CN116135888A - Oxime ester fluorene photoinitiator, photo-curing resin composition and application - Google Patents
Oxime ester fluorene photoinitiator, photo-curing resin composition and application Download PDFInfo
- Publication number
- CN116135888A CN116135888A CN202111363587.9A CN202111363587A CN116135888A CN 116135888 A CN116135888 A CN 116135888A CN 202111363587 A CN202111363587 A CN 202111363587A CN 116135888 A CN116135888 A CN 116135888A
- Authority
- CN
- China
- Prior art keywords
- oxime ester
- photoinitiator
- alkyl
- ester fluorene
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 150000002148 esters Chemical class 0.000 title claims abstract description 73
- 150000002923 oximes Chemical class 0.000 title claims abstract description 73
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 30
- 239000011342 resin composition Substances 0.000 title claims abstract description 22
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000002541 furyl group Chemical group 0.000 claims description 9
- 125000001544 thienyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000001637 1-naphthyl group Chemical class [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 210000004899 c-terminal region Anatomy 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 238000004383 yellowing Methods 0.000 abstract description 39
- 239000000126 substance Substances 0.000 abstract description 12
- 230000009471 action Effects 0.000 abstract description 11
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 8
- 230000036211 photosensitivity Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 125000001424 substituent group Chemical group 0.000 abstract description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 238000001723 curing Methods 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 10
- -1 oxime ester Chemical class 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229940125904 compound 1 Drugs 0.000 description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 5
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000005885 boration reaction Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 206010034960 Photophobia Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 208000013469 light sensitivity Diseases 0.000 description 3
- 238000006146 oximation reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000001934 cyclohexanes Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-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
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BHLUXDZTRBOEGG-UHFFFAOYSA-N 2-(2-butoxyethoxy)acetyl chloride Chemical compound C(CCC)OCCOCC(=O)Cl BHLUXDZTRBOEGG-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- GFXQBWUWIQBIKN-UHFFFAOYSA-N 2-[3-fluoro-n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC(F)=C1 GFXQBWUWIQBIKN-UHFFFAOYSA-N 0.000 description 1
- AVCNDQUBVOMMSL-UHFFFAOYSA-N 2-bromo-9,9-dibutylfluorene Chemical compound C1=C(Br)C=C2C(CCCC)(CCCC)C3=CC=CC=C3C2=C1 AVCNDQUBVOMMSL-UHFFFAOYSA-N 0.000 description 1
- VDYXCTNJHWITDQ-UHFFFAOYSA-N 2-butoxyacetyl chloride Chemical compound CCCCOCC(Cl)=O VDYXCTNJHWITDQ-UHFFFAOYSA-N 0.000 description 1
- CYSUDFINAJICND-UHFFFAOYSA-N 2-chloro-2-phenoxyacetyl chloride Chemical compound ClC(=O)C(Cl)OC1=CC=CC=C1 CYSUDFINAJICND-UHFFFAOYSA-N 0.000 description 1
- FGEAOSXMQZWHIQ-UHFFFAOYSA-N 2-chloro-2-phenylacetyl chloride Chemical compound ClC(=O)C(Cl)C1=CC=CC=C1 FGEAOSXMQZWHIQ-UHFFFAOYSA-N 0.000 description 1
- KKODFXJVTSZBIP-UHFFFAOYSA-N 2-chloro-4,6-dimethoxy-1h-triazine Chemical compound COC1=CC(OC)=NN(Cl)N1 KKODFXJVTSZBIP-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- ZPMWWAIBJJFPPQ-UHFFFAOYSA-N 2-ethoxyacetyl chloride Chemical compound CCOCC(Cl)=O ZPMWWAIBJJFPPQ-UHFFFAOYSA-N 0.000 description 1
- ZRVFFIXOCFUHDA-UHFFFAOYSA-N 2-ethoxynaphthalene-1-carbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(OCC)=CC=C21 ZRVFFIXOCFUHDA-UHFFFAOYSA-N 0.000 description 1
- OFTKFKYVSBNYEC-UHFFFAOYSA-N 2-furoyl chloride Chemical compound ClC(=O)C1=CC=CO1 OFTKFKYVSBNYEC-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- JJKWHOSQTYYFAE-UHFFFAOYSA-N 2-methoxyacetyl chloride Chemical compound COCC(Cl)=O JJKWHOSQTYYFAE-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- GPZXFICWCMCQPF-UHFFFAOYSA-N 2-methylbenzoyl chloride Chemical compound CC1=CC=CC=C1C(Cl)=O GPZXFICWCMCQPF-UHFFFAOYSA-N 0.000 description 1
- QJBYTRDQNQKJJJ-UHFFFAOYSA-N 2-nitro-2-phenoxyacetyl chloride Chemical compound [O-][N+](=O)C(C(Cl)=O)OC1=CC=CC=C1 QJBYTRDQNQKJJJ-UHFFFAOYSA-N 0.000 description 1
- HDEJNKJOYFWBCW-UHFFFAOYSA-N 2-nitro-2-phenylacetyl chloride Chemical compound [O-][N+](=O)C(C(Cl)=O)C1=CC=CC=C1 HDEJNKJOYFWBCW-UHFFFAOYSA-N 0.000 description 1
- PKUPAJQAJXVUEK-UHFFFAOYSA-N 2-phenoxyacetyl chloride Chemical compound ClC(=O)COC1=CC=CC=C1 PKUPAJQAJXVUEK-UHFFFAOYSA-N 0.000 description 1
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- PITHYUDHKJKJNQ-UHFFFAOYSA-N 2-propylpentanoyl chloride Chemical compound CCCC(C(Cl)=O)CCC PITHYUDHKJKJNQ-UHFFFAOYSA-N 0.000 description 1
- ZJIOBDJEKDUUCI-UHFFFAOYSA-N 3,5-dimethylbenzoyl chloride Chemical compound CC1=CC(C)=CC(C(Cl)=O)=C1 ZJIOBDJEKDUUCI-UHFFFAOYSA-N 0.000 description 1
- RPYNKMZXEALWOJ-UHFFFAOYSA-N 3-(dichloromethyl)pyridine Chemical compound ClC(Cl)C1=CC=CN=C1 RPYNKMZXEALWOJ-UHFFFAOYSA-N 0.000 description 1
- INUNLMUAPJVRME-UHFFFAOYSA-N 3-chloropropanoyl chloride Chemical compound ClCCC(Cl)=O INUNLMUAPJVRME-UHFFFAOYSA-N 0.000 description 1
- JUADTOTVJUYCRQ-UHFFFAOYSA-N 3-cyclohexylpropanoyl chloride Chemical compound ClC(=O)CCC1CCCCC1 JUADTOTVJUYCRQ-UHFFFAOYSA-N 0.000 description 1
- NRHMXMBVLXSSAX-UHFFFAOYSA-N 3-methylsulfanylpropanoyl chloride Chemical compound CSCCC(Cl)=O NRHMXMBVLXSSAX-UHFFFAOYSA-N 0.000 description 1
- MFEILWXBDBCWKF-UHFFFAOYSA-N 3-phenylpropanoyl chloride Chemical compound ClC(=O)CCC1=CC=CC=C1 MFEILWXBDBCWKF-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- USEDMAWWQDFMFY-UHFFFAOYSA-N 4-cyanobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(C#N)C=C1 USEDMAWWQDFMFY-UHFFFAOYSA-N 0.000 description 1
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 1
- JPVUWCPKMYXOKW-UHFFFAOYSA-N 4-phenylbenzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=CC=C1 JPVUWCPKMYXOKW-UHFFFAOYSA-N 0.000 description 1
- VQDQISMDUHBUFF-UHFFFAOYSA-N 4-phenylbutanoyl chloride Chemical compound ClC(=O)CCCC1=CC=CC=C1 VQDQISMDUHBUFF-UHFFFAOYSA-N 0.000 description 1
- SVNNWKWHLOJLOK-UHFFFAOYSA-N 5-chloropentanoyl chloride Chemical compound ClCCCCC(Cl)=O SVNNWKWHLOJLOK-UHFFFAOYSA-N 0.000 description 1
- HBPVGJGBRWIVSX-UHFFFAOYSA-N 6-bromohexanoyl chloride Chemical compound ClC(=O)CCCCCBr HBPVGJGBRWIVSX-UHFFFAOYSA-N 0.000 description 1
- BWOCDJBMOYTZLN-UHFFFAOYSA-N 6-phenylhexanoyl chloride Chemical compound ClC(=O)CCCCCC1=CC=CC=C1 BWOCDJBMOYTZLN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 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
- 238000007922 dissolution test Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- NSNPSJGHTQIXDO-UHFFFAOYSA-N naphthalene-1-carbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=CC2=C1 NSNPSJGHTQIXDO-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WVJVHUWVQNLPCR-UHFFFAOYSA-N octadecanoyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCCCC WVJVHUWVQNLPCR-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- WFVMVMAUXYOQSW-UHFFFAOYSA-N quinoline-2-carbonyl chloride Chemical compound C1=CC=CC2=NC(C(=O)Cl)=CC=C21 WFVMVMAUXYOQSW-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
- C07D251/20—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with no nitrogen atoms directly attached to a ring carbon atom
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides an oxime ester fluorene photoinitiator, a photo-curing resin composition and application thereof. The oxime ester fluorene photoinitiator contains a 4, 6-alkoxy substituted triazine ring group, and has a structure shown in a general formula (I):
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to an oxime ester fluorene photoinitiator, a photo-curing resin composition and application thereof.
Background
The flat panel display technology is widely applied to the aspects of television, computer, mobile phone, vehicle-mounted equipment, airplane, high-speed rail information display and the like, and the flat panel display photoresist is provided with a colored photoresist and a black photoresist, and the two photoresists are key materials for realizing flat panel display. The flat panel display photoresist consists of a photoinitiator, resin, a monomer, pigment, an additive and the like, and the structures of the photoresist, the resin and the monomer which are different in display definition are not greatly different, and the main difference is the structure of the photoinitiator. The higher the definition of the flat panel display, the higher the sensitivity of the photoresist initiator is required, and the photoinitiator is a key raw material for high definition flat panel display processing.
The development of the high definition display field puts higher demands on the photoresist, not only higher photosensitivity, but also better resolution and better color saturation are required, and the photoinitiator is required to have high photosensitivity on one hand, and low yellowing property on the other hand. However, most of the existing oxime ester initiators have too large yellowing coefficient and poor yellowing resistance, so that the color saturation of a display picture is reduced and the display picture cannot be used, and the market is urgent to need a photoinitiator product with low yellowing and high sensitivity, and the solubility of the initiator is a key factor for determining whether the initiator can be practically applied.
On the basis, a photoinitiator product with good solubility, low yellowing and high sensitivity is researched and developed, and has important significance.
Disclosure of Invention
The invention mainly aims to provide an oxime ester fluorene photoinitiator, a photo-curing resin composition and application thereof, so as to solve the problem that the existing photoinitiator cannot meet the requirements of high solubility, high light sensitivity and good yellowing resistance.
In order to achieve the above purpose, the invention provides an oxime ester fluorene photoinitiator, which contains a 4, 6-alkoxy substituted triazine ring group, and has a structure shown in a general formula (I):
in the general formula (I), R 1 And R is 1 ' same or different, and R 1 And R is 1 ' are independently selected from hydrogen atom, halogen, C 1 ～C 10 Alkyl, C of (2) 4 ～C 10 Aryl or C of (2) 2 ～C 10 Alkenyl of (2), wherein alkyl, aryl, alkenyl may be interrupted by O, N or carbon groups, respectively; or R is 1 And R is 1 ' may also be linked into a ring; r is R 2 And R is 3 Are respectively and independently selected from R 2 And R is 3 Are independently selected from C 1 ～C 20 Straight or branched alkyl, C 3 ～C 20 Cycloalkyl, C 3 ～C 8 Cycloalkyl-substituted C of (C) 1 ～C 10 Alkyl, C of (2) 1 ～ C 20 Alkyl substituted C 3 ～C 8 At least one hydrogen atom in cycloalkyl, phenyl is C 1 ～C 4 A group obtained after alkyl substitution, C 1 ～C 4 Alkoxy, C 1 ～C 4 Groups obtained by substitution of one or more hydrogen atoms in the alkoxy group by fluorine atoms, furyl, thienyl, C-terminal with furyl 1 ～C 4 C terminated with alkyl groups, or with thienyl groups 1 ～C 4 An alkyl group; r is R 4 And R is 5 Are independently selected from C 1 ～C 5 Is a hydrocarbon group.
Further, in the general formula (I), R 2 Selected from C 1 ～C 10 Alkyl substituted C 3 ～C 8 Cycloalkyl, phenyl, naphthyl, furyl or thienyl; r is R 3 Selected from C 1 ～C 10 At least one hydrogen atom of the linear or branched alkyl, phenyl or phenyl group being C 1 ～C 4 Alkyl groups are substituted to give the groups.
Further, R 1 And R is 1 ' selected from C 1 ～C 5 Straight chain alkyl of (a).
Further, R 1 And R is 1 ' selected from C 1 ～C 4 Branched or branched alkyl of (a); r is R 2 Selected from C 1 ～C 4 Alkylene substituted cyclohexane, C 1 ～C 4 Alkylene substituted cyclopentane, phenyl, 1-naphthyl, α -furyl or α -thienyl; r is R 3 Selected from methyl, ethyl, phenyl or 2-methylphenyl; r is R 4 And R is 5 Selected from C 1 ～C 4 Straight or branched alkyl of (a).
Further, the oxime ester fluorene photoinitiator is selected from one or more of the following compounds 1 to 10:
in order to achieve the above object, another aspect of the present invention also provides a photocurable resin composition comprising a photoinitiator, an alkali-soluble resin, and a polymeric monomer, wherein the photoinitiator comprises the above oxime ester fluorene-based photoinitiator provided herein.
Further, the photo-curing resin composition comprises 0.5 to 10 parts of oxime ester fluorene photoinitiator, 20 to 80 parts of alkali-soluble resin and 20 to 80 parts of polymerized monomer; preferably, the photocurable resin composition further comprises 0 to 200 parts of a solvent.
In a further aspect, the present invention provides an oxime ester fluorene photoinitiator as described above, or an application of the above-described photocurable resin composition as described above, in the field of photocuring.
By applying the technical scheme of the invention, the oxime ester fluorene photoinitiator with the structure shown in the general formula (I) is provided. The triazine ring group is introduced into the 7-position of fluorene in the chemical structure of oxime ester fluorene, so that the electron delocalization range of the conjugated structure in the existing chemical structure of oxime ester fluorene can be enlarged, the stability of the structure is greatly improved, and the sensitivity and yellowing resistance of the oxime ester fluorene photoinitiator are greatly improved. The introduction of specific types of substituents at the 4-position and the 6-position of the triazine ring in the structure shown in the general formula (I) is beneficial to further improving the solubility of oxime ester fluorene photoinitiators. Because the oxime ester fluorene photoinitiator with the structure has good alkali solubility, when the oxime ester fluorene photoinitiator is applied to a photo-curing composition, the curing efficiency under the irradiation of a light source can be well improved, and the oxime ester fluorene photoinitiator has the characteristics of low yellowing and excellent solubility. In addition, the oxime ester fluorene photoinitiator can be used for a UV-LED photocuring system (especially under the action of a 365nm light source) and can remarkably improve yellowing resistance.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background art, the existing photoinitiator has the problems of low solubility, low photosensitivity and poor yellowing resistance. In order to solve the technical problems, the application provides an oxime ester fluorene photoinitiator, which contains a 4, 6-alkoxy substituted triazine ring group, and has a structure shown in a general formula (I):
in the general formula (I), R 1 And R is 1 ' same or different, and R 1 And R is 1 ' each independently includes but is not limited to a hydrogen atom, halogen, C 1 ～C 10 Alkyl, C of (2) 4 ～C 10 Aryl or C of (2) 2 ～C 10 Alkenyl of (2), wherein alkyl, aryl, alkenyl may be interrupted by O, N or carbon groups, respectively; or R is 1 And R is 1 ' may also be linked into a ring; r is R 2 And R is 3 Respectively and independently include but are not limited toAt R 2 And R is 3 Each independently include but are not limited to C 1 ～C 20 Straight or branched alkyl, C 3 ～C 20 Cycloalkyl, C 3 ～C 8 Cycloalkyl-substituted C of (C) 1 ～C 10 Alkyl, C of (2) 1 ～C 20 Alkyl substituted C 3 ～C 8 At least one hydrogen atom in cycloalkyl, phenyl is C 1 ～C 4 A group obtained after alkyl substitution, C 1 ～C 4 Alkoxy, C 1 ～C 4 Groups obtained by substitution of one or more hydrogen atoms in the alkoxy group by fluorine atoms, furyl, thienyl, C-terminal with furyl 1 ～C 4 C terminated with alkyl groups, or with thienyl groups 1 ～C 4 An alkyl group; r is R 4 And R is 5 Each independently include but are not limited to C 1 ～C 5 Is a hydrocarbon group.
The triazine ring group is introduced into the 7-position of fluorene in the chemical structure of oxime ester fluorene, so that the electron delocalization range of the conjugated structure in the existing chemical structure of oxime ester fluorene can be enlarged, the stability of the structure is greatly improved, and the sensitivity and yellowing resistance of the oxime ester fluorene photoinitiator are greatly improved. The introduction of specific types of substituents at the 4-position and the 6-position of the triazine ring in the structure shown in the general formula (I) is beneficial to further improving the solubility of oxime ester fluorene photoinitiators. Because the oxime ester fluorene photoinitiator with the structure has good alkali solubility, when the oxime ester fluorene photoinitiator is applied to a photo-curing composition, the curing efficiency under the irradiation of a light source can be well improved, and the oxime ester fluorene photoinitiator has the characteristics of low yellowing and excellent solubility. In addition, the oxime ester fluorene photoinitiator can be used for a UV-LED photocuring system (especially under the action of a 365nm light source) and can remarkably improve yellowing resistance.
In a preferred embodiment, R in the above formula (I) 2 And R is 3 Each independently include but are not limited to C 1 ～C 10 Alkyl substituted C 3 ～C 8 Cycloalkyl, phenyl, naphthyl, furyl or thienyl; r is R 3 Including but not limited to C 1 ～C 10 Straight-chain or branched alkyl, phenyl or phenylAt least one hydrogen atom being replaced by C 1 ～C 4 Alkyl groups are substituted to give the groups. R is compared with other kinds of groups 2 And R is 3 The species of (2) are respectively limited in the above ranges, which is favorable for further improving the photosensitivity, the solubility and the yellowing resistance of the oxime ester fluorene photoinitiator.
In a preferred embodiment, R 1 And R is 1 ' include but are not limited to C 1 ～C 5 Straight chain alkyl of (a). R is compared with other kinds of groups 1 And R is 1 The' kinds are respectively limited in the above ranges, which are favorable for further improving the sensitivity, the solubility and the yellowing resistance of the oxime ester fluorene photoinitiator.
In order to further increase the sensitivity and solubility of oxime ester fluorene type photoinitiators, R is preferably 1 And R is 1 ' include but are not limited to C 1 ～C 4 Branched or branched alkyl of (a); r is R 2 Including but not limited to C 1 ～C 4 Alkylene substituted cyclohexane, C 1 ～C 4 Alkylene substituted cyclopentane, phenyl, 1-naphthyl, α -furyl or α -thienyl; r is R 3 Including but not limited to methyl, ethyl, phenyl or 2-methylphenyl; r is R 4 And R is 5 Are all C 1 ～C 4 Straight or branched alkyl of (a). R is compared with other kinds of groups 1 、R 1 ’、R 2 、 R 3 、R 4 And R is 5 The species of (2) are respectively limited in the above ranges, which is favorable for further improving the photosensitivity, the solubility and the yellowing resistance of the oxime ester fluorene photoinitiator.
In a preferred embodiment, the oxime ester fluorene type photoinitiator includes, but is not limited to, one or more of the following compounds 1 to 10:
compared with the combination of other substituents, the compounds 1 to 10 have the characteristics of high sensitivity, high curing efficiency and excellent yellowing resistance, can be used for a UV-LED photocuring system, and can be used as an initiator under the action of a 365nm light source to obviously improve the yellowing resistance.
The second aspect of the application also provides a preparation method of the preferable oxime ester fluorene photoinitiator, which comprises the following synthetic route:
the preparation method of the oxime ester fluorene photoinitiator comprises the following steps:
s1, under the action of n-butyllithium, enabling the 9 site of fluorene to be R 1 And R is 1 The method comprises the steps of (1) carrying out boration reaction and hydrolysis reaction on substituted halogenated fluorene and a borate compound in a first solvent to obtain a first intermediate; the first intermediate is
R 1 And R is 1 ' R in the structure shown in the general formula (I) 1 And R is 1 ' have the same definition; preferably, the temperature of the boration reaction is-50 to-78 ℃, and the hydrolysis reaction process also comprises 1mol/L of dilute hydrochloric acid or the pH of the hydrolysis reaction is 4-5;
s2, under the condition of a first catalyst, carrying out Suzuki coupling reaction on the first intermediate and a 2-halogen-4, 6-alkoxy substituted triazine compound in a second solvent to obtain a second intermediate; 2-halo-4, 6-alkoxy-substituted triazine compounds are
The second intermediate is->
Wherein R is 1 、R 1 ’、R 4 And R is 5 R in the structure respectively shown in the general formula (I) 1 、R 1 ’、R 4 And R is 5 X is a halogen atom; preferably, the temperature of the Suzuki coupling reaction is 60-120 ℃;
s3, under the condition of a second catalyst, performing Friedel-crafts acylation reaction on the second intermediate and a propyl chloride compound in a third solvent to obtain a third intermediate; the third intermediate is
Preferably, the temperature of the friedel-crafts acylation reaction is-10 to 40 ℃, more preferably 0 to 5 ℃;
s4, under the action of concentrated hydrochloric acid, enabling the third intermediate to perform oximation reaction with nitrous acid or nitrous acid alkyl ester to obtain a fourth intermediate; the fourth intermediate is
Wherein R is 1 、R 1 ’、R 4 And R is 5 R in the structure respectively shown in the general formula (I) 1 、R 1 ’、R 4 And R is 5 Have the same definition; preferably, the temperature of the oximation reaction is-15 to 50 ℃, more preferably 0 to 25 ℃;
s5, in a fourth solvent, enabling the fourth intermediate and an acylating reagent to perform esterification reaction under the action of alkali to obtain the oxime ester fluorene photoinitiator;
the oxime ester fluorene photoinitiator has a structure shown in a general formula (I):
in the general formula (I), R 1 、R 1 ’、R 2 、R 3 、R 4 And R is 5 Respectively have the same definition as the foregoing; preferably, the temperature of the oximation reaction is from-15 to 50 ℃, more preferably from 0 to 25 ℃.
In a preferred embodiment, the boration reaction is carried out in a first solvent, and the type of the first solvent is not particularly limited as long as the first solvent can dissolve the reaction reagent and has no adverse effect on the boration reaction, and for example, the first solvent may be Tetrahydrofuran (THF), diethyl ether, 1, 4-dioxane, or the like, and preferably Tetrahydrofuran (THF).
In a preferred embodiment, the second solvent is selected according to the actual condition of the reaction system (e.g., the kind of the reaction reagent) of the Suzuki coupling reaction, and the kind of the second solvent is not particularly limited as long as the second solvent can dissolve the reaction reagent of the Suzuki coupling reaction and has no adverse effect on the Suzuki coupling reaction. For example, the second solvent may be Tetrahydrofuran (THF), dioxane, N-Dimethylformamide (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), or the like. In a preferred embodiment, the first catalyst includes, but is not limited to, a palladium catalyst in a Suzuki coupling reaction.
In a preferred embodiment, the third solvent used in the friedel-crafts acylation reaction is not particularly limited as long as it can dissolve the reaction reagent without adversely affecting the reaction, and may be, for example, dichloromethane or dichloroethane, preferably dichloromethane. In a preferred embodiment, the second catalyst comprises, but is not limited to, aluminum chloride in a friedel-crafts acylation reaction.
In a preferred embodiment, the fourth solvent in the esterification reaction includes, but is not limited to, one or more of the group consisting of diethyl ether, acetonitrile, t-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, methylene chloride, chloroform, chlorobenzene, dimethylacetamide, and dimethylformamide.
In a preferred embodiment, the acylating agent includes, but is not limited to, an acyl halide and/or an anhydride compound in the esterification reaction. Preferably, the method comprises the steps of, acylating agents include, but are not limited to, cyclohexanoyl chloride, 2-propylpentanoyl chloride, 3, 5-trimethylhexanoyl chloride, 3-chloropropionyl chloride, 5-chloropentanoyl chloride, 3-chloropivaloyl chloride, 6-bromohexanoyl chloride, methoxyacetyl chloride, ethoxyacetyl chloride, butoxyacetyl chloride, 3- (methylthio) propionyl chloride, (2-butoxyethoxy) acetyl chloride, benzoyl chloride, toluoyl chloride, 3, 5-dimethylbenzoyl chloride, 4-methoxybenzoyl chloride, 4-cyanobenzoyl chloride, 4-nitrobenzoyl chloride, 4-phenylbenzoyl chloride, chlorobenzoyl chloride, phenylacetyl chloride, phenylpropionyl chloride, chlorophenyl acetyl chloride, 4-phenylbutyryl chloride, 6-phenylhexanoyl chloride, nitrophenylacetyl chloride, phenoxyacetyl chloride, chlorophenoxyacetyl chloride, nitrophenoxy acetyl chloride, 2-thiophen-2-acetyl chloride, chloronicotinyl chloride, 2-furanoyl chloride, quinolinoyl chloride, naphthoyl chloride, 2-ethoxy-1-naphthoyl chloride, anthracene anhydride, decanoyl anhydride, stearic anhydride, acetic anhydride, and acetic anhydride.
In a preferred embodiment, the base in the esterification reaction includes, but is not limited to, one or more of the group consisting of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, and sodium hydride.
In a preferred embodiment, the alkyl nitrite includes, but is not limited to, one or more of the group consisting of methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite and isoamyl nitrite in the esterification reaction.
The third aspect of the present application also provides a photocurable resin composition comprising a photoinitiator, an alkali-soluble resin, and a polymeric monomer, wherein the photoinitiator comprises the above oxime ester fluorene photoinitiator provided herein.
Under the irradiation of a light source, compared with other types of photoinitiators, the oxime ester fluorene photoinitiator with high sensitivity can absorb energy from the light source more efficiently and generate free radicals with higher activity, so that monomers in a photo-curing system are initiated to generate photopolymerization reaction more rapidly, and the photo-curing resin can be obtained after further curing reaction. Meanwhile, the oxime ester fluorene photoinitiator with the specific structure has good compatibility with alkali-soluble resin and polymerized monomers, which is beneficial to further improving the curing efficiency of the photo-curing resin. In a word, the photo-curing resin composition provided by the application has the characteristics of high light sensitivity, high curing efficiency and excellent yellowing resistance; and the oxime ester fluorene photoinitiator can be used for a UV-LED photocuring system (especially under the action of a 365nm light source), and can remarkably improve yellowing resistance.
In a preferred embodiment, the photocurable resin composition includes 0.5 to 10 parts of an oxime ester fluorene-based photoinitiator, 20 to 80 parts of an alkali-soluble resin, and 20 to 80 parts of a polymeric monomer. Compared with other dosages, the dosage of the oxime ester fluorene photoinitiator, the alkali-soluble resin and the polymeric monomer is limited in the range, which is favorable for further improving the curing efficiency of the photo-curing resin composition, and simultaneously further improving the yellowing resistance, in particular to the yellowing resistance under the action of a 365nm light source.
In order to further improve the compatibility between the oxime ester fluorene photoinitiator of the above-described specific structure and the alkali-soluble resin and the polymerization monomer, and at the same time, to further improve the curing efficiency of the photocurable resin composition and the yellowing resistance of the photocurable resin, it is preferable that the photocurable resin composition further comprises 0 to 200 parts of a solvent.
In a preferred embodiment, the polymeric monomer includes, but is not limited to, one or more of the group consisting of methyl methacrylate, methyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, and cetyl methacrylate.
In a preferred embodiment, the alkali-soluble binder resin includes, but is not limited to, C containing polymerizable groups 4 ～C 20 (meth) acrylate monomer, C 4 ～C 20 Epoxy monomer, C 4 ～C 20 Oxa monomers of (C) 4 ～C 20 One or more of the group consisting of acid anhydride monomers. Preferably, the polymerizable groups include, but are not limited to, one or more of the group consisting of allyl, epoxy, oxa, and anhydride. When the polymerizable group is an oxa group, the oxa group isA quaternary epoxy group.
In a preferred embodiment, the solvent includes, but is not limited to, one or more of the group consisting of ethyl acetate, acetone, benzene, toluene, xylene, cyclohexane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, ethyl 3-ethoxypropionate.
In an alternative embodiment, the fluorene main structure in the oxime ester fluorene photoinitiator provided in the present application may be replaced by a main group such as carbazole, diphenyl sulfide or biphenyl.
The fourth aspect of the present application also provides an oxime ester fluorene photoinitiator as described above, or an application of the photo-curable resin composition as described above, in the photo-curing field.
Under the irradiation of a light source, compared with other types of photoinitiators, the oxime ester fluorene photoinitiator with high sensitivity can absorb energy from the light source more efficiently and generate free radicals with higher activity, so that monomers in a photo-curing system are initiated to generate photopolymerization reaction more rapidly, and the photo-curing resin can be obtained after further curing reaction. Meanwhile, the oxime ester fluorene photoinitiator with the specific structure has good compatibility with alkali-soluble resin and polymerized monomers, which is beneficial to further improving the curing efficiency of the photo-curing resin. In a word, the photo-curing resin composition provided by the application has the characteristics of high light sensitivity, high curing efficiency and excellent yellowing resistance; and the oxime ester fluorene photoinitiator can be used for a UV-LED photocuring system (especially under the action of a 365nm light source), and can remarkably improve yellowing resistance.
The oxime ester fluorene photoinitiator provided by the application can be applied to the fields of paint, coating, ink, forming materials and the like, and comprises but is not limited to: coating materials coated on plastic, metal, glass, ceramic, wood, wall and other substrates; a photo-curable adhesive, a photo-degradable coating; printing inks for screen printing, offset printing, gravure printing, and the like; photo-curable ink for inkjet printing and 3D printing; film materials such as hard coating agents, antifouling films, antireflection films, impact-buffer films, interlayer insulating films, light-extraction films, brightness enhancement films, sealing films, and the like; optical components such as a lens, a lens array, a light guide plate, a light diffusion plate, and a diffraction element; optical molding resins such as color filters and black matrices (light shielding films); optical recording media such as holographic image materials; photoresist for manufacturing electronic circuits and semiconductors; an optical spacer; a rib wall; a nanoimprint material; quantum dots, and the like.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
The synthetic route for compound 1 in this example 1 is as follows:
a preparation method of oxime ester fluorene photoinitiator comprises the following steps:
(1) Preparation of first intermediate
To a four-necked flask, 150g, 0.42mol of 2-bromo-9, 9-dibutylfluorene and 900mL of tetrahydrofuran (first solvent) were charged, and the solution was stirred and cooled to-78 ℃. 176mL of a tetrahydrofuran solution (2.5 mol/L) of n-butyllithium was added dropwise; after the dripping, the temperature is kept and stirring is continued for 30min. Then 79.0g of triisopropyl borate was added to naturally warm the reaction system to room temperature and stirring was continued for 1h. 500mL of water was added to the reaction system, quenched (reaction was completed), 420mL of diluted hydrochloric acid (1 mol/L) was further added, pH was adjusted to 5, hydrolysis of triisopropyl borate was started, and stirring was performed at room temperature for 30min. Adding ethyl acetate into the system after the reaction is finished, stirring, standing for layering, and separating an upper organic phase; the organic phase was washed 3 times with 500mL of water and concentrated to give 106.4g of a yellow oil, first intermediate 1b.
The yield of the first intermediate was 78.6%. The obtained first intermediate is directly used as a raw material for the next reaction.
(2) Preparation of the second intermediate
106.4g of the first intermediate obtained in the previous step, 0.33mol of the second intermediate was dissolved in 500mL of DMF (second solvent), and 63.7g of 2-chloro-4, 6-dimethoxytriazine and 3.8g of Pd (PPh) were added in this order 3 ) 4 86.6g triphenylphosphine and 66.8g triethylamine. Heating the reaction tank system of the Suzuki coupling reaction to 80 ℃, and stirring for 6 hours to obtain a reaction solution. The reaction mixture was filtered through celite while it was still hot, 500mL of water was added to the obtained filtrate, followed by extraction with ethyl acetate; the upper organic phase is washed with water for 3 times, the organic phase is concentrated, the obtained pale yellow oily substance is dissolved by methanol, stirred for 30min at room temperature, cooled to 5-10 ℃ and stirred for 1h, and a milky solid is separated out. After filtration 99.5g of white solid was collected, second intermediate 1c.
The yield of the second intermediate was 72.2% and the purity was 98.46%. The second intermediate obtained was directly used as starting material for the next reaction.
(3) Preparation of the third intermediate
Under the protection of nitrogen, 83.5g, 0.2mol of the second intermediate and 400mL of dichloromethane (third solvent) are sequentially added into a reaction bottle, the mixture is stirred and dissolved, and 36.7g of cyclohexyl propionyl chloride is added; 29.3g of aluminum chloride (second catalyst) was added at room temperature and stirring was continued for 1h. And adding the reaction solution of Friedel-crafts acylation reaction into ice water, stirring for 30min, standing for layering, and separating out a lower organic phase. The organic phase is washed to be neutral by water, and is concentrated to obtain a residue, then methanol is added, the mixture is stirred until solid is separated out, and the mixture is cooled to 5-10 ℃ and is continuously stirred for crystallization for 2 hours. The solid was filtered and collected to give 82.6g of an off-white solid, third intermediate 1d.
The yield of the third intermediate was 74.3% and the purity was 97.79%. The obtained third intermediate is directly used as a raw material for the next reaction.
(4) Preparation of fourth intermediate
80g, 0.14mol of the third intermediate and 480mL of ethyl acetate are added into a reaction bottle, and the solution is stirred; 24.6g of isoamyl nitrite and 21mL of concentrated hydrochloric acid were added and stirred at room temperature for 2h. The reaction was stopped, 500mL of water was added and stirring was continued for 30min. Standing for layering, separating out the lower organic phase, washing with water to neutrality, and concentrating the organic phase. The resulting viscous material was dissolved in methanol and stirred well at room temperature for 4h, and a pale yellow solid was precipitated. Continuously cooling to 5-10 ℃ and stirring for 2h. After filtration 56.2g of yellow solid are collected, fourth intermediate 1e.
The yield of the fourth intermediate was 68.7% and the purity was 96.75%. The fourth intermediate obtained was directly used as a starting material for the next reaction.
(5) Preparation of Compound 1
To the reaction flask was added 50g of fourth intermediate (0.085 mol), 9.5g of Triethylamine (TEA) and 200mL of methylene chloride under nitrogen atmosphere, and the solution was stirred. 9.2g of acetic anhydride was added dropwise at room temperature and stirred for 3h. 300g of water was added to the reaction solution and stirred for 30 minutes. Standing for layering, separating out a lower organic phase, washing with water to be neutral, and concentrating the organic phase to obtain a solid. The obtained solid was dissolved in methanol, stirred for 1 hour, and the solid was gradually precipitated. Continuously cooling to 5-10 ℃ and stirring for 2h. Filtering to obtain a filter cake, and washing the filter cake with methanol to obtain a crude product of the compound 1. The crude product was dissolved in 100mL of acetone and added to 300mL of methanol and stirring continued for 1h under ice-bath. The mixture was filtered to obtain a cake, which was rinsed with methanol, and the cake was collected to obtain 42.3g of pale yellow solid, namely, compound 1.
The yield of compound 1 was 79.4% and the purity was 99.28%.
The chemical structure of the compound 1 is confirmed by nuclear magnetic resonance hydrogen spectrum 1H-NMR and mass spectrum MS, and the characterization result is as follows:
(1) The nuclear magnetic hydrogen spectrum data for compound 1 is as follows: 1H-NMR (500 MHz, chloroform-d)
δ7.96-7.81(m,3H),7.76(d,J＝1.4Hz,1H),7.58(dd,J＝7.4,1.5Hz,1H),3.91(s,4H),2.91(d,J＝7.0Hz,2H ),2.15(s,2H),2.01-1.89(m,3H),1.84(dt,J＝12.5,7.0Hz,2H),1.58-1.49(m,3H),1.52-1.40(m,12H),1.42-1. 31(m,4H),0.88(t,J＝7.9Hz,5H)。
(2) Mass spectrum data for compound 1 are as follows: MS (m/z): 567[ M-OAc ]] + 。
Examples 2 to 10
According to the preparation method of the oxime ester fluorene photoinitiator of example 1, the following compounds 2 to 10 were prepared by replacing the corresponding reaction raw materials or reagents. The data for the corresponding chemical structural formulae and the corresponding nmr hydrogen spectrum characterization for compounds 2 to 10, respectively, are listed in table 1 below.
TABLE 1
The following performance evaluations were performed on the compounds 1 to 10 and the existing oxime ester photoinitiators (compound a and compound B) prepared in examples 1 to 10 described above, including:
1. dissolution test
The solubility of the oxime ester fluorene photoinitiator in Propylene Glycol Methyl Ether Acetate (PGMEA) is one of index parameters representing the solubility and measuring the application performance of the photoinitiator. The compounds of the structure shown in the general formula (I) were selected for comparison with the existing oxime ester photoinitiators (compound A and compound B), and the solubility of the compounds 1 to 10 and the compounds A and B in PGMEA at 25℃was tested, respectively, and the test results are shown in Table 2.
TABLE 2
| Oxime ester fluorene photoinitiator | Solubility in PGMEA (wt.%) | |
| Example 1 | Compound 1 | >15％ |
| Example 2 | Compound 2 | >15％ |
| Example 3 | Compound 3 | >15％ |
| Example 4 | Compound 4 | >15％ |
| Example 5 | Compound 5 | >15％ |
| Example 6 | Compound 6 | >15％ |
| Example 7 | Compound 7 | >15％ |
| Example 8 | Compound 8 | >15％ |
| Example 9 | Compound 9 | >15％ |
| Example 10 | Compound 10 | >15％ |
| Comparative example 1 | Compound A | <5％ |
| Comparative example 2 | Compound B | >15％ |
| Comparative example 3 | Compound C | <10％ |
Wherein, the chemical structural formula of the compound A is as follows:
the chemical structural formula of the compound B is as follows: />
Compound C: />
2. Photosensitive Performance test
The photocurable compositions used in the photosensitive test in all examples and comparative examples of the present application were formulated in the following proportions. Wherein, the light-curing composition comprises the following components in parts by weight: 200 parts of an acrylic ester copolymer, 100 parts of dipentaerythritol hexaacrylate, 5 parts of a photoinitiator, 900 parts of butanone (solvent), 5 parts of dye blue 15 (CAS: 147-14-8), and the acrylic ester copolymer (manufacturer: hemsl) is a benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio of 70:10:20) copolymer, mw=10000.
In the photo-curing composition, the photoinitiator is an oxime ester fluorene compound shown in the general formula (I) in the content of the application or similar photoinitiators known in the prior art for comparison. The specific formulations of all examples and comparative examples of the present application are shown in table 3.
TABLE 3 Table 3
(1) Sensitivity test
The photo-setting composition was stirred in the absence of light and coated on PET film with a 6# wire rod to form a wet film having a thickness of about 6. Mu.mAnd (3) coating. Using mercury lamp (RW-LED-YT 200gl, single exposure of 100 mj/cm) 2 ) UV-LED light source irradiation (RW-UVAP 202-20gl, single exposure of 1000 mj/cm) 2 ) The film was exposed to light at different wavelengths, and cured to form a film, which was evaluated by the finger touch method.
The finger touch evaluation criteria were as follows: 1: oil, not solid; 2: surface oil and bottom layer solidification; 3: the surface is sticky, and the fingerprint is heavier after hand touch; 4: basic surface dryness, slightly astringent after touching with hands, and light fingerprint; 5: completely cured, smooth in surface and free of fingerprints after hand touch.
The results of the sensitivity tests for all examples and comparative examples of the present application are shown in table 4.
TABLE 4 Table 4
(2) Yellowing resistance test
Referring to the specific formulations shown in table 2, photocurable compositions were formulated. After the above-mentioned photocurable composition was sufficiently stirred in a yellow room, the composition was applied onto tin plate using a 15# bar to prepare a coating film having a wet film thickness of 10 μm. The light source of 365nm-LED is adopted for exposure, and 2000mJ/cm is received 2 And the energy of the (c) is sufficient to cure the (c) completely.
And (3) carrying out yellowing test by using an alicolor difference meter, and judging the yellowing resistance of the photo-curing resin according to the delta b value. The higher the Δb value, the more pronounced the yellowing, and the worse the yellowing resistance. The results of the yellowing resistance tests of all the examples and comparative examples of the present application are shown in Table 5.
TABLE 5
The photocurable compositions in comparative examples 1 and 3 were precipitated due to poor compatibility between the respective raw materials, and the yellowing resistance thereof could not be evaluated.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
(1) As can be seen from table 2, the photoinitiator compound a as a comparison was poor in solubility in PGMEA (only < 5%), whereas the compounds 1 to 10 prepared in examples 1 to 10 of the present application all had good solubility in PGMEA (solubility all > 15%), and all satisfied the requirement that the solubility of the photoinitiator was greater than 8% by weight at the time of industrial application. In combination with their respective chemical structures, the fluorene in compound a has a 7-position substituted with a triazine ring, but the 4-and 6-positions on the triazine ring are not substituted with an alkoxy group, and has a solubility of only < 5%; in contrast, the chemical structure of the photoinitiator compound C is that the triazine ring is not directly connected to the fluorene ring, but is used as a substituent of an oxime ester structure, the solubility of the compound A is only less than 10%, and the solubility of the compound A and the compound C is poorer than that of the compound 1, which shows that the introduction of the substituent of the preferred type in the application at the 4 position and the 6 position of the triazine ring is beneficial to improving the solubility of the oxime ester fluorene photoinitiator.
(2) As can be seen from table 3, each example and comparative example differ only in the kind of photoinitiator. As can be seen from the combination of table 4, the photocurable compositions in comparative examples 1 and 3 are difficult to cure under irradiation of a mercury lamp or LED light source, and the curing efficiency is far lower than examples 1 to 10; whereas the photocurable composition of comparative example 2 was capable of achieving only substantial surface drying under irradiation with a mercury lamp or LED light source, and failed to be fully cured, the curing effect was inferior to examples 1 to 10. Therefore, the oxime ester fluorene photoinitiator with the specific structure can be applied to a conventional ultraviolet light curing system, can be completely cured under the irradiation of a mercury lamp and an LED light source, and has a good curing effect.
(3) As can be seen from table 5, the Δb value of comparative example 2 is much higher than that of examples 1 to 10 under 365nm LED light source exposure, indicating that the yellowing resistance of comparative example 2 is much worse than that of examples 1 to 10, i.e., the photosensitivity of compounds 1 to 10 is more excellent and has a characteristic of less yellowing than that of the existing initiators (compounds A, B and C of comparative examples 1 to 3) having better photosensitivity. Therefore, when the oxime ester fluorene photoinitiator with the specific structure provided by the application is applied to a photo-curing composition, the curing efficiency under the irradiation of a light source can be improved, and the oxime ester fluorene photoinitiator has the characteristics of low yellowing and excellent solubility. Meanwhile, the oxime ester fluorene photoinitiator can be used for a UV-LED photocuring system, and particularly can be used as an initiator under the action of a 365nm light source to remarkably improve yellowing resistance.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The oxime ester fluorene photoinitiator is characterized by comprising a 4, 6-alkoxy substituted triazine ring group, and has a structure shown in a general formula (I):
in the general formula (I), the R 1 And said R 1 'same or different' and R is as defined above 1 And said R 1 ' are independently selected from hydrogen atom, halogen, C 1 ～C 10 Alkyl, C of (2) 4 ～C 10 Aryl or C of (2) 2 ～C 10 Wherein said alkyl, said aryl, said alkenyl may be interrupted by O, N or carbon groups, respectively; or said R 1 And said R 1 ' may also be linked into a ring;
the R is 2 And said R 3 Are independently selected from the R 2 And R is 3 Are independently selected from C 1 ～C 20 Straight or branched alkyl, C 3 ～C 20 Cycloalkyl, C 3 ～C 8 Cycloalkyl-substituted C of (C) 1 ～C 10 Alkyl, C of (2) 1 ～C 20 Alkyl substituted C 3 ～C 8 At least one hydrogen atom in cycloalkyl, phenyl is C 1 ～C 4 A group obtained after alkyl substitution, C 1 ～C 4 Alkoxy, C 1 ～C 4 Groups obtained by substitution of one or more hydrogen atoms in the alkoxy group by fluorine atoms, furyl, thienyl, C-terminal with furyl 1 ～C 4 C terminated with alkyl groups, or with thienyl groups 1 ～C 4 An alkyl group;
the R is 4 And said R 5 Are independently selected from C 1 ～C 5 Is a hydrocarbon group.
2. The oxime ester fluorene photoinitiator according to claim 1, wherein in the general formula (I), the R 2 Selected from C 1 ～C 10 Alkyl substituted C 3 ～C 8 Cycloalkyl, phenyl, naphthyl, furyl or thienyl; the R is 3 Selected from C 1 ～C 10 At least one hydrogen atom of the linear or branched alkyl, phenyl or phenyl group being C 1 ～C 4 Alkyl groups are substituted to give the groups.
3. Oxime ester fluorene photoinitiator according to claim 1 or 2, wherein R 1 And said R 1 ' selected from C 1 ～C 5 Straight chain alkyl of (a).
4. An oxime ester fluorene photoinitiator according to claim 3 wherein R 1 And said R 1 ' selected from C 1 ～C 4 Branched or branched alkyl of (a); the R is 2 Selected from C 1 ～C 4 Alkylene substituted cyclohexane, C 1 ～C 4 Alkylene substituted cyclopentane, phenyl, 1-naphthyl, α -furyl or α -thienyl; the R is 3 Selected from methyl, ethyl, phenyl or 2-methylphenyl; the R is 4 And said R 5 Selected from C 1 ～C 4 Straight or branched alkyl of (a).
5. The oxime ester fluorene photoinitiator according to claim 4, wherein the oxime ester fluorene photoinitiator is selected from one or more of the following compounds 1 to 10:
6. a photocurable resin composition comprising a photoinitiator, an alkali-soluble resin, and a polymeric monomer, wherein the photoinitiator comprises the oxime ester fluorene-based photoinitiator according to any one of claims 1 to 5.
7. The photocurable resin composition according to claim 6, wherein the photocurable resin composition comprises 0.5-10 parts of an oxime ester fluorene photoinitiator, 20-80 parts of an alkali-soluble resin and 20-80 parts of a polymeric monomer;
preferably, the photocurable resin composition further comprises 0 to 200 parts of a solvent.
8. Use of an oxime ester fluorene photoinitiator according to any one of claims 1 to 5, or a photocurable resin composition according to claim 6 or 7 in the field of photocuring.
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