CN116731063A - Silane coupling agent, application thereof and photosensitive resin composition containing silane coupling agent - Google Patents
Silane coupling agent, application thereof and photosensitive resin composition containing silane coupling agent Download PDFInfo
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- CN116731063A CN116731063A CN202210670553.2A CN202210670553A CN116731063A CN 116731063 A CN116731063 A CN 116731063A CN 202210670553 A CN202210670553 A CN 202210670553A CN 116731063 A CN116731063 A CN 116731063A
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- halogen
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 70
- 239000011342 resin composition Substances 0.000 title claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 229910052736 halogen Inorganic materials 0.000 claims description 71
- 150000002367 halogens Chemical class 0.000 claims description 71
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 125000002947 alkylene group Chemical group 0.000 claims description 23
- -1 cyano, carboxyl Chemical group 0.000 claims description 22
- 229920001721 polyimide Polymers 0.000 claims description 22
- 239000004642 Polyimide Substances 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 229920005575 poly(amic acid) Polymers 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 125000000962 organic group Chemical group 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000001174 sulfone group Chemical group 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 150000003462 sulfoxides Chemical class 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- UWQPDVZUOZVCBH-UHFFFAOYSA-N 2-diazonio-4-oxo-3h-naphthalen-1-olate Chemical group C1=CC=C2C(=O)C(=[N+]=[N-])CC(=O)C2=C1 UWQPDVZUOZVCBH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims 5
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims 5
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 28
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 12
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 238000010382 chemical cross-linking Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 125000003545 alkoxy group Chemical group 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 150000004985 diamines Chemical class 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000000732 arylene group Chemical group 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- ZSXGLVDWWRXATF-UHFFFAOYSA-N N,N-dimethylformamide dimethyl acetal Chemical compound COC(OC)N(C)C ZSXGLVDWWRXATF-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JIMMXGXOJQXOQA-UHFFFAOYSA-N 1-bromo-4-(methoxymethyl)benzene Chemical compound COCC1=CC=C(Br)C=C1 JIMMXGXOJQXOQA-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 125000003375 sulfoxide group Chemical group 0.000 description 3
- YOZIDEHIYNEGMS-UHFFFAOYSA-N 1-chloro-4-(methoxymethyl)benzene Chemical compound COCC1=CC=C(Cl)C=C1 YOZIDEHIYNEGMS-UHFFFAOYSA-N 0.000 description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012858 packaging process Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002577 polybenzoxazole Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- OZPOTRRLBSVXKP-UHFFFAOYSA-N 1-ethoxypropan-2-yl formate Chemical compound CCOCC(C)OC=O OZPOTRRLBSVXKP-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VIOQEHXYEOORLQ-UHFFFAOYSA-N 1-methoxypropan-2-yl formate Chemical compound COCC(C)OC=O VIOQEHXYEOORLQ-UHFFFAOYSA-N 0.000 description 1
- KNOQHCDCNJJLDH-UHFFFAOYSA-N 4-(3-trimethoxysilylpropyl)phenol Chemical compound CO[Si](OC)(OC)CCCC1=CC=C(O)C=C1 KNOQHCDCNJJLDH-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 229910014455 Ca-Cb Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- CBVJWBYNOWIOFJ-UHFFFAOYSA-N chloro(trimethoxy)silane Chemical compound CO[Si](Cl)(OC)OC CBVJWBYNOWIOFJ-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- NLUNLVTVUDIHFE-UHFFFAOYSA-N cyclooctylcyclooctane Chemical group C1CCCCCCC1C1CCCCCCC1 NLUNLVTVUDIHFE-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PBMIETCUUSQZCG-UHFFFAOYSA-N n'-cyclohexylmethanediimine Chemical compound N=C=NC1CCCCC1 PBMIETCUUSQZCG-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention provides a silane coupling agent and application thereof, and a photosensitive resin composition containing the same, wherein the silane coupling agent has a structure shown in a formula I, and can form stable adhesion with a substrate through the special design of a molecular structure, has excellent heat resistance on the one hand, and has good compatibility with resin and strong acting force, and can form a stable chemical crosslinking network in a resin system in a high-temperature curing process, so that the adhesive force, adhesive force and adhesion of the photosensitive resin composition/photoresist film containing the same and the substrate are remarkably improved, and the heat resistance and moisture resistance are excellent, so that the reliability of a device is effectively improved. After the photosensitive resin composition containing the silane coupling agent is cured at a high temperature, the adhesion force between the formed film and the substrate is 5B grade, the adhesion force between the photoresist film and the substrate is strong, the stability is good, the adhesion force of 5B grade is still maintained after PCT treatment, the moisture-heat resistance property is excellent, and the reliability of the product is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of photosensitive materials, and particularly relates to a silane coupling agent and application thereof, and a photosensitive resin composition containing the same.
Background
With the progress of electronic communication technology, semiconductor devices, display panels and the like gradually develop to miniaturization, thinning and flexibility, which puts higher and higher demands on packaging technology and process of products. In general, resin materials such as polyimide and polybenzoxazole are widely used in the field of packaging of electronic devices such as semiconductors due to their excellent heat resistance and physical and chemical characteristics such as high strength, and specifically, such as a rewiring layer (ridistribution layer, RDL), a Bump layer in an IC device, a radiation-resistant protection and insulation layer of a device, a Pixel Defining Layer (PDL) and a Planarization Layer (PLN) in an OLED device. However, in order to obtain good performance, the resins such as polyimide and polybenzoxazole are required to have a high ring closure rate (close to 100%) to reduce performance defects caused by uncyclized sites (e.g., the uncyclized sites are easily degraded to break molecular bonds, resulting in poor material stability, poor tensile strength, etc.). In addition, in order to improve the adhesion between the film and the substrate, a component for improving the adhesion, such as a silane coupling agent, is generally introduced into the formulation. In order to achieve higher ring closure rate, polyimide resin needs to cure the resin precursor at high temperature (200-500 ℃), which easily causes the decomposition of the silane coupling agent to weaken the action effect; meanwhile, the existing silane coupling agent also has the problem of weak force between the silane coupling agent and resin, so that the adhesion force between the film and the substrate is insufficient, and the performance cannot be improved.
In order to improve the adhesion between the resin and the substrate, the development of a coupling agent which has good heat resistance and strong force with the resin film is one of the important points of current industry, and is also a problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a silane coupling agent and application thereof, and a photosensitive resin composition containing the silane coupling agent, wherein the silane coupling agent can form stable adhesion with a substrate through the design of a molecular structure, has good compatibility with a resin matrix and strong acting force, and can form a stable chemical crosslinking network in a resin system in a high-temperature curing process, so that the adhesive force of the photosensitive resin composition containing the silane coupling agent and the substrate is obviously improved, and the reliability of a device is effectively improved.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a silane coupling agent having a structure as shown in formula I:
in the formula I, R 1 、R 2 、R 3 Each independently represents a C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) monovalent organic group.
In the formula I, R 4 Is that* Representing the attachment site of the group.
L represents a C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.) divalent organic group.
R 5 Selected from any one of C1-C8 (e.g., C2, C3, C4, C5, C6, or C7, etc.) straight or branched chain alkyl groups.
R 6 is-CH 2 -or phenylene group
j is 0 or 1; when j is 0, represents a Si atom and R in formula I 4 The benzene ring of the medium benzyl ether is directly connected through a single bond; when j is 1, represents a Si atom and R in formula I 4 R in (a) 6 Are connected.
h represents-CH 2 -O-R 5 An integer selected from 1-5, for example, 1, 2, 3, 4 or 5; when h is equal to or greater than 2, a plurality of (at least 2) R 5 Are the same or different groups.
The silane coupling agent provided by the invention has a structure shown in a formula I, and the molecular structure contains a benzyl ether group R 4 In the high temperature curing processCan react with resin and other auxiliary agents in the photoresist film (solidified by photosensitive resin composition) to generate stable covalent bonds; meanwhile, the structure contains alkoxy silane groups, and the alkoxy silane groups can react with hydroxyl groups on the surface of the substrate to generate stable Si-O-Si bonds, so that the photoresist film has excellent adhesion with the substrate after being cured at high temperature. In the silane coupling agent, R 4 Is thatWhen the structure is the former, a flexible chain segment is arranged between Si and benzyl ether groups in the molecule, so that the adhesion between the resin and the substrate is further improved; when the structure is the latter, si is directly bonded with the aromatic ring, so that the structure has better heat resistance, and even if the photoresist film is cured at a higher temperature (more than 300 ℃), the structure can be kept stable, the coupling performance is not reduced due to high-temperature curing (imidization), and the formed photoresist film has excellent adhesive force with a substrate after high-temperature curing. Therefore, the silane coupling agent provided by the invention can form stable adhesion with a substrate through the design of a molecular structure, has good compatibility with a resin matrix and strong acting force, and forms a stable covalent bond crosslinking network with components in a resin system in a high-temperature curing process, so that the adhesive force of a photosensitive resin composition/photoresist film containing the silane coupling agent and the substrate is obviously improved, the heat resistance is excellent, and the reliability and other comprehensive properties of a device are effectively improved.
In the present invention, unless otherwise specified, the expression of chemical elements includes the concept of isotopes having the same chemical properties, for example, hydrogen (H) includes 1 H (protium), 2 H (deuterium, D), 3 H (tritium, T), etc.; carbon (C) then comprises 12 C、 13 C, etc.
In the present invention, the expression "Ca-Cb" means that the group has a carbon number of a-b; unless otherwise specified, generally the number of carbon atoms excludes the number of carbon atoms of a substituent.
In the present invention, "each independently" means that the subject has a plurality of subjects, and the subjects may be the same or different from each other.
In the present invention, the terms "monovalent organic group", "divalent organic group", "tetravalent organic group" include any organic group satisfying the chemical environment.
In the present invention, the expression "the ring structure" indicates that the linking site is located at any position on the ring structure that is capable of bonding.
Preferably, said R 1 、R 2 、R 3 Each independently selected from any of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.), and more preferably any of C1-C6, linear or branched alkyl, illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and the like.
Preferably, the L is selected from C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.) linear or branched alkylene, or one or at least two (e.g., 2, 3, or 4, etc.) -CH of the C1-C20 linear or branched alkylene 2 -is-O-, -S-, -NR N1 -CO-, C6-C20 (e.g. C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) arylene.
R N1 Any one selected from hydrogen, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.), straight or branched alkyl, C6-C20 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc.), and the like, is further preferred.
Preferably, the L is selected from C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) linear alkylene, or one or at least two (e.g., 2, 3, or 4, etc.) -CH of the C1-C10 linear alkylene 2 -any one of the groups replaced by-O-, -NH-, -CO-, phenylene.
Preferably, said R 4 Selected from any one of the following structures:
wherein represents the attachment site of the group.
i. x represents-CH respectively 2 -number, wherein i is selected from integers from 1 to 7, which may be for example 1, 2, 3, 4, 5, 6 or 7; x is selected from integers from 0 to 7 and may be, for example, 1, 2, 3, 4, 5, 6 or 7.
Preferably, said R 5 Any one of C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) straight-chain or branched alkyl group, and more preferably methyl group.
Preferably, h is an integer from 1 to 3.
Preferably, said R 4 Selected from the group consisting of Represents the attachment site of the group.
In a second aspect, the present invention provides the use of a silane coupling agent as described in the first aspect in a photosensitive material.
In a third aspect, the present invention provides a photosensitive resin composition comprising a combination of an alkali-soluble resin, a photosensitive compound, and a silane coupling agent as described in the first aspect.
Preferably, the alkali-soluble resin includes any one or a combination of at least two of polyimide precursor resin, polyamic acid-polyimide copolymer, polyisoimide-polyamic acid copolymer, polyisoimide or polyimide.
Preferably, the alkali-soluble resin comprises at least one of structural units represented by formula II, formula III or formula IV:
wherein R is 10 、R 12 、R 14 、R 16 Each independently represents a C4-C60 (e.g., C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C35, C36, C38, C40, C42, C45, C48, C50, C52, C55, C58, etc.) tetravalent organic group.
R 11 、R 13 、R 15 、R 17 Each independently represents a divalent organic group of C3-C60 (e.g., 4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C35, C36, C38, C40, C42, C45, C48, C50, C52, C55, or C58, etc.).
R 18 、R 19 Each independently selected from any of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight or branched chain alkyl groups.
The photosensitive resin composition provided by the invention comprises a combination of an alkali-soluble resin, a photosensitive compound and a silane coupling agent as described in the first aspect; the silane coupling agent has good compatibility with alkali-soluble resin, strong acting force and excellent heat resistance, can react with hydroxyl groups on the surface of a substrate to form stable silicon-oxygen-silicon bonds, and can react with other components such as the alkali-soluble resin in the high-temperature curing (curing and/or imidizing) process to generate a stable covalent cross-linked network, so that a photoresistance film formed by the photosensitive resin composition has excellent cohesive force and adhesiveness with the substrate, and the reliability of a device is effectively improved.
As a preferred embodiment of the present invention, the alkali-soluble resin includes any one or a combination of at least two of polyimide precursor resins (polyamic acid and/or polyamic acid ester, preferably comprising structural units represented by formula II), polyamic acid-polyimide copolymers (preferably comprising structural units represented by formula III), or polyimides (preferably comprising structural units represented by formula IV).
Preferably, the alkali-soluble resin has a number of structural units represented by formula II of f and a number of structural units represented by formula IV of g, each of f and g being independently an integer of 2 to 200, for example, 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, 130, 150, 170, 190 or the like.
Preferably, the structural unit of formula III in the alkali-soluble resin comprises a polyimide fragmentAnd a polyamic acid (polyamic acid ester) fragment->The two fragments are linked by chemical bonds, the number of which is each independently an integer from 2 to 200, such as 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, 130, 150, 170, 190, etc.
Preferably, said R 10 、R 12 、R 14 、R 16 Each independently selected from any of a substituted or unsubstituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) tetravalent aromatic group, a substituted or unsubstituted C4-C20 (e.g., C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc.) tetravalent cycloaliphatic group.
R 10 、R 12 、R 14 、R 16 Each independently selected from at least one of halogen, hydroxy, unsubstituted or halogen substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.), straight or branched alkyl, unsubstituted or halogen substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.) alkoxy.
Preferably, the "substituted or unsubstituted" group may be substituted with one substituent or may be substituted with a plurality of substituents, and when the substituents are a plurality (at least 2), they may be the same or different substituents; when the following description refers to the same expression mode, the same meaning is provided, and the selection ranges of the substituents are shown above and are not repeated.
In the present invention, the C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) tetravalent aromatic group includes C6-C30 aryl (e.g., phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, anthracenyl, phenanthrenyl, triphenylenyl, tetracenyl, etc.) or aryl linked by a bridging linkage (single bond, O, S, sulfoxide, sulfone, substituted or unsubstituted alkylene, etc.). The following description refers to examples of "C6-C30 divalent aromatic groups".
The C4-C20 (e.g., C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc.) tetravalent alicyclic group, "alicyclic group" means a non-aromatic saturated or unsaturated cyclic structure including single, bridged, spiro, or fused rings, etc., and illustratively includes but is not limited to: cyclobutyl, cyclopentyl, cyclohexyl, bicyclooctyl, and the like. The following references to "C4-C20 divalent cycloaliphatic radicals" have similar examples.
The C1-C20 straight or branched alkyl groups may be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18 straight or branched alkyl groups; exemplary include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl, n-decyl and the like.
Specific examples of the C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18) alkoxy group include monovalent groups obtained by linking the above-mentioned examples of the linear or branched alkyl groups to O.
In the present invention, the halogen includes fluorine, chlorine, bromine or iodine; by "halogen substituted" is meant that at least 1 hydrogen in the group is substituted with halogen (fluorine, chlorine, bromine or iodine), preferably fluorine.
Preferably, said R 10 、R 12 、R 14 、R 16 Each independently selected from, e.g.Any one of the following groups:
wherein represents the attachment site of the group.
R 21 、R 22 、R 23 、R 24 、R 25 、R 26 Each independently selected from any of hydrogen, halogen, hydroxy, unsubstituted or halogen substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.), straight or branched chain alkyl, unsubstituted or halogen substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.) alkoxy, further preferably hydrogen, fluoro, methyl, methoxy, perfluoromethyl, or perfluoromethoxy.
L 21 Selected from single bonds, -O-, -S-, sulfone groupsSulfoxide group->Unsubstituted or R '-substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight or branched chain alkylene, unsubstituted or R' -substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) arylene, -. L 22 -Ar 21 -L 23 Any one of.
L 22 、L 23 Each independently selected from any of-O-, -S-, sulfone group, sulfoxide group, unsubstituted or R' substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight or branched alkylene groups.
Ar 21 Any one selected from unsubstituted or R' substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) arylene.
R' is selected from at least one of halogen, hydroxy, unsubstituted or halogen substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.), straight or branched chain alkyl, unsubstituted or halogen substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.) alkoxy.
Preferably, the L 21 Selected from single bond, -O-,-CH 2 -、/> any one of the following.
Preferably, said R 10 、R 12 、R 14 、R 16 Each independently selected from any one of the following groups:
wherein represents the attachment site of the group.
Preferably, said R 11 、R 13 、R 15 、R 17 Each independently selected from any of a group of formula V, a substituted or unsubstituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.), a substituted or unsubstituted C4-C20 (e.g., C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc.), a divalent cycloaliphatic group.
R 11 、R 13 、R 15 、R 17 Each independently selected from at least one of halogen, hydroxy, unsubstituted or halogen substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.), straight or branched alkyl, unsubstituted or halogen substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, or C18, etc.) alkoxy.
* Representing the attachment site of the group.
A is selected from any one of a single bond, -O-, -S-, sulfonyl, substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) divalent aliphatic hydrocarbon group, substituted or unsubstituted C3-C20 (e.g., C4, C5, C6, C7, C8, C9, C10, C12, C14, C15, C17, or C18, etc.) divalent cycloaliphatic group, substituted or unsubstituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) divalent aromatic group.
The substituents in A are each independently selected from at least one of halogen, unsubstituted or halogen substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight or branched chain alkyl, unsubstituted or halogen substituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) aryl, unsubstituted or halogen substituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) phenol.
R 31 、R 32 Each independently selected from any of halogen, nitro, cyano, carboxyl, unsubstituted or halogen substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight or branched chain alkyl, unsubstituted or halogen substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkoxy, unsubstituted or halogen substituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) aryl, amido, benzyl ether, or benzyl alcohol.
R 33 、R 34 Each independently selected from any of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.), straight or branched chain alkylene, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.), alkyleneoxy, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.), si-containing divalent groups.
R 35 、R 36 Each independently selected from the group consisting of 2 -O-C m H 2m+1 M is an integer from 0 to 8, and may be, for example, 0, 1, 2, 3, 4, 5, 6, 7 or 8.
R 37 、R 38 Each independently selected from any of halogen, hydroxy, nitro, cyano, carboxy, unsubstituted or halogen substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight or branched chain alkyl, unsubstituted or halogen substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkoxy, unsubstituted or halogen substituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) aryl, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) ester group, or amide group.
k 1 、k 2 、s 1 、s 2 、p 1 、p 2 、q 1 、q 2 Each independently selected from integers from 0 to 4, for example, 0, 1, 2, 3, 4.
n 1 、n 2 Each independently 0 or 1; when n is 1 、n 2 When 0, it means that the benzene ring is directly connected with-CO-through a single bond.
Preferably, in formula V the A is selected from any one of sulphone, substituted or unsubstituted C1-C6 (e.g. C1, C2, C3, C4, C5 or C6) straight or branched alkylene; the substituents in A are each independently selected from at least one of halogen, phenol, unsubstituted or halogen substituted C1-C6 (e.g., C1, C2, C3, C4, C5 or C6) straight or branched alkyl, unsubstituted or halogen substituted C1-C6 (e.g., C1, C2, C3, C4, C5 or C6) alkoxy.
Further preferably, in formula V, the A is selected from the group consisting of sulfone groups,
Preferably, R in formula V 33 、R 34 Each independently selected from any one of C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) straight or branched chain alkylene, C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkyleneoxy, further preferably-CH 2 -*、*-CH 2 -O-or-O-CH 2 -*。
Preferably, R in formula V 35 、R 36 Each independently is-CH 2 -OH or-CH 2 -O-CH 3 。
Preferably, said p in formula V 1 、p 2 、q 1 、q 2 Each independently selected from integers from 1 to 3, more preferably 1 or 2.
Preferably, the group represented by formula V has any one of the following structures:
/>
wherein represents the attachment site of the group.
Preferably, said R 11 、R 13 、R 15 、R 17 Each independently selected from the group represented by formula V, Any one of them;
wherein represents the attachment site of the group.
R 41 、R 42 Each independently selected from halogen, hydroxy, unsubstituted or halogen substituted C1-C20 (e.g., C2, C3, C4, C5,C6, C7, C8, C9, C10, C12, C15, C17, or C19, etc.), a linear or branched alkyl group, an unsubstituted or halogen-substituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C17, or C19, etc.) alkoxy group, further preferably a hydroxyl group, fluorine, methyl, methoxy, perfluoromethyl, or perfluoromethoxy group.
L 41 Selected from single bond, -O-, -S-, sulfone group, sulfoxide group, unsubstituted or halogen substituted C1-C10 (e.g. C2, C3, C4, C5, C6, C7, C8 or C9, etc.) straight or branched chain alkylene, unsubstituted or halogen substituted C6-C20 (e.g. C6, C9, C10, C12, C14, C16 or C18, etc.) arylene, -L 42 -Ar 41 -L 43 Any one of.
L 42 、L 43 Each independently selected from any of-O-, -S-, sulfone group, sulfoxide group, unsubstituted or halogen substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight or branched alkylene group.
Ar 41 Any one selected from unsubstituted or R' substituted C6-C20 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) arylene.
R' is selected from any one of halogen, hydroxyl, unsubstituted or halogen substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) straight or branched chain alkyl, unsubstituted or halogen substituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkoxy.
u 1 、u 2 Each independently selected from integers from 0 to 4, for example, may be 0, 1, 2, 3 or 4.
Preferably, the L 41 Selected from single bond, -O-,-CH 2 -、/> any one of the following.
Preferably, said R 11 、R 13 、R 15 、R 17 Each independently selected from the group represented by formula V,
Any one of them;
* Representing the attachment site of the group.
Preferably, the alkali-soluble resin has a weight average molecular weight of 2000 to 100000, for example, 3000, 5000, 8000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 70000, 80000, 90000, or the like, and more preferably 5000 to 50000.
Preferably, the alkali-soluble resin comprises a polyimide precursor resin (polyamic acid and/or polyamic acid ester, preferably comprising structural units represented by formula II), which can be prepared in a manner well known in the art, and illustratively comprises the following routes: (1) Diamine is directly polymerized with dianhydride to obtain polyamic acid, and then the polyamic acid ester is generated through esterification reaction; (2) Reacting dianhydride with alcohol to generate dicarboxylic acid diester, reacting with thionyl chloride to generate diacyl chloride diester, and polymerizing with diamine compound to obtain polyamic acid ester; (3) The dicarboxylic acid anhydride reacts with alcohol to generate dicarboxylic acid diester, and then reacts with diamine compound in the presence of dehydrating agents such as cyclohexyl carbodiimide and the like to polymerize to obtain polyamic acid ester.
Preferably, the preparation method of the polyimide precursor resin comprises the following steps: first, a diamine monomer (NH) 2 -R 11 -NH 2 ) With dianhydride monomers Polymerizing to obtain polyamic acid; and (3) carrying out esterification reaction on the polyamide acid to obtain the polyimide precursor resin.
Preferably, the reagent for the esterification reaction comprises N, N-dimethylformamide dimethyl acetal.
Preferably, the polyimide precursor resin can introduce a blocking agent into the end group, and in order to further improve the performance, the blocking agent can introduce groups such as alkenyl, alkynyl, benzyl ether, benzyl alcohol and the like, and the performance such as the strength of the film is improved through a crosslinking reaction in the subsequent curing process.
Preferably, the capping agent illustratively includes, but is not limited to:
preferably, the photosensitive compound is a compound containing a diazonaphthoquinone group.
Preferably, the diazonaphthoquinone group has the structure of* Representing the attachment site of the group.
Preferably, the photosensitive resin composition further comprises a crosslinking agent.
Preferably, a solvent and/or other auxiliary agents are also included in the photosensitive resin composition.
Preferably, the solvent is a solvent commonly used in the art, including but not limited to any one or a combination of at least two of gamma-butyrolactone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether formate, propylene glycol monoethyl ether formate, ethyl lactate, butyl lactate, azamethylpyrrolidone, N-dimethylformamide, or N, N-dimethylacetamide.
Preferably, the other auxiliary agents include other silane coupling agents and/or surfactants.
In the present invention, the "other silane coupling agent" means other silane coupling agents than the silane coupling agent having the structure shown in formula I provided in the present invention.
The other silane coupling agent contains at least one reactive functional group in addition to the alkoxy silicon group; preferably, the other silane coupling agent contains at least one of vinyl, allyl, oxy, styryl, acyloxy, acryloxy, ureido, amino, imidazolyl, tertiary amino, secondary amino, mercapto or isocyanate groups.
Preferably, the surfactant comprises any one or a combination of at least two of a fluorosurfactant, a polyethylene glycol-containing surfactant, or a silicone-containing surfactant.
Preferably, the other auxiliary agents help to improve the planarization degree of the film, further improve the adhesion between the photoresist film and the substrate, reduce the residual film after development, and the like.
Preferably, the other auxiliary agents further comprise photoacid generators, thermal acid generators, photobase generators, thermal base generators and the like, which can promote the crosslinking reaction between the resin and the crosslinking agent and/or the ring-closure reaction of the resin in the curing process.
Preferably, the photosensitive resin composition comprises the following components in percentage by mass:
wherein the alkali-soluble resin is contained in an amount of 4 to 30% by mass, for example, 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28% by mass, and the like, and more preferably 5 to 20% by mass.
The mass percentage of the photosensitive compound is 0.4-8%, for example, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7% or 7.5%, etc.
The mass percentage of the silane coupling agent having the structure shown in the formula I is 0.001-0.5%, for example, 0.003%, 0.005%, 0.008%, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4% or 0.45% and the like.
The cross-linking agent is 0.4-10% by mass, and may be, for example, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% or 9.5%.
The content of the other auxiliary agent is 0.001-0.5% by mass, for example, 0.005%, 0.008%, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4% or 0.45% by mass, etc.
The solvent is 55-95% by mass, for example, 58%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 93% by mass, etc.
Preferably, the photosensitive resin composition has a solid content of 5 to 45%, more preferably 8 to 30%, and an excessively low solid content is unfavorable for forming a continuous film having a certain thickness, whereas an excessively high solid content may cause an excessively high viscosity and thus cause problems of generation of bubbles during coating, deterioration of flatness, and the like.
In a fourth aspect, the present invention provides a use of the photosensitive resin composition according to the third aspect in a flat panel display device or a semiconductor device.
Preferably, the photosensitive resin composition is used for a stress buffer material of a semiconductor device, a passivation layer, a pixel defining layer in a display device, a planarization layer, and the like.
Preferably, the photosensitive resin composition can form a cured film after being coated, pre-baked, photo-etched, developed and cured, and is permanently reserved in a semiconductor device or a flat panel display device (display panel), and the cured film has excellent substrate adhesion and can be used in the packaging process of flexible semiconductors, flat panel displays and other devices.
Compared with the prior art, the invention has the following beneficial effects:
(1) The silane coupling agent provided by the invention has a structure shown in a formula I, and can form stable adhesion with a substrate on one hand, and has excellent heat resistance on the other hand, good compatibility with resin and strong acting force, and can form a stable chemical crosslinking network in a resin system in a high-temperature curing process, so that the adhesion, adhesive force and adhesion of a photosensitive resin composition/photoresist film containing the silane coupling agent and the substrate are obviously improved, the heat resistance and moisture resistance are excellent, and the reliability of a device is effectively improved.
(2) After the photosensitive resin composition containing the silane coupling agent is cured at a high temperature, the adhesion force between the formed film and the substrate is 5B grade, the adhesion force between the photoresist film and the substrate is strong, the stability is good, the excellent adhesion force of 5B grade is still maintained after PCT high-temperature steam treatment, the moisture-heat resistance property is excellent, and the reliability of the product is remarkably improved.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In one embodiment, the silane coupling agent having the structure shown in formula I can be prepared by using the following synthetic route a, synthetic route B or synthetic route C:
Synthetic route a: the R is 4 Is thatThe specific method comprises the following steps: />
Synthetic route B: the R is 4 Is thatThe specific method comprises the following steps:
synthetic route C: the R is 4 Is thatY is O or NH, and the specific method is as follows:
in the aforementioned synthetic route, U 1 、U 2 Each independently selected from halogen, preferably chlorine, bromine or iodine; r is R 1 、R 2 、R 3 、R 5 H has the same defined range as in formula I; i is selected from integers from 1 to 7.
The preparation method of the silane coupling agent shown in the formula I comprises, but is not limited to, the synthesis method, and a person skilled in the art can also perform routine adjustment on the preparation method according to actual needs, and the silane coupling agent with the structure shown in the formula I synthesized by adopting other methods also belongs to the protection scope of the invention.
The present invention provides, by way of example, a specific method of synthesizing a representative silane coupling agent, and the solvents and reagents used in the synthesis examples are commercially available or customizable from the chemical product market. The structure of the product in the synthesis example was tested by ZAB-HS type mass spectrometer (manufactured by Micromass Co., UK).
Synthesis example 1
A silane coupling agent A1 has the structure ofThe specific synthesis method is as follows:
under the protection of nitrogen, 164g of methyl orthosilicate and 0.5mol of metallic sodium are added into a three-mouth bottle, the metallic sodium is stirred by heating to form sodium sand, then a mixed solution of 0.5mol of 1-chloro-4- (methoxymethyl) benzene and 0.6mol of trimethoxy chlorosilane is dripped into the three-mouth bottle at 105 ℃, after the dripping is finished, the reaction is continued for 1.5h, and the crude product is obtained by reduced pressure distillation; purifying the crude product by column chromatography to obtain the silane coupling agent A1; mass spectrometry test results: m/z value (m+1): 243.
Synthesis example 2
A silane coupling agent A2 has the structure ofThe specific synthesis method is different from synthesis example 1 only in that 1-chloro-4- (methoxymethyl) benzene is replaced by 4-chloro-1, 2-bis (methoxymethyl) benzene with the same molar quantity, and other raw materials and process parameters are the same as those of synthesis example 1, so as to obtain the silane coupling agent A2; mass spectrometry test results: m/z value (m+1): 287.
synthesis example 3
A silane coupling agent A3 has the structure ofThe specific synthesis method is as follows:
palladium acetate (0.004 mol), 2- (di-tert-butylphosphine) biphenyl (0.01 mol), sodium tert-butoxide (0.2 mol), anhydrous toluene (75 mL) and gamma-aminopropyl trimethoxysilane (0.1 mol) are put into a 250mL three-necked glass flask, and after deoxidization, nitrogen flow is introduced for protection. After 1-bromo-4- (methoxymethyl) benzene (0.08 mol) in anhydrous toluene (75 mL) was added dropwise to the reaction system, the reaction mixture was heated to 80℃and the content of 1-bromo-4- (methoxymethyl) benzene in the reaction system was monitored by gas chromatography-mass spectrometry during the reaction until the reaction was completed, and then the reaction was completed and cooled to room temperature naturally. Diluting the reaction solution with dichloromethane, filtering the reaction solution by diatomite to remove solid components, rotationally evaporating the solvent, and purifying the crude product by column chromatography to obtain the silane coupling agent A3; mass spectrometry test results: m/z value (m+1): 300.
Synthesis example 4
A silane coupling agent A4 has the structure ofThe specific synthesis method is different from synthesis example 3 only in that 1-bromo-4- (methoxymethyl) benzene is replaced by equimolar amount of 4-bromo-1, 2-bis (methoxymethyl) benzene, and other raw materials and process parameters are the same as those of synthesis example 3, so as to obtain the silane coupling agent A4; mass spectrometry testingResults: m/z value (m+1): 344.
synthesis example 5
A silane coupling agent A5 has the structure ofThe specific synthesis method is as follows:
anhydrous toluene (75 mL) and gamma-aminopropyl trimethoxysilane (0.1 mol) were placed in a 250mL three-necked glass flask and deoxygenated and then protected by nitrogen flow. An anhydrous toluene solution (75 mL) of 1-isocyanato-4- (methoxymethyl) benzene (0.95 mol) was added dropwise to the reaction system, and the reaction mixture was heated to 60℃to react for 24 hours and then cooled naturally to room temperature. Diluting the reaction solution with dichloromethane, filtering with diatomite, removing the solvent by rotary evaporation, and purifying the crude product by column chromatography to obtain the silane coupling agent A5; mass spectrometry test results: m/z value (m+1): 343.
synthesis example 6
A silane coupling agent A6 has the structure ofThe specific synthesis method is as follows:
anhydrous toluene (75 mL) and gamma-hydroxypropyl trimethoxysilane (0.1 mol) were placed in a 250mL three-necked glass flask and deoxygenated and then protected by nitrogen flow. An anhydrous toluene solution (75 mL) of 1-isocyanato-4- (methoxymethyl) benzene (0.95 mol) was added dropwise to the reaction system, and the reaction mixture was heated to 60℃to react for 24 hours and cooled naturally to room temperature. Diluting the reaction solution with dichloromethane, filtering with diatomite, removing the solvent by rotary evaporation, and purifying the crude product by column chromatography to obtain the silane coupling agent A6; mass spectrometry test results: m/z value (m+1): 344.
Synthesis example 7
A silane coupling agent A7 has the structure ofThe specific synthesis method is as follows:
anhydrous toluene (75 mL) and 4- ((trimethoxysilyl) propyl) phenol (0.1 mol) were placed in a 250mL three-necked glass flask and deoxygenated and then protected by a nitrogen flow. An anhydrous toluene solution (75 mL) of 1-isocyanato-4- (methoxymethyl) benzene (0.95 mol) was added dropwise to the reaction system, and the reaction mixture was heated to 60℃to react for 24 hours and cooled naturally to room temperature. Diluting the reaction solution with dichloromethane, filtering with diatomite, removing the solvent by rotary evaporation, and purifying the crude product by column chromatography to obtain the silane coupling agent A7; mass spectrometry test results: m/z value (m+1): 420.
in the following embodiments of the present invention, the weight average molecular weight of the alkali-soluble resin is measured by gel chromatography (GPC), and the measuring instrument is a malvern Viscotek gel permeation chromatograph, D6000M column.
Preparation example 1
An alkali-soluble resin B1, specifically a polyimide precursor resin, is prepared by the following steps:
6.04g of diamine compound 1 was dissolved in 20mL of N-methylpyrrolidone (NMP) under nitrogen protection, cooled to 0℃and a mixture of 3.87g of 3, 4-diphenylether tetraanhydride and 12g of anhydrous NMP was rapidly added to the reaction system, and the reaction was maintained at 0℃for 5 hours. Heating to 60 ℃, slowly dropwise adding 2.68g of N, N-dimethylformamide dimethyl acetal into a reaction system, keeping the temperature of 60 ℃ for reaction for 2 hours, cooling to room temperature, pouring the reaction solution into 300mL of deionized water, filtering, collecting precipitate, and vacuum drying the precipitate at 50 ℃ for 24 hours to obtain the alkali-soluble resin B1 with the weight average molecular weight of 8500.
Diamine compound 1:
preparation example 2
An alkali-soluble resin B2, specifically a polyimide precursor resin, was prepared by the same method as that of preparation example 1 except that diamine compound 1 was replaced with an equimolar amount of diamine compound 2, and other raw materials and process parameters were the same as those of preparation example 1, to obtain the alkali-soluble resin B2 having a weight average molecular weight of 8300.
Diamine compound 2:
preparation example 3
An alkali-soluble resin B3, specifically a polyimide precursor resin, is prepared by the following steps:
under the protection of nitrogen, 0.692g of diamine compound 3 and 5.44g of diamine compound 2 are dissolved in 20mL of NMP, the temperature is reduced to 0 ℃, and a mixture of 3.87g of 3, 4-diphenyl ether tetraanhydride and 12g of NMP is quickly added into a reaction system, and the reaction is kept at 0 ℃ for 5 hours. Heating to 60 ℃, slowly dropwise adding 2.68g of N, N-dimethylformamide dimethyl acetal into a reaction system, keeping the temperature of 60 ℃ for reaction for 2 hours, cooling to room temperature, pouring the reaction solution into 300mL of deionized water, filtering, collecting precipitate, and vacuum drying the precipitate at 50 ℃ for 24 hours to obtain the alkali-soluble resin B3 with the weight average molecular weight of 8500.
Diamine compound 3:
preparation example 4
An alkali-soluble resin B4, specifically a polyimide precursor resin, is prepared by the following steps:
Under the protection of nitrogen, 1.10g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1.00g of 4, 4-diaminodiphenyl ether are dissolved in 15mL of NMP, the temperature is reduced to 0 ℃, and a mixture of 2.92g of 3, 4-diphenylether tetraanhydride and 8g of NMP is rapidly added into a reaction system, and the reaction is kept at 0 ℃ for 5 hours. Heating to 60 ℃, slowly dropwise adding 2.68g of N, N-dimethylformamide dimethyl acetal into a reaction system, keeping the temperature of 60 ℃ for reaction for 2 hours, cooling to room temperature, pouring the reaction solution into 300mL of deionized water, filtering, collecting precipitate, and vacuum drying the precipitate at 50 ℃ for 24 hours to obtain the alkali-soluble resin B4 with the weight average molecular weight of 8400.
Preparation example 5
An alkali-soluble resin B5, specifically a polyamide acid-polyimide copolymer resin, is prepared by the following steps:
under the protection of nitrogen, 1.10g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1.00g of 4, 4-diaminodiphenyl ether are dissolved in 15mL of NMP, the temperature is reduced to 0 ℃, and a mixture of 2.92g of 3, 4-diphenylether tetraanhydride and 8g of NMP is rapidly added into a reaction system, and the reaction is kept at 0 ℃ for 5 hours. Maintaining the temperature at 0 ℃, adding 0.7g of N, N' -diisopropylcarbodiimide and 0.01g of 4-dimethylaminopyridine into a reaction system, reacting for 10 hours, pouring the reaction solution into 300mL of deionized water, filtering and collecting precipitate, and vacuum-drying the precipitate at 50 ℃ for 24 hours to obtain the alkali-soluble resin B5 with the weight average molecular weight of 8300.
Example 1
A photosensitive resin composition comprising the following components: 10g of the alkali-soluble resin B1 provided in preparation example 1,2g of a photosensitive compound, 1.5g of a crosslinking agent, 0.1g of a fluorosurfactant, 0.08g of the silane coupling agent A1 provided in Synthesis example 1, 85g of gamma-butyrolactone;
wherein the photosensitive compound isQ is->* Represents the attachment site of the group; the cross-linking agent is->
The preparation method of the photosensitive resin composition comprises the following steps: and mixing all the components according to the formula amount and fully and uniformly dissolving to obtain the photosensitive resin composition.
Examples 2 to 25, comparative examples 1 to 3
A photosensitive resin composition differing from example 1 only in the kind of alkali-soluble resin and/or the kind thereof; the kinds and amounts of other components were the same as in example 1, and the specific components are shown in Table 1.
TABLE 1
/>
In table 1, "-" represents that the component was not added; KBM-573 and KBM-503 are commercially available silane coupling agents from more belief chemistry.
The photosensitive resin compositions provided in examples 1 to 25 and comparative examples 1 to 3 were subjected to performance test by the following methods:
(1) Adhesion test
Adhesion test one: the photosensitive resin compositions provided in examples 1 to 6 and comparative examples 1 to 3 were applied to a 4-inch square ITO glass substrate by spin coating (250 rpm), pre-baked at 120℃for 180 seconds to remove most of the solvent, exposed to a maskless exposure to ultraviolet light to promote decomposition of the photosensitive compound, and then the coated glass substrate was cured for 60 minutes under nitrogen protection (oxygen concentration < 20 ppm) in a clean oven at 320℃and tested according to ASTM D3359 after removal, with adhesion of 5B being excellent, 4B being acceptable, and 3B and below being unacceptable.
Adhesion test two: the photosensitive resin compositions provided in examples 7 to 25 and comparative examples 1 to 3 were applied to a 4-inch square ITO glass substrate by spin coating (250 rpm), pre-baked at 120℃for 180 seconds to remove most of the solvent, exposed to a maskless exposure to ultraviolet light to promote decomposition of the photosensitive compound, and then the coated glass substrate was cured in a 270℃clean oven under nitrogen protection (oxygen concentration < 20 ppm) for 60 minutes, and after removal, the prepared glass substrate was tested according to the method of ASTM D3359 to have an adhesion of 5B of good quality, and 4B of good quality and 3B or less of bad quality.
(2) Reliability test
Samples prepared according to the adhesion test method in (1) (examples 1 to 6 according to the "adhesion test one" method, examples 7 to 25 according to the "adhesion test two" method, comparative examples 1 to 3 were tested under both methods) were cross-hatched according to the method of ASTM D3359, and after the samples were placed in a high-pressure steam sterilization pot at 121 ℃ and 2atm for 100 hours (PCT treatment), cooled to room temperature, and then taken out, and adhesion test was performed according to the method of ASTM D3359, with adhesion reaching 5B excellent, with 4B being acceptable, and 3B and below being unacceptable.
The test results of examples 1 to 6 and comparative examples 1 to 3 (the method of preparation is the method of "adhesion test one") are shown in Table 2, and the test results of examples 7 to 25 and comparative examples 1 to 3 (the method of preparation is the method of "adhesion test two") are shown in Table 3.
TABLE 2
| Adhesion rating | Adhesion after PCT | |
| Example 1 | Excellent and excellent properties | Excellent and excellent properties |
| Example 2 | Excellent and excellent properties | Excellent and excellent properties |
| Example 3 | Excellent and excellent properties | Excellent and excellent properties |
| Example 4 | Excellent and excellent properties | Excellent and excellent properties |
| Example 5 | Excellent and excellent properties | Excellent and excellent properties |
| Example 6 | Excellent and excellent properties | Excellent and excellent properties |
| Comparative example 1 | Failure to pass | Failure to pass |
| Comparative example 2 | Failure to pass | Failure to pass |
| Comparative example 3 | Failure to pass | Failure to pass |
TABLE 3 Table 3
| Adhesion rating | Adhesion after PCT | |
| Example 7 | Excellent and excellent properties | Excellent and excellent properties |
| Example 8 | Excellent and excellent properties | Excellent and excellent properties |
| Example 9 | Excellent and excellent properties | Excellent and excellent properties |
| Example 10 | Excellent and excellent properties | Excellent and excellent properties |
| Example 11 | Excellent and excellent properties | Excellent and excellent properties |
| Example 12 | Excellent and excellent properties | Excellent and excellent properties |
| Example 13 | Excellent and excellent properties | Excellent and excellent properties |
| Example 14 | Excellent and excellent properties | Excellent and excellent properties |
| Example 15 | Excellent and excellent properties | Excellent and excellent properties |
| Example 16 | Excellent and excellent properties | Excellent and excellent properties |
| Example 17 | Excellent and excellent properties | Excellent and excellent properties |
| Example 18 | Excellent and excellent properties | Excellent and excellent properties |
| Example 19 | Excellent and excellent properties | Excellent and excellent properties |
| Example 20 | Excellent and excellent properties | Excellent and excellent properties |
| Example 21 | Excellent and excellent properties | Excellent and excellent properties |
| Example 22 | Excellent and excellent properties | Excellent and excellent properties |
| Example 23 | Excellent and excellent properties | Excellent and excellent properties |
| Example 24 | Excellent and excellent properties | Excellent and excellent properties |
| Example 25 | Excellent and excellent properties | Excellent and excellent properties |
| Comparative example 1 | Qualified product | Failure to pass |
| Comparative example 2 | Failure to pass | Failure to pass |
| Comparative example 3 | Qualified product | Failure to pass |
In combination with the above performance data, compared with the existing silane coupling agents (such as comparative examples 1-3 and KBM-503), the silane coupling agent provided by the invention has obvious improvement on the adhesion force of a substrate after being used in a photosensitive resin composition and cured into a film, and forms obvious technical advantages. The reason for analysis is that the silane coupling agent of the invention introduces a structure containing benzene rings, so that the heat resistance of the coupling agent can be effectively improved; meanwhile, due to the introduction of the benzyl ether group in the structure, the benzyl ether group can react with components in the photoresist film to form a firm covalent bond in the high-temperature curing process, so that the interaction force between the photoresist film and the substrate is improved, and the adhesion force of the film to the substrate is improved. For the examples 1-6, the main bodies of the two silane coupling agents A1 and A2 are heat-resistant aromatic rings and silicon-oxygen silicon bonds after curing, have higher heat-resistant temperature, and still show good adhesion enhancing performance after being cured at a high temperature of more than 300 ℃; in contrast, the silane coupling agents used in comparative examples 1 to 3 were easily decomposed during high temperature curing, and the effect of enhancing adhesion was substantially lost. In comparison with examples 7 to 25, comparative examples 1 to 3 have some thermal decomposition during curing, and although they exert a function of partially enhancing adhesion, they have reduced adhesion due to reduced adhesion effect after PCT treatment due to intolerance to the attack of high temperature steam during PCT treatment, and correspondingly, the silane coupling agent provided by the present invention exhibits excellent adhesion under the moist heat environment of PCT high temperature steam, resulting in excellent reliability of the photoresist film comprising the same.
The applicant states that the present invention is described by way of the above examples as a silane coupling agent of the present invention, its use, and photosensitive resin compositions comprising the same, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (14)
1. A silane coupling agent, which is characterized by having a structure shown in a formula I:
wherein R is 1 、R 2 、R 3 Each independently represents a C1-C10 monovalent organic group;
R 4 is that* Represents the attachment site of the group;
l represents a C1-C20 divalent organic group;
R 5 any one of C1-C8 straight chain or branched alkyl;
R 6 is-CH 2 -or phenylene;
j is 0 or 1;
h is selected from integers from 1 to 5.
2. The silane coupling agent according to claim 1, wherein the R 1 、R 2 、R 3 Each independently selected from any of C1-C10 linear or branched alkyl groups, preferably any of C1-C6 linear or branched alkyl groups.
3. The silane coupling agent according to claim 1, wherein L is selected from a C1-C20 linear or branched alkylene group, or the C1-C20 linear or branched alkylene group One or at least two-CH 2 -is-O-, -S-, -NR N1 -any one of the groups replaced by CO-, C6-C20 arylene;
R N1 any one selected from hydrogen, C1-C10 straight-chain or branched-chain alkyl and C6-C20 aryl;
preferably, said L is selected from C1-C10 linear alkylene, or one or at least two-CH of said C1-C10 linear alkylene 2 -any one of the groups replaced by-O-, -NH-, -CO-, phenylene.
4. A silane coupling agent according to claim 1 or 3, wherein R 4 Selected from any one of the following structures:
wherein represents the attachment site of the group;
i is selected from integers from 1 to 7, and x is selected from integers from 0 to 7;
preferably, said R 5 Any one of C1-C6 straight chain or branched alkyl;
preferably, h is an integer from 1 to 3.
5. Use of the silane coupling agent as defined in any one of claims 1 to 4 in photosensitive materials.
6. A photosensitive resin composition comprising a combination of an alkali-soluble resin, a photosensitive compound and the silane coupling agent according to any one of claims 1 to 4.
7. The photosensitive resin composition according to claim 6, wherein the alkali-soluble resin comprises any one or a combination of at least two of polyimide precursor resin, polyamic acid-polyimide copolymer, polyisoimide-polyamic acid copolymer, polyisoimide or polyimide;
Preferably, the alkali-soluble resin comprises at least one of structural units represented by formula II, formula III or formula IV:
wherein R is 10 、R 12 、R 14 、R 16 Each independently represents a C4-C60 tetravalent organic group;
R 11 、R 13 、R 15 、R 17 each independently represents a C3-C60 divalent organic group;
R 18 、R 19 each independently selected from any one of C1-C10 straight chain or branched alkyl.
8. The photosensitive resin composition as claimed in claim 7, wherein said R 10 、R 12 、R 14 、R 16 Each independently selected from any one of a substituted or unsubstituted C6-C30 tetravalent aromatic group, a substituted or unsubstituted C4-C20 tetravalent alicyclic group;
R 10 、R 12 、R 14 、R 16 wherein each of said substituted substituents is independently selected from at least one of halogen, hydroxy, unsubstituted or halogen substituted C1-C20 straight or branched alkyl, unsubstituted or halogen substituted C1-C20 alkoxy;
preferably, said R 10 、R 12 、R 14 、R 16 Each independently selected from any one of the following groups:
wherein represents the attachment site of the group;
R 21 、R 22 、R 23 、R 24 、R 25 、R 26 each independently selected from hydrogen, halogenAny one of a plain, a hydroxyl, an unsubstituted or halogen substituted C1-C20 straight or branched alkyl, an unsubstituted or halogen substituted C1-C20 alkoxy;
L 21 selected from single bond, -O-, -S-, sulfonyl, sulfoxide, unsubstituted or R '-substituted C1-C10 straight or branched chain alkylene, unsubstituted or R' -substituted C6-C20 arylene, -L 22 -Ar 21 -L 23 Any one of;
L 22 、L 23 each independently selected from any one of-O-, -S-, sulfonyl, sulfoxide, unsubstituted or R' -substituted C1-C10 straight-chain or branched alkylene;
Ar 21 any one selected from unsubstituted or R' substituted C6-C20 arylene;
r' is at least one selected from halogen, hydroxy, unsubstituted or halogen substituted C1-C20 straight or branched alkyl, unsubstituted or halogen substituted C1-C20 alkoxy;
preferably, said R 10 、R 12 、R 14 、R 16 Each independently selected from any one of the following groups:
wherein represents the attachment site of the group.
9. The photosensitive resin composition as claimed in claim 7, wherein said R 11 、R 13 、R 15 、R 17 Each independently selected from any one of a group shown in a formula V, a substituted or unsubstituted C6-C30 divalent aromatic group and a substituted or unsubstituted C4-C20 divalent alicyclic group;
R 11 、R 13 、R 15 、R 17 wherein each of said substituted substituents is independently selected from at least one of halogen, hydroxy, unsubstituted or halogen substituted C1-C20 straight or branched alkyl, unsubstituted or halogen substituted C1-C20 alkoxy;
* Represents the attachment site of the group;
a is selected from any one of single bond, -O-, -S-, sulfonyl, substituted or unsubstituted C1-C10 divalent aliphatic hydrocarbon group, substituted or unsubstituted C3-C20 divalent alicyclic group and substituted or unsubstituted C6-C30 divalent aromatic group;
Each of the substituted substituents in A is independently selected from at least one of halogen, unsubstituted or halogen substituted C1-C10 straight or branched alkyl, unsubstituted or halogen substituted C6-C30 aryl, unsubstituted or halogen substituted C6-C30 phenolic;
R 31 、R 32 each independently selected from any one of halogen, nitro, cyano, carboxyl, unsubstituted or halogen substituted C1-C10 straight or branched alkyl, unsubstituted or halogen substituted C1-C10 alkoxy, unsubstituted or halogen substituted C6-C30 aryl, amido, benzyl ether or benzyl alcohol;
R 33 、R 34 each independently selected from any one of C1-C10 straight or branched chain alkylene, C1-C10 alkyleneoxy, C1-C10 Si-containing divalent groups;
R 35 、R 36 each independently selected from the group consisting of 2 -O-C m H 2m+1 M is an integer of 0 to 8;
R 37 、R 38 each independently selected from any one of halogen, hydroxy, nitro, cyano, carboxy, unsubstituted or halogen substituted C1-C10 straight or branched alkyl, unsubstituted or halogen substituted C1-C10 alkoxy, unsubstituted or halogen substituted C6-C30 aryl, C1-C10 ester or amide;
k 1 、k 2 、s 1 、s 2 、p 1 、p 2 、q 1 、q 2 each independently selected from integers from 0 to 4;
n 1 、n 2 each independently is 0 or 1.
10. The photosensitive resin composition according to claim 7 or 9, wherein a in formula V is selected from any one of a sulfone group, a substituted or unsubstituted C1-C6 linear or branched alkylene group;
Each of the substituents in A is independently selected from at least one of halogen, phenol, unsubstituted or halogen substituted C1-C6 straight or branched alkyl, unsubstituted or halogen substituted C1-C6 alkoxy;
preferably, R in formula V 33 、R 34 Each independently selected from any one of C1-C6 straight or branched chain alkylene, C1-C6 alkyleneoxy;
preferably, R in formula V 35 、R 36 Each independently is-CH 2 -OH or-CH 2 -O-CH 3 ；
Preferably, said p in formula V 1 、p 2 、q 1 、q 2 Each independently selected from integers from 1-3;
preferably, the group represented by formula V has any one of the following structures:
wherein represents the attachment site of the group.
11. The photosensitive resin composition according to any one of claims 7, 9 to 10, wherein R 11 、R 13 、R 15 、R 17 Each independently selected from the group represented by formula V, Any one of them;
wherein represents the attachment site of the group;
R 41 、R 42 each independently selected from any one of halogen, hydroxy, unsubstituted or halogen substituted C1-C20 straight or branched alkyl, unsubstituted or halogen substituted C1-C20 alkoxy;
L 41 selected from single bond, -O-, -S-, sulfonyl, sulfoxide, unsubstituted or halogen-substituted C1-C10 straight or branched chain alkylene, unsubstituted or halogen-substituted C6-C20 arylene, -L 42 -Ar 41 -L 43 Any one of;
L 42 、L 43 each independently selected from any one of-O-, -S-, sulfonyl, sulfoxide, unsubstituted or halogen-substituted C1-C10 straight-chain or branched-chain alkylene;
Ar 41 any one selected from unsubstituted or R' substituted C6-C20 arylene;
r' is selected from any one of halogen, hydroxyl, unsubstituted or halogen substituted C1-C10 straight or branched alkyl, unsubstituted or halogen substituted C1-C10 alkoxy;
u 1 、u 2 each independently selected from integers from 0 to 4;
preferably, said R 11 、R 13 、R 15 、R 17 Each independently selected from the group represented by formula V, Any one of them;
* Representing the attachment site of the group.
12. The photosensitive resin composition according to claim 6 or 7, wherein the alkali-soluble resin has a weight average molecular weight of 2000-100000, preferably 5000-50000;
preferably, the photosensitive compound is a compound containing a diazonaphthoquinone group;
preferably, the photosensitive resin composition further comprises a crosslinking agent;
preferably, the photosensitive resin composition further comprises a solvent and/or other auxiliary agents;
preferably, the other auxiliary agents include other silane coupling agents and/or surfactants;
preferably, the other silane coupling agent contains at least one of vinyl, allyl, oxy, styryl, acyloxy, acryloxy, ureido, amino, imidazolyl, tertiary amino, secondary amino, mercapto or isocyanate groups.
13. The photosensitive resin composition according to claim 6 or 7, wherein the photosensitive resin composition comprises the following components in mass percent:
14. use of the photosensitive resin composition according to any one of claims 6 to 13 in a flat panel display device or a semiconductor device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210670553.2A CN116731063A (en) | 2022-06-14 | 2022-06-14 | Silane coupling agent, application thereof and photosensitive resin composition containing silane coupling agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210670553.2A CN116731063A (en) | 2022-06-14 | 2022-06-14 | Silane coupling agent, application thereof and photosensitive resin composition containing silane coupling agent |
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| Publication Number | Publication Date |
|---|---|
| CN116731063A true CN116731063A (en) | 2023-09-12 |
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| CN202210670553.2A Pending CN116731063A (en) | 2022-06-14 | 2022-06-14 | Silane coupling agent, application thereof and photosensitive resin composition containing silane coupling agent |
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| Country | Link |
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| CN (1) | CN116731063A (en) |
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