CN117534983A - Application method of high-glass-transition-temperature photo-curing solder resist ink - Google Patents
Application method of high-glass-transition-temperature photo-curing solder resist ink Download PDFInfo
- Publication number
- CN117534983A CN117534983A CN202310860092.XA CN202310860092A CN117534983A CN 117534983 A CN117534983 A CN 117534983A CN 202310860092 A CN202310860092 A CN 202310860092A CN 117534983 A CN117534983 A CN 117534983A
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- CN
- China
- Prior art keywords
- epoxy resin
- photo
- curing
- alkyne
- solder resist
- 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.)
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 92
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003822 epoxy resin Substances 0.000 claims abstract description 102
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 102
- 239000000178 monomer Substances 0.000 claims abstract description 64
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 230000009477 glass transition Effects 0.000 claims abstract description 35
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims description 28
- LUEHNHVFDCZTGL-UHFFFAOYSA-N but-2-ynoic acid Chemical group CC#CC(O)=O LUEHNHVFDCZTGL-UHFFFAOYSA-N 0.000 claims description 25
- 239000003112 inhibitor Substances 0.000 claims description 22
- -1 cyclic ester Chemical group 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 125000003700 epoxy group Chemical group 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 13
- 150000008065 acid anhydrides Chemical class 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 12
- 239000004843 novolac epoxy resin Substances 0.000 claims description 12
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 12
- 239000002685 polymerization catalyst Substances 0.000 claims description 11
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 10
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 8
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 8
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 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 claims description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000002474 experimental method Methods 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000005886 esterification reaction Methods 0.000 abstract description 5
- 238000007142 ring opening reaction Methods 0.000 abstract description 4
- 239000000976 ink Substances 0.000 description 81
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 125000000304 alkynyl group Chemical group 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 7
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005476 soldering Methods 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- YIIPOGLCNUDSBG-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.OCC(CO)(CO)CO YIIPOGLCNUDSBG-UHFFFAOYSA-N 0.000 description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
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- RTWCHRMHGXBETA-UHFFFAOYSA-N prop-1-yn-1-amine Chemical compound CC#CN RTWCHRMHGXBETA-UHFFFAOYSA-N 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 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
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WUKLIEYWIVJLAT-UHFFFAOYSA-N 3-[tris(3-sulfanylpropyl)silyl]propane-1-thiol Chemical compound SCCC[Si](CCCS)(CCCS)CCCS WUKLIEYWIVJLAT-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- UHMARZNHEMRXQH-UHFFFAOYSA-N 3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CCCC2C(=O)OC(=O)C21 UHMARZNHEMRXQH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- MINRDQDGBLQBGD-UHFFFAOYSA-N pent-2-ynoic acid Chemical compound CCC#CC(O)=O MINRDQDGBLQBGD-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
-
- 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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides an application method of high glass transition temperature photo-curing solder resist ink, which mainly comprises alkyne-containing active monomer modified alkali-soluble photo-curing epoxy resin and a photoinitiator, wherein the alkyne-containing active monomer modified alkali-soluble photo-curing epoxy resin is prepared by performing ring opening reaction on epoxy resin and alkyne-containing active monomer, and then performing esterification reaction on the epoxy resin and unsaturated anhydride. The invention prepares the photo-curing solder resist ink with high glass transition temperature by grafting modified epoxy resin with alkyne-containing active monomer, and is suitable for the production and manufacture of PCB substrates for development and application in high-end fields. In addition, experiments show that when the high glass transition temperature photo-curing solder resist ink is applied, the high glass transition temperature can still be realized when the three-bond conversion rate is low under specific curing conditions, and the traditional knowledge of the curing conditions and the unsaturated bond conversion rate in the past is broken.
Description
The application is a divisional application, and the original application number is: 202210645518.5, filing date: 2022, 6-8, title: a novel photo-curable solder resist ink having a high glass transition temperature.
Technical Field
The invention belongs to the technical field of photo-curing solder resist ink, and particularly relates to novel photo-curing solder resist ink with high glass transition temperature.
Background
A printed circuit board (Printed circuit board, abbreviated as PCB), which is the substrate for modern electrical installation and connection elements, is an important basic assembly in the electronics industry.
The photo-curing solder resist ink is one of key materials of a Printed Circuit Board (PCB), and is a protective coating covered on a printed circuit copper wire, so as to prevent circuit corrosion and disconnection, prevent short circuit between wires caused by a plurality of solder joints, adjust the attachment amount of soldering tin, reduce the dissolved pollution of copper in the solder joints, save soldering tin, reduce the weight of an instrument, increase the high density of wiring, avoid cold solder joint and improve the inspection speed.
With the advent of high frequency communications, PCB substrates have also evolved to high density and fine, with higher and higher performance requirements for solder resist coatings. In general, the PCB is processed through a lead soldering process of 260 ℃ or higher, namely, a soldering heat treatment resistant is required, wherein the glass transition temperature of solder resist ink is the most critical.
Conventional photo-curing solder resist ink is generally composed of components such as a polymerization monomer, a photoinitiator, a polymerization inhibitor and the like. Currently, a large number of photo-curable solder resist inks are used in solder resist films, which generally include a photopolymerization initiator and a photo-curable and thermosetting resin composition containing carboxyl groups. The photo-curable and thermosetting resin is generally epoxy acrylic resin, and has the advantages of good photo-curability, developability, mechanical properties and the like, but the cured film has low crosslinking density after curing, so that the cured film has poor heat resistance, is easy to foam or drop oil during soldering, and cannot meet the requirements on high-requirement electrical circuit boards. In addition, the resolution is low, and the solder resist ink is not suitable for manufacturing high-precision circuit boards and is not beneficial to development and application of solder resist ink in high-end fields.
Through long-term research experience summary of the inventor and reference to the prior art documents, in order to improve the glass transition temperature of the photo-curing solder resist ink, the prior art personnel mostly adopts modified photo-curing epoxy resin to improve the content of unsaturated double bonds in an ink system, and further improve the crosslinking density, so as to obtain the solder resist ink with high glass transition temperature.
For example, the inventor of the present invention previously issued the patent "a high heat-resistant high crosslinking degree photo-curing solder mask ink and its preparation method" (CN 110527350B) by increasing the hydroxyl density of the system, increasing the unsaturated double bond density in the system, and increasing the crosslinking density after curing, so that the cured product has good heat resistance. However, in the above technical solution, it is obvious that in order to increase the density of unsaturated double bonds in the system, on one hand, it is necessary to replace acrylic acid on the photo-curing epoxy resin by selecting dihydroxy group carboxylic acid with longer carbon chain and more branched chain, and on the other hand, it is necessary to add unsaturated anhydride with double molar quantity corresponding to more hydroxyl groups, so as to achieve higher double bond density, and further, the product has higher crosslinking density.
In the specific production practice of the prior patent, when the content of the added unsaturated anhydride is larger than a certain value (the threshold values of different systems possibly differ), the double bond content is overlarge in the resin synthesis process, the air resistance effect in the system is enhanced, the gel phenomenon easily occurs in the preparation process, the reaction is failed, and the preparation is difficult; when the addition amount of the acid anhydride is too large, the acid value of the prepared solder resist ink is too high, and the solder resist ink is easy to develop excessively when in use. Meanwhile, when the chain length of the grafted compound in the system is large, namely the flexible chain density in the system is increased, the glass transition temperature of the cured material is reduced, and the heat resistance of the material is damaged.
Therefore, from a new perspective, it is necessary to provide a high glass transition temperature photo-curable solder resist ink which has both excellent heat resistance and excellent product quality.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides novel photo-curing solder resist ink with high glass transition temperature, which is prepared by grafting modified epoxy resin with alkyne-containing active monomer.
In order to achieve the above object, the present invention is realized by adopting the technical scheme comprising the following technical measures.
The novel photo-curing solder resist ink with high glass transition temperature mainly comprises the following raw materials in parts by weight:
100 parts of alkali-soluble photo-curing epoxy resin modified by alkyne-containing active monomer,
1-10 parts of photoinitiator;
the alkali-soluble photo-curing epoxy resin modified by the alkyne-containing active monomer is prepared by performing ring-opening reaction on the epoxy resin and the alkyne-containing active monomer, and then performing esterification reaction on the epoxy resin and unsaturated anhydride;
the alkyne-containing active monomer is a monomer with a molecular structure containing an active group capable of reacting with epoxy groups and at least one alkynyl, and the number of carbon atoms is not higher than 5;
the unsaturated anhydride is any one of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride;
the addition of the alkyne-containing active monomer is carried out according to the mole ratio of the alkyne-containing active monomer to the epoxy group of the epoxy resin of (1-1.2): 1 is added in such a manner that the molar ratio of the unsaturated acid anhydride to the epoxy group of the epoxy resin is (1 to 1.2): 1.
Wherein the epoxy resin is selected from the epoxy resins with the viscosity of 700-20000 mPas and the epoxy equivalent of 180-280 g/eq at 25 ℃.
Preferably, the epoxy resin is selected from any one of bisphenol a type epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, p-tert-butylphenol novolac epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl phthalate, diglycidyl tetrahydrophthalate, triglycidyl isocyanurate, and dicyclodiene epoxide.
Typically, the photoinitiator is one commonly known in the art of photo-curable solder resist inks, and a person skilled in the art can choose a suitable photoinitiator by himself according to prior art documents or actual process conditions.
Typically, the alkyne-containing active monomer is a monomer containing an active group capable of reacting with an epoxy group and at least one alkynyl group in a molecular structure, wherein the active group capable of reacting with the epoxy group comprises any one of carboxyl, amino and anhydride.
In order to further reduce the influence of steric hindrance, it is preferable that the number of active groups capable of reacting with epoxy groups is 1 in the alkyne-containing active monomer, and the number of alkyne groups is 1 in the alkyne-containing active monomer.
To better illustrate the invention and to provide a choice of alkyne-containing reactive monomer that can be referenced, the alkyne-containing reactive monomer is preferably any one of propiolic acid, 2-butynoic acid, 1-pentynoic acid, 2-pentynoic acid, and propioamine.
The invention is characterized in that unsaturated bonds are provided through alkynyl groups, one mole of alkynyl groups have two moles of unsaturated degrees, and one mole of unsaturated degrees are larger than one mole of alkenyl groups, so that a network space structure with larger crosslinking density can be formed in the crosslinking curing process theoretically. Therefore, one mole of alkynyl can replace two moles of alkenyl, so that the steric hindrance effect in the system can be reduced, and the crosslinking reaction efficiency is higher.
For better illustrating the principles of the present invention, one of the technical solutions will be described by taking an example:
when the unsaturated acid anhydride is selected to be tetrahydrophthalic anhydride, and when the alkyne-containing reactive monomer is selected to be propiolic acid or 2-butynoic acid, the reaction scheme of the alkyne-containing reactive monomer modified alkali-soluble photocurable epoxy resins (named (a) EPAT and (b) EBAT, respectively) is as follows:
through the reaction route, it is obvious that each mole of epoxy groups can correspond to one mole of propiolic acid or 2-butynoic acid through ring opening reaction, so that one mole of unsaturated triple bonds are introduced, each branched chain of the obtained product has 1 hydroxyl group, and 1 mole of unsaturated anhydride (especially monoanhydride) can correspond to 1 mole of unsaturated anhydride through esterification reaction, and at the moment, each branched chain of the obtained product has 1 carboxyl group, so that the alkyne-containing active monomer modified alkali-soluble photocurable epoxy resin is obtained.
Further, when the alkyne-containing active monomer is selected, according to the common knowledge in the art, the activity of the propiolic acid is higher than that of 2-butynoic acid due to the terminal alkynyl group, so that the conversion rate of unsaturated triple bonds is higher than that of the photocuring solder resist ink prepared by adopting 2-butynoic acid in the photocuring process, for example, the photocuring conversion rate is 98.5% under the conditions of ultraviolet irradiation for 40min and heat curing for 1h, and the photocuring conversion rate is only 38.5% under the same conditions of the photocuring solder resist ink prepared by adopting 2-butynoic acid. The degree of photocuring conversion can be laterally stated, that is, only by the above comparative experiment, it can be considered that the crosslinking density of the coating film by selecting the propiolic acid technical scheme is higher than that of the coating film by selecting the 2-butynoic acid technical scheme, so that the glass transition temperature of the former coating film should be significantly higher than that of the latter coating film theoretically without considering the influence of steric hindrance.
However, the inventors of the present invention have unexpectedly found that, when experiments are conducted, the obtained photo-curable solder resist ink is actually prepared using propiolic acid, and the glass transition temperature of the coating film after use is 140.6 ℃; the glass transition temperature of the coating film after the use of the photo-curing solder resist ink prepared by using 2-butynoic acid is 143.2 ℃, the experimental result obviously does not accord with the theory, and the technical effect of the prepared product obviously exceeds the expectation of the person skilled in the art. The mechanism why the technical solution employing 2-butynoic acid has a higher glass transition temperature is unclear.
It is important to note that the inventors have also found, through control experiments, that the choice of unsaturated anhydride is a key element. The inventor found by comparing the conventional unsaturated acid anhydride in the field that when the unsaturated acid anhydride is selected to be itaconic anhydride, maleic anhydride and other conventional unsaturated acid anhydrides, a very serious gel phenomenon occurs after the esterification reaction, but the photo-curing solder resist ink cannot be further prepared, and the same phenomenon occurs after other types of epoxy resins are replaced. Therefore, through practical experiments, the unsaturated anhydride in the technical scheme of the invention can be limited to any one of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.
The above-mentioned gelation phenomenon is presumably caused by the excessively high activity of the alkynyl group, which is similar to the gelation phenomenon caused by the relatively complex spatial conformation and the excessively large addition ratio of the acid anhydride in the prior art of the invention of the photo-curing solder resist ink suitable for high frequency communication and the preparation method thereof, but in the experimental record of the prior art of the invention, the above-mentioned gelation phenomenon can be prevented by adjusting the molar amount of the unsaturated acid anhydride, and only when the unsaturated acid anhydride is added in a large amount (the addition of the unsaturated acid anhydride is performed in a molar ratio of the unsaturated acid anhydride to the epoxy group of the epoxy resin of 4:1). In the case of adding an appropriate amount of unsaturated anhydride (the unsaturated anhydride is added in a mode of a molar ratio of 1:1 with the epoxy group of the epoxy resin), a very serious gel phenomenon occurs, so that a solder resist ink product cannot be prepared. The cause of the technical problem cannot be reasonably inferred. Therefore, the fact based on experimental facts is that the technical scheme of the invention only limits the selection of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride which are proved by experiments to be free from gel phenomenon as unsaturated anhydrides.
Further, in order to better illustrate the present invention, there is provided a method for preparing an alkali-soluble photocurable epoxy resin modified with an alkyne-containing reactive monomer, which can be referred to as follows:
(1) Preheating a solvent to 70-90 ℃ in a nitrogen atmosphere, adding epoxy resin, dissolving the epoxy resin, cooling to 50-60 ℃, adding an alkyne-containing active monomer and a polymerization inhibitor, heating to 70-80 ℃, adding a cyclic ester ring-opening polymerization catalyst, heating to 80-120 ℃, stirring and reacting for 3-6 hours until the acid value of a reaction solution is less than 3mgKOH/g, and obtaining an epoxy resin solution containing alkyne-containing active monomer;
(2) And (2) cooling the epoxy resin solution containing the alkyne active monomer obtained in the step (1) to 70-80 ℃, then adding unsaturated anhydride and polymerization inhibitor to mix, and continuing stirring and reacting for 3-7 hours at the temperature of 90-100 ℃ to obtain the alkali-soluble photo-curing epoxy resin modified by the alkyne active monomer.
Generally, the cyclic ester ring-opening polymerization catalyst in the step (1) is a cyclic ester ring-opening polymerization catalyst commonly used in the epoxy resin ring-opening polymerization reaction in the technical field, and a person skilled in the art can select a suitable cyclic ester ring-opening polymerization catalyst according to actual requirements. For more convenience in explaining the present invention, it is preferable that the cyclic ester ring-opening polymerization catalyst in the step (1) is one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylammonium chloride, N-dimethylbenzylamine and triphenylphosphine; the addition amount of the cyclic ester ring-opening polymerization catalyst is 0.2-1 wt% of the epoxy resin.
Generally, the solvent in step (1) is a solvent commonly used in the art for preparing epoxy resin into an epoxy resin solution, and a person skilled in the art can select a suitable solvent according to the choice and actual requirements of the epoxy resin. In order to more conveniently illustrate the invention, the solvent in the step (1) is at least one of dibasic ester high-boiling point environment-friendly solvent, ethylene glycol diethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether, propylene glycol methyl ether, trimethylbenzene and tetramethylbenzene; in step (1), the mass of the solvent: epoxy resin mass= (0.5-1.5): 1.
in step (1), the alkyne-containing active monomer is added, and in order to improve the reaction efficiency and reduce the loss caused by sticking the solid reactant to the wall of the reaction vessel, the alkyne-containing active monomer is usually dissolved in a proper amount of solvent and then added; the solvent may be the same solvent as the above-mentioned solvent in which the epoxy resin is dissolved.
In step (1), the cyclic ester ring-opening polymerization catalyst is added, and in order to improve the reaction efficiency and reduce the loss caused by the adhesion of the solid reactant and the wall of the reaction vessel, the cyclic ester ring-opening polymerization catalyst is usually selected to be dissolved in a proper amount of solvent and then added; the solvent may be the same solvent as the above-mentioned solvent in which the epoxy resin is dissolved.
In step (2), the unsaturated anhydride is added, and in order to improve the reaction efficiency and reduce the loss caused by the adhesion of the solid reactant and the wall of the reaction vessel, the unsaturated anhydride is usually selected to be dissolved in a proper amount of solvent and then added; the solvent may be the same solvent as the above-mentioned solvent in which the epoxy resin is dissolved.
Wherein, the polymerization inhibitor in the step (1) and the step (2) is a polymerization inhibitor commonly used in photo-curing solder resist ink in the technical field, and a proper polymerization inhibitor can be selected by a person skilled in the technical field according to the selection and actual requirements of the epoxy resin. For more convenience in explaining the present invention, the polymerization inhibitor in the steps (1) and (2) is selected from at least one of hydroquinone, o-methyl hydroquinone, p-hydroxyanisole, p-benzoquinone and 2, 6-di-tert-butyl-4-methylphenol. Preferably, the polymerization inhibitor added twice is the same polymerization inhibitor, and the addition amount of the polymerization inhibitor is 0.4-2.5 wt% of the epoxy resin in the step (1).
In general, the stirring reaction in the steps (1) and (2) is a stirring reaction conventionally used in the art, including magnetic stirring or mechanical stirring, and a person skilled in the art can select a suitable stirring reaction mode according to the production scale or the current state of the process conditions. To better illustrate the present invention and to provide a process scheme suitable for laboratory operating environments, the agitation reaction may be carried out at an agitation rate of 100 to 300 rpm.
Further, the novel photo-curing solder resist ink with high glass transition temperature mainly comprises the following raw materials in parts by weight:
in order to improve the physical strength of the coating film after the use of the solder resist ink, the solder resist ink comprises a filler which is one or more of known conventional inorganic or organic fillers, preferably titanium pigment, bentonite, barium sulfate, spherical silica, nano calcium carbonate and talc, and further preferably a known conventional metal oxide which is both a filler and a pigment.
Wherein the additive is one or a combination of more of pigment, thermal polymerization inhibitor, tackifier, defoamer, leveling agent, coupling agent, antioxidant and antirust agent. In general, the above pigments, thermal inhibitors, tackifiers, defoamers, leveling agents, coupling agents, antioxidants and rust inhibitors are known and customary.
The preparation method of the novel photo-curing solder resist ink with high glass transition temperature can be used for preparing the novel photo-curing solder resist ink by mixing all components according to the prior art. For example, after the components are mixed in a stirrer, the components are milled and mixed by a three-roller mill, and the novel photo-curing solder resist ink is obtained.
When the solder resist ink is used, it is applied to a substrate, dried appropriately (about 60 to 120 ℃), exposed to light through a pattern film or the like to obtain a cured coating film, and the unexposed portion is developed. In the development, the solvent may be used for the solvent development, or a known and customary halogen-based solvent such as trichloroethylene may be used, but since carboxyl groups are introduced into the alkali-soluble photocurable epoxy resin modified with an alkyne-containing reactive monomer, the unexposed portions are dissolved in an alkali aqueous solution, and alkali development is preferable. Alkali metal compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. can be selected for alkaline solvent development; alkaline earth metal compounds such as calcium hydroxide and the like can also be selected; alkaline solution ammonia water can also be selected; water-soluble organic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine, and the like may also be selected.
After development, the photo-cured coating film is preferably further heat-cured by heat treatment at about 140 to 200℃for 1 hour.
In general, the above-described novel photo-curable solder resist ink having a high glass transition temperature may be used in a state having a dry film of a solder resist layer formed by coating and drying a film of PET or the like in advance, in addition to a method of directly coating the ink in a liquid state onto a substrate.
Further, although the glass transition temperature of the photo-curing solder mask ink after use can be greatly increased by adopting the technical scheme, the inventor of the invention notes that the novel photo-curing solder mask ink prepared by adopting the technical scheme needs long time ultraviolet light curing or adopts a heat curing auxiliary mode to achieve better coating quality.
Therefore, in order to improve the photo-curing reaction rate, the invention also provides an improvement scheme:
the novel photo-curing solder resist ink prepared by utilizing click chemistry reaction mainly comprises the following raw materials in parts by weight:
100 parts of alkali-soluble photo-curing epoxy resin modified by alkyne-containing active monomer,
10 to 20 parts of a thiol compound,
3-5 parts of photoinitiator;
the alkali-soluble photo-curing epoxy resin modified by the alkyne-containing active monomer is prepared by performing ring-opening reaction on the epoxy resin and the alkyne-containing active monomer, and then performing esterification reaction on the epoxy resin and unsaturated anhydride;
the alkyne-containing active monomer is a monomer with a molecular structure containing an active group capable of reacting with epoxy groups and at least one alkynyl, and the number of carbon atoms is not higher than 5;
the unsaturated anhydride is any one of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride;
the addition of the alkyne-containing active monomer is carried out according to the mole ratio of the alkyne-containing active monomer to the epoxy group of the epoxy resin of (1-1.2): 1 is added in such a manner that the molar ratio of the unsaturated acid anhydride to the epoxy group of the epoxy resin is (1 to 1.2): 1.
In the improvement, the thiol-alkyne reaction is generated by adding the thiol compound, and is a free radical mediated click reaction, and the reaction is carried out in two steps: thiols add to the carbon-carbon triple bond to form an intermediate vinyl thioether, which then reacts with the remaining thiol to form a 1, 2-bis-adduct. By adding the click reaction, the photo-curing reaction rate of the novel photo-curing solder resist ink prepared is greatly improved.
Wherein the mercaptan compound comprises any one of dipentaerythritol hexa (3-mercaptopropionate), tetra (3-mercaptopropyl) trimethoxysilane, tetra (3-mercaptopropionic) pentaerythritol ester and the like, but is not limited to the mercaptan compound. The person skilled in the art can choose the appropriate thiol compound according to the thiol-alkyne reaction described above.
Through a control experiment, under the condition of ultraviolet light curing for 20min, the photocuring solder resist ink prepared by adopting the method is not added with thiol compounds, and the photocuring conversion rate is 16.79 percent (propiolic acid) and 3.61 percent (2-butynoic acid) respectively; the novel photo-curing solder resist ink is prepared by adding mercaptan compounds and utilizing click chemistry reaction, and the photo-curing conversion rate is 82.13% (propiolic acid) and 52.59% (2-butynoic acid) respectively.
Further, the novel photo-curing solder resist ink prepared by utilizing click chemistry reaction mainly comprises the following raw materials in parts by weight:
the specific selection and precautions of the above raw materials, the methods of use and the methods of application may be adjusted by referring to the above technical solutions or according to the actual situation of the person skilled in the art.
The invention has the following beneficial effects:
1. according to the invention, the alkyne-containing active monomer is grafted to modify the epoxy resin, so that the crosslinking density after curing is increased, and the epoxy resin is endowed with high glass transition temperature, so that the epoxy resin is suitable for the production and manufacture of PCB substrates for development and application in the high-end field.
2. According to the technical scheme, through practical experiments, the application coating film of the novel photo-curing solder resist ink prepared by adopting the alkali-soluble photo-curing epoxy resin modified by the 2-butynoic acid with lower activity has better glass transition temperature.
3. According to the technical scheme, through practical experiments, the unsaturated anhydride is found to be selected as a key element. In the technical scheme of the invention, unsaturated anhydride can be limited to any one of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, so that the phenomenon of gel in the preparation process is avoided.
4. The preparation method is simple, the reaction degree of each step is high, and the influence of the related side reaction is small, so that the overall quality of the product is improved. The technical scheme of the invention is suitable for industrial application and popularization.
Drawings
FIG. 1 is a photograph showing the results of the alkali-soluble photocurable epoxy resin containing a modification of propiolic acid and the alkali-soluble photocurable epoxy resin (EBAT) containing a modification of 2-butynoic acid prepared in Synthesis example 1 and Synthesis example 2 of the present invention.
FIG. 2 is an infrared spectrum of the alkali-soluble photocurable epoxy resin containing the modification of propiolic acid and the alkali-soluble photocurable epoxy resin (EBAT) containing the modification of 2-butynoic acid prepared in Synthesis example 1 and Synthesis example 2 of the present invention.
FIG. 3 is a graph showing the comparative curves of thermal weight loss of coating films under different curing conditions of the photo-curable solder resist ink prepared in example 3 and the photo-curable solder resist ink prepared in example 4 according to the present invention. In the figure, subscripts 20, 60 and 20-1 respectively refer to ultraviolet light curing for 20min, ultraviolet light curing for 60min and reheat curing for 1h after ultraviolet light curing for 20 min.
FIG. 4 is a graph showing the comparison of the loss tangent curves of the DMA test of the photo-curable solder resist inks prepared in examples 1 to 4 of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given should not be construed as limiting the scope of the present invention, but rather as merely providing for the benefit of this disclosure.
In the following examples, reagents and instrumentation were used:
epoxy cresol novolac (EOCN, epoxy equivalent 200-230 g/equiv) is supplied by guangdong ink technologies, inc.
The catalyst 4-Dimethylaminopyridine (DMAP), the polymer inhibitor Hydroquinone (HQ) and 1-hydroxycyclohexyl phenyl ketone (photoinitiator 184) for photopolymerization were all purchased from Chengdu China chemical company, inc.
1,2,5, 6-tetrahydrophthalic anhydride (THPA), pentaerythritol tetrakis (3-mercaptopropionic acid), ethanol and ethyl 2- (2-ethoxyethoxy) acetate (DCAC) were supplied as solvents by Chenopodium chemical engineering reagent factories.
Propiolic acid was purchased from alfa elsa chemical company.
2-butynoic acid was purchased from hadamard corporation.
Fourier transform infrared (FT-IR) was measured using a Nicolet 560 fourier transform infrared spectrometer; the thermal stability of the samples was determined by TG 209F1 thermogravimetric analyzer (Netzsch, germany).
The infrared testing method comprises the following steps: the resin is coated on the surface of the potassium bromide flaky crystal and tested by adopting a transmission method;
the thermal weight loss test method comprises the following steps: weighing 3-8 mg of cured film sample, and heating from 25 ℃ to 700 ℃ per minute at 10 ℃ under the protection of nitrogen;
the DMA test method comprises the following steps: the cured film was formed into bars of about 15-25 um thick, 8mm wide and 10-12 mm long, and tested at a frequency of 1Hz with a temperature rise of 5 degrees Celsius per minute from 25 to 200 degrees Celsius.
Specific parameters of ultraviolet curing: ultraviolet wavelength: 395nm, intensity: 25.0mW/cm 2 。
Specific parameters for thermal curing are: the oven was air-dried at 150℃and heat-cured for 1 hour.
Synthesis example 1
The preparation method of the alkyne-containing active monomer modified alkali-soluble photo-curable epoxy resin comprises the following steps:
(1) Under nitrogen atmosphere, adding 100g of diethylene glycol diethyl ether acetate (DCAC) into a 1L three-neck flask with a stirrer, heating to 85 ℃, adding 100g of phenolic epoxy resin (EOCN), keeping the temperature for one hour to fully dissolve, cooling to 60 ℃, adding 1g of propiolic acid and polymerization inhibitor hydroquinone which are dissolved in 40g of diethylene glycol diethyl ether acetate (DCAC), heating to 70 ℃, adding 1g of catalyst 4-dimethylaminopyridine which is dissolved in 1g of diethylene glycol diethyl ether acetate, keeping the temperature at 90 ℃, stirring and reacting for 1 hour, heating to 100 ℃ and keeping the temperature and stirring and reacting for 5 hours, and obtaining the epoxy resin solution containing propiolic acid groups when the acid value of the reaction solution is less than 3 mgKOH/g;
(2) And (3) cooling the epoxy resin containing the propargyl acid group obtained in the step (1) to 80 ℃, adding 71g of tetrahydrophthalic anhydride (THPA) and 0.5g of hydroquinone serving as a polymerization inhibitor dissolved in 70g of diethylene glycol diethyl ether acetate, heating to 95 ℃, stirring and reacting for 3 hours, and thus obtaining the alkali-soluble photo-curing epoxy resin containing the propargyl acid modification.
The alkali-soluble photocurable epoxy resin containing the modification of propiolic acid obtained in this synthesis example was designated as EPAT.
Synthesis example 2
The preparation method of the alkyne-containing active monomer modified alkali-soluble photo-curable epoxy resin comprises the following steps:
(1) Under nitrogen atmosphere, adding 100g of diethylene glycol diethyl ether acetate (DCAC) into a 1L three-neck flask with a stirrer, heating to 85 ℃, adding 100g of phenolic epoxy resin (EOCN), keeping the temperature for one hour to fully dissolve, cooling to 60 ℃, adding 1g of butynoic acid 39g and hydroquinone inhibitor dissolved in 40g of diethylene glycol diethyl ether acetate (DCAC), heating to 70 ℃, adding 1g of catalyst 4-dimethylaminopyridine dissolved in 1g of diethylene glycol diethyl ether acetate, keeping the temperature at 90 ℃, stirring and reacting for 1 hour, heating to 100 ℃ and keeping the temperature and stirring and reacting for 5 hours until the acid value of the reaction solution is less than 3mgKOH/g, and obtaining the epoxy resin solution containing 2-butynoic acid groups;
(2) And (3) cooling the epoxy resin containing the 2-butynoic acid group obtained in the step (1) to 80 ℃, adding 71g of tetrahydrophthalic anhydride (THPA) and 0.5g of hydroquinone serving as a polymerization inhibitor dissolved in 70g of diethylene glycol diethyl ether acetate, heating to 95 ℃, stirring and reacting for 3 hours, and thus obtaining the alkali-soluble photo-curing epoxy resin containing the 2-butynoic acid modification.
The alkali-soluble photocurable epoxy resin containing 2-butynoic acid modification obtained in this synthesis example was designated as EBAT.
Example 1
The novel photo-curing solder resist ink with high glass transition temperature in the embodiment mainly comprises the following raw materials in parts by weight:
100 parts of an EPAT, which is used for the production of a product,
3 parts of a photoinitiator;
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Through testing, when the photo-curing condition is that ultraviolet light irradiates for 40min and then is thermally cured for 1h, the glass transition temperature of the coating film is 140.6 ℃.
Example 2
The novel photo-curing solder resist ink with high glass transition temperature in the embodiment mainly comprises the following raw materials in parts by weight:
100 parts of an EBAT (electronic toll Collection),
3 parts of a photoinitiator;
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Through testing, when the photo-curing condition is that ultraviolet light irradiates for 40min and then is thermally cured for 1h, the glass transition temperature of the coating film is 143.2 ℃.
Example 3
The novel photo-curing solder resist ink is prepared by utilizing click chemistry reaction, and the raw materials of the novel photo-curing solder resist ink mainly comprise the following components in parts by weight:
100 parts of an EPAT, which is used for the production of a product,
15 parts of pentaerythritol tetra (3-mercaptopropionic acid),
3 parts of a photoinitiator;
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Through testing, when the photo-curing condition is that ultraviolet light irradiates for 40min and then is thermally cured for 1h, the glass transition temperature of the coating film is 100.4 ℃;
example 4
The novel photo-curing solder resist ink is prepared by utilizing click chemistry reaction, and the raw materials of the novel photo-curing solder resist ink mainly comprise the following components in parts by weight:
100 parts of an EBAT (electronic toll Collection),
15 parts of pentaerythritol tetra (3-mercaptopropionic acid),
3 parts of a photoinitiator;
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Through testing, when the photo-curing condition is that ultraviolet light irradiates for 40min and then is thermally cured for 1h, the glass transition temperature of the coating film is 105.8 ℃.
The photo-curable solder resist inks prepared in examples 1 to 4 above were then tested for triple bond conversion under different curing conditions, and the results are shown in the following table:
synthesis of comparative example 1
The tetrahydrophthalic anhydride (THPA) in synthesis example 1 was replaced with itaconic anhydride, and the remaining process conditions were identical to those of synthesis example 1.
During the reaction stirred for 3 hours at the temperature of 95 ℃ in the step (2), a very serious gel phenomenon occurs, so that the reaction cannot be continued.
Synthesis of comparative example 2
The process conditions were the same as in Synthesis example 1 except that tetrahydrophthalic anhydride (THPA) in Synthesis example 1 was replaced with maleic anhydride.
During the reaction stirred for 3 hours at the temperature of 95 ℃ in the step (2), a very serious gel phenomenon occurs, so that the reaction cannot be continued.
Synthesis of comparative example 3
The tetrahydrophthalic anhydride (THPA) in synthesis example 2 was replaced with itaconic anhydride, and the remaining process conditions were identical to those of synthesis example 2.
During the reaction stirred for 3 hours at the temperature of 95 ℃ in the step (2), a very serious gel phenomenon occurs, so that the reaction cannot be continued.
Synthesis of comparative example 4
The tetrahydrophthalic anhydride (THPA) in synthesis example 2 was replaced with maleic anhydride, and the remaining process conditions were identical to those of synthesis example 2.
During the reaction stirred for 3 hours at the temperature of 95 ℃ in the step (2), a very serious gel phenomenon occurs, so that the reaction cannot be continued.
Synthesis example 3
The preparation method of the alkyne-containing active monomer modified alkali-soluble photo-curable epoxy resin comprises the following steps:
(1) Preheating propylene glycol methyl ether to 70 ℃ under nitrogen atmosphere, adding bisphenol A epoxy resin, dissolving the bisphenol A epoxy resin, cooling to 50 ℃, adding 2-butynoic acid and para-hydroxyanisole, heating to 70 ℃, adding triethanolamine, heating to 100 ℃, stirring and reacting for 5 hours until the acid value of the reaction solution is less than 3mgKOH/g, and obtaining the epoxy resin solution containing alkyne active monomers;
wherein, propylene glycol methyl ether mass: bisphenol a type epoxy resin mass=0.8: 1, a step of;
the molar ratio of 2-butynoic acid to bisphenol A epoxy resin epoxy group is 1.2:1, a step of;
the addition amount of the para-hydroxyanisole is 0.5 weight percent of bisphenol A type epoxy resin;
the addition amount of triethanolamine is 0.5wt% of bisphenol A type epoxy resin;
(2) Cooling the epoxy resin solution containing the alkyne active monomer obtained in the step (1) to 70 ℃, then adding methyl tetrahydrophthalic anhydride and p-hydroxyanisole, mixing, and continuing stirring and reacting for 7 hours at 90 ℃ to obtain the alkali-soluble photo-curing epoxy resin modified by the alkyne active monomer;
wherein, the mole ratio of methyl tetrahydrophthalic anhydride to bisphenol A epoxy resin epoxy group is 1.2:1, a step of;
the addition amount of the para-hydroxyanisole is 0.5 weight percent of the bisphenol A type epoxy resin.
Synthesis example 4
The preparation method of the alkyne-containing active monomer modified alkali-soluble photo-curable epoxy resin comprises the following steps:
(1) Preheating trimethylbenzene to 90 ℃ in nitrogen atmosphere, adding diglycidyl phthalate to dissolve the diglycidyl phthalate, cooling to 60 ℃, adding 2-butynoic acid and 2, 6-di-tert-butyl-4-methylphenol, heating to 80 ℃, adding tetrabutylammonium bromide, adjusting the temperature to 120 ℃, and stirring for reacting for 3 hours until the acid value of the reaction solution is less than 3mgKOH/g, thus obtaining an epoxy resin solution containing alkyne active monomers;
wherein, the quality of trimethylbenzene: diglycidyl phthalate mass=1.5: 1, a step of;
the molar ratio of 2-butynoic acid to diglycidyl phthalate epoxy group is 1:1, a step of;
the addition amount of the 2, 6-di-tert-butyl-4-methylphenol is 2wt% of the diglycidyl phthalate;
the added amount of tetrabutylammonium bromide is 1wt% of diglycidyl phthalate;
(2) Cooling the epoxy resin solution containing the alkyne active monomer obtained in the step (1) to 80 ℃, then adding hexahydrophthalic anhydride and 2, 6-di-tert-butyl-4-methylphenol to mix, and continuing stirring and reacting for 3 hours at 100 ℃ to obtain the alkali-soluble photo-curing epoxy resin modified by the alkyne active monomer;
wherein, the mole ratio of methyl tetrahydrophthalic anhydride to diglycidyl phthalate epoxy group is 1.2:1, a step of;
the addition amount of 2, 6-di-tert-butyl-4-methylphenol was 2% by weight of diglycidyl phthalate.
Synthesis example 5
The preparation method of the alkyne-containing active monomer modified alkali-soluble photo-curable epoxy resin comprises the following steps:
(1) Preheating propylene glycol methyl ether to 80 ℃ in nitrogen atmosphere, adding p-tert-butylphenol novolac epoxy resin, dissolving the epoxy resin, cooling to 55 ℃, adding propynylamine and p-benzoquinone, heating to 75 ℃, adding triphenylphosphine, heating to 100 ℃, stirring and reacting for 5 hours until the acid value of the reaction solution is less than 3mgKOH/g, and obtaining the epoxy resin solution containing alkyne active monomers;
wherein, propylene glycol methyl ether mass: p-tert-butylphenol novolac epoxy resin mass=1: 1, a step of;
the mole ratio of propynylamine to epoxy group of p-tert-butylphenol novolac epoxy resin is 1:1, a step of;
the adding amount of the p-benzoquinone is 1wt% of the p-tert-butylphenol novolac epoxy resin;
the adding amount of the triphenylphosphine is 0.8wt% of the p-tert-butylphenol novolac epoxy resin;
(2) Cooling the epoxy resin solution containing the alkyne active monomer obtained in the step (1) to 75 ℃, then adding methyl hexahydrophthalic anhydride and p-benzoquinone, mixing, and continuing stirring and reacting for 5 hours at 95 ℃ to obtain the alkali-soluble photo-curing epoxy resin modified by the alkyne active monomer;
wherein, the mole ratio of methyl hexahydrophthalic anhydride to epoxy group of the p-tert-butylphenol phenolic epoxy resin is 1:1, a step of;
the addition amount of the p-benzoquinone is 1wt% of the p-tert-butylphenol novolac epoxy resin.
Example 5
The novel photo-curing solder resist ink with high glass transition temperature in the embodiment mainly comprises the following raw materials in parts by weight:
100 parts of an EPAT, which is used for the production of a product,
8 parts of a photoinitiator (photoinitiator 907);
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Example 6
The novel photo-curing solder resist ink with high glass transition temperature in the embodiment mainly comprises the following raw materials in parts by weight:
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Example 7
The novel photo-curing solder resist ink with high glass transition temperature in the embodiment mainly comprises the following raw materials in parts by weight:
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Example 8
The novel photo-curing solder resist ink with high glass transition temperature in the embodiment mainly comprises the following raw materials in parts by weight:
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Example 9
The novel photo-curing solder resist ink is prepared by utilizing click chemistry reaction, and the raw materials of the novel photo-curing solder resist ink mainly comprise the following components in parts by weight:
100 parts of an EPAT, which is used for the production of a product,
10 parts of dipentaerythritol hexa (3-mercaptopropionate),
5 parts of a photoinitiator;
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Example 10
The novel photo-curing solder resist ink is prepared by utilizing click chemistry reaction, and the raw materials of the novel photo-curing solder resist ink mainly comprise the following components in parts by weight:
100 parts of an EBAT (electronic toll Collection),
20 parts of tetra (3-mercaptopropyl) silane,
3 parts of a photoinitiator;
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Example 11
The novel photo-curing solder resist ink is prepared by utilizing click chemistry reaction, and the raw materials of the novel photo-curing solder resist ink mainly comprise the following components in parts by weight:
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
Example 12
The novel photo-curing solder resist ink is prepared by utilizing click chemistry reaction, and the raw materials of the novel photo-curing solder resist ink mainly comprise the following components in parts by weight:
the above-described components and the component ratios (parts by weight) were mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photo-curable solder resist ink.
It is noted that the selection and the proportion of each component in the above embodiments are only for convenience of illustrating the technical effects of the present invention, and those skilled in the art will understand that, on the premise that the alkyne-containing active monomer modified alkali-soluble photocurable epoxy resin is determined, any selection and adjustment of other components except for the alkyne-containing active monomer modified alkali-soluble photocurable epoxy resin are performed according to the related art of the photo-curable solder resist ink, which has the technical effects of the present invention.
Claims (5)
1. The application method of the high-glass-transition-temperature photo-curing solder resist ink is characterized in that when the high-glass-transition-temperature photo-curing solder resist ink is used, the photo-curing condition is that ultraviolet light irradiates for 40min and then is thermally cured for 1h;
the high glass transition temperature photo-curing solder resist ink mainly comprises the following raw materials in parts by weight:
100 parts of alkali-soluble photo-curing epoxy resin modified by alkyne-containing active monomer,
3 parts of a photoinitiator;
the preparation method of the alkyne-containing active monomer modified alkali-soluble photo-curing epoxy resin comprises the following steps:
(1) Preheating a solvent to 70-90 ℃ in a nitrogen atmosphere, adding epoxy resin, dissolving the epoxy resin, cooling to 50-60 ℃, adding an alkyne-containing active monomer and a polymerization inhibitor, heating to 70-80 ℃, adding a cyclic ester ring-opening polymerization catalyst, heating to 80-120 ℃, stirring and reacting for 3-6 hours until the acid value of a reaction solution is less than 3mgKOH/g, and obtaining an epoxy resin solution containing alkyne-containing active monomer;
(2) Cooling the epoxy resin solution containing the alkyne active monomer obtained in the step (1) to 70-80 ℃, then adding unsaturated anhydride and polymerization inhibitor to mix, and continuing stirring and reacting for 3-7 hours at the temperature of 90-100 ℃ to obtain the alkali-soluble photo-curing epoxy resin modified by the alkyne active monomer;
the epoxy resin is selected from any one of phenol novolac epoxy resin, o-cresol novolac epoxy resin and p-tert-butylphenol novolac epoxy resin;
the alkyne-containing active monomer is 2-butynoic acid;
the unsaturated anhydride is any one of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride;
the addition of the alkyne-containing active monomer is carried out according to the mole ratio of the alkyne-containing active monomer to the epoxy group of the epoxy resin of (1-1.2): 1 is added in such a manner that the molar ratio of the unsaturated acid anhydride to the epoxy group of the epoxy resin is (1 to 1.2): 1.
2. The application method according to claim 1, wherein: the cyclic ester ring-opening polymerization catalyst in the step (1) is one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethyl ammonium chloride, N-dimethylbenzylamine and triphenylphosphine; the addition amount of the cyclic ester ring-opening polymerization catalyst is 0.2-1 wt% of the epoxy resin.
3. The application method according to claim 1, wherein: the solvent in the step (1) is at least one of dibasic ester high-boiling point environment-friendly solvent, ethylene glycol diethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether, propylene glycol methyl ether, trimethylbenzene and tetramethylbenzene; in step (1), the mass of the solvent: epoxy resin mass= (0.5-1.5): 1.
4. the application method according to claim 1, wherein: the polymerization inhibitor in the steps (1) and (2) is selected from at least one of hydroquinone, o-methyl hydroquinone, p-hydroxyanisole, p-benzoquinone and 2, 6-di-tert-butyl-4-methylphenol; the addition amount of the polymerization inhibitor is 0.4-2.5 wt% of the epoxy resin in the step (1).
5. The application method according to claim 1, wherein the high glass transition temperature photo-curing solder resist ink mainly comprises the following raw materials in parts by weight:
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