, R 2、R3 each independently comprises at least one of hydrogen, alkyl of substituted or unsubstituted C 1-4, alkoxy of substituted or unsubstituted C 1-7, epoxy of substituted or unsubstituted C 1-7, hydroxy, keto, R 4 comprises at least one of hydrogen, alkyl of substituted or unsubstituted C 1-4, carboxy, R 5 comprises at least one of hydrogen, tetrahydrofuranyl, sulfonic, boric acid.
In any embodiment, the acrylate group is derived from a group comprising the formulaThe compound of the structure shown in the figure,
And,
Wherein R 11 comprises at least one of hydrogen, substituted or unsubstituted C 1-6 alkyl, and R 12 comprises at least one of substituted or unsubstituted C 1-6 alkylene.
In any embodiment, the vinyl silicone oil monomer comprises the formulaThe compound of the structure shown in the figure,
And,
Wherein R 13、R14 each independently comprises at least one of a substituted or unsubstituted C 1-3 alkyl group, a substituted or unsubstituted phenyl group, and R 15、R16、R17 each independently comprises at least one of a substituted or unsubstituted C 1-3 alkyl group.
In any embodiment, the photo-curable compound includes at least one of an acrylate compound, an epoxy compound, a polyurethane compound, and an organosiloxane compound.
In any embodiment, the photoinitiator comprises at least one of a free radical type photoinitiator, a cationic type photoinitiator.
In any embodiment, the monofunctional high refractive monomer comprises a monofunctional acrylate monomer comprising at least one of ortho-phenylphenoxyethyl acrylate, (2 ethoxy) ortho-phenylphenoxyethyl acrylate, (ethoxy) phenol acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 2 (ethoxy) phenol acrylate, 4 (ethoxy) phenol acrylate, 3 (ethoxy) ortho-phenylphenoxyethyl acrylate, biphenylmethanol acrylate, and modifications thereof.
In any embodiment, the multifunctional high refractive monomer comprises at least one of a difunctional high refractive monomer comprising at least one of a polyethylene glycol (600) diacrylate, a dimethylol-tricyclodecane diacrylate, a bisphenol AEO modified diacrylate, a1, 9-nonanediol diacrylate, a1, 10-decane diol diacrylate, a propoxylated bisphenol a diacrylate, a tricyclodecane dimethanol diacrylate, a diethylene glycol diacrylate, a neopentyl glycol diacrylate, a1, 4-butanediol diacrylate, a polyethylene glycol (200) diacrylate, a tetraethylene glycol diacrylate, a polyethylene glycol (400) diacrylate, a cyclohexane dimethanol diacrylate, and modifications thereof, the trifunctional high refractive monomer comprising at least one of pentaerythritol triacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, an isocyanuric acid EO modified triacrylate, an epsilon-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, a trimethylolpropane triacrylate, an epsilon-caprolactone modified tris (acryloxyethyl) acrylate, and modifications thereof, and the at least one of the tetra-hydroxy-3-acryloxyethyl) triacrylate, a tetra-hydroxy-3-acryloxypropyl methacrylate, and modifications thereof, and the tetra-hydroxy-propane triacrylate.
In any embodiment, the mass content of the nanoparticle is 40% -80%, optionally 40% -60%, the mass content of the photo-curing compound is 5% -56%, optionally 5% -40%, the mass content of the reactive dispersing agent is 0.1% -5%, optionally 0.5% -2%, and the mass content of the photoinitiator is 0.5% -3%, optionally 1% -2% based on the total mass of the photo-curing coating.
In any embodiment, the average particle diameter D of the nanoparticles is 5nm to 60nm, preferably 10nm to 50nm, and more preferably 10nm to 30nm.
The average particle diameter D of the nano particles is relatively smaller, which is beneficial to improving the stability of the nano particles in the photo-curing coating and reducing the defects of the coating formed after the photo-curing coating is cured.
In any embodiment, the number average molecular weight of the reactive dispersant is 400 to 10000, preferably 500 to 8000.
In any embodiment, the mass content of the nanoparticles is 60% -80% based on the total mass of the photo-curable coating.
The mass content of the nano particles is further controlled to be 60% -80%, and the viscosity and refractive index of the photo-curing coating and the refractive index and stability of the coating after the photo-curing coating are combined.
In any embodiment, the photocurable coating further comprises a functional monomer comprising at least one of thiol acrylate, amine acrylate, ether acrylate.
The functional monomer introduced in the application can provide active hydrogen to consume oxygen so as to avoid oxygen polymerization inhibition, improve polymerization speed and realize full curing, thereby avoiding the conditions of poor adhesive force, poor high-temperature and high-humidity resistance, poor weather resistance and the like caused by insufficient curing.
In any embodiment, the refractive index of the photocurable compound is greater than 1.5 at 20 ℃.
The refractive index of the acrylate oligomer is controlled to be higher than 1.5, so that a coating prepared by the photo-curing coating has higher refractive index, and the application field of the photo-curing coating is widened.
In any embodiment, the photocurable coating does not contain a solvent.
The photo-curing coating has lower viscosity, the coating can be prepared without dilution of a solvent, in addition, the viscosity of the photo-curing coating is obviously reduced by adding the reactive dispersing agent, the coating effect of the photo-curing coating is improved, and the process window of the photo-curing coating is widened.
In any embodiment, the viscosity of the photocurable coating is 100 cps to 4000cps at 25 ℃.
The photo-curing coating with proper viscosity can be widely applied to various optical fields.
In any embodiment, the viscosity of the photo-curable coating is 100cps to 200cps at 25 ℃.
The photo-curing coating with the viscosity of 100 cps-200 cps can be applied to the field of nano 3D printing.
In any embodiment, the viscosity of the photocurable coating is 100 cps to 4000cps at 25 ℃.
The photo-curing coating with the viscosity of 100 cps-4000 cps can be applied to the field of nano-imprinting.
In a second aspect of the present application, there is provided an optical film comprising a substrate and a coating layer on at least one side of the substrate, the coating layer being prepared from the photocurable coating material provided in the first aspect of the present application.
In any embodiment, the thickness of the coating is 300nm to 1200nm, optionally 500nm to 1000nm.
In any embodiment, the substrate comprises at least one of ceramic, glass, metal, natural or man-made stone, polymeric material, paint, powder coating, wood, fibrous substrate.
In a third aspect of the present application, there is provided an application of the optical film in any embodiment in the field of nano 3D printing, nano imprinting or printing high refraction.
Compared with the traditional printing adhesive, the nano 3D printing adhesive is required to have lower viscosity (less than or equal to 200cps/25 ℃), higher curing speed, smaller curing shrinkage and higher refractive index so as to realize the stability and practicability of printed patterns.
The photo-curing coating has proper viscosity range, curing speed, curing shrinkage and refractive index, can be solvent-free, and is widely applicable to the fields of nano 3D printing and nano imprinting.
Detailed Description
Hereinafter, embodiments of the photocurable coating material, the optical film and the application thereof of the present application are specifically disclosed. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the following description is provided for a thorough understanding of the present application by those skilled in the art, and is not intended to limit the subject matter recited in the claims. Any product that is the same or similar to the present application, whether made by any person in the light of the present application or by combining the present application with other prior art features, falls within the scope of the present application.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-7" means that all real numbers between "0-7" have been listed throughout, and "0-7" is only a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 3 or more, it is disclosed that the parameter is, for example, an integer of 3, 4, 5, 6, 7, 8, 9, 10, 11 or the like.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (1) and (2), meaning that the method may comprise steps (1) and (2) performed sequentially, or may comprise steps (2) and (1) performed sequentially. For example, it is mentioned that the method may further comprise step (3), meaning that step (3) may be added to the method in any order, e.g. the method may comprise steps (1), (2) and (3), may also comprise steps (1), (3) and (2), may also comprise steps (3), (1) and (2), etc.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either condition satisfies the condition "A or B" that A is true (or present) and B is false (or absent), that A is false (or absent) and B is true (or present), or that both A and B are true (or present).
The application provides a photo-curing coating, which comprises a photo-curing compound, nano particles, a photoinitiator and a reactive dispersing agent, wherein the reactive dispersing agent comprises a hydrophilic group, a lipophilic group and an acrylic ester group;
Wherein the lipophilic group is derived from a lipophilic compound comprising a monofunctional high refractive monomer having a refractive index greater than 1.5.
The term "photoinitiator" as used herein refers to a compound that absorbs energy at a wavelength in the ultraviolet light region (250 nm to 420 nm) to generate free radicals or cations to initiate further polymerization, crosslinking and curing of monomers or oligomers, and includes, but is not limited to, free radical photoinitiators or cationic photoinitiators.
As used herein, the term "photocurable compound" refers to a monomer or oligomer that undergoes polymerization crosslinking reaction under the influence of a photoinitiator, the photocurable compound comprising a reactive group, which may be an unsaturated bond, such as a carbon-carbon double bond. The photo-curable compounds include, but are not limited to, acrylate compounds, epoxy compounds, or polyurethane compounds.
Herein, "nanoparticle" refers to inorganic oxide particles having an average particle size of less than 1 micron and surface-modified or unmodified, including but not limited to surface-modified or unmodified ZnS、ZnO、CeO2、GeO2、Ta2O5、Bi4Ti3O2、Nb2O5、ITO、HfO2、SnO2、MoO3、Sb2O3、Sb2O5、Nd2O3、ZrO2 or TiO 2.
Herein, the term "reactive dispersant" refers to a dispersant having both a hydrophilic group, a lipophilic group and a reactive site, and the reactive dispersant includes anionic dispersants, cationic dispersants, nonionic dispersants and zwitterionic dispersants. Reactive dispersants are used to disperse particles in a liquid to form a stable dispersion, for example, reactive dispersants may be used to disperse nanoparticles in a photocurable compound while having reactive sites that react with the photocurable compound, e.g., reactive dispersants having carbon-carbon double bonds that react with the photocurable compound under the influence of a photoinitiator and light to form chemical bonds.
Herein, the "hydrophilic group" is derived from a hydrophilic compound, which refers to a compound having at least one carbon-carbon unsaturated double bond in a compound capable of undergoing radical polymerization, and at least one hydrophilic group in the molecular structure of the compound, and includes, but is not limited to, an amide group, a carboxyl group, a tetrahydrofuranyl group, a pyrrolidone group, an acyl morpholino group, a phosphate or a sulfonate.
As used herein, the term "acrylate group" is meant to include at leastStructure orThe structure of the utility model is that,Is a junction site.
As used herein, the term "lipophilic compound" refers to a compound comprising a monofunctional high-refractive monomer and containing at least one carbon-carbon unsaturated double bond within a free-radically polymerizable compound, the hydrophilic compound and the lipophilic compound being free-radically polymerizable to form a polymeric segment, the hydrophilic group and the lipophilic group being located in side chains.
As used herein, the term "monofunctional high refractive monomer" refers to a monomer having a refractive index of greater than 1.5 at 20℃and at least one carbon-carbon unsaturated double bond and capable of undergoing free radical polymerization. The monofunctional high refractive monomer includes a monofunctional acrylate monomer including, but not limited to, o-phenylphenoxyethyl acrylate, (2 ethoxy) o-phenylphenoxyethyl acrylate, (ethoxy) phenol acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 2 (ethoxy) phenol acrylate, 4 (ethoxy) phenol acrylate, 3 (ethoxy) o-phenylphenoxyethyl acrylate, or biphenylmethanol acrylate.
It can be understood that, due to incompatibility between the nanoparticles and the photocurable compound, the manner of improving the dispersibility of the nanoparticles in the photocurable compound by compounding the nanoparticles with the organic substance is generally disadvantageous, for example, the nano ZrO 2 powder is ball milled in an organic solvent to prepare a slurry by the action of a high molecular dispersant, and then the nano ZrO 2 slurry is added into a coating as an additive to prepare a nano composite coating, while the high molecular dispersant is favorable for the dispersion of ZrO 2, the nano ZrO 2 particles are easily separated in the organic resin coating due to the problems of unsuitable molecular weight of the dispersant or the mismatch between the dispersant and the nano ZrO 2 particles and resin, resulting in the defects of low content of ZrO 2, poor transparency and the like of the prepared coating.
The addition of the reactive dispersing agent in the application can obviously reduce the viscosity of the photo-curing coating, reduce flocculation phenomenon in the photo-curing coating, not only can improve the optical performance of the coating after the photo-curing coating is cured, but also can prevent the coating from generating the phenomena of bloom and whitening after the photo-curing coating is cured due to poor dispersion stability of nano particles in the photo-curing coating, and obviously improve the stability of the photo-curing coating. In addition, the lipophilic group in the reactive dispersing agent can react with the photo-curing compound in the photo-curing coating to generate excellent binding force, and the hydrophilic group in the reactive dispersing agent can react with the nano particles to generate excellent binding force, for example, the carboxyl or amido in the hydrophilic group can react with the hydroxyl on the surface of the nano particles, so that the stability of the photo-curing coating and the wear resistance and structural stability of the coating formed by curing the photo-curing coating are effectively improved, the preparation of the photo-curing coating with high transparency and high nano particle content is facilitated, and the reactive dispersing agent participates in the reaction in the curing process of the photo-curing coating, and the structural unit derived from the monofunctional high-folding monomer is introduced into the reactive dispersing agent, so that the influence of the introduction of the reactive dispersing agent on the photo-curing coating and the mechanical property and optical property of the coating are reduced.
In some embodiments, the photocurable coating further includes, but is not limited to, some auxiliary agents, such as diluents, leveling agents, or wetting agents.
In some embodiments, the reactive dispersant further comprises structural units derived from a vinyl silicone oil monomer.
In some embodiments, the vinyl silicone oil monomer has a number average molecular weight of 300 to 1000. In some embodiments, the number average molecular weight of the vinyl silicone oil monomer may be selected to be 300, 400, 500, 600, 700, 800, 900, 1000, or any value in the range consisting of any two points described above.
In some embodiments, the vinyl silicone oil monomer comprises formula (vi)The compounds of the formula (I) are shown,
And,
Wherein R 13、R14 each independently comprises at least one of a substituted or unsubstituted C 1-3 alkyl group, a substituted or unsubstituted phenyl group, and R 15、R16、R17 each independently comprises at least one of a substituted or unsubstituted C 1-3 alkyl group.
In some embodiments, the vinyl silicone oil monomer comprises at least one of a single-ended vinyl phenyl silicone oil, a single-ended vinyl methylphenyl silicone oil, a single-ended vinyl silicone oil.
As used herein, the term "single-ended" means that the vinyl silicone oil monomer contains a vinyl group at only one end.
In the present application, the number average molecular weight of the vinyl silicone oil monomer may be measured by a method known in the art, such as a viscosity method, gel permeation chromatography, GPC.
The introduction of the vinyl silicone oil monomer can obviously improve the dispersion effect of the reactive dispersing agent, further reduce the viscosity of the photo-curing coating, greatly improve the dispersion stability of the nano particles in the photo-curing compound, further improve the refractive index of the photo-curing coating and the wear resistance of the coating, simultaneously play roles in leveling and defoaming, and improve the wear resistance, fingerprint resistance and smoothness of the cured coating. In addition, the single-end vinyl silicone oil monomer has vinyl at one end, so that the reaction type dispersing agent can be prevented from being crosslinked to form a network structure to influence the performance of the reaction type dispersing agent when the reaction type dispersing agent is prepared.
In some embodiments, the reactive dispersant further comprises urethane groups.
Herein, the term "urethane group" refers to the "x-NHCOO-structure" x "is the attachment site.
The reactive dispersing agent containing urethane groups has excellent dispersing effect and strength, and is beneficial to improving the storage stability of the photo-curing coating and the wear resistance of the coating prepared by the reactive dispersing agent.
In some embodiments, the nanoparticle comprises at least one of an unmodified nanoparticle, a modified nanoparticle comprising a multifunctional high refractive monomer modified nanoparticle having a refractive index greater than 1.5.
In this context, the term "unmodified nanoparticle" refers to an inorganic metal oxide particle whose surface has not been modified with an organic substance, and the surface of the unmodified particle contains hydroxyl groups. Unmodified nanoparticles include, but are not limited to ZnS、ZnO、CeO2、GeO2、Ta2O5、Bi4Ti3O2、Nb2O5、ITO、HfO2、SnO2、MoO3、Sb2O3、Sb2O5、Nd2O3、ZrO2 or TiO 2.
In the present application, the "modified nanoparticle includes a nanoparticle modified by a multifunctional high-refractive monomer having a refractive index greater than 1.5" may be a modified nanoparticle prepared by chemical reaction between a coupling agent and the nanoparticle and the multifunctional high-refractive monomer, respectively, to modify the nanoparticle by the multifunctional high-refractive monomer, or may be another preparation method, and the modified nanoparticle obtained by the preparation method capable of grafting the multifunctional high-refractive monomer to the surface of the nanoparticle is all the protection scope of the present application.
As used herein, the term "multifunctional high refractive monomer" refers to a multifunctional high refractive monomer comprising at least one reactive group that reacts with a photocurable compound and one reactive group that is capable of grafting to the surface of the nanoparticle, e.g., the multifunctional high refractive monomer comprises at least one reactive group that reacts with a thiol-based coupling agent and one reactive group that reacts with a photocurable compound, the reactive group comprising an unsaturated bond, e.g., the reactive group is a reactive double bond, and the multifunctional high refractive monomer comprises a multifunctional acrylate monomer.
In some embodiments, the multifunctional acrylate monomer includes at least one of a difunctional acrylate monomer, a trifunctional acrylate monomer, a tetrafunctional acrylate monomer.
In some embodiments, the difunctional acrylate monomer includes at least one of 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene, bisphenol fluorene diacrylate, 2-acrylic acid- [ [1, 1-binaphthyl ] -2, 2-bis (oxy-2, 1-ethylidene) ] ester, ethoxylated bisphenol a diacrylate, ethoxylated bisphenol a dimethacrylate, polyethylene glycol (600) diacrylate, dimethylol-tricyclodecane diacrylate, bisphenol AEO modified diacrylate, 1, 9-nonanediol diacrylate, 1, 10-decanediol diacrylate, propoxylated bisphenol a diacrylate, tricyclodecane dimethanol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1, 4-butanediol diacrylate, polyethylene glycol (200) diacrylate, tetraethylene glycol diacrylate, polyethylene glycol (400) diacrylate, cyclohexane dimethanol diacrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, and modifications thereof.
In some embodiments, the trifunctional acrylate monomer includes at least one of pentaerythritol triacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO-modified triacrylate, epsilon-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, trimethylolpropane triacrylate, epsilon-caprolactone-modified tris (acryloxyethyl) acrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, and modifications thereof.
In some embodiments, the tetrafunctional acrylate monomer includes at least one of bis-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, bis-pentaerythritol hexaacrylate, and modifications thereof.
In this context, the term "modifier" refers to some variants that proceed based on the bulk structure, still possessing the basic properties of the bulk structure. For example, bisphenol fluorene diacrylate modifier refers to a modification of bisphenol fluorene diacrylate by chemical reaction, but bisphenol fluorene diacrylate modifier may still react with coupling agent and also have reactive double bonds to react with acrylate resin.
It is understood that either the unmodified nanoparticles or the modified nanoparticles can be mixed with the reactive dispersant, the photocurable compound, and the photoinitiator to produce a low viscosity, high transparency, high refractive index photocurable coating. According to research, the modified nano particles obtained by modifying the nano particles by adopting the multifunctional high-refraction monomer are beneficial to further combination between the modified nano particles and the reactive dispersing agent due to the introduction of the multifunctional high-refraction monomer, so that the modified nano particles are dispersed in the photo-curing compound, the surface modification of the nano particles by the multifunctional high-refraction monomer is beneficial to improving the compatibility between the modified nano particles and the photo-curing compound, the dispersion stability of the modified nano particles is greatly improved, the photo-curing coating with high quality content is further beneficial to preparing the photo-curing coating with the modified nano particles, the refractive index and the transparency of the photo-curing coating are obviously improved, the curing shrinkage rate of the photo-curing coating is reduced, the improvement of the dispersion stability of the modified nano particles can reduce the generation of defects on the surface of the coating, such as uneven surface of the coating or obvious particle feel on the surface of the coating, the photo-curing coating is further beneficial to the improvement of the refractive index of the coating, meanwhile, the photo-curing coating with high quality content of the modified nano particles has lower photo-curing shrinkage rate, and the wear resistance and the adhesive force of the coating are improved, and on the other hand, the surface of the modified nano particles contains the reactive groups which can react with the photo-curing compound, the wear-resistant bond and the formed after the photo-curing coating is cured, and the chemical bond strength of the photo-curing coating is improved.
In some embodiments, the mass ratio of the nanoparticle to the reactive dispersant is 1 (0.001 to 0.1). In some embodiments, the mass ratio of nanoparticle to reactive dispersant may be selected to be 1:0.001, 1:0.005, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, or a ratio in the range consisting of any two ratios described above.
The reactive dispersing agent can effectively disperse the nano particles in the acrylate monomer compound, and control the mass ratio of the nano particles to the reactive dispersing agent within a proper range, so that the viscosity of the photo-curing coating can be reduced, the dispersion stability of the photo-curing coating can be improved, the risk that excessive reactive dispersing agent is agglomerated to influence the performance of the photo-curing coating can be reduced, and the preparation of the solvent-free photo-curing coating with high refractive index is facilitated.
In some embodiments, the product of the number average molecular weight Mn of the reactive dispersant and the average particle size D of the nanoparticles is 10000.ltoreq.Mn.times.D.ltoreq.100000, where the number average molecular weight Mn of the reactive dispersant is in Da and the average particle size D of the nanoparticles is in nm. In some embodiments, the product of the number average molecular weight Mn of the reactive dispersant and the average particle diameter D of the modified nanoparticles may be selected to be 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, or a value in the range consisting of any two points described above.
In the present application, the number average molecular weight of the reactive dispersant may be measured by a method known in the art, such as a viscosity method, a gel permeation chromatography GPC, and a terminal group analysis method.
The number average molecular weight of the reactive dispersant may be selected according to the average particle diameter D of the nanoparticles to be dispersed. The smaller the average particle diameter D of the nano particles is, the larger the specific surface area is, the higher the viscosity of the photo-curing coating is, but the nano particles with smaller average particle diameter D are favorable for combining hydrophilic groups in the reactive dispersing agent, the reactive dispersing agent with large molecular weight is adopted to increase the steric hindrance among the nano particles, reduce the aggregation among the nano particles and reduce the viscosity of the photo-curing coating, and the larger the average particle diameter D of the nano particles is, the reactive dispersing agent with small molecular weight can play a good role in blocking, and meanwhile the viscosity of the photo-curing coating cannot be increased due to the fact that the number average molecular weight of the reactive dispersing agent is too large. Therefore, a reactive dispersant having a relatively small number average molecular weight is preferably selected as the average particle diameter D of the nanoparticles is larger, and a reactive dispersant having a large number average molecular weight is preferably selected as the average particle diameter D of the nanoparticles is smaller. The product of the number average molecular weight Mn of the reactive dispersing agent and the average particle diameter D of the nano particles is controlled to meet a certain range, and the viscosity, the stability and the refractive index of the photo-curing coating can be considered.
In some embodiments, the hydrophilic group is derived from formula (la)Compounds of the structure shownCompounds of the structure shownAt least one of the compounds of the structure shown,
And,
And,
And,
Wherein R 1、R6、R7、R8、R9 each independently comprises at least one of hydrogen, alkyl of substituted or unsubstituted C 1-4, R 2、R3 each independently comprises at least one of hydrogen, alkyl of substituted or unsubstituted C 1-4, alkoxy of substituted or unsubstituted C 1-7, epoxy of substituted or unsubstituted C 1-7, hydroxy, keto, R 4 comprises at least one of hydrogen, alkyl of substituted or unsubstituted C 1-4, carboxy, R 5 comprises at least one of hydrogen, tetrahydrofuranyl, sulfonic, boric acid.
In some embodiments, the compound of formula I includes at least one of acrylamide, methacrylamide, (1, 1-dimethyl-3-oxobutyl) methacrylamide, N-dimethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-butoxymethacrylamide, N-isobutoxymethyl acrylamide, acryloylmorpholine, methacryloylmorpholine. In some embodiments, the compound of formula I comprises acrylamide. In some embodiments, the compound of formula I comprises N-methylol (meth) acrylamide.
In some embodiments, the compound of formula II includes at least one of acrylic acid, methacrylic acid, maleic acid, tetrahydrofuranyl acrylate, tetrahydrofuranyl methacrylate, sodium 2-ethanesulfonate methacrylate, potassium 3-methacrylate sulfonate, hydroxypropyl methacrylate phosphate, 2-hydroxyethyl methacrylate phosphate. In some embodiments, the compound of formula II comprises acrylic acid. In some embodiments, the compound of formula II comprises tetrahydrofuranyl acrylate.
In some embodiments, the compound of formula III includes at least one of vinyl pyrrolidone, 4-methyl-1-vinyl-2-pyrrolidone, 1-vinyl-3-methyl-2-pyrrolidone. In some embodiments, the compound of formula III comprises vinylpyrrolidone.
The hydrophilic groups can be adsorbed on the surfaces of the nanoparticles, the affinity is good, the dispersibility of the nanoparticles in the photocuring compound can be effectively improved, and carboxyl groups and amide groups can react with hydroxyl groups on the surfaces of the nanoparticles to further improve the dispersibility of the nanoparticles, for example, the carboxyl groups and the amide groups can react with the hydroxyl groups on the surfaces of the nanoparticles to form chemical bonds, so that the bonding strength between the reactive dispersing agent and the nanoparticles is improved, and the dispersion stability of the nanoparticles is further improved. In addition, the hydrophilic group has higher refractive index, can improve the refractive index of the reactive dispersing agent, is beneficial to the preparation of the high refractive index photo-curing coating, such as the acryloylmorpholine and the vinyl pyrrolidone, not only has higher refractive index, but also has good complexation with the nano particles, can improve the dispersion stability of the nano particles, and reduces the influence on the refractive index of the photo-curing coating due to the introduction of the reactive dispersing agent.
In some embodiments, the acrylate group is derived from a group comprising formula (la)The compound of the structure shown in the figure,
And,
Wherein R 11 comprises at least one of hydrogen, substituted or unsubstituted C 1-6 alkyl, and R 12 comprises at least one of substituted or unsubstituted C 1-6 alkylene.
In some embodiments, a formulaThe compound with the structure comprises at least one of isocyanate ethyl acrylate and isocyano ethyl methacrylate.
In some embodiments, the photocurable compound includes at least one of an acrylate compound, an epoxy compound, a polyurethane compound, and an organosiloxane compound.
In some embodiments, the acrylic compound comprises at least one of an acrylic oligomer, an acrylic monomer, the acrylic compound comprises at least one of 2-phenoxyethyl acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene, 2-acrylic- [ [1, 1-binaphthyl ] -2, 2-bis (oxy-2, 1-ethylidene) ] ester, ethoxylated bisphenol a diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, 2-phenoxyethyl acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate, and oligomers thereof.
In some embodiments, the epoxy compound includes at least one of an epoxy oligomer, an epoxy monomer, the epoxy compound includes at least one of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, 4-bis [ (3-ethyl-3 oxetane) methoxymethyl ] biphenyl, 3-ethyl-3- (phenoxymethyl) oxetane, 1, 4-bis ((3-ethyl-3-oxetanylmethoxy) methyl) benzene, 3-ethyl-3-oxetanylmethanol, 3' - (oxybis methylene) bis (3-ethyl) oxetane, 3-ethyl-3- [ (phenylmethoxy) methyl ] -oxetane, and oligomers thereof.
In some embodiments, the photoinitiator comprises at least one of a free radical type photoinitiator, a cationic type photoinitiator.
In some embodiments, the free radical photoinitiator comprises at least one of benzophenone, thioxanthone, anthraquinone, a-hydroxyalkylphenone, a-aminoalkylphenone, benzil compounds. In some embodiments, the free radical photoinitiator comprises at least one of methyl benzoate, benzoin dimethyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator 1173), photoinitiator 184, photoinitiator BDk, photoinitiator TPO, photoinitiator 369.
In some embodiments, the cationic photoinitiator comprises at least one of diazonium salts, diaryliodonium salts, triaryliodonium salts, alkyl sulfonium salts, iron arene salts, sulfonyloxy ketones, triarylsiloxane ethers.
In some embodiments, the monofunctional high-refractive monomer comprises at least one of ortho-phenylphenoxyethyl acrylate, (2 ethoxy) ortho-phenylphenoxyethyl acrylate, (ethoxy) phenol acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 2 (ethoxy) phenol acrylate, 4 (ethoxy) phenol acrylate, 3 (ethoxy) ortho-phenylphenoxyethyl acrylate, biphenyl methanol acrylate, and modifications thereof.
In some embodiments, the photocurable coating further comprises a leveling agent comprising at least one of BYK-333, BYK-381, BYK-399.
In some embodiments, the mass content of the nanoparticles is 40% -80%, the mass content of the photo-curing compound is 5% -56%, the mass content of the reactive dispersant is 0.1% -5%, and the mass content of the photoinitiator is 0.5% -3% based on the total mass of the photo-curing coating.
In some embodiments, the mass content of the nanoparticle may be 40%、42%、44%、45%、46%、48%、50%、52%、54%、55%、56%、58%、60%、62%、64%、65%、66%、68%、70%、72%、74%、75%、76%、78%、80%、 or a value in the range consisting of any two of the above, the mass content of the photocurable compound may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 56%, or a value in the range consisting of any two of the above, the mass content of the photoinitiator may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, or a value in the range consisting of any two of the above, and the mass content of the reactive dispersant may be 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or a value in the range consisting of any two of the above, based on the total mass of the photocurable coating.
Controlling the components in the photo-curable coating in the proper ranges is beneficial to preparing the photo-curable coating with low viscosity, high refractive index, low curing shrinkage and curing time. In addition, the content of the nano particles in the photo-curing coating is relatively high, the refractive index of the photo-curing coating is favorably improved, the curing shrinkage rate of the photo-curing coating is reduced, the performance of the coating prepared by the photo-curing coating is comprehensively improved, and when the content of the nano particles in the photo-curing coating is higher than 80%, the viscosity is too high due to the fact that the content of the nano particles in the photo-curing coating is too high, the subsequent coating is not favorably prepared, and even the photo-curing coating is flocculated. Meanwhile, the effect of the low mass content of the reactive dispersing agent is not obvious, the viscosity of the photo-curing coating is reduced and the dispersion stability of the modified nano particles is improved along with the increase of the mass content of the reactive dispersing agent, but after the mass content of the reactive dispersing agent exceeds a certain value, the reactive dispersing agent has the risk of agglomeration, so that the haze of the coating is obviously increased, and the preparation of the transparent coating is not facilitated. The mass content of the nano particles, the photo-curing compound and the reactive dispersing agent is controlled within a proper range, so that the photo-curing coating has proper adhesion and photo-curing speed, and is beneficial to the preparation of subsequent coatings.
In some embodiments, the mass content of the nanoparticles is 60% -80% based on the total mass of the photocurable coating.
The mass content of the nano particles is further controlled to be 60% -80%, and the viscosity, refractive index and curing shrinkage of the photo-curing coating and the refractive index, stability and wear resistance of the coating after the photo-curing coating is cured are considered.
In some embodiments, the photocurable coating further comprises a functional monomer including at least one of thiol acrylate, amine acrylate, ether acrylate.
In some embodiments, the functional monomer comprises at least one of Asign 002, photo 5006, gernomer 7302, gernomer 5271.
It is found that, since the photo-curing process is performed in an air environment, the free radical polymerization of the photo-curing system is not neglected by oxygen, and particularly when the thickness of the coating is thin, not only the dissolved oxygen in the formulation system can prevent polymerization, but also the oxygen in the air on the surface of the coating can diffuse into the cured coating rapidly along with the consumption of oxygen molecules in the curing system in the photo-initiation process, and the polymerization is further prevented, so that the curing is incomplete. The functional monomer introduced in the application can be used as an antioxidant polymerization inhibitor, and can provide active hydrogen to consume oxygen so as to avoid oxygen polymerization inhibition, improve polymerization speed and realize full curing, thereby avoiding the phenomena of poor adhesive force, poor high-temperature and high-humidity resistance, poor weather resistance and the like caused by insufficient curing.
It should be noted that the introduction of amine acrylate makes the photo-curable coating alkaline, and the reactive dispersant is preferably a cationic dispersant or a nonionic dispersant, and is not preferably an anionic reactive dispersant, for example, a reactive dispersant having a hydrophilic group of a carboxyl group is not preferably used, so that the reactive dispersant can be stably dispersed in the photo-curable coating to exert a dispersing effect.
In some embodiments, the photocurable compound comprises an epoxy compound and the photoinitiator comprises a cationic photoinitiator.
Generally, the epoxy compound and the cationic photoinitiator are used in combination, and it is found that the presence of the anion not only reacts with the cationic photoinitiator, such as a carboxyl group, but also causes the epoxy ring-opening reaction of the epoxy compound to cause instability of the photo-curing coating system, so that the reactive dispersant is preferably a cationic dispersant or a nonionic dispersant, rather than an anionic dispersant, so that the reactive dispersant can be stably dispersed in the photo-curing coating to exert a dispersing effect.
In some embodiments, the average particle size D of the nanoparticles is 5nm to 60nm. In some embodiments, the average particle size D of the nanoparticle may be selected to be 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, or a value in the range consisting of any two of the above.
The average particle diameter D of the nano particles is relatively smaller, which is beneficial to improving the stability of the nano particles in the photo-curing coating and reducing the defects of the coating formed after the photo-curing coating is cured.
In some embodiments, the reactive dispersant has a number average molecular weight of 400 to 10000. In some embodiments, the number average molecular weight of the dispersant is any value selected from the range consisting of 400, 500, 1000, 5000, 6000, 7000, 8000, 10000, or any two points described above.
In some embodiments, the refractive index of the photocurable compound is greater than 1.5 at 20 ℃. In some embodiments, the refractive index of the photocurable compound may be selected to be a value in the range of 1.51, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, or any two points above at 20 ℃.
The refractive index of the photo-curing compound is controlled to be higher than 1.5, so that the coating after the photo-curing coating is cured has higher refractive index, and the application scene of the coating is widened.
In some embodiments, the photocurable coating comprises a solvent. The solvent comprises fluorine-containing solvent, ether solvent, alcohol solvent, ester solvent and combination thereof, wherein the fluorine-containing solvent comprises at least one of perfluorinated alkane and partially fluorinated alkane, the alcohol solvent comprises at least one of aliphatic hydrocarbon mono-alcohol and aliphatic hydrocarbon di-alcohol, the alcohol ether solvent comprises aliphatic hydrocarbon alcohol ether, and the ester solvent comprises aliphatic alkane ester.
The alcohol solvent comprises alcohol with 1-6 carbon atoms, including but not limited to methanol, ethanol, isopropanol or butanol, the ether solvent comprises but not limited to propylene glycol monomethyl ether, dipropylene glycol methyl ether or propylene glycol methyl ether acetate, the ester solvent comprises but not limited to ethyl acetate or butyl acetate, and the ether alcohol solvent comprises but not limited to propylene glycol monomethyl ether or dipropylene glycol methyl ether.
The solvent can dilute the photo-curing coating and reduce the difficulty of coating the photo-curing coating.
In some embodiments, the photocurable coating does not contain a solvent.
At present, the conventional coupling agent modified nano particles have limited dissolution in a photo-curing resin system due to poor compatibility with the photo-curing resin with high refractive index, so that the photo-curing coating with high particle content cannot be obtained, and the stability of the system can be improved only by adding a solvent, but the addition of the solvent brings adverse effects on environmental protection, a coating process and the surface performance of the coating.
The reactive dispersing agent can generate excellent binding force with the nano particles and the photo-curing compound respectively, has remarkable viscosity reduction effect, can effectively promote the dispersion of the nano particles in the photo-curing compound, and can stably disperse the nano particles in the photo-curing compound even if a solvent is not introduced, thereby realizing the preparation of the photo-curing coating with high nano particle content. In addition, the modified nano particles are beneficial to further improving the compatibility with the photo-curing compound, further improving the stability of the photo-curing coating and widening the process window of the photo-curing coating.
In some embodiments, the viscosity of the photocurable coating is 100cps to 4000cps at 25 ℃.
The photo-curing coating with proper viscosity can be widely applied to various optical fields.
In some embodiments, the viscosity of the photocurable coating is 100cps to 4000cps at 25 ℃.
The photo-curing coating with the viscosity of 100 cps-4000 cps can be applied to the field of nano-imprinting, and the photo-curing coating in the application not only has excellent curing speed, curing shrinkage and refractive index, but also has the advantages that compared with the traditional solvent type nano-imprinting adhesive which needs a heating procedure to volatilize a solvent to prepare a coating, the solvent-free photo-curing coating with the viscosity of 100 cps-4000 cps can be filled in an imprinting template without the heating procedure to prepare a nano-sized pattern, the size stability of the pattern is good, the imprinting defect is few, the integrity of the pattern is maintained, the thicker film which is difficult to realize by the traditional solvent type nano-imprinting adhesive can be realized, and the application is widened.
In some embodiments, the viscosity of the photocurable coating is 100cps to 200cps at 25 ℃.
The conventional 3D printing instrument is difficult to manufacture high-precision devices such as various optical elements, so that more researchers focus on nano 3D printing, nano 3D printing can realize three-dimensional printing of multi-material nano-scale materials, can enable resin to generate photo-curing reaction in a very small area, and can customize and design a lens with excellent optical performance, ultrahigh precision and ultrathin scale without being limited by processing of lens size, shape and thickness. The nano 3D printing technology has the advantages of high processing speed, wide material selection range and low manufacturing cost, and is relatively suitable for industrial application. The micro-nano ultra-thin lens can be widely applied to the fields of ultra-thin mobile phone cameras, VR/AR lenses, vehicle-mounted cameras, endoscopes, micro-array lenses, flexible lenses and the like.
Compared with the traditional printing adhesive, the nano 3D printing adhesive is required to have lower viscosity (less than or equal to 200cps/25 ℃), higher curing speed, smaller curing shrinkage and higher refractive index so as to realize the stability and practicability of printed patterns. The viscosity of the photo-curing coating can be controlled to be 100 cps-200 cps, and the photo-curing coating has excellent curing speed, curing shrinkage and refractive index, can be applied to the field of nano 3D printing, and can be used for preparing patterns with stable patterns, no surface defects, high refractive index, high content of modified nano particles, good wear resistance and good temperature resistance.
In some embodiments, the refractive index of the photocurable coating is greater than 1.65.
The photo-curing coating with refractive index higher than 1.65 can be used for preparing high refractive index coating, and can be widely applied to various optical fields.
The present application also provides an optical film comprising a substrate and a coating on at least one side of the substrate, the coating being prepared from a photocurable coating in some embodiments.
In some embodiments, the thickness of the coating is 300nm to 1200nm. In some embodiments, the thickness of the coating may be selected to be 300nm, 500nm, 600nm, 800nm, 1000nm, 1200nm, or a value in the range consisting of any two of the foregoing.
The thickness of the coating is controlled within a proper range, so that the wear resistance, corrosion resistance and chemical stability of the coating can be effectively improved, the increase of production cost caused by the excessive thickness of the coating and the reduction of coating adhesive force and edge warping phenomenon caused by internal stress of the coating due to the curing shrinkage of the photo-curing coating can be avoided, the dimensional stability of the coating is improved, and the difficulty of coating process is also avoided from being increased due to the excessive thinness of the coating.
In some embodiments, the optical film has a light transmittance of greater than 95%.
The light transmittance of the optical film exceeds 95%, and the optical film can be widely applied to various optical fields.
In some embodiments, the substrate comprises at least one of ceramic, glass, metal, natural or man-made stone, polymeric material, paint, powder coating, wood, fibrous substrate.
The application also provides applications of the optical film in some embodiments in the fields of nano 3D printing, nano imprinting or printing high refraction.
The photo-curing coating has proper viscosity range, curing speed, curing shrinkage and refractive index, can be solvent-free, and is widely applicable to the fields of nano 3D printing and nano imprinting.
Examples
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope and spirit of the present invention. The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge. Unless otherwise specified, the starting materials in examples and comparative examples were purchased from Sigma-Aldrich.
1. Preparation method
Example 1:
1) Preparation of photo-curable coatings
The preparation of the reactive dispersant comprises the steps of adding acrylamide and 3-phenoxybenzyl acrylate (PBA) into a reaction flask according to a mass ratio of 1:5, adding 2wt% of mercaptoethanol and 2wt% of hydrogen peroxide, heating to 80 ℃ for reaction for 4 hours to obtain a hydroxyl-containing dispersant, measuring the hydroxyl content of the hydroxyl-containing dispersant, adding 0.2wt% of dibutyltin dilaurate into the hydroxyl-containing dispersant, dropwise adding isocyanate ethyl acrylate with a mass ratio of 1:1 to the hydroxyl-containing dispersant at 60 ℃, and preserving heat for 2 hours at 60 ℃ after the dropwise adding is completed to obtain the reactive dispersant with the number average molecular weight of 2900.
The preparation of modified nano particles comprises the steps of placing 6g of zirconium dioxide nano particles (with the average particle diameter of 20 nm) in 10% alkali solution, stirring for 10 hours, then stirring and dripping 0.1g of hydrogen peroxide, stirring for 1h hours, centrifuging, adding an acid solution, washing and settling for many times, drying to PH7 to obtain hydroxylated nano particles, adding 54g of ethanol, 6g of water and 0.6g of 3-mercaptopropyl trimethoxysilane into the hydroxylated nano particles, carrying out ultrasonic reaction for 1 hour at 60 ℃, centrifuging and washing to obtain mercapto-modified zirconium dioxide particles, placing 3g of bisphenol fluorene diacrylate and 3g of toluene solvent into a reactor, adding mercapto-modified zirconium dioxide particles in batches for many times, reacting for 1 hour at 25 ℃, and then carrying out ethanol precipitation, centrifuging and washing to obtain the modified nano particles with the average particle diameter of 24 nm.
The photo-curing coating comprises the following components in percentage by mass:
60wt% of modified nano particles,
1.5 Wt.% of a photoinitiator TPO,
37.3Wt% of 3-phenoxybenzyl acrylate,
1Wt% of reactive dispersant,
0.2Wt% of leveling agent BYK-333.
The preparation method comprises the steps of respectively weighing modified nano-particles ZrO 2 -bisphenol fluorene diacrylate, 3-phenoxy benzyl acrylate, a photoinitiator TPO, a reactive dispersing agent and a flatting agent BYK-333 according to the mass content, adding the materials into a reaction kettle with an ultrasonic device, mixing and stirring at the stirring speed of 400rmp and the ultrasonic frequency of 35KHZ, and preparing the transparent photocuring paint.
2) Preparation of optical films
Using PET as a base material, coating the light-cured coating on the PET base material by using a bar coater to prepare a coating with the thickness of 1um, then placing a PET sheet on a 70 ℃ hot table for baking for 1.5min, and curing under 365nm UV-LED with the curing energy of 7000mJ to prepare the optical film.
Example 2
The photo-curable coating material and the optical film of example 2 are similar to the photo-curable coating material and the optical film of example 1, except that the structural unit derived from the single-ended vinyl phenyl silicone oil is introduced into the reactive dispersant of example 1, and the preparation method of the reactive dispersant is specifically as follows:
Adding acrylamide, 3-phenoxybenzyl acrylate (PBA) and single-ended vinyl phenyl silicone oil (with the weight ratio of 1:5:0.5 into a reaction flask, adding 2wt% of mercaptoethanol and 2wt% of hydrogen peroxide, heating to 80 ℃ for reaction for 4 hours to obtain a hydroxyl-containing dispersing agent, measuring the hydroxyl content of the hydroxyl-containing dispersing agent, adding 0.2wt% of dibutyltin dilaurate into the hydroxyl-containing dispersing agent, dropwise adding ethyl isocyanate acrylate with the weight ratio of 1:1 to the hydroxyl-containing dispersing agent at 60 ℃, and preserving heat for 2 hours at 60 ℃ after the dropwise adding is completed to obtain the reactive dispersing agent with the number average molecular weight of 3100.
Example 3
The photo-curable coating and optical film of example 3 were similar to the photo-curable coating and optical film of example 2, except that amine acrylate photo-meter 5006 was introduced into the photo-curable coating of example 2, and the photo-curable coating was prepared as follows:
the photo-curing coating comprises the following components in percentage by mass:
60wt% of modified nano particles,
1.5 Wt.% of a photoinitiator TPO,
36.3Wt% of 3-phenoxybenzyl acrylate,
Photomer 5006 1wt%,
1Wt% of reactive dispersant,
0.2Wt% of leveling agent BYK-333.
The preparation method comprises the steps of respectively weighing modified nano-particles ZrO 2 -bisphenol fluorene diacrylate, 3-phenoxybenzyl acrylate, photo 5006 (purchased from IGM), a photoinitiator TPO, a reactive dispersing agent and a flatting agent BYK-333 according to the mass content, adding the modified nano-particles ZrO 2 -bisphenol fluorene diacrylate, the 3-phenoxybenzyl acrylate, the photo-initiator TPO, the reactive dispersing agent and the flatting agent BYK-333 into a reaction kettle with an ultrasonic device, mixing and stirring, wherein the stirring speed is 400rmp, and the ultrasonic frequency is 35KHZ, so as to prepare the transparent photo-curing coating.
Example 4
The photo-curable coating material and the optical film of example 4 were similar to the photo-curable coating material and the optical film of example 3, except that the hydrophilic group in the reactive dispersant of example 3 was modified to be a carboxyl group, and the preparation method of the reactive dispersant was specifically as follows:
Adding acrylic acid, 3-phenoxybenzyl acrylate (PBA) and single-ended vinyl phenyl silicone oil (number average molecular weight 400) into a reaction flask according to the mass ratio of 1:5:0.5, adding 2wt% of mercaptoethanol and 2wt% of hydrogen peroxide, heating to 80 ℃ for reaction for 4 hours to obtain a hydroxyl-containing dispersing agent, measuring the hydroxyl content of the hydroxyl-containing dispersing agent, adding 0.2wt% of dibutyltin dilaurate into the hydroxyl-containing dispersing agent, dropwise adding isocyanate ethyl acrylate with the mass ratio of 1:1 to the hydroxyl-containing dispersing agent at 60 ℃, and preserving heat for 2 hours at 60 ℃ after the dropwise adding is completed to obtain the reactive dispersing agent.
Example 5
The photo-curable coating material and optical film of example 5 were similar to the photo-curable coating material and optical film of example 3, except that the photo-curable compound in the photo-curable coating material of example 3 was modified to an epoxy compound 3-ethyl-3- (phenoxymethyl) oxetane and the photoinitiator was modified to a cationic photoinitiator Omincat (available from IGM), as shown in table 1.
Examples 6 to 8
The photo-curable coating and optical film of examples 6 to 8 were similar to the photo-curable coating and optical film of example 3 except that the mass content of the modified nanoparticles in example 3 was adjusted to 40%, 70% or 80%, as shown in table 1.
Examples 9 to 10
The photo-curable coating materials and optical films of examples 9 to 10 were similar to the photo-curable coating materials and optical films of example 3, except that the average particle diameter D of the modified nanoparticles of example 3 was adjusted to 13nm or 57nm, as shown in Table 1.
Examples 11 to 13
The photo-curable coating materials and the optical films of examples 11 to 13 were similar to the photo-curable coating materials and the optical films of example 3, except that the mass content of the reactive dispersant of example 3 was adjusted to 0.1%, 5.0% or 3.0%, as shown in Table 1.
Example 14
The photo-curable coating material and optical film of example 14 were similar to the photo-curable coating material and optical film of example 3, except that the photo-curable compound of example 3 was adjusted to 3-phenoxybenzyl acrylate +9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene (31.3% + 5%), as shown in Table 1.
Example 15
The photo-curable coating material and optical film of example 15 were similar to the photo-curable coating material and optical film of example 3, except that the photo-curable compound of example 3 was adjusted to 3-phenoxybenzyl acrylate+acryloylmorpholine (31.3% +5%), as shown in Table 1.
Example 16
The photo-curable coating material and the optical film of example 16 were similar to the photo-curable coating material and the optical film of example 3, except that the modified nanoparticle type of example 3 was modified to be TiO 2 -bisphenol fluorene diacrylate, as shown in Table 1.
Example 17
The photo-curable coating material and the optical film of example 17 were similar to the photo-curable coating material and the optical film of example 3, except that modified nanoparticles in the preparation method of the photo-curable coating material of example 3 were modified to unmodified nanoparticles (commercially available nanoparticles) as follows:
the photo-curing coating comprises the following components in percentage by mass:
60wt% of unmodified nano particles,
1.5 Wt.% of a photoinitiator TPO,
36.3 Wt percent of 3-phenoxybenzyl acrylate,
Photomer 5006 1wt%,
1Wt% of reactive dispersant,
0.2Wt% of leveling agent BYK-333.
The preparation method comprises the steps of respectively weighing unmodified nano particles ZrO 2 (purchased from Sigma-Aldrich and having an average particle size D of 20 nm), 3-phenoxybenzyl acrylate, photo-initiator TPO, reactive dispersing agent and flatting agent BYK-333 according to the mass content, adding the materials into a reaction kettle with an ultrasonic device, mixing and stirring the materials at a stirring speed of 400rmp and an ultrasonic frequency of 35KHZ, and preparing the photocuring paint.
Comparative example
Comparative example 1
The photo-curable coating material and the optical film of comparative example 1 were similar to those of example 1, except that the dispersing agent was not added in example 1, as specifically shown in Table 1.
Comparative example 2
The photo-curable coating material and optical film of comparative example 2 were similar to the photo-curable coating material and optical film of example 1, except that the reactive dispersant of example 1 was modified to a commercially available dispersant Px4701 (available from basf), as shown in table 1.
Comparative example 3
The photo-curable coating material and the optical film of comparative example 3 were similar to those of example 3, except that the lipophilic compound in the reactive dispersant of example 3 was adjusted to isooctyl acrylate, and the reactive dispersant was not introduced with an acrylate group, and the specific preparation method was as follows:
acrylamide, isooctyl acrylate and single-ended vinyl phenyl silicone oil (number average molecular weight 400) are added into a reaction flask according to the mass ratio of 1:5:0.5, 2wt% of mercaptoethanol and 2wt% of hydrogen peroxide are added, and the mixture is heated to 80 ℃ for reaction for 4 hours, so that the dispersing agent is obtained.
TABLE 1 preparation parameters of photo-curable coatings
"/" Means that no corresponding substances are added
2. Test method
1) Testing of the hydroxyl content in hydroxyl-containing dispersants
The determination of the hydroxyl content in the hydroxyl-containing dispersants is carried out with reference to standard GB-T7193.2-1987, and the number average molecular weight of the reactive dispersants can be calculated subsequently by means of end-group analysis.
2) Testing of nanoparticle average particle size D
The average particle diameter D of the nanoparticles (unmodified nanoparticles/modified nanoparticles) was tested with reference to GB/T19077.1-2003 standard. Dissolving the nano particles in toluene solvent to form colorless transparent solution, and testing by using a Horiba SZ-100V2 nano particle size analyzer to obtain a particle size distribution curve of the nano particles, wherein the average particle size D of the nano particles can be directly obtained from the particle size distribution curve.
3) Determination of appearance of photo-curable coating
Visual inspection. The appearance of the photo-cured coating was observed, and the photo-cured coating was judged to be "transparent" if the photo-cured coating was a clear transparent liquid, to be "translucent" if the photo-cured coating was a translucent light-permeable liquid, and to be "white" if the photo-cured coating was a white cloudy opaque liquid.
4) Refractive index testing of photo-curable coatings
The refractive index of the photo-curable coating was tested with reference to the GB/T6488-2008 standard. The refractive index of the photocurable coating to be tested was measured using an Abbe refractometer (Abbemat 300,300) at 20 ℃.
5) Viscosity test
The viscosity of the photo-curable coating was tested with reference to the GB/T10247 standard. The viscosity of the freshly prepared photo-cured coating to be tested was tested at 25℃using a cone-plate viscometer, model DVNXRVCP, precision of the cone-plate viscometer being + -5 cps.
6) Testing of cure shrinkage
The cure shrinkage of the photo-curable coatings was tested with reference to standard GB/T24148.9-2014.
7) Testing of storage stability
The storage stability of the photo-curable coatings was tested with reference to GB/T6753.3-1986.
The photo-curing paint is placed in a transparent glass bottle which is wrapped with shading tinfoil, after the transparent glass bottle is stored for 30 days in a 50 ℃ blowing drying box, whether nano particles are precipitated at the bottom of the glass bottle or not or whether the photo-curing paint is layered or not is observed, if the nano particles are precipitated or the photo-curing paint is layered, the storage stability of the photo-curing paint is judged to be poor, and if the bad phenomenon is not generated, the storage stability of the photo-curing paint is judged to be good.
8) Optical film transmittance test
The optical film transmittance was tested with reference to GB/T2410-2008 standard. And testing the transmittance of the optical film prepared by the glass substrate in the range of 400-800 nm by using a UV-vis wind-light photometer, wherein the model of testing equipment adopts Shimadzu UV-1800.
9) Testing of coating adhesion
The adhesion of the coating was tested with reference to the GB/T9286-1998 standard. The measurement was performed by the hundred cell method.
10 Testing of the wear resistance of the coating
The abrasion resistance of the coating was tested with reference to GB/T1768-2006 standard.
11 Determination of the appearance of the coating
Visual inspection. And (3) placing the prepared optical film with the size of 5cm multiplied by 5cm under a light source, observing whether the surface of the coating of the optical film has uneven, pitted, bubble and other bad phenomena, and whether the cured coating has blushing, flow marks and other problems, judging the appearance of the coating to be good if the bad phenomena or problems are not generated, and describing specific bad phenomena or problems if the bad phenomena or problems are generated.
12 Testing of cure time
The curing time of the photocurable coating was measured by referring to the GB 1728-1979 standard and the set time was measured by finger touch.
Using PET as a base material, coating a photo-curing coating to be detected on the PET base material by adopting a bar coater to prepare a coating with the thickness of 1um, then placing a PET sheet on a 70 ℃ hot table for baking for 1.5min, curing under 365nm UV-LED, and preparing the optical film with the curing energy of 7000 mJ. And setting the curing time to be 5s for finger touch test, recording the curing time to be 5s if the finger touch is dry, and taking a parallel sample to increase the curing time to 10s if the finger touch is not dry for measurement. Each time 5s was added until the touch was dry.
Table 2 performance parameters of the photocurable coatings of the examples and comparative examples
"/" Indicates that the value is outside the range of the instrument or that the photocurable coating cannot be tested accordingly
Table 3 performance parameters of the coating/optical films of each example and comparative example
"/" Indicates that the photo-cured coating cannot be prepared into a coating for corresponding performance test
3. Analysis of test results for examples and comparative examples
As can be seen from the comparison of examples 3, 11 to 13 and comparative examples 1 to 2, the photocurable coating using the reactive dispersant of the present application is advantageous in reducing the viscosity, curing shrinkage and curing time, and improving the storage stability thereof, compared with the conventional dispersant used or not used, and the coating prepared therefrom has more excellent adhesion, light transmittance, abrasion resistance and surface properties. As can be seen from the comparison of examples 3, 11 to 13 with comparative example 3, the reactive dispersant comprising acrylate groups and structural units derived from monofunctional high-refractive monomers has lower viscosity and curing time, more excellent storage stability, and the coating prepared therefrom has more excellent light transmittance, abrasion resistance and surface properties.
From a comparison of example 2 with example 1, it can be seen that the introduction of structural units derived from single-ended vinylphenyl silicone oil into the reactive dispersant is beneficial to reducing the viscosity of the photo-curable coating and improving the abrasion resistance of the coating.
From a comparison of example 3 with example 2, it can be seen that the incorporation of amine acrylate photo 5006 in the photo-curable coating is advantageous for further reducing the viscosity and curing time of the photo-curable coating. As can be seen from a comparison of example 3 with example 4, in the photocurable coating containing 3-phenoxybenzyl acrylate and amine acrylate, the hydrophilic group in the reactive dispersant is selected from amide groups more favorable to reduce the viscosity of the photocurable coating than the hydrophilic group in the reactive dispersant is selected from carboxyl groups, favorable to prepare a transparent photocurable coating so as to prepare a coating excellent in surface properties and light transmittance, and favorable to improve the storage stability of the photocurable coating.
As can be seen from a comparison of example 5 with example 3, the photocurable coating containing 3-ethyl-3- (phenoxymethyl) oxetane has lower viscosity and cure shrinkage than the photocurable coating containing 3-phenoxybenzyl acrylate, and the coating prepared therefrom has more excellent abrasion resistance.
As can be seen from examples 3, 6 to 8, the mass content of the nanoparticles is controlled to 40% to 80% based on the total mass of the photo-curable coating material, so as to prepare a transparent photo-curable coating material having low viscosity, high refractive index, low curing shrinkage and curing time, and excellent storage stability, and so that the coating layer prepared from the photo-curable coating material has excellent adhesion, light transmittance, abrasion resistance and surface properties. As can be seen from comparison of examples 3, 7 to 8 and example 6, the mass content of the nanoparticles is further controlled to be 60% -80% based on the total mass of the photo-curing coating, which is further beneficial to improving the refractive index of the photo-curing coating, reducing the curing shrinkage of the photo-curing coating, and improving the adhesive force and wear resistance of the coating.
As can be seen from examples 3, 9 to 10, controlling the average particle diameter D of the nanoparticles to be 5nm to 60nm can produce a transparent photocurable coating having low viscosity, high refractive index, low curing shrinkage and curing time, and excellent storage stability, and can provide a coating produced from the photocurable coating with excellent adhesion, light transmittance, abrasion resistance, and surface properties.
As can be seen from examples 3, 11 to 13, the mass content of the reactive dispersant was controlled to be 0.1% to 5% based on the total mass of the photo-curable coating material, to prepare a transparent photo-curable coating material having low viscosity, high refractive index, low curing shrinkage and curing time, and excellent storage stability, and to provide a coating layer prepared from the photo-curable coating material with excellent adhesion, light transmittance, abrasion resistance and surface properties. As can be seen from comparison of examples 3, 12-13 and example 11, the mass content of the reactive dispersant is further controlled to be 1% -5% based on the total mass of the photo-curing coating, which is beneficial to reducing the viscosity and curing shrinkage of the photo-curing coating.
As can be seen from a comparison of example 14 and example 3, the use of two photo-curable compounds in combination is more advantageous in improving the refractive index of the photo-curable coating and the abrasion resistance of the coating thereof than one photo-curable compound. As can be seen from a comparison of example 15 with example 14, the photocurable coating contains acryloylmorpholine and has a lower viscosity and cure shrinkage than the photocurable coating contains 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene.
As can be seen from examples 3 and 16 to 17, zrO 2 -bisphenol fluorene diacrylate, tiO 2 -bisphenol fluorene diacrylate or non-surface-modified ZrO 2 can be used together with the reactive dispersant and 3-phenoxybenzyl acrylate to form a transparent photocurable coating with low viscosity, high refractive index, low cure shrinkage and cure time and excellent storage stability, and the prepared coating has excellent adhesion, light transmittance, abrasion resistance and surface properties.
It should be noted that the above embodiments are only used to illustrate the technical solution of the present application, but not to limit the technical solution of the present application, and although the detailed description of the present application is given with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present application, and all the modifications or substitutions are included in the scope of the claims and the specification of the present application. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (10)
1. The photocureable coating is characterized by comprising a photocureable compound, nanoparticles, a photoinitiator and a reactive dispersing agent with a number average molecular weight of 400-10000, wherein the reactive dispersing agent comprises a hydrophilic group, a lipophilic group and an acrylate group;
wherein the lipophilic group is derived from a lipophilic compound comprising a monofunctional high-refractive monomer having a refractive index greater than 1.5;
the hydrophilic group is derived from at least one of a compound with a structure shown in a formula I and a compound with a structure shown in a formula II,
The compound of the formula I,
The compound of the formula II is shown in the specification,
Wherein R 1 comprises at least one of hydrogen, substituted or unsubstituted alkyl of C 1-4, R 2、R3 each independently comprises at least one of hydrogen, substituted or unsubstituted alkyl of C 1-4, substituted or unsubstituted alkoxy of C 1-7, hydroxy, keto, R 4 comprises at least one of hydrogen, substituted or unsubstituted alkyl of C 1-4, carboxy, R 5 comprises at least one of hydrogen, tetrahydrofuranyl, boronate;
the acrylate group is derived from a compound comprising a structure represented by formula IV,
The compound of the formula IV,
Wherein R 11 comprises at least one of hydrogen, methyl, and R 12 comprises at least one of a substituted or unsubstituted alkylene of C 1-6;
The monofunctional high-folding monomer comprises at least one of o-phenylphenoxyethyl acrylate, (2 ethoxy) o-phenylphenoxyethyl acrylate, (ethoxy) phenol acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 2 (ethoxy) phenol acrylate, 4 (ethoxy) phenol acrylate, 3 (ethoxy) o-phenylphenoxyethyl acrylate and biphenyl methanol acrylate;
based on the total mass of the photo-curing coating, the mass content of the reactive dispersing agent is 0.1% -5%;
the reactive dispersing agent has a carbon-carbon double bond and reacts with the light-curable compound under the action of the photoinitiator and light to form a chemical bond;
The acrylate group is at least one of Structure orStructure, is the attachment site.
2. The photocurable coating of claim 1, wherein said reactive dispersant further comprises structural units derived from a vinyl silicone oil monomer.
3. The photocurable coating of claim 1, wherein said nanoparticles comprise at least one of unmodified nanoparticles, modified nanoparticles comprising nanoparticles modified with a multifunctional high refractive monomer having a refractive index greater than 1.5, said multifunctional high refractive monomer comprising at least one of a difunctional high refractive monomer, a trifunctional high refractive monomer, a tetrafunctional high refractive monomer, the difunctional high-refraction monomers comprise at least one of 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene, bisphenol fluorene diacrylate, 2-acrylic acid- [ [1, 1-binaphthyl ] -2, 2-bis (oxy-2, 1-ethylidene) ] ester, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, polyethylene glycol (600) diacrylate, dimethylol-tricyclodecane diacrylate, bisphenol AEO modified diacrylate, 1, 9-nonanediol diacrylate, 1, 10-decanediol diacrylate, propoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1, 4-butanediol diacrylate, polyethylene glycol (200) diacrylate, tetraethylene glycol diacrylate, polyethylene glycol (400) diacrylate, cyclohexane dimethanol diacrylate, the trifunctional high-refraction monomers comprise pentaerythritol triacrylate, methacrylic acid 2-hydroxy-3-acryloxypropyl ester, EO modified triacrylate, at least one of epsilon-caprolactone modified tri- (2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate, epsilon-caprolactone modified tri (acryloyloxyethyl) acrylate and tri (2-hydroxyethyl) isocyanurate triacrylate, and the tetrafunctional high-folding monomer comprises at least one of di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate and di-pentaerythritol hexaacrylate.
4. The photocurable coating according to claim 1, wherein the mass ratio of the nanoparticle to the reactive dispersant is 1 (0.001-0.1).
5. A photocurable coating according to claim 2, wherein said vinyl silicone oil monomer comprises a compound having a structure represented by formula V,
The characteristic of the V-shaped alloy is that,
Wherein R 13、R14 each independently comprises at least one of a substituted or unsubstituted C 1-3 alkyl group, a substituted or unsubstituted phenyl group, and R 15、R16、R17 each independently comprises at least one of a substituted or unsubstituted C 1-3 alkyl group.
6. A photocurable coating according to claim 3, wherein said photocurable compound comprises at least one of an acrylate compound, an epoxy compound, a polyurethane compound, and an organosiloxane compound;
the photoinitiator comprises at least one of a free radical photoinitiator and a cationic photoinitiator.
7. The photocurable coating according to any one of claims 1 to 6, characterized in that the mass content of the nanoparticles is 40% -80%, the mass content of the photocurable compound is 5% -56%, and the mass content of the photoinitiator is 0.5% -3% based on the total mass of the photocurable coating;
the average particle diameter D of the nano particles is 5 nm-60 nm.
8. The light-curable coating according to claim 1, further comprising a functional monomer comprising at least one of thiol acrylate, amine acrylate, ether acrylate.
9. An optical film comprising a substrate and a coating on at least one side of the substrate, the coating being prepared from the photocurable coating of any one of claims 1-8.
10. Use of a photocurable coating according to any one of claims 1 to 8 in the field of nano 3D printing, nanoimprinting or printing high refraction.
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