TWI830302B - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- TWI830302B TWI830302B TW111127829A TW111127829A TWI830302B TW I830302 B TWI830302 B TW I830302B TW 111127829 A TW111127829 A TW 111127829A TW 111127829 A TW111127829 A TW 111127829A TW I830302 B TWI830302 B TW I830302B
- Authority
- TW
- Taiwan
- Prior art keywords
- photosensitive resin
- resin composition
- epoxy resin
- group
- liquid photosensitive
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims description 62
- 229920000647 polyepoxide Polymers 0.000 claims description 62
- 229920005989 resin Polymers 0.000 claims description 56
- 239000011347 resin Substances 0.000 claims description 56
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 19
- 239000000178 monomer Substances 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
- 239000002253 acid Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002993 cycloalkylene group Chemical group 0.000 claims 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical group CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 16
- 229910000679 solder Inorganic materials 0.000 description 15
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 14
- 229910052753 mercury Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000000049 pigment Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 238000007650 screen-printing Methods 0.000 description 8
- -1 oxime ester Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000004843 novolac epoxy resin Substances 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 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 description 5
- 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 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical group OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- KDAKNYMYAISKCO-UHFFFAOYSA-N ethyl 2-isocyanatoprop-2-enoate Chemical compound CCOC(=O)C(=C)N=C=O KDAKNYMYAISKCO-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229960003505 mequinol Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- 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 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- SVFBPYWZNHLAGQ-UHFFFAOYSA-N 1-isocyanatopropan-2-yl prop-2-enoate Chemical compound O=C=NCC(C)OC(=O)C=C SVFBPYWZNHLAGQ-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
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- XOAKHODFHUHKSO-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C(C)C1=CC=2C(C3=CC=CC=C3SC2C(=C1)CC)=O.C(C)C1=CC=2C(C3=CC=CC=C3SC2C(=C1)CC)=O XOAKHODFHUHKSO-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- CXZBMXTURQVMCU-UHFFFAOYSA-N 3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione;7a-methyl-4,5,6,7-tetrahydro-3ah-2-benzofuran-1,3-dione Chemical compound C1CCCC2C(=O)OC(=O)C21.C1CCCC2C(=O)OC(=O)C21C CXZBMXTURQVMCU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- PCDHSSHKDZYLLI-UHFFFAOYSA-N butan-1-one Chemical compound CCC[C]=O PCDHSSHKDZYLLI-UHFFFAOYSA-N 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
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- 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 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical group OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 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
- 238000004448 titration Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- Chemical & Material Sciences (AREA)
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- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
實施例涉及一種具有優異的顯影性和深部固化性的光敏感樹脂組成物。 The embodiment relates to a photosensitive resin composition having excellent developability and deep curability.
可用於透過光蝕刻法原理的應用形成精細圖案，光敏感樹脂組成物以各種形式用在電子裝置或印刷電路板上形成精細的電路圖案。這種光敏感樹脂組成物包含溶劑顯影類型和鹼性顯影類型，近年來，隨著對環境議題的關注增加，鹼性顯影類型的光敏感樹脂組成物的使用增加，使用弱鹼性溶液以減少溶劑的使用。 It can be used to form fine patterns through the application of photolithography principles. Photosensitive resin compositions are used in various forms to form fine circuit patterns on electronic devices or printed circuit boards. This type of photosensitive resin composition includes solvent development type and alkaline development type. In recent years, as concerns about environmental issues have increased, the use of alkaline development type photosensitive resin compositions has increased. Weak alkaline solutions are used to reduce Solvent use.
例如，鹼性顯影類型的光敏感樹脂組成物用於包含印刷線路板、液晶顯示面板或印刷板的製造等廣泛的領域。特別是，光敏感樹脂組成物可作為焊料光阻(solder resist,SR)，用於保護在印刷線路板的製備中不應該在焊接時暴露於鉛的基板部分。 For example, alkaline developing type photosensitive resin compositions are used in a wide range of fields including the production of printed wiring boards, liquid crystal display panels, and printed boards. In particular, the photosensitive resin composition can be used as a solder resist (SR) for protecting portions of the substrate that should not be exposed to lead during soldering in the preparation of printed wiring boards.
焊料光阻作為印刷電路板上的保護材料，當在基板上形成焊料時，焊料光阻防止焊料黏著到不需要的部分(未形成鉛的部分，需要絕緣的部分)，對例如焊接的高溫條件具有耐熱性，以確保不會形成焊料橋(solder bridge)，且維持導電部分的電性絕緣。此外，隨著近來電子裝置小型化、輕量化、薄型 化和多功能化的趨勢，以及對環境法規的嚴格化，對高整合、高密度封裝和薄型化印刷線路板的需求增加，因此，對於焊料光阻組成物除了耐熱性和絕緣性外，也需要在冷卻/加熱循環時防止裂紋的特性。此外，對於具有非常精細圖案的高精度焊料光阻的需求增加，以用於更寬的塗膜厚度和高密度封裝。 Solder photoresist is used as a protective material on the printed circuit board. When solder is formed on the substrate, the solder photoresist prevents the solder from adhering to unnecessary parts (parts where lead is not formed, parts that require insulation), and is suitable for high-temperature conditions such as soldering. It is heat-resistant to ensure that solder bridges are not formed and electrical insulation of conductive parts is maintained. In addition, with the recent miniaturization, weight reduction, and thinness of electronic devices, The trend of globalization and multi-functionality, as well as the tightening of environmental regulations, have increased the demand for high integration, high-density packaging and thin printed circuit boards. Therefore, in addition to heat resistance and insulation, the solder photoresist composition also has Properties to prevent cracking during cooling/heating cycles are required. Additionally, there is increased demand for high-precision solder photoresists with very fine patterns for wider film thicknesses and high-density packaging.
因此，根據需要，正在進行各種研究以改善焊料光阻的特性。例如，專利No.10-1,063,048揭露一種鹼性顯影類型焊料光阻包含含有羧基的光敏感樹脂、肟酯類(oxime ester-based)光聚合引發劑、具有烯系不飽和(ethylenically)基團的化合物和熱固性成分。然而，當典型的液體鹼性顯影類型的焊料光阻固化形成塗膜時，深部在超過特定厚度時不能被充分固化，導致底切(undercut)和可靠性問題產生。 Therefore, various studies are being conducted to improve the characteristics of solder photoresist as needed. For example, Patent No. 10-1,063,048 discloses an alkaline development type solder photoresist containing a carboxyl-containing photosensitive resin, an oxime ester-based photopolymerization initiator, and an ethylenically unsaturated (ethylenically) group. compounds and thermoset ingredients. However, when a typical liquid alkaline development type solder resist is cured to form a coating, the deep portions cannot be fully cured beyond a certain thickness, resulting in undercut and reliability issues.
本發明的一態樣提供一種具有優異的顯影性和深部固化性的液態光敏感樹脂組成物。 One aspect of the present invention provides a liquid photosensitive resin composition having excellent developability and deep curability.
根據至少一個實施例，液態光敏感樹脂組成物包含含有胺甲酸乙酯基團(urethane group)的光敏感樹脂、環氧樹脂、以及光引發劑。 According to at least one embodiment, the liquid photosensitive resin composition includes a photosensitive resin containing a urethane group, an epoxy resin, and a photoinitiator.
本發明的一態樣提供一種具有優異的顯影性和深部固化性的液態光敏感樹脂組成物。尤其是，本發明的光敏感樹脂組成物使用具有胺甲酸乙酯基團(urethane group)的光敏感樹脂，其中聚氨酯丙烯酸酯(urethane acrylate)基團的當量在特定範圍內，即使在弱光線到達深部的情況下也能有效地發生光固化反應(photocuring reaction)，因此，隨著深部固化的改善，由該組成物形成的 焊料光阻具有減少底切和優異的可靠性。 One aspect of the present invention provides a liquid photosensitive resin composition having excellent developability and deep curability. In particular, the photosensitive resin composition of the present invention uses a photosensitive resin having a urethane group, in which the equivalent weight of the urethane acrylate group is within a specific range, even when weak light reaches The photocuring reaction (photocuring reaction) can effectively occur even in deep areas. Therefore, with the improvement of deep area curing, the photocuring reaction formed by this composition Solder photoresist offers reduced undercutting and excellent reliability.
在下文中，將更詳細地描述本發明。然而，本說明書並非旨在將本發明限制於以下內容，且在必要時可以以各種方式修改各種組件或可選地相互使用。應當理解的是，本發明目包含落入在本發明精神和範圍內的所有變化、均等物、及替代物。 In the following, the invention will be described in more detail. However, this description is not intended to limit the invention to what follows, and the various components may be modified in various ways or alternatively used with each other when necessary. It should be understood that the present invention includes all changes, equivalents, and substitutions that fall within the spirit and scope of the invention.
如本文所使用，諸如「酸值(acid value)」的官能基的值通過本領域已知的典型方法測量，且可以通過例如滴定法(titration)測量。「重量平均分子量(weight average molecular weight)」通過本領域已知的典型方法測量，且可以通過例如凝膠滲透層析法(gel permeation chromatography,GPC)測量。「軟化點(softening point)」通過本領域已知的典型方法測量，且可以使用例如來自Mettler Toledo的滴點(dropping point)系統熱量測定法(calorimetry)DP70測量。 As used herein, the value of a functional group such as "acid value" is measured by typical methods known in the art, and may be measured, for example, by titration. "Weight average molecular weight" is measured by typical methods known in the art, and can be measured by, for example, gel permeation chromatography (GPC). The "softening point" is measured by typical methods known in the art and can be measured using, for example, the dropping point system calorimetry DP70 from Mettler Toledo.
本發明的液態光敏感樹脂組成物包含具有胺甲酸乙酯基團(urethane group)的光敏感樹脂、環氧樹脂、以及光引發劑。本發明的液態光敏感樹脂組成物可以包含丙烯酸類單體和溶劑，且當需要時可以更包含本領域常用的添加劑，例如催化劑、離子捕捉劑(ion catcher)、填料、和顏料。 The liquid photosensitive resin composition of the present invention includes a photosensitive resin having a urethane group, an epoxy resin, and a photoinitiator. The liquid photosensitive resin composition of the present invention may contain acrylic monomers and solvents, and when necessary, may further contain additives commonly used in the art, such as catalysts, ion catchers, fillers, and pigments.
具有胺甲酸乙酯基團(urethane group)的光敏感樹脂 Photosensitive resin with urethane group
本發明的液態光敏感樹脂組成物包含一含有胺甲酸乙酯基團(-NH-COO-)的光敏感樹脂。含有胺甲酸乙酯基團的光敏感樹脂提供響應光固化光敏感樹脂組成物的光固化特性和能夠形成圖案的顯影性。特別是，使用具有聚氨酯丙烯酸酯(urethane acrylate)基團的含有胺甲酸乙酯基團的光敏感樹脂作為對光響應的光敏感基團，該光敏感樹脂組成物具有優異的深部固化性，因此展現出改善的顯影性和分辨率。此外，本發明之含有胺甲酸乙酯基團的光敏感樹脂幫助改善諸如光敏感樹脂組成物的UV固化特性、黏著性、彈性和耐化學性。 The liquid photosensitive resin composition of the present invention includes a photosensitive resin containing a urethane group (-NH-COO-). The photosensitive resin containing a urethane group provides photocurable properties responsive to the photocurable photosensitive resin composition and developability capable of forming a pattern. In particular, a urethane group-containing photosensitive resin having a urethane acrylate group is used as a photosensitive group that responds to light. This photosensitive resin composition has excellent deep curability, and therefore Demonstrates improved developability and resolution. In addition, the photosensitive resin containing urethane groups of the present invention helps improve the UV curing properties, adhesion, elasticity and chemical resistance of the photosensitive resin composition.
含有胺甲酸乙酯基團的光敏感樹脂可通過包含由酚基樹脂製備的多元醇、具有異氰酸酯基團的丙烯酸酯的加成反應、以及酸式變形(acid modification)的製造方法來製備。 The photosensitive resin containing a urethane group can be prepared by a manufacturing method including a polyol prepared from a phenol-based resin, an addition reaction of an acrylate having an isocyanate group, and acid modification.
例如，含有胺甲酸乙酯基團的光敏感樹脂可通過使環氧烷(alkylene oxide)或烷基碳酸酯(alkylene carbonate)與酚基樹脂反應來製備，所述酚基樹脂如苯酚、甲酚或其衍生物的酚醛清漆樹脂(novolac resin)，使具有異氰酸酯基團的(甲基)丙烯酸單體與通過反應生成的多元醇反應來製備，以及使具有酸酐基團的化合物與殘留的羥基反應來製備。 For example, photosensitive resins containing urethane groups can be prepared by reacting alkylene oxide or alkylene carbonate with phenol-based resins such as phenol, cresol Novolac resin or a derivative thereof is prepared by reacting a (meth)acrylic acid monomer having an isocyanate group with a polyol generated by the reaction, and reacting a compound having an anhydride group with a residual hydroxyl group to prepare.
環氧烷的非限制性例子可包含環氧乙烷、環氧丙烷等，且這些可單獨或組合使用。烷基碳酸酯的非限制性例子可包含碳酸伸乙酯(ethylene carbonate)、碳酸丙烯酯等，且這些可以單獨或組合使用。 Non-limiting examples of alkylene oxides may include ethylene oxide, propylene oxide, and the like, and these may be used alone or in combination. Non-limiting examples of alkyl carbonates may include ethylene carbonate, propylene carbonate, and the like, and these may be used alone or in combination.
具有異氰酸酯基團的(甲基)丙烯酸單體的非限制性例子可包含2-丙烯醯氧基乙基異氰酸酯(2-acryloyloxyethyl isocyanate)、2-甲基2-丙烯醯氧基乙基異氰酸酯(2-methacryloyloxyethyl isocyanate)，且這些可單獨或組合使用。 Non-limiting examples of (meth)acrylic monomers having isocyanate groups may include 2-acryloyloxyethyl isocyanate (2-acryloyloxyethyl isocyanate), 2-methyl 2-acryloyloxyethyl isocyanate (2-acryloyloxyethyl isocyanate). -methacryloyloxyethyl isocyanate), and these can be used alone or in combination.
具有酸酐基團的化合物的非限制性例子可包含四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride)、六氫鄰苯二甲酸酐(hexahydrophthalic anhydride)、甲基-六氫鄰苯二甲酸酐(methyl-hexahydrophthalic anhydride)、鄰苯二甲酸酐(phthalic anhydride)等，且這些可以單獨或組合使用。 Non-limiting examples of compounds having anhydride groups may include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride hexahydrophthalic anhydride), phthalic anhydride (phthalic anhydride), etc., and these can be used alone or in combination.
含有胺甲酸乙酯基團的光敏感樹脂可包含由下式1所表示的重複單元；以及由下式2所表示的重複單元或下式3所表示的重複單元中的至少一種重複單元。 The photosensitive resin containing a urethane group may include a repeating unit represented by the following formula 1; and at least one repeating unit represented by a repeating unit represented by the following formula 2 or a repeating unit represented by the following formula 3.
[式1]
[式2]
式[3]
在上述式1至3中，R1和R2為氫或具有1-5個碳原子烷基，且R3為具有1-10個碳原子烷基、具有2-9個碳原子脂肪族伸烷基(alkylene)、環伸烷基、或芳香族二價化合物。 In the above formulas 1 to 3, R 1 and R 2 are hydrogen or an alkyl group having 1 to 5 carbon atoms, and R 3 is an alkyl group having 1 to 10 carbon atoms, an aliphatic extension having 2 to 9 carbon atoms. Alkylene, cycloalkyl, or aromatic divalent compound.
例如，含有胺甲酸乙酯基團的光敏感樹脂可包含由上述式1表示的重複單元和由上述式2表示的重複單元。又例如，含有胺甲酸乙酯基團的光敏感樹脂可包含由上述式1表示的重複單元、由上述式2表示的重複單元和由上述式3表示的重複單元。 For example, the photosensitive resin containing a urethane group may include a repeating unit represented by the above-mentioned Formula 1 and a repeating unit represented by the above-mentioned Formula 2. As another example, the photosensitive resin containing a urethane group may include a repeating unit represented by the above formula 1, a repeating unit represented by the above formula 2, and a repeating unit represented by the above formula 3.
例如，含有胺甲酸乙酯基團的光敏感樹脂可包含2至50個由上述式1表示的重複單元和2至50個由上述式2表示的重複單元。又例如，含有胺甲酸乙酯基團的光敏感樹脂可包含2至50個由上述式1表示的重複單元、2至50個由上述式2表示的重複單元和5個以下的由上述式3表示的重複單元。 For example, the photosensitive resin containing a urethane group may contain 2 to 50 repeating units represented by the above-mentioned Formula 1 and 2 to 50 repeating units represented by the above-mentioned Formula 2. As another example, the photosensitive resin containing a urethane group may include 2 to 50 repeating units represented by the above formula 1, 2 to 50 repeating units represented by the above formula 2, and 5 or less repeating units represented by the above formula 3. represents the repeating unit.
含有胺甲酸乙酯基團的光敏感樹脂可具有260至700g/eq(例如300至600g/eq)的聚氨酯丙烯酸酯基團的當量。當含有胺甲酸乙酯基團的光敏感樹脂中的聚氨酯丙烯酸酯基團的當量在上述範圍內時，不僅可響應光到達塗膜的表面還可到達塗膜的深部而有效地發生固化，從而表現出優異的圖案形成。當聚氨酯丙烯酸酯基團的當量小於上述範圍時，可響應光交聯的丙烯酸酯的數量太多，導致固化密度過度增加，可能反而降低鹼性顯影劑(alkali developer)顯影性並在基板上留下殘留物。另一方面，當含有胺甲酸乙酯基團的光敏感樹脂中的聚氨酯丙烯酸酯基團的當量大於上述範圍時，可響應光交聯的丙烯酸酯的數量太少，導致固化密度顯著下降，可能反而透過顯影劑蝕刻不應該顯影的固化的塗膜部分(應該形成圖案的部分)而失去圖案，因此，可能無法獲得期望的圖案和分辨率，且可能會降低固化的塗膜的物理特性。 The photosensitive resin containing urethane groups may have an equivalent weight of urethane acrylate groups of 260 to 700 g/eq (eg, 300 to 600 g/eq). When the equivalent of the urethane acrylate group in the photosensitive resin containing the urethane group is within the above range, curing can occur effectively in response to light reaching not only the surface of the coating film but also the depth of the coating film, thereby Exhibits excellent pattern formation. When the equivalent weight of the polyurethane acrylate group is less than the above range, the number of acrylates that can respond to photo-crosslinking is too large, resulting in an excessive increase in the cured density, which may actually reduce the developability of the alkaline developer and leave traces on the substrate. Lower residue. On the other hand, when the equivalent weight of the polyurethane acrylate group in the photosensitive resin containing urethane groups is greater than the above range, the number of acrylates that can respond to photo-crosslinking is too small, resulting in a significant decrease in the cured density, which may Instead, the part of the cured coating film that should not be developed (the part that should be patterned) is etched by the developer and the pattern is lost. Therefore, the desired pattern and resolution may not be obtained, and the physical properties of the cured coating film may be reduced.
含有胺甲酸乙酯基團的光敏感樹脂可具有40-120mgKOH/g的酸值，例如50-100mgKOH/g。當酸值小於上述範圍時，可能會降低使用鹼性顯影劑的顯影性，且可能會在基板上留下殘留物，當酸值大於上述範圍時，圖案可能會脫落。 The photosensitive resin containing urethane groups may have an acid value of 40-120 mgKOH/g, for example, 50-100 mgKOH/g. When the acid value is less than the above range, developability using an alkaline developer may be reduced and residue may be left on the substrate, and when the acid value is greater than the above range, the pattern may fall off.
含有胺甲酸乙酯基團的光敏感樹脂可具有2000至20000g/mol的重量平均分子量，例如2000至10000g/mol。當重量平均分子量小於上述範圍時，在組成物中的組分之間的黏合需要作為黏合劑樹脂(binder resin)，即表示黏合功 能衰減，因此，由於顯影時的物理外力，圖案的形狀可能失去或破碎，且耐熱性、耐溶劑性等可能會劣化(deteriorate)。另一方面，當重量平均分子量大於上述範圍時，鹼性顯影劑的顯影性和流動性可能會劣化，導致難以控制塗膜厚度或確保均勻性。 The photosensitive resin containing urethane groups may have a weight average molecular weight of 2000 to 20000 g/mol, for example, 2000 to 10000 g/mol. When the weight average molecular weight is less than the above range, the binding between the components in the composition requires a binder resin, which means the binding function It can decay, so due to physical external force during development, the shape of the pattern may be lost or broken, and the heat resistance, solvent resistance, etc. may deteriorate (deteriorate). On the other hand, when the weight average molecular weight is greater than the above range, the developability and fluidity of the alkaline developer may be deteriorated, making it difficult to control the coating film thickness or ensure uniformity.
本發明的液態光敏感樹脂組成物相對於該液態光敏感樹脂組成物的總重量，可包含25至55wt%(例如30至50wt%)的含有胺甲酸乙酯基團的光敏感樹脂。當光敏感樹脂的含量低於上述範圍時，可能會降低諸如耐熱性和耐溶劑性的特性，當光敏感樹脂的含量大於上述範圍時，可能會降低儲存穩定性，且由於流動性差，加工性可能會劣化(deteriorated)。 The liquid photosensitive resin composition of the present invention may include 25 to 55 wt% (eg, 30 to 50 wt%) of the photosensitive resin containing urethane groups relative to the total weight of the liquid photosensitive resin composition. When the content of the photosensitive resin is lower than the above range, characteristics such as heat resistance and solvent resistance may be reduced, and when the content of the photosensitive resin is greater than the above range, the storage stability may be reduced, and due to poor fluidity, processability May be deteriorated.
環氧樹脂 Epoxy resin
本發明的液態光敏感樹脂組成物包含環氧樹脂。環氧樹脂提供響應於熱固化光敏感樹脂組成物的熱固性質(thermosetting property)。 The liquid photosensitive resin composition of the present invention contains epoxy resin. The epoxy resin provides thermosetting properties to the photosensitive resin composition in response to thermal curing.
作為環氧樹脂可以使用多元酚(polyhydric phenol)的聚縮水甘油醚及其衍生物。例如，可以使用作為多元酚的聚縮水甘油醚的雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂(hydrogenated bisphenol A type)、雙酚F型環氧樹脂、酚醛環氧樹脂(novolac epoxy resin)、苯酚酚醛環氧樹脂(phenol-novolac epoxy resin)、甲酚酚醛環氧樹脂(cresol-novolac epoxy resin)、N-環氧丙基環氧樹脂(N-glycidyl epoxy resin)、雙酚A型酚醛環氧樹脂(bisphenol A type novolac epoxy resin)、螯合型環氧樹脂(chelate-type epoxy resin)、乙二醛環氧樹脂(glyoxane epoxy resin)、含胺基環氧樹脂、橡膠改質環氧樹脂(rubber-modified epoxy resin)、二環戊二烯酚系環氧樹脂(dicyclopentadiene phenolic epoxy resin)、矽烷改質環氧樹脂(silicon-modified epoxy resin)、ε-己內酯改質環氧樹脂(ε-caprolactone-modified epoxy resin)、雙酚S型環氧樹脂、酞酸二環氧丙酯樹脂(diglycidyl phthalate resin)、雜環環氧樹脂、聯苯環氧樹脂等。 As the epoxy resin, polyglycidyl ether of polyhydric phenol and its derivatives can be used. For example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin (hydrogenated bisphenol A type), bisphenol F type epoxy resin, novolac epoxy resin (novolac) which is polyglycidyl ether of polyhydric phenol can be used. epoxy resin), phenol-novolac epoxy resin (phenol-novolac epoxy resin), cresol-novolac epoxy resin (cresol-novolac epoxy resin), N-glycidyl epoxy resin (N-glycidyl epoxy resin), bisphenol Bisphenol A type novolac epoxy resin, chelate-type epoxy resin, glyoxane epoxy resin, amine-containing epoxy resin, rubber modified Rubber-modified epoxy resin, dicyclopentadiene phenolic epoxy resin, silicon-modified epoxy resin, ε-caprolactone modified Epoxy resin (ε-caprolactone-modified epoxy resin), bisphenol S-type epoxy resin, diglycidyl phthalate resin (diglycidyl phthalate resin), heterocyclic epoxy resin, biphenyl epoxy resin, etc.
例如，環氧樹脂包含雙酚型環氧樹脂、聯苯環氧樹脂、或其混合。當混合上述兩種環氧樹脂時，可以從雙酚型環氧樹脂中獲得優異的黏著性和耐化學性，且可從聯苯環氧樹脂獲得在熱乾燥條件下補充的耐熱性和熱穩定性。 For example, the epoxy resin includes bisphenol epoxy resin, biphenyl epoxy resin, or a mixture thereof. When the above two epoxy resins are mixed, excellent adhesion and chemical resistance can be obtained from the bisphenol-type epoxy resin, and supplementary heat resistance and thermal stability under heat drying conditions can be obtained from the biphenyl epoxy resin. sex.
作為雙酚型環氧樹脂，可以使用具有200至600g/eq的環氧當量(epoxy equivalent)(例如400至500g/eq)、50至100℃的軟化點(softening point)(例如60至70℃)及1000至5000g/mol重量平均分子量(例如1500至2500g/mol)的雙酚型環氧樹脂。當雙酚型環氧樹脂的特性滿足上述範圍時，可獲得優異的黏著性和耐化學性。 As the bisphenol type epoxy resin, one having an epoxy equivalent of 200 to 600 g/eq (for example, 400 to 500 g/eq) and a softening point of 50 to 100° C. (for example, 60 to 70° C. ) and a bisphenol-type epoxy resin with a weight average molecular weight of 1000 to 5000g/mol (for example, 1500 to 2500g/mol). When the characteristics of the bisphenol-type epoxy resin satisfy the above range, excellent adhesion and chemical resistance can be obtained.
例如，雙酚型環氧樹脂可為雙酚A型環氧樹脂，且可由下式4所表示。 For example, the bisphenol type epoxy resin may be a bisphenol A type epoxy resin, and may be represented by the following formula 4.
[式4]
作為聯苯環氧樹脂，可以使用具有100至1000g/eq的環氧當量(epoxy equivalent)(例如350至600g/eq)及300至20000g/mol重量平均分子量(例如1000至3000g/mol)的聯苯環氧樹脂。當聯苯環氧樹脂的特性滿足上述範圍時，可獲得優異的耐熱性和熱穩定性。 As the biphenyl epoxy resin, a biphenyl epoxy resin having an epoxy equivalent of 100 to 1000 g/eq (for example, 350 to 600 g/eq) and a weight average molecular weight of 300 to 20000 g/mol (for example, 1000 to 3000 g/mol) may be used. Benzene epoxy resin. When the characteristics of the biphenyl epoxy resin satisfy the above range, excellent heat resistance and thermal stability can be obtained.
作為聯苯環氧樹脂，可以使用脂肪族環氧樹脂(aliphatic epoxy resin)、衍生自天然物的脂肪酸基環氧樹脂(fatty acid-based epoxy resin)、聚丁二 烯基環氧樹脂(polybutadiene-based epoxy resin)、環脂族環氧樹脂(cycloaliphatic epoxy resin)等。 As the biphenyl epoxy resin, aliphatic epoxy resin, fatty acid-based epoxy resin derived from natural products, polybutylene glycol Alkenyl epoxy resin (polybutadiene-based epoxy resin), cycloaliphatic epoxy resin (cycloaliphatic epoxy resin), etc.
本發明的液態光敏感樹脂組成物相對於該液態光敏感樹脂組成物的總重量可包含6至40wt%的環氧樹脂，例如10至30wt%。例如，相對於該液態光敏感樹脂組成物的總重量，可以包含3至20wt%(例如5至15wt%)的雙酚A型環氧樹脂及3至20wt%(例如5至15wt%)的聯苯環氧樹脂。當各環氧樹脂的含量小於上述範圍時，可能無法充分促進固化，當各環氧樹脂的含量大於上述範圍時，塗膜外觀可能較差或塗膜強度可能降低。 The liquid photosensitive resin composition of the present invention may contain 6 to 40 wt% of epoxy resin, such as 10 to 30 wt%, relative to the total weight of the liquid photosensitive resin composition. For example, relative to the total weight of the liquid photosensitive resin composition, 3 to 20 wt% (for example, 5 to 15 wt%) bisphenol A-type epoxy resin and 3 to 20 wt% (for example, 5 to 15 wt%) bisphenol A-type epoxy resin may be included. Benzene epoxy resin. When the content of each epoxy resin is less than the above range, curing may not be sufficiently promoted, and when the content of each epoxy resin is greater than the above range, the appearance of the coating film may be poor or the strength of the coating film may be reduced.
光引發劑 photoinitiator
本發明的液態光敏感樹脂組成物包含光引發劑。作為光引發劑，可使用苯甲酮類(benzophenone-based)化合物、安息香烷基醚類(benzoin alkyl ether-based)化合物、苯乙酮類(acetophenone-based)化合物、噻噸酮類(thioxanthone-based)化合物、烷基蒽醌類(alkylanthraquinone-based)化合物及醯基氧化膦類(acylphosphine oxide-based)化合物。 The liquid photosensitive resin composition of the present invention contains a photoinitiator. As the photoinitiator, benzophenone-based compounds, benzoin alkyl ether-based compounds, acetophenone-based compounds, thioxanthone-based compounds can be used. based) compounds, alkylanthraquinone-based compounds and acylphosphine oxide-based compounds.
光引發劑可包含具有不同有效吸收波長的二或多種類型的光引發劑。當混合具有不同有效吸收波長的兩種類型的光引發劑時，具有不同有效吸收波長的光引發劑可充分支持在塗膜的表面和深部的每個中的固化。因此，減少了固化後使用鹼性顯影劑顯影時的底切現象，從而改善分辨率以確保優異的精細圖案成形性(formability)。例如，可以包含至少一種具有250至320nm有效吸收波長的第一光引發劑和至少一種具有370至450nm有效吸收波長的第二光引發劑。 The photoinitiator may include two or more types of photoinitiators with different effective absorption wavelengths. When two types of photoinitiators having different effective absorption wavelengths are mixed, the photoinitiators having different effective absorption wavelengths can fully support curing in each of the surface and deep parts of the coating film. Therefore, undercutting during development with an alkaline developer after curing is reduced, thereby improving resolution to ensure excellent fine pattern formability. For example, at least one first photoinitiator having an effective absorption wavelength of 250 to 320 nm and at least one second photoinitiator having an effective absorption wavelength of 370 to 450 nm may be included.
例如，第一光引發劑可為α-胺基苯乙酮類(α-amino acetophenone-based)化合物，例如2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-1-丁酮(2-benzyl-2-dimethylamino-1-(4-morpholino-phenyl)-1-butanone)、2-甲基-1-[(4-甲硫基)苯基]-2-(4-嗎啉基)-1-丙醇(2-methyl-1-[(4-methylthio)phenyl]-2-(4-morpholinyl)-1-propanol)、2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-嗎啉代苯基)丁-1-酮(2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one)或其混合。 For example, the first photoinitiator can be an α-amino acetophenone-based compound, such as 2-benzyl-2-dimethylamino-1-(4-morpholinobenzene) methyl)-1-butanone (2-benzyl-2-dimethylamino-1-(4-morpholino-phenyl)-1-butanone), 2-methyl-1-[(4-methylthio)phenyl]- 2-(4-morpholinyl)-1-propanol (2-methyl-1-[(4-methylthio)phenyl]-2-(4-morpholinyl)-1-propanol), 2-(4-methyl Benzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one(2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- morpholinophenol)butan-1-one) or mixtures thereof.
例如，第二光引發劑可為噻噸酮類化合物，例如2,4-二乙基噻噸酮(2,4-diethylthioxanthone)、2,4-二甲基噻噸酮、2,4-二異丙基噻噸酮、2-氯噻噸酮或其混合。 For example, the second photoinitiator can be a thioxanthone compound, such as 2,4-diethylthioxanthone (2,4-diethylthioxanthone), 2,4-dimethylthioxanthone, 2,4-dimethylthioxanthone, Isopropylthioxanthone, 2-chlorothioxanthone or mixtures thereof.
第一光引發劑和第二光引發劑的混合比(重量比)可為7：3至9：1，例如7：3至8：2。當第一光引發劑以超過上述範圍的混合比混合時，表面可能會過度固化，而深部可能會固化較少。同時，當第二光引發劑以超過上述範圍的混合比混合時，表面可能會固化較少，且可能會劣化儲存穩定性。 The mixing ratio (weight ratio) of the first photoinitiator and the second photoinitiator may be 7:3 to 9:1, such as 7:3 to 8:2. When the first photoinitiator is mixed at a mixing ratio exceeding the above range, the surface may be over-cured and the deep portion may be less cured. Meanwhile, when the second photoinitiator is mixed at a mixing ratio exceeding the above range, the surface may be less cured, and storage stability may be deteriorated.
本發明的液態光敏感樹脂組成物相對於該液態光敏感樹脂組成物的總重量可包含1.1至15wt%的光引發劑，例如1.1至6wt%。當光引發劑的含量小於上述範圍時，自由基引發反應可能無法順利進行，而當光引發劑的含量大於上述範圍時，雙鍵與光引發劑的自由基之間的反應速率太快難以形成高分子量。例如相對於液態光敏感樹脂組成物的總重量，可包含1至10wt%的第一光引發劑(例如1至5wt%)及0.1至5wt%(例如0.1至1wt%)的第二光引發劑。 The liquid photosensitive resin composition of the present invention may contain 1.1 to 15 wt% of the photoinitiator relative to the total weight of the liquid photosensitive resin composition, for example, 1.1 to 6 wt%. When the content of the photoinitiator is less than the above range, the free radical initiation reaction may not proceed smoothly, and when the content of the photoinitiator is greater than the above range, the reaction rate between the double bond and the free radical of the photoinitiator is too fast and it is difficult to form High molecular weight. For example, relative to the total weight of the liquid photosensitive resin composition, 1 to 10 wt% of the first photoinitiator (eg, 1 to 5 wt%) and 0.1 to 5 wt% (eg, 0.1 to 1 wt%) of the second photoinitiator may be included. .
丙烯酸單體 Acrylic monomer
本發明的液態光敏感樹脂組成物可包含丙烯酸單體。丙烯酸單體用於提供光固化性。 The liquid photosensitive resin composition of the present invention may contain an acrylic monomer. Acrylic monomers are used to provide photocurability.
丙烯酸單體可為多官能的丙烯酸單體，例如可以是三官能或更多，或例如3至6官能的(甲基)丙烯酸酯單體。 The acrylic monomer may be a polyfunctional acrylic monomer, for example it may be trifunctional or more, or for example a 3 to 6 functional (meth)acrylate monomer.
多官能的丙烯酸單體的非限制性例子可包含三官能的(甲基)丙烯酸酯單體，例如三羥甲基丙烷三(甲基)丙烯酸酯(trimethylolpropane tri(meth)acrylate)和季戊四醇三(甲基)丙烯酸酯(pentaerythritol tri(meth)acrylate)；四官能的(甲基)丙烯酸酯單體，例如季戊四醇四(甲基)丙烯酸酯(pentaerythritol tetra(meth)acrylate)和二三羥甲基丙烷四(甲基)丙烯酸酯(ditrimethylolpropane tetra(meth)acrylate)；二季戊四醇聚(甲基)丙烯酸酯(dipentaerythritol poly(meth)acrylate)，例如二季戊四醇六(甲基)丙烯酸酯(dipentaerythritol hexa(meth)acrylate)等，且這些可單獨使用或以兩種或以上混合使用。 Non-limiting examples of multifunctional acrylic monomers may include trifunctional (meth)acrylate monomers, such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Pentaerythritol tri(meth)acrylate; tetrafunctional (meth)acrylate monomers, such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane ditrimethylolpropane tetra(meth)acrylate; dipentaerythritol poly(meth)acrylate, such as dipentaerythritol hexa(meth) acrylate), etc., and these can be used alone or in combination of two or more.
本發明的液態光敏感樹脂組成物相對於該液態光敏感樹脂組成物的總重量，可包含3至30wt%的丙烯酸單體，例如5至20wt%。當丙烯酸單體的含量小於上述範圍時，光固化性可能不足，導致在光照後通過鹼性顯影劑難以形成圖案，而當丙烯酸單體的含量大於上述範圍時，可能會降低塗膜的觸乾燥性(touch dryness)，或者可能會降低光敏感樹脂組成物在作為顯影劑的鹼性水溶液中的溶解度，從而使塗膜變脆弱。 The liquid photosensitive resin composition of the present invention may include 3 to 30 wt% of acrylic monomer, such as 5 to 20 wt%, relative to the total weight of the liquid photosensitive resin composition. When the content of acrylic monomer is less than the above range, the photocurability may be insufficient, making it difficult to form a pattern with an alkaline developer after light exposure. When the content of acrylic monomer is greater than the above range, the touch dryness of the coating film may be reduced. (touch dryness), or may reduce the solubility of the photosensitive resin composition in the alkaline aqueous solution used as a developer, thereby making the coating film fragile.
添加劑 additives
當需要時，本發明的液態光敏感樹脂組成物可在不降低本發明的液態光敏感樹脂組成物的特性的範圍內更包含有機溶劑和其他添加劑。 When necessary, the liquid photosensitive resin composition of the present invention may further contain organic solvents and other additives within the scope that does not reduce the characteristics of the liquid photosensitive resin composition of the present invention.
有機溶劑是用於控制黏度，且只要是本領域使用的有機溶劑並沒有特別限制。例如可使用二丙二醇單乙醚(dipropylene glycol monoethyl ether)、石腦油(naphtha)等。 The organic solvent is used to control the viscosity, and is not particularly limited as long as it is an organic solvent used in this field. For example, dipropylene glycol monoethyl ether, naphtha, etc. can be used.
此外，可以使用本領域常用的添加劑，例如催化劑、離子捕捉劑(ion catcher)、填充劑和顏料。催化劑是用於促進熱固性反應，且只要是本領域使用的，催化劑並沒有特別限制。例如可以使用三聚氰胺等。離子捕捉劑是用於移除溶析(eluted)離子，且只要是本領域使用的，離子捕捉劑並沒有特別限制。例如可使用Al、Mg、Zr基的無機材料等。只要是本領域使用作為填充劑的，填充劑並沒有特別限制，可以使用例如硫酸鋇、滑石、氧化矽、氧化鋁和氫氧化鋁等無機填充劑。例如可以使用具有20μm以下粒徑(D50)的硫酸鋇，例如10μm以下，又例如1μm以下。顏料是用於提供著色效果，且只要是本領域使用的，顏料沒有特別限制。例如可以使用偶氮類顏料、酞菁類(phthalocyanine-based)顏料等。 In addition, additives commonly used in the art, such as catalysts, ion catchers, fillers and pigments, may be used. Catalysts are used to promote thermosetting reactions, and are not particularly limited as long as they are used in the art. For example, melamine etc. can be used. The ion trapping agent is used to remove eluted ions, and is not particularly limited as long as it is used in the art. For example, Al, Mg, Zr-based inorganic materials, etc. can be used. The filler is not particularly limited as long as it is used as a filler in this field. Inorganic fillers such as barium sulfate, talc, silicon oxide, aluminum oxide and aluminum hydroxide can be used. For example, barium sulfate having a particle size (D50) of 20 μm or less, for example 10 μm or less, or 1 μm or less can be used. The pigment is used to provide a coloring effect, and is not particularly limited as long as it is used in the art. For example, azo pigments, phthalocyanine-based pigments, etc. can be used.
此外，可以包含用於提供觸變性(thixotropy)的細粉氧化矽(pulverized silica)、用於輔助填充劑分散的分散劑和用於形成光滑塗膜表面的消泡劑。 In addition, finely powdered silica (pulverized silica) for providing thixotropy, a dispersant for assisting filler dispersion, and an antifoaming agent for forming a smooth coating film surface may be included.
本發明的光敏感樹脂組成物可以液體形式使用，作為用於需要微影像的印刷電路板光敏感組成物，或用於需要負型(negative type)圖像的印刷電路板的光敏感組成物。 The photosensitive resin composition of the present invention can be used in liquid form as a photosensitive composition for printed circuit boards that require micro-images, or as a photosensitive composition for printed circuit boards that require negative type images.
例如，本發明的光敏感樹脂組成物可以液體形式直接施加於基板上以形成圖案。作為基板，可以使用具有預成型電路的印刷線路板或可撓性印刷線路板、浸漬酚樹脂(phenol resin)的玻璃纖維、浸漬環氧樹脂的玻璃纖維、浸 漬雙馬來醯亞胺三嗪樹脂(bismaleimide triazine resin)的玻璃纖維、銅箔基板(copper clad laminate)、聚醯亞胺膜、PET膜、玻璃基板、陶瓷基板、晶圓基板等。 For example, the photosensitive resin composition of the present invention can be directly applied to a substrate in liquid form to form a pattern. As the substrate, a printed wiring board or a flexible printed wiring board having a preformed circuit, glass fiber impregnated with phenol resin, glass fiber impregnated with epoxy resin, or glass fiber impregnated with epoxy resin can be used. Glass fiber impregnated with bismaleimide triazine resin, copper clad laminate, polyimide film, PET film, glass substrate, ceramic substrate, wafer substrate, etc.
具體地，在本發明的光敏感樹脂組成物中加入有機溶劑以適當調節黏度，接著通過浸塗法(dip coating method)、流動塗布法(flow coating method)、輥塗法、棒塗法、網版印刷法、簾塗布法(curtain coating method)等施用於基板上，且在約60至120℃下將組成物中所含的有機溶劑蒸發並乾燥。當蒸發和乾燥溶劑時，可以使用熱氣循環乾燥爐、紅外線乾燥爐、加熱板等。 Specifically, an organic solvent is added to the photosensitive resin composition of the present invention to appropriately adjust the viscosity, and then the viscosity is adjusted by a dip coating method, a flow coating method, a roller coating method, a rod coating method, or a net coating method. A plate printing method, a curtain coating method, or the like is applied to the substrate, and the organic solvent contained in the composition is evaporated and dried at about 60 to 120°C. When evaporating and drying solvents, hot gas circulation drying ovens, infrared drying ovens, heating plates, etc. can be used.
之後，將透過上述方法獲得的塗膜暴露於活性能量以固化。作為用於活性能量照射的曝光裝置，直接光刻裝置(lithography device)(例如以電腦使用CAD數據直接以雷射表達圖案的雷射直接成像裝置)、配有金屬鹵素燈的曝光裝置、配有超高壓水銀燈((ultra)high pressure mercury lamp)的曝光裝置、使用例如超高壓水銀燈的紫外線燈的直接光刻裝置。作為活性能量，可以使用具有最大波長340至420nm的雷射光和紫外線燈，且可以使用氣體雷射和固態雷射兩者。例如可以通過具有以接觸或非接觸方法形成圖案的光罩，以活性能量選擇性曝光來形成圖案，或者以雷射直接曝光裝置直接曝光圖案並顯影未曝光的部分。 Thereafter, the coating film obtained by the above method is exposed to active energy to cure. As an exposure device for active energy irradiation, a direct lithography device (such as a laser direct imaging device that uses a computer to directly express patterns with laser using CAD data), an exposure device equipped with a metal halide lamp, an exposure device equipped with An exposure device using an ultrahigh pressure mercury lamp and a direct lithography device using an ultraviolet lamp such as an ultrahigh pressure mercury lamp. As active energy, laser light and ultraviolet lamp with a maximum wavelength of 340 to 420 nm can be used, and both gas laser and solid-state laser can be used. For example, the pattern can be formed by selectively exposing the pattern with active energy using a photomask that forms the pattern with a contact or non-contact method, or directly exposing the pattern with a laser direct exposure device and developing the unexposed portions.
作為顯影方法，可以使用浸漬法、噴淋法(shower method)、噴灑法、塗刷法(brush method)等，且作為顯影液可以使用鹼性水溶液，例如氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、或胺等。例如可以通過鹼性水溶液(0.1至3.0%碳酸鈉水溶液)顯影來形成圖案。 As a development method, a dipping method, a shower method, a spray method, a brush method, etc. can be used, and as a developer, an alkaline aqueous solution, such as potassium hydroxide, sodium hydroxide, and sodium carbonate can be used. , potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amine, etc. The pattern can be formed, for example, by development with an alkaline aqueous solution (0.1 to 3.0% sodium carbonate aqueous solution).
特別是，本發明的光敏感樹脂組成物包含具有熱固性質的環氧樹脂，且當加熱至130至160℃時，含有不飽和雙鍵的高耐熱樹脂的羧基與分子中 具有二個以上環(硫)醚基的熱固性成分反應，以形成具有優異的耐熱性、耐化學性、耐吸濕性(moisture absorption resistance)、黏著性和電氣特性的固化膜。 In particular, the photosensitive resin composition of the present invention includes an epoxy resin with thermosetting properties, and when heated to 130 to 160° C., the carboxyl group of the highly heat-resistant resin containing unsaturated double bonds is in the molecule. Thermosetting components with more than two cyclic (thio)ether groups react to form a cured film with excellent heat resistance, chemical resistance, moisture absorption resistance, adhesion and electrical properties.
本發明的其他態樣，提供一種通過使用該光敏感樹脂組成物獲得的焊料光阻、光敏感樹脂組成物的圖案化固化產物和包含該光敏感樹脂組成物的圖案化固化產物層的印刷線路板。 Other aspects of the present invention provide a solder photoresist obtained by using the photosensitive resin composition, a patterned cured product of the photosensitive resin composition, and a printed circuit including a patterned cured product layer of the photosensitive resin composition. plate.
在下文中，將通過實施例更詳細的描述本發明。以下所示的實施例僅用於理解本發明，且本發明的範圍不受任何意義上的限制。 Hereinafter, the present invention will be described in more detail through examples. The examples shown below are only for understanding the present invention, and the scope of the present invention is not limited in any sense.
[合成例1：含有胺甲酸乙酯基團的光敏感樹脂1的製備] [Synthesis Example 1: Preparation of photosensitive resin 1 containing urethane group]
在配有溫度計、攪拌裝置、回流冷凝器、壓力泵、空氣注射裝置(air injection device)和氮氣注射裝置的壓力反應器中，在氮氣輸入下，加入240g甲酚酚醛清漆樹脂(cresol novolac resin)(酚性羥基(phenolic hydroxyl)當量為120)、2.4g氫氧化鉀、240g甲苯，攪拌並加熱至125℃。之後，緩慢滴加128g環氧丙烷，並將混合物在125至135℃、5kg/cm2以下的壓力下反應15小時，接著冷卻至室溫，加入1.5g的90%磷酸並攪拌以中和氫氧化鉀。加入503g乙酸丁酯到所獲得的503g反應溶液中，將混合物攪拌10分鐘，以去離子水洗滌，並以卡必醇乙酸酯(carbitol acetate)取代溶劑，以獲得甲酚醛清漆多元醇(cresol novolac polyol)(不揮發物68%、羥值182g/eq(相對於固含量))。 In a pressure reactor equipped with a thermometer, stirring device, reflux condenser, pressure pump, air injection device and nitrogen injection device, add 240g of cresol novolac resin under nitrogen input. (phenolic hydroxyl equivalent is 120), 2.4g potassium hydroxide, and 240g toluene, stir and heat to 125°C. After that, 128g of propylene oxide was slowly added dropwise, and the mixture was reacted at 125 to 135°C and a pressure below 5kg/cm for 15 hours, then cooled to room temperature, 1.5g of 90% phosphoric acid was added and stirred to neutralize the hydrogen Potassium oxide. Add 503g butyl acetate to the obtained 503g reaction solution, stir the mixture for 10 minutes, wash with deionized water, and replace the solvent with carbitol acetate to obtain cresol varnish polyol (cresol). novolac polyol) (non-volatile matter 68%, hydroxyl value 182g/eq (relative to solid content)).
加入280g產生的多元醇、86g混合的芳香族溶劑(Kocosol#150)、0.1g作為聚合抑制劑的對苯二酚甲醚(methyl ether hydroquinone)、77.6g異氰酸基丙烯酸乙酯(isocyanato ethyl acrylate)(Showa Denko Corporation Karenz AOI)和0.1g錫催化劑(二月桂酸二丁基錫(dibutyltin dilaurate))，並在60℃下維持超過3小時，接著通過NCO%濕式測定將反應維持直到NCO%變成0.05%以下。 Add 280g of the produced polyol, 86g of mixed aromatic solvent (Kocosol#150), 0.1g of methyl ether hydroquinone as a polymerization inhibitor, and 77.6g of isocyanato ethyl acrylate) (Showa Denko Corporation Karenz AOI) and 0.1 g of tin catalyst (dibutyltin dilaurate) and maintained at 60°C for more than 3 hours, then the reaction was maintained by NCO% wet measurement until NCO% became Below 0.05%.
當NCO%變成0.05%以下時，加入0.5g對苯二酚甲醚、0.36g三苯膦(triphenylphosphine)和63.9g四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride)並維持在90℃，當通過紅外線光譜發現酸酐峰消失時，將反應終止以合成含有胺甲酸乙酯基團的光敏感樹脂1(固含量64%、聚氨酯丙烯酸酯基團當量377g/eq、酸值73mgKOH/g、重量平均分子量4,100g/mol)。 When the NCO% becomes below 0.05%, add 0.5g hydroquinone methyl ether, 0.36g triphenylphosphine and 63.9g tetrahydrophthalic anhydride and maintain it at 90°C. When the acid anhydride peak disappeared from the spectrum, the reaction was terminated to synthesize a photosensitive resin 1 containing urethane groups (solid content 64%, polyurethane acrylate group equivalent 377g/eq, acid value 73mgKOH/g, weight average molecular weight 4,100 g/mol).
[合成例2：含有胺甲酸乙酯基團的光敏感樹脂2的製備] [Synthesis Example 2: Preparation of photosensitive resin 2 containing urethane group]
在配有溫度計、攪拌裝置、回流冷凝器、空氣注射裝置和氮氣注射裝置的反應器中，在氮氣輸入下，加入240g甲酚酚醛清漆樹脂(酚性羥基當量為120)、1.2g三苯膦和206g碳酸丙烯酯(propylene carbonate)，攪拌並加熱至180℃。將混合物在180℃下反應10小時，冷卻至40℃，加入200g卡必醇乙酸酯、180g混合的芳香族溶劑(Kocosol#150)、0.1g作為聚合抑制劑的對苯二酚甲醚、170g異氰酸基丙烯酸乙酯(Showa Denko Corporation Karenz AOI)和0.3g錫催化劑(二月桂酸二丁基錫)，並在60℃下維持超過3小時，通過NCO%濕式測定將反應維持直到NCO%變成0.05%以下。 In a reactor equipped with a thermometer, stirring device, reflux condenser, air injection device and nitrogen injection device, under nitrogen input, add 240g of cresol novolac resin (phenolic hydroxyl equivalent is 120) and 1.2g of triphenylphosphine and 206g propylene carbonate, stir and heat to 180°C. The mixture was reacted at 180°C for 10 hours, cooled to 40°C, and 200g of carbitol acetate, 180g of mixed aromatic solvent (Kocosol#150), 0.1g of hydroquinone methyl ether as a polymerization inhibitor, and 170g ethyl isocyanatoacrylate (Showa Denko Corporation Karenz AOI) and 0.3g tin catalyst (dibutyltin dilaurate), and maintained at 60°C for more than 3 hours, the reaction was maintained until NCO% by NCO% wet measurement becomes less than 0.05%.
當NCO%變成0.05%以下時，加入1g對苯二酚甲醚、2.5g三苯膦和116g四氫鄰苯二甲酸酐並維持在90℃，當通過紅外線光譜發現酸酐峰消失時，將反應終止以合成含有胺甲酸乙酯基團的光敏感樹脂2(固含量62%、聚氨酯丙烯酸酯基團當量536g/eq、酸值66mgKOH/g、重量平均分子量4,010g/mol)。 When the NCO% becomes less than 0.05%, add 1g hydroquinone methyl ether, 2.5g triphenylphosphine and 116g tetrahydrophthalic anhydride and maintain it at 90°C. When the anhydride peak disappears through the infrared spectrum, stop the reaction. It was terminated to synthesize the photosensitive resin 2 containing urethane groups (solid content 62%, polyurethane acrylate group equivalent weight 536g/eq, acid value 66mgKOH/g, weight average molecular weight 4,010g/mol).
[合成例3：含有胺甲酸乙酯基團的光敏感樹脂3的製備] [Synthesis Example 3: Preparation of photosensitive resin 3 containing urethane group]
除了使用113g異氰酸基丙烯酸乙酯(Showa Denko Co.,Ltd.Karenz AOI)和30.4g四氫鄰苯二甲酸酐外，使用與合成例1中相同的方法合成含 有胺甲酸乙酯基團的光敏感樹脂3(固含量64%、聚氨酯丙烯酸酯基團當量250g/eq、酸值35mgKOH/g、重量平均分子量3,900g/mol)。 The same method as in Synthesis Example 1 was used except that 113 g of ethyl isocyanatoacrylate (Showa Denko Co., Ltd. Karenz AOI) and 30.4 g of tetrahydrophthalic anhydride were used. Photosensitive resin 3 with urethane groups (solid content 64%, polyurethane acrylate group equivalent 250g/eq, acid value 35mgKOH/g, weight average molecular weight 3,900g/mol).
[合成例4：含有胺甲酸乙酯基團的光敏感樹脂4的製備] [Synthesis Example 4: Preparation of Photosensitive Resin 4 Containing Urethane Groups]
除了使用35.3g異氰酸基丙烯酸乙酯(Showa Denko Co.,Ltd.Karenz AOI)和114g四氫鄰苯二甲酸酐外，使用與合成例1中相同的方法合成含有胺甲酸乙酯基團的光敏感樹脂4(固含量64.4%、聚氨酯丙烯酸酯基團當量830g/eq、酸值128mgKOH/g、重量平均分子量4,120g/mol)。 The same method as in Synthesis Example 1 was used to synthesize ethyl urethane groups except that 35.3 g of ethyl isocyanatoacrylate (Showa Denko Co., Ltd. Karenz AOI) and 114 g of tetrahydrophthalic anhydride were used. Photosensitive resin 4 (solid content 64.4%, polyurethane acrylate group equivalent 830g/eq, acid value 128mgKOH/g, weight average molecular weight 4,120g/mol).
[實驗例1至7] [Experimental Examples 1 to 7]
根據下表1顯示的組成物混合成分以製備各實驗例的光敏感樹脂組成物。 The components were mixed according to the composition shown in Table 1 below to prepare the photosensitive resin composition of each experimental example.
光敏感樹脂1：合成例1之含有胺甲酸乙酯基團的光敏感樹脂1(固含量64%、聚氨酯丙烯酸酯基團當量377g/eq、酸值73mgKOH/g、重量平均分子量4,100g/mol)。 Photosensitive resin 1: Photosensitive resin 1 containing urethane groups in Synthesis Example 1 (solid content 64%, polyurethane acrylate group equivalent 377g/eq, acid value 73mgKOH/g, weight average molecular weight 4,100g/mol ).
光敏感樹脂2：合成例2之含有胺甲酸乙酯基團的光敏感樹脂2(固含量62%、聚氨酯丙烯酸酯基團當量536g/eq、酸值66mgKOH/g、重量平均分子量4,010g/mol)。 Photosensitive resin 2: Photosensitive resin 2 containing urethane groups in Synthesis Example 2 (solid content 62%, polyurethane acrylate group equivalent 536g/eq, acid value 66mgKOH/g, weight average molecular weight 4,010g/mol ).
光敏感樹脂3：合成例3之含有胺甲酸乙酯基團的光敏感樹脂3(固含量64%、聚氨酯丙烯酸酯基團當量250g/eq、酸值35mgKOH/g、重量平均分子量3,900g/mol)。 Photosensitive resin 3: Photosensitive resin 3 containing urethane groups in Synthesis Example 3 (solid content 64%, polyurethane acrylate group equivalent 250g/eq, acid value 35mgKOH/g, weight average molecular weight 3,900g/mol ).
光敏感樹脂4：合成例4之含有胺甲酸乙酯基團的光敏感樹脂4(固含量64.4%、聚氨酯丙烯酸酯基團當量830g/eq、酸值128mgKOH/g、重量平均分子量4,120g/mol)。 Photosensitive resin 4: Photosensitive resin 4 containing urethane groups in Synthesis Example 4 (solid content 64.4%, polyurethane acrylate group equivalent 830g/eq, acid value 128mgKOH/g, weight average molecular weight 4,120g/mol ).
光敏感樹脂5：酸改質的環氧丙烯酸酯(用THFA改質的環氧丙烯酸酯、酸值52至56mgKOH/g、Mw 7,500g/mol)。 Photosensitive resin 5: acid-modified epoxy acrylate (epoxy acrylate modified with THFA, acid value 52 to 56 mgKOH/g, Mw 7,500g/mol).
環氧樹脂1：雙酚A型環氧樹脂(EEW 450g/eq、Mw 2,000g/mol)。 Epoxy resin 1: Bisphenol A type epoxy resin (EEW 450g/eq, Mw 2,000g/mol).
環氧樹脂2：聯苯環氧樹脂(EEW 180g/eq、Mw 354g/mol)。 Epoxy resin 2: biphenyl epoxy resin (EEW 180g/eq, Mw 354g/mol).
丙烯酸單體：DPHA(二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate)，6官能的)。 Acrylic monomer: DPHA (dipentaerythritol hexaacrylate, 6-functional).
光引發劑1：2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-1-丁酮(有效吸收波長：250至315nm)。 Photoinitiator 1: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (effective absorption wavelength: 250 to 315 nm).
光引發劑2：2,4-二乙基噻噸酮(DETX)(有效吸收波長：375至450nm)。 Photoinitiator 2: 2,4-diethylthioxanthone (DETX) (effective absorption wavelength: 375 to 450nm).
反應催化劑：三聚氰胺。 Reaction catalyst: melamine.
離子捕捉劑：70%Mg6Al2[(OH)16CO3]*4H2O和30% Zr(HPO4)2的混合物。 Ion trapping agent: a mixture of 70%Mg 6 Al 2 [(OH) 16 CO 3 ]*4H 2 O and 30% Zr(HPO 4 ) 2 .
填充劑：硫酸鋇(D50 0.3μm)。 Filler: barium sulfate (D50 0.3μm).
顏料1：偶氮類顏料。 Pigment 1: Azo pigment.
顏料2：酞菁類顏料。 Pigment 2: Phthalocyanine pigment.
溶劑1：二丙二醇單甲醚(dipropylene glycol monomethyl ether)。 Solvent 1: dipropylene glycol monomethyl ether.
溶劑2：溶劑石腦油。 Solvent 2: solvent naphtha.
[性能評估] [Performance evaluation]
通過以下方法量測根據各實驗例製備的光敏感樹脂組成物的性能，結果顯示於下表2。 The performance of the photosensitive resin composition prepared according to each experimental example was measured by the following method, and the results are shown in Table 2 below.
1.敏感度 1. Sensitivity
通過網版印刷將各實驗例的樹脂組成物施用於基板上，在80℃下乾燥30分鐘，並在室溫下冷卻。將用於敏感度評估的41段曝光表(41-step tablet)壓在乾燥的塗層上，並通過配有高壓水銀燈的曝光裝置以700mJ/cm2曝光，接著 在30℃下以1%碳酸鈉水溶液顯影90秒並水洗。之後，觀察光澤段(gloss step)中的最大段(largest step)以評估敏感度。 The resin composition of each experimental example was applied to the substrate by screen printing, dried at 80° C. for 30 minutes, and cooled at room temperature. A 41-step tablet for sensitivity evaluation was pressed onto the dried coating and exposed to 700 mJ/cm through an exposure device equipped with a high-pressure mercury lamp, followed by 1% carbonic acid at 30°C. Develop with sodium aqueous solution for 90 seconds and wash with water. Afterwards, the largest step among the gloss steps was observed to evaluate the sensitivity.
2.顯影寬容度(development margin) 2. Development margin
通過網版印刷將各實驗例的樹脂組成物施用於基板上，在80℃下從30分鐘到100分鐘每隔10分鐘取出，並在室溫下冷卻。之後，生成的產物在30℃下以1%碳酸鈉水溶液顯影120秒，並量測沒有任何殘留物的最大允許乾燥時間(顯影寬容度)。 The resin composition of each experimental example was applied to the substrate by screen printing, taken out every 10 minutes from 30 minutes to 100 minutes at 80° C., and cooled at room temperature. Afterwards, the resulting product was developed with 1% sodium carbonate aqueous solution at 30° C. for 120 seconds, and the maximum allowable drying time (development latitude) without any residue was measured.
3.分辨率 3. Resolution
通過網版印刷將各實驗例的樹脂組成物施用於基板上，在80℃下乾燥30分鐘，並在室溫下冷卻。將用於圖案光罩的薄膜壓在如上所述製備的基板上，並通過配有高壓水銀燈的曝光裝置以700mJ/cm2曝光，接著在30℃下以1%碳酸鈉水溶液顯影90秒並水洗以形成圖案。量測維持圓形的最小開口尺寸(分辨率)。 The resin composition of each experimental example was applied to the substrate by screen printing, dried at 80° C. for 30 minutes, and cooled at room temperature. The film used for the pattern mask was pressed onto the substrate prepared as above and exposed at 700 mJ/cm through an exposure device equipped with a high -pressure mercury lamp, followed by development with 1% sodium carbonate aqueous solution at 30°C for 90 seconds and water washing. to form patterns. Measure the minimum opening size (resolution) required to maintain a circular shape.
4.深部固化性 4. Deep curability
通過網版印刷將各實驗例的樹脂組成物施用於基板上，在80℃下乾燥30分鐘，並在室溫下冷卻。通過對乾燥樣品的FT-IR分析量測在丙烯酸特徵峰(1,410cm-1)處的峰面積(a)。將乾燥的塗層通過配有高壓水銀燈的曝光裝置曝光至700mJ/cm2，通過熱風烘箱在150℃下加熱固化1小時，接著通過配有高壓水銀燈的曝光裝置額外曝光至1,200mJ/cm2。將最終固化的樣品表面拋光以減少塗層厚度，並通過FT-IR分析量測丙烯酸特徵峰處的峰面積(b)。通過下式對丙烯酸固化性(深部固化性)進行評估。 The resin composition of each experimental example was applied to the substrate by screen printing, dried at 80° C. for 30 minutes, and cooled at room temperature. The peak area (a) at the characteristic peak of acrylic acid (1,410 cm −1 ) was measured by FT-IR analysis of the dried sample. The dried coating was exposed to 700 mJ/cm 2 through an exposure device equipped with a high-pressure mercury lamp, heated and cured in a hot air oven at 150°C for 1 hour, and then additionally exposed to 1,200 mJ/cm 2 through an exposure device equipped with a high-pressure mercury lamp. The surface of the final cured sample was polished to reduce the coating thickness, and the peak area (b) at the characteristic peak of acrylic acid was measured by FT-IR analysis. Acrylic curability (deep curability) was evaluated by the following formula.
(a-b)/a*100 (a-b)/a*100
5.底切 5.Undercut
通過網版印刷將各實驗例的樹脂組成物施用於基板上，在80℃下乾燥30分鐘，並在室溫下冷卻。將具有SR壩(Dam)(寬度：100μm)的圖案光罩的薄膜壓在乾燥基板上，通過配有高壓水銀燈的曝光裝置以700mJ/cm2曝光，接著在30℃下以1%碳酸鈉水溶液顯影90秒並水洗。之後，生成的產物通過熱風烘箱在150℃下加熱固化1小時，接著通過配有高壓水銀燈的曝光裝置額外曝光至1,200mJ/cm2。用剪刀將通過上述製程製備的基板切割成形成SR壩(寬度100μm)的部分，並用成型液(molding solution)成型，接著拋光壩的橫切面以使用顯微鏡(X 500放大率)量測底切共10次並記錄平均值。 The resin composition of each experimental example was applied to the substrate by screen printing, dried at 80° C. for 30 minutes, and cooled at room temperature. The film of the pattern mask with SR dam (width: 100 μm) was pressed on the dry substrate, exposed at 700 mJ/cm through an exposure device equipped with a high-pressure mercury lamp, and then exposed to 1% sodium carbonate aqueous solution at 30°C. Develop for 90 seconds and wash with water. After that, the resulting product was heated and cured in a hot air oven at 150°C for 1 hour, and then additionally exposed to 1,200 mJ/cm 2 through an exposure device equipped with a high-pressure mercury lamp. The substrate prepared by the above process was cut with scissors into the part forming the SR dam (width 100 μm), and molded with molding solution. Then the cross section of the dam was polished to measure the undercut total using a microscope (X 500 magnification). 10 times and record the average.
6.焊料耐熱性 6. Solder heat resistance
通過網版印刷將各實驗例的樹脂組成物施用於基板上，在80℃下乾燥30分鐘，並在室溫下冷卻。將用於圖案光罩的薄膜壓在乾燥的基板上，通過配有高壓水銀燈的曝光裝置曝光至700mJ/cm2，並通過熱風烘箱在150℃下加熱固化1小時，接著通過配有高壓水銀燈的曝光裝置額外曝光至1,200mJ/cm2。將通過上述製程製備的基板浸入設定為260℃的焊料浴中10秒。重複3次浸漬步驟後，目視觀察外觀的外部變化和SR層的剝落。 The resin composition of each experimental example was applied to the substrate by screen printing, dried at 80° C. for 30 minutes, and cooled at room temperature. The film used for the pattern mask is pressed on the dry substrate, exposed to 700mJ/cm 2 through an exposure device equipped with a high-pressure mercury lamp, and heated and cured by a hot air oven at 150°C for 1 hour, and then passed through an exposure device equipped with a high-pressure mercury lamp. The exposure device additionally exposes to 1,200mJ/cm 2 . Immerse the substrate prepared by the above process into a solder bath set at 260°C for 10 seconds. After repeating the dipping step three times, external changes in appearance and peeling of the SR layer were visually observed.
[評估標準] [Evaluation Criteria]
○：外觀無變化且無剝落 ○: No change in appearance and no peeling
△：外觀變化小且剝落小 △: Little change in appearance and little peeling
X：外觀嚴重變化和膜剝落 X: Severe change in appearance and film peeling
7. PCT耐性 7. PCT resistance
通過網版印刷將各實驗例的樹脂組成物施用於基板上，在80℃下乾燥30分鐘，並在室溫下冷卻。將乾燥的基板通過配有高壓水銀燈的曝光裝置曝光至700mJ/cm2，並通過熱風烘箱在150℃下加熱固化1小時，接著通過配有高壓水銀燈的曝光裝置額外曝光至1,200mJ/cm2。將通過上述製程製備的基板在121℃、100%濕度和2 atm的條件下以PCT設備(PCT-80,Iretech)處理168小時，接著觀察膜的狀態。 The resin composition of each experimental example was applied to the substrate by screen printing, dried at 80° C. for 30 minutes, and cooled at room temperature. The dried substrate was exposed to 700 mJ/cm 2 through an exposure device equipped with a high-pressure mercury lamp, heated and cured in a hot air oven at 150°C for 1 hour, and then additionally exposed to 1,200 mJ/cm 2 through an exposure device equipped with a high-pressure mercury lamp. The substrate prepared by the above process was treated with PCT equipment (PCT-80, Iretech) for 168 hours under the conditions of 121°C, 100% humidity and 2 atm, and then the state of the film was observed.
[評估標準] [Evaluation Criteria]
○：外觀無變化、無變色、無溶析 ○: No change in appearance, no discoloration, no dissolution
△：外觀變化小、有些變色和溶析 △: Little change in appearance, some discoloration and dissolution
X：外觀、變色和溶析嚴重變化 X: Severe changes in appearance, discoloration and dissolution
8. HAST耐性 8. HAST tolerance
通過網版印刷將各實驗例的樹脂組成物施用於形成有電極(線間距：30μm)的BT基板上，在80℃下乾燥30分鐘，並在室溫下冷卻。將乾燥的基板通過配有高壓水銀燈的曝光裝置曝光至700mJ/cm2，並通過熱風烘箱在150℃下加熱固化1小時，接著通過配有高壓水銀燈的曝光裝置額外曝光至1,200mJ/cm2。在130℃和85%濕度的條件下，對通過上述製程製備的基板施加5V電壓，並進行168小時的HAST評估。168小時後，量測絕緣電阻。 The resin composition of each experimental example was applied to a BT substrate on which electrodes (line spacing: 30 μm) were formed by screen printing, dried at 80° C. for 30 minutes, and cooled at room temperature. The dried substrate was exposed to 700 mJ/cm 2 through an exposure device equipped with a high-pressure mercury lamp, heated and cured in a hot air oven at 150°C for 1 hour, and then additionally exposed to 1,200 mJ/cm 2 through an exposure device equipped with a high-pressure mercury lamp. Under conditions of 130°C and 85% humidity, a voltage of 5V was applied to the substrate prepared through the above process, and a HAST evaluation was performed for 168 hours. After 168 hours, measure the insulation resistance.
[評估標準] [Evaluation Criteria]
○：108Ω以上 ○: 10 8 Ω or more
△：106至108Ω △: 10 6 to 10 8 Ω
X：106Ω以下 X: 10 6 Ω or less
[表2]
由表2結果可知，使用本發明的含有胺甲酸乙酯基團的光敏感樹脂的實驗例1至4的光敏感樹脂組成物在所有測定項目中表現出優異的特性。另一方面，與實驗例1至4相比，使用本發明的特性範圍以外的含有胺甲酸乙酯基團的光敏感樹脂的實驗例5和6的光敏感樹脂組成物和使用不具有胺甲酸乙酯基團的丙烯酸樹脂取代含有胺甲酸乙酯基團的光敏感樹脂的實驗例7的光敏感樹脂組成物在特性方面顯示出較差的結果。 As can be seen from the results in Table 2, the photosensitive resin compositions of Experimental Examples 1 to 4 using the urethane group-containing photosensitive resin of the present invention exhibit excellent characteristics in all measurement items. On the other hand, compared with Experimental Examples 1 to 4, the photosensitive resin compositions of Experimental Examples 5 and 6 using a photosensitive resin containing a urethane group outside the characteristic range of the present invention and using a photosensitive resin without a urethane group were used. The photosensitive resin composition of Experimental Example 7 in which the acrylic resin containing an ethyl ester group replaced the photosensitive resin containing an ethyl urethane group showed poor results in terms of characteristics.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW201042381A (en) * | 2009-04-10 | 2010-12-01 | Taiyo Ink Mfg Co Ltd | Solder resist composition, dry film using same, and printed wiring board |
| US20110189591A1 (en) * | 2008-10-01 | 2011-08-04 | Marc-Stephan Weiser | Prepolymer-based polyurethane formulations for producing holographic media |
| CN104698754A (en) * | 2015-03-23 | 2015-06-10 | 江南大学 | Photoresist composition prepared on basis of PCDL type urethane acrylate |
| KR20170104843A (en) * | 2016-03-08 | 2017-09-18 | 주식회사 엘지화학 | Photosensitive resin composition and photoimageable dielectric film |
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| EP1402321A1 (en) * | 2001-07-04 | 2004-03-31 | Showa Denko K.K. | Resist curable resin composition and cured article thereof |
| KR20100002574A (en) * | 2008-06-30 | 2010-01-07 | 주식회사 코오롱 | Photoresist composition, dry film resist, relief pattern, patterning method and electronic parts |
| US20110151195A1 (en) * | 2008-08-27 | 2011-06-23 | Kazuyuki Mitsukura | Photosensitive adhesive composition, and film adhesive, adhesive sheet, adhesive pattern, semiconductor wafer with adhesive layer and semiconductor device using the photosensitive adhesive composition |
| JP6201325B2 (en) | 2012-02-29 | 2017-09-27 | 東洋インキＳｃホールディングス株式会社 | Kinophthalone dye monomer, colorable polymer using the same, colored photosensitive composition using the same, and use thereof |
| JP6095023B2 (en) * | 2012-05-25 | 2017-03-15 | エルジー・ケム・リミテッド | Photosensitive resin composition, pattern, pattern manufacturing method, bezel pattern manufacturing method, and display panel |
| JP7085791B2 (en) * | 2017-04-21 | 2022-06-17 | 日本化薬株式会社 | Photosensitive resin composition and its cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110189591A1 (en) * | 2008-10-01 | 2011-08-04 | Marc-Stephan Weiser | Prepolymer-based polyurethane formulations for producing holographic media |
| TW201042381A (en) * | 2009-04-10 | 2010-12-01 | Taiyo Ink Mfg Co Ltd | Solder resist composition, dry film using same, and printed wiring board |
| CN104698754A (en) * | 2015-03-23 | 2015-06-10 | 江南大学 | Photoresist composition prepared on basis of PCDL type urethane acrylate |
| KR20170104843A (en) * | 2016-03-08 | 2017-09-18 | 주식회사 엘지화학 | Photosensitive resin composition and photoimageable dielectric film |
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