CN111018763B - Bis-triphenyl sulfonium salt compound and application thereof - Google Patents
Bis-triphenyl sulfonium salt compound and application thereof Download PDFInfo
- Publication number
- CN111018763B CN111018763B CN201811171951.XA CN201811171951A CN111018763B CN 111018763 B CN111018763 B CN 111018763B CN 201811171951 A CN201811171951 A CN 201811171951A CN 111018763 B CN111018763 B CN 111018763B
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- CN
- China
- Prior art keywords
- group
- bis
- alkyl
- salt compound
- triphenylsulfonium salt
- Prior art date
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- 125000006575 electron-withdrawing group Chemical group 0.000 claims abstract description 11
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- -1 phenyl Chemical group 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- 125000002252 acyl group Chemical group 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 11
- 125000004423 acyloxy group Chemical group 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 229920002120 photoresistant polymer Polymers 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000004450 alkenylene group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 3
- 230000000269 nucleophilic effect Effects 0.000 claims description 3
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000003211 polymerization photoinitiator Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims 1
- 239000000976 ink Substances 0.000 claims 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 18
- 239000002253 acid Substances 0.000 abstract description 8
- 125000001424 substituent group Chemical group 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- 230000003321 amplification Effects 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 description 3
- 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 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 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 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910016855 F9SO2 Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 230000002165 photosensitisation Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- 229910016861 F9SO3 Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MIOPJNTWMNEORI-UHFFFAOYSA-M camphorsulfonate anion Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-M 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000004790 diaryl sulfoxides Chemical class 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000000268 heptanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
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Abstract
The invention discloses a novel bis-triphenyl sulfonium salt compound which has a structure shown as a general formula (I), wherein R is1Represents an electron withdrawing group, R2Represents an amplifying group. The compound has excellent solubility and photosensitive activity, and can be used as a high-quality substitute of a resist acid generator and a photoinitiator for cationic polymerization.
Description
Technical Field
The invention belongs to the technical field of radiation curing, and particularly relates to a bis-triphenylsulfonium salt compound and application thereof.
Background
Compared with a free radical type photo-curing system, the cationic photo-curing system has the advantages of small oxygen inhibition, small volume shrinkage during curing, wider selection of resin types and the like, and is widely used for manufacturing electronic parts and semiconductor components. Triphenylsulfonium salts have high photosensitivity to exposure light sources such as KrF or ArF excimer laser, and are generally used as photoacid generators/photoinitiators for chemically amplified resists for mass production of semiconductor devices. However, the triphenylsulfonium salt has a symmetrical cationic structure and high crystallinity, and is poor in solubility in a photocurable monomer and a conventional organic solvent, so that the amount of addition is limited, and problems such as uneven dispersion in a composition and precipitation during use are likely to occur.
To improve the solubility, JP2005091976A and JP2002193925A introduce a substituent group such as an alkyl group or a fluoroalkyl group at the para-position of the benzene ring group, and WO2005037778A introduces an alkyl group at the meta-position of the benzene ring group, and they have improved solubility in a solvent but greatly reduced photosensitive activity as compared with those having no substituent group. TW201444790A introduced an electron-withdrawing group in the meta-position of the benzene ring group, which was able to maintain the photosensitivity at the same level while increasing the solubility compared to the unsubstituted one.
There is a continuing technical and market need to optimize the structure of triphenylsulfonium salts to obtain alternatives with better application properties.
Disclosure of Invention
Aiming at the demands of application markets, the invention aims to provide a novel bis-triphenylsulfonium salt compound which has very excellent solubility and photosensitive activity and can be used as a high-quality substitute for a resist acid generator and a photoinitiator for cationic polymerization through structural improvement on the basis of the prior art.
Specifically, the bis-triphenylsulfonium salt compound of the invention has a structure shown as a general formula (I):
wherein,
R1represents an electron withdrawing group;
R2represents an amplifying group;
R3each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R3The groups may be linked to each other to form a ring; n tableRepresents an integer of 0 to 5;
R4each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R4The groups may be linked to each other to form a ring; m represents an integer of 0 to 4;
R5each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R5The groups may be linked to each other to form a ring; p represents an integer of 0 to 4;
a and M each independently represent a linking group;
X-denotes a non-nucleophilic anion.
Without being bound by any theory known, applications show that by designing the bis-triphenylsulfonium salt structure and arranging an electron-withdrawing group and an amplifying group at the meta-position and the para-position of the benzene ring group of the bis-triphenylsulfonium salt structure respectively, the bis-triphenylsulfonium salt structure can have obviously improved solubility and photosensitive activity compared with unsubstituted triphenylsulfonium salt, and also has obvious advantages in performance compared with the prior improved substitutes described in the background art.
Detailed Description
The prior literature shows that the introduction of a substituent at the para position of a benzene ring group is beneficial to improving the solubility of the triphenyl sulfonium salt, but can generate adverse effect on the photosensitive activity. However, applicants have found that solubility and photoactivity are compatible when a para-substituent selected from a specific range is combined with a meta-electron withdrawing group.
The variable groups in the structure of formula (I) are described in more detail below.
It should be noted that, in the specification of the present application, C1-CxIn addition to 1 and x, all integers having a carbon number between 1 and x are includedNumerical values, e.g. C1-C8Alkyl of (2) includes C1、C2、C3、C4、C5、C6、C7And C8All alkyl groups of (1) straight-chain or branched. Without being bound by theory, the meaning of which is not expressly set forth in the specification, but which is unambiguously and unambiguously determinable by a person skilled in the art, it being understood that the individual values included therein can serve as a basis for further modifications/limitations.
Variable group
(1)R1Electron withdrawing groups
It is believed that the introduction of an electron-withdrawing group at the benzene ring meta-position can effectively improve the solubility of the sulfonium salt, and meanwhile, the negative influence on the photosensitive activity is not generated.
As suitable electron withdrawing groups R1Selected from the group consisting of halogen, cyano, nitro, haloalkyl, acyl, acyloxy, sulfonyl.
Halogen may be fluorine, chlorine, bromine or iodine. From the viewpoint of environmental protection, fluorine is preferred.
Haloalkyl means an alkyl group in which at least one hydrogen atom is substituted with halogen, and the alkyl group may be a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, or the like C1-C8Is a straight-chain alkyl group or C such as isopropyl, isobutyl, sec-butyl, tert-butyl and the like3-C8Or a branched alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like3-C8A cycloalkyl group of (a). When the haloalkyl group is selected from the group consisting of fluorine-substituted alkyl groups, the photosensitizing activity on the compound is favorable, more preferably C1-C4A perfluoroalkyl group of (a).
The acyl group may have
The structure shown in the specification, wherein R6Represents hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl. Preferably, R6Represents hydrogen, fluorine, chlorine, C1-C7Linear or branched alkyl of (2), C1-C7Linear or branched haloalkyl (more preferably, C)1-C7Linear or branched perfluoroalkyl group of (2), C6-C12Aryl of, or C7-C16An aralkyl group of (2).
The acyl group in the acyloxy group has the same meaning as shown in the above paragraph.
The sulfonyl group may be a methylsulfonyl group, difluoromethanesulfonyl group, trifluoromethanesulfonyl group, phenylsulfonyl group, tosyl group or the like.
In the general formula (I) of the present invention, an electron-withdrawing group R1Preference is given to halogen, cyano, nitro, haloalkyl, in particular those radicals which are preferred above.
(2)R2Amplifying group
The prior literature reports that the solubility can be improved by introducing a substituent at the para position of a benzene ring group of the triphenylsulfonium salt, but the photosensitive activity can be obviously reduced. Unexpectedly, there is an electron withdrawing group R in the meta position of the phenyl ring group1In the case of (3), an amplifying group R is introduced at the para-position2The compound can produce an amplification effect on the solubility and/or the photosensitive activity of the compound, and can not generate adverse effects on other properties while further improving the properties.
As the group capable of exhibiting an amplification action in the present invention, R2Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aralkyl.
The alkyl group is preferably an unsubstituted alkyl group, and may be a C group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, etc1-C8Is a straight-chain alkyl group or C such as isopropyl, isobutyl, sec-butyl, tert-butyl and the like3-C8Branched alkyl groups of (a). More preferably, the alkyl group as the amplifier group is C1-C4The straight or branched alkyl group of (1) includes methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
The alkoxy groups are preferably unsubstituted, wherein the alkyl groups have the same meaning as indicated in the preceding paragraph.
Aralkyl radicals being blocked by aryl radicalsThe alkyl group of (2) is preferably C terminated with a phenyl group from the viewpoint of amplification effect1-C8More preferably C terminated with phenyl1-C4The linear alkyl group of (1) includes benzyl, phenethyl, phenylpropyl or phenylbutyl. Optionally, at least one hydrogen atom in the aralkyl group is substituted with a halogen (particularly fluorine).
Without being bound by the existing known theory, the combination of the amplification group and the electron-withdrawing group has a synergistic effect on the microscopic electronic structure of the triphenyl sulfonium salt, and the performance of the compound is improved. More specifically, the invention can further improve the solubility of the bis-triphenylsulfonium salt by adopting the amplification group, and simultaneously does not generate negative influence on the photosensitive activity, and even part of compounds show relatively better photosensitive activity.
(3)R3Substituent group
Optionally containing R in the structure of the general formula (I)3A substituent group provided that the photocurable application properties of the compound are not adversely affected.
Under this precondition, R is from the perspective of providing more of the same type of substitute3Each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R3The groups may be linked to each other to form a ring.
n represents R3The number of groups may be an integer of 0 to 5.
Those skilled in the art can understand that R is based on the basic theory of the organic field3The existence of the substituent group can influence the conjugated structure of the benzene ring and the overall structural characteristics of the bis-triphenylsulfonium. Without being bound by any theory, the results from this effect are often unpredictable, and depend more on the final presentation of the experiment.
Preferably, n is 0, in which case side reactions, which may occur during the subsequent photocuring process, or unknown negative effects on the effect, caused by the substituent groups, are avoided.
More preferably, n is 2 and two R on the same phenyl ring3Each represents R1And R2R of the uppermost benzene ring1And R2The bis-triphenylsulfonium salt is symmetrical up and down, namely the bis-triphenylsulfonium salt has a structure shown in the following general formula (II):
wherein each substituent group has the same meaning as described above.
Unexpectedly, when the bis-triphenylsulfonium salt contains symmetric electron-withdrawing groups and amplifying groups as shown in the above structure in the upper and lower four benzene ring groups, the compound exhibits significantly further improved solubility and photosensitizing activity as compared with the improved triphenylsulfonium salt in the prior art.
(4)R4Substituent group
Optionally containing R in the structure of the general formula (I)4A substituent group provided that the photocurable application properties of the compound are not adversely affected.
Under this precondition, R is from the perspective of providing more of the same type of substitute4Each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R4The groups may be linked to each other to form a ring.
Halogen may be fluorine, chlorine, bromine or iodine. Fluorine is preferred from the viewpoint of cost and environmental performance.
The acyl group may be selected from: c2-C8Aliphatic acyl groups of (2) such as acetyl, propionyl, butyryl, valeryl, isovaleryl, hexanoyl, octanoyl, heptanoyl and the like; c7-C12Aromatic acyl groups of (2), e.g. benzoyl, methylbenzoyl, trimethylbenzoyl, alpha-phenylpropanoyl, naphthoylAnd the like.
The acyl group in the acyloxy group may have the same meaning as shown in the above paragraph.
The sulfonyl group may be a methylsulfonyl group, difluoromethanesulfonyl group, trifluoromethanesulfonyl group, phenylsulfonyl group, tosyl group or the like.
Alkyl groups may be substituted or unsubstituted. The alkyl group may be selected from C1-C8Linear, branched or cyclic alkyl groups of (a), for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1, 2-dimethylbutyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. Preferably, the alkyl group is selected from C1-C4Straight or branched alkyl of, or C3-C6The cyclic alkyl group of (1). Substituents in substituted alkyl groups include (but are not limited to): halogen (fluorine, chlorine, bromine, iodine), amino, hydroxyl, and the like.
Alkoxy groups may be substituted or unsubstituted, wherein alkyl and substituent groups may have the same meaning as indicated in the preceding paragraph.
The aryl group may be substituted or unsubstituted. The aryl group may be phenyl, naphthyl, anthracenyl, pyrenyl, and the like. As substituents, there may be: c1-C4Alkyl such as methyl, ethyl, propyl, butyl, etc., halogen such as fluorine, chlorine, bromine, iodine, C1-C3Such as methoxy, ethoxy, propoxy, acyl, sulfonyl, hydroxy, amino, nitro, phenyl, and the like.
Aralkyl is an alkyl group that terminates with an aryl group, which may be substituted or unsubstituted. Wherein the aryl moiety and the substituent may have the same meaning as indicated in the preceding paragraph. As the alkyl moiety therein, C is preferred1-C6The alkylene group of (1) includes methylene, ethylene and the like. Particularly preferably, aralkyl is benzyl, phenethyl or phenylpropyl, optionally with at least one hydrogen on the phenyl group being substituted by a substituent as indicated in the preceding paragraph.
In the general formula (I) of the present invention, R4Preferably hydrogen,Nitro, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, especially those groups preferred above.
m represents R4The number of groups may be an integer of 0 to 4. Preferably, m represents 0, 1 or 2, more preferably 0 or 1. When m is 1, R4Preferably in the ortho position to the side of the A group.
(5)R5Substituent group
Optionally containing R in the structure of the general formula (I)5A substituent group provided that the photocurable application properties of the compound are not adversely affected.
In terms of selection range, R5May have the same general formula as R4The substituents have the same meaning.
p represents R5The number of groups may be an integer of 0 to 4. Preferably, p represents 0, 1 or 2, more preferably 0 or 1. When p takes 1, R5Preferably in the ortho position to the side of the A group.
(6) Linking group
As the linking group of the two triphenylsulfonium structures, A represents a linking bond (i.e., a single bond),＊O*＊S＊Alkylene or alkenylene, M represents a null,
＊O＊*S*Or
A group, wherein R represents a linking site7、R8、R9Each independently represents hydrogen or C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20An alkylcycloalkyl group of (a).
Preferably, alkylene is C1-C4The straight chain alkylene group of (a), alkenylene group is-CH ═ CH-.
When M is empty, it represents that the two benzene rings are linked only through the linking group A. When M is not empty, preferably A represents a bond.
(7) Connection site
In the bis-triphenylsulfonium salt compound shown in the general formula (I), S atoms on the left and right sides are respectively connected with three benzene rings. The linking position of the S atom on the two central phenyl rings is preferably para to the group A.
(8) Non-nucleophilic anions
X-Denotes non-nucleophilic anions including (but not limited to): q-、ClO4 -、CN-、HSO4 -、NO3 -、CF3COO-、(BQ4)-、(SbQ6)-、(AsQ6)-、(PQ6)-、Al[OC(CF3)3]4 -、R10SO3 -、(R10SO2)3C-、(R10SO2)2N-、B(C6Q5)4 -、Ga(C6Q5)4 -Or [ (Rf)bPF6-b]-。
Q represents halogen, such as fluorine, chlorine, bromine, iodine, preferably fluorine.
R10Is represented by C1-C20Alkyl of (C)1-C20Perfluoroalkyl group of (A), or C6-C20The alkyl group and the perfluoroalkyl group may be any of linear, branched, or cyclic.
Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and the alkyl group includes: straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and the like, branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl and the like, and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. In Rf, the ratio of substitution with fluorine atoms is preferably 80% or more, more preferably 90% or more, and still more preferably 100% based on the number of moles of hydrogen atoms originally contained in the alkyl group. When the fluorine atom substitution ratio is within these ranges, the photosensitivity of the compound becomes better. Further, the air conditioner is provided with a fan,rf may be exemplified by: CF (compact flash)3 -、CF3CF2 -、(CF3)2CF-、CF3CF2CF2 -、CF3CF2CF2CF2 -、(CF3)2CFCF2 -、CF3CF2(CF3)CF-And (CF)3)3C-. b represents an integer of 1 to 5, and b Rf groups may be the same or different from each other.
Q-Examples of the anion represented include: cl-、Br-、F-。
(BQ4)-、(SbQ6)-、(AsQ6)-、(PQ6)-Examples of the anion represented include: BF (BF) generator4 -、SbF6 -、AsF6 -、PF-。
R10SO3 -Examples of the anion represented include: CF (compact flash)3SO3 -、C2F5SO3 -、C3F7SO3 -、C4F9SO3 -、C6F5SO3 -、C3F7SO3 -P-toluenesulfonate anion, benzenesulfonate anion, camphorsulfonate anion, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion and butanesulfonate anion.
(R10SO2)3C-Examples of the anion represented include: (CF)3SO2)3C-、(C2F5SO2)3C-、(C3F7SO2)3C-And (C)4F9SO2)3C-。
(R10SO2)2N-The anion ofExamples thereof include: (CF)3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-And (C)4F9SO2)2N-。
B(C6Q5)4 -、Ga(C6Q5)4 -Examples of the anion represented include: b (C)6F5)4 -、Ga(C6F5)4 -。
[(Rf)bPF6-b]-Examples of the anion represented include: (CF)3CF2)2PF4 -、(CF3CF2)3PF3 -、[(CF3)2CF]2PF4 -、[(CF3)2CF]3PF3 -、(CF3CF2CF2)2PF4 -、(CF3CF2CF2)3PF3 -、[(CF3)2CFCF2]2PF4 -、[(CF3)2CFCF2]3PF3 -、(CF3CF2CF2CF2)2PF4 -And (CF)3CF2CF2CF2)3PF3 -And the like.
Preparation method
The method for preparing the bis-triphenylsulfonium salt compound of the present invention is not particularly limited, and a well-known organic synthesis process can be employed. For example, the bis-triphenylsulfonium salt compound of the present invention can be obtained by subjecting a diaryl sulfoxide and a diaryl compound to a sulfonium sulfonation reaction by a production method described in patent document CN1871212A, and introducing an anion through a salt exchange reaction as needed.
Applications of
The bis-triphenylsulfonium salt compound of the present invention has a property of releasing a lewis acid by irradiation with active energy rays, and can act on an acid-reactive organic substance to decompose or polymerize, and therefore, can be used as a photoacid generator for a photoresist or a cationic polymerization photoinitiator.
As the energy ray to be used, a low-pressure, medium-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, LED lamp, xenon lamp, carbon arc lamp, fluorescent lamp, semiconductor solid-state laser, argon laser, He-Cd laser, KrF excimer laser, ArF excimer laser or F excimer laser can be used2As the energy ray in the ultraviolet-visible light region obtained by laser or the like, a radiation having high energy such as an electron beam or an X-ray may be used.
The bis-triphenylsulfonium salt compound of the present invention can be mixed with a photosensitive active monomer (e.g., a cationically polymerizable compound) to form a photosensitive composition, and can be used in the fields of production of a lithographic printing plate, a relief printing plate, a photoresist for a printed circuit board, an IC, an LSI, a photocurable ink, a coating material, an adhesive, etc.
The bis-triphenylsulfonium salt compound shown in the general formula (I) has excellent solubility, higher light generation efficiency and photosensitive activity and good market application value.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Preparation examples
Example 1: preparation of sulfonium salt A-1
(1) Intermediate a1
110.0g of o-fluorotoluene, 59.5g of thionyl chloride and 200mL of dichloromethane are put into a 500mL four-neck flask, cooled in an ice-water bath, controlled at about 5 ℃, 66.5g of aluminum trichloride is added in batches, the addition is finished for about 1h, stirring is continued for 2h, and the liquid phase tracking reaction is carried out until the completion. The dichloromethane solution of the product was poured into 500g of ice water, stirred continuously, the dichloromethane layer was separated, washed with water, and the dichloromethane product solution was rotary evaporated to obtain 106g of a pale yellow solid, i.e., intermediate a1, yield 79.7%, HPLC purity: 98 percent.
The product structure of the intermediate is confirmed by nuclear magnetic resonance hydrogen spectrum and mass spectrum, and the specific characterization result is as follows:
1H-NMR(CDCl3，500MHz)：2.3512(6H，s)，7.2438-7.3305(6H，m)。
MS(m/Z)：267(M+H)+。
(2) intermediate b1
Adding 66.5g of intermediate a1 and 200mL of acetic anhydride into a 500mL four-neck flask, stirring in an ice-water bath, controlling the temperature to be about 0 ℃, dropwise adding 35g of concentrated sulfuric acid (mass fraction is 70%), dropwise adding the concentrated sulfuric acid for about 1h, adding 23.3g of diphenyl sulfide into the reaction system in batches after the dropwise adding is finished, continuously stirring for 12h, slowly dropwise adding 100mL of deionized ice water, extracting the solution with benzene for 2-3 times, separating out a water layer, combining the benzene layer, washing once, and combining the water layer to obtain the aqueous solution of the intermediate b 1.
(3) Target product Compound A-1
179.5g of potassium tetrakis- (pentafluorophenyl) borate solid was added to the aqueous solution of the intermediate b1 for ion exchange, deionized water was appropriately added with stirring, the target product a-1 was gradually precipitated with the dissolution of the potassium tetrakis- (pentafluorophenyl) borate solid, and filtered and dried to obtain 158g of a white solid with a yield of 62.0%, HPLC purity: 99 percent.
The structure of the target product is confirmed by a nuclear magnetic resonance hydrogen spectrum and a mass spectrum, and the specific characterization result is as follows:
1H-NMR(CDCl3，500MHz)：2.3512(12H，s)，6.8038-7.2818(20H，m)。
MS(m/Z)：684(M)+。
example 2
Referring to the preparation method of example 1, compounds a2-a25 as shown in table 1 were prepared starting from thionyl chloride and the corresponding substituted benzene.
Structure of target product and MS (m/Z) and1the H-NMR data are shown in Table 1.
TABLE 1
Evaluation of Performance
The application properties of the photoinitiators of formula (I) of the present invention were tested by formulating exemplary photocurable compositions.
1. Dissolution Performance test
The solubility of the compounds A-1 to A-25 of the present invention and the comparative compounds B-1 and B-2 in 3-ethyl-3-hydroxymethyloxetane monomer was determined as the maximum gram dissolved in 100g of solvent at 20 ℃.
The test results are shown in table 2.
2. Acid yield test
The above-mentioned compounds were prepared in the form of 0.02mmol/g acetonitrile solutions. 5.00g of the prepared acetonitrile solution was added to a petri dish having an inner diameter of 100mm, and then irradiated with an ultraviolet lamp (model FL10BL) at 0.8mw/cm2The light intensity of (1) is received in an accumulated manner at 200mj/cm2The energy of (a). The solution after exposure was titrated with 0.05N ethanolic potassium hydroxide solution using BTB as an indicator. Titrating the corresponding solution before illumination to obtain a blank value, deducting the blank value from the titration measured value, and calculating the acid yield through the following formula:
acid yield% (% acid titration-blank value) (mol)/theoretical number of moles of compound (mol) × 100%.
The test results are shown in table 2.
3. Photosensibility test
The sensitivity of the compounds of formula (I) of the present invention was tested by configuring an exemplary photoresist.
Composition of the photoresist:
wherein,
resin A represents
The resin B is novolac resin obtained by condensing m-cresol and p-cresol at a molar ratio of 1:1 under the catalysis of formaldehyde and acid, and has a molecular weight of about 10000;
the photoinitiator was the above-mentioned compounds A-1 to A-25 or comparative example compounds B-1 and B-2.
The components are uniformly stirred according to the proportion and filtered by a membrane filter with the aperture of 1 mu m to prepare the resist composition with the solid content of 40 percent.
The resist composition was uniformly coated on a silicon wafer substrate by a spin coater, and dried to obtain a photoresist coating layer of 20 μm thickness. Prebaking at 130 ℃ for 6min, then pattern exposure (i-line) using TME-150RSC, and exposure at 75 ℃ for 5min with a hotplate. Then, developing for 5min by adopting a tetramethylammonium hydroxide solution with the mass fraction of 2.38%, cleaning by using running water, and drying by using nitrogen to obtain a 10-micron line pattern. The lowest exposure amount at which no pattern residue is visible, i.e., the lowest exposure amount required for forming a resist pattern, is measured, and a lower value indicates a higher sensitivity of the initiator.
The test results are shown in table 2.
TABLE 2
As can be seen from the test results in Table 2, the bis-triphenylsulfonium salt compound shown in the general formula (I) shows satisfactory solubility, and has excellent acid production rate and photosensitive activity, and compared with the existing improved triphenylsulfonium salts B-1 and B-2, the bis-triphenylsulfonium salt compound has obvious performance advantages and wide application prospects.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A bis-triphenylsulfonium salt compound has a structure shown as a general formula (I):
wherein,
R1represents an electron withdrawing group;
R2represents an amplifying group selected from alkyl, alkoxy, aralkyl, wherein alkyl is C1-C4The alkyl moiety of the alkoxy group is C1-C4With a linear or branched alkyl radical, aralkyl being C terminated by phenyl1-C4The linear alkyl group of (1);
n is 0 or 2; when n is 2, two R on the same benzene ring3Each represents R1And R2And R of the uppermost benzene ring1And R2The bis-triphenyl sulfonium salt is in upper and lower symmetry, namely the bis-triphenyl sulfonium salt has a structure shown in the following general formula (II):
R4selected from hydrogen, C1-C4M represents 0 or 1; and when m represents 1, R4Ortho to the side of the A group;
R5selected from hydrogen, C1-C4P represents 0 or 1; and when p represents 1, R5Ortho to the side of the A group;
a represents a bond, perylene, alkylene or alkenylene;
m represents null,
＊O＊Or
Group, wherein R7、R8、R9Each independently represents hydrogen or C1-C20Linear or branched alkyl of (a);
and when M is not empty, A is a connecting key;
X-denotes a non-nucleophilic anion.
2. The bis-triphenylsulfonium salt compound according to claim 1, wherein: r1Selected from the group consisting of halogen, cyano, nitro, haloalkyl, acyl, acyloxy, sulfonyl.
3. The bis-triphenylsulfonium salt compound according to claim 2, wherein:
halogen is fluorine;
the alkyl moiety in haloalkyl being C1-C8Straight chain alkyl group of (1), C3-C8Branched alkyl of, or C3-C8Cycloalkyl groups of (a);
the acyl moiety of the acyl and acyloxy groups having
In which R is6Represents hydrogen, halogen, alkyl, aryl, aralkyl;
the sulfonyl group is selected from methylsulfonyl, difluoromethylsulfonyl, trifluoromethanesulfonyl, phenylsulfonyl and tosyl.
4. The bis-triphenylsulfonium salt compound according to claim 3, wherein: haloalkyl is C1-C4A perfluoroalkyl group of (a).
5. The bis-triphenylsulfonium salt compound according to claim 1, wherein: in the group represented by A, alkylene is C1-C4Linear chain of (1)Alkyl, alkenylene is-CH ═ CH-.
6. The bis-triphenylsulfonium salt compound according to claim 1, wherein: on the middle two phenyl rings, the linking position of the S atom is para to the group A.
7. Use of the bis-triphenylsulfonium salt compound described in any of claims 1 to 6 as a photoacid generator for a photoresist or as a cationic polymerization photoinitiator.
8. A photosensitive composition comprising the bis-triphenylsulfonium salt compound described in any one of claims 1 to 6.
9. Use of the photosensitive composition of claim 8 for the production of lithographic, relief printing plates, printing substrates, photoresists, photocurable inks, coatings, adhesives.
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| CN201811171951.XA CN111018763B (en) | 2018-10-09 | 2018-10-09 | Bis-triphenyl sulfonium salt compound and application thereof |
| EP23154959.3A EP4198019A1 (en) | 2018-10-09 | 2019-09-27 | Triphenylphosphonium salt compound, and uses thereof |
| KR1020217013626A KR102636084B1 (en) | 2018-10-09 | 2019-09-27 | Triphenylsulfonium salt compounds and their applications |
| US17/284,274 US11746085B2 (en) | 2018-10-09 | 2019-09-27 | Triphenylsulfonium salt compound, and uses thereof |
| JP2021519803A JP7345544B2 (en) | 2018-10-09 | 2019-09-27 | Triphenylsulfonium salt compounds and their uses |
| PCT/CN2019/108369 WO2020073822A1 (en) | 2018-10-09 | 2019-09-27 | Triphenylphosphonium salt compound, and uses thereof |
| EP19871797.7A EP3865473A4 (en) | 2018-10-09 | 2019-09-27 | Triphenylphosphonium salt compound, and uses thereof |
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| CN111694215B (en) * | 2019-03-14 | 2022-04-19 | 常州强力先端电子材料有限公司 | Photoresist composition and method for forming photolithographic pattern |
| CN113336686B (en) * | 2021-05-20 | 2023-09-19 | 泰兴先先化工有限公司 | Synthesis method of mixed sulfonium salt |
| CN113801042B (en) * | 2021-08-25 | 2022-09-27 | 上海新阳半导体材料股份有限公司 | A kind of polynium salt type photoacid generator for dry lithography with ArF light source |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2042487A2 (en) * | 2007-09-28 | 2009-04-01 | FUJIFILM Corporation | Production method of sulfonium salt compound |
| CN100486963C (en) * | 1999-12-27 | 2009-05-13 | 和光纯药工业株式会社 | Sulfonium salt compound |
| CN104703809A (en) * | 2012-09-26 | 2015-06-10 | 富士胶片株式会社 | Lithographic printing original plate and plate making method |
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| JP6240409B2 (en) * | 2013-05-31 | 2017-11-29 | サンアプロ株式会社 | Sulfonium salt and photoacid generator |
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| CN100486963C (en) * | 1999-12-27 | 2009-05-13 | 和光纯药工业株式会社 | Sulfonium salt compound |
| EP2042487A2 (en) * | 2007-09-28 | 2009-04-01 | FUJIFILM Corporation | Production method of sulfonium salt compound |
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