CN108341921A - Polyurethane-modified flexible epoxy acrylic resin, preparation method, photocuring marking ink and flexible circuit board - Google Patents
Polyurethane-modified flexible epoxy acrylic resin, preparation method, photocuring marking ink and flexible circuit board Download PDFInfo
- Publication number
- CN108341921A CN108341921A CN201810259469.5A CN201810259469A CN108341921A CN 108341921 A CN108341921 A CN 108341921A CN 201810259469 A CN201810259469 A CN 201810259469A CN 108341921 A CN108341921 A CN 108341921A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- diisocyanate
- flexible epoxy
- modified
- acrylic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 56
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 42
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000016 photochemical curing Methods 0.000 title abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 74
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 59
- -1 hydroxy ester Chemical class 0.000 claims abstract description 55
- 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 46
- 238000007711 solidification Methods 0.000 claims abstract description 15
- 230000008023 solidification Effects 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 75
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 59
- 229920000647 polyepoxide Polymers 0.000 claims description 41
- 239000003822 epoxy resin Substances 0.000 claims description 37
- 239000000376 reactant Substances 0.000 claims description 26
- 239000003112 inhibitor Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 239000005062 Polybutadiene Substances 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 15
- 229920002857 polybutadiene Polymers 0.000 claims description 15
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 13
- 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 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 abstract description 15
- 239000000945 filler Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 15
- 238000001723 curing Methods 0.000 abstract description 2
- 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 34
- 239000000047 product Substances 0.000 description 33
- 239000003795 chemical substances by application Substances 0.000 description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 20
- 229940106691 bisphenol a Drugs 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 239000000049 pigment Substances 0.000 description 14
- 239000002318 adhesion promoter Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000012544 monitoring process Methods 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical class CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000013877 carbamide Nutrition 0.000 description 5
- 125000000118 dimethyl group Polymers [H]C([H])([H])* 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
- 229920005573 silicon-containing polymer Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- ITHBATHHUGYRSW-UHFFFAOYSA-N [2-hydroxyethoxy(methoxy)phosphoryl] prop-2-enoate Chemical compound COP(=O)(OCCO)OC(=O)C=C ITHBATHHUGYRSW-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-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
- 238000012797 qualification Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- RDHSUTIDSFVNJL-UHFFFAOYSA-N OC(=O)C=C.CCCCCCCCCCCC(O)=O Chemical compound OC(=O)C=C.CCCCCCCCCCCC(O)=O RDHSUTIDSFVNJL-UHFFFAOYSA-N 0.000 description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- 150000001336 alkenes Chemical class 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 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 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
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004258 Ethoxyquin Substances 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
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical group CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 2
- 235000019285 ethoxyquin Nutrition 0.000 description 2
- 229940093500 ethoxyquin Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical group CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000007639 printing 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
- 150000003672 ureas Chemical class 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 group C=CC(=O)OOC1=CC=CC=C1C1=CC=CC=C1 ITKPCHYKBRFJPV-UHFFFAOYSA-N 0.000 description 1
- ZMTBGVBNTHTBEC-UHFFFAOYSA-N (3,3,5-trimethylcyclohexyl) prop-2-enoate Chemical class CC1CC(OC(=O)C=C)CC(C)(C)C1 ZMTBGVBNTHTBEC-UHFFFAOYSA-N 0.000 description 1
- 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 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
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-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
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical class 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
- UAZLJXALDUIFJV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol 2-methylbut-2-ene Chemical group CC(=CC)C.C(COCCO)O UAZLJXALDUIFJV-UHFFFAOYSA-N 0.000 description 1
- XISFOXBYRQWDNK-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine;hydrochloride Chemical compound [Cl-].CC1=CC=CC=C1C(C)(C)[NH3+] XISFOXBYRQWDNK-UHFFFAOYSA-N 0.000 description 1
- HMRPNNORSXVXDY-UHFFFAOYSA-N 2-(oxolan-2-ylmethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)CC1CCCO1 HMRPNNORSXVXDY-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
- DFHHICWDTCBHEX-UHFFFAOYSA-N 2-ethoxycyclohexa-2,5-diene-1,4-dione Chemical compound CCOC1=CC(=O)C=CC1=O DFHHICWDTCBHEX-UHFFFAOYSA-N 0.000 description 1
- WYUHTVDGHDRPDW-UHFFFAOYSA-N 3-hydroxy-N-phenyl-4-phenyldiazenylnaphthalene-2-carboxamide Chemical compound C1(=CC=CC=C1)N=NC1=C(C(=CC2=CC=CC=C12)C(=O)NC1=CC=CC=C1)O WYUHTVDGHDRPDW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 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 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
- CEOFSVWWRXFPSG-UHFFFAOYSA-N [hydroxy(propoxy)phosphoryl] prop-2-enoate Chemical compound CCCOP(O)(=O)OC(=O)C=C CEOFSVWWRXFPSG-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates 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
- 229920001577 copolymer Polymers 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
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical class CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 1
- ZOJPTQRKWVDKTP-UHFFFAOYSA-N decane methanol prop-2-enoic acid Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.CO.CO.CCCCCCCCCC ZOJPTQRKWVDKTP-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VVTZNCQOVBDXRL-UHFFFAOYSA-N guanidine;propanoic acid Chemical compound NC(N)=N.CCC(O)=O VVTZNCQOVBDXRL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229940091853 isobornyl acrylate Drugs 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 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
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical class O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 125000003944 tolyl group Chemical group 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
- 239000002966 varnish Substances 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 polyurethane-modified flexible epoxy acrylic resin, preparation method, photocuring marking ink and flexible circuit boards.The preparation method of the polyurethane-modified flexible epoxy acrylic resin is：First prepare half addition product and flexible epoxy acrylate of diisocyanate and crylic acid hydroxy ester, then diisocyanate is reacted with half addition product of crylic acid hydroxy ester and flexible epoxy acrylate, obtains polyurethane-modified flexible epoxy acrylate；Polyurethane-modified flexible epoxy acrylic resin is made of the above method；It includes 30 50 parts of the polyurethane-modified flexible epoxy acrylate, 15 parts of photoinitiator, 10 30 parts of reactive diluent, 15 40 parts of filler that ultraviolet light, which cures marking ink,；Flexible circuit board includes circuit board body and the identification piece that is attached in circuit board body, and identification piece is formed by curing by ultraviolet light solidification marking ink.
Description
Technical field
The present invention relates to resin and its applied technical fields, and in particular to polyurethane-modified flexible epoxy acrylic resin,
Preparation method, photocuring marking ink and flexible circuit board.
Background technology
Flexible printed circuit designs to improve space availability ratio and product design flexibility.It can meet smaller and more
The design requirement of high-density installation, it helps reduce assembling procedure and increase reliability, be to meet miniaturization of electronic products, light
Unique solution of quantization and movement requirement.Flexible print version can be moved, is bent, be reversed, without damaging conducting wire, Ke Yiyou
Different shapes and special package dimension, in space flight, military affairs, mobile communication, laptop computer, computer peripheral equipment, PDA, number
It is widely used on the fields such as camera or product.
Ultraviolet light cures marking ink and is applied on printed circuit board, and the plug-in unit as electronic component, which identifies, to be used, printing
Circuit board will also pass through the techniques such as spray tin, punch forming after the good marking ink of silk-screen.Common ultraviolet light solidification mark oil
Ink will appear marking ink heat resistance and with great difficulty do not shelled with solder mask in the process due to resin material and auxiliary material
Fall, that coating embrittlement is easy to fall off and wearability bad generation wiping is spent etc. is bad, influence later stage plug-in unit technique, eventually lead to printing
Quality of circuit board is bad, and traditional ultraviolet light solidification marking ink can not meet its need in flexibility, wear-resisting, heat-resisting etc.
It asks.
Invention content
Based on this, the present invention, can it is necessary to provide a kind of preparation method of polyurethane-modified flexible epoxy acrylic resin
To prepare high temperature resistant, good toughness and the good polyurethane-modified flexible epoxy acrylic resin of wear-resisting property.
The present invention, which there is a need to, provides a kind of polyurethane-modified flexible epoxy acrylic resin.
The present invention there is a need to the ultraviolet light for providing that a kind of flexibility is good, coating is not easily to fall off and wear-resisting, heat resistance is good
Cure marking ink.
The present invention, which there is a need to, provides a kind of flexible circuit board.
In order to achieve the object of the present invention, the present invention uses following technical scheme：
A kind of preparation method of polyurethane-modified flexible epoxy acrylic resin comprising following steps：
Diisocyanate, dibutyl tin laurate, crylic acid hydroxy ester and polymerization inhibitor are separately added into diethylene glycol two
Methacrylate is heated to 50 DEG C -70 DEG C and carries out the first reaction, monitor the content of-NCO groups in reactant in, when -
When NCO group content is the 50%-55% of initial content, the first reaction terminates, and obtains diisocyanate and crylic acid hydroxy ester
Half addition product；
Dimethacrylate first is added in carboxyl-terminated polybutadiene, epoxy resin, catalyst and polymerization inhibitor
In, it is heated to 80-120 DEG C and carries out the second reaction, monitor the variation of acid value in reactant, when acid value is less than 3mgKOH/g, add
Entering acrylic acid, the reaction was continued, and when acid value is less than 5mgKOH/g, the second reaction terminates to obtain flexible epoxy acrylate；
Half addition product of the diisocyanate and crylic acid hydroxy ester and the flexible epoxy is acrylic ester mixed
Close, be heated to 50 DEG C -70 DEG C progress third reactions, measure reactant in-NCO group be 0 when, third reaction terminates, gathered
Urethane is modified flexible epoxy acrylate.
Above-mentioned polyurethane-modified flexible epoxy acrylic resin first prepares the half of diisocyanate and dihydroxypropyl fat
There is isocyanate group in half addition product of addition product and flexible epoxy acrylate, diisocyanate and dihydroxypropyl fat,
Carboxyl and the pendant hydroxyl group in epoxy group esterification formation flexible epoxy acrylate, diisocyanate and crylic acid hydroxy ester
Isocyanate group is reacted with pendant hydroxyl group in flexible epoxy acrylic resin in half addition product, obtains polyurethane-modified flexible ring
Oxypropylene acid resin that is, by polyurethane-modified, and introduces carbamate groups, improves attachment, heat-resisting, wear-resisting and elastic etc.
Performance is reacted with PART EPOXY base by carboxyl-terminated polybutadiene and introduces soft segment, increases the toughness of entire resin, thus
The polyurethane-modified flexible epoxy acrylic resin arrived has preferable high temperature resistant, wear-resisting property and good toughness.
In some of embodiments, the molar ratio of the crylic acid hydroxy ester and the diisocyanate is 1:1-1.1；
The mass ratio of the diisocyanate and the dibutyl tin laurate is 100：0.1-1；The diisocyanate with it is described
The mass ratio of dimethacrylate is 1:0.2-0.5；The mass ratio of the diisocyanate and the polymerization inhibitor
It is 100：0.1-1.Accurately control the amount of each reaction, it is ensured that reaction occurs towards expected direction, reduces by-product
And the waste of reactant.
In some of embodiments, the epoxy group in the epoxy resin and-COOH in the carboxyl-terminated polybutadiene
The molar ratio of group is 1:0.05-0.3；The mass ratio of the epoxy resin and the catalyst is 100:0.1-1；The ring
Oxygen resin is 100 with the polymerization inhibitor mass ratio:0.1-1；In the epoxy resin and the acrylic acid-mole of COOH group
Than being 1:0.7-0.9.Accurately control the amount of each reactant, it is ensured that reaction occurs towards expected direction, reduces secondary
The waste of product and reactant.
In some of embodiments, side-OH groups and diisocyanate and acrylic acid in the flexible epoxy acrylate
In half addition product of hydroxy ester-molar ratio of NCO group is 1:0.1-0.5.
The present invention, which there is a need to, provides a kind of polyurethane-modified flexible epoxy acrylic resin, is changed by the polyurethane
The preparation method of property flexible epoxy acrylic resin is made.
The present invention, which there is a need to, provides a kind of ultraviolet light solidification marking ink comprising the component of following 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 filler；
The polyurethane-modified flexible epoxy acrylate is by the polyurethane-modified flexible epoxy acrylic resin
Preparation method is made.
Above-mentioned ultraviolet light cures marking ink, and high temperature resistant, good toughness and good polyurethane-modified of wear-resisting property is added
Flexible epoxy acrylic resin, solve marking ink poor in flexibility coating embrittlement be easy to fall off, the bad easy wiping of wearability
The problems such as flower and heat resistance are not with great difficulty peeled off from solder mask obtains the ultraviolet light solidification marking ink of more excellent performance.
In some of embodiments, the ultraviolet light cures marking ink, further includes the component of following parts by weight：
It shakes and becomes 0.5-2 parts of agent
0.1-2 parts of levelling agent
1-5 parts of adhesion promoter
1-10 parts of pigment.
In a wherein embodiment, the ultraviolet light solidification marking ink is used for flexible circuit board.
The present invention, which there is a need to, provides a kind of flexible circuit board, including circuit board body and is attached to the circuit board
Identification piece on ontology, the identification piece are formed by curing by the ultraviolet light solidification marking ink.
Specific implementation mode
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.Make on the contrary, purpose of providing these embodiments is
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all of technologies and scientific terms used here by the article and belong to the technical field of the present invention
The normally understood meaning of technical staff is identical.Used term is intended merely to description tool in the description of the invention herein
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The present invention provides a kind of preparation method of polyurethane-modified flexible epoxy acrylic resin comprising following steps：
Diisocyanate, dibutyl tin laurate, crylic acid hydroxy ester and polymerization inhibitor are separately added into diethylene glycol two
Methacrylate is heated to 50 DEG C -70 DEG C and carries out the first reaction, the first reaction terminates to obtain diisocyanate and propylene in
Half addition product of sour hydroxy ester.Such as it is heated to 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C.Diisocyanate and dihydroxypropyl
Contain isocyanate group in half addition product of ester.
Dimethacrylate first is added in carboxyl-terminated polybutadiene, epoxy resin, catalyst and polymerization inhibitor
In, it is heated to 80-120 DEG C and carries out the second reaction, monitor the variation of acid value in reactant, when acid value is less than 3mgKOH/g, add
Entering acrylic acid, the reaction was continued, and when acid value is less than 5mgKOH/g, the second reaction terminates to obtain flexible epoxy acrylate, carboxyl with
Epoxy group esterification forms the pendant hydroxyl group in flexible epoxy acrylate.Such as be heated to 80 DEG C, 85 DEG C, 90 DEG C, 100 DEG C,
110℃、120℃。
By half addition product and the flexible epoxy crylic acid ester mixture of diisocyanate and crylic acid hydroxy ester, heating
To 50 DEG C of -70 DEG C of progress third reactions, isocyanate group and flexibility in half addition product of diisocyanate and crylic acid hydroxy ester
Pendant hydroxyl group is reacted in epoxy acrylic resin, and third reaction terminates to obtain polyurethane-modified flexible epoxy acrylate tree
Fat.Such as it is heated to 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C.
Wherein, when the first reaction carries out ,-the content of NCO group is monitored in reactant, when-NCO group content is initially to contain
When the 50%-55% of amount, reaction terminates.Monitoring method is：It is measured with di-n-butylamine titrimetric standard, principle is：NCO group with
The reaction of excessive di-n-butylamine generates urea, and excessive di-n-butylamine is again using bromocresol green as indicator, with titration with hydrochloric acid, thus
- the amount of di-n-butylamine that is consumed of NCO group is calculated ,-the percentage composition of NCO group and then is extrapolated in tested object.Tool
Body is：Using in di-n-butylamine back titration method measurement system-NCO group content, isocyanates and di-n-butylamine rise quantitative anti-
Urea should be generated： R-NCO+(C4H9)2NH→RHCON(C4H9)2；Excessive di-n-butylamine is titrated with Hydrochloric Standard Titration, salt
It is sour to be reacted with excessive di-n-butylamine：(C4H9)2NH+HCl→(C4H9)2NH·HCl.The calculating that di-n-butylamine titrimetric standard measures
Mode is：The calculation formula of NCO group content：NCO%=((V1-V2) NM)/G × 100%, in formula, V1It is used for blank test
The hydrochloric acid standard solution ml gone；V2The hydrochloric acid standard solution ml spent for burette test；N is standard hydrochloric acid solution
Molar concentration, mol/L；M is per the grams of milliequivalent isocyanates 0.042；G is sample mass, g.
When second reaction carries out, when monitoring acid value to less than 5mgKOH/g, reaction terminates.Monitoring method is：Use hydroxide
Potassium standard solution measures, and calculates acid value；Principle is：Potassium hydroxide is reacted with remaining-COOH, KOH+RCOOH → H2O+
RCOOK.Concrete operations are：About 0.5g samples are added in 100ml beakers, precise weight, accurately to 0.0002g, are added
About 20ml acetone, is uniformly stirred to NR-2 with glass bar and is completely dissolved, and if room temperature cannot dissolve, can suitably be heated；It is completely dissolved
Afterwards, 2% cresol red indicator of 2-3 drops is added to be titrated to by yellow with about 0.2mol/L standard potassium hydroxide liquid after agitation uniformly
Become aubergine, writes down consumed volume (ml numbers).Acid value (mg (KOH)/g) is calculated as follows：Acid value (mg (KOH))/g=
VC (KOH) × 56.1/G, in formula：V- consumes potassium hydroxide volume, ml；C- standard potassium hydroxide solution concentrations, mol/L；G-
Example weight, g.
Third reaction carry out when, measure reactant in-NCO group be 0 when, reaction terminates.Phase in detection reactant in real time
Close the content of group, it is ensured that reaction generates target product, reduces the generation of by-product and the waste of reactant.Monitoring side
Method is：IR measurement is carried out to reaction product, 3400cm in infrared spectrum-1Nearby there are the N-H features on carbamic acid base and inhales in place
Receive peak and 1715cm-1Appearance-C=O base characteristic peaks；And in 2260cm-1Nearby characteristic absorption peak disappears at place, explanation-NCO reactions
Completely.
Wherein, the molar ratio of crylic acid hydroxy ester and diisocyanate is 1:1-1.1, when reaching this ratio, reaction
It is more advantageous to the direction for half addition product for generating diisocyanate and crylic acid hydroxy ester and carries out, reaction can be promoted to carry out,
Reduce by-product.Such as the molar ratio of crylic acid hydroxy ester and diisocyanate is 1:1、 1:1.05 and 1:1.1.
The mass ratio of diisocyanate and dibutyl tin laurate is 100：0.1-1.Such as diisocyanate and February
The mass ratio of dilaurylate is 100：0.1、100：0.3、100：0.5、100：0.8、100： 1.
The mass ratio of diisocyanate and dimethacrylate is 1:0.2-0.5.Such as diisocyanate
Mass ratio with dimethacrylate is 1:0.2、1:0.25、1:0.3、1:0.4、1:0.5.
The mass ratio of diisocyanate and polymerization inhibitor is 100：0.1-1.Such as the mass ratio of diisocyanate and polymerization inhibitor
It is 100：0.1、100：0.3、100：0.5、100：0.8、100：1.
In epoxy group and carboxyl-terminated polybutadiene in epoxy resin-molar ratio of COOH group is 1:0.05-0.3.
Such as in the epoxy group and carboxyl-terminated polybutadiene in epoxy resin-molar ratio of COOH group is 1:0.05、1:0.1、1:
0.15、1:0.2、1:0.3。
The mass ratio of epoxy resin and catalyst is 100:0.1-1.Such as the mass ratio of epoxy resin and catalyst is
100:0.1、100:0.3、100:0.5、100:0.8、100:1。
Epoxy resin is 100 with polymerization inhibitor mass ratio:0.1-1.Such as epoxy resin and polymerization inhibitor mass ratio are 100：
0.1、100：0.3、100：0.5、100：0.8、100：1.
In epoxy resin and acrylic acid-molar ratio of COOH group is 1:0.7-0.9.Such as epoxy resin and acrylic acid
In-molar ratio of COOH group is 1:0.7、1:0.75、1:0.8、1:0.85、1:0.9.
Half addition product of side-OH groups and diisocyanate and crylic acid hydroxy ester in the flexible epoxy acrylate
In-molar ratio of NCO group is 1:0.1-0.5.Such as-OH groups in side add with diisocyanate half in flexible epoxy acrylate
At in object-molar ratio of NCO group is 1:0.1、1:0.2、1:0.3、1:0.35、1:0.5.
Above-mentioned reactant accurately controls the amount of each reactant, it is ensured that reaction occurs towards expected direction, subtracts
The waste of few by-product and reactant.
Wherein, diisocyanate is methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), isophorone diisocyanate
The one or more of ester and hexamethylene diisocyanate.
Crylic acid hydroxy ester is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate
The one or more of propyl ester, pentaerythritol triacrylate.
Epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy resin and o-cresol formaldehyde epoxy
One or more of resin.
Catalyst is N, N- dimethyl benzylamines, N, accelerine, DMP-30, triethylamine, trimethyl benzyl ammonia chloride,
One or more of triphenyl phosphorus, antimony triphenyl, tetraethylammonium bromide, chromium acetylacetonate.
Polymerization inhibitor is p methoxy phenol, hydroquinone, 2,5- dimethyl hydroquinones, 2,6- di-t-butyls to toluene
One or more of phenol, 2,2,6,6- tetramethyl piperidines-NO free radical.
Above-mentioned polyurethane-modified flexible epoxy acrylic resin first prepares the half of diisocyanate and dihydroxypropyl fat
There is isocyanate group in half addition product of addition product and flexible epoxy acrylate, diisocyanate and dihydroxypropyl fat,
Carboxyl and the pendant hydroxyl group in epoxy group esterification formation flexible epoxy acrylate, diisocyanate and crylic acid hydroxy ester
Isocyanate group is reacted with pendant hydroxyl group in flexible epoxy acrylic resin in half addition product, obtains polyurethane-modified flexible ring
Oxypropylene acid resin that is, by polyurethane-modified, and introduces carbamate groups, improves attachment, heat-resisting, wear-resisting and elastic etc.
Performance is reacted with PART EPOXY base by carboxyl-terminated polybutadiene and introduces soft segment, increases the toughness of entire resin, thus
The polyurethane-modified flexible epoxy acrylic resin arrived has preferable high temperature resistant, wear-resisting property and good toughness.
Polyurethane-modified flexible epoxy acrylic resin of the present invention, using above-mentioned polyurethane-modified flexible epoxy
The preparation method of acrylic resin is made.
Ultraviolet light of the present invention cures marking ink comprising the component of following 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 filler；
Above-mentioned polyurethane-modified flexible epoxy acrylate is by above-mentioned polyurethane-modified flexible epoxy acrylic resin
Preparation method be made.Such as polyurethane-modified 30,35,40,45,50 parts of flexible epoxy acrylate；Photoinitiator 1,2,3,
4,5 parts；Reactive diluent 10,15,20,22,25,28,30 parts；Filler 15,20,25,30,35,40 parts.
Photoinitiator therein is 2- hydroxy-2-methyl -1- phenylacetones -1,2- methyl-1s-(4- first mercaptophenyl) -
2- morpholines acetone -1,2- phenyl -2- dimethylaminos -1- (4- morpholinyl phenyls)-butanone -1, isopropyl thioxanthone, 2,4- diethyls
Base thioxanthone, 2,4,6- trimethylbenzoyls diphenyl phosphine oxide, bis- (2,4,6- trimethylbenzoyls) phenyl phosphine oxides,
Bis- (2,6- bis- fluoro- 3- (1H- pyrrole radicals -1) phenyl) cyclopentadienyl titanium, 9- anthracene methyl Ns, N- diethylaminos formic acid esters, 2- (3- benzene first
Aminosulfonylphenyl) one or more of propionic acid guanidine and 1- (anthraquinone -2- bases) ethyl imidazol(e) carboxylate.
Reactive diluent is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, methacrylic acid hydroxypropyl
Ester, diphenyl-ethyl acrylate, ethoxyquin phenoxy group acrylate, adjacent phenylphenoxy acrylate, 2- (p- isopropylbenzenes
Base-phenoxy group)-ethyl propylene acid esters, 3,3,5- trimethylcyclohexyl acrylates, ethoxyethoxyethyl acrylate,
Glycidyl methacrylate, iso-bornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylic acid
Ester, lauric acid acrylate, bay acid methacrylate, ring trimethylolpropane dimethoxym ethane acrylate diethylene glycol diformazan
Base acrylate, dipropylene glycol diacrylate, tripropylene glycol acrylate, neopentyl glycol acrylate, the third oxidation new penta 2
Alcohol acrylate, 1.6-hexanediyl esters, tricyclic decane dimethanol diacrylate, three (2- ethoxys) isocyanide ureas
Sour triacrylate, trimethylolpropane trimethacrylate, the third oxidation trimethylolpropane trimethacrylate, three hydroxyl first of ethoxyquin
One or more of base propane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate.
Filler be sulfuric acid dam, huge sum of money mountain flour, silica flour, talcum powder, mica powder, clay, magnesium carbonate, calcium carbonate, aluminium oxide,
One or more of aluminium hydroxide, kaolin, silicon powder, bentonite, aerosil.
Further, above-mentioned ultraviolet light cures marking ink, further includes the component of following parts by weight：
It shakes and becomes 0.5-2 parts of agent
0.1-2 parts of levelling agent.
Such as shake become agent 0.5,1,1.5,2 parts；Levelling agent 0.1,0.3,0.5,1,1.5,2 parts.
Wherein, shake become agent be modification urea solution, polyhydroxycarboxylicacid amides solution, one kind in urea-modified polyurethane solutions or
It is several.
Levelling agent is polyether-modified dimethyl silicone polymer, polyester modification dimethyl silicone polymer, aralkyl modified poly- first
The poly- methyl alkyl siloxane of radical siloxane, polyester modification, polyether-modified poly- methyl alkyl siloxane, polyester modification hydroxyl function
Reunion dimethyl siloxane, polyester modification dimethyl silicone polymer containing acrylic-functional, polyether polyester are modified hydroxyl function
Reunion dimethyl siloxane, polyether modified siloxane, Siloxane-Oxyalkylene Copolymers, fluorine-containing surfactant polymer, polypropylene
The combination of one or more of acid esters or fluorine richness polyacrylate.
Further, above-mentioned ultraviolet light cures marking ink, further includes the component of following parts by weight：
1-5 parts of adhesion promoter；
1-10 parts of pigment.
Such as adhesion promoter 1,2,3,4,5 parts；Pigment 1,3,4,6,7,9,10 parts.
Adhesion promoter therein is, for example, polyester chloride acrylic ester, hydroxyethyl methyl acryloyl phosphate, dihydroxy
One or more of ethyl-methyl acryloyl phosphate, propyl trihydroxyethyl methacryl titanate esters.
Pigment be dark green, blue or green blue, titanium dioxide, carbon black, bronze red, paratonere, permanent violet, permanent yellow, pigment yellow or
One or more of ultramarine.Color as needed carries out dispensing.
The embodiment that will be further illustrated the present invention below by several embodiments.
Embodiment one
The preparation method of the polyurethane-modified flexible epoxy acrylic resin of the embodiment of the present invention, including following step：
By methyl diphenylene diisocyanate, dibutyl tin laurate, hydroxy-ethyl acrylate and p methoxy phenol point
60 DEG C Jia Ru not be heated to and carry out the first reaction in dimethacrylates, monitor in reactant-NCO group
Content, when-NCO group content is the 50%-55% of initial content, reaction terminates, and the first reaction terminates to obtain diisocyanate
Half addition product of ester and crylic acid hydroxy ester；By carboxyl-terminated polybutadiene, bisphenol A type epoxy resin, N, N- dimethyl benzylamines and
Polymerization inhibitor is added in dimethacrylate, is heated to 100 DEG C and carries out the second reaction, monitors acid value in reactant
Variation, when acid value is less than 3mgKOH/g, acrylic acid is added, and the reaction was continued, monitors the variation of acid value in reactant in real time, works as acid
Value to less than when 5mgKOH/g, reaction terminates, and the second reaction terminates to obtain flexible epoxy acrylate；By diisocyanate and third
Half addition product and flexible epoxy crylic acid ester mixture of olefin(e) acid hydroxy ester are heated to 60 DEG C of progress third reactions, measure reactant
In-NCO group be 0 when, reaction terminates, third reaction terminate obtain polyurethane-modified flexible epoxy acrylate.
Wherein, the molar ratio of hydroxy-ethyl acrylate and methyl diphenylene diisocyanate is 1:1；Two isocyanide of diphenyl methane
The mass ratio of acid esters and dibutyl tin laurate is 100：1；Methyl diphenylene diisocyanate and diethylene glycol dimethyl propylene
The mass ratio of olefin(e) acid ester is 1:0.5；The mass ratio of methyl diphenylene diisocyanate and p methoxy phenol is 100：1.Bisphenol-A
In epoxy group and carboxyl-terminated polybutadiene in type epoxy resin-molar ratio of COOH group is 1:0.2；Bisphenol type epoxy
With N in resin, the mass ratio of N- dimethyl benzylamines is 100:1；The mass ratio of bisphenol A type epoxy resin and p methoxy phenol is
100:1；In bisphenol A type epoxy resin and acrylic acid-molar ratio of COOH group is 1:0.8；Side-in flexible epoxy acrylate
In half addition product of OH groups and diisocyanate and crylic acid hydroxy ester-molar ratio of NCO group is 1:0.3.With reference to above-mentioned
The amount of each reactant is controlled accurate in scalely, it is ensured that reaction occurs towards expected direction, reduces by-product and anti-
Answer the waste of object.
Wherein, in the first reaction-NCO group content monitoring method is：Di-n-butylamine solution is added in reactant, to survey
In fixed reaction-NCO group content.Acid value is measured with standard potassium hydroxide solution in second reaction.When third reaction carries out, to anti-
Product is answered to carry out IR measurement, 3400cm in infrared spectrum-1Place nearby occur N-H characteristic absorption peaks on carbamic acid base and
1715cm-1Appearance-C=O base characteristic peaks；And in 2260cm-1Nearby characteristic absorption peak disappears at place, and the reaction was complete by explanation-NCO, i.e.,
Obtain polyurethane-modified flexible epoxy acrylate.
Embodiment two
The preparation method of the polyurethane-modified flexible epoxy acrylic resin of the embodiment of the present invention is different from embodiment one
It is：The molar ratio of hydroxy-ethyl acrylate and methyl diphenylene diisocyanate is 1:1；Methyl diphenylene diisocyanate and February
The mass ratio of dilaurylate is 100：1；The matter of methyl diphenylene diisocyanate and dimethacrylate
Amount is than being 1:0.5；The mass ratio of methyl diphenylene diisocyanate and p methoxy phenol is 100：1.Bisphenol A type epoxy resin
In epoxy group and carboxyl-terminated polybutadiene in-molar ratio of COOH group is 1:0.2；In bisphenol A type epoxy resin with N,
The mass ratio of N- dimethyl benzylamines is 100:1；The mass ratio of bisphenol A type epoxy resin and p methoxy phenol is 100:1；Bis-phenol
In A types epoxy resin and acrylic acid-molar ratio of COOH group is 1:0.8；Side-OH groups and two in flexible epoxy acrylate
In half addition product of isocyanates and crylic acid hydroxy ester-molar ratio of NCO group is 1:0.3.Accurately with reference to aforementioned proportion
Control the amount of each reactant, it is ensured that reaction occurs towards expected direction, reduces the waste of by-product and reactant.
Embodiment three
The preparation method of the polyurethane-modified flexible epoxy acrylic resin of the embodiment of the present invention is different from embodiment one
It is that crylic acid hydroxy ester is hydroxyethyl methacrylate and hydroxypropyl acrylate with 1:1 molar ratio is made into；Diisocyanate is
Toluene di-isocyanate(TDI)；Epoxy resin is bisphenol f type epoxy resin；Catalyst is DMP-30, triethylamine and tetraethylammonium bromide
With 1:1:1 molar ratio is made into；Polymerization inhibitor is hydroquinone.The temperature of first reaction is 70 DEG C, and the temperature of the second reaction is 80
℃；The temperature of third reaction is 70 DEG C.
The molar ratio of crylic acid hydroxy ester and diisocyanate is 1:1.1；Diisocyanate and dibutyl tin laurate
Mass ratio be 100：0.1；The mass ratio of diisocyanate and dimethacrylate is 1:0.4；Diisocyanate
Ester is 100 with the mass ratio to polymerization inhibitor：0.5.In epoxy group and carboxyl-terminated polybutadiene in epoxy resin-COOH group
Molar ratio be 1:0.3；In epoxy resin with the mass ratio of catalyst be 100:0.8；Epoxy resin and the quality to polymerization inhibitor
Than being 100:0.8；In epoxy resin and acrylic acid-molar ratio of COOH group is 1:0.9；Side-in flexible epoxy acrylate
In half addition product of OH groups and diisocyanate and crylic acid hydroxy ester-molar ratio of NCO group is 1:0.5.With reference to above-mentioned
The amount of each reactant is controlled accurate in scalely, it is ensured that reaction occurs towards expected direction, reduces by-product and anti-
Answer the waste of object.
Example IV
The preparation method of the polyurethane-modified flexible epoxy acrylic resin of the embodiment of the present invention is different from embodiment one
It is that crylic acid hydroxy ester is pentaerythritol triacrylate；Diisocyanate is hexamethylene diisocyanate and diphenylmethyl
Alkane diisocyanate 1：2 molar ratios are made into；Epoxy resin is novolac epoxy resin and o-cresol formaldehyde epoxy resin 1:1 molar ratio is matched
At；Catalyst is triethylamine and DMP-301:1 molar ratio is made into；Polymerization inhibitor is 2,6- toluene di-tert-butyl phenols.First reaction
Temperature be 50 DEG C, second reaction temperature be 120 DEG C；The temperature of third reaction is 50 DEG C.
The molar ratio of crylic acid hydroxy ester and diisocyanate is 1:1.05；Diisocyanate and dibutyl tin laurate
Mass ratio be 100：0.8；The mass ratio of diisocyanate and dimethacrylate is 1:0.2；Diisocyanate
Ester is 100 with the mass ratio to polymerization inhibitor：0.1.In epoxy group and carboxyl-terminated polybutadiene in epoxy resin-COOH group
Molar ratio be 1:0.05；In epoxy resin with the mass ratio of catalyst be 100:0.1；Epoxy resin and the quality to polymerization inhibitor
Than being 100:0.1；In epoxy resin and acrylic acid-molar ratio of COOH group is 1:0.7；Side-in flexible epoxy acrylate
In half addition product of OH groups and diisocyanate and crylic acid hydroxy ester-molar ratio of NCO group is 1:0.1.With reference to above-mentioned
The amount of each reactant is controlled accurate in scalely, it is ensured that reaction occurs towards expected direction, reduces by-product and anti-
Answer the waste of object.
Embodiment five
The preparation method of the polyurethane-modified flexible epoxy acrylic resin of the embodiment of the present invention, specifically：By 174.2g
Toluene di-isocyanate(TDI), 0.5g dibutyl tin laurates, 0.5g 2,6 di tert butyl 4 methyl phenols are added separately to 50g
In dimethacrylate, 130.1g hydroxyethyl methacrylates are added dropwise, keep reaction temperature at 50-70 DEG C, instead
Answer 2-4h.When monitor in system-content of NCO group be the 50% of initial content when stop reaction, obtain diisocyanate
With half addition product of crylic acid hydroxy ester, it is cooled to room temperature.By 200g bisphenol A epoxide resins (NPEL-128), 100g end carboxyls
Polybutadiene, 0.9g triphenyl phosphorus, 0.5g 2,6 di tert butyl 4 methyl phenols are added to 50g diethylene glycol dimethyl allenes
In acid esters, 110 DEG C are heated to, when monitoring acid value in system<When 1mgKOH/g, 68.4g acrylic acid is added, and the reaction was continued, works as prison
Measure acid value in system<When 5mgKOH/g, being cooled to 70 DEG C of half addition products of addition 71g diisocyanate, the reaction was continued, works as monitoring
To in system-NCO group disappear when stop reaction, IR measurement is carried out to reaction product, 3400cm in infrared spectrum-1Near place
There is the N-H characteristic absorption peaks and 1715 cm on carbamic acid base-1Appearance-C=O base characteristic peaks；And in 2260cm-1Near place
Characteristic absorption peak disappears, and the reaction was complete by explanation-NCO to get polyurethane-modified flexible epoxy acrylate A.
Embodiment six
The preparation method of the polyurethane-modified flexible epoxy acrylic resin of the embodiment of the present invention, specifically：By 222.3g
Isophorone diisocyanate, 0.5g dibutyl tin laurates, 0.5g 2,6 di tert butyl 4 methyl phenols are separately added into
Into 50g dimethacrylates, 130.1g hydroxyethyl methacrylates are added dropwise, keep reaction temperature in 50-70
DEG C, react 2-4h.When monitor in system-content of NCO group be the 50% of initial content when stop reaction, obtain two isocyanides
Half addition product of acid esters and crylic acid hydroxy ester, is cooled to room temperature.By 200g bisphenol A epoxide resins (NPEL-128), the ends 100g
Carboxy terminatedpolybutadiene, 0.9g triphenyl phosphorus, 0.5g 2,6- di-tert-butyl-4-methy phenols are uniformly mixed, and are heated to 110 DEG C,
When monitoring acid value in system<When 1mgKOH/g, 68.4g acrylic acid is added, and the reaction was continued, when monitoring acid value in system<
It when 5mgKOH/g, is cooled to 70 DEG C and half addition products of 80.1g diisocyanate is added the reaction was continued, when monitoring-NCO bases in system
Stop reaction when group disappears, IR measurement is carried out to reaction product, 3400 cm in infrared spectrum-1Nearby there is carbamic acid base in place
On N-H characteristic absorption peaks and 1715cm-1Appearance-C=O base characteristic peaks；And in 2260cm-1Nearby characteristic absorption peak disappears at place,
Up to polyurethane-modified flexible epoxy acrylate B.
Embodiment seven
The preparation method of the polyurethane-modified flexible epoxy acrylic resin of the embodiment of the present invention, specifically：By 174.2g
Toluene di-isocyanate(TDI), 0.5g dibutyl tin laurates, 0.5g 2,6 di tert butyl 4 methyl phenols are added separately to 50g
In dimethacrylate, 130.1g hydroxyethyl methacrylates are added dropwise, keep reaction temperature at 50-70 DEG C, instead
Answer 2-4h.When monitor in system-content of NCO group be the 50% of initial content when stop reaction, obtain diisocyanate
With half addition product of crylic acid hydroxy ester, it is cooled to room temperature.By 200g bisphenol A epoxide resins (NPEL-128), 100g end carboxyls
Polybutadiene, 0.9g triphenyl phosphorus, 0.5g 2,6 di tert butyl 4 methyl phenols are added to 50g diethylene glycol dimethyl allenes
In acid esters, 110 DEG C are heated to, when monitoring acid value in system<When 1mgKOH/g, 68.4g acrylic acid is added, and the reaction was continued, works as prison
Measure acid value in system<When 5mgKOH/g, being cooled to 70 DEG C of half addition products of addition 106.6g diisocyanate, the reaction was continued, works as prison
Measure in system-NCO group stops reaction when disappearing, IR measurement is carried out to reaction product, 3400cm in infrared spectrum-1Near place
There is the N-H characteristic absorption peaks and 1715cm on carbamic acid base-1Appearance-C=O base characteristic peaks；And in 2260cm-1Near place
Characteristic absorption peak disappears to get polyurethane-modified flexible epoxy acrylate C.
Embodiment eight
The ultraviolet light of the embodiment of the present invention cures marking ink, is grouped as by the group of following parts by weight：It is polyurethane-modified soft
Property 40 parts of epoxy acrylate, 3 parts of photoinitiator, 20 parts of reactive diluent, 25 parts of filler, shake and become 1 part of agent, 1 part of levelling agent, attached
3 parts of adhesion promoter, 5 parts of pigment.Polyurethane-modified flexible epoxy acrylate therein is by the method system described in embodiment one
At photoinitiator is phenylacetone -1 2- hydroxy-2-methyl -1-, and reactive diluent is hydroxy-ethyl acrylate, and filler is sulfuric acid dam
With talcum powder 1:1 mass ratio is made into, and is shaken and is become agent as modified urea solution, levelling agent is polyether-modified dimethyl silicone polymer, attachment
Power accelerating agent is, for example, polyester chloride acrylic ester, and pigment is blue or green blue color.
Embodiment nine
The ultraviolet light of the embodiment of the present invention cures marking ink, is grouped as by the group of following parts by weight：It is polyurethane-modified soft
Property 30 parts of epoxy acrylate, 1 part of photoinitiator, 10 parts of reactive diluent, 15 parts of filler, shake become 0.5 part of agent, levelling agent 0.1
Part, 1 part of adhesion promoter, 1 part of pigment.Polyurethane-modified flexible epoxy acrylate therein is by the side described in embodiment two
Method is made, and photoinitiator is 2- phenyl -2- dimethylaminos -1- (4- morpholinyl phenyls)-butanone -1 and 2,4,6- trimethylbenzoyls
Diphenyl phosphine oxide 1:1 mass ratio is made into, and reactive diluent is glycidyl methacrylate and lauric acid acrylate 1:2
Mass ratio be made into, filler is kaolin, shake become agent into urea-modified polyurethane solutions, levelling agent be the poly- methyl alkyl of polyester modification
Siloxanes, adhesion promoter are, for example, hydroxyethyl methyl acryloyl phosphate, and pigment is titanium dioxide.
Embodiment ten
The ultraviolet light of the embodiment of the present invention cures marking ink, is grouped as by the group of following parts by weight：It is polyurethane-modified soft
Property 50 parts of epoxy acrylate, 5 parts of photoinitiator, 30 parts of reactive diluent, 40 parts of filler, shake and become 2 parts of agent, 2 parts of levelling agent, attached
5 parts of adhesion promoter, 10 parts of pigment.Polyurethane-modified flexible epoxy acrylate therein is by the method system described in embodiment three
At photoinitiator is 2- phenyl -2- dimethylaminos -1- (4- morpholinyl phenyls)-butanone -1 and 2,4,6- trimethylbenzoyl hexichol
Base phosphine oxide 1:1 mass ratio is made into, and reactive diluent is diphenyl-ethyl acrylate, and filler is kaolin, is shaken and is become agent as urea
Modified polyurethane solution, levelling agent are the poly- methyl alkyl siloxane of polyester modification, and adhesion promoter is, for example, hydroxyethyl methyl
Acryloyl phosphate, pigment are titanium dioxide.
Embodiment 11
The ultraviolet light of the embodiment of the present invention cures marking ink, is grouped as by the group of following parts by weight：It is polyurethane-modified soft
45 parts of epoxy acrylate of property, 3 parts of photoinitiator, 22 parts of reactive diluent, 15 parts of filler, 1 part of adhesion promoter, pigment 1
Part.Polyurethane-modified flexible epoxy acrylate therein is made of the method described in embodiment two, and photoinitiator is 2- phenyl-
2- dimethylaminos -1- (4- morpholinyl phenyls)-butanone -1 and 2,4,6- trimethylbenzoyls diphenyl phosphine oxide 1:1 mass ratio is matched
At reactive diluent is glycidyl methacrylate and lauric acid acrylate 1:2 mass ratio is made into, and filler is kaolinite
Soil shakes and becomes agent as urea-modified polyurethane solutions, and levelling agent is the poly- methyl alkyl siloxane of polyester modification, and adhesion promoter is for example
For hydroxyethyl methyl acryloyl phosphate, pigment is titanium dioxide.
Embodiment 12
The ultraviolet light of the embodiment of the present invention cures marking ink, is grouped as by the group of following parts by weight：It is polyurethane-modified soft
Property 35 parts of epoxy acrylate, 4 parts of photoinitiator, 30 parts of reactive diluent, 35 parts of filler, shake become 2 parts of agent, 1 part of levelling agent.Its
In polyurethane-modified flexible epoxy acrylate be made of the method described in embodiment one, photoinitiator be 2- hydroxyl -2- first
Phenylacetone -1 base -1-, reactive diluent are hydroxy-ethyl acrylate, and filler is sulfuric acid dam and talcum powder 1:1 mass ratio is made into, and is shaken
Become agent as modified urea solution, levelling agent is polyether-modified dimethyl silicone polymer, and adhesion promoter is, for example, polyester chloride third
Olefin(e) acid ester, pigment are blue or green blue color.
Comparative example one
Epoxy acrylate is prepared using following methods：By 200g bisphenol A epoxide resins (NPEL-128), 0.9g triphens
Base phosphorus, 72.1g acrylic acid, 0.5g 2,6 di tert butyl 4 methyl phenols are added to 50g dimethacrylates
In, 110 DEG C are heated to, when monitoring acid value in system<When 5mgKOH/g, reaction was completed, obtains bisphenol-A epoxy acrylic acid tree
Fat.
Embodiment 13
The ultraviolet light of the embodiment of the present invention cures marking ink, and each component is configured to by the mass percentage that table one is listed
Ultraviolet light cures marking ink.The each component that table one is listed is uniformly mixed, being ground to fineness with three-roll grinder is less than 12 μm,
250dPa.s is sticked to hydroxyethyl methacrylate tune, obtains ultraviolet light solidification marking ink.The ultraviolet light is cured and is identified
Ink by 100T silk-screen printings in having made on the flexible circuit board surface of solder mask, the circuit board that will be printed
Uv cure machine is crossed, it is 1200mJ/cm to add up light energy2.Marking ink is cured on flexible circuit board to ultraviolet light
Flexibility, adhesive force, abrasion resistance, heat resistance carry out test evaluation.
Table one
Resin A, B, C are to be made in embodiment five, embodiment six, embodiment seven, are respectively used to above-mentioned composition 1,2,3
In, control group resin is bisphenol-A epoxy acrylic resin made from comparative example one.
Photoinitiator TPO：JRCURE-1108 (general trade mark TPO), Tianjin Jiu new materials limited liability company.
Photoinitiator 184：JRCURE-1104 (the general trade mark 184), Tianjin Jiu new materials limited liability company.
IBOA：IBOA/ isobornyl methacrylates, the beautiful sun of Mitsubishi.
(EO)3TMPTA：(EO)3TMPTA, ethoxyquin trimethylolpropane trimethacrylate, Changxing chemical industry.
Talcum powder：Talcum powder, GD-25, Liaoning Dong Yuxin meter Materials Co., Ltd.
Aerosil：Aerosil A200, German Degussa
Titanium dioxide：Titanium dioxide R706, Dupont.
Shake change agent：BYK-R605, German Bi Ke.
Levelling agent：BYK-354, German Bi Ke.
Adhesion promoter：CD9050, U.S.'s Sartomer.
Cure the performance of marking ink below by way of ultraviolet light in experimental test embodiment 13, as a result as shown in Table 2.
1, flexibility
By the flexible printed circuit of coated ultraviolet light solidification marking ink after ultraviolet light cures, 180 ° of bendings 100
It is secondary.Observing bending place marking ink coating, whether there is or not fall oil.For coating without oil is fallen for qualification, it is unqualified to have oil.
2, adhesive force
By the flexible printed circuit of coated ultraviolet light solidification marking ink after ultraviolet light cures, with reference to GB/T9286-
1998《Paint and varnish paint film draws lattice experiment》.Coating has that fall off be unqualified without falling off for qualification.
3, wearability
It is resistance to using RCA paper tapes by the flexible printed circuit of coated ultraviolet light solidification marking ink after ultraviolet light cures
Experimental machine is ground, load 175g, frictional experiment 600 times, observing coating surface has no marking.Coating no marking is qualification, there is cut
It is unqualified.
4, heat resistance
By the flexible printed circuit of coated ultraviolet light solidification marking ink after ultraviolet light cures, surface coating rosin helps
Solder flux, 280 ± 5 DEG C × 10s × 2 time of wicking.It is pullled 3 times with 3M adhesive tapes (600 type), whether there is or not fall off for observation mark ink.Coating
Without oil is fallen for qualification, it is unqualified to have oil.
Table two
| 1 | 2 | 3 | Control group | |
| Flexibility | It is qualified | It is qualified | It is qualified | It is unqualified |
| Adhesive force | It is qualified | It is qualified | It is qualified | It is qualified |
| Wearability | It is qualified | It is qualified | It is qualified | It is unqualified |
| Heat resistance | It is qualified | It is qualified | It is qualified | It is unqualified |
Known by table two, is cured by the ultraviolet light prepared containing polyurethane-modified flexible epoxy acrylic resin in the present embodiment
Marking ink 1,2,3 is compared with ultraviolet light solidification marking ink prepared by common bisphenol A epoxide resin, is both had excellent
Adhesive force.The ultraviolet light solidification mark ink prepared using polyurethane-modified flexible epoxy acrylic resin has superior soft
Toughness, wearability and heat resistance.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
1. a kind of preparation method of polyurethane-modified flexible epoxy acrylic resin, which is characterized in that include the following steps：
Diisocyanate, dibutyl tin laurate, crylic acid hydroxy ester and polymerization inhibitor are separately added into diethylene glycol dimethyl
Acrylate is heated to 50 DEG C -70 DEG C and carries out the first reaction,-the content of NCO group is monitored in reactant, when-NCO bases in
When mass contg is the 50%-55% of initial content, the first reaction terminates, and obtain diisocyanate and crylic acid hydroxy ester half adds
At object；
First carboxyl-terminated polybutadiene, epoxy resin, catalyst and polymerization inhibitor are added in dimethacrylate, added
Heat carries out second to 80-120 DEG C and reacts, and monitors the variation of acid value in reactant, and when acid value is less than 3mgKOH/g, propylene is added
The reaction was continued for acid, and when acid value is less than 5mgKOH/g, the second reaction terminates to obtain flexible epoxy acrylate；
By half addition product of the diisocyanate and crylic acid hydroxy ester and the flexible epoxy crylic acid ester mixture, add
Heat to 50 DEG C -70 DEG C progress third reactions, measure reactant in-NCO group be 0 when, third reaction terminates, obtain polyurethane and change
Property flexible epoxy acrylate.
2. the preparation method of polyurethane-modified flexible epoxy acrylic resin according to claim 1, it is characterised in that：Institute
The molar ratio for stating crylic acid hydroxy ester and the diisocyanate is 1:1-1.1；The diisocyanate and the tin dilaurate
The mass ratio of dibutyl tin is 100：0.1-1；The quality of the diisocyanate and the dimethacrylate
Than being 1:0.2-0.5；The mass ratio of the diisocyanate and the polymerization inhibitor is 100：0.1-1.
3. the preparation method of polyurethane-modified flexible epoxy acrylic resin according to claim 1, it is characterised in that：Institute
State epoxy group in epoxy resin in the carboxyl-terminated polybutadiene-molar ratio of COOH group is 1:0.05-0.3；Institute
The mass ratio for stating epoxy resin and the catalyst is 100:0.1-1；The epoxy resin is with the polymerization inhibitor mass ratio
100:0.1-1；In the epoxy resin and the acrylic acid-molar ratio of COOH group is 1:0.7-0.9.
4. the preparation method of polyurethane-modified flexible epoxy acrylic resin according to claim 1, it is characterised in that：Institute
State in flexible epoxy acrylate in half addition product of side-OH groups and diisocyanate and crylic acid hydroxy ester-NCO group
Molar ratio is 1:0.1-0.5.
5. a kind of polyurethane-modified flexible epoxy acrylic resin, it is characterised in that：Gathered by claim 1-7 any one of them
The preparation method that urethane is modified flexible epoxy acrylic resin is made.
6. a kind of ultraviolet light cures marking ink, which is characterized in that include the component of following parts by weight：
The polyurethane-modified flexible epoxy acrylate is by the polyurethane-modified flexible epoxy of claim 1-7 any one of them
The preparation method of acrylic resin is made.
7. ultraviolet light according to claim 6 cures marking ink, which is characterized in that further include the group of following parts by weight
Point：
8. ultraviolet light according to claim 7 cures marking ink, which is characterized in that the ultraviolet light cures marking ink
For flexible circuit board.
9. a kind of flexible circuit board, which is characterized in that including circuit board body and be attached in the circuit board body
Identification piece, the identification piece are formed by curing by the ultraviolet light solidification marking ink described in claim 6 or 7.
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| CN201810259469.5A CN108341921B (en) | 2018-03-27 | 2018-03-27 | Polyurethane modified flexible epoxy acrylic resin, preparation method thereof, photocuring identification ink and flexible printed circuit board |
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| CN201810259469.5A CN108341921B (en) | 2018-03-27 | 2018-03-27 | Polyurethane modified flexible epoxy acrylic resin, preparation method thereof, photocuring identification ink and flexible printed circuit board |
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| CN110183616A (en) * | 2019-05-29 | 2019-08-30 | 三求(德庆)光固材料有限公司 | Polyfunctionality urethane acrylate and its preparation method and application |
| CN110698642A (en) * | 2019-09-18 | 2020-01-17 | 江南大学 | Polyurethane modified epoxy acrylate resin and preparation method thereof |
| CN111171282A (en) * | 2020-01-22 | 2020-05-19 | 黎明化工研究设计院有限责任公司 | Method for synthesizing polyurethane-epoxy acrylate |
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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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| CN111171282B (en) * | 2020-01-22 | 2022-02-08 | 黎明化工研究设计院有限责任公司 | Method for synthesizing polyurethane-epoxy acrylate |
| CN111171282A (en) * | 2020-01-22 | 2020-05-19 | 黎明化工研究设计院有限责任公司 | Method for synthesizing polyurethane-epoxy acrylate |
| CN112646538A (en) * | 2020-12-22 | 2021-04-13 | 深圳市宏进科技有限公司 | Novel UV thermal dual-curing adhesive and preparation method thereof |
| CN113174030A (en) * | 2021-06-03 | 2021-07-27 | 东胜化学(上海)有限公司 | PCB solder resist ink resin and preparation method thereof |
| CN113512341A (en) * | 2021-07-30 | 2021-10-19 | 华南农业大学 | Graphene oxide/epoxy vinyl ester resin heavy-duty anti-corrosion solvent-free composite coating and preparation method and application thereof |
| CN113698563A (en) * | 2021-08-05 | 2021-11-26 | 明光科迪新材料有限公司 | Thioxanthone polyurethane modified epoxy acrylate LED (light-emitting diode) photocuring resin |
| CN113912823A (en) * | 2021-09-23 | 2022-01-11 | 肇庆市宝骏化工有限公司 | Polyurethane and anhydride modified hydrogenated bisphenol A epoxy acrylic resin and preparation method and application thereof |
| CN114106291A (en) * | 2021-12-28 | 2022-03-01 | 巩义市泛锐熠辉复合材料有限公司 | Toughening auxiliary agent, preparation method and application thereof in unsaturated resin |
| CN116855130A (en) * | 2023-07-07 | 2023-10-10 | 佛山市迈瑞思科技有限公司 | Inkjet printing ink for calcium silicate board and preparation method thereof |
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