CN108341921B - Polyurethane modified flexible epoxy acrylic resin, preparation method thereof, photocuring identification ink and flexible printed circuit board - Google Patents
Polyurethane modified flexible epoxy acrylic resin, preparation method thereof, photocuring identification ink and flexible printed circuit board Download PDFInfo
- Publication number
- CN108341921B CN108341921B CN201810259469.5A CN201810259469A CN108341921B CN 108341921 B CN108341921 B CN 108341921B CN 201810259469 A CN201810259469 A CN 201810259469A CN 108341921 B CN108341921 B CN 108341921B
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- CN
- China
- Prior art keywords
- acrylate
- parts
- diisocyanate
- flexible epoxy
- polyurethane modified
- Prior art date
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 72
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 53
- 239000004593 Epoxy Substances 0.000 title claims abstract description 41
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000016 photochemical curing Methods 0.000 title abstract description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 65
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 54
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 80
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 46
- 239000003822 epoxy resin Substances 0.000 claims description 39
- 229920000647 polyepoxide Polymers 0.000 claims description 39
- 239000000376 reactant Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 239000003112 inhibitor Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- 239000005062 Polybutadiene Substances 0.000 claims description 16
- 239000000049 pigment Substances 0.000 claims description 16
- 229920002857 polybutadiene Polymers 0.000 claims description 16
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 15
- 239000002318 adhesion promoter Substances 0.000 claims description 15
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 15
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- 238000012544 monitoring process Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000013008 thixotropic agent Substances 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001723 curing Methods 0.000 abstract description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 35
- 239000000976 ink Substances 0.000 description 34
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 20
- 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 description 16
- -1 2,2,6, 6-tetramethyl piperidine-nitroxide free radical Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 9
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 4
- STWYYQVVABMBIZ-UHFFFAOYSA-N [hydroxy(2-hydroxyethoxy)phosphoryl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OP(O)(=O)OCCO STWYYQVVABMBIZ-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 125000005376 alkyl siloxane group Chemical group 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- MRIKSZXJKCQQFT-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) prop-2-enoate Chemical compound OCC(C)(C)COC(=O)C=C MRIKSZXJKCQQFT-UHFFFAOYSA-N 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- RDHSUTIDSFVNJL-UHFFFAOYSA-N OC(=O)C=C.CCCCCCCCCCCC(O)=O Chemical compound OC(=O)C=C.CCCCCCCCCCCC(O)=O RDHSUTIDSFVNJL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- ITKPCHYKBRFJPV-UHFFFAOYSA-N (2-phenylphenyl) prop-2-eneperoxoate Chemical compound C=CC(=O)OOC1=CC=CC=C1C1=CC=CC=C1 ITKPCHYKBRFJPV-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- CQHYICHMGNSGQH-UHFFFAOYSA-N 1,3-oxazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CO1 CQHYICHMGNSGQH-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- HLDSNTBYNBFQQM-UHFFFAOYSA-N 2,2-diphenylethyl prop-2-enoate Chemical compound C=1C=CC=CC=1C(COC(=O)C=C)C1=CC=CC=C1 HLDSNTBYNBFQQM-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- 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 compound 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 1
- NQOGBCBPDVTBFM-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(C)COC(C)CO NQOGBCBPDVTBFM-UHFFFAOYSA-N 0.000 description 1
- UMTXKRPANUNUCO-UHFFFAOYSA-N 2-[4-(2-phenylpropan-2-yl)phenoxy]ethyl prop-2-enoate Chemical compound C=1C=C(OCCOC(=O)C=C)C=CC=1C(C)(C)C1=CC=CC=C1 UMTXKRPANUNUCO-UHFFFAOYSA-N 0.000 description 1
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- PRFFNSYDNSUDOI-UHFFFAOYSA-N C(CC)(=O)O.C(C1=CC=CC=C1)(=O)C=1C=C(C=CC1)N=C(N)N Chemical compound C(CC)(=O)O.C(C1=CC=CC=C1)(=O)C=1C=C(C=CC1)N=C(N)N PRFFNSYDNSUDOI-UHFFFAOYSA-N 0.000 description 1
- BPWRBIIRZIJEFN-UHFFFAOYSA-N C1=C(C=CC=2C(C3=CC=CC=C3C(C12)=O)=O)C(C)C=1NC=CN1 Chemical compound C1=C(C=CC=2C(C3=CC=CC=C3C(C12)=O)=O)C(C)C=1NC=CN1 BPWRBIIRZIJEFN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- COZFFUSJRISXLV-UHFFFAOYSA-N [2,2-dihydroxyethoxy(hydroxy)phosphoryl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OP(=O)(O)OCC(O)O COZFFUSJRISXLV-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- HXTCWLNZDIPLCA-UHFFFAOYSA-N dodecanoic acid;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCCCCCCCCC(O)=O HXTCWLNZDIPLCA-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- APRJFNLVTJWEPP-UHFFFAOYSA-M n,n-diethylcarbamate Chemical compound CCN(CC)C([O-])=O APRJFNLVTJWEPP-UHFFFAOYSA-M 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WZESLRDFSNLECD-UHFFFAOYSA-N phenyl prop-2-eneperoxoate Chemical class C=CC(=O)OOC1=CC=CC=C1 WZESLRDFSNLECD-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/581—Reaction products of epoxy resins with less than equivalent amounts of compounds containing active hydrogen added before or during the reaction with the isocyanate component
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0266—Marks, test patterns or identification means
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a polyurethane modified flexible epoxy acrylic resin, a preparation method thereof, photocuring marking ink and a flexible printed circuit board. The preparation method of the polyurethane modified flexible epoxy acrylic resin comprises the following steps: firstly, preparing a semi-adduct of diisocyanate and hydroxyl acrylate and flexible epoxy acrylate, and then reacting the diisocyanate with the semi-adduct of hydroxyl acrylate and flexible epoxy acrylate to obtain polyurethane modified flexible epoxy acrylate resin; the polyurethane modified flexible epoxy acrylic resin is prepared by the method; the ultraviolet curing marking ink comprises 30-50 parts of polyurethane modified flexible epoxy acrylate, 1-5 parts of photoinitiator, 10-30 parts of reactive diluent and 15-40 parts of filler; the flexible printed circuit board comprises a circuit board body and an identification piece attached to the circuit board body, wherein the identification piece is formed by curing ultraviolet curing identification ink.
Description
Technical Field
The invention relates to the technical field of resin and application thereof, in particular to polyurethane modified flexible epoxy acrylic resin, a preparation method thereof, photocuring marking ink and a flexible printed circuit board.
Background
The flexible printed board is designed to improve space utilization and product design flexibility. The design requirement of smaller and higher density installation can be met, the reduction of assembly processes and the increase of reliability are facilitated, and the method is the only solution for meeting the requirements of miniaturization, light weight and movement of electronic products. The flexible printing plate can be moved, bent and twisted without damaging the lead, can have different shapes and special packaging sizes, and is widely applied to the fields or products of aerospace, military, mobile communication, portable computers, computer peripherals, PDAs, digital cameras and the like.
The ultraviolet light curing marking ink is applied to a printed circuit board and used as a plug-in identification of an electronic component, and the printed circuit board is required to be subjected to processes of tin spraying, punch forming and the like after the marking ink is printed by silk. Due to the resin materials and auxiliary materials, the conventional ultraviolet curing marking ink has poor heat resistance, is easy to peel off from a solder resist layer, is brittle and easy to fall off, has poor wear resistance, is easy to scratch and the like, affects the later-stage plug-in process, and finally causes poor quality of a printed circuit board.
Disclosure of Invention
Therefore, the invention needs to provide a preparation method of polyurethane modified flexible epoxy acrylic resin, and the polyurethane modified flexible epoxy acrylic resin with high temperature resistance, good toughness and good wear resistance can be prepared.
The invention also needs to provide a polyurethane modified flexible epoxy acrylic resin.
The invention also needs to provide the ultraviolet curing marking ink which has good flexibility, is not easy to fall off, and has good wear resistance and heat resistance.
The present invention also provides a flexible printed circuit board.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of polyurethane modified flexible epoxy acrylic resin comprises the following steps:
adding diisocyanate, dibutyltin dilaurate, acrylic acid hydroxy ester and a polymerization inhibitor into diethylene glycol dimethacrylate respectively, heating to 50-70 ℃ for a first reaction, monitoring the content of-NCO groups in reactants, and finishing the first reaction when the content of-NCO groups is 50-55% of the initial content to obtain a semi-adduct of diisocyanate and acrylic acid hydroxy ester;
firstly adding carboxyl-terminated polybutadiene, epoxy resin, a catalyst and a polymerization inhibitor into diethylene glycol dimethacrylate, heating to 80-120 ℃ for a second reaction, monitoring the change of acid value in reactants, adding acrylic acid for continuous reaction when the acid value is less than 3mgKOH/g, and finishing the second reaction when the acid value is less than 5mgKOH/g to obtain flexible epoxy acrylate;
and (3) mixing the diisocyanate, the semi-adduct of the hydroxyl acrylate and the flexible epoxy acrylate, heating to 50-70 ℃ for a third reaction, and when determining that the-NCO group in the reactants is 0, finishing the third reaction to obtain the polyurethane modified flexible epoxy acrylate resin.
The polyurethane modified flexible epoxy acrylic resin is prepared by firstly preparing a semi-adduct of diisocyanate and hydroxyl acrylate and flexible epoxy acrylate, wherein the semi-adduct of diisocyanate and hydroxyl acrylate has isocyanate groups, carboxyl groups and epoxy groups are subjected to esterification reaction to form side hydroxyl groups in the flexible epoxy acrylate, the isocyanate groups in the semi-adduct of diisocyanate and hydroxyl acrylate are subjected to reaction with the side hydroxyl groups in the flexible epoxy acrylic resin to obtain the polyurethane modified flexible epoxy acrylic resin, namely the polyurethane modified flexible epoxy acrylic resin is modified by polyurethane, urethane groups are introduced to improve the performances of adhesion, heat resistance, wear resistance, elasticity and the like, and carboxyl-terminated polybutadiene reacts with partial epoxy groups to introduce flexible chain segments to increase the toughness of the whole resin Wear resistance and good toughness.
Wherein in some embodiments, the molar ratio of the hydroxy acrylate to the diisocyanate is 1:1 to 1.1; the mass ratio of the diisocyanate to the dibutyltin dilaurate is 100:0.1 to 1; the mass ratio of the diisocyanate to the diethylene glycol dimethacrylate is 1: 0.2-0.5; the mass ratio of the diisocyanate to the polymerization inhibitor is 100: 0.1-1. By precisely controlling the amount of each reaction, it is possible to ensure that the reaction proceeds in the desired direction, reducing the waste of by-products and reactants.
Wherein in some embodiments, the molar ratio of epoxy groups in the epoxy resin to-COOH groups in the carboxyl-terminated polybutadiene is 1: 0.05-0.3; the mass ratio of the epoxy resin to the catalyst is 100: 0.1-1; the mass ratio of the epoxy resin to the polymerization inhibitor is 100: 0.1-1; the molar ratio of the epoxy resin to the-COOH groups in the acrylic acid is 1: 0.7-0.9. The precise control of the amounts of the individual reactants ensures that the reaction proceeds in the desired direction, reducing the waste of by-products and reactants.
In some of these embodiments, the flexible epoxy acrylate has a molar ratio of pendant-OH groups to-NCO groups in the semi-adduct of diisocyanate and hydroxy acrylate of 1:0.1 to 0.5.
The invention also needs to provide a polyurethane modified flexible epoxy acrylic resin, which is prepared by the preparation method of the polyurethane modified flexible epoxy acrylic resin.
The invention also needs to provide the ultraviolet curing marking ink, which comprises the following components in parts by weight:
30-50 parts of polyurethane modified flexible epoxy acrylate
1-5 parts of photoinitiator
10-30 parts of reactive diluent
15-40 parts of a filler;
the polyurethane modified flexible epoxy acrylate is prepared by the preparation method of the polyurethane modified flexible epoxy acrylate resin.
According to the ultraviolet curing marking ink, the polyurethane modified flexible epoxy acrylic resin with high temperature resistance, good toughness and good wear resistance is added, so that the problems that a coating is not good in flexibility and easy to fall off due to brittleness, a coating is not good in wear resistance and easy to scratch, heat resistance is not good and easy to fall off from a solder mask and the like are solved, and the ultraviolet curing marking ink with better performance is obtained.
In some embodiments, the ultraviolet light curing marking ink further comprises the following components in parts by weight:
0.5-2 parts of thixotropic agent
0.1-2 parts of flatting agent
1-5 parts of adhesion promoter
1-10 parts of pigment.
In one embodiment, the ultraviolet light curing identification ink is used for a flexible printed circuit board.
The invention also needs to provide a flexible printed circuit board, which comprises a circuit board body and an identification piece attached to the circuit board body, wherein the identification piece is formed by curing the ultraviolet curing identification ink.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a preparation method of polyurethane modified flexible epoxy acrylic resin, which comprises the following steps:
adding diisocyanate, dibutyltin dilaurate, acrylic acid hydroxy ester and a polymerization inhibitor into diethylene glycol dimethacrylate, heating to 50-70 ℃ for a first reaction, and obtaining a semi-adduct of the diisocyanate and the acrylic acid hydroxy ester after the first reaction is finished. For example, heated to 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃. The half-adduct of diisocyanate and hydroxy acrylate contains an isocyanate group.
Firstly adding carboxyl-terminated polybutadiene, epoxy resin, a catalyst and a polymerization inhibitor into diethylene glycol dimethacrylate, heating to 80-120 ℃ for a second reaction, monitoring the change of acid value in reactants, adding acrylic acid for continuous reaction when the acid value is less than 3mgKOH/g, finishing the second reaction when the acid value is less than 5mgKOH/g to obtain flexible epoxy acrylate, and carrying out esterification reaction on carboxyl and epoxy groups to form side hydroxyl in the flexible epoxy acrylate. For example, the temperature is increased to 80 ℃, 85 ℃, 90 ℃, 100 ℃, 110 ℃ and 120 ℃.
Mixing the diisocyanate and the semi-adduct of the hydroxyl acrylate and the flexible epoxy acrylate, heating to 50-70 ℃ for a third reaction, reacting isocyanate groups in the diisocyanate and the semi-adduct of the hydroxyl acrylate with lateral hydroxyl groups in the flexible epoxy acrylate resin, and finishing the third reaction to obtain the polyurethane modified flexible epoxy acrylate resin. For example, heated to 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃.
Wherein, when the first reaction is carried out, the content of-NCO groups in the reactants is monitored, and when the content of the-NCO groups is 50-55% of the initial content, the reaction is finished. The monitoring method comprises the following steps: the principle of titration standard determination by using di-n-butylamine is as follows: reacting the-NCO group with excessive di-n-butylamine to generate urea, titrating the excessive di-n-butylamine with hydrochloric acid by taking bromocresol green as an indicator, thereby calculating the amount of the di-n-butylamine consumed by the-NCO group, and further calculating the percentage content of the-NCO group in the tested object. The method specifically comprises the following steps: the content of-NCO groups in the system is determined by a di-n-butylamine back titration method, isocyanate and di-n-butylamine react quantitatively to generate urea: R-NCO + (C)4H9)2NH→RHCON(C4H9)2(ii) a The excess di-n-butylamine was titrated with a standard titration solution of hydrochloric acid, which reacted with excess di-n-butylamine: (C)4H9)2NH+HCl→(C4H9)2NH. HCl. The calculation mode of the titration standard determination of the di-n-butylamine is as follows: formula for the calculation of the NCO group content: NCO% (((V))1-V2) NM)/Gx 100%, wherein V1The number of milliliters of hydrochloric acid standard solution used for the blank test; v2Hydrochloric acid standard solution milli used for titration testThe number of liters; n is the molar concentration of a standard hydrochloric acid solution, mol/L; m is grams per milliequivalent of isocyanate, 0.042; g is the sample mass, G.
While the second reaction was proceeding, the reaction was terminated by monitoring the acid value to less than 5 mgKOH/g. The monitoring method comprises the following steps: measuring with potassium hydroxide standard solution, and calculating acid value; the principle is as follows: reaction of potassium hydroxide with the remainder of-COOH, KOH + RCOOH → H2O + RCOOK. The specific operation is as follows: adding about 0.5g of sample into a 100ml beaker, accurately weighing the sample to 0.0002g, adding about 20ml of acetone, and uniformly stirring the mixture by using a glass rod until NR-2 is completely dissolved, wherein the sample can be properly heated if the NR-2 cannot be dissolved at normal temperature; after complete dissolution, 2-3 drops of 2% cresol red indicator are added, after stirring well, the solution is titrated with about 0.2mol/L potassium hydroxide standard solution until the color changes from yellow to purple, and the volume consumed (ml) is recorded. The acid value (mg (KOH)/g) was calculated as follows: acid value (mg (koh))/G ═ V · c (koh) x 56.1/G, where: v-volume of potassium hydroxide consumed, ml; c-potassium hydroxide standard solution concentration, mol/L; g-sample weight, G.
When the third reaction was carried out, the reaction was terminated when the-NCO group in the reactant was measured to be 0. The content of related groups in the reactants is detected in real time, so that the target product can be generated by the reaction, and the generation of byproducts and the waste of the reactants are reduced. The monitoring method comprises the following steps: performing IR measurement on the reaction product, wherein the infrared spectrum of the reaction product is 3400cm-1The characteristic absorption peak of N-H on carbamate and 1715cm-1The appearance of a characteristic peak of the-C ═ O group; and in 2260cm-1The characteristic absorption peak near (A) disappeared, indicating that the-NCO reaction was complete.
Wherein the molar ratio of the hydroxyl acrylate to the diisocyanate is 1:1-1.1, and when the ratio is reached, the reaction is more favorable to the direction of generating a semi-adduct of the diisocyanate and the hydroxyl acrylate, the reaction can be promoted, and the byproducts can be reduced. For example, the molar ratio of hydroxy acrylate to diisocyanate is 1:1, 1:1.05 and 1: 1.1.
The mass ratio of diisocyanate to dibutyltin dilaurate is 100: 0.1-1. For example, the mass ratio of diisocyanate to dibutyltin dilaurate is 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100: 1.
The mass ratio of the diisocyanate to the diethylene glycol dimethacrylate is 1: 0.2-0.5. For example, the mass ratio of diisocyanate to diethylene glycol dimethacrylate is 1:0.2, 1:0.25, 1:0.3, 1:0.4, 1: 0.5.
The mass ratio of diisocyanate to polymerization inhibitor is 100: 0.1-1. For example, the mass ratio of diisocyanate to polymerization inhibitor is 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100: 1.
the mol ratio of the epoxy group in the epoxy resin to the-COOH group in the carboxyl-terminated polybutadiene is 1: 0.05-0.3. For example, the molar ratio of epoxy groups in the epoxy resin to-COOH groups in the carboxyl-terminated polybutadiene is 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1: 0.3.
The mass ratio of the epoxy resin to the catalyst is 100: 0.1-1. For example, the mass ratio of the epoxy resin to the catalyst is 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100: 1.
The mass ratio of the epoxy resin to the polymerization inhibitor is 100: 0.1-1. For example, the mass ratio of the epoxy resin to the polymerization inhibitor is 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100: 1.
the molar ratio of the epoxy resin to the-COOH groups in the acrylic acid is 1: 0.7-0.9. For example, the molar ratio of epoxy resin to-COOH groups in acrylic acid is 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1: 0.9.
The molar ratio of side-OH groups in the flexible epoxy acrylate to-NCO groups in a semi-adduct of diisocyanate and hydroxyl acrylate is 1: 0.1-0.5. For example, the molar ratio of pendant-OH groups in the flexible epoxy acrylate to-NCO groups in the diisocyanate half-adduct is 1:0.1, 1:0.2, 1:0.3, 1:0.35, 1: 0.5.
The reactants, the amount of each reactant is accurately controlled, the reaction can be ensured to be carried out towards the expected direction, and the waste of byproducts and reactants is reduced.
Wherein, the diisocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
The hydroxyl acrylate is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and pentaerythritol triacrylate.
The epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin and o-cresol novolac epoxy resin.
The catalyst is one or more of N, N-dimethylbenzylamine, N-dimethylaniline, DMP-30, triethylamine, trimethyl benzyl ammonium chloride, triphenyl phosphorus, triphenyl antimony, tetraethyl ammonium bromide and chromium acetylacetonate.
The polymerization inhibitor is one or more of p-methoxyphenol, hydroquinone, 2, 5-dimethyl hydroquinone, 2, 6-di-tert-butyl-p-cresol and 2,2,6, 6-tetramethyl piperidine-nitroxide free radical.
The polyurethane modified flexible epoxy acrylic resin is prepared by firstly preparing a semi-adduct of diisocyanate and hydroxyl acrylate and flexible epoxy acrylate, wherein the semi-adduct of diisocyanate and hydroxyl acrylate has isocyanate groups, carboxyl groups and epoxy groups are subjected to esterification reaction to form side hydroxyl groups in the flexible epoxy acrylate, the isocyanate groups in the semi-adduct of diisocyanate and hydroxyl acrylate are subjected to reaction with the side hydroxyl groups in the flexible epoxy acrylic resin to obtain the polyurethane modified flexible epoxy acrylic resin, namely the polyurethane modified flexible epoxy acrylic resin is modified by polyurethane, urethane groups are introduced to improve the performances of adhesion, heat resistance, wear resistance, elasticity and the like, and carboxyl-terminated polybutadiene reacts with partial epoxy groups to introduce flexible chain segments to increase the toughness of the whole resin Wear resistance and good toughness.
The polyurethane modified flexible epoxy acrylic resin is prepared by the preparation method of the polyurethane modified flexible epoxy acrylic resin.
The ultraviolet curing marking ink comprises the following components in parts by weight:
30-50 parts of polyurethane modified flexible epoxy acrylate
1-5 parts of photoinitiator
10-30 parts of reactive diluent
15-40 parts of a filler;
the polyurethane modified flexible epoxy acrylate is prepared by the preparation method of the polyurethane modified flexible epoxy acrylate resin. For example, 30, 35, 40, 45 and 50 parts of polyurethane modified flexible epoxy acrylate; 1, 2, 3, 4 and 5 parts of a photoinitiator; 10, 15, 20, 22, 25, 28 and 30 parts of reactive diluent; 15, 20, 25, 30, 35 and 40 parts of filler.
Wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone-1, 2-methyl-1- (4-methylmercaptophenyl) -2-morpholinoacetone-1, 2-phenyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, isopropyl thioxanthone, 2, 4-diethyl thioxanthone, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-difluoro-3- (1H-pyrrolyl-1) phenyl) titanocene, 9-anthracenemethyl N, N-diethylcarbamate, 2- (3-benzoylphenyl) guanidine propionate and 1- (anthraquinone-2-yl) ethyl imidazole One or more of oxazole carboxylic acid ester.
The reactive diluent is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, diphenylethyl acrylate, ethoxylated phenoxy acrylate, o-phenylphenoxy acrylate, 2- (p-cumyl-phenoxy) -ethyl acrylate, 3, 5-trimethylcyclohexyl acrylate, ethoxyethoxyethyl acrylate, glycidyl methacrylate, isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylate, lauric acid methacrylate, cyclotrimethylolpropane formal acrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol acrylate, neopentyl glycol acrylate, propoxylated neopentyl glycol acrylate, di (meth), 1.6-hexanediol diacrylate, tricyclodecane dimethanol diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate.
The filler is one or more of sulfuric acid dam, heavy metal stone powder, quartz powder, talcum powder, mica powder, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, kaolin, silica micropowder, bentonite and fumed silica.
Further, the ultraviolet curing marking ink also comprises the following components in parts by weight:
0.5-2 parts of thixotropic agent
0.1-2 parts of a leveling agent.
For example, 0.5, 1, 1.5, 2 parts of thixotropic agent; 0.1, 0.3, 0.5, 1, 1.5 and 2 parts of leveling agent.
Wherein the shaking agent is one or more of modified urea solution, polyhydroxy carboxylic acid amide solution and urea modified polyurethane solution.
The leveling agent is one or the combination of more than two of polyether modified polydimethylsiloxane, polyester modified polydimethylsiloxane, aralkyl modified polydimethylsiloxane, polyester modified polymethylalkylsiloxane, polyether modified polymethylalkylsiloxane, polyester modified polydimethylsiloxane containing hydroxyl functional groups, polyester modified polydimethylsiloxane containing acrylic functional groups, polyether polyester modified polydimethylsiloxane containing hydroxyl functional groups, polyether modified siloxane, polyether modified polysiloxane, fluorine-containing surfactant polymer, polyacrylate or fluorine modified polyacrylate.
Further, the ultraviolet curing marking ink also comprises the following components in parts by weight:
1-5 parts of an adhesion promoter;
1-10 parts of pigment.
For example, 1, 2, 3, 4, 5 parts of adhesion promoter; 1, 3, 4,6, 7, 9 and 10 parts of pigment.
The adhesion promoter is one or more of chlorinated polyester acrylate, hydroxyethyl methacryloyl phosphate, dihydroxyethyl methacryloyl phosphate and propyl trihydroxyethyl methacryloyl titanate.
The pigment is one or more of phthalocyanine green, phthalocyanine blue, titanium dioxide, carbon black, aurora red, pigment red, permanent violet, permanent yellow, pigment yellow or ultramarine. And (4) batching according to the required color.
Embodiments of the present invention will be further illustrated by the following examples.
Example one
The preparation method of the polyurethane modified flexible epoxy acrylic resin provided by the embodiment of the invention comprises the following steps:
respectively adding diphenylmethane diisocyanate, dibutyltin dilaurate, hydroxyethyl acrylate and p-methoxyphenol into diethylene glycol dimethacrylate, heating to 60 ℃ to perform a first reaction, monitoring the content of-NCO groups in reactants, finishing the reaction when the content of the-NCO groups is 50-55% of the initial content, and finishing the first reaction to obtain a semi-adduct of diisocyanate and hydroxy acrylate; adding carboxyl-terminated polybutadiene, bisphenol A epoxy resin, N-dimethylbenzylamine and a polymerization inhibitor into diethylene glycol dimethacrylate, heating to 100 ℃ to perform a second reaction, monitoring the change of the acid value in a reactant, adding acrylic acid to continue the reaction when the acid value is less than 3mgKOH/g, monitoring the change of the acid value in the reactant in real time, finishing the reaction when the acid value is less than 5mgKOH/g, and finishing the second reaction to obtain flexible epoxy acrylate; mixing diisocyanate, a semi-adduct of hydroxyl acrylate and flexible epoxy acrylate, heating to 60 ℃ for a third reaction, and when determining that-NCO groups in the reactants are 0, finishing the reaction, and finishing the third reaction to obtain the polyurethane modified flexible epoxy acrylate resin.
Wherein the molar ratio of the hydroxyethyl acrylate to the diphenylmethane diisocyanate is 1: 1; the mass ratio of the diphenylmethane diisocyanate to the dibutyltin dilaurate is 100: 1; the mass ratio of the diphenylmethane diisocyanate to the diethylene glycol dimethacrylate is 1: 0.5; the mass ratio of the diphenylmethane diisocyanate to the p-methoxyphenol is 100: 1. the molar ratio of epoxy groups in the bisphenol A epoxy resin to-COOH groups in the carboxyl-terminated polybutadiene is 1: 0.2; the mass ratio of the bisphenol A type epoxy resin to the N, N-dimethylbenzylamine is 100: 1; the mass ratio of the bisphenol A type epoxy resin to the p-methoxyphenol is 100: 1; the mol ratio of the bisphenol A type epoxy resin to the-COOH groups in the acrylic acid is 1: 0.8; the molar ratio of pendant-OH groups in the flexible epoxy acrylate to-NCO groups in the semi-adduct of diisocyanate and hydroxy acrylate was 1: 0.3. By precisely controlling the amounts of the respective reactants with reference to the above ratios, it is possible to ensure that the reaction proceeds in a desired direction, reducing the by-products and the waste of the reactants.
Wherein the method for monitoring the content of the-NCO group in the first reaction comprises the following steps: a solution of di-n-butylamine was added to the reaction mixture to determine the-NCO group content in the reaction. The acid number in the second reaction was determined using a potassium hydroxide standard solution. When the third reaction is carried out, the IR measurement is carried out on the reaction product, and the infrared spectrum is 3400cm-1The characteristic absorption peak of N-H on carbamate and 1715cm-1The appearance of a characteristic peak of the-C ═ O group; and in 2260cm-1And (4) eliminating the characteristic absorption peak nearby, and indicating that the-NCO reaction is complete, thus obtaining the polyurethane modified flexible epoxy acrylate resin.
Example two
The preparation method of the polyurethane modified flexible epoxy acrylic resin provided by the embodiment of the invention is different from the first embodiment in that: the molar ratio of the hydroxyethyl acrylate to the diphenylmethane diisocyanate is 1: 1; the mass ratio of the diphenylmethane diisocyanate to the dibutyltin dilaurate is 100: 1; the mass ratio of the diphenylmethane diisocyanate to the diethylene glycol dimethacrylate is 1: 0.5; the mass ratio of the diphenylmethane diisocyanate to the p-methoxyphenol is 100: 1. the molar ratio of epoxy groups in the bisphenol A epoxy resin to-COOH groups in the carboxyl-terminated polybutadiene is 1: 0.2; the mass ratio of the bisphenol A type epoxy resin to the N, N-dimethylbenzylamine is 100: 1; the mass ratio of the bisphenol A type epoxy resin to the p-methoxyphenol is 100: 1; the mol ratio of the bisphenol A type epoxy resin to the-COOH groups in the acrylic acid is 1: 0.8; the molar ratio of pendant-OH groups in the flexible epoxy acrylate to-NCO groups in the semi-adduct of diisocyanate and hydroxy acrylate was 1: 0.3. By precisely controlling the amounts of the respective reactants with reference to the above ratios, it is possible to ensure that the reaction proceeds in a desired direction, reducing the by-products and the waste of the reactants.
EXAMPLE III
The preparation method of the polyurethane modified flexible epoxy acrylic resin is different from the first embodiment in that the hydroxy acrylate is prepared by hydroxyethyl methacrylate and hydroxypropyl acrylate according to a molar ratio of 1: 1; the diisocyanate is toluene diisocyanate; the epoxy resin is bisphenol F type epoxy resin; the catalyst is prepared from DMP-30, triethylamine and tetraethyl ammonium bromide in a molar ratio of 1:1: 1; the polymerization inhibitor is hydroquinone. The temperature of the first reaction is 70 ℃, and the temperature of the second reaction is 80 ℃; the temperature of the third reaction was 70 ℃.
The molar ratio of the hydroxyl acrylate to the diisocyanate is 1: 1.1; the mass ratio of diisocyanate to dibutyltin dilaurate is 100: 0.1; the mass ratio of diisocyanate to diethylene glycol dimethacrylate is 1: 0.4; the mass ratio of diisocyanate to polymerization inhibitor is 100: 0.5. the molar ratio of epoxy groups in the epoxy resin to-COOH groups in the carboxyl-terminated polybutadiene is 1: 0.3; the mass ratio of the epoxy resin to the catalyst is 100: 0.8; the mass ratio of the epoxy resin to the polymerization inhibitor is 100: 0.8; the molar ratio of the epoxy resin to the-COOH groups in the acrylic acid is 1: 0.9; the molar ratio of pendant-OH groups in the flexible epoxy acrylate to-NCO groups in the semi-adduct of diisocyanate and hydroxy acrylate is 1: 0.5. By precisely controlling the amounts of the respective reactants with reference to the above ratios, it is possible to ensure that the reaction proceeds in a desired direction, reducing the by-products and the waste of the reactants.
Example four
The preparation method of the polyurethane modified flexible epoxy acrylic resin is different from the first embodiment in that the hydroxy acrylate is pentaerythritol triacrylate; the diisocyanate is hexamethylene diisocyanate and diphenylmethane diisocyanate 1:2, preparing the mixture according to a molar ratio; the epoxy resin is prepared from novolac epoxy resin and o-cresol novolac epoxy resin in a molar ratio of 1: 1; the catalyst is prepared from triethylamine and DMP-301 in a molar ratio of 1; the polymerization inhibitor is 2, 6-di-tert-butyl-p-cresol. The temperature of the first reaction is 50 ℃, and the temperature of the second reaction is 120 ℃; the temperature of the third reaction was 50 ℃.
The molar ratio of the hydroxyl acrylate to the diisocyanate is 1: 1.05; the mass ratio of diisocyanate to dibutyltin dilaurate is 100: 0.8; the mass ratio of diisocyanate to diethylene glycol dimethacrylate is 1: 0.2; the mass ratio of diisocyanate to polymerization inhibitor is 100: 0.1. the molar ratio of epoxy groups in the epoxy resin to-COOH groups in the carboxyl-terminated polybutadiene is 1: 0.05; the mass ratio of the epoxy resin to the catalyst is 100: 0.1; the mass ratio of the epoxy resin to the polymerization inhibitor is 100: 0.1; the molar ratio of the epoxy resin to the-COOH groups in the acrylic acid is 1: 0.7; the molar ratio of pendant-OH groups in the flexible epoxy acrylate to-NCO groups in the semi-adduct of diisocyanate and hydroxy acrylate is 1: 0.1. By precisely controlling the amounts of the respective reactants with reference to the above ratios, it is possible to ensure that the reaction proceeds in a desired direction, reducing the by-products and the waste of the reactants.
EXAMPLE five
The preparation method of the polyurethane modified flexible epoxy acrylic resin provided by the embodiment of the invention specifically comprises the following steps: 174.2g of toluene diisocyanate, 0.5g of dibutyltin dilaurate and 0.5g of 2, 6-di-tert-butyl-4-methylphenol were added to 50g of diethylene glycol dimethacrylate, 130.1g of hydroxyethyl methacrylate was added dropwise, and the reaction temperature was maintained at 50-70 ℃ for 2-4 hours. When the content of-NCO group in the system is monitored to be 50% of the initial content, the reaction is stopped to obtain a semi-adduct of diisocyanate and hydroxyl acrylate, and the semi-adduct is cooled to room temperature. 200g of bisphenol A epoxy resin (NPEL-128), 100g of carboxyl-terminated polybutadiene, 0.9g of triphenylphosphine and 0.5g of 2, 6-di-tert-butyl-4-methylphenol were added to 50g of diethylene glycol dimethacrylate, the mixture was heated to 110 ℃ and, when the acid value in the system was monitored<When the concentration of KOH in the reaction mixture was 1mgKOH/g, 68.4g of acrylic acid was added thereto to continue the reaction, and when the acid value was monitored to be in the system<When the concentration of the diisocyanate is 5mgKOH/g, the temperature is reduced to 70 ℃, 71g of diisocyanate semi-adduct is added for continuous reaction, the reaction is stopped when the-NCO group in the system disappears, the reaction product is subjected to IR measurement, and 3400cm in an infrared spectrogram-1The characteristic absorption peak of N-H on carbamate and 1715cm-1By the occurrence of-C ═ O groupsA characteristic peak; and in 2260cm-1And (4) eliminating the characteristic absorption peak nearby, and indicating that the-NCO reaction is complete, thus obtaining the polyurethane modified flexible epoxy acrylate resin A.
EXAMPLE six
The preparation method of the polyurethane modified flexible epoxy acrylic resin provided by the embodiment of the invention specifically comprises the following steps: 222.3g of isophorone diisocyanate, 0.5g of dibutyltin dilaurate and 0.5g of 2, 6-di-tert-butyl-4-methylphenol were added to 50g of diethylene glycol dimethacrylate, 130.1g of hydroxyethyl methacrylate was added dropwise, and the reaction temperature was maintained at 50-70 ℃ for 2-4 hours. When the content of-NCO group in the system is monitored to be 50% of the initial content, the reaction is stopped to obtain a semi-adduct of diisocyanate and hydroxyl acrylate, and the semi-adduct is cooled to room temperature. 200g of bisphenol A epoxy resin (NPEL-128), 100g of carboxyl terminated polybutadiene, 0.9g of triphenylphosphine and 0.5g of 2, 6-di-tert-butyl-4-methylphenol are uniformly mixed, heated to 110 ℃, and when the acid value in the system is monitored<When the concentration of KOH in the reaction mixture was 1mgKOH/g, 68.4g of acrylic acid was added thereto to continue the reaction, and when the acid value was monitored to be in the system<When the concentration of the diisocyanate is 5mgKOH/g, the temperature is reduced to 70 ℃, 80.1g of diisocyanate semi-adduct is added for continuous reaction, the reaction is stopped when the-NCO group in the system disappears, the reaction product is subjected to IR measurement, and 3400cm is in an infrared spectrogram-1The characteristic absorption peak of N-H on carbamate and 1715cm-1The appearance of a characteristic peak of the-C ═ O group; and in 2260cm-1And (4) eliminating the characteristic absorption peak nearby to obtain the polyurethane modified flexible epoxy acrylate resin B.
EXAMPLE seven
The preparation method of the polyurethane modified flexible epoxy acrylic resin provided by the embodiment of the invention specifically comprises the following steps: 174.2g of toluene diisocyanate, 0.5g of dibutyltin dilaurate and 0.5g of 2, 6-di-tert-butyl-4-methylphenol were added to 50g of diethylene glycol dimethacrylate, 130.1g of hydroxyethyl methacrylate was added dropwise, and the reaction temperature was maintained at 50-70 ℃ for 2-4 hours. When the content of-NCO group in the system is monitored to be 50% of the initial content, the reaction is stopped to obtain a semi-adduct of diisocyanate and hydroxyl acrylate, and the semi-adduct is cooled to room temperature. 200g of bisphenol A epoxy resin (NPEL-128) and 100g of terminal carboxyl groupsPolybutadiene, 0.9g of triphenylphosphine and 0.5g of 2, 6-di-tert-butyl-4-methylphenol were added to 50g of diethylene glycol dimethacrylate, the mixture was heated to 110 ℃ and the acid value in the system was monitored<When the concentration of KOH in the reaction mixture was 1mgKOH/g, 68.4g of acrylic acid was added thereto to continue the reaction, and when the acid value was monitored to be in the system<When the temperature is reduced to 70 ℃ when the KOH/g is 5mgKOH/g, 106.6g of diisocyanate semi-adduct is added for continuous reaction, the reaction is stopped when the-NCO group in the system disappears, the reaction product is subjected to IR measurement, and 3400cm is arranged in an infrared spectrogram-1The characteristic absorption peak of N-H on carbamate and 1715cm-1The appearance of a characteristic peak of the-C ═ O group; and in 2260cm-1And (4) eliminating the characteristic absorption peak nearby to obtain the polyurethane modified flexible epoxy acrylate resin C.
Example eight
The ultraviolet curing marking ink provided by the embodiment of the invention comprises the following components in parts by weight: 40 parts of polyurethane modified flexible epoxy acrylate, 3 parts of photoinitiator, 20 parts of reactive diluent, 25 parts of filler, 1 part of thixotropic agent, 1 part of leveling agent, 3 parts of adhesion promoter and 5 parts of pigment. The polyurethane modified flexible epoxy acrylate is prepared by the method of the embodiment one, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone-1, the reactive diluent is hydroxyethyl acrylate, the filler is prepared by mixing a sulfuric acid dam and talcum powder in a mass ratio of 1:1, the shaking agent is modified urea solution, the leveling agent is polyether modified polydimethylsiloxane, the adhesion promoter is chlorinated polyester acrylate for example, and the pigment is phthalocyanine blue.
Example nine
The ultraviolet curing marking ink provided by the embodiment of the invention comprises the following components in parts by weight: 30 parts of polyurethane modified flexible epoxy acrylate, 1 part of photoinitiator, 10 parts of reactive diluent, 15 parts of filler, 0.5 part of thixotropic agent, 0.1 part of flatting agent, 1 part of adhesion promoter and 1 part of pigment. The polyurethane modified flexible epoxy acrylate is prepared by the method described in the second embodiment, the photoinitiator is prepared from 2-phenyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide in a mass ratio of 1:1, the active diluent is prepared from glycidyl methacrylate and lauric acid acrylate in a mass ratio of 1:2, the filler is kaolin, the thixotropic agent is a urea modified polyurethane solution, the leveling agent is polyester modified polymethyl alkyl siloxane, the adhesion promoter is hydroxyethyl methacryloyl phosphate, and the pigment is titanium dioxide.
Example ten
The ultraviolet curing marking ink provided by the embodiment of the invention comprises the following components in parts by weight: 50 parts of polyurethane modified flexible epoxy acrylate, 5 parts of photoinitiator, 30 parts of reactive diluent, 40 parts of filler, 2 parts of thixotropic agent, 2 parts of flatting agent, 5 parts of adhesion promoter and 10 parts of pigment. The polyurethane modified flexible epoxy acrylate is prepared by the method described in the third embodiment, the photoinitiator is 2-phenyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide in a mass ratio of 1:1, the active diluent is diphenyl ethyl acrylate, the filler is kaolin, the shaking agent is urea modified polyurethane solution, the leveling agent is polyester modified polymethyl alkyl siloxane, the adhesion promoter is hydroxyethyl methacryl phosphate, and the pigment is titanium dioxide.
EXAMPLE eleven
The ultraviolet curing marking ink provided by the embodiment of the invention comprises the following components in parts by weight: 45 parts of polyurethane modified flexible epoxy acrylate, 3 parts of photoinitiator, 22 parts of reactive diluent, 15 parts of filler, 1 part of adhesion promoter and 1 part of pigment. The polyurethane modified flexible epoxy acrylate is prepared by the method described in the second embodiment, the photoinitiator is prepared from 2-phenyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide in a mass ratio of 1:1, the active diluent is prepared from glycidyl methacrylate and lauric acid acrylate in a mass ratio of 1:2, the filler is kaolin, the thixotropic agent is a urea modified polyurethane solution, the leveling agent is polyester modified polymethyl alkyl siloxane, the adhesion promoter is hydroxyethyl methacryloyl phosphate, and the pigment is titanium dioxide.
Example twelve
The ultraviolet curing marking ink provided by the embodiment of the invention comprises the following components in parts by weight: 35 parts of polyurethane modified flexible epoxy acrylate, 4 parts of photoinitiator, 30 parts of reactive diluent, 35 parts of filler, 2 parts of thixotropic agent and 1 part of flatting agent. The polyurethane modified flexible epoxy acrylate is prepared by the method of the embodiment one, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone-1, the reactive diluent is hydroxyethyl acrylate, the filler is prepared by mixing a sulfuric acid dam and talcum powder in a mass ratio of 1:1, the shaking agent is modified urea solution, the leveling agent is polyether modified polydimethylsiloxane, the adhesion promoter is chlorinated polyester acrylate for example, and the pigment is phthalocyanine blue.
Comparative example 1
The following method was used to prepare the epoxy acrylates: 200g of bisphenol A epoxy resin (NPEL-128), 0.9g of triphenylphosphine, 72.1g of acrylic acid and 0.5g of 2, 6-di-tert-butyl-4-methylphenol are added into 50g of diethylene glycol dimethacrylate, the mixture is heated to 110 ℃, and when the acid value in the system is monitored to be less than 5mgKOH/g, the reaction is ended, so that the bisphenol A epoxy acrylic resin is obtained.
EXAMPLE thirteen
The ultraviolet curing marking ink provided by the embodiment of the invention is prepared from the components in percentage by mass according to the mass listed in the table. The components listed in the table are uniformly mixed, ground by a three-roll grinder until the fineness is less than 12 mu m, and then regulated to 250dPa.s by hydroxyethyl methacrylate, thus obtaining the ultraviolet curing marking ink. Printing the ultraviolet curing marking ink on the surface of a flexible printed circuit board with a manufactured solder mask layer by 100T screen printing, passing the printed circuit board through an ultraviolet curing machine, and accumulating the light energy to 1200mJ/cm2. And testing and evaluating the flexibility, adhesive force, wear resistance and heat resistance of the ultraviolet curing marking ink on the flexible printed circuit board.
Watch 1
Resin A, B, C was prepared as in example five, example six, and example seven, and was used in compositions 1, 2, and 3, respectively, and the control resin was the bisphenol a epoxy acrylic resin prepared in comparative example one.
Photoinitiator TPO: JRCURE-1108 (general brand TPO), New Material Ltd for Tianjin long time.
Photoinitiator 184: JRCURE-1104 (general reference 184), New Material Ltd for Tianjin.
IBOA: IBOA/isobornyl methacrylate, Mitsubishi Yang, Japan.
(EO)3TMPTA：(EO)3TMPTA, ethoxylated trimethylolpropane triacrylate, Changxing chemical industry.
Talc powder: talcum powder, GD-25, Niaoning Dongyu Xinmi materials Co., Ltd.
Fumed silica: fumed silica A200, Germany degussa
Titanium dioxide: titanium dioxide R706, U.S. dupont.
Shaking change agent: BYK-R605, Byk, Germany.
Leveling agent: BYK-354, BYK Germany.
An adhesion promoter: CD9050, sartomer usa.
The UV curable marking ink of example thirteen was tested for performance by the following test, and the results are shown in Table two.
1. Flexibility
And (3) after the flexible printed circuit coated with the ultraviolet curing identification ink is subjected to ultraviolet curing, bending the flexible printed circuit at 180 degrees for 100 times. And observing whether the ink coating of the mark at the bent part has oil falling or not. The coating is qualified if no oil is dropped, and is unqualified if the oil is dropped.
2. Adhesion force
After the flexible printed circuit coated with the ultraviolet curing marking ink is cured by ultraviolet light, refer to GB/T9286-1998 'test for marking grids of paint films of colored paint and varnish'. The coating is qualified if no shedding occurs, and is unqualified if the shedding occurs.
3. Wear resistance
And (3) after the flexible printed circuit coated with the ultraviolet curing identification ink is subjected to ultraviolet curing, observing whether scratches exist on the surface of the coating by adopting an RCA (Rolling circle amplification) paper tape abrasion resistance tester with a load of 175g and a friction test for 600 times. The coating is qualified if no scratch exists, and is unqualified if the coating has the scratch.
4. Heat resistance
And (3) after the flexible printed circuit coated with the ultraviolet curing identification ink is subjected to ultraviolet curing, coating rosin soldering flux on the surface, and carrying out tin immersion for 280 +/-5 ℃ multiplied by 10s multiplied by 2 times. The sheet was pulled 3 times with a 3M tape (type 600) and the presence or absence of the drop of the marking ink was observed. The coating is qualified if no oil is dropped, and is unqualified if the oil is dropped.
Watch two
| 1 | 2 | 3 | Control group | |
| Flexibility | Qualified | Qualified | Qualified | Fail to be qualified |
| Adhesion force | Qualified | Qualified | Qualified | Qualified |
| Wear resistance | Qualified | Qualified | Qualified | Fail to be qualified |
| Heat resistance | Qualified | Qualified | Qualified | Fail to be qualified |
As shown in the table two, the uv curable marking inks 1, 2, and 3 prepared from the flexible epoxy acrylic resin containing polyurethane in this example have better adhesion than the uv curable marking ink prepared from the common bisphenol a epoxy resin. The ultraviolet curing marking ink prepared from the polyurethane modified flexible epoxy acrylic resin has more excellent flexibility, wear resistance and heat resistance.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A preparation method of polyurethane modified flexible epoxy acrylic resin is characterized by comprising the following steps:
respectively adding diisocyanate, dibutyltin dilaurate, acrylic acid hydroxy ester and a polymerization inhibitor into diethylene glycol dimethacrylate, heating to 50-70 ℃ for a first reaction, monitoring the content of-NCO groups in reactants, and finishing the first reaction when the content of-NCO groups is 50-55% of the initial content to obtain a semi-adduct of diisocyanate and acrylic acid hydroxy ester;
firstly adding carboxyl-terminated polybutadiene, epoxy resin, a catalyst and a polymerization inhibitor into diethylene glycol dimethacrylate, heating to 80-120 ℃ for a second reaction, monitoring the change of acid value in reactants, adding acrylic acid for continuous reaction when the acid value is less than 3mgKOH/g, and finishing the second reaction when the acid value is less than 5mgKOH/g to obtain flexible epoxy acrylate;
mixing the diisocyanate, the semi-adduct of the hydroxyl acrylate and the flexible epoxy acrylate, heating to 50-70 ℃ for a third reaction, and when determining that-NCO groups in the reactants are 0, finishing the third reaction to obtain polyurethane modified flexible epoxy acrylate resin; the molar ratio of side-OH groups in the flexible epoxy acrylate to-NCO groups in a semi-adduct of diisocyanate and hydroxyl acrylate is 1: 0.1-0.5.
2. The method for preparing polyurethane modified flexible epoxy acrylic resin according to claim 1, wherein: the molar ratio of the hydroxyl acrylate to the diisocyanate is 1: 1-1.1; the mass ratio of the diisocyanate to the dibutyltin dilaurate is 100:0.1 to 1; the mass ratio of the diisocyanate to the diethylene glycol dimethacrylate is 1: 0.2-0.5; the mass ratio of the diisocyanate to the polymerization inhibitor is 100: 0.1-1.
3. The method for preparing polyurethane modified flexible epoxy acrylic resin according to claim 1, wherein: the molar ratio of epoxy groups in the epoxy resin to-COOH groups in the carboxyl-terminated polybutadiene is 1: 0.05-0.3; the mass ratio of the epoxy resin to the catalyst is 100: 0.1-1; the mass ratio of the epoxy resin to the polymerization inhibitor is 100: 0.1-1; the molar ratio of the epoxy resin to the-COOH groups in the acrylic acid is 1: 0.7-0.9.
4. A polyurethane modified flexible epoxy acrylic resin is characterized in that: prepared by the preparation method of the polyurethane modified flexible epoxy acrylic resin as described in any one of claims 1 to 3.
5. The ultraviolet curing marking ink is characterized by comprising the following components in parts by weight:
30-50 parts of polyurethane modified flexible epoxy acrylate
1-5 parts of photoinitiator
10-30 parts of reactive diluent
15-40 parts of a filler;
the polyurethane modified flexible epoxy acrylate is prepared by the preparation method of the polyurethane modified flexible epoxy acrylate resin as claimed in any one of claims 1 to 3.
6. The UV-curable marking ink according to claim 5, further comprising the following components in parts by weight:
0.5-2 parts of thixotropic agent
0.1-2 parts of flatting agent
1-5 parts of adhesion promoter
1-10 parts of pigment.
7. The UV-curable marking ink according to claim 6, wherein the UV-curable marking ink is used for a flexible printed circuit board.
8. A flexible printed circuit board comprising a circuit board body and a marking member attached to the circuit board body, wherein the marking member is formed by curing the UV-curable marking ink of claim 5 or 6.
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| CN109734860A (en) * | 2019-01-10 | 2019-05-10 | 四川东树新材料有限公司 | A kind of urethane composition for vacuum introducing technology |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08311152A (en) * | 1995-05-24 | 1996-11-26 | Asahi Denka Kogyo Kk | Urethane-modified epoxy resin composition |
| CN101175787A (en) * | 2005-05-16 | 2008-05-07 | 昭和电工株式会社 | Carboxyl group-containing polyurethane, heat-curable resin composition and uses thereof |
| CN101200527A (en) * | 2007-11-30 | 2008-06-18 | 江南大学 | Liquid rubber modified epoxy acrylic ester prepolymer and use for preparation of ultraviolet curing paint |
| CN104448212A (en) * | 2014-12-23 | 2015-03-25 | 北京化工大学常州先进材料研究院 | Preparation of epoxy resin modified polyurethane-acrylate photopolymerisable oligomer |
| CN106832221A (en) * | 2017-02-17 | 2017-06-13 | 佛山市三求光固材料股份有限公司 | The photocuring of structure containing oxazolidone heat reactive resin, its preparation method and the photosensitive solder resist material containing it |
-
2018
- 2018-03-27 CN CN201810259469.5A patent/CN108341921B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08311152A (en) * | 1995-05-24 | 1996-11-26 | Asahi Denka Kogyo Kk | Urethane-modified epoxy resin composition |
| CN101175787A (en) * | 2005-05-16 | 2008-05-07 | 昭和电工株式会社 | Carboxyl group-containing polyurethane, heat-curable resin composition and uses thereof |
| CN101200527A (en) * | 2007-11-30 | 2008-06-18 | 江南大学 | Liquid rubber modified epoxy acrylic ester prepolymer and use for preparation of ultraviolet curing paint |
| CN104448212A (en) * | 2014-12-23 | 2015-03-25 | 北京化工大学常州先进材料研究院 | Preparation of epoxy resin modified polyurethane-acrylate photopolymerisable oligomer |
| CN106832221A (en) * | 2017-02-17 | 2017-06-13 | 佛山市三求光固材料股份有限公司 | The photocuring of structure containing oxazolidone heat reactive resin, its preparation method and the photosensitive solder resist material containing it |
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